Accepted Manuscript

Title: Production of Aromatic Hydrocarbons by Catalytic

Co-pyrolysis of Microalgae and Polypropylene using HZSM-5

Authors: Pengyu Qi, Guozhang Chang, Hongchao Wang,

Xiuli Zhang, Qingjie Guo

PII: S0165-2370(18)30653-3
DOI: https://doi.org/10.1016/j.jaap.2018.10.007
Reference: JAAP 4448

To appear in: J. Anal. Appl. Pyrolysis

Received date: 16-7-2018

Revised date: 20-9-2018
Accepted date: 8-10-2018

Please cite this article as: Qi P, Chang G, Wang H, Zhang X, Guo Q,

Production of Aromatic Hydrocarbons by Catalytic Co-pyrolysis of Microalgae and
Polypropylene using HZSM-5, Journal of Analytical and Applied Pyrolysis (2018),
https://doi.org/10.1016/j.jaap.2018.10.007

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Production of Aromatic Hydrocarbons by Catalytic Co-pyrolysis of

Microalgae and Polypropylene using HZSM-5

Pengyu Qia, Guozhang Changa,b, Hongchao Wanga, Xiuli Zhanga, Qingjie Guoa,b*

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a
Key Laboratory of Clean Chemical Processing of Shandong Province, College of Chemical Engineering,

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Qingdao University of Science and Technology, Qingdao 266042, PR China

b
State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering, College of

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Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, PR China
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GRAPHICAL ABSTRACT
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*Corresponding author.

Address: College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao

266042, China. Tel.: +86 053284022757.

E-mail address: qj_guo@yahoo.com (Q. Guo).

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Highlights
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 A synergistic effect was found in catalytic co-pyrolysis of NS/PP for

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aromatics production.
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 The maximum content of aromatic hydrocarbons could reach to

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77.04 area%.

 3 The maximum mass yield of monoaromatic hydrocarbons could

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reach to 0.1223 g/(g·sample) by external standard method.

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A B S T R A C T：

In the current study, the thermogravimetric behavior of Nannochloropsis sp. (NS),

polypropylene (PP) and mixed samples (NS: PP = 1:1) with and without catalyst were

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investigated by TGA analysis. To promote the efficient production of aromatic

hydrocarbons, co-pyrolysis of NS and PP over the HZSM-5 zeolite catalyst were carried

out in a bench-scaled fixed bed reactor. The effects of the reaction temperature

(500-900 °C), NS/PP mass ratio (1:0, 3:1, 2:1, 1:1, 1:2,1:3 and 0:1) and

feedstock/catalyst mass ratio (1:0-1:10) on the relative content of aromatics were

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investigated. The results showed that the catalytic co-pyrolysis of NS and PP exhibited a

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synergistic effect on the generation of aromatic hydrocarbons compared to their

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individual pyrolysis.The relative content of aromatic hydrocarbons compounds and

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mass yield of monoaromatic hydrocarbons in oil from catalytic co-pyrolysis of NS and

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PP with HZSM-5 could reach to 77.04 area%, and 0.1223 g/(g·sample), respectively.
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Based on chemical composition analysis of the oil, the mechanisms for the formation of
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major aromatic hydrocarbons during the catalytic co-pyrolysis of NS and PP were

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further discussed.
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Keywords: microalgae; polypropylene; co-pyrolysis; aromatic hydrocarbons; mechanism

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1. Introduction

Because of coal, oil, natural gas and other non-renewable energy shortages and
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environmental problems, the search for a renewable energy source and chemicals has

become a global effort[1]. Aromatic hydrocarbons are important raw material that are

used in the chemical industry, and their acquisition route is mainly the secondary

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processing of oil and coal. Biomass, which is abundant and inexpensive, is considered

to be the most attractive ingredient for producing renewable chemicals[2-4]. In many

biomass conversion technologies, catalytic pyrolysis technology is considered as a

potentially useful technology because it can convert biomass directly into petroleum

chemical products, such as aromatics and phenols[5-6]. At the same time, the

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production of biomass-based aromatic chemicals is of great significance for alleviating

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energy shortages and reducing greenhouse gas emissions. Several authors have studied

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in catalytic pyrolysis biomasses or the acquisition of aromatic compounds based on a

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biomass[7-8].

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Previously, Huber[9] proposed the catalytic pyrolysis of lignocellulosic biomass to
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produce aromatic hydrocarbons. This technology references the crude oil refining
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process and acts through the catalytic pyrolysis of lignocellulose biomass directly into

liquid aromatic hydrocarbons to produce a high high-value product (benzene, toluene,

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xylene, etc.) that greatly improves the energy density and stability of the liquid
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hydrocarbon products. The products can be directly used as a high-octane number

gasoline fuel or important chemical raw material in the petrochemical industry.

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Subsequently, many scholars have carried out research on the production of aromatic
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hydrocarbons through catalytic pyrolysis. Zheng et al [10] and Foster et al[11] showed
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that cellulose, hemicellulose, and lignin had different effects on the catalysis of biomass

fast pyrolysis and that different terrestrial biomasses generated aromatic hydrocarbons

under the action of the ZSM-5 catalyst. However, there are obvious problems with a

high carbon content and relatively low target yield. The low yield of the target product

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of biomass catalytic pyrolysis is the main bottleneck in the development of this

technology, and the root cause of the low yield of the target product is the poor

hydrogen oxygen enrichment characteristics of the raw materials.

For biomass, the essential factor that limits its further conversion to high quality

fuels or chemicals is the hydrogen to carbon effective (H/Ceff)ratio[12], as shown in eqn

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(1). The H, C and O in eqn (1) are the moles of hydrogen, carbon, and oxygen in the

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feed, respectively.

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H  2O
H / C eff  (1)
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The literature shows that the increment of the H/Ceff ratio can increase the yield of
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hydrocarbons and reduce the coke rate of the catalyst. Zhang et al[13] confirmed that
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co-pyrolysis of biomass and high H/Ceff ratio materials had obvious synergistic effects
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on the production of aromatic hydrocarbons and olefins. Solid waste plastic is a cheap
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hydrogen-rich raw material, which has a high H/Ceff ratio, high calorific value and low

oxygen content, making it an ideal hydrogen feedstock for biomass[14].In addition,

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plastics are particularly attractive synthetic polymers, because they have a low recycling
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rate and most of them are non-biogradable. Moreover, waste plastics have constituted
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not only serious environmental problems but also a huge waste of fossil fuel resources

considering their high-value chemicals and high energy density even though they have
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contributed immensely to our daily activities.[15]. A wide variety of strategies for the

thermochemical conversion of waste polyolefins have been developed in the last

decades. The most studied one is undoubtedly pyrolysis. However, when the plastic is

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pyrolyzed alone, it is not conducive to the production of oil due to high gas

yield.[16-17]. Co-pyrolysis of biomass and plastics not only improves the yield and

quality of biomass pyrolysis oil products but also serve as an optional solution or

alternative waste management method for the future that will have a significant impact

on waste reduction and thus reduce the dependency on fossil fuels.[16,18]. Many

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studies have been carried out regarding the production of aromatic hydrocarbons from a

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catalytic co-pyrolysis biomass and plastic, including on the materials, catalysts and

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parameter conditions[19-21]. However, there are few studies on the direct catalytic

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co-pyrolysis of microalgae and plastics.

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As an important type of biomass resource, microalgae are considered to be a
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potential feedstock for bio-oil production due to their good photosynthetic efficiency,
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high growth rate and high area-specific yield[22]. Furthermore, microalgae can greatly

reduce CO2 emissions since they can be cultivated using industrial waste gases that
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contain CO2[23]. However, bio-oil obtained from the thermochemical conversion of

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microalgae has some disadvantages, which severely hinder its practical applications[24].

Hence, it is necessary to explore how the quality of oils can be improved. Currently,
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studies have confirmed that microalgae and plastics have a synergistic effect on the
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kinetics of co-pyrolysis. The kinetics of microalgae and plastic show that their
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interaction can reduce the pyrolysis activation energy of microalgae[25-26]. There are

also related reports on co-liquefaction[27-28]. In the supercritical state, the interaction

between microalgae and plastics can improve the production and quality of oil[29].

However, there are few reports on the interaction mechanism of microalgae and plastics

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in the catalytic co-pyrolysis process, especially during the generation of aromatic

compounds.

As a consequence, the thermogravimetric behavior of Nannochloropsis salina, PP,

and mixed samples (NS: PP=1: 1) with and without catalyst were investigated by TGA.

Co-pyrolysis of NS and PP was carried out in a bench-scaled fixed bed reactor over a

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temperature range of 500-900 °C with varying NS and PP mass ratios of 3:1, 2:1, 1:1,

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1:2 and 1:3 under different conditions of catalyst addition. The objective of this research

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was to study the interaction between NS and PP during the catalytic pyrolysis process

and explore the possible aromatic generation reaction mechanism by analyzing the

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chemical composition of the obtained bio-oil under different operating conditions.
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2. Materials and methods
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2.1. Materials
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Nannochloropsis sp (Yan Tai HaiRong Biochemical Co., China) and PP (Sinopec

zhanjiang dongxing petrochemical co., LTD., China) were used in this study. NS were
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dried at 105 °C for 24 h and sieved to obtain a fraction under a 120 mesh (<125 μm). PP
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was dried at 80 °C for 24 h. The HZSM-5 molecular sieve catalyst was obtained from
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the Catalyst Plant of Nankai University. The Si/Al ratio of ZSM-5 was about 25. The
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HZSM-5 was calcined at 550 °C for 6 h and sieved to obtain a particle size between 80

and 120 mesh (125-177 μm). Pure argon gas (99.99%, Qingdao ruifeng gas co., LTD.)

and high purity nitrogen gas (99.999%, Qingdao ruifeng gas co., LTD.) were used in

this study. The ASTM Standard Test Methods for proximate analysis were used to

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determine the weight fractions of the volatile, ash and fixed carbon contents. Identifying

compounds above 80% probability were selected for qualitative analysis. The external

standard method was proposed for the quantitative analysis of monoaromatic

hydrocarbons in oils. A calibration curve of content VS peak area of monoaromatic

hydrocarbons was firstly established using standard solutions, which was shown in Fig.

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S1. Seven monoaromatic hydrocarbons were selected as the standard curve, and other

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monoaromatic hydrocarbons were based on the average vaue. The coefficient of

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determination R2 value for the calibration curve was higher than 0.9467.Then the mass

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yield of monoaromatic hydrocarbons in each oil could be calculated from the calibration

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curve.The C, H, O and N contents of the samples were determined in an elemental
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analyzer (Leco CHN628 Series). The calorific value of the samples were analyzed using
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Bomb calorimete r(WELL8000). The microalgae protein content and lipid content were
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examined by Kjeldahl method and solvent extraction method (chloroform/methanol

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with a volume ratio of 2:1), respectively[30]. The main properties of the samples are

listed in Table S1.The Brunauer-Emmett-Teller (BET) surface areas of the HZSM-5

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catalyst were determined using a Micromeritics ASAP-2020 N2 physical adsorption

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instrument. Samples were degassed overnight in vacuum at 200 °C before nitrogen

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adsorption at -196 °C. Temperature Programed Desorption (NH3–TPD) was performed

using TP-5080 instrument. Before each NH3–TPD measurement, 100 mg of catalyst

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was loaded into a quartz tube, was outgassed for 1 h in He at 650 °C, and then cooled

down to 20 °C to absorb ammonia for 1 h. After purged with He stream for removal of

weak adsorbates at 120 °C, temperature was increased to 650 °C in the rate of 5 °C/min

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to record the NH3-TPD profiles.The physicochemical characterization of

HZSM-5catalysts are listed in Table S2.

2.2.Thermogravimetric (TG) analysis

A thermogravimetric analyzer (NETZSCH STA 409PC DE) was used for these

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（NS, PP and NS:PP = 1:1 at the same weight
experiments. In a typical experiment, 10 mg

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as HZSM-5 and mixed well）of sample was evenly placed into an alumina crucible and

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pyrolyzed under a high purity nitrogen flow of 60 mL/min. The temperature increased

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from room temperature to 900 °C at a heating rate of 20 °C/min. The experimental

errors were found to lower than 3% in three runs repeated under the same conditions.
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2.3. Co-pyrolysis experiment
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Co-pyrolysis of NS and PP was performed in a bench-scaled fixed bed reactor

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(OTF-1200X), as shown in Fig. S2. The reactor in this apparatus was a quartz tube with
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a length of 70 cm, an internal diameter of 5 cm and an outer diameter of 6 cm. Before

each test, an approximately 10 g of samples (NS, PP or mixed sample) was transferred

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into a custom-built porcelain boat (9 cm × 3 cm × 1.5 cm) and the HZSM-5 catalyst
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with a sample-to-catalyst mass ratio of 1:0, 1:1, 1:3, and 1:10 was putted into another
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layer on the top of the sample layer in the custom-built porcelain boat.Then,the
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porcelain boat with sample was placed in the cold zone of the quartz tube, after which

Argon at a flow rate of 200 mL/min was used to purge air from the interior of the

reactor for 30 min. The reactor was subsequently heated electrically to the target

temperature (500, 600, 700, 800, or 900 °C) and detection of reaction zone temperature

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by thermocouple. Once the reactor had stabilized at the desired temperature, the

porcelain boat holding the samples was rapidly moved into the heated zone (30 cm) and

held there for 15 min to allow the samples to react completely. Two duplicate trials were

performed under the same conditions to ensure the accuracy and reliability of

results.The pyrolytic volatiles were condensed in the ice-water mixtures, the liquid

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products were collected in the oil collector, and the non-condensable gas was disposed.

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After each experiment, the reactor was cooled to room temperature under an Argon

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purge. The char yield was determined according to the weight difference of the

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porcelain boat. Similarly, the oil yield was determined according to the initial and final

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weights of the oil collector, while the gas yield (wt%) was calculated by the
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difference[31].
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2.4. Product analysis

The oil components were analyzed using Phenergan-trace DSQ type gas
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chromatography-mass spectrometry (GC-MS), with an HP-5 capillary column (60 m ×

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0.25 mm × 0.25 μm). High purity nitrogen was used as the carrier gas. The injection

size was 1.0 μL, with a split ratio of 1:30, and the MS source was set to 70 eV. The
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column temperature of the GC used in this study was programmed to be heated from an

initial temperature of 80 to 280°C with a heating rate of 10 °C/min, with a final hold at
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280°C for 20 min. Identification of compounds was performed using the NIST library

software. In addition, the synergy of co-pyrolysis was determined according to the

difference between the experimental and calculated results of the co-pyrolysis as

follows[32-33].
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 Ydifference=Yexpr.mix-Ytheo.mix

Ytheo.mix=XNSYexpr.NS+XPPYexpr.PP

where XNS and XPP represent the mass percent of NS and PP in mixed samples,

respectively. Yexpr.NS and Yexpr.PP are the experimental results of NS and PP pyrolysis

alone, respectively. Yexpr.mix and Ytheo.mix are the experimental and calculated results of

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the pyrolysis mixed samples, respectively. Ydifference > 0 indicates a promoting effect of

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co-pyrolysis, while Ydifference < 0 implies an inhibiting effect.

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3. Results and discussion

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3.1. Thermogravimetric (TG) analysis

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3.1.1. Pyrolysis behavior of NS, PP and mixed samples without catalyst
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Fig. 1. TG(a) and DTG(b) curves of NS, PP and mixed samples without catalyst at a heating rate of
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20 °C/min.
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Fig. 1 shows the TG (a) and DTG (b) curves of NS, PP and mixed samples without

catalyst at a heating rate of 20 °C/min. The pyrolysis behaviors of the two samples are

similar to those in the literature[25]. According to the TG and DTG curves of NS,

pyrolysis can be divided into three steps. The first step was from room temperature to

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approximately 140 °C, where there was a slight weight loss on the TG curve and a small

peak on the DTG curve, which was mainly due to the loss of water and low volatile

compounds. The second step was the main decomposition step, with a temperature

range from 140-550 °C, and most of the organic compounds were released in this stage.

Multiple peaks were observed in the DTG curves, representing the decomposition of

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lipids, proteins and carbohydrates[22]. The third step was from 550-900 °C, with a very

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slight weight loss in the TG curves, and the solid residual decomposition rate was very

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slow during this process. The same phenomenon was shown in previous studies[34].

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The pyrolysis of PP was different from that of NS, and the weight loss interval was

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narrower. Only one strong peak between 280-510 °C as observed in the DTG curve. The
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maximum weight loss rate of PP was much higher than that of NS, which shows that PP
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released more volatile components than NS in the main pyrolysis process. During
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co-pyrolysis of NS and PP, the peak pyrolytic temperature of NS was slightly reduced
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compared to that of the sole NS pyrolysis. Therefore, it can be concluded that PP

accelerates the pyrolysis process of NS and reduces the pyrolysis temperature of NS. In
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addition, Wu et al[25] also reported that PP with a smaller particle size promoted the
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pyrolysis of NS. On the contrary, the peak of the pyrolysis temperature of PP slightly
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increased in the presence of NS. The most likely reason for this phenomenon is that

pyrolysis of small molecules or radicals emitted during early pyrolysis of PP react with
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the residues of NS. Additionally, the lack of initiator leads to an increase of the required

pyrolytic temperature of PP[35-36].

3.1.2. Pyrolysis behavior of NS, PP and mixed samples with the HZSM-5 catalyst

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 As shown by the TG and DTG curves in Fig. S3, the weight loss rate of NS was not

significantly changed and the peak of the pyrolysis temperature slightly increased when

the NS/catalyst ratio was 1:1. These results indicate that the addition of the catalyst did

not significantly promote the pyrolysis of NS. The use of HZSM-5 has a negligible

influence on the peak pyrolysis temperature of PP, but leads to a significant

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improvement of the weight loss rate of PP. This result is different from the report of

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Sebestyén et al[37] possibly because of the different sizes of the samples. During

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co-pyrolysis of NS and PP (1:1) with a mixed HZSM-5 catalyst at a 1:1 mass ratio, the

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peak pyrolytic temperature of NS further increased and the weight loss rate was slightly

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reduced compared to those of co-pyrolysis of NS and PP without a catalyst, indicating
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that the residues of NS pyrolysis are difficult to remove from the reaction system in the
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presence of the HZSM-5 catalyst. Meanwhile, it was observed that the weight loss rate
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of PP was improved and the pyrolysis peak temperature was significantly increased
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compared to those in the absence of a catalyst. The most likely explanation for this

phenomenon is that the retention time of NS pyrolysis is prolonged and it more easily
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reacts with the small molecules or radicals emitted during early pyrolysis of PP when
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the HZSM-5 catalyst is added, which leads to the PP lacking an initiator to continue the
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reaction. Therefore, the pyrolysis temperature peak of PP is further improved. At higher

temperatures, the pyrolysis of PP is accompanied by the decomposition of NS residues;

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thus, the rate of weight loss is increased. In conclusion, the addition of the HZSM-5

catalyst makes the interaction between NS and PP more intense during pyrolysis, which

increases the possibility of synergistic action between NS and PP in co-pyrolysis.

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3.2. Catalytic co-pyrolysis of NS and PP

3.2.1. Influence of the reaction temperature on the co-pyrolysis process

The key to the synergistic effect of co-pyrolysis is that the volatiles generated by

the mixed pyrolysis materials contact one another. Thus, a series of experiments was

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carried out at different temperatures. To study the effect of temperature on the yield of

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pyrolysis products and liquid product distribution, the NS and PP mass ratio was 1:1,

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which was under the mass ratio of the sample to catalyst was 1:1. The yield of the

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pyrolysis products is shown in Fig. 2a. From this figure, it is clear that as the

temperature increased from 500 °C to 900 °C, the oil and char yields gradually
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decreased, while the gas yield rapidly increased. Several other studies have also
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reported similar observations, indicating that at high temperature, a strong cracking
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reaction takes place and a secondary decomposition of char residue occurs with the

decrease of the liquid yield[38].

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Fig. 2. Products distribution and main compositions of oils from catalytic co-pyrolysis of NS with

PP under different temperature conditions（NS/PP=1:1）

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 The main compositions of the oils from the co-pyrolysis of NS with PP under

different temperature is shown in Fig. 2b. The main chemical compounds (area%) and

mass yield of monoaromatic hydrocarbons identified in oil are listed in Table S3.The

total ion chromatograms (TICs) obtained from GC/MS analysis of oils is shown in Fig.

S4.The main compositions of the oils are categorized as aromatic hydrocarbons, olefins,

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N-containing compounds, small molecular O-containing species (alcohols /esters

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/phenols /ketones /acids) and others. At 500 °C, the oils mainly contain olefins, which

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are produced by polypropylene pyrolysis and small molecular O-containing species

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(alcohols /esters /phenols /ketones /acids), which are produced by microalgae. Moreover,

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the nitrogen compound content is up to 17.61%, which is not conducive to the
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processing and utilization of oil. With the further increase of the pyrolysis temperature,
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the content of aromatics in the oil is greatly increased and that of olefins is significantly
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decreased, possibly because the main pyrolysis temperature ranges of NS and PP are not
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synchronized, resulting in pyrolysis of volatiles that do not fully contact at low

temperature. At high temperatures, the volatiles can be rapidly released and more fully
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exposed than at low temperatures. Small molecules produced by polypropylene have a

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promoting effect on the decomposition of microalgae. The lipids, carbohydrates, and

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proteins in microalgae undergo decarbonylation, deoxygenation, and deamidation

reactions, which generate a large number of small molecules that undergo aromatization
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under the action of catalysts and promote the formation of large amounts of aromatics.

With the increase in temperature, the N-containing compounds in oil gradually decrease.

It is speculated that the possible reason for the decrease in N-containing compounds is

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because pyrolysis of microalgae, N-containing compounds are more likely to bduring e

converted into gas and char under high temperature. At 800 °C, the content of aromatics

reached 77.04% and that of nitrogen was only 3.29%, and the mass yield of

monoaromatic hydrocarbons could reach 0.1223 (g/g·sample), significantly better than

previous reports[39-41], HZSM-5 has been used to catalyze the pyrolysis of

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Nannochloropsis sp, corn stalk and food waste, mushroom waste, with aromatics yields

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of 50.23, 37.5, and 19.8 area%, respectively. However, with a further temperature

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increase, the content of aromatics increased to 84.93% and content of nitrogen

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decreased to 2.54%, while the yield of bio-oil significantly decreased due to severe

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secondary cracking. Therefore, with comprehensive consideration of the yield of oil, oil
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quality and energy consumption, 800 °C was found to be a suitable temperature for the
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production of aromatic hydrocarbons by catalytic co-pyrolysis of microalgae and

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polypropylene using HZSM-5.

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3.2.2. Influence of the reactant proportion on the co-pyrolysis process

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Fig. 3. Products distribution of catalytic co-pyrolysis of NS with PP at 800 °C

The mixture ratio of materials is an important factor that affects the yield and

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quality of oil. Thus, a series of experiments was carried out with different mass ratios of

NS and PP and with a mass ratio of the sample to the catalyst of 1:1 at 800 °C to study

the effect of the reactant proportion on the yield of pyrolysis products and the liquid

product distribution. As shown in Fig. 3, it is clearly evident that the yield of char is

approximately 23% when NS alone catalyzes pyrolysis due to the low H/Ceff ratio of the

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microalgae, whereas the PP pyrolysis product alone mainly consisted of gas (67.5%)

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and liquid (32.5%), which contained almost no char, indicating that PP was completely

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decomposed into small molecular gases and liquid at high temperatures. In addition, the

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suitable mass ratio of NS and PP was beneficial for increasing the oil yield during the

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co-pyrolysis of microalgae and polypropylene. When the mass ratio of NS to PP was
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from 1:0 to 0:1, the char yield decreased almost linearly and the gas yield increased
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rapidly, while the oil yield gradually increased from a mass ratio of NS to PP from 3:1 to
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1:1 and significantly decreased from a mass ratio of NS to PP from 1:1 to 1:3, reaching a
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maximum (45%) when the mass ratio of NS to PP was 1:1. It should be noted that the

small molecules generated by PP promoted the pyrolysis of microalgae and thus

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promoted the production of gas products of oil and smaller molecules generated at a
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relatively small PP mixture ratio. When a large amount of PP was mixed, a large
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number of small molecules generated by the pyrolysis of PP promoted the secondary

cracking reaction, and thus, the oil and char were converted into small molecules, which
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entered the gas.

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Fig. 4. Main compositions of oils from catalytic co-pyrolysis and the differences between the

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experimental (a) and theoretical results (b)(a positive value means promotion, while a negative

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value means inhibition).

The compositions of oils from the catalytic co-pyrolysis of NS and PP is shown in

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Fig. 4. And the main chemical compounds (area%) and mass yield of monoaromatic
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hydrocarbons identified in oil are listed in Table S4. The TICs obtained from GC/MS
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analysis of oils is shown in Fig. S5. NS pyrolysis generated 64.73% aromatic

hydrocarbons, 7.47% O-containing species (alcohols /esters /phenols /ketones /acids)

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and a small amount of olefins (4.7%), in oil, but a large amount of N-containing
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compounds (19.59%) were produced. The main product of the catalytic pyrolysis of NS

used HZSM-5 as a catalyst, which is an aromatic hydrocarbon[39], while fewer

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O-containing species were found due to the lower oxygen contents of NS and

N-containing species, which mainly resulted from the decomposition of proteins[42].

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Nitrogenous compounds mostly entered the liquid phase during pyrolysis, which

accounted for the increased bio-oil nitrogen content.

For PP, different properties were found for liquid products, as large amounts of

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aromatic hydrocarbons (59.25%) and olefins (32.21%) formed, as well as a few

O-containing species (only 0.21%) and no N-containing compounds[38,43]. Aromatic

hydrocarbons mainly came from the aromatization of monomers produced by PP

pyrolysis using HZSM-5 as the catalyst. At the same time, olefins mainly resulted from

the cracking of PP, and no N-containing compounds were formed because the material

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did not contain nitrogen. In particular, with the mixing of PP, the N-containing

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compounds in oil largely decreased (Fig. 4(a)) compared with those from NS pyrolysis

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and decreased largely with the increasing PP/NS mass ratio, as the NS content decreased

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and N-containing compounds mainly came from NS decomposition.

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To discuss the interaction effect on oil during NS and PP co-pyrolysis in detail, the
N
differences between the experimental results and theoretical results are shown in Fig.
A
M

4(b). N-containing compounds were obviously lower than the theoretical result, and the

maximum difference reached -7.35%, possibly due to co-pyrolysis, which could inhibit
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the generation of N-containing compounds in oil and drive more of them into gas and
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char. This was good for the utilization of biofuel with fewer N-containing compounds,

as N-containing compounds may release NOx during the combustion of oil. Moreover,
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the experimental result of aromatic hydrocarbons was significantly higher than the
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theoretical result, and the maximum difference reached 15.05% at a NS: PP ratio of 1:1,
A

which indicates that the catalytic co-pyrolysis of microalgae and polypropylene is

synergistic to the formation of aromatic hydrocarbons. Meanwhile, co-pyrolysis of NS

and PP might inhibit the secondary cracking of aromatic compounds, promoting the

high content of aromatic hydrocarbons in oil. In addition, catalytic co-pyrolysis inhibits

19
the production of O-containing species at different mixing ratios of NS and PP, which

might contribute as follows: First, mixing PP can effectively increase the H/Ceff and

reduce the content of oxygen in the samples; second, the molecular sieve catalyst

HZSM-5 has a good deoxygenation effect during the pyrolysis of biomass and reduces

the oxygen content in oil.

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3.2.3. Influence of the catalyst proportion on the co-pyrolysis process

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At a mass ratio of NS/PP was 1:1 and a catalytic temperature was 800 °C, the

SC
yields of different products from co-pyrolysis of NS and PP under different

feedstock/catalyst ratios (1:0, 1:1, 1:3, and 1:10) are shown in Fig. 5a. The addition of
U
N
catalysts significantly influenced the product yields during catalytic co-pyrolysis. The
A
gas yields increased and the char yields first decreased and then increased with the
M

addition of the catalyst. Additionally, the char yield reached a minimum of 9% when the

feedstock/catalyst mass ratio was 1:3. With increased catalyst addition, the rate of
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catalytic cracking improved, thereby aiding the formation of gaseous compounds[44].

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In addition, the oil yields decreased with increased catalyst loading. This phenomenon

occurred because the secondary cracking of the vapors from the co-pyrolysis of NS and
E
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PP passed through the HZSM-5 zeolites.

A

20
 T
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Fig. 5. Products distribution and main compositions of oils from catalytic co-pyrolysis of NS with

PP under different feedstock/catalyst ratios （NS/PP=1:1）

R
SC
The main compositions of oils from co-pyrolysis under different feedstock/catalyst

ratios are depicted in Fig. 5b. And the main chemical compounds (area%) and mass
U
N
yield of monoaromatic hydrocarbons identified in oil are listed in Table S5. The TICs
A
obtained from GC/MS analysis of oils is shown in Fig. S6.The oil from co-pyrolysis
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without added catalyst showed the low content of aromatic hydrocarbons and a high

proportion of nitrogen compounds. Considering the high amount of nitrogen compounds

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and low amount of aromatic hydrocarbons in the oil, which are not conducive to the
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further refining and utilization of bio-oil, HZSM-5 was used as a catalyst to improve the

quality of the oil. With the addition of HZSM-5, a zeolite catalyst, co-pyrolysis
E
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significantly increased the content of aromatic hydrocarbons (43.38% to 93.29%) and

reduced the content of olefins (33.19% to 2.29%). Meanwhile, the value of the nitrogen
A

compound proportion changed from 18.37% to 0.59% with the feedstock/catalyst mass

ratio varying from 1:0 to 1:10. This phenomenon occurred because with the appropriate

HZSM-5 addition, the vapor from the co-pyrolysis of NS and PP sufficiently reached the

surface of zeolite catalysts, and the pyrolysis of microalgae generated an intermediate

21
polar product through a degradation reaction. The nitrogen-containing functional group

was destroyed and removed to generate more hydrocarbons and other non-polar

compounds, thus reducing the content of nitrogen compounds. This result is similar to

the studies of Yang et.al[39]and Zhang et al[44]. Therefore, adding the appropriate

amount of HZSM-5 molecular sieve catalyst can greatly increase the selectivity of

T
aromatics and reduce the contents of nitrogen compounds in oil, which is conducive to

IP
the further processing and utilization of bio-oil.

R
SC
3.3. Mechanism of major aromatic hydrocarbons formation

U
N
A
M
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Fig. 6. Proposed mechanisms for the formation of major aromatic hydrocarbons

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There are no interpretations available for the formation of aromatic hydrocarbon in

E

the in situ catalytic co-pyrolysis of NS and PP over a zeolite catalyst at the mechanistic
CC

level. Therefore, the thermal behavior of NS, PP and mixed samples with and without
A

catalyst was investigated by TGA, and the influence of the reaction temperature, NS/PP

ratio and feedstock/catalyst ratio was also investigated. Based on thermal analysis and

catalytic co-pyrolysis experiments in a fixed bed, a reaction pathway for aromatic

hydrocarbon formation is proposed and shown in Fig. 6. The catalytic pyrolysis

22
mechanism of microalgae includes the deoxygenation and cracking of carbohydrates,

decarboxylation, decarbonylation and cracking of lipids, and deamination and cracking

of proteins for oil formation[45]. These volatiles are converted into olefins and further

converted into aromatic hydrocarbons through a series of reactions that take place on

the surface of the zeolite catalyst. According to the proposed mechanism, olefins are

T
important intermediates for aromatic formation. Co-pyrolysis of biomass and plastics

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can significantly increase the production of olefins and aromatics in bio-oil, which has

R
been confirmed in previous studies[13].

SC
The proposed mechanism for the formation of major aromatic hydrocarbons is

U
mainly from three routes: In the first process, smaller organic moieties (mainly furans)
N
derived from the carbohydrates of microalgae and olefins from PP form aromatic
A
M

hydrocarbons through Diels-Alder and dehydration reaction. As a cyclization reaction,

the Diels-Alder reaction results in a one-step formation of compounds with

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six-membered ring structures with the HZSM-5 catalyst.[46] Therefore, using HZSM-5
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during the catalytic co-pyrolysis, the Diels-Alder reaction is reinforced, accelerating the

formation of aromatic hydrocarbons and the consumption of alkenes[47]. In the second

E

process, small organic moieties derived from carbohydrates experience deoxygenation

CC

and are cracked into olefins, and triglycerides are thermally decomposed to heavy
A

oxygenated hydrocarbons, which undergo decarboxylation coupled with

decarbonylation and are then cracked into olefins, and proteins through deamination,

which are then cracked into olefins. Furthermore, the olefins derived from PP and the

volatiles produced by NS pyrolysis can enter the same hydrocarbon pool in the presence

23
of the HZSM-5 catalyst. These olefins are eventually converted to aromatic

hydrocarbons as the catalyst increases via the hydrocarbon pool mechanism. In the third

process, the olefins produced by PP pyrolysis are converted into aromatic hydrocarbons

by HZSM-5 zeolite through cyclization, aromatization, and oligomerization

reactions[48].

T
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4. Conclusions

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The catalytic co-pyrolysis of NS combined with PP was conducted using a

SC
bench-scaled fixed bed reactor, to generate aromatic hydrocarbons. Aromatic

hydrocarbons is the main component of oil, and the strongest synergistic effect of
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N
catalytic co-pyrolysis on the content of aromatic hydrocarbons in oil occurred when the
A
NS/PP mass ratio was 1:1 at 800 °C.
M

The relative content of aromatic hydrocarbons compounds and mass yield of

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monoaromatic hydrocarbons could reach to 77.04 area%, and 0.1223 g/(g·sample),

respectively. The significant synergistic effect observed in this study suggests that the
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catalytic copyrolysis of NS and PP is a promising technique for the production of

E

aromatics. In the future work, it is recommended to design a suitable catalyst to reduce

CC

the pyrolysis temperature in order to optimize energy consumption and catalyst

deactivation.
A

Conflict of interest

The authors declare no competing financial interest.

24
Acknowledgements

This work was supported by the introduction of scientific and technological

innovation team of Ningxia Hui Autonomous Region (2016), the Key Research &

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Development Program of Shandong Province (2018GGX104013), and the Key Project

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of the Natural Science Foundation of Shandong Province (ZR2015QZ02)

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SC
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N
A
M
ED
E PT
CC
A

25
References

[1] Cha, J. S.; Park, S. H.; Jung, S.-C.; Ryu, C.; Jeon, J.-K.; Shin, M.-C.; Park, Y.-K.,

Production and utilization of biochar: A review. Journal of Industrial and Engineering

Chemistry 2016, 40, 1-15.

T
[2] Solantausta, Y.; Oasmaa, A.; Sipila, K.; Lindfors, C.; Lehto, J.; Autio, J.; Jokela, P.;

IP
Alin, J.; Heiskanen, J., Bio-oil Production from Biomass: Steps toward Demonstration.

R
Energy Fuels 2012, 26 (1), 233-240

SC
[3] Chen, Y.; Wu, Y.; Zhang, P.; Hua, D.; Yang, M.; Li, C.; Chen, Z.; Liu, J., Direct

U
liquefaction of Dunaliella tertiolecta for bio-oil in sub/supercritical ethanol–water.
N
Bioresource Technology 2012, 124, 190-198.
A

[4] Yu, G.; Zhang, Y. H.; Guo, B.; Funk, T.; Schideman, L., Nutrient Flows and Quality
M

of Bio-crude Oil Produced via Catalytic Hydrothermal Liquefaction of Low-Lipid

ED

Microalgae. BioEnergy Res. 2014, 7 (4), 1317-1328.

PT

[5] Huber, G. W.; Iborra, S.; Corma, A., Synthesis of Transportation Fuels from

Biomass:  Chemistry, Catalysts, and Engineering. Chemical Reviews 2006, 106 (9),
E

4044-4098.
CC

[6] Chang, G.; Miao, P.; Yan, X.; Wang, G.; Guo, Q., Phenol preparation from catalytic
A

pyrolysis of palm kernel shell at low temperatures. Bioresource Technology 2018, 253,

214-219.

[7] French, R.; Czernik, S., Catalytic pyrolysis of biomass for biofuels production. Fuel

26
Processing Technology 2010, 91 (1), 25-32.

[8] Carlson, T. R.; Tompsett, G. A.; Conner, W. C.; Huber, G. W., Aromatic Production

from Catalytic Fast Pyrolysis of Biomass-Derived Feedstocks. Topics in Catalysis 2009,

52 (3), 241.

T
[9] Carlson T R, Vispute T P, Huber G W. Green Gasoline by Catalytic Fast Pyrolysis of

IP
Solid

R
Biomass Derived Compounds[J]. ChemSusChem,2008,1(5): 397-400.

SC
[10] Zheng, A.; Zhao, Z.; Chang, S.; Huang, Z.; Wu, H.; Wang, X.; He, F.; Li, H., Effect

U
of crystal size of ZSM-5 on the aromatic yield and selectivity from catalytic fast
N
pyrolysis of biomass. Journal of Molecular Catalysis A: Chemical 2014, 383-384,
A

23-30.
M

[11] Foster, A. J.; Jae, J.; Cheng, Y.-T.; Huber, G. W.; Lobo, R. F., Optimizing the
ED

aromatic yield and distribution from catalytic fast pyrolysis of biomass over ZSM-5.
PT

Applied Catalysis A: General 2012, 423-424, 154-161.

[12] Rezaei, P. S.; Shafaghat, H.; Daud, W. M. A. W., Production of green aromatics and
E
CC

olefins by catalytic cracking of oxygenate compounds derived from biomass pyrolysis:

A review. Applied Catalysis A: General 2014, 469, 490-511.

A

[13] Zhang, B.; Zhong, Z.; Ding, K.; Song, Z., Production of aromatic hydrocarbons

from catalytic co-pyrolysis of biomass and high density polyethylene: Analytical

Py–GC/MS study. Fuel 2015, 139, 622-628.

27
[14] Anuar Sharuddin, S. D.; Abnisa, F.; Wan Daud, W. M. A.; Aroua, M. K., A review

on pyrolysis of plastic wastes. Energy Conversion and Management 2016, 115,

308-326.

[15] Uzoejinwa, B. B.; He, X.; Wang, S.; El-Fatah Abomohra, A.; Hu, Y.; Wang, Q.,

Co-pyrolysis of biomass and waste plastics as a thermochemical conversion technology

T
IP
for high-grade biofuel production: Recent progress and future directions elsewhere

R
worldwide. Energy Conversion and Management 2018, 163, 468-492.

SC
[16] Lopez, G.; Artetxe, M.; Amutio, M.; Bilbao, J.; Olazar, M., Thermochemical routes

for the valorization of waste polyolefinic plastics to produce fuels and chemicals. A
U
N
review. Renewable and Sustainable Energy Reviews 2017, 73, 346-368.
A
[17] Veksha, A.; Giannis, A.; Oh, W.-D.; Chang, V. W. C.; Lisak, G., Upgrading of
M

non-condensable pyrolysis gas from mixed plastics through catalytic decomposition and
ED

dechlorination. Fuel Processing Technology 2018, 170, 13-20.

[18] Sannita, E.; Aliakbarian, B.; Casazza, A. A.; Perego, P.; Busca, G.,
PT

Medium-temperature conversion of biomass and wastes into liquid products, a review.

E

Renewable and Sustainable Energy Reviews 2012, 16 (8), 6455-6475.

CC

[19] Kim, B.-S.; Kim, Y.-M.; Lee, H. W.; Jae, J.; Kim, D. H.; Jung, S.-C.; Watanabe, C.;
A

Park, Y.-K., Catalytic Copyrolysis of Cellulose and Thermoplastics over HZSM-5 and

HY. ACS Sustainable Chemistry & Engineering 2016, 4 (3), 1354-1363.

[20] Xue, Y.; Kelkar, A.; Bai, X., Catalytic co-pyrolysis of biomass and polyethylene in

a tandem micropyrolyzer. Fuel 2016, 166, 227-236.

28
[21] Zhang, X.; Lei, H.; Chen, S.; Wu, J., Catalytic co-pyrolysis of lignocellulosic

biomass with polymers: a critical review. Green Chemistry 2016, 18 (15), 4145-4169.

[22] Shuping, Z.; Yulong, W.; Mingde, Y.; Chun, L.; Junmao, T., Pyrolysis

characteristics and kinetics of the marine microalgae Dunaliella tertiolecta using

thermogravimetric analyzer. Bioresource Technology 2010, 101 (1), 359-365.

T
IP
[23] Yu, G.; Zhang, Y.; Schideman, L.; Funk, T.; Wang, Z., Distributions of carbon and

R
nitrogen in the products from hydrothermal liquefaction of low-lipid microalgae.

SC
Energy & Environmental Science 2011, 4 (11), 4587-4595.

U
[24] Shihadeh, A.; Hochgreb, S., Impact of Biomass Pyrolysis Oil Process Conditions
N
on Ignition Delay in Compression Ignition Engines. Energy & Fuels 2002, 16 (3),
A
552-561.
M

[25] Wu, X.; Wu, Y.; Wu, K.; Chen, Y.; Hu, H.; Yang, M., Study on pyrolytic kinetics
ED

and behavior: The co-pyrolysis of microalgae and polypropylene. Bioresource

Technology 2015, 192, 522-528.

PT

[26] Tang, Y.; Ma, X.; Lai, Z., Thermogravimetric analysis of the combustion of
E

microalgae and microalgae blended with waste in N2/O2 and CO2/O2 atmospheres.
CC

Bioresource Technology 2011, 102 (2), 1879-1885.

A

[27] Pei, X.; Yuan, X.; Zeng, G.; Huang, H.; Wang, J.; Li, H.; Zhu, H., Co-liquefaction

of microalgae and synthetic polymer mixture in sub- and supercritical ethanol. Fuel

Processing Technology 2012, 93 (1), 35-44.

29
[28] Duan, P.; Jin, B.; Xu, Y.; Wang, F., Co-pyrolysis of microalgae and waste rubber

tire in supercritical ethanol. Chemical Engineering Journal 2015, 269, 262-271.

[29] Wu, X.; Liang, J.; Wu, Y.; Hu, H.; Huang, S.; Wu, K., Co-liquefaction of

microalgae and polypropylene in sub-/super-critical water. RSC Advances 2017, 7 (23),

13768-13776.

T
IP
[30] Wang X, Zhao B, Tang X, Yang X. Comparison of direct and indirect pyrolysis of

R
micro-algae Isochrysis. Bioresour Technol 2015;179:58–62.

SC
[31] Huang, F.; Tahmasebi, A.; Maliutina, K.; Yu, J., Formation of nitrogen-containing

U
compounds during microwave pyrolysis of microalgae: Product distribution and
N
reaction pathways. Bioresource Technology 2017, 245, 1067-1074.
A

[32] Yao, Z.; Ma, X.; Wu, Z.; Yao, T., TGA–FTIR analysis of co-pyrolysis
M

characteristics of hydrochar and paper sludge. Journal of Analytical and Applied

ED

Pyrolysis 2017, 123, 40-48.

PT

[33] Chen, W.; Chen, Y.; Yang, H.; Xia, M.; Li, K.; Chen, X.; Chen, H., Co-pyrolysis of

lignocellulosic biomass and microalgae: Products characteristics and interaction effect.

E

Bioresource Technology 2017, 245, 860-868.

CC

[34] Wu, K.; Liu, J.; Wu, Y.; Chen, Y.; Li, Q.; Xiao, X.; Yang, M., Pyrolysis
A

characteristics and kinetics of aquatic biomass using thermogravimetric analyzer.

Bioresource Technology 2014, 163, 18-25.

[35] Li, X.; Zhang, H.; Li, J.; Su, L.; Zuo, J.; Komarneni, S.; Wang, Y., Improving the

30
aromatic production in catalytic fast pyrolysis of cellulose by co-feeding low-density

polyethylene. Applied Catalysis A: General 2013, 455, 114-121.

[36] Park, H. J.; Heo, H. S.; Yoo, K.-S.; Yim, J.-H.; Sohn, J. M.; Jeong, K.-E.; Jeon,

J.-K.; Park, Y.-K., Thermal degradation of plywood with block polypropylene in TG and

batch reactor system. Journal of Industrial and Engineering Chemistry 2011, 17 (3),

T
IP
549-553.

R
[37] Sebestyén, Z.; Barta-Rajnai, E.; Bozi, J.; Blazsó, M.; Jakab, E.; Miskolczi, N.; Sója,

SC
J.; Czégény, Z., Thermo-catalytic pyrolysis of biomass and plastic mixtures using

HZSM-5. Applied Energy 2017, 207, 114-122.

U
N
[38] Song,Z., Zhong, Z., Zhang, B., Lv, Z.,Ding, K., Catalytic co-pyrolysis of corn
A
straw and polypropylene. Journal of Zhejiang University (Engineering Science)
M

2016 ,50 (2): 333-340.

ED

[39] Yang, W.,Zeng, Y., Luo. J., Tong, D., Qing, R., Fan, Y., Hu, C., Production of

bio-oil by direct and catalytic pyrolysis of Nannochloropsis sp. Journal of Fuel

PT

Chemistry and Technology. 2011, 39(9): 664-669.

E

[40] Zhang B, Zhong Z, Min M, Ding K, Xie Q, Ruan R. Catalytic fast co-pyrolysis of
CC

biomass and food waste to produce aromatics: analytical Py-GC/MS study. Bioresour
A

Technol 2015;189:30–5

[41] Long X, Zhang Q, Liu Z, Qi P, Lu J, Liu Z. Magnesia modified H-ZSM-5 as an

efficient acidic catalyst for steam reforming of dimethyl ether. Appl Catal B: Environ

2013;134:381–8.
31
[42] Chen, W.; Yang, H.; Chen, Y.; Xia, M.; Chen, X.; Chen, H., Transformation of

Nitrogen and Evolution of N-Containing Species during Algae Pyrolysis.

Environmental Science & Technology 2017, 51 (11), 6570-6579.

[43] Zheng, Y.; Tao, L.; Yang, X.; Huang, Y.; Liu, C.; Zheng, Z., Study of the thermal

behavior, kinetics, and product characterization of biomass and low-density

T
IP
polyethylene co-pyrolysis by thermogravimetric analysis and pyrolysis-GC/MS. Journal

R
of Analytical and Applied Pyrolysis 2018, 133, 185-197.

SC
[44] Zhang, X.; Lei, H.; Zhu, L.; Qian, M.; Yadavalli, G.; Wu, J.; Chen, S., From

plastics to jet fuel range alkanes via combined catalytic conversions. Fuel 2017, 188,
U
N
28-38.
A
[45] Gayubo, A. G.; Aguayo, A. T.; Atutxa, A.; Aguado, R.; Bilbao, J., Transformation
M

of Oxygenate Components of Biomass Pyrolysis Oil on a HZSM-5 Zeolite. I. Alcohols

ED

and Phenols. Industrial & Engineering Chemistry Research 2004, 43 (11), 2610-2618.

[46] Li, X.; Li, J.; Zhou, G.; Feng, Y.; Wang, Y.; Yu, G.; Deng, S.; Huang, J.; Wang, B.,
PT

Enhancing the production of renewable petrochemicals by co-feeding of biomass with

E

plastics in catalytic fast pyrolysis with ZSM-5 zeolites. Applied Catalysis A: General
CC

2014, 481, 173-182.

A

[47] Cheng, Y.-T.; Huber, G. W., Production of targeted aromatics by using Diels-Alder

classes of reactions with furans and olefins over ZSM-5. Green Chemistry 2012, 14 (11),

3114-3125.

[48] Xue, Y.; Kelkar, A.; Bai, X., Catalytic co-pyrolysis of biomass and polyethylene in
32
a tandem micropyrolyzer. Fuel 2016, 166, 227-236.

T
RIP
SC
U
N
A
M
ED
E PT
CC
A

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