Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-019-07267-4

RESEARCH ARTICLE

Effect of operating parameters on hydrothermal liquefaction

of corn straw and its life cycle assessment
Shiqiu Zhang 1 & Shengnan Zhou 2 & Xue Yang 1 & Wen Xi 1 & Kui Zheng 3 & Chunli Chu 1 & Meiting Ju 1 & Le Liu 1

Received: 1 July 2019 / Accepted: 2 December 2019

# Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
As the shortage of non-renewable fossil fuels, the renewable fuels should be further developed. Biomass energy has emerged the great
utilization potential, and liquefaction of biomass is a typical technology. This paper studied the effect of the operation parameters on the
hydrothermal liquefaction of corn straw using a batch reactor, including liquefaction temperature, initial pressure, retention time,
solvent, and catalyst. The optimal liquefaction conditions for corn straw were 300 °C under 4 MPa for 15 min using the mixture of
water and methanol as the solvent. After the addition of catalyst, NKC-11 catalyst showed the excellent performance, and the primary
components were phenol and derivatives, alkane, furan, and the low concentration of organic acids. Lastly, the life cycle assessment on
the hydrothermal liquefaction of corn straw for bio-oil production was executed. The results of LCA suggested that a net 1.31 kg of
CO2 equivalent was produced for 1 kg of bio-oil product without considering syngas, while the value changed to 13.03 kg with
considering syngas. Moreover, the results of sensitivity analysis further suggested that the syngas was a key factor on the environmental
impacts in the hydrothermal liquefaction of corn straw process.

Keywords Biomass . Bio-oil . Syngas . Environmental impact

Introduction would meet the demands of human for a few hundred years,
these resources would be eventually exhausted (Zhao and Li,
Coal, oil, and natural gas are the familiar non-renewable fossil 2016). Moreover, with the consumption of these non-
energies, which play a significant role in the human activities renewable energies, the excessive emission of greenhouse
and industrial developments (Zhang et al. 2019). Although the gases into the atmosphere would destroy the ecological bal-
total reserves of the non-renewable energies on the earth ance (Zhang et al. 2019; Bridgwater 2003). Therefore, the
renewable clean fuels must be further developed, e.g., solar
Responsible editor: Ta Yeong Wu energy, nuclear energy, wind energy, and biomass energy
Electronic supplementary material The online version of this article (Vaughan et al. 2018; Xu and Chen 2018). Among these re-
(https://doi.org/10.1007/s11356-019-07267-4) contains supplementary newable energies, biomass energy has emerged the great uti-
material, which is available to authorized users. lization potential (Nayaret et al. 2018), as more than 20% of
the world’s energy supply would come from biomass energy
* Meiting Ju (Abdulrahman et al. 2017). An estimated 2 × 109 tons per year
[email protected]
of biomass waste would be produced (Zhang et al. 2019),
* Le Liu while only about 40% is utilized, and the rest portion would
[email protected]
be disposed in the extensive modes, e.g., landfill, incineration,
1
College of Environmental Science and Engineering, Nankai
and centralized stacking, leading to a terrible waste of biomass
University, 38 Tongyan Road, Jinnan District, Tianjin 300350, resource and serious environmental pollution (Zhang et al.,
People’s Republic of China 2018a). Therefore, it is time to improve the utilization rate of
2
Key Laboratory of Cardiovascular Remodeling and Function biomass resource and reduce the environmental pollution.
Research, Qilu Hospital, Shandong University, So far, the primary methods for the utilization of biomass
Jinan 250014, Shandong, People’s Republic of China resource include physical method, thermochemical method,
3
Analytical and Testing Center, Southwest University of Science and and biological method, e.g., gasification technology
Technology, Mianyang 621010, Sichuan, People’s Republic of China (Valderrama et al. 2018), liquefaction technology (Lim et al.
 Environ Sci Pollut Res

2012), biorefinery technology (Saxena et al. 2009), and com- temperature, initial pressure, retention time, solvent type, and
bustion technology (Kumar et al. 2015). For dry biomass (such catalyst type. Moreover, the environmental impacts of bio-oil
as straw and wood), the mainstream technologies are combus- produced from hydrothermal liquefaction of corn straw were
tion, gasification, and liquefaction (Yilmaz and Selim, 2013), reported by LCA, and the global warming potential (GWP),
while hydrolysis fermentation, biorefinery, and liquefaction are acidification, eutrophication, toxicity, and photo-oxidant for-
the primary technologies for wet biomass (such as kitchen gar- mation are taken into consideration.
bage and hydrophyte) (Laird et al. 2009; Abdullah and
Gerhauser, 2008). Bio-oil is one of the representative degrada-
tion products of biomass which has huge application prospect Materials and methods
(Imman et al., 2017), due to its high energy density output and
more simple transportation and storage (Xiu and Shahbazi, Materials and reagents
2012). For bio-oil production, it is usually generated via fast
pyrolysis (Lu et al. 2018; Zhang et al. 2018b) and hydrothermal In this experiment, the raw material was corn straw which was
liquefaction (Xue et al. 2016). During the fast pyrolysis pro- collected from Ninghe District in Tianjin. The sample was
cess, biomass would be degraded under high temperature and washed with deionized water and air-dried. Then, the corn straw
anoxic condition, and the primary products are condensable sample was passed through a 0.5-mm mesh size sieve and col-
pyrolysis vapor (bio-oil), incondensable gases, and solid bio- lected without further processing. The model components used
char (Huang et al., 2016). However, the energy consumption of in this paper were xylan (CAS: 9014-63-5), microcrystalline
this process is usually very high (Kim et al. 2013), because it cellulose (CAS: 9005-53-2), and alkali lignin (CAS: 8068-05-
would be carried out at a very high temperature and the raw 1), which were purchased from Tianjin Kemiou Chemical
material with high moisture content should be dried before Reagent Co., Ltd. Acetone (CH3COCH3, analytical reagent
treatment (Angin, 2013). Compared to fast pyrolysis, hydro- (AR) = 99%) was purchased from Aladdin Chemistry Co.,
thermal liquefaction process is usually executed under moder- Ltd. Methanol (CH4O, AR = 99%), ethyl alcohol (C2H5O, chro-
ate temperature (< 400 °C) with suitable solvents (e.g., water, matographically pure (GC) = 99.9%), and isopropanol (C3H8O,
organic solvent, or a mixture of water and organic solvent) (Yin AR = 99%) were purchased from Tianjin Kemiou Chemical
et al. 2010), which could not only low the reaction temperature Reagent Co., Ltd. The catalysts of HZSM-5 and NKC-11 were
but also dilute the concentration of products and prevent the purchased from Nankai Catalyst Co., Ltd. The water used was
formation of tar components (Sugano et al. 2008). During the deionized water with a resistivity of 18.25 MΩ·cm.
hydrothermal liquefaction process, the complex lignocellulosic
structure would be broken down, and then the organic solvents Experimental design
are used for extracting the generated bio-oil product (Zhang
et al. 2009). Hence, we intend to produce bio-oil by the hydro- The liquefaction experiments of corn straw were subjected in
thermal liquefaction method. Besides, in order to evaluate the a 10-mL autoclave. For the experimental design, the reaction
environmental impacts in the hydrothermal liquefaction pro- temperature ranged from 260 to 320 °C with a 20 °C interval,
cess, the life cycle assessment (LCA) is conducted and pro- and the initial pressure ranged from 0 to 6 MPa with a 2 MPa
posed. LCA is a systematic method, and it has been employed interval. In addition, the retention time was chosen from 5 to
in a wide range of applications (Dunmade et al. 2019), e.g., the 60 min, the catalyst dosage was fixed at 10:1 for the mass ratio
concept production of bioenergy from wheat straw (Cherubini of corn straw to catalyst, and the reaction solvents were water,
and Ulgiati, 2010), the discussion of environmental impacts of methanol, ethyl alcohol, isopropanol, and the mixture of water
presented landfill and advanced incineration equipment (Woon and methanol with the mass ratio of 6:1. For each experiment,
and Lo, 2014), and the effectiveness of the domestic wastewa- 1.5 g of corn straw and corresponding amounts of catalyst
ter treatments (Saad et al. 2018). Although there are some pub- were mixed and soaked by 6 mL of solvent for a certain time,
lished researches about the LCA of the comparisons on the and then the mixture was transferred into the autoclave and
biomass conversion technologies (Zheng et al. 2018; sealed firmly. Before heating, the air in the autoclave was
Lombardi et al. 2017), the environmental impacts of bio-oil purged by N2 flow with a low rate for 5 min. Then, the auto-
obtained from hydrothermal liquefaction of corn straw for clave was pressurized to the set value. Next, the reaction was
bio-oil production have not been widely reported (Cherubini started to heat and maintained for a certain time with 800
and Ulgiati, 2010). Hence, it is very necessary to proceed a r/min, then the reaction was quenched by cool water to room
LCA study on this theme to provide an insight into the envi- temperature. The syngas was collected. The mixture of solid
ronmental impacts. matter and liquid matter was carefully washed with acetone
This overall goal of this paper was to explore the optimal and collected. Then, the mixture was separated by a vacuum
operating parameters of bio-oil production from corn straw via filter holder and extracted with acetone for several times, pro-
the hydrothermal liquefaction method, including liquefaction ducing acetone-soluble matter and solid biochar. The acetone
Environ Sci Pollut Res

and water in acetone-soluble matter were separated using a District to Nankai University using a diesel truck with the
rotary evaporator operating under vacuum pressure at 55 °C transportation distance of 89 km.
water bath, then the bio-oil was obtained. All of the experi-
ments were repeated thrice at each reaction condition, and the Pretreatment of raw material In general, the raw material
average values were reported. The yields of liquefaction prod- should be pretreated before hydrothermal liquefaction to pro-
ucts were calculated using Eqs. (1)–(3). duce bio-oil, and the primary pretreatment was mechanical
mbio−oil milling with electricity consumption during the hydrothermal
W ðbio−oilÞ ¼  100% ð1Þ liquefaction process. The data on milling pretreatment were
mcornstraw
identified and adjusted based on the published literatures (Liu
mbiochar
W ðbiocharÞ ¼  100% ð2Þ et al. 2013).
mcornstraw
 
mbiochar þ mbio−oil Production of bio-oil After pretreatment, the next step was
W ðsyngasÞ ¼ 1−  100% ð3Þ
mcornstraw liquefaction, and the bio-oil production was extracted using
acetone as solvent. In this study, the yields of bio-oil and by-
products were based on the data obtained from the experimen-
LCA of hydrothermal liquefaction of corn straw
tal works. The electricity consumption of this stage was iden-
tified and adjusted based on the similar reported liquefaction
Based on the standard ISO 14041 series LCA standards, the
process (Chan et al., 2014a). The solvent loss during the ex-
complete LCA of biomass liquefaction should include four
traction process is based on the recovery of solvent obtained
primary sections (ISO 14041, n.d.; Foulet et al. 2018).
from the experimental works.

Goal and scope definition

Life cycle impact assessment
The goal in this LCA study was to identify and compare the
environmental impacts of the thermochemical conversion pro- According to the system boundary, there were five envi-
cess of converting corn straw to bio-oil via hydrothermal liq- ronmental impact categories to evaluate, including climate
uefaction. The system boundary of this LCA study is shown in change, acidification, eutrophication, photo-oxidant for-
Fig. 1, and 1 kg of bio-oil was selected as the functional unit. mation, and human toxicity (Tayefeh et al. 2018). The
sensitivity analysis of the LCA study was evaluated by
Life cycle inventory the yield of bio-oil and thermal efficiency of boilers.
These impacts were assessed based on the conversion fac-
Transportation of corn straw In this study, the raw material of tors reported in the Handbook of Life Cycle Assessment
corn straw was collected and then transported from Ninghe (Guinee, 2002).

Fig. 1 The system boundary for

bio-oil production via the
hydrothermal liquefaction of corn
straw
 Environ Sci Pollut Res

Interpretation solvent was water without catalyst. From the figure, it indicat-
ed that the initial pressure played a vital role in the yield of
The results about the LCA of the hydrothermal liquefaction of bio-oil. The yield of bio-oil increased from 1.16 to 32.52%
corn straw for bio-oil production on the environment were with the initial pressure increased from 0 to 4 MPa, and the
interpreted and discussed, and the limitations were also report- yield of syngas increased from 24.04 to 36.45%, while the
ed. The system boundary was from the acquisition of the corn yield of biochar decreased from 74.80 to 31.04%, which could
straw to the production of bio-oil, and this LCA was a gate-to- be explained by the fragmentation reaction of corn straw.
gate study. Hence, the increase in initial pressure could be beneficial to
bio-oil product. In this system, the suitable initial pressure was
4 MPa. The operating retention time was another vital factor
Results and discussions for the distributions of the liquefaction products. The effect of
retention time on the product distributions was executed under
Effects of liquefaction parameters the pyrolysis temperature of 300 °C, initial pressure of 4 MPa,
and the solvent of water without catalyst. As shown in the
As everyone knows, temperature was one of the most impor- figure, as the retention time increased from 0 to 15 min, the
tant parameters for the hydrothermal liquefaction of corn yield of bio-oil increased from 10.33 to 32.53%. It was worth
straw. Figure 2 a shows the impact of liquefaction temperature noting that the yield of bio-oil was relative high at 0 min,
on the yields of liquefaction products. For this experiment, the which was the result of depolymerization reaction before
other parameters were 4 MPa of initial pressure and 15 min of 300 °C. In this system, the heating time was about 40 min
retention time using water as the solvent without catalyst. As from room temperature to the desired level, and a portion of
shown in the results, it released the following conclusions: (1) corn straw was degenerated to bio-oil. The result could be
As the liquefaction temperature increased from 260 to 300 °C, confirmed by the liquefaction temperature section: the bio-
the yield of syngas remained at relatively consistent level, the oil could be produced below 300 °C (Fig. 2a). Moreover, the
yield of bio-oil increased from 28.08 to 32.52%, while the result could also be supported by the discussion that hemicel-
yield of biochar decreased from 31.72 to 25.02%, which lulose and lignin began to liquefy at 190 °C. When the reten-
caused by the decomposition of corn straw or secondary de- tion time was longer than 15 min, the yield of bio-oil de-
composition of biochar. (2) When the liquefaction temperature creased from 32.52 to 19.29%, suggesting that the longer re-
was 320 °C in this experiment, the yield of bio-oil decreased tention time was more favorable for biochar product. Hence,
distinctly, while the yields of by-products (biochar and syn- the liquefaction of corn straw would be completed within 15
gas) increased. Apparently, the optimal liquefaction tempera- min. Therefore, the liquefaction of corn straw with a shorter
ture in this system was 300 °C. Our conclusions on liquefac- retention time was favorable, which had the higher yield of
tion temperature were consistent with previous literatures, bio-oil and the lower heat loss, resulting in better energy effi-
which showed that temperature was the most critical parame- ciency. Liquefaction solvent was also another important factor
ter during the hydrothermal liquefaction of corn straw process. for the reaction. The effect of reaction solvents is shown in
When the liquefaction temperature was higher than 190 °C, Fig. 2 d. During the reaction, the reaction temperature was 300
hemicellulose and lignin would be gradually degraded °C, the initial pressure was 4 MPa, and the retention time was
(Akhtar and Amin, 2011), and the intermediates would be 15 min without catalyst. As shown in the results, the mixture
produced from the dissolved hemicellulose and lignin when solvent (methanol and water) presented the highest yield of
the temperature was greater than 220 °C (Asadullah et al. bio-oil, and the more complex structures of alcohols led to the
2013). Next, the intermediates would endure a supernormal lower yield of bio-oil (methanol > ethyl alcohol >
variety of reactions, including isomerization, dehydration, isopropanol). Considering the catalyst, the homogeneous
fragmentation, and condensation (Demirbas, 2004), and bio- and heterogeneous catalysts were comparison. As shown in
oil, syngas, and biochar were finally formed (Demirbaş 2001). Fig. 2 e, the yields of bio-oil obtained by homogeneous cata-
Therefore, the optimal liquefaction temperature for bio-oil lysts (Na2CO3 and K2CO3) were lower than the values obtain-
production was the competitive result of hydrolysis, fragmen- ed by heterogeneous catalysts (HZSM-5 and NKC-11), and
tation, and repolymerization (Zhou et al. 2010). As the depo- the highest yield of bio-oil was obtained by NKC-11.
lymerization of biomass was much more complex, there was
no proposed reaction mechanism. As N2 gas was the chemi- Differential thermogravimetric analysis of corn straw
cally inert substance which could not be involved in the liq-
uefaction process, it was introduced to this system. The effect In order to obtain the thermal degradation behaviors of corn
of initial pressure on the yields of liquefaction products is straw, the differential thermogravimetric analysis (DTG) was
shown in Fig. 2 b. During this reaction, the reaction tempera- employed. As the high-pressure thermogravimetric analysis
ture was 300 °C, the retention time was 15 min, and the was difficult to executed, this study was carried out in an inert
Environ Sci Pollut Res

60 80
a Syngas Bio-oil Biochar b Syngas Bio-oil Biochar
70
50

60

40
Percentage (%)

50

Percentage (%)
30 40

30
20

20

10
10

0 0
260 280 300 320 0 2 4 6
Temperature (°C) Pressure (MPa)

80 80
c Syngas Bio-oil Biochar d Syngas Bio-oil Biochar
70 70

60 60

50
Percentage (%)

50
Percentage (%)

40 40

30 30

20 20

10 10

0 0
0 5 15 25 35 Water Methanol Methanol Ethyl alcohol Isopropanol
Time (min) & water

80
e Syngas Bio-oil Biochar
70

60
Percentage (%)

50

40

30

20

10

0
Na2CO3 K2CO3 HZSM-5 NKC-11
Fig. 2 Effect of reaction parameters on the yields of products (a liquefaction temperature; b initial pressure; c retention time; d reaction solvent; e
reaction catalyst)

pyrolytic condition under atmospheric pressure to speculate microcrystalline cellulose (Fig. 3a), xylan (Fig. 3b), and alkali
the degradation behaviors of corn straw. The DTG curves lignin (Fig. 3c) started at about 290 °C, 175 °C, and 210 °C,
for the model components and corn straw are shown in Fig. respectively, and the maximum rates of weight loss occurred
3. From the results, it suggested that the degradation of at about 360 °C, 300 °C, and 340 °C, respectively. Moreover,
 Environ Sci Pollut Res

Fig. 3 Differential thermogravimetric analysis results of model components and corn straw (a cellulose; b xylan, c alkali lignin; d corn straw)

the lignin could be degraded over a wide temperature range liquefaction temperature, it indicated that (1) the contents of
(210–850 °C). The degradation of corn straw started at about C element and H element increased with the increased lique-
200 °C, and the maximum rate of weight loss occurred at faction temperature, while the content of O element decreased
about 340 °C, which was a result of the interaction between obviously; (2) the HHVs were in a constant low level; and (3)
the primary components in corn straw. However, the maxi- the viscosity (at 50 °C) decreased with the increased liquefac-
mum rate of weight loss for corn straw was higher than the tion temperature. For the initial pressure, (1) the content of C
experimental results (300 °C). It suggested that the hydrother- element increased from 33.75 to 54.16% with the increased
mal liquefaction under subcritical condition could reduce the initial pressure; (2) the lowest contents of H element and O
degradation temperature of corn straw, due to low dielectric element and the highest HHV were obtained under 4 MPa;
constant, weak hydrogen bond, and high isothermal com- and (3) the viscosity (at 50 °C) decreased with the increased
pressibility (Chan et al., 2014b). initial pressure. For the retention time, the samples with the
highest content of C element and HHV and the lowest content
Physicochemical prosperities of bio-oil of O element were obtained at 15 min; (2) the viscosity (at 50
°C) of this sample was in the low level. For the solvent, the
Table S1 lists the elemental (C/H/N/S/O) component, higher contents of C element and H element in all of the samples
heating value (HHV), moisture content (MC), viscosity, and presented the obvious enhancement, and the sample using a
ash content of the bio-oil sample. From the results, there were mixture of water and methanol as the solvent had the highest
small quantities of N element and S element in all of the bio- contents of C element and H element. For the catalyst, the
oil samples; the moisture contents were in a low level, which contents of C element and H element with homogeneous cat-
may be caused by the extraction treatment of bio-oil; the pH alyst were lower than these with heterogeneous catalyst, and
values of all of the bio-oil samples were acid; the ash contents the contents of O element using catalysts decreased obviously.
in all of the bio-oil samples were low except the samples The ash contents in all of the samples except K and Na was
obtained from homogeneous catalysis. Considering the very low, and the high ash contents in K and Na were caused
Environ Sci Pollut Res

by the homogeneous catalysts in the liquid products. The intensities of –OH stretching vibration, C–O stretching vibra-
moisture contents in the samples without catalyst ranged from tion, C–H bending vibrations, and aromatic compound bend-
2.3 to 4.5, and the moisture contents in the samples with cat- ing vibrations in the sample obtained with NKC-11 catalyst
alyst decreased. Considering the HHV, the samples without enhanced obviously, while the intensities of C=O stretching
catalysts were very low, and the sample using NKC-11 as the vibration and C–C stretching vibration decreased, suggesting
catalyst presented the highest HHV. The samples using the that there were abundant carboxylic acids in the bio-oil sample
alcohols as the solvents released the low pH value. without catalyst and a lot of aromatic compounds in the bio-oil
sample obtained with NKC-11 catalyst. These conclusions
FT-IR analysis were consistent with the physicochemical prosperity analysis.

Figure 4 shows the FT-IR spectra of corn straw, bio-oil sam- GC-MS analysis
ples without catalyst and with NKC-11 catalyst. From the
results, the spectra of bio-oil samples exhibited the peaks dif- In order to obtain more details on the chemical components in
ferent from those of the corn straw sample, which indicated the bio-oil samples, GC-MS analysis was employed and the
that the corn straw could be liquefied in this system, and primary chemical compounds in the bio-oil samples are
chemical transformations occurred during hydrothermal lique- shown in Fig. S1 and listed in Table 1. As shown in the results,
faction, including decarboxylation, dehydration, hydrogena- the primary compounds in the bio-oil sample without catalyst
tion, and deoxygenation (Zheng et al. 2008). For the bio-oil were organic acids, phenol, and alcohols, while the primary
samples (Wang et al. 2012), the broadband range from 3600 to compounds in the bio-oil sample obtained by the NKC-11
3050 cm−1 was attributed to the stretching vibration of –OH in catalyst were phenol and derivatives alkane and furan, and
hydroxyl or carboxyl groups; the bands ranging from 3000 to the concentration of organic acids decreased, which was in
2800 cm−1 were attributed to the stretching vibration of C–H accordance with the FT-IR spectra and physicochemical pros-
in aliphatic series or aromatic ring; the bands near 1711 cm−1 perity analysis.
and 1514 cm−1 were attributed to the stretching vibration of
C=O in carboxyl and ester carbonyl groups; the band near LCA of corn straw liquefaction
1605 cm−1 was attributed to the stretching vibration of C–C
in aliphatic series; the band near 1452 cm−1 was attributed to Life cycle inventory analysis
the scissoring bending vibration of aliphatic CH2; the band
near 1257 cm−1 was attributed to the stretching vibrations of Table 2 lists the life cycle inventory (LCI) data for hydrother-
C–O in alcohols, ether, or phenols; the bands near 1097 cm−1 mal liquefaction of corn straw. Table 3 lists the emissions
and 1016 cm−1 were attributed to the bending vibrations of C– associated with each activity. All of the data in LCI and its
H in aromatic ring; the bands near 796 cm−1 and 694 cm−1 emissions were based on the relevant literatures in the table. In
were attributed to the bending vibrations of aromatic com- this study, carbon dioxide (CO2), carbon monoxide (CO), vol-
pounds. Compared to the bio-oil sample without catalyst, the atile organic compounds (VOCs), nitrogen oxides (N2O,
NOx), sulfur dioxide (SO2), particulate matters, and methane
(CH4) were taken into consideration for the emissions.
Moreover, biochar product accompanied by bio-oil during
the hydrothermal liquefaction of corn straw could be used as
soil amendment, and it could be regarded as the carbon
abatement.
694

Life cycle impact assessment analysis

1514
1452
2982

1605
1711

The emissions during the hydrothermal liquefaction of corn

3304

straw were normalized to environmental impacts based on the

Bio-oil with NKC-1 catalyst Handbook of Life Cycle Assessment. Table S2 lists the con-
1097
1016
1257

796

Bio-oil without catalyst version factors, and Fig. 5 shows the plot of GWP indicating
Corn straw the emission and abatement of CO2, whereas Fig. S2 shows
the plot of other environmental impacts. In addition, GWP
4000 3500 3000 2500 2000 1500 1000 500
was the global warming potential and carbon credit was car-
Wavenumbers (cm )
-1
bon immobilization, as biochar was another by-product ac-
Fig. 4 FT-IR spectra of corn straw, bio-oil sample without catalyst and companied by bio-oil during the liquefaction process, and it
with NKC-11 catalyst could be applied to soil remediation to reduce atmospheric
 Environ Sci Pollut Res

Table 1 Tentative identification

of bio-oil compounds by GC-MS Time Compound
analysis
Bio-oil without catalyst
6.475 Bicyclo[4.2.0]octa-1,3,5-triene
6.947 Ethanol
8.369 Methyl isobutyl ketone
9.344 4-Heptanol
10.465 Benzene
11.363 3-Buten-2-ol
12.229 Phenol
13.999 Phenol
14.45 Butanamide
14.637 Cyclohexasiloxane
14.891 5-Methyl-3-propylhexanoic acid
15.005 Phenol
15.244 Phenol
16.069 1-Butanone
16.276 1,2,3-Trimethoxybenzene
16.333 Eugenol
16.889 3-Isopropoxy-1,1,1,7,7,7-hexamethyl-3,5,5-tris(trimethylsiloxy)tetrasiloxane
17.273 Ethanone
18.269 4-Propyl-1,1′-diphenyl
19.083 (O-Butylphenoxy)acetic acid
21.595 Hexadecanoic acid
22.254 Hexadecanoic acid
22.544 i-Propyl 14-methyl-pentadecanoate
23.271 9-Octadecenoic acid
23.878 E-11-Hexadecenoic acid
24.132 Elaidic acid
Bio-oil with NKC-11 catalyst
6.501 Styrene
6.973 Butanal
9.355 1,3-Dioxolane-2-pentanol
11.124 4(1H)-Pyridone
11.441 2(1H)-Pyridinone
12.24 Phenol
12.312 3-Pyridinol
12.676 Furan
12.764 1,2-Benzenediol
13.059 Benzaldehyde
13.526 1,2-Benzenediol
13.801 1,2-Benzenediol
14.85 1,3-Benzenediol
14.881 Methanone
15.005 Phenol
15.067 1,3-Bis(trimethylsiloxy)benzene
15.41 Phenol
15.503 2-(Cyclohex-1-enyl)-furan
15.566 Ethanone
16.022 9,10-Anthracenedione
16.064 Vinyl benzoate
Environ Sci Pollut Res

Table 1 (continued)
Time Compound

16.126 Benzene
16.276 1,2,4-Trimethoxybenzene
16.339 Phloroglucinol
16.562 Benzene
17.07 Phenol
17.273 Ethanone
17.397 Benzoic acid
18.279 5-Acetamido-4,7-dihydroxybenzofurazan
18.834 Methylphosphonic acid
19.675 Ethanone
22.01 Phthalic acid
22.306 Eicosane
23.245 Heneicosane
24.142 Tetracosane
24.22 1-Heneicosanol
25.824 Eicosane
26.078 Phenol
26.612 Eicosane

greenhouse gas levels; net GWP was obtained from GWP industrial boilers ranged from 75 to 85%, with 80% being
minus carbon credit. selected as the base case. The results of the sensitivity analysis
on different thermal efficiency levels of industrial boilers are
illustrated in Fig. 6 c and d.
Sensitivity analysis

Based on the results of experimental section, the optimal yield Interpretation of LCA results
of bio-oil obtained by the NKC-11 catalyst was about 40.21
wt%, which was selected in LCA study. In order to investigate As far as we know, the syngas had not been widely taken into
the sensitivity, the effect of bio-oil yield change on the envi- consideration for hydrothermal liquefaction of corn straw. As
ronmental impacts had been considered, and 35 wt% was the shown in Fig. 5 a, it was suggested that the emission of CO2
lower bound and 50 wt% was the upper bound (Tables S3 and equivalent for 1 kg of bio-oil was about 1.32 kg throughout
S4). The results of the sensitivity analysis on different bio-oil the liquefaction life cycle when the syngas was not taken into
yields are shown in Fig. 6 a and b. The thermal efficiency of consideration. In this context, the contribution to GWP was

Table 2 LCI of corn straw hydrothermal liquefaction to produce bio-oil

Item Amount Remark Ref

Transportation Corn straw 2.487 kg

Travel distance 89 km
Transportation energy: diesel truck 0.429 MJ 1.94 MJ diesel/ton/km (Joelsson and Gustavsson, 2010)
Pretreatment Milling electricity consumption 0.124 kW h (Iribarren et al., 2012
Pretreated corn straw 2.487 kg
Hydrothermal liquefaction Bio-oil 1 kg
Ash 0.0035 kg
Gas 0.931 kg
Biochar 0.556 kg
Make-up solvent (acetone) 0.01 kg Based on the experimental results (Sangaletti-Gerhard et al., 2014)
Electricity consumption 0.483 kWh Adjusted from reported data (Liu et al. 2013; Chan et al. 2015)

One kilogram of bio-oil was selected as the functional unit

 Environ Sci Pollut Res

Table 3 Environmental emissions of the corn straw hydrothermal liquefaction process

Item Emissions (kg)

CO2 VOC CO NOx PM SO2 CH4 N2O

Transportation energy 0.0364 0.00338 0.00453 0.02538 0.00512 0.00203 0.004 0.0000017
Milling electricity consumption 0.7929927 0.0000014 0.0004049 0.0025053 0.0000048 0.0059976 0.0000013 0.0000007
Biochar − 1.5734 – – − 0.01571 – − 0.002168 – –
Syngas 0.00357 – 0.1544 – – – 0.4682 –
Make-up solvent 0.0484 – 0.00002 0.00002 – 0.00002 – –
Electricity consumption 0.3409868 0.0000006 0.0001741 0.0010773 0.0000021 0.0025789 0.0000006 0.0000003

due to the release of greenhouse gases, and the estimated for photo-oxidant formation were produced without consider-
emission of CO2 contributed 92.42% of the GWP with ing syngas. The emission of NOx contributed to about 52% of
64.88% of emission of CO2 caused by the electricity con- the calculated acidification impact, particularly in the trans-
sumption for pretreatment of corn straw. Moreover, biochar portation stage due to diesel truck. The remaining 48% of
was another by-product accompanied by bio-oil during the acidification was contributed by the emission of SO2, partic-
liquefaction process, and it could be applied to soil remedia- ularly in the biomass pretreatment stage due to electricity con-
tion to reduce atmospheric greenhouse gas levels. In this sumption. In this context, the biomass transportation stage
study, the biochar product was equal to 1.57 kg of CO2 equiv- contributed most to the overall eutrophication impact due to
alent, leading to a net GWP of − 0.25 kg CO2 equivalent for the release of NOx as a result of diesel truck. The release of
1 kg of bio-oil product. However, when the syngas was taken particulate matter (PM) to the atmosphere mostly contributed
into consideration (Fig. 5b), the emission of CO2 equivalent to 83.81% of toxicity impact, and 99.82% of PM was estimat-
increased to 13.03 kg for 1 kg of bio-oil product, which was ed from the biomass transportation stage for diesel truck. For
about 10 times greater than the value shown in Fig. 5 a. In this photo-oxidant formation, it had the weakest impact on the
case, the estimated emission of syngas contributed 89.87% of environment and SO2 emission dominated 90.62% of the
the GWP, in which CH4 in syngas contributed 89.83% of the overall impact in biomass pretreatment stage. When the syn-
GWP, leading to 11.45 kg of CO2 equivalent for 1 kg of bio- gas was taken into consideration, there were no obvious
oil. Hence, the impact of syngas should not be overlooked. changes in acidification, eutrophication, and toxicity except
Although CO and CH4 in syngas made a great contribution to photo-oxidant formation. Considering photo-oxidant forma-
GWP, they could be utilized as the clean fuels as 9510 kJ/kg tion, the value was about 10 times greater than that obtained
for the calorific value of CH4 was greater than 8000 kJ/kg for without considering syngas as 79.80% of the overall impact
that of traditional coal. The emission leading to acidification, was dominated by CH4 emission and 99.15% of CH4 came
eutrophication, toxicity, and photo-oxidant formation was less from syngas.
severe and is shown in Fig. S2. For 1 kg of bio-oil product, As shown in the results of the sensitivity analysis (Fig. 6), the
0.0178 kg of SO2 equivalent for acidification, 0.0343 kg of change in the yield of bio-oil had the high more significant than
PO43− equivalent for eutrophication, 0.0050 kg of 1,4-DCB the change in the thermal efficiency of industrial boilers on the
equivalent for toxicity, and 0.0004 kg of ethylene equivalent environmental impacts. If we did not take syngas into

1.5
14
1.0
12
kg CO2 eq. /kg bio-oil

0.5 10
kg CO2 eq. /kg bio-oil

8
0.0
6
-0.5 4

-1.0 2
0
-1.5
-2
-2.0
a -4 b
Fig. 5 GWP of hydrothermal liquefaction process (a irrespective of syngas, b taking syngas into consideration; black bar, GWP; red bar, carbon credit;
green bar, net GWP)
Environ Sci Pollut Res

Fig. 6 Sensitivity analysis of hydrothermal liquefaction process (a, c irrespective of syngas, b, d taking syngas into consideration; x-axis, the percentage
of sensitivity change)

consideration, the sensitive order was GWP > acidification > syngas were not taken into consideration for the system
photo-oxidant formation > toxicity > eutrophication for the boundary in this LCA study. Besides, as the preparation pro-
change in the yield of bio-oil, and the sensitive order was cess of NKC-11 catalyst purchased from the commercial cor-
GWP > photo-oxidant formation > acidification > toxicity > poration was kept secret, and the environmental impacts in
eutrophication for the change in the thermal efficiency of indus- this process were not taken into consideration. Therefore, the
trial boilers, while if the syngas was taken into consideration, overall life cycle analysis for bio-oil production was beyond
photo-oxidant formation had an obvious increase for the change the scope of this LCA study. The combination of different
in the yield of bio-oil, and there was a decrease in the GWP for industrial assumptions, data sources, and determination of
the change in the thermal efficiency of industrial boilers. system boundaries made the results of this LCA study differ-
ent from the results in the published literatures (Chan et al.
Limitations of this LCA study 2015; Fortier et al. 2014).

As we know, this LCA of corn straw liquefaction for bio-oil

production was conducted based on the conceptual process, Conclusion
because many industrial data were not accurate and deviated
from the actual process, e.g., the electrical consumption at Bio-oil was one of the representative degradation products of
each stage for liquefaction. In addition, the utilizations of biomass due to the high energy density output and more
 Environ Sci Pollut Res

simple transportation and storage. For bio-oil production, the Dunmade I, Madushele N, Adedeji PA, Esther TA (2019) A streamlined
life cycle assessment of a coal-fired power plant: The South African
hydrothermal liquefaction was deemed to the potential meth-
case study. Environ Sci Pollut Res 26: 18484–18492
od. In this study, the effect of the operation parameters on the Fortier MOP, Roberts GW, Staggwilliams SM, Sturm BSM (2014) Life
hydrothermal liquefaction of corn straw using a batch reactor cycle assessment of bio-jet fuel from hydrothermal liquefaction of
had been explored, including liquefaction temperature, initial microalgae. Appl Energ 122(5):73–82
Foulet A, Bouchez T, Quéméner EDL, Giard L, Renvoisé L, Aissani L
pressure, retention time, solvent, and catalyst. Moreover, the
(2018) Life cycle assessment of a bioelectrochemical system as a
life cycle assessment on the hydrothermal liquefaction of corn new technological platform for biosuccinic acid production from
straw for bio-oil production was also executed. The results of waste. Environ Sci Pollut Res 25:36485–36502
the optimum operating parameters and the LCA of hydrother- Guinee JB (2002) Handbook on life cycle assessment operational guide
to the ISO standards. Int J Life Cycle Ass 7(5):311
mal liquefaction of corn straw for bio-oil production were
Huang AN, Hsu CP, Hou BR, Kuo HP (2016) Production and separation
important for the future development of the process into in- of rice husk pyrolysis bio-oils from a fractional distillation column
dustrial scale. connected fluidized bed reactor. Powder Technol 323:588–593
Imman S, Laosiripojana N, Champreda V (2017) Effects of liquid hot
Acknowledgments The authors appreciate and thank the editor and re- water pretreatment on enzymatic hydrolysis and physicochemical
viewers for their very useful suggestions and comments. changes of corncobs. Appl Biochem Biotech 184(2):1–12
Iribarren D, Peters JF, Dufour J (2012) Life cycle assessment of transpor-
tation fuels from biomass pyrolysis. Fuel 97:812–821
Funding information This study was supported by the National Natural
ISO 14041 (n.d.): Environmental management-life cycle assessment-goal
Science Foundation of China (51708301, 21878163); Young Elite
and scope definition-inventory analysis.
Scientists Sponsorship Program by Tianjin (TJSQNTJ-2018-06);
Joelsson JM, Gustavsson L (2010) Reduction of CO2 emission and oil
Natural Science Foundation of Tianjin, China (17JCZDJC39500); and
dependency with biomass-based polygeneration. Biomass Bioenerg
2017 Science and Technology Demonstration Project of Industrial
34(7):967–984
Integration and Development, Tianjin, China (17ZXYENC00100).
Kim SW, Koo BS, Ryu JW, Lee JS, Kim CJ, Lee DH, Kim GR, Choi S
(2013) Bio-oil from the pyrolysis of palm and Jatropha wastes in a
fluidized bed. Fuel Process Technol 108:118–124
Kumar A, Kumar N, Baredar P, Shukla A (2015) A review on biomass
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