Bioresource Technology 294 (2019) 122097

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Catalytic hydrothermal liquefaction of rice straw for production of T

monomers phenol over metal supported mesoporous catalyst
⁎
Yong-Jie Ding , Chun-Xiang Zhao, Zeng-Chen Liu
College of Chemistry and Chemical Engineering, Zhoukou Normal University, Zhouou 466001, China

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: The catalytic (SBA-15, Ni/SBA-15, Al/SBA-15 and Ni-Al/SBA-15) hydrothermal liquefaction (HTL) of rice straw
Rice straw biomass was examined at different temperature with different amount of catalyst in the presence of different
Catalytic liquefaction solvents. In comparison with water solvent liquefaction, the bio-oil yield significantly increased under alcoholic
Phenolic monomer solvent (ethanol and methanol). The highest bio-oil yield was observed for water (44.3 wt%) with Ni-Al/SBA-15,
Quality bio-oil
while for ethanol (56.2 wt%), and for methanol (48.1 wt%) with, Ni/SBA-15 catalyst. The loading of Ni and Al
on SBA-15, the acid strength of the catalyst enhanced. Bio-oils yield were analyzed with the help of GC–MS, FT-
IR, NMR, GPC and CHNS. From the GC–MS analysis, the main monomeric phenolic compounds were produced,
phenol, 4-ethyl-phenol, 2-methoxy-phenol, 2-methoxy-4-ethyl-phenol and Vanillin. It was observed by CHNS
and GPC analysis of the bio-oil, compared to the non-catalytic liquefaction reaction, the catalytic liquefaction
reaction promotes the hydrogenation/hydrodeoxygenation and produced lower molecular weight bio-oils.

1. Introduction methods such as pyrolysis and hydrothermal liquefaction are the most
used for the production of energy (bio-oil and bio-char) (Chen et al.,
For the fast development of society and economy, the uses of the 2019; Biswas et al., 2017a,b; Mathimani and Mallick, 2019). Several
finite fossil fuels are continuously increased (Biswas et al., 2017a). researchers showed that the liquefaction of the rice straw biomass
Hence the reserved fossil fuels continuously decreased, for this reason formed high excellence bio-oil properties that can be used as transport
we need to search the alternative energy source. It has been observed fuels (Younas et al., 2017; Chen et al., 2018; Yuan et al., 2007; Li et al.,
that the biomass can be alternative energy source to fossil fuel as it is 2009; Zhou et al., 2016; Abraham et al., 2016).
sustainable, renewable and cheap for the production of fuels/chemicals Yuan et al., studied the non-catalytic liquefaction of rice straw with
(Leong et al., 2018; Biswas et al., 2017b). Hence, from the past 10 years different solvent at 300 °C. They obtained the maximum bio-oil yield
many research groups are working on the different type of biomass 39.7 wt% with 2-propanol: water (ratio of 5:5 (Yuan et al., 2007). Li
conversion (lignocellulosic, agriculture residues and aquatic waste) into and Yuan reported the maximum bio-oil yield 57.30 wt% with 1,4-di-
valuable products that can be replaced the petroleum products (Biswas oxane solvent at 300 °C through rice straw liquefaction (Li and Yuan
et al., 2017b; Lu et al., 2018; Leong et al., 2018). The thermochemical et al., 2009). Younas et al., studied the catalytic and non-catalytic

⁎
Corresponding author.
E-mail address: [email protected] (Y.-J. Ding).

https://doi.org/10.1016/j.biortech.2019.122097
Received 22 July 2019; Received in revised form 29 August 2019; Accepted 30 August 2019
Available online 03 September 2019
0960-8524/ © 2019 Published by Elsevier Ltd.
Y.-J. Ding, et al. Bioresource Technology 294 (2019) 122097

hydrothermal liquefaction at different reaction temperature at catalysts are label as Ni/SBA-15 and Ni-Al/SBA-15.
200–300 °C with NiO nano-catalyst for 120 min. They observed that
when used NiO catalyst, the maximum bio-oil yield was 17.2 wt%. The 2.2. Reaction procedure
catalytic liquefaction showed higher carbon recovery 52.8% compared
to the non-catalytic liquefaction reaction bio-oil. GC–MS analysis Hydrothermal liquefaction (HTL) experiments were carried out in a
showed that the bio-oil majorly composed of phenol, alcohol and ke- 100 ml high-pressure autoclave (Parr reactor) at different reaction
tones compounds (Younas et al., 2017). Chen et al., (2018) examined conditions. In a typical hydrothermal liquefaction experiment, the re-
the Ni/CeO2 catalyst on the liquefaction of rice straw with different actor was loaded with rice straw and solvent (water or ethanol and
temperature, reaction time, and H2 pressure. The maximum bio-oil methanol) (1:6 by weight). While for catalytic reaction, the amount of
yield (66.7 wt%) and conversion (89.08%) was obtained with Ni/Ce catalyst (10.0 wt%) was taken. The inside air was take out by five times
(ratio 2:10). The obtained bio-oil majorly composed of phenolic com- purged the reactor with nitrogen gas. The inside biomass sample agi-
pounds that can be used in industries. They also explored the reaction tated using stirrer (~280 rpm). The desire temperature (260, 280, and
mechanism. Zhou et al., 2016, investigated the reductive catalytic li- 300 °C) was used for the reaction, and the autogenously pressure was
quefaction of rice straw in water and water–ethanol mixture solvent by range of 55–120 bar. From TGA/DTGA analysis result, the second stage
using CuZnAl catalyst. The results showed that the five monomeric of decomposition ranging from 240 to 430 °C was the major weight loss,
phenolic compounds were obtained with higher selectively. The max- in which major pyrolysis or decomposition takes place, based on this
imum phenolic compounds area was obtained 26.8%. They examined results temperature has choose. After the holding the reaction to desire
the reusability of the catalyst and showed that till five times a less time, the reactor was cool down to room temperature. The gases pro-
amount of activity of the catalyst dropped. duct vent out from the reactor and the liquid portion separated from the
The liquefaction of rice straw into monomeric phenols was obtained solid residue with the addition of diethyl ether when used water/and
by using hydrogen gas. However the phenolic compounds amount was alcoholic solvents when used alcoholic solvent and using filtered. The
very low and process become more costly as hydrogen gas used. Now organic fraction was separated by using evaporated in a rotary eva-
day’s researchers are paying attention on the use of whole rice straw porator at 45 °C temperature. The obtained solid fraction dried at
biomass for the catalytic conversion into higher and quality bio-oil 100 °C for overnight. The reaction was carried out two times and the
production in the presence of hydrogen donor solvents (ethanol and deviations of the product yield are range of ± 1%. For the calculation of
methanol). The uses of suitable catalyst can be showed the path for the the products yield a various equation was used and those are given
quality bio-oil production (Mathimani and Mallick, 2019). The novel below.
metals as well as the nano-catalyst are highly cost so we have to focused
Weight of rice straw feed − Weight of bio − residue
on the other catalyst e.g., commercials abundant metal catalyst and Conversion (%) = x
Weight of rice straw feed
support metal catalysts that are huge abundant, and can be easily re-
cycling for the reaction (Murnieks et al., 2014; Mathimani and Mallick, 100
2019). Weight of bio − oil
The main aim of the present work was exploration the simple hy- Biooil yield (wt . %) = x100
Weight of rice straw feed
drothermal liquefaction (HTL) of the rice straw into valuable and
quality bio-oil. In this studied, mesoporous SBA-15, Al/SBA-15, Ni/ Weight of bio − residue
Solid residue yield (wt . %) = x100
SBA-15 and Ni-Al/SBA-15 catalyst synthesized and investigated on the Weight of rice straw feed
HTL of rice straw in the presence of different solvent (water, ethanol
and methanol), reaction temperature (260, 280 and 300 °C), and dif- Gas yield (wt . %)
ferent amount of catalyst. The obtained bio-oils were characterized by = (W (vessel + feed + water ) before HTL − W (vessel + feed + water )
the help of gas chromatography-mass spectroscopy (GC–MS), Nuclear
after HTL)/(Amount of feed taken (g ) + amount of water
Magnetic Resonance (NMR), Fourier Transform Infrared (FT-IR), Gel
Permeation Chromatography (GPC) and elemental analysis (CHNS). added (g )) x100
Thus this process could be the effective for the rice straw biomass
Other yield (wt . %) = 100 − (bio − oil + solid residue + gas )
conversion into valuable products.

2. Materials and methods 2.3. Characterization methods

The rice straw biomass collected from Panyu District, Guangdong, The TGA/DTGA was examined by Shimadzu DTG-60 instrument.
China. Pluronic P123, Nickel nitrate (Ni(NO3)2·6H2O), Aluminium ni- For the TGA analysis 3–5 mg rice straw sample was taken and heating
trate nonahydrate (Al(NO3)3·(9H2O), tetraethyl orthosilicate (TEOS) from 25 to 900 °C with the heating rate of 10 °C/min under nitrogen
were purchased from Sigma-Aldrich, china. Other chemicals used in the gas. The functional group was analyses by the use of FT-IR using
reaction such as ethanol, THF, HCl, all analytical grades were pur- NEXUS670 with the sample powder diluted in KBr. The scan of the
chased from Fisher Scientific. sample was carried out with the resolution of 4 cm−1, the range of
between 400 and 4000 cm−1. The type of proton present in the bio-oil
2.1. Catalyst synthesis procedure was analyzed by the help of NMR-Bruker 500 Plus instrument using a
CDCl3 as solvent. The monomer phenol compound present in the bio-oil
The synthesis of SBA-15 and Al/SBA-15 are followed from other was characterized by utilization of gas chromatography-mass spectro-
researcher group (Zhao et al., 1998; Yue et al., 1999). Ni/SBA-15 and scopy (GC–MS, HP7890 arrangement GC with a HP-5975 MS indicator).
Ni-Al/SBA-15 were synthesized by using wetness impregnation The column was 30 m × 0.25 mm i.d. × 0.25 μm d.f. The sample was
methods with Ni(NO3)2·6H2O) as the Ni precursor. For the preparation injected 1 μL with split mode. The GC oven temperature; 50 °C for 2 min
of desired catalyst the projected amount of nickel salt was dissolved in then to 280 °C with heating rate 5 °C/min, and helium gas used, finally
distilled water for 30 min under stirring conditions. Then the powdered the oven temperature maintained 280 °C for 10 min the compounds are
support SBA-15 or Al/SBA-15 was added in the nitrate solution. After identified by NIST library. The acidity of the catalyst was characterized
that the solution heated at 90 °C by using hot plate and kept it till the by the help of NH3-TPD (Thermo Finnigan TPDRO 1100 series) with
water evaporated. The obtained sample dried for 6 h at 100 °C and then TCD detector. The Brunauere Emmette Teller (BET) surface area mea-
calcined at 550 °C for 5 h with heating rate of 5 °C/min. These prepared surement was analyzed in a Micromeritics ASAP-2010 apparatus

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Y.-J. Ding, et al. Bioresource Technology 294 (2019) 122097

Table 1 Table 2
Properties of different catalysts. Ultimate and proximate analysis of rice straw, wt.%.
Catalyst Surface area Pore volume, Pore diameter, Total Ultimate analysis, wt.% Proximate analysis, wt.% HHV (MJ/kg)
m2/g m/g nm acidity
(mmol/g) C 37.8 Moisture 11.8 15.87
H 5.4 Volatiles 79.7
SBA-15 647 1.20 8.60 – N 0.7 Fixed Carbon 6.3
Al/SBA-15 596 0.94 8.51 – S 0.3 Ash 10.5
Ni/SBA-15 578 1.08 8.42 0.80 O 55.8
Ni-Al/SBA-15 555 0.89 8.45 1.35

employing N2 adsorption and desorption isotherms data at 77 K. The

monomer or oligomer molecular weight was analyzed with the Gel
Permeation Chromatography (GPC) on an Agilent 1260 HPLC. CHNS/O
elementary analyzer (Vario Micro Cube, Germany) was used for an
ultimate analysis of biomass.

3. Results and discussions

3.1. Catalyst characterization

The prepared catalysts were characterized by Brunauere Emmette

Teller surface analyzer (BET), XRD, NH3-TPD. The catalysts character-
ization results are shown in Table 1. It was seen that the catalysts
showed type IV BET isotherms, mesoporous materials according to
IUPAC (Condon et al., 2006). The SBA-15 showed the higher surface
area 647 m2/g compared to the metal supported catalyst. As the metal
Ni or Al incorporated on SBA-15, the surface area of the catalyst de-
creased to Al/SBA-15 (596 m2/g), Ni/SBA-15 (578 m2/g) and Ni-Al/ Fig. 1. TGA/DTGA of the rice straw biomass.
SBA-15 (555 m2/g). The highest pore diameter and Pore volume was
observed for SBA-15 catalyst (8.6 nm) and (1.2 cm3/g) while lowest from ambient temperature to 125 °C exist due to the loss of moisture.
pore diameter obtained for Ni/SBA-15 (8.42 nm) and pore volume for The thermal conversion of the rice straw showed maximum decom-
Ni-Al/SBA-15 (0.89 cm3/g). The decreased the surface area and pore position between 240 and 430 °C. After 430 °C, the decomposition
volume of the Ni- metal supported catalyst may be due to the Ni metal proceeds at a relatively slower rate. This can be attributed to the fact
blocked the pore of support and partially deposited on SBA-15 and Al/ that the feedstock mixture predominantly comprised of hemicellulose
SBA-15 support (Gbadamasi et al., 2016). and cellulose which undergo decomposition before 430 °C. This second
The mesoporous silica peak of the catalyst SBA-15 and Al/SBA-15 stage of decomposition can be treated as an active pyrolysis zone and is
were observed by the XRD at 2θ = 22–24°. As the metal incorporated characterized by increases in depolymerization degree due to maximum
on the support, metal supported catalyst showed various new peaks at degradation (Biswas et al., 2017a; White et al., 2011). The third stage
2θ of 37.3, 43.4 and 63.2° to the planes of (1 1 1), (2 0 0) and (2 2 0) of degraded was observed due to the lignin contained in the rice straw
Ni metal respectively (JCPDS 01-075-0197). This observation con- biomass which is decomposed at higher temperature above 450 °C.
firmed that the Ni metal was dispersed in the pore of the SBA-15 sup- The FT-IR of the rice straw biomass feedstock characterized for the
port. The acidic properties of the prepared catalyst was estimated by the understanding the functional group present in the raw biomass. The
help of NH3-TPD analysis and shown in Table 1. The SBA-15 and Al/ absorbance at 3397–3420 cm−1 was observed due to carbohydrates or
SBA-15 catalyst did not show any acidic behavior due to inert in nature. moisture OeH functional group present in the rice straw biomass. The
However, the prepared metal supported catalyst showed acidic prop- bands at 2929–2915 cm−1 and 1312–1400 cm−1 were observed due to
erties (Wang et al., 2015; Yang et al., 2014). The acidic site was ob- the symmetric and symmetric stretching of CH2 and CH3 of the carbo-
served for Ni/SBA-15 and Ni-Al/SBA-15 catalyst may be due to the hydrates compositions (Biswas et al., 2017a). The nitrogen (CeN),
impregnation of Ni metal into the silica matrix (Fang et al., 2005). The carbonyls (C]O) and ester (CeO) functional groups present are con-
acidic site in the catalyst plays a key role for the reaction. Ni-Al/SBA-15 firmed by peaks observed at 1312 cm−1, 1742–1620 cm−1, and
catalyst showed the higher amount of acidic site (1.35 mmol/g) com- 1026 cm−1 (Biswas et al., 2017a,b). The band at 1633–1500 cm−1 are
pared to the Ni/SBA-15 catalyst (0.80 mmol/g). obtained due to the aromatic functional group (C]C).

3.2. Feedstock analysis 3.3. Product yields

From the proximate analysis it was observed that the rice straw 3.3.1. Effects of catalysts and reaction solvent
biomass hold higher volatile matter (79.7%). Higher the volatile matter The effect of solvents (water, ethanol, and methanol) on different
could be the good for fuels/chemicals production. The rice straw con- catalysts (SBA-15, Ni/SBA-15, Al/SBA-15 and Ni-Al/SBA-15) during the
tained, fixed carbon (6.3%), moisture (11.8%), and ash (10.5%) shown hydrothermal liquefaction (HTL) of rice straw at 280 for 15 min reac-
in Table 2. Whereas, elemental analysis showed that the rice straw tion time was investigated. The products yields are provided in Fig. 2a
biomass content C (37.8%), H (5.4%), N (0.7%), S (0.3%) and high O with water, 2b with ethanol and 2c with methanol solvents.
(55.8%). When used water as a reaction solvent, the maximum bio-oil yield
The TGA/DTGA analysis showed that the rice straw biomass de- 44.3 wt% was observed with Ni-Al/SBA-15 catalyst while non-catalytic
graded to three stages and shown Fig. 1 and the degradation was reaction produced very lower bio-oil yield 22.7 wt%. SBA-15 catalytic
compared to the other researcher results (Biswas et al., 2017a; liquefaction reaction produced 24.5 wt% bio-oil, while metal im-
Dewangan et al., 2016). The peaks in the DTG curves of the rice straw pregnated on SBA-15 produced significantly higher bio-oil yield such as

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Y.-J. Ding, et al. Bioresource Technology 294 (2019) 122097

Fig. 2. Effect of different solvents (a) water (b) ethanol and (c) methanol with SBA-15, Ni/SBA-15, Al/SBA-15 and Ni-Al/SBA-15 catalysts on products yield.

Al/SBA-15 (35.6 wt%), Ni/SBA-15 (32.8 wt%) and Ni-Al/SBA-15 of active hydrogen generated from the supported catalyst. Hence the
(44.3 wt%). The maximum bio-char yield was obtained with non-cat- catalysts acidic strength played a crucial role for the product yields.
alytic reaction (34.1 wt%) while minimum was observed with Ni-Al/ Rana et al. showed that the higher acidic catalyst promoted the
SBA-15 (27.9 wt%). Meanwhile, the gas yield observed higher in the cracking, conversion and hydrogenation of the biomass macromolecule
case of Ni/SBA-15 catalytic liquefaction (25.3 wt%), and lowest ob- (Rana et al., 2000). The acids site of the catalyst provoked the dehy-
served (18.8 wt%) with non-catalytic reaction. With ethanol solvent, dration and isomerization, which enhance the hydrogenation and en-
the maximum bio-oil yield (56.2 wt%) was obtained with Ni/SBA-15 courage for hydrodeoxygenation reaction (Xinghua et al., 2010).
catalyst and lowest observed (24.8 wt%) with non-catalytic liquefaction Younas et al. investigated the HTL of rice straw biomass, they observed
reaction. The liquefaction reaction with SBA-15, Al/SBA-15 and Ni-Al/ maximum bio-oil yield was (17.2 wt%) which is lowered compared to
SBA-15 produced 35.2 wt%, 38.5 wt% and 43.1 wt% bio-oil yields. The our result (Younas et al., 2017). Similarly Shi et al. was observed lower
maximum bio-char yield (22.1 wt%), exclude the non-catalytic reac- bio-oil yield (32.5 wt%) at higher temperature 300 °C (Shi et al., 2013),
tion; was observed Ni-Al/SBA-15 catalytic liquefaction reaction hence our proceed might be the future direction for the rice straw li-
whereas minimum was observed (18.4 wt%) with Ni/SBA-15 which is quefaction.
produced maximum bio-oil yield. Higher percentage of gas yield
26.4 wt% was observed for Ni-Al/SBA-15 catalytic liquefaction. The
hydrothermal liquefaction with methanol solvent produced maximum 3.3.2. Effect of amount of Ni/SBA-15 catalyst
bio-oil yield (48.1 wt%) with Ni/SBA-15 catalyst, which is showed The effect of different catalyst amount such as 5, 10, 15, and 20 wt%
lower bio-char yield (18.8 wt%). The maximum gas yield (30.2 wt%) of Ni/SBA-15 catalyst at 280 °C on the HTL reaction on product yields
was observed for Ni-Al/SBA-15 catalytic liquefaction reaction. was investigated. The effects of different amount of catalyst on product
The bio-oil yield trend showed Ni-/SBA-15 (56.2 wt%) with ethanol yield are shown in Fig. 3. It was clearly observed that the 10 and 15 wt
solvent > Ni-/SBA-15 (48.1 wt%) with methanol solvent > Ni-Al/ % of catalyst effectively produced maximum bio-oil yield in the range
SBA-15 (44.3 wt%) with water solvent. It was can be say that the dif- of 56.2–56.6 wt%. When used 5 wt% Ni/SBA-15 catalyst, the bio-oil
ferent solvent as well as the catalysts properties influenced the products observed minimum (40.6 wt%) due to the lower amount of catalyst did
yield. The higher acidity (1.35 mmol/g) and a medium surface area not provide the required active surface or acidity, and showed lower
(555 M2/g) catalyst Ni-Al/SBA-15 was suitable for the water solvent bio-oil yield. Where, also higher amount (20 wt%) of catalyst was given
and as the solvent change to the ethanol and methanol the bio-oil yield lower bio-oil (55.1 wt%) compared to the 10 and 15 wt% catalyst
became lowered. Although, the surface area showed higher for SBA-15 amount. The higher amount of catalyst enhanced the cracking of the
catalyst, the bio-oil yield did not enhance by applying SBA-15 catalyst. rice straw macromolecule into non condensable gas (Chen et al., 2018).
In the presence of the alcoholic solvent, the Ni/SBA-15 catalyst could be Lower bio-char (18.4 wt%) and higher bio-char (32.2 wt%) was ob-
best catalyst for the bio-oil production from the rice straw liquefaction. served with 5 wt% and 10 wt% catalyst. From the product yield it can
Also, the solubility of lignin in ethanol can be greatly enhanced, which be say that the different amount of catalyst performed different effect
in turn enhances the production of higher bio-oil through the reduction on biomass composition.

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Y.-J. Ding, et al. Bioresource Technology 294 (2019) 122097

3.4. Bio-oil analysis

3.4.1. Bio-oil composition analyzed by GC–MS

The obtained bio-oil with catalyst and non-catalyst liquefaction
reaction at optimal condition was analyzed by the Gas chromatography-
Mass spectrometry (GC–MS) and represented in Table 3. It was ob-
served that non-catalytic bio-oil majorly contains, 2-pentanone, 4-hy-
droxy-4-methyl for water (10.5%), ethanol (3.5%) and methanol
(2.1%); 4-ethyl phenol for water (2.4%), ethanol (11.3%) and methanol
(9.4%), Phenol for water (3.5%), ethanol (6.4%) and methanol (4.2%);
2-methoxy Phenol for water (7.4%), ethanol (7.3%) and methanol
(3.2%); Vanillin for water (12.2%), ethanol (10.3%) and methanol
(12.1%). Interestingly, 2-methoxy-6-methyl phenol compounds higher
area % observed for water solvent (6.5%) compared to the alcoholic
solvents. The water during the liquefaction, dissociate into H+ and
OH−, which is hydrolysis the cellulose, hemicellulose as well as the
lignin with higher rate and produced higher aliphatic compounds (2-
pentanone, 4-hydroxy-4-methyl) compared to the alcoholic solvent.
While the phenolic compounds observed due to the breaking of β-O-4
bond by the H+ ion.
Fig. 3. Effect of catalyst amount on products yields.
While for the catalytic liquefaction reaction the selectivity of the
phenolic derivative compounds increased significantly. The ethanol
3.3.3. Effect of different reaction temperature on Ni/SBA-15 catalyst solvent with Ni/SBA-15 catalysts showed higher percentage of Phenol
The effect reaction temperature 260, 280 and 300 °C on the product (18.2%), 4-ethyl phenol (23.5%), 2–6-dimethoxy phenol (5.8%), 3,5-
yield with Ni/SBA-15 (10 wt%) catalyst has been investigated and the dimethyl phenol (6.8%) and Vanillin (17.8%). Whereas as for catalytic
product yield shown in Fig. 4. It can be seen in Fig. 4, the bio-oil yield liquefaction in the presence of water solvent did not enhance the
increased 36.8 wt% to 56.2 wt% as the temperature increased compounds selectivity while for methanol showed some selective phe-
260–280 °C. Further increased the temperature to 300 °C, the bio-oil nolic compounds such as 2-methoxy 4-vinyl phenol (7.3%) and Vanillin
yield decreased to 48.7 wt% however the bio-char yield observed (16.2%) which is lower than the ethanol solvents. The used of Ni/SBA-
higher 22.1 wt% compare to the 280 °C (18.4 wt%). The lower amount 15 catalyst with ethanol solvent during the liquefaction reaction de-
of bio-char yield observed at 280 °C due to at lower temperature 260 °C; oxygenation reaction enhanced compared to the other catalytic reac-
the rice straw macromolecule did not efficiently decomposed. While at tion which is good agreed with the elemental analysis (Chen et al.,
higher temperature 300 °C, the secondary reaction occurred between 2018). Hence, from the GC–MS analysis it can be seen that Ni/SBA-15
the non-condensable gas/condensable gas and bio-char and which is catalyst capable to do the deoxygenating and produce selectively higher
increased the bio-char yield (Chen et al., 2018). When the temperature mono alkyl phenolic compound. The formation of phenolic compounds
increased to 300 °C, the gas yield was observed maximum 34.2 wt% as obtained mainly from the lignin degradation as lignin contained higher
at higher temperature enhanced the cracking of the rice straw macro- aromatic functional monomer and some are obtained from carbohy-
molecule into non-condensable products. Meanwhile, the overall con- drates by the rearrangement with the several reaction steps (Cao et al.,
version observed highest 81.6 wt% in the case of 280 °C reaction tem- 2016; Biswas et al., 2017b, 2016). The higher amount of phenol are
perature. The products distribution also agreed with the several studied obtained by catalyst accelerate of β-O-4 and C–C bond breaking.
(Gai et al., 2015; Tran, 2016). The new compounds formed during the Moreover, Vanillin is obtained due to the breaking of β-O-4 bond.
liquefaction reaction by the hydrolysis and repolymerization with Hence, it can be say that the catalyst Ni/SBA-15 with ethanol solvent
condensation, cyclization, and polymerization reactions. selectively broken the β-O-4 and C–C bonds. Alcohol is a simple polar
one hydroxyl containing solvent which is enhanced the hydrogen
bonding with O-containing functional groups (Mahmood et al., 2015).
The induced effect by the hydrogen bonding enhanced the degradation
of the lignin and carbohydrates matrix (Li et al., 2016).

3.4.2. FT-IR analysis

The functional groups present in the bio-oils have been analysis by
the help of FT-IR. Peak at 3378–3310 cm−1 is articulated to the O–H
functional group due to the phenolic or moisture content in the bio-oil
(Biswas et al., 2017a). The aliphatic functional group (–C–H) presence
was confirmed from the peak obtained at 2962 and 2826 cm−1 as well
as in the finger print region at 1377–1395 cm−1 for C–H stretching
bending (Cao et al., 2016; Biswas et al., 2016). The lower intensity band
at 1700 cm−1 for carbonyl functional group and higher intensity of the
alkyl group absorbance band was obtained at 2982 cm−1 due to the
alkyl group with phenolic compounds present in the catalytic bio-oil
with Ni/SBA-15 catalyst under ethanol solvent. From the GC–MS result
it was seen that methoxy group containing compound present in the
bio-oil and it agreed with the FT-IR as C–O and –CH3 functional group
vibration observed at 1650–1595 cm−1 and 2800–2900 cm−1 (Biswas
et al., 2016). This peak with lower intensity was observed for non-
Fig. 4. Effect of hydrothermal liquefaction reaction temperature on product catalytic catalyst bio-oil and higher observed for catalytic bio-oil. The
yield. finger print region absorbance peak at (1220–900) cm−1 was observed

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Table 3
Compounds identified from the bio-oil obtained by non-catalytic and catalytic hydrothermal liquefaction at optimum condition by the GC–MS analysis.
Compound identified from GC–MS, Area % Blank water Ethanol methanol Ni-Al/SBA-15 with water Ni-SBA/15 with ethanol Ni/SBA-15 with methanol

Benzene 1.33 – 1.7 1.8 1.1 2.1

2-Cyclopenten-1-one 5.4 – 2.1 3.6 – –
2-Cyclopenten-1-one, 2-methyl- 2.2 – – – – –
2-Pentanone, 4-hydroxy-4-methyl 10.5 3.5 2.1 7.8 3.1 2.5
Phenol 3.5 6.4 4.2 12.0 18.2 8.6
2-Methoxy Phenol 7.4 7.3 3.2 6.5 2.4 5.2
4-Ethyl phenol 2.4 11.3 9.4 8.6 23.5 10.2
2-Methoxy, 4-ethyl phenol 3.5 10.5 4.3 7.8 10.2 8.8
2-6-Dimethoxy phenol 4.2 2.4 2.6 – 5.8 5.2
2-Methoxy 4-vinyl phenol 2.5 2.6 2.1 2.2 5.8 7.3
p-Cresol 4.5 – 1.1 5.7 – 2.1
2-Ethyl, 5-methyl phenol
Di methoxy toluene 2.0 – – 4.2 – –
3,5-Dimethyl phenol 3.1 2.3 1.2 4.3 6.8 3.1
3,4-Dimethyl phenol
1,2-Benzene diol-4-methyl 3.2 – – – – –
2-Methoxy-6-methyl phenol 6.5 – 2.1 1.2 – 2.1
Benzofuran, 2-3-dihydro – – – 4.1 – –
Eugenol – – 2.7 3.8 4.2 3.1
1,4-Benzene diol, 2-methoxy 2.1 3.6 – 1.6 1.2 –
Vanillin 12.2 10.3 12.1 8.9 17.8 16.2
Phenol, 2-methoxy-4-propyl 4.8 2.5 – 3.3 – –
Apocynin 3.0 – – – – –
Homovanillyl alcohol 1.8 2.5 – 2.1 – –
4-Ethoxy-3-anisaldehyde 1.7 – – – – –
Hydroquinone 2.1 2.6 – 3.3 2.8 –
Methyl syringol – – – 3.6 – –
Methyl guaiacol 0. 2.1 2.1 4.2 – 3.2

due to the ester or acids C–O functional group (Biswas et al., 2017a). amount of protons was observed in the case of Ni-Al/SBA-15 catalytic
The higher methoxy ester functional group was obtained in the case of bio-oil 46.0% (Putun et al., 2007). The heterocyclic and methoxy pro-
Ni-SBA-15 and Al-Ni/SBa-15 catalyst with ethanol and water solvent tons in the region between (3.0–6.0 ppm) were observed very less
liquefaction bio-oil compared to the other bio-oil and it is well agreed amount in the all bio-oil (0.8–8.3%). The aromatic region 6.0–8.5, in
with GC–MS compounds. this region higher percentage of protons observed for catalytic lique-
faction bio-oil (32.6–34.6%) compared to the non catalytic reaction
(Ozbay et al., 2008). The observed protons are concluded that the
3.4.3. NMR analysis catalytic bio-oil mainly consisting of aromatic compounds while a less
From the NMR analysis of the bio-oil it was observed that a different amount of aromatic or phenolic compounds are observed for non-cat-
type of protons present in the bio-oil and the NMR results are shown in alytic bio-oil. The aromatic (C]C) compounds increased in the cata-
Fig. 5. The alkyl proton region 0.5–1.5 ppm, showed (11.0–15.0%) in lytic liquefaction are good agreed with FT-IR and GC–MS character-
the all bio-oil, while higher observed for catalytic liquefaction bio-oil. ization of the bio-oil.
15.0% aliphatic protons was observed for bio-oil obtained with lique-
faction Ni-Al/SBA-15 catalysts in the presence of water solvent. The
region 1.5–3.0 belongs to sp2 hybridized carbon protons and higher

Fig. 5. 1HNMR spectral distribution of functional groups present in bio-oil from non-catalytic and catalytic liquefaction at optimum condition.

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Table 4 3.4.5. GPC analysis of bio-oils

Elementary analysis of bio-oil obtained from optimum conditions. GPC analysis results of rice straw biomass, non-catalytic and cata-
Sample C, % H, % N, % O, % HHV (MJ/kg) lytic reaction products listed in Fig. 6. It demonstrated clearly that the
average molecular weight (Mw) was decreased from raw rice straw
Rice straw 58.7 5.6 0.6 31.7 25.4 2470 g/mol to liquefaction bio-oil in the range of 456–1120 g/mol.
Water 65.1 5.2 0.4 29.5 30.7
Which confirmed the rice straw depolymerization was performed well
Ethanol 80.3 9.3 0.3 9.2 35.2
Methanol 79.4 8.6 0.3 12.1 32.8
in the liquefaction process. Compared to the non-catalytic liquefaction
Ni-Al/SBA-15-W 80.6 9.4 0.3 10.0 33.2 bio-oil, the catalytic liquefaction bio-oils were showed lower Mw value.
Ni/SBA-15-E 84.2 8.8 0.2 7.0 36.6 The presence of Ni/SBA-15 catalyst in the presence of methanol solvent,
Ni/SBA-15-M 81.4 9.2 0.3 9.4 35.4 the Mw (456 g/mol) and dispersion degree (1.3) significantly de-
where, W = water, E = ethanol and M = methanol solvent
creased, in line with the increase of monomer product yield and low-
ering the solid yield, which presented a great promoting effect on de-
3.4.4. Elemental analysis polymerization. The extent of repolymerization of the unsaturated bond
The element content in the bio-oils obtained at optimum conditions in rice straw molecular was observed higher in the case of liquefaction
with and without catalytic reactions is given in Table 4. The rice straw with water solvent without catalyst as the bio-oil showed higher Mw
feedstock had element content C (37.8), H (5.4), N (0.7), and O (55.8) value (1120 g/mol) (Heitner et al., 2010). Therefore, the decreases the
and higher heating value (HHV) 25.4 MJ/kg. It has been observed that Mw weight of the bio-oil can be endorsed to the higher depolymer-
the oxygen content in the catalytic liquefaction bio-oil showed lower ization of the phenolic oligomer into the monomer phenolic compounds
(7.0–10%) followed by liquefaction reaction with non-catalytic lique- (Klamrassamee et al., 2015). However, the Mw (730 g/mol) and dis-
faction reaction (9.2–29.5%). The minimum oxygen (7.0%) was ob- persion degree (1.6) of products were increased in Ni/SBA-15 with
served in the case of Ni/SBA-15 catalytic liquefaction with ethanol ethanol solvent liquefaction bio-oil, indicating the repolymerization
solvent bio-oil. During the catalytic liquefaction reaction the oxygen happened in the reactor. Meanwhile, the catalytic properties as well as
content in the raw biomass deoxygenated by decarboxylation reaction the solvents affected the rice straw macromolecule depolymerization
with evolution of CO and CO2 and water (Hu et al., 2019). The hy- during the liquefaction reaction.
drogen content in the bio-oil was increased as the catalyst used in the
reaction and maximum observed (9.4%) for Ni-Al/SBA-15 catalytic 4. Conclusions
reaction with water solvent while lower the nitrogen contented (0.2%)
was observed in Ni/SBA-15 catalytic bio-oil with ethanol solvent. The The maximum bio-oil yield (56.2 wt%) was obtained with Ni/SBA-
hydrogen content lowest amount (5.2%) was observed for non-catalytic 15 (10.0 wt%) catalyst under ethanol solvent. The liquefaction bio-oil
liquefaction reaction under water solvent when used catalyst (Ni-Al/ majorly composed phenolic compounds such as phenol (18.2%), 4-ethyl
SBA-15), the hydrogen content significantly increased to 9.45. while for phenol (23.5%); were obtained with Ni/SBA-15 catalyst under ethanol
alcoholic solvent, the content of the hydrogen not increased as much. solvent. The catalytic liquefaction bio-oil showed higher C and H ele-
The main element carbon was to be found higher amount in the cata- ment content as well as the higher heating value (HHV) compared to
lytic bio-oil in the range of 80.6–84.2% while in the non-catalytic bio- the non-catalytic liquefaction bio-oil. Bio-oil obtained by Ni/SBA-15
oil observed (65.1–80.3%), which was in accordance with the reported catalyst with ethanol solvent showed maximum heating value of
results (Chen et al., 2018). The higher heating value (HHV) was in- 36.6 Mg/KJ. The extent of repolymerization of the unsaturated bond in
creased ranging of 33.2 and 36.6 MJ/kg for the catalytic liquefaction non-catalytic liquefaction bio-oil showed as it’s showed higher mole-
compared to the non-catalytic bio-oil (30.7–35.2 MJ/kg). It was seen cular weight.
that from the table as the O content decreased the HHV value of the bio-
oil increased (Ma et al., 2015). Acknowledgments

The authors are tanks to Zhoukou Normal University for the

Fig. 6. Average molecular weight (GPC) analysis of bio-oil obtained from non-catalytic and catalytic liquefaction.

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permission to conducts the experiments. Li, H., Yuan, X., 2009. Liquefaction of rice straw in sub- and supercritical 1,4-dioxane-
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Appendix A. Supplementary data crystalline cellulose, xylan and industrial lignin in different supercritical solvents.
Bioresour. Technol. 219, 281–288.
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