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Energy Procedia 105 (2017) 675 – 680

The 8th International Conference on Applied Energy – ICAE2016

Process and techno-economic analysis of bio-jet fuel-range

hydrocarbon production from lignocellulosic biomass via
aqueous phase deconstruction and catalytic conversion
Yuping Li, Lungang Chen, Xinghua Zhang, Qi Zhang, Tiejun Wang, Songbai
Qiu, Jin Tan, Kai Li, Longlong Ma
Key Laboratory of Renewable Energy, Chinese Academy of Sciences˗Guangzhou Institute of Energy Conversion, Chinese
Academy of Sciences, 510640,Guangzhou , P. R. China

Abstract

The integrated 1000 tonne/a-scale bio-jet fuel-range hydrocarbon (C8-C15) synthesis system via aqueous phase
deconstruction and catalytic conversion process was analyzed for its techno-economics of biomass residue utilization.
The operation characterization, mass flow and cost in the system were discussed. A two-step deconstruction of
corncob, steam stripping and acidic hydrolysis, was designed for the production of the platform chemicals, furfural
and levulinic acid from hemicellulose and cellulose respectively. The oxygenate intermediates with the increased
carbon chain length was produced by alkali catalyzed aldol condensation from furfural and levulinic acid. The
oxygenate intermediates were catalytically converted to jet fuel-range hydrocarbon (C8-C15) by the tandem steps of
low-temperature hydrogenation, high-temperature hydrodeoxygenation and upgrading over noble metal catalysts. The
results indicated that bio-jet fuel yield is 139 kg/h or 8 tonne of dried corncob for 1 tonne fuel production. The
operation cost of bio-jet fuel is about $1540/tonne and the cost on corncob, catalytic catalyst and H2 contributed 23%,
19% and 16% respectively. The cost sensitivity analysis showed that the catalytic lifetime was one of the main factors
that affected the economics of bio-jet fuel production, which could increase bio-jet fuel price to $1820/tonne when its
lifetime was reduced to 0.5 year.
© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
Keywords: techno-economic analysis, bio-jet fuel, aqueous phase deconstruction, biomass, cost

1. Introduction
The annual growing aviation transportation fuel demand and environmental issues have stimulated the
research on renewable fuels as alternatives. Bio-jet fuel production technologies and the flight testing

Corresponding author. Tel.: +86 20 87057790. E-mail address: mall @ms.giec.ac.cn(L.L. Ma),
liyp@ms.giec.ac.cn(Y. Li)

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 8th International Conference on Applied Energy.
doi:10.1016/j.egypro.2017.03.374
676 Yuping Li et al. / Energy Procedia 105 (2017) 675 – 680

using bio-jet fuels have been developed [1, 2]. However the prices of bio-jet fuels are at least two-fold of
traditional fossil fuels. In the same time, the production capacity of bio-jet fuel are quite limited. Thus the
effort on optimize the conversion pathways is still in great urgent to advance and industrialize the bio-jet
fuel technologies [3, 4].
In this paper, the design and techno-economic analysis of 1000 tonne/a bio-jet fuel production plant
was investigated to optimize bio-jet fuel production. The conversion process included aqueous phase
hydrolysis of lignocellulosic biomass and the following catalytic conversion of oxygenate intermediates.
Cost sensitivity analysis was performed by changing the key variables that affect process economy,
including feedstock price, carbohydrate fraction in feedstock, platform chemical yield, H2 price and
methanol consumption ratio.

2. Experimental section
The process design and simulation was performed using ASPEN PLUS software. The feed stock of
lignocellulosic biomass was corncob and its composition was 39.2% cellulose, 36.9% xylan, 16.5% lignin,
3.3% ash, 4.1% of other compounds, on a dry weight basis [5]. The moisture content of the feedstock is
20%. The final products are jet-fuel range hydrocarbons from C8 to C15. The bio-jet fuel production
capacity was1,000 tonnes/year at 300 operating days per year. For the process simulation, the R-Yield
reactor type was used since the more detailed kinetic data was not available. Yields of components are
based on literature data and expert advices [6][7].

Fig.1 Flowsheet of the integrated 1000 tonne/a bio-jet fuel production system from aqueous phase conversion of biomass
The integrated system is made up of four main units: platform chemical production in hydrolyzer, aldol
condensation in batch reactor, hydrogenation in autoclave reactor, HDO and upgrading in fixed-bed
reactor and waste treatment.
Corncob was firstly impregnated by 8.0 wt% of sulfuric acid solution at solid-to liquid ratio of 2.5.
Furfural was steam stripped by saturated steam of 9.88 atm at steam to furfural ratio of 30[6]. The furfural-
water vapor stream was condensed with 95% of furfural recovery. Acidic water was poured to steam-
strippted residue (SSR) to maintain a solid-to-water ratio of ca. 9. H2SO4 concentration was set as 0.24M
for SSR hydrolysis to levulinc acid(LA). LA yield was designed as 34.4% (based on the initial cellulose
content) [7]. After neutralization of hydrolysate solution by lime to pH value of ca.7, double aldol
condensation of furfural and LA for long -chain C15 oxygenates was operated at 50 oC for 1h with 90
 Yuping Li et al. / Energy Procedia 105 (2017) 675 – 680 677

mol% yield to C15 oxygenates (C15H12O5) and 10 mol% yield to C10 oxygenates (C10H10O4 ) by NaOH as
basic catalyst. Then acidification with H2SO4 precipitated the oxygenated solid, which was separated as
bio-jet fuel precursors. Low-temperature pre-hydrogenation (150oC, 4MPa, 33wt% oxygenate in
methanol solution) over Ru/C catalyst and high-temperature HDO (280 oC, 4MPa, LHSV=0.5h-1) and
upgrading ((300 oC, 4MPa, LHSV=1.0h-1) over Ru/Al2O3 was adopted for oxygen removal from the
precursor as described in our previous experiments in batch reactor and fixed-bed reactor respectively.
Three kinds of double bonds (alkene C=C, furan C=C and ketone C=O bonds) in the oxygenate
intermediates of C15 and C10 was saturated and the yield to hydrogenated oxygenates was 72 mol%. C8-C15
yield was set as 72 mol% and 55 wt% during HDO reaction.

3. Results and discussion

3.1 Material and energy balance

Table 1 Material balance

Material flow (kg/h)
Operating units Input (kg/h) Output (kg/h)
Corncob 1389 (20% moisture) Concentrated FFA solution 1103
Furfural Steam 7368 SSR(water contained) 2212
&Concentration Water 409 Waste water 5886
Acid 35.6
SSR(water contained) 2212 Hydrolysate 5446
Steam 1180 Acid hydrolysis Residual 473
Hydrolysis Water 4391 CaSO4(wet) 613
Acid 128 Ash(WET) 337
Lime 156 Waste water 1200
Hydrolysate 5446 Oxygenate precursor 272
Concentrated FFA solution 1103 Waste water 6332
Aldol condensation
NaOH 24.9
Acid 30.5
Oxygenate precursor 272 Gas 140
Hydrogenation H2 24.5 Aqueous phase 552
/HDO/Upgrading Solvent 544 Jet fuel 139
Waste 11
Due to the stoichiometric ratio requirement of 2.0 for double aldol condensation reaction between
furfural and LA, high furfural yield of 59.5% (based on initial corncob hemicellulose content) was
designed by applying high steam ratio of 30 during modelling steam stripping unit, which leaded to 244
kg/h of furfural. However, furfural concentration is low of ca. 3.36 wt% after cooling condensation. This
stream is fed to a distillation tower with 24 plates of theoretical trays to improve furfural concentration to
ca. 20%. Although the amount of waste water from distillation is high, it could be recycled to the system
after treatment.
The usage amount of acid for LA production from SSR is higher than that used in bio-ethanol process,
due to the tandem steps from cellulose to LA, including glucose and 5-hydroxymethyl furfural (HMF) as
intermediates under acidic condition. Acid concentration of 2.4 wt% and hydrolysis temperature of 175
o
C is designed in this context to achieve LA yield of 34.4 wt% (based on cellulose content) or 13.48 wt%
(based on corncob) at water to solid ratio of 9.0[7, 8]. Saturated steam is used to provide heat for hydrolysis
at 175 oC, which became water in the hydrolysate solution. Acid hydrolysis residual (AHR) is separated
from hydrolysate by filtration. 157 kg Lime was used to adjust the pH value of hydrolysate to ca.7 and the
produced CaSO4 is filtered. Hydrolysate of 5446 kg is produced with LA concentration of 2.5 wt%. LA
lost during filtration and pH adjustment treatment is about 9.3 wt%. The concentrated furfural solution
and as-prepared hydrolysate, with the molar ratio of 2.0 for furfural and LA, was used for double aldol
678 Yuping Li et al. / Energy Procedia 105 (2017) 675 – 680

condensation under NaOH catalysed condition for 2h. The yield of oxygenates of bio-jet fuel precursors
is 272 kg, with ca.5% lost during acidification to precipitate solids. The precursors, with molar ratio of
9.0 for C15 oxygenate (F2LA) and C10 oxygenate, is supposed to 100% converted to the corresponding
hydrogenated oxygenates (HF2LA and HFLA) during low temperature hydrogenation. The carbon
selectivity to CO, CO2, CH4, C2-C7 and C8-C15 is designed to be 1.4%, 8.2%, 10.8%, 7.2%, 72%
respectively during high temperature HDO unit, according to the result from our lab experiments.
Oxygenate is further removed after upgrading treatment over the same Ru/Al2O3 catalyst, which
contributes 7.2 wt% lost of HDO products. The final bio-jet fuel yield is 139 kg/h and 0.125 tonne/tonne
dried corncob.
The total energy balance of the process is shown in Table 2. Due to the high ratio of steam usage for
furfural production and its usage for hydrolysis step, it comprises about 40% of total energy input. The
energy from corncob made up 38.9% of the total energy input. Another significant fraction of total energy
input is from furfural concentration, which is approximately 7.8%. It could be deduced that about 86% of
total energy input is consumed for platform chemical production in this process system. Ca. 34.7% of
corncob energy is converted to jet fuel energy, which is increased to 81.8% % when the energy from
AHR and tail gas is accounted. Thermal efficiency of whole energy conversion, including
process/treatment energy input and feedstock energy input, is ca. 31.8% when the tail gas and AHR are
used to generate steam at 85% of energy conversion efficiency. However the value is 13.5% when bio-jet
fuel is the only product as energy output. So it is still necessary to make use of by-products to improve
system efficiency.
Table 2 Energy analysis of corn stover aqueous conversion to jet fuel-range hydrocarbons
Total Energy flow˄ ˄MJ/hr˅ ˅
Input Output
Corncob 17444 AHR 6634
Steam 17692 Gas 1577
H2 2977 Jet fuel 6056
Concentration 3514
HDO 447
Compressor 1815
Filtrationǃbump&others 960
Total 44849 14266
Thermal energy conversion efficiency(%) 31.8

3.2 Economic analysis

3.2.1 Total capital investment

The fixed capital investment and total capital cost is ca. $3.76MM and $3.95 MM, respectively.
3.2.2 Operation costs
Table 3 Variable operation cost
Operation unit Stream Usage(kg/hr) Cost($/tonne) MM$/a
Feedstock Corncob 1111.11 45 0.36
Furfural
H2SO4(93%) 38.23
&Concentration 60 0.02
H2SO4(93%) 137.88 60 0.06
Hydrolysis&pH adjustment
Lime 157 90 0.10
NaOH 24.855 358 0.06
Aldol condensation
H2SO4(93%) 32.8 60 0.01
Hydrogenation MeOH 43.54 343 0.11
 Yuping Li et al. / Energy Procedia 105 (2017) 675 – 680 679

/HDO/Upgrading H2 24.65 1343 0.24

Catalyst-A 0.003059 194030 0.00
HDO catalyst 0.200204 194030 0.28
Catalyst-B 0.008038 223881 0.01
Boiler chemicals 0.066 1194 0.00
Makeup water 3543.601 1 0.01
Steam generation&Utilities
Ash disposal 36.66 45 0.01
Electricity 220kw $ 0.07/kWh
0.12 
Total variable operation costs 1.40

The variable operation cost include feedstock, chemicals for pretreament and hydrolysis, solvent, H2,
catalysts and waste disposal that incurred only when the process is opearating. Raw materials used were
determined using Aspen material balance. The total variable operation costs were $1.40MM. H2 here was
assumed to be purchased at $0.12/Nm3. However H2 demand in the present pathway is substantially
higher than that in hydrogenated ester and fatty acids due to the high oxygen content in the intermediates.
It can be seen that the costs on feedstock, HDO catalyst and H2 were the three main contribution to the
total variable operation costs. In the same time, the cost on H2SO4, Lime and NaOH was also relatively
high, due to the adjustment of pH value of hydrolysate and precipiation of solid intermediate. So the
utilization of solild acidic or alkali catalyst to reduce chemical costs and new thechnologies for platform
chemical production should be investigated for efficient fuel production.
The fixed operation costs is calculated to be $138/tonne bio-jet fuel, including labors used in the plant.
The total operation cost for 1 tonne bio-jet fuel was $1,540 and the operation cost distribution is shown
in Fig.2. the cost on corncob, catalytic catalyst and H2 contributed 23%, 19% and 16% respectively.
Chemicals for furfural and LA production, H2SO4 and lime, contributed ca.12% of $185. Methanl
consuption during HDO was also consideration, which is designed at 8% consumption ratio.

Fig 2 Operation cost distribution for bio-jet fuel production

The results of single-point cost sensitivity analysis of the fatal factor is shown in Fig.3. The base
scenario for the varibles of corncob price, HDO catalyst lifetime, H2 price, hydrolysis acid concentration
and methanol consumption ratio was set as $45/tonne, 1 year, $0.12/Nm3, 2.4 wt% and 7% respectively.
Minima and maxima values for each variable were chosen to quantify the resulting cost impact on overall
operation cost. The catalytic lifetime was the main factor that affected the economics of bio-jet fuel
production, which increased bio-jet fuel prices to $1,820/tonne when catalyst lifetime was reduced to 0.5
year. Corncob price was the second factor that affect bio-jet fuel operaiton cost, which chould reduced
bio-jet fuel price to $1,420/tonne when the price of corncob is decreased to $30.0/tonne.
680 Yuping Li et al. / Energy Procedia 105 (2017) 675 – 680

Fig. 3 Sigle-point cost sensitivity chart for bio-jet production

4. Conclusions
The design and analysis of an integrated 1000 tonne/a-scale bio-jet fuel synthesis system was
investigated, which includes two-step of acidic hydrolysis of corncob to platform chemicals and catalytic
conversion of oxygenated intermediates. The efficient production of platform chemicals (furfural and LA)
and stable catalyst are essential for the system efficiency. The bio-jet fuel yield is 0.125 tonne/tonne
corncob and the whole system thermal efficiency is ca. 31.6% when the energy from process and
chemical energy of corncob is counted together. However the bio-jet fuel operation cost of $1,540/tonne
is still high due to the low bio-jet yield and chemical consumption. Future investigation on solid catalyst
usage for aldol condensation, hydrolysis, and improvement of catalyst lifetime are still urgent for this new
pathway for bio-jet fuel production.
5. Acknowledgment
We acknowledge financial support from the National Natural Research Foundation of China (No.
51276183) and the National Key Basic Research Program 973 Project founded by MOST of China (No.
2012CB215304).
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Biography
Yuping Li, Ph. D, Associate Professor of GIEC, CAS. Research interest: Biomass-based
chemical production and liquid fuel synthesis technologies; Pyrolysis, gasification and
combustion technologies for converting biomass to fuels and power; Bio-oil upgrading and
cellulosic ethanol technologies.