Fuel Processing Technology 210 (2020) 106562

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Fuel Processing Technology

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Research article

Effects of steam to enhance the production of light olefins from ex-situ T

catalytic fast pyrolysis of biomass
Changsong Hu1, Chao Liu1, Qingyu Liu, Huiyan Zhang, Shiliang Wu, Rui Xiao
⁎

Key Laboratory of Energy Thermal Conversion and Control, Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, PR China

ARTICLE INFO ABSTRACT

Keywords: This study aims to report on the feasibility of enhancing light olefins production from ex-situ catalytic fast
Biomass pyrolysis (CFP) of biomass by co-feeding with steam and determine the role of steam. Effects of steam on catalyst
Pyrolysis and pyrolysis/catalysis reactions in ex-situ CFP were investigated using a two-stage fluidized-bed/fixed-bed
HZSM-5 reactor. Carbon yield of olefins + monocyclic aromatic hydrocarbons (MAHs) increased by 23.80% after proper
Steam
steam dealumination of HZSM-5 framework, which suggests that HZSM-5 can be activated at the initial exposure
Light olefins
to steam. For activated HZSM-5, olefins carbon yield increased by 35.65% and olefins to MAHs (O/M) ratio
boosted from 0.83 to 1.60 as steam concentration in carrier gas increased from 0% to 40%, while the total carbon
yield of olefins and MAHs still kept at the same level. Steam enhanced olefins production by: (1) promoting the
formation of light compounds in bio-oil, which are the main precursors of hydrocarbons, during pyrolysis; (2)
inhibiting aromatization reactions during catalysis. It provides a possibility for the control of O/M ratio of
hydrocarbon products and the enhancement of light olefins production from CFP of biomass.

1. Introduction components. According to their results, cellulose, hemicellulose and

Lignocellulosic biomass, which is the only renewable source of or-
ganic carbon, has great potential to substitute fossil resources to pro-
duct fuels and chemicals [1]. Catalytic fast pyrolysis (CFP) is a pro-
mising thermochemical method for biomass utilization, that converts
biomass into hydrocarbons including monocyclic aromatic hydro-
carbons (MAHs), polycyclic aromatic hydrocarbons (PAHs), light ole-
fins and light alkanes in one step [2,3]. HZSM-5 aluminosilicate zeolite
is the most effective catalyst in this field and attracts much attention
[4]. It gives the highest yield of hydrocarbons among all the zeolite
catalysts due to its suitable pore size [4,5].
MAHs and light olefins are the two most abundant and valuable
hydrocarbon products of CFP over HZSM-5. While MAHs always ac-
count for the majority and are commonly considered as the most im-
portant products [6–8]. Cheng et al. [6] performed CFP of pine sawdust
in a fluidized-bed reactor. Carbon yields of MAHs and olefins were
10.8% and 7.1% respectively at the optimized temperature of 550 °C,
resulting in the olefins to MAHs (O/M) ratio of 0.66. Jae et al. [7]
studied CFP of pine sawdust in a developed fluidized-bed reactor where
HZSM-5 catalyst was continuously added and removed. An O/M ratio of
0.63 was obtained under the optimized conditions. Wang et al. [8]
reported the product distributions from CFP of lignocellulosic biomass
lignin got an O/M ratio of 0.25, 0.58 and 0.98, respectively. There is a
phenomenon that most of research in this field is aimed at the pro-
motion of aromatics production, while light olefins are rarely con-
cerned [3,9].
Both light olefins and MAHs are basic feedstocks and key platform
chemicals in the petrochemical industry. The value and importance of
light olefins are not lower than that of MAHs. At present, the production
of light olefins mainly relies on fossil resources [10]. Enhancing light
olefins production from CFP of renewable biomass can provide an al-
ternative route for the sustainable production of light olefins. This is
also of great significance to driving the development of the substitution
of biomass for fossil resources. However, few studies have focused on
the development of CFP technology with giving priority to the pro-
duction of light olefins over MAHs, and they were mainly centered on
catalyst modification [11,12]. There is also a disadvantage in these
studies that aromatics products are completely ignored, resulting in a
reduction in the economic efficiency of the overall process. The product
distribution of CFP is highly dependent on the application mode of
HZSM-5 catalyst (in-situ and ex-situ) [13–15]. In our previous work
[13], ex-situ CFP was found to strongly promote the production of light
olefins compared with in-situ CFP. Ex-situ CFP not only gave a sig-
nificant increase in light olefins carbon yield (increased by 75.9%) but

⁎
Corresponding author.
E-mail address: ruixiao@seu.edu.cn (R. Xiao).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.fuproc.2020.106562
Received 12 June 2020; Received in revised form 8 August 2020; Accepted 12 August 2020
Available online 29 August 2020
0378-3820/ © 2020 Elsevier B.V. All rights reserved.
C. Hu, et al.
also an increase in the total carbon yield of light olefins and MAHs
(increased by 9.7%). Therefore, a study to further enhance the pro-
duction of light olefins on the basis of ex-situ CFP is feasible and re-
quired.
Steam may affect CFP of biomass in several ways. First, deal-
umination of HZSM-5 framework under steam atmosphere has been
widely accepted [16–18], while the influence of steam dealumination
on the catalytic performance of HZSM-5 in ex-situ CFP is still unknown.
Besides, it has also been reported that steam has direct impacts on both
pyrolysis and catalysis reactions in CFP [16,19,20]. Kantarelis et al.
[19] showed that the distribution of biomass pyrolysis products is sig-
nificantly different under N2 and steam atmospheres. Mukarakate et al.
[20] proved that phenol, naphthol and their derivatives can be gener-
ated from the reactions between aromatic intermediates and steam
during CFP. Yang et al. [16] explored the effects of steam on in-situ CFP
of cellulose using a fluidized-bed reactor. The results indicated that
steam affects CFP through both irreversible changes to the catalyst
structure and direct interference with chemical reactions, while only a
slight increase in olefins with increasing steam concentration was ob-
served in in-situ CFP. The remarkable promotion of steam on light
olefins production from ex-situ CFP of biomass has never been reported.
There is a lack of systematic study on the effects of steam on ex-situ CFP
of biomass.
The purpose of this paper is to report on the feasibility of enhancing
the production of light olefins from ex-situ CFP of biomass by co-
feeding with steam and determine the role of steam. The effects of
steam on ex-situ CFP of biomass were studied from the following three
aspects: (1) the direct interference with biomass pyrolysis reactions; (2)
the influence of steam dealuminization on the physicochemical prop-
erties and catalytic performance of HZSM-5 catalyst; (3) the direct in-
terference with HZSM-5 catalysis reactions.
2. Materials and methods
2.1. Materials
The biomass feedstock was pine sawdust in the particle size range of
0.4–1.4 mm. Its ultimate composition was 46.5 wt% carbon, 6.3 wt%
hydrogen, 0.3 wt% nitrogen and 47.0 wt% oxygen (calculated by dif-
ference). The result of proximate analysis was 10.4 wt% moisture,
76.4 wt% volatile, 13.0 wt% fixed carbon and 0.3 wt% ash. Both the
ultimate and proximate analyses were given on an air-dry basis. The
bed material in fluidized-bed was silica sand in the particle size range of
0.15–0.25 mm. The powdery pure HZSM-5 (Nankai University Catalyst
Co., Ltd.) with a SiO2/Al2O3 ratio of 38 was calcined at 600 °C for 6 h,
and then compression-molded, ground and sieved to prepare particles
with size between 0.3 and 0.9 mm. Prior to use, the prepared catalyst
was calcined again at 600 °C for 1 h.
2.2. Experimental setup
All the pyrolysis experiments were conducted in a bench scale
continuous feeding two-stage fluidized-bed/fixed-bed reactor in this
work, as shown in Fig. 1. Biomass pyrolysis took place in the fluidized-
bed, while the generated pyrolysis vapors were catalyzed over HZSM-5
in the fixed-bed. Both the two reactors were maintained at 550 °C. The
temperature of the connecting pipe between the two reactors was also
controlled at 550 °C by independent thermocouple and heater. The time
required for pyrolysis vapors to pass through the connecting pipe was
about 0.2 s. A mixture of N2 (99.999%) and steam was used as the
carrier gas. Steam was formed by the vaporization of deionized water in
the vaporizer (180 °C), which was injected by a syringe pump. There
were two parts of N2, one was applied to create positive pressure for the
feeding system, and the other was mixed with steam in the vaporizer to
ensure the stability of steam flow. The volume concentration of steam
in carrier gas (N2 + steam) varied from 0% to 60%, while the total
2
Fuel Processing Technology 210 (2020) 106562
volume flow rate of carrier gas remained constant at 550 °C to keep a
gas velocity of 0.07 m/s. The biomass feeding rate was set at 20 g/h
with a total feeding amount of 4 g for each run. For catalytic pyrolysis
experiments, HZSM-5 catalyst was added in the fixed-bed with a total
amount of 15 g, resulting in a weight hourly space velocity of 1.33 h−1.
The condensing system consisted of 4 condensers in series. Each con-
denser was filled with ~20 ml isopropanol and placed in an ice water
bath. After stopping biomass feeding, the carrier gas and reaction
temperatures were kept for 18 min to ensure complete pyrolysis of
biomass and complete collection of products. A more detailed de-
scription can be found elsewhere [13]. Each run was repeated at least
three times.
2.3. Products analysis
Gaseous products were analyzed using a Shimadzu GC-2014 gas
chromatograph (GC). Olefins and alkanes were determined by a flame
ionization detector (FID) with a HP-PLOT/Q column, while CO and CO2
were determined by a thermal conductivity detector with a TDX-01
column.
The components of liquid products were identified using an Agilent
7890B-5977B gas chromatography–mass spectrometry (GC–MS) at first,
and then quantified by GC-FID with the effective carbon method
[21,22]. Both GC–MS and GC-FID were equipped with a Rtx-VMS ca-
pillary column.
Solid products, including coke (organic residue on used catalyst)
and char (solid residue from biomass pyrolysis), were burned to pro-
duce a mixed gas composed of CO, CO2 and H2O. The mixed gas was
catalyzed over CuO to convert CO into CO2, and then desiccated with
anhydrous silica gel. Ascarite was used to absorb all the residual CO2
and the carbon yield of char/coke was calculated on the basis of its
additional weight [13].
2.4. Catalyst characterization
The porosity characteristics of HZSM-5 catalyst samples were
measured by N2 adsorption-desorption using a TriStar II 3020 system
(Micromeritics, USA). All the catalyst samples were degassed in a va-
cuum at 300 °C for 600 min prior to adsorption. NH3 temperature-
programmed desorption experiments were carried out with a FINES-
ORB-3010 chemisorption analyzer (Finetec, China) to determine the
acidity of HZSM-5 catalyst samples. All the catalyst samples were pre-
treated at 600 °C in He (99.999%) flow for 120 min. Relative amount
and relative content of acid sites were calculated by the following
formulas:
Relative amount of acid sites
Amount of acid sites on a catalyst
= × 100%
Amount of acid sites on fresh catalyst (1)
Relative content of acid sites
Amount of weak or strong acid sites
= × 100%
Amount of total acid sites (2)
3. Results and discussion
3.1. Effects of steam on fast pyrolysis of biomass
The effects of steam on fast pyrolysis of biomass were investigated
in this section. All the pyrolysis experiments were performed without
HZSM-5 catalyst.
Fig. 2 shows the product distribution of non-CFP at different steam
concentrations in the range of 0% to 60%. As to the analysis of bio-oil,
only compounds volatile at injection temperature of GC (270 °C) were
able to be detected by MS and FID, thus there existed large amounts of
unidentified compounds in bio-oil based on GC–MS and GC-FID results
C. Hu, et al. Fuel Processing Technology 210 (2020) 106562

Fig. 1. Schematic of the experimental pyrolysis system.

50 yield of around 48%. The whole process of biomass pyrolysis mainly

includes two stages: (1) the decomposition of biomass particles to
generate pyrolysis vapors and char; (2) the secondary cracking of
40 thermally unstable compounds in pyrolysis vapors to form smaller and
more stable chemicals [26]. The reduction of char indicates that steam
Carbon yield (%)

can participate in the primary pyrolysis of biomass and improve the

30 thermal decomposition degree of biomass particles to form less solid
residue [27]. This may be because H2O molecule can serve as a hy-
drogen-donor to inhibit the polycondensation reactions [19]. In addi-
20 tion, since the secondary cracking of pyrolysis vapors is a major source
of gaseous products, the reduction of gas shows that steam also affects
the secondary cracking of pyrolysis vapors and inhibits the excessive
cracking of pyrolysis vapors into non-condensable gaseous products
10
[19,28].
It is important to emphasize that the increase of light compounds
was significant. Carbon yield of identified compounds increased by
0
43.84% (from 8.15% to 11.73%) as steam concentration increased from
0 20 40 60
0% to 60%. Since most of light compounds have a sufficiently small
Steam concentration (%)
molecular size to diffuse into HZSM-5 channels, they are the main
Char Identified compounds in bio-oil precursors of the final hydrocarbon products [5,29]. The increase of
Gas Unidentified compounds in bio-oil light compounds caused by the introduction of steam is beneficial to the
production of hydrocarbons.
Fig. 2. Product distribution as a function of steam concentration in carrier gas
for non-CFP. The gaseous product distribution of non-CFP at different steam
concentrations in the range of 0% to 60% are listed in Table 1. Carbon
yield of CO decreased monotonously with increasing steam concentra-
[5,23–25]. The identified compounds are light compounds that have a tion. This suggests that steam has an inhibitory effect on decarbonyla-
sufficiently small boiling point and usually have a small molecular size, tion reactions. Meanwhile, carbon yield of CO2 increased slightly. There
while the unidentified compounds can be regarded as heavy com- are primarily two possible sources for its growth: (1) steam reforming of
pounds with a larger molecular size. The carbon yield of unidentified pyrolysis vapors; (2) slight water-gas shift reaction [19,30]. Carbon
compounds was estimated by difference according to the law of con- yields of methane, C2-C4 alkanes and olefins showed a continuous
servation of carbon. According to Fig. 2, carbon yields of char and gas downward trend. It is due to the suppression of secondary cracking
decreased continuously with increasing steam concentration. Con- reactions by steam, as mentioned previously. In addition, a slight effect
versely, bio-oil carbon yield (the sum of the carbon yields of identified of steam on the carbon selectivity distribution of olefins was observed
and unidentified compounds in bio-oil) exhibited an opposite trend. according to the results. Carbon selectivities of propylene and butylene
Among liquid products, light compounds increased obviously, while decreased marginally as steam concentration increased. This may be
heavy compounds remained relatively constant, maintaining a carbon

3
C. Hu, et al. Fuel Processing Technology 210 (2020) 106562

Table 1 inhibition of steam on the secondary cracking of pyrolysis vapors. The

Gaseous product distribution as a function of steam concentration in carrier gas increase of other products can be explained in the following two as-
for non-CFP. pects: (1) secondary cracking reactions are suppressed by steam to
Steam concentration (%) avoid the consumption of light compounds; (2) steam takes part in the
primary pyrolysis of biomass and improves the thermal decomposition
0 20 40 60 degree of biomass particles to form more light compounds. In addition,
it should be noted that some furans, ketones and esters decreased
Carbon yield (%)
CO 13.44 12.68 12.31 11.98 slightly as steam concentration increased from 40% to 60%. Furans,
CO2 3.87 3.96 4.04 4.10 ketones and esters can be assumed to be the molecular fragments of
CH4 2.85 2.65 2.59 2.55 cellulose and hemicellulose [33]. Pyrolysis of cellulose and hemi-
C2-C4 alkanes 0.63 0.59 0.56 0.56
cellulose also produces large amounts of heavy carbohydrates, which
Olefins 3.22 3.00 2.84 2.75
can continue to decompose into light compounds through cracking
Olefins carbon selectivity (%) reactions [25,34,35]. Therefore, it can be inferred that steam tends to
Ethylene 50.40 51.28 52.29 53.19
Propylene 33.19 32.31 32.21 31.75
inhibit the secondary cracking of heavy carbohydrates at a relatively
Butylene 16.40 16.42 15.50 15.06 high steam concentration, resulting in the reduction of some light
compounds.

Table 2 3.2. Effects of steam on catalyst

Carbon yields of identified compounds in bio-oil as a function of steam con-
centration in carrier gas for non-CFP.
3.2.1. Catalyst characterizations
Carbon yield (%) Steam concentration (%) It is widely reported in the literature that steam can hydrolytically
remove Al atoms from HZSM-5 zeolite framework (dealumination) at
0 20 40 60
elevated temperatures, thereby causing irreversible changes in the
Aromatics 0.43 0.35 0.29 0.28 structure and catalytic performance of HZSM-5 catalyst [16–18]. In
Benzene 0.12 0.09 0.06 0.06 order to explore the effects of steam on HZSM-5 catalyst, the fresh
Toluene 0.20 0.16 0.12 0.12 HZSM-5 was treated with 60% steam at 550 °C for 15, 30, 60, 120, 240,
Phenols 1.97 2.72 3.10 3.29
360 and 480 min respectively. The physicochemical properties and
Phenol 0.14 0.18 0.21 0.22
2-Methyl-phenol 0.09 0.12 0.13 0.13 catalytic performance of fresh and steam treated HZSM-5 samples were
p-Cresol 0.07 0.10 0.11 0.12 compared.
3-Methyl-phenol 0.06 0.08 0.09 0.10 The porosity characteristics of HZSM-5 catalyst samples were de-
2,4-Dimethyl-phenol 0.10 0.13 0.15 0.15 termined by N2 adsorption-desorption, as shown in Table 3. With in-
Catechol 0.50 0.68 0.78 0.82
creasing steam treating time, the micropore area and micropore volume
2-Allylphenol 0.08 0.11 0.12 0.13
4-Methyl-1,2-benzenediol 0.29 0.42 0.49 0.52 decreased monotonously, while the external surface area and mesopore
Hydroquinone 0.07 0.09 0.09 0.10 volume presented an opposite trend. This indicates that steam deal-
4-Ethylcatechol 0.15 0.21 0.25 0.28 umination causes the collapse of micropores and the generation of
1-Naphthalenol 0.04 0.09 0.11 0.11
mesopores. In addition, a rapid collapse of micropores was observed in
Furans 0.60 0.73 0.81 0.79
3-Furaldehyde 0.07 0.11 0.13 0.14
the initial stage of steam treatment, especially in the first 30 min, and
Furfural 0.25 0.27 0.28 0.26 the dealumination rate gradually slowed down with increasing of
5-Hydroxymethylfurfural 0.11 0.13 0.15 0.15 dealumination degree.
Ketones 2.43 2.92 3.27 3.28 Fig. 3 shows the acidity of HZSM-5 catalyst as a function of steam
1-Hydroxy-2-propanone 1.46 1.61 1.80 1.89
treating time. Relative amount and relative content of acid sites were
2-Cyclopenten-1-one 0.19 0.21 0.22 0.21
2-Methyl-2-cyclopenten-1-one 0.10 0.13 0.15 0.13 calculated according to Eqs. (1) and (2), respectively. Both weak and
1,2-Cyclopentanedione 0.36 0.55 0.62 0.60 strong acid sites showed a downward trend in relative amount with
3-Methyl-2-cyclopenten-1-one 0.11 0.14 0.15 0.13 steam treating. The relative amount of strong acid sites decreased more
2-Hydroxy-3-methyl-2-cyclopenten-1-one 0.14 0.19 0.22 0.22
than weak acid sites, which led to a decrease in the relative content of
Acids 1.19 1.67 1.89 1.95
Acetic acid 1.19 1.67 1.89 1.95
strong acid sites. The relative amounts of total, weak and strong acid
Esters 0.24 0.26 0.27 0.25 sites decreased sharply by 67.72%, 60.25% and 76.48% respectively in
Butyrolactone 0.11 0.12 0.13 0.12 the first 30 min, and then the decreasing rate became much lower. This
Sugars 1.29 1.73 1.85 1.88 phenomenon is consistent with the trend of porosity characteristics of
1,6-Anhydro-β-d-talopyranose 0.07 0.09 0.10 0.10
Levoglucosan 1.22 1.64 1.75 1.78
Total 8.15 10.39 11.47 11.73 Table 3
Porosity characteristics of HZSM-5 catalyst samples with different steam
treating time.
related to the hydrogen-donating capacity of steam which helps small Steam Sbet Smicroa Sexta Vtotalb Vmicroa Vmeso
molecular fragments stabilize quickly and thereby increasing the diffi- treating time (m2/g) (m2/g) (m2/g) (cm3/g) (cm3/g) (cm3/g)
culty of larger molecules formation. (min)
As shown in Table 2, the identified light compounds in the bio-oils
0 333.7 241.4 92.3 0.196 0.124 0.072
obtained from non-CFP at different steam concentrations in the range of 15 327.4 202.5 125.0 0.193 0.104 0.089
0% to 60% were classified into 7 categories. The important chemicals 30 332.2 189.7 142.5 0.196 0.098 0.098
with a carbon yield higher than 0.1% were also given. Carbon yields of 60 325.9 171.1 154.7 0.193 0.088 0.105
120 316.1 130.8 185.4 0.191 0.069 0.122
phenols, furans, ketones, acids, esters and sugars showed an upward
240 315.2 129.5 185.6 0.190 0.066 0.124
trend as steam concentration increased from 0% to 60%, only aromatics 360 316.3 125.3 191.0 0.191 0.064 0.127
carbon yield decreased monotonously. Aromatics mainly arise from the 480 306.7 112.5 194.2 0.186 0.057 0.128
natural aromatic benzene rings which are abundant in lignin
a
[26,31,32]. The main reason for the reduction of aromatics is the Based on t-plot method.
b
Single point total pore volume.

4
C. Hu, et al.
100
(a)
Relative amount (%)
80
Total acid sites
60 Weak acid sites
Strong acid sites
40
20
0 0
0 100 200 300 400
Steam treating time (min)
Fig. 3. Acidity of HZSM-5 catalyst samples with different steam treating time.
catalyst samples. Overall, there is a rapid dealumination of HZSM-5
zeolite framework in the first 30 min of steam treatment, resulting in
the rapid adjustment of its physicochemical properties [16,18].
3.2.2. Catalytic performance
Fig. 4 shows the influence of steam treating of HZSM-5 catalyst on
product distribution of CFP. These pyrolysis experiments were carried
out under 100% N2 atmosphere to avoid the continued effects of steam
on catalyst samples. With increasing steam treating time, olefins carbon
yield exhibited an upward trend, while MAHs carbon yield increased
obviously in the first 30 min and decreased with further steam treating.
Carbon yield of olefins + MAHs was only 20.40% for fresh HZSM-5 but
increased by 23.80% and reached 25.25% after 30 min steam treating.
It decreased gradually to 24.21% as steam treating time increased to
480 min. This result suggests that proper steam dealumination of
HZSM-5 is beneficial to the generation of hydrocarbons from biomass
pyrolysis vapors. The rapid adjustment of physicochemical properties
and improvement of catalytic performance of HZSM-5 in the first
30 min steam treating can be regarded as a steam activation process for
catalyst. This phenomenon may be explained by the following two main
reasons: (1) steam dealumination enlarges HZSM-5 channels in varying
degrees, resulting in the generation of hierarchically porous structure
which can promote the conversion of heavy compounds and reduce
diffusional limitations; (2) both strength and density of acid sites are
reduced by steam dealumination, thereby suppressing the formation of
catalyst coke and upgrading the use efficiency of precursors of hydro-
carbon products [36–39]. The rapid decrease of coke carbon yield in the
first 30 min is consistent with the above explanation. After the steam
activation process, the structure and acidity of HZSM-5 are destroyed
excessively with further steam treating, leading to a reduction of its
catalytic aromatization ability. As a result, more olefins and less MAHs
were produced when steam treating time exceeded 30 min.
CO carbon yield decreased by 10.68% (from 21.29% to 19.01%),
while CO2 carbon yield increased by 24.44% (from 5.36% to 6.67%)
with the first 30 min steam treating. It indicates that steam activation
slightly weakens the decarbonylation ability and strengthens the dec-
arboxylation ability of HZSM-5 catalyst. The decrease in gaseous al-
kanes is caused by the reduction of cracking ability which is related to
the loss of catalyst acidity.
Shape selective reactions and deoxygenation reactions are also in-
hibited with the destruction of micropores and weakening of acidity.
Thus, carbon yield of oxygenated compounds increased with steam
treating. The increase of heavy compounds is mainly due to the
weakening of catalyst acidity. Although heavy compounds cannot dif-
fuse into catalyst channels, they are active for cracking or aggregating
on the external surface of HZSM-5 [40,41]. More heavy compounds can
be retained with the loss of external acid sites. As mentioned above,
proper introduction of mesopores is conducive to the conversion of
heavy compounds. However, according to the growth trend of heavy
Fuel Processing Technology 210 (2020) 106562
100
(b) Weak acid sites
Strong acid sites
80
Rela tive con tent (%)
60
40
20
500 0 100 200 300 400 500
Steam treating time (min)
compounds, it can be inferred that the impacts of catalyst acidity are
more important. Distinct from the rising trend of MAHs carbon yield in
the first 30 min, PAHs carbon yield decreased monotonously with steam
treating, while its decreasing rate was much lower in the first 30 min.
On the other hand, carbon selectivity of PAHs decreased rapidly in the
first 30 min and decreased slowly with further dealumination. An im-
portant pathway for the generation of PAHs is the combination of
oxygenated fragments with MAHs [42,43]. It is highly dependent on the
acidity of catalyst. The decrease of acidity has a negative effect on the
conversion from MAHs to PAHs.
Steam dealumination was also observed to affect the carbon se-
lectivity distribution of both olefins and aromatics. Carbon selectivities
of ethylene and benzene decreased monotonously with increasing
steam treating time, while carbon selectivities of larger olefins and
MAHs showed an opposite trend. It is because of the reduction of
cracking ability caused by the decreasing of catalyst acidity.
3.3. Effects of steam on catalytic fast pyrolysis over activated catalyst
The above results show that fresh HZSM-5 catalyst can be activated
at the initial stage (the first 30 min) of steam dealumination. After
steam treating for more than 60 min, the physicochemical properties
and catalytic performance of HZSM-5 become relatively stable and
change slowly with further dealumination. Therefore, activated HZSM-
5, which was treated with 60% steam at 550 °C for 60 min, was em-
ployed as the catalyst to explore the effects of steam on CFP, as well as
avoid the influence of steam activation process.
Fig. 5 shows the product distribution of CFP at different steam
concentrations in the range of 0% to 60% with the use of activated
HZSM-5 catalyst (steam treating for 60 min). Olefins carbon yield in-
creased by 47.44%, while MAHs carbon yield decreased by 53.00% as
steam concentration increased from 0% to 60%. Indeed, the effects of
steam on CFP over activated catalyst including two parts, effects on
pyrolysis process and effects on catalysis process. It can be seen from
Table 1, increasing steam concentration yielded less olefins from pyr-
olysis reactions. Therefore, the increase of olefins mainly relies on
catalysis process. The results suggest that aromatization reactions are
significantly inhibited with the introduction of steam [44,45]. On the
other hand, the increase of oxygenated compounds indicates steam also
weakens the deoxygenation ability of HZSM-5. It seems that the cata-
lytic effects of HZSM-5 on pyrolysis vapors are reduced in all aspects
under the influence of steam. One possible reason is the competitive
adsorption between pyrolysis vapors and steam on catalyst acid sites.
Steam can be adsorbed on acid sites and block the adsorption of pyr-
olysis vapors, thereby leading to a reduction in catalyst activity
[16,20,46,47].
Carbon yield of olefins + MAHs increased by 5.98% as steam
concentration increased from 0% to 20%, but decreased continuously
with further increases in steam concentration. The production of
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C. Hu, et al. Fuel Processing Technology 210 (2020) 106562

30 1.05
(a)
25 1.00

Carbon yield (%)

20 0.95

O/M ratio
15 0.90

10 0.85
Olefins+MAHs O/M ratio
5 Olefins 0.80
MAHs
0 0.75
0 100 200 300 400 500
Steam treating time (min)

25 20
(b) (c)
20
15
Carbon yield (%)

Carbon yield (%)

15 Char Coke CO
CO2 CH4 C2-C4 Alkanes 10 PAHs
Oxygenated compounds in bio-oil
10
Unidentified compounds in bio-oil
5
5

0 0
0 100 200 300 400 500 0 100 200 300 400 500
Steam treating time (min) Steam treating time (min)

80 50

(d) (e)
40
Carbon selectivity (%)

Carbon selectivity (%)

60 Benzene Toluene
Xylenes Other MAHs
30 PAHs
40
Ethylene 20
Propylene
20 Butylene
10

0 0
0 100 200 300 400 500 0 100 200 300 400 500
Steam treating time (min) Steam treating time (min)

Fig. 4. Product distribution as a function of steam treating time of HZSM-5 catalyst for CFP with 100% N2 as carrier gas.

hydrocarbons is positively affected by the increase of light compounds
derived from pyrolysis reactions and negatively affected by the de-
crease of catalyst activity with increasing steam concentration. The
increase of hydrocarbons at low steam concentration is due to the
strong enhancement of light compounds formation, as shown in
Table 2. In addition, O/M ratio increased sharply as steam concentra-
tion increased from 0% to 60%. Even though carbon yield of olefins +
MAHs decreased when steam concentration increased from 20% to
40%, it was still at the same level as that obtained under 0% steam
atmosphere. Whereas 40% steam atmosphere gave a 35.65% increase in
olefins carbon yield and a 92.61% increase in O/M ratio (from 0.83 to
1.60) compared with 0% steam atmosphere. The results provide an
effective way to greatly enhance the production of light olefins as well
as avoid the reduction of total hydrocarbons. The formation of catalyst
coke was also inhibited with the decrease of catalyst activity when
steam concentration increased. It is helpful for extending catalyst life-
time [48].
No apparent trend was observed in CO carbon yield, while carbon
yield of CO2 increased obviously as steam concentration increased. It
can be explained by the enhanced catalytic steam reforming of pyrolysis
vapors at higher steam concentration. The increase of heavy com-
pounds is caused by both promoting their generation from biomass
pyrolysis and inhibiting their conversion during catalysis process.
Affected by the reduction of catalyst activity, carbon yield of PAHs
decreased continuously with increasing steam concentration. However,
carbon selectivity of PAHs presented an upward trend as steam con-
centration increased from 20% to 60%. This is because that the for-
mation of MAHs from aromatization of light compounds is suppressed
more seriously.
According to the carbon selectivity distribution of olefins and aro-
matics, the cracking of C3+ olefins and dealkylation of alkylbenzenes
were found to be inhibited with increasing steam concentration. It can
be attributed to the decline in the cracking ability of HZSM-5 which is
caused by the enhanced competitive adsorption between pyrolysis va-
pors and steam at higher steam concentration.
3.4. Effects of steam on catalytic fast pyrolysis over fresh catalyst
CFP of biomass over fresh HZSM-5 catalyst at different steam con-
centrations in the range of 0% to 60% were also performed to ascertain

6
C. Hu, et al. Fuel Processing Technology 210 (2020) 106562

30 2.75
(a)
25
Olefins+MAHs 2.25

Carbon yield (%)

20 Olefins

O/M ratio
MAHs
15 1.75

10 O/M ratio
1.25
5

0 0.75
0 20 40 60
Steam concentration (%)

25 20
(b) (c)
20
15
Carbon yield (%)

Carbon yield (%)

15 Char Coke CO
CO2 CH4 C2-C4 Alkanes 10 PAHs
Oxygenated compounds in bio-oil
10
Unidentified compounds in bio-oil
5
5

0 0
0 20 40 60 0 20 40 60
Steam concentration (%) Steam concentration (%)

60 50
(e)
40
Carbon selectivity (%)

Carbon selectivity (%)

Benzene Toluene
40 Xylenes Other MAHs
30 PAHs
Ethylene
Propylene
20
20 Butylene (d)
10

0 0
0 20 40 60 0 20 40 60
Steam concentration (%) Steam concentration (%)

Fig. 5. Product distribution as a function of steam concentration in carrier gas for CFP over activated HZSM-5 catalyst.

the integrated effects of steam on CFP, as shown in Fig. 6. Compared
with activated catalyst, the product distribution from fresh catalyst
under steam atmosphere is additionally affected by the steam activation
process of HZSM-5. Steam dealumination of HZSM-5 framework slows
down at low steam concentration. Thus, the influence of steam acti-
vation process on the product distribution is weaker under the same
reaction time.
An increase in MAHs carbon yield was observed as steam con-
centration increased from 0% to 40%. As a result, carbon yield of ole-
fins + MAHs increased monotonously with increasing steam con-
centration and showed a much higher growth rate at low steam
concentration. Meanwhile, there was a continuous decline in CO carbon
yield and a stable low carbon yield of oxygenated compounds with the
initial increase in steam concentration. These trends are quite different
from those given by activated catalyst and consistent with the changes
caused by steam activation process. The results verify the existence of
steam activation phenomenon for fresh HZSM-5 in CFP of biomass
again. Catalytic performance of HZSM-5 is affected by steam activation
and competitive adsorption at the same time. At low steam
concentration, the steam activation of catalyst proceeds slowly, and the
competitive adsorption between steam and pyrolysis vapors is also re-
latively weak. With the increase of steam concentration, the influence
of competitive adsorption becomes more and more obvious. Based on
all the product distribution information, it can be inferred that steam
activation of catalyst exerts a dominant influence on product distribu-
tion at the initial exposure of catalyst to steam.
4. Conclusion
The effects of steam on ex-situ CFP of biomass were investigated
using a two-stage fluidized-bed/fixed-bed reactor in this work. The
results show steam promotes the thermal decomposition of biomass
feedstock and prevents the secondary cracking of pyrolysis vapors to
some extent, resulting in an increase of bio-oil, especially light com-
pounds which are the main precursors of hydrocarbons. HZSM-5 cata-
lyst can be activated at the initial exposure to steam (the first 30 min
with 60% steam) through the adjustment of physicochemical properties
caused by framework dealumination, leading to an improvement of its

7
C. Hu, et al. Fuel Processing Technology 210 (2020) 106562

30 1.55
(a)
25

Carbon yield (%)

20 1.35
Olefins+MAHs

O/M ratio
Olefins
15 MAHs

10 1.15
O/M ratio
5

0 0.95
0 20 40 60
Steam concentration (%)

25 20
(b) (c)
20
15
Carbon yield (%)

Carbon yield (%)

15 Char Coke CO
CO2 CH4 C2-C4 Alkanes 10 PAHs
Oxygenated compounds in bio-oil
10
Unidentified compounds in bio-oil
5
5

0 0
0 20 40 60 0 20 40 60
Steam concentration (%) Steam concentration (%)

80 50

(d)
Benzene Toluene (e)
Xylenes Other MAHs
40
Carbon selectivity (%)

Carbon selectivity (%)

60 PAHs
Ethylene
Propylene 30
40 Butylene
20

20
10

0 0
0 20 40 60 0 20 40 60
Steam concentration (%) Steam concentration (%)

Fig. 6. Product distribution as a function of steam concentration in carrier gas for CFP over fresh HZSM-5 catalyst.

catalytic performance for the production of olefins + MAHs (increased Conceptualization, Writing - Review & Editing. Shiliang Wu:
by 23.80%). In addition, there is a competitive adsorption between Validation, Data Curation. Rui Xiao: Conceptualization, Resources,
pyrolysis vapors and steam on catalyst acid sites, which reduces the Supervision, Project administration, Funding acquisition.
catalytic effects of HZSM-5 on pyrolysis vapors in all aspects, especially
the aromatization reactions. Fresh catalyst is affected by catalyst acti-
Declaration of competing interest
vation and competitive adsorption at the same time, and catalyst acti-
vation exerts a dominant influence on product distribution at the initial
stage. For activated catalyst (60 min with 60% steam), when steam The authors declare that they have no known competing financial
fraction increased from 0% to 40%, olefins + MAHs carbon yield kept interests or personal relationships that could have appeared to influ-
at the same level, while olefins carbon yield increased by 35.65% and ence the work reported in this paper.
O/M ratio boosted from 0.83 to 1.60. It provides an effective method
for controlling the O/M ratio of hydrocarbon products and enhancing Acknowledgements
light olefins production from ex-situ CFP of biomass.
This work was supported by the National Science Fund for
CRediT authorship contribution statement Distinguished Young Scholars (Grant No. 51525601), the International
(Regional) Cooperation and Exchange Program of the National Natural
Changsong Hu: Conceptualization, Investigation, Methodology, Science Foundation of China (Grant No. 51561145010) and the
Writing - original draft, Visualization. Chao Liu: Investigation, Scientific Research Foundation of the Graduate School of Southeast
Methodology. Qingyu Liu: Methodology. Huiyan Zhang: University (Grant No. YBJJ1756).

8
C. Hu, et al.
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