Applied Energy 311 (2022) 118685

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

CO2-negative biomass conversion: An economic route with co-production

of green hydrogen and highly porous carbon
Li Liu a, Peng Jiang a, Hongliang Qian b, Liwen Mu a, Xiaohua Lu a, Jiahua Zhu a, *
a
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
b
Department of Pharmaceutical Engineering, China Pharmaceutical University, Nanjing 210009, China

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

• Efficient process converts biomass C&H

elements into H2 and activated carbon.
• Coupled chemical looping and biochar
activation reduces CO2 emission.
• Chemical looping process realizes both
CO2 separation and H2 enrichment.
• CO2 internal utilization realizes AC
valorization and negative CO2 emission.
• Practical techno-economic evaluation
with combined experimental and simu­
lation approach.

A R T I C L E I N F O A B S T R A C T

Keywords: The global consensus of carbon neutralization calls for new ideas of CO2 capture, conversion and utilization,
Biomass especially CO2-negative technologies. In this work, a CO2-negative process was developed to convert three
Chemical looping different types of biomass species into valuable products, green hydrogen and activated carbon (AC). Four re­
Atomic economy
action modules including pyrolysis, activation, flue gas reforming, and chemical looping were integrated and
Process simulation
Techno-economic analysis
balanced in terms of mass and energy. After optimization, green H2 with up to 95.54% purity can be produced
with price as low as $3.10/kg. The solid AC product can fix 10–20 wt% of carbon element from biomass to
achieve a similar proportion of reduced CO2 emission. Part of the separated CO2 can be reused in the activation
process and converted to CO product for internal use. Overall, this process demonstrates an economic route for
biomass conversion with the co-production of green hydrogen and value-added AC products. Moreover, CO2-
negative emission is also realized.

1. Introduction
The impact of global warming on climate change and extreme
weather has aroused great concern worldwide and the responsibility for
our future generation calls for immediate action of carbon neutralization
at all different levels. It is projected that the dominating energy supply
will shift from traditional petroleum/coal resources to electricity from
sustainable sectors such as solar, wind and hydropower [1–4]. Biomass
can be considered a storage media of solar-energy and CO2, and any
technological route starting from biomass have a low-carbon nature,
which is very needed under the global demand of carbon neutralization
[5–8]. Moreover, the huge amount of biomass produced every year and
the advancement of biomass utilization technologies in recent years
enable a great potential of CO2 reduction by biomass technologies.
Biomass can be converted to green energy, sustainable materials and
chemicals via physical, chemical and biological approaches [9–15]. In

* Corresponding author.
E-mail address: jhzhu@njtech.edu.cn (J. Zhu).

https://doi.org/10.1016/j.apenergy.2022.118685
Received 26 October 2021; Received in revised form 8 January 2022; Accepted 6 February 2022
Available online 17 February 2022
0306-2619/© 2022 Elsevier Ltd. All rights reserved.
L. Liu et al.
the past a few decades, even though new technologies have been
developed such as hydrolysis [16], liquefaction [17], direct catalytic
conversion [18], plant-scale biomass utilization facilities are limited to
direct burning [19], pyrolysis [11,20], gasification [21,22] and
fermentation [6,23] with energy as dominating output. Such processes
broke down the large bio-molecules into small molecules with pyrolysis
and gasification technologies and then burn into heat, while the low heat
value of biomass restricts the valorization of bio-energy that makes the
processes not economically competitive. It is well recognized that the
economic feasibility of a biomass conversion process depends on the
efficiency of the entire process and value of the output products.
Therefore, integrating high value-added products into biomass conver­
sion process is critically important to up-shift the value of the entire
process. For example, our earlier work has demonstrated that the inte­
gration of activated carbon (AC) into an bio-energy process shortens
payback period and makes it an economically promising approach for
biomass conversion [24]. Besides, facing to the global demand of carbon
neutralization and CO2 tax being imposed in many countries, processes
which are capable of mitigating CO2 emission are more likely to be
adopted and have great potential to shift the perspective of biomass
industry.
A well-known fact in biomass pyrolysis/gasification is that CO2 is an
inevitable product, and the separation of CO2 is required to upgrade the
flue gas streams. The CO2 separation technologies include solid
adsorption[25,26], liquid amine absorption [27–29], chemical looping
process[30,31], etc. Among them, chemical looping process not only
separates CO2 separation, but also completes other related reactions
such as steam-methane reforming and water–gas shift reaction[32–34].
Combining chemical looping and biomass conversion has been explored
earlier [5,35], while the further utilization of separated CO2 in a biomass
conversion process has rarely been investigated. The integration of
chemical looping and biomass conversion has at least two benefits: one
is to separate CO2 from the product gas stream and internally circulate it
for other processes such as solid carbon activation that consumes CO2;
the other is to enrich H2 in the fluent gas stream by associated chemical
looping reactions.
Targeting the value-added activated carbon (AC) product out of the
entire process seemed an inefficient route in terms of atomic economy
since only partial carbon element was utilized (10–20 wt% of biomass)
while other elemental composition was just wasted. Converting biomass
to H2 has limited technical obstacles, while the economic side is still not
very promising compared to coal, oil and natural gas. United States
Department of Energy (US-DOE) made a strategic plan aiming to lower
the H2 price to less than $4/kg at commercial stage [36]. To reach this
goal, tremendous efforts have been devoted to explore new resources,
new processes, and new products. Especially, value-added products
need to be implemented to change the economic chain of the entire
process. Therefore, co-production of “AC + x” becomes a solution,
where x could be H2, methanol, energy and etc. “AC + H2” has numerous
benefits including but not limited to: firstly, carbon and hydrogen ele­
ments in biomass can be converted to products separately where atomic
efficiency can be greatly improved; secondly, H2 out of biomass is
featured as green H2, its zero-carbon feature is urgently demanded in
industry; thirdly, taking solid AC (carbon) out of the process endows a
negative CO2 cycle.
In this work, a combined process involving pyrolysis, flue gas
reforming, chemical looping, and carbon activation was constructed and
process simulation was carried out with experimental inputs. Three low-
grade biomass species, spent mushroom substrate (SMS), wheat straw
(WS) and bagasse, were selected as raw materials and the process was
optimized to produce green hydrogen and AC. Techno-economic anal­
ysis of processing each biomass species was performed with Aspen
Process Economic Analysis (APEA). To bridge the gap between process
simulation and practical operation, experimental results such as flue gas
components and optimal operational parameters for carbon activation
were used as inputs for process simulation. Overall, this work presented
2
Applied Energy 311 (2022) 118685
a technical and economic view of processing low grade biomass into
green hydrogen and value-added AC products based on a newly devel­
oped process. With a negative CO2 feature, it has the potential to be both
technically and economically competitive under the global climate of
carbon neutralization.
2. Methodology
2.1. Technical and design criteria
A detailed process flow chart for Aspen Plus process simulation was
shown in Fig. 1. The system consisted of five main modules: biomass
drying, pyrolysis, bio-char activation/combustion, flue gas reforming,
and chemical looping. In scenario 1, the biomass was delivered to a
dryer, where the moisture was collected for steam generation and the
dried biomass was sent to the pyrolysis unit. After pyrolysis, the solid
bio-char product was further processed in an activation reactor and the
flue gas was sent to the flue gas reforming unit as reactant. Combining
the flue gas and steam in a mixer, reforming reactions took place where
partial steam was converted to H2. The product gas mixture was further
transported to a chemical looping unit, where CO2 can be effectively
separated, and CO and CH4 react with steam to form H2. Part of the
separated CO2 can be internally consumed by the activation reaction,
generating highly porous AC and CO gas [37]. Looking at the entire
process in terms of mass flow, the inputs were biomass and steam, and
the outputs were AC, H2 and CO2. Since solid AC was taken out of the
entire cycle, the biomass conversion in this design was a negative CO2
process which was analyzed in a separated section of carbon footprint
calculation. Highly porous AC product can be delivered to environ­
mental sector as adsorbent while H2 can be sent to energy sector as clean
fuel.
Scenario 2 was designed for comparison purpose, where the biomass
was converted to hydrogen. In this process, the AC production unit
(activation reactor) was replaced by a combustor. The bio-char was sent
to the combustor for combustion reaction with the aim to recover heat
and produce CO. Based on the Gibbs energy minimization method, the
incomplete combustion reaction was optimized to generate a flue gas
with CO/CO2 ratio of 1.8 which was further send to following modules.
The other modules in scenario 2 was the same as scenario 1, and the final
output product was only hydrogen in scenario 2.
Three representative biomass species, SMS, WS and bagasse, were
used as raw material in this work. For higher reliability of process
simulation, experimental results such as physical property of biomass
and flue gas composition, were tested and used as inputs for Aspen Plus
process simulation and APEA. Following realistic assumptions were
made in this work: (1) biomass was collected within a radius distance of
100 km and the cost of three biomass species was estimated to be $54
per dry ton, here the price of biomass largely depended on the cost of
transportation; (2) the market price of AC with defined quality was
around $1138/ton; (3) assuming the plant ran 300 days per year, the
feeding rate of SMS, WS and bagasse in the process was all assumed to be
6944 kg/h [24]. The physical properties of biomass species such as
proximate analysis, ultimate analysis, and heating value, were measured
and used as inputs for Aspen simulation. The enthalpy of combustion,
heat capacity, enthalpy of formation and enthalpy benchmark of
biomass species were obtained from the HCOALGEN module. The PR-
BM equation of state was used throughout the simulation process.
Since the system included solid, gas and unconventional components,
MIXCINE was selected as the stream type in Aspen Plus global setting.
2.2. Experimental method
The proximate and ultimate properties of three biomass species were
summarized in Table 1. The proximate analysis was based on air dried
basis, and the elemental analysis was based on dry and ash-free basis
[38]. Three biomass species were milled into particles and sifted to take
L. Liu et al. Applied Energy 311 (2022) 118685

Scenario 1

Scenario 2

Fig. 1. Aspen plus flowchart of the designed process (Scenario 1) and biomass to hydrogen process (Scenario 2).

samples within the size range of 75 ~ 150 μm. The elemental compo­
Table 1
sition of biomass was characterized by an elemental analyzer (Vario EL
Proximate and ultimate analysis of three biomass species.
cube by Elementa). In addition, the moisture, fixed carbon, volatile, and
Biomass SMS Bagasse WS ash composition of biomass were analyzed following the standard
a
Proximate analysis (wt%) method of China (GB/T 28731–2012). Heat duty was measured by the
Moisture 12.25 7.48 5.30 heat of combustion using Calorimeter (Parr Instrument Company
Volatile matter 62.33 84.48 80.13
Moline, IL 61,265 USA).
Fixed carbon 30.15 14.63 14.92
Ash 7.52 0.89 4.95 The process can be mainly divided into two routes, namely hydrogen
Elemental analysisb (wt%) route and carbon route. Two routes were integrated with carbon ex­
C 50.87 48.9 43.64 change in the form of flue gas, CO2 and other species. The carbon route
H 4.72 5.78 5.82 targeted for AC production which included three modules such as dry­
N 2.6 0.25 0.68
ing, pyrolysis (carbonization) and activation. Pyrolysis products mainly
S 0.34 0.03 0.82
O 33.95 44.15 44.09 included bio-char and volatile matters. However, the variety of biomass
Heat value (MJ/kg) 20.12 18.56 17.97 species and the inherent complexity of pyrolysis process posed great
a uncertainty to precisely define the volatile components after pyrolysis
dry basis.
b
dry and ash-free basis. [14]. Therefore, the kinetic pyrolysis model in Aspen plus cannot be
simply applied for all types of biomass [39,40]. To overcome this
challenge, pyrolysis experiment on three biomass species was performed

3
L. Liu et al. Applied Energy 311 (2022) 118685

and the gas species were collected and analyzed by gas chromatograph 35
(SP-3420A, BFRL). The pyrolysis experiment was performed in a tube
1000
furnace at 700 ◦ C for 30 mins. Both effluent gas and solid char were 30
collected for analysis, and the reported data in Table 2 took the average
of three duplicate samples. Experimental data in Table 2 was used as 25 800
input for process simulation. In this work, the yield of pyrolysis products

SBET (m2/g)
was used to simulate the pyrolysis process of biomass in a Ryield model. 20

Yield (%)
600
Activation process was completed in RGibbs module. Earlier exper­
imental studies revealed a certain relationship between the yield of AC 15
and its BET surface area (SBET) [37]. Therefore, a suitable yield of AC can 400
be used as a parameter to ensure the quality of AC produced out of the 10
process. In this work, experimental work was also carried out to find the SMS SMS 200
optimized yield for each biomass species, and the results were summa­ 5 WS WS
rized in Fig. 2. Activation experiments were carried out at different Bagasse Bagasse
temperatures ranging from 700 to 950 ◦ C in CO2 environment at a gas 0 0
700 750 800 850 900 950
flow rate of 40 mL/min. As seen in Fig. 2, the maximum SBET of AC
product was obtained at the activation temperature of 900 ◦ C, corre­ Temperature (oC)
sponding to the yield of 20, 15 and 10 wt% for SMS, WS and bagasse,
respectively. Thus, in this work, to ensure the AC products with desired Fig. 2. SBET and yield of AC distribution under different activation tempera­
tures (activation agent: CO2, flow rate: 40 mL/min; duration: 30 min).
quality, i.e. SBET larger than 900 m2/g, the yield of AC prepared by SMS,
WS and bagasse was set at 20, 15 and 10 wt%.
3. Results and discussion
2.3. Carbon footprint calculation rules
3.1. Process optimization and analysis
The carbon footprint analysis of scenario 1 and scenario 2 was car­
ried out and compared in this work with a cradle-to-gate scope. The Bio-char can be activated by H2O and CO2, and the type and amount
carbon emission was mainly composed of three parts: (1) carbon emis­ of activation agents has great influence on the quality of AC [12,43]. To
sions from purchasing, collecting and transporting biomass from farm­ ensure the quality of AC products, it is necessary to calculate the amount
land; (2) carbon emissions from process that involves reaction and of activation agents needed to reach desired yield and then analyze the
separation; (3) carbon emissions equivalent to the energy of producing composition of flue gas sending to the next module. Since H2O and CO2
by-products. The carbon emission of the entire process can be expressed react with bio-char differently, the composition of flue gas changes with
by global warming potential (GWP), which is calculated by equations the input mass flow and composition. Then, design specs in Aspen Plus
(1–4) [41,42]: process simulation were used to calculate the activated agent dosage and
seven groups of activation agents with different H2O/CO2 compositions
∑ were tested (details summarized in Table S1). Based on Gibbs energy
3
GWP = GWPn (1)
n=1 minimization method, the sensitivity analysis in Aspen Plus can be used
to optimize the reforming reaction conditions with the goal of highest
D × TE × TEF hydrogen concentration, i.e. Figure S2. The range of flue gas reforming
GWP1 = (2)
x temperature was set at 300–1000 ◦ C, and the flow rate of reforming
∑ agent was set at 1000–10000 kg/hr. By varying the ratio of CO2 and H2O
GWP2 = Xi × EFi (3) in the activation agents, the demanded quantity of the activation agents,
steam consumption during flue gas reforming as well as reforming re­
i

∑ action temperature were optimized, and the detailed results were sum­
GWP3 = − Ej × EFj (4)
j
where GWP1, GWP2, GWP3 are carbon emissions of part 1, 2, 3,
respectively. D is the distance of biomass transportation, here D = 100
km. TE is the intensity of transportation energy, here TE = 0.02 which is
calculated based on a round trip transportation with a two-ton diesel
truck. TEF is transportation energy factor, TEF = 0.86 kgC/kg taken from
Intergovernmental Panel on Climate Change (IPCC 2013) [41]. x is the
product yield. Xi is the energy consumption during product conversion
in kwh. EFi is the carbon emission factor of electric energy consumption
during biomass conversion that is calculated with raw data from Chinese
Life Cycle Database (CLCD), EFi = 0.36 kg/kwh in this work. Ej is the
equivalent energy for producing by-products, EFj is the carbon emission
factor of coal, EFj = 26.37 kgC/GJ (from IPCC 2013)[41].
marized in Table S1.
Fig. 3 showed the effect of reforming temperature and the amount of
steam usage on the purity of produced H2 with varied composition of
H2O/CO2 activation agents. Using pure CO2 as activation agent pro­
duces H2 at the lowest purity, and the larger proportion of H2O in the gas
flow favored the production of H2 with higher purity. Since both acti­
vation and flue gas reforming produced H2, the related mass and energy
flow needed to be systematically evaluated to optimize the output of H2.
When using CO2 as activation agent, the reforming reaction temperature
can be remained below 700 ◦ C for all three types of biomass species. By
using pure steam as activation agent, higher reforming reaction tem­
perature was often required which meant more energy consumption
[44,45]. More importantly, CO2 activation generated side product CO,
which required extra amount of steam in the following flue gas
reforming step for complete reaction. The flue gas reforming step

Table 2
Composition of effluent gas and char after pyrolysis process in wt%.
Composition CO H2 CO2 H2O N2 CH4 O2 Ash Char

SMS 13.11 0.11 33.99 10.08 1.95 1.61 0.60 7.52 38.55
Bagasse 22.67 3.79 46.51 – 0.01 2.97 – 0.89 24.04
WS 19.85 0.60 46.89 5.55 0.66 0.84 – 4.69 25.61

4
L. Liu et al.
Fig. 3. H2 concentration under the optimized flue gas reforming environment (a) SMS, (b) WS and (c) bagasse.
converted hydrogen element in the steam into H2 and subsequently led
to a maximized production of H2. Certainly, the addition of steam in the
activation step also produced H2, while the energy cost was significantly
higher because the activation temperature of 900 ◦ C was about 200 ◦ C
higher than the reforming reaction temperature. Therefore, considering
the system level optimization, the addition of steam at lower tempera­
ture zone was always favorable for better energy efficiency. Comparing
the total consumption of steam at both activation and flue gas reforming
in Table S1.1–1.3, the selection of CO2 activation agent involved the
largest consumption of steam among the listed seven groups. It can be
concluded that pure CO2 activation agent was favorable to produce
more H2 while CO2 from external sources did not demonstrate an eco­
nomic solution. In this work, the integration of chemical looping and
activation processes provided numerous advantages including but not
limit to: (1) internal circulation and on-site use of CO2; (2) avoidance of
external CO2 supply for activation; (3) output of CO by-product as
feedstock in flue gas reforming; (4) more steam consumption for
hydrogen production.
Following the hydrogen production route, flue gas reforming prod­
ucts were sent to following chemical looping process. Chemical looping
process was mainly designed for CO2 capture, while H2 formation
Fig. 4. The flue gas composition after each main reaction module including pyrolysis, activation, flue gas reforming, and chemical looping for three different biomass
species: (a) SMS, (b) WS and (c) bagasse.
5
Applied Energy 311 (2022) 118685
reactions were also occurred during the process, which positively
contributed to the hydrogen production in the process. Chemical loop­
ing process circulated the calcined limestone (CaO) and CaCO3 between
calcining furnace and carbonizing furnace, which absorbed and released
CO2 via following reaction (5):
CaO(s) + CO2(g) ↔ CaCO3(s)[5] (5)
CaO was used to absorb CO2 by carbonation reaction, this
exothermic reaction released tremendous amout of heat and promoted
the reaction of CO and CH4 as well during CO2 absorption. As a result,
CO and CH4 were converted to CO2 and H2 where CO2 can be in-situ
absorbed and H2 was subsequently enriched upto 95.98% purity in the
output stream.
Flue gas reaction and conversion played a dominating role in the
mass flow of biomass throughout the entire process, and a systematic
analysis of the gas composition was required to optimize the operation
in each reaction module and lead the mass conversion to desired di­
rection. Fig. 4 showed the flue gas composition after each reaction
module including pyrolysis, activation, flue gas reforming, and chemical
looping for the selected biomass species SMS, WS and bagasse. The size
of the pie chart represented the quantity of the flue gas. The pyrolysis
L. Liu et al. Applied Energy 311 (2022) 118685

flue gas was mainly composed of CO2 CO, H2 and CH4. After the acti­
vation reaction (6), a large fraction of bio-char was reacted and con­
verted to CO, and thus a significant increase of CO fraction in the flue gas
was observed after the activation reaction, as seen in Fig. 4.
C + CO2 → 2CO
The structural and compositional uniqueness of each biomass species
excluded a universal process to be applied for all types of biomass spe­
cies. Instead, the process needed to be customized according to the
specific feature of each biomass. For example, to reach the desired
quality of AC products (BET surface area greater than 900 m2/g), the
yield of AC needed to be well tuned typically within the range of 10–20
wt%. In this work, the specific yield of AC for SMS, WS and bagasse was
experimentally optimized to be 20, 15, 10 wt%, respectively. These yield
values were then used as design specs in the activation module. Once the
process for AC production was fixed, more efforts were devoted to the
optimization of H2 production. Taking Flue 1 and Flue 2 as inputs, the
flue gas reforming process enhanced both H2 production and mole
fraction in the output stream. Two main reactions were involved during
flue gas reforming: the steam-methane reaction (7) converted hydrogen
element in both steam and CH4 into H2; the water–gas shift reaction (8)
further extracted H2 from stream by CO.
CH4 + H2O → CO + 3H2
CO + H2O → CO2 + H2
After flue gas reforming reaction, the enriched H2 stream was then
sent to chemical looping process. It is worth mentioning that chemical
looping process not only separates CO2 by the exothermic carbonization
reaction, but also the reforming reactions by utilizing the released heat
from carbonization reaction. After chemical looping process, H2 fraction
was significantly improved to 94.54, 95.98 and 88.17% with SMS, WS
and bagasse resources, respectively. Moreover, part of the separated CO2
can be further used as activation agent for AC activation. Therefore, the
combined chemical looping and AC activation processes not only real­
ized the internal consumption of CO2 but also valorized the “bio-char +
CO2” into “AC + CO”. The taken-out of solid-product AC out of the
carbon cycling loop guaranteed a CO2 negative process, in addition, the
AC products provided critical economic support for the entire system.
3.2. Evaluation of techno-economy
Based on the optimized process above, economic analysis was carried
out considering the equipment, operation and utility costs collected
from APEA. The cost of biomass feedstock was estimated to be $54/ton
based on the transportation cost with a radius distance of 100 km. The
total cost of raw material was the same for each process since each
process was designed and operated to handle the same biomass capacity
of 50,000 ton/year. However, due to the uniqueness of each biomass
species in terms of physical composition and chemical properties, their
material conversion and energy balance throughout the entire process
differed from each other. As a result, the operational parameters,
product yield, energy conversion and the related techno-economy of the
processes were totally different. A detailed list of price assumptions used
(6)
in the economic calculation was provided in Table S2. All the formulas
involved in the H2 cost calculation were provided in the supplementary
material (SM 2 and SM 3).
Table 3 and Fig. 5 compared the techno-economic analysis of two
different processes, scenario 1 and scenario 2: one was biomass to “AC +
H2” with a biochar activation unit (scenario 1), the other was the direct
biomass to H2 (scenario 2). Using H2 production cost as reference, the
techno-economy of the two different processes was compared in Table 3.
It is true that the steam consumption was higher in the “AC + H2” route,
and the related energy consumption was more as revealed in the larger
utility cost. However, the output of valuable AC products can easily
compensate the additional energy and facility cost. More importantly,
H2 production was 14%-39% higher in “AC + H2” route which created
extra revenue for the entire process. As a result, by compensating the H2
cost with AC revenue in “AC + H2” route, the final H2 cost can be
reduced by 36.9%-59.3% depending on the biomass species.
Comparing the two case scenarios, the main difference lied in the
adoption of activation unit in scenario 1. The biomass to H2 route used
(7) oxygen for complete combustion reaction, while the “AC + H2” route
used CO2 separated from upstream chemical looping unit as activation
(8)
agent for high-quality AC production in the activation unit. The added
activation unit raised the equipment cost by approximately 14%, while
such one-time investment had little impact on the TCI of the entire
process. The benefits were obvious of adding activation unit: (1) internal
CO2 consumption that reduced CO2 emission; (2) generation of side
product CO that further reacted with steam in flue gas reforming unit to
produce H2; (3) production of high valuable AC materials that signifi­
cantly improved the techno-economy of the entire process. Not to
mention the carbon tax revenue from reduced CO2 emission, the cost of
CO2 storage can be greatly reduced.
As can be seen in Fig. 5, systematic analysis was performed on each
biomass considering the TCI, H2 cost, amount of CO2 captured, H2
production per unit mass of biomass, and steam consumption. Using H2
cost as a reference, the process techno-economy was evaluated with
three biomass species in two case scenarios. Compared to the biomass to
H2 approach, the advantage of the co-production of “AC + H2” in this
work was the obvious economic benefits after adding the value of AC.
The amount of H2 produced from the “AC + H2” route was 1.14–1.39
times of the H2 from single H2 route. In terms of hydrogen element
utilization, the quantity of H2 produced from “AC + H2” route could be
1.01–1.62 times of the hydrogen content in the biomass (the excess
amount of hydrogen comes from steam). These results indicated that
maximized H2 production and lowest H2 cost can be simultaneously
achieved by taking the “AC + H2” route. Specifically, by compensating

Table 3
Hydrogen cost calculation with two different processing routes.
Biomass → AC + H2 Biomass → H2

Biomass SMS Bagasse WS SMS Bagasse WS

Input
Utilities (USD/hr) 1728.12 1950.42 1475.21 1568.00 1827.89 1401.18
Steam (kg/hr) 3237 2817 2516 2186 1757 2436
Biomass (kg/hr) 6944 6944 6944 6944 6944 6944
Output
AC (ton/day) 33.33 16.67 25.00 – – –
H2 (kmol/day) 6336 6778 4848 4560 5983 3504
Annual operation time (days) 300 300 300 300 300 300
Plant life (years) 15 15 15 15 15 15
Annual discount rate 15% 15% 15% 15% 15% 15%
H2 cost (USD/kmol) 6.24 9.78 8.06 15.38 13.51 18.18
H2 cost (USD/kg) 3.10 4.85 4.00 7.61 6.64 9.00

6
L. Liu et al. Applied Energy 311 (2022) 118685

Fig. 5. A comprehensive evaluation of two biomass conversion routes (biomass to H2 vs. biomass to AC and H2) with three biomass species: (a) SMS, (b) WS and
(c) bagasse.

the H2 price with AC value, the H2 cost produced with SMS can be
reduced from $7.61/kg to $3.10/kg, which accounted for a 59.3% price
reduction. This price is comparable to blue hydrogen according to the
1 1
International Energy Agency (IEA) and it is lower than the DOE target of H2
$4/kg for green H2. 0 0
AC

GWP(kgC/kg AC)

GWP(kgC/kg H2)
H2 H2
AC H2
3.3. Carbon footprint analysis -1 AC -1
H2

Fig. 6 compared the carbon footprint of the biomass conversion

routes with three biomass species. The largest GWP of 1.08 kgC/kg H2 -2 H2 -2
was found in the bagasse to H2 route, which was the only positive GWP
case among the two different routes with three biomass species but still Biomass to AC and H2
-3 -3
less than one-sixth of the carbon emissions from coal to H2 (7.06 kgC/kg
Biomass to H2
H2 according to CLCD). The positive GWP was mainly contributed by the
high energy consumption in the bagasse pyrolysis process (Table S7). -4 -4
All other processes showed negative GWP values as seen in Fig. 6, SMS Bagasee WS
indicating a “CO2 negative emission” process. Moreover, the co-
production of “AC + H2” led to more negative carbon emission Fig. 6. GWP of two biomass conversion routes (biomass to H2 vs. biomass to AC
and H2) with three biomass species.
comparing to the single H2 production process. Whether AC or H2 was
selected as the main product of the process, scenario 1 led to negative
carbon emission with all three different biomass species, which saved at also adds extra economic benefits to the process. Overall, this work
least 0.24 kgC/kg product. The largest carbon mitigation was observed demonstrates an economic and CO2-negative process to convert low-
in WS, where − 2.03 kgC/kg AC and − 3.66 kgC/kg H2 was achieved with grade biomass into green H2 and AC products, which is urgently
process scenario 1. It is obvious that no matter which biomass was demanded in the current climate of global carbon neutralization.
selected as raw resource, the much lower GWP compared to coal or the
majority negative GWP processes demonstrate their great advantages in CRediT authorship contribution statement
addressing global warming. Detailed calculations of the energy con­
sumption and carbon emission in each processing were provided in the Li Liu: Data curation, Writing – original draft. Peng Jiang: Data
supplementary material (SM 4, Table S7 & S8). curation, Investigation. Hongliang Qian: Methodology. Liwen Mu:
Methodology, Validation. Xiaohua Lu: Supervision, Funding acquisi­
4. Conclusions tion. Jiahua Zhu: Conceptualization, Supervision, Funding acquisition.

This work presented a combined experimental and process simula­
tion study on the systematic conversion of low-grade biomass species
into green hydrogen and AC products with a unique CO2-negative pro­
cess. Four reaction modules including pyrolysis, activation, flue gas
reforming, and chemical looping were inter-connected to form a
balanced process. Experimental results were utilized as inputs for pro­
cess simulation. Results indicated that high purity (up to 95.54%) green
H2 can be produced out of the process and H2 cost was reduced to $3.10/
kg after compensating the AC value. The taken-out of solid AC products
from the processing loop guarantees an absolute reduction of CO2
emission, which accounts for a 10–20 wt% of the carbon element in the
biomass. By further circulating the separated CO2 back to the activation
module, internal utilization of CO2 can be realized that produces valu­
able AC product and side-product CO. Comparing to the single H2 route,
co-production of H2 plus AC not only enhances the H2 production, but
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors appreciate the financial support from National Science
Foundation of China (21978128, 91934302), partial support from the
State Key Laboratory of Materials-oriented Chemical Engineering
(ZK202006), Jiangsu Agriculture Science and Technology Innovation
Fund (JASTIF) (CX(18)3039), Postgraduate Research & Practice Inno­
vation Program of Jiangsu Province (KYCX20_1019) are also
acknowledged.

7
L. Liu et al.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apenergy.2022.118685.
References
[1] Olabi AG. 100% sustainable energy. Energy 2014;77:1–5. https://doi.org/
10.1016/j.energy.2014.10.083.
[2] Kabir E, Kumar P, Kumar S, Adelodun AA, Kim KH. Solar energy: potential and
future prospects. Renew Sust Energy Rev 2018;82:894–900. https://doi.org/
10.1016/j.rser.2017.09.094.
[3] Oh KY, Nam W, Ryu MS, Kim JY, Epureanu BI. A review of foundations of offshore
wind energy convertors: current status and future perspectives. Renew Sust Energy
Rev 2018;88:16–36. https://doi.org/10.1016/j.rser.2018.02.005.
[4] Balkhair KS, Rahman KU. Sustainable and economical small-scale and low-head
hydropower generation: a promising alternative potential solution for energy
generation at local and regional scale. Appl Energy 2017;188:378–91. https://doi.
org/10.1016/j.apenergy.2016.12.012.
[5] Zhao X, Zhou H, Sikarwar VS, Zhao M, Park A-H, Fennell PS, et al. Biomass-based
chemical looping technologies: the good, the bad and the future. Energy Environ
Sci 2017;10(9):1885–910. https://doi.org/10.1039/C6EE03718F.
[6] Łukajtis R, Hołowacz I, Kucharska K, Glinka M, Rybarczyk P, Przyjazny A, et al.
Hydrogen production from biomass using dark fermentation. Renew Sust Energy
Rev 2018;91:665–94. https://doi.org/10.1016/j.rser.2018.04.043.
[7] Hu Q, Shen Ye, Chew JW, Ge T, Wang C-H. Chemical looping gasification of
biomass with Fe2O3/CaO as the oxygen carrier for hydrogen-enriched syngas
production. Chem Eng J 2020;379:122346. https://doi.org/10.1016/j.
cej.2019.122346.
[8] Favero A, Daigneault A, Sohngen B. Forests: carbon sequestration, biomass energy,
or both? Sci Adv 2020;6(13). https://doi.org/10.1126/sciadv.aay6792.
[9] Ji T, Chen L, Mu L, Yuan R, Knoblauch M, Bao FS, et al. Green processing of plant
biomass into mesoporous carbon as catalyst support. Chem Eng J 2016;295:301–8.
https://doi.org/10.1016/j.cej.2016.03.033.
[10] Chen L, Ji T, Brisbin L, Zhu J. Hierarchical porous and high surface area tubular
carbon as dye adsorbent and capacitor electrode. ACS Appl Mater Inter 2015;7(22):
12230–7. https://doi.org/10.1021/acsami.5b02697.
[11] Situmorang YA, Zhao Z, An P, Yu T, Rizkiana J, Abudula A, et al. A novel system of
biomass-based hydrogen production by combining steam bio-oil reforming and
chemical looping process. Appl Energy 2020;268:115–22. https://doi.org/
10.1016/j.apenergy.2020.115122.
[12] Wang L, Sun F, Hao F, Qu Z, Gao J, Liu M, et al. A green trace K2CO3 induced
catalytic activation strategy for developing coal-converted activated carbon as
advanced candidate for CO2 adsorption and supercapacitors. Chem Eng J 2020;
383:123205. https://doi.org/10.1016/j.cej.2019.123205.
[13] Xia Q, Chen C, Yao Y, He S, Wang X, Li J, et al. In situ lignin modification toward
photonic wood. Adv Mater 2021;33(8):2001588. https://doi.org/10.1002/
adma.202001588.
[14] Li Y, Xing Bo, Ding Y, Han X, Wang S. A critical review of the production and
advanced utilization of biochar via selective pyrolysis of lignocellulosic biomass.
Bioresour Technol 2020;312:123614. https://doi.org/10.1016/j.
biortech.2020.123614.
[15] Harshvardhan K, Suri M, Goswami A, Goswami T. Biological approach for the
production of vanillin from lignocellulosic biomass (Bambusa tulda). J Cleaner
Prod 2017;149:485–90. https://doi.org/10.1016/j.jclepro.2017.02.125.
[16] Hemalatha M, Sarkar O, Mohan SV. Self-sustainable azolla-biorefinery platform for
valorization of biobased products with circular-cascading design. Chem Eng J
2019;373:1042–53. https://doi.org/10.1016/j.cej.2019.04.013.
[17] Lee J-H, Lee EY. Preparation of biopolyol from empty fruit bunch saccharification
residue using glycerol and PEG#300-mediated liquefaction for application to bio-
polyester and bio-polyurethane production. J Wood Chem Technol 2017;37(4):
283–93. https://doi.org/10.1080/02773813.2017.1297831.
[18] Ren X-Y, Feng X-B, Cao J-P, Tang W, Wang Z-H, Yang Z, et al. Catalytic conversion
of coal and biomass volatiles: a review. Energ Fuel 2020;34(9):10307–63. https://
doi.org/10.1021/acs.energyfuels.0c01432.
[19] He C, Tang C, Li C, Yuan J, Tran K-Q, Bach Q-V, et al. Wet torrefaction of biomass
for high quality solid fuel production: a review. Renew Sust Energy Rev 2018;91:
259–71. https://doi.org/10.1016/j.rser.2018.03.097.
[20] Mohamed BA, Ellis N, Kim CS, Bi X. Microwave-assisted catalytic biomass
pyrolysis: effects of catalyst mixtures. Appl Catal B 2019;253:226–34. https://doi.
org/10.1016/j.apcatb.2019.04.058.
[21] Guo F, Jia X, Liang S, Zhou N, Chen P, Ruan R. Development of biochar-based
nanocatalysts for tar cracking/reforming during biomass pyrolysis and gasification.
Bioresour Technol 2020;298:122263. https://doi.org/10.1016/j.
biortech.2019.122263.
[22] Susastriawan AAP, Saptoadi H, Purnomo. Small-scale downdraft gasifiers for
biomass gasification: a review. Renew Sust Energy Rev 2017;76:989–1003.
https://doi.org/10.1016/j.rser.2017.03.112.
Applied Energy 311 (2022) 118685
[23] Wang P, Chen YM, Wang Y, Lee YY, Zong W, Taylor S, et al. Towards
comprehensive lignocellulosic biomass utilization for bioenergy production:
efficient biobutanol production from acetic acid pretreated switchgrass with
clostridium saccharoperbutylacetonicum N1–4. Appl Energy 2019;236:551–9.
https://doi.org/10.1016/j.apenergy.2018.12.011.
[24] Liu L, Qian H, Mu L, Wu J, Feng X, Lu X, et al. Techno-economic analysis of
biomass processing with dual outputs of energy and activated carbon. Bioresour
Technol 2021;319:124108. https://doi.org/10.1016/j.biortech.2020.124108.
[25] Hu X, Liu L, Luo X, Xiao G, Shiko E, Zhang R, et al. A review of N-functionalized
solid adsorbents for post-combustion CO2 capture. Appl Energy 2020;260:114244.
https://doi.org/10.1016/j.apenergy.2019.114244.
[26] Pardakhti M, Jafari T, Tobin Z, Dutta B, Moharreri E, Shemshaki NS, et al. Trends
in solid adsorbent materials development for CO2 capture. ACS Appl Mater Inter
2019;11(38):34533–59. https://doi.org/10.1021/acsami.9b08487.
[27] Yang J, Yu X, An L, Tu S-T, Yan J. CO2 capture with the absorbent of a mixed ionic
liquid and amine solution considering the effects of SO2 and O2. Appl Energy 2017;
194:9–18. https://doi.org/10.1016/j.apenergy.2017.02.071.
[28] Guo H, Li C, Shi X, Li H, Shen S. Nonaqueous amine-based absorbents for energy
efficient CO2 capture. Appl Energy 2019;239:725–34. https://doi.org/10.1016/j.
apenergy.2019.02.019.
[29] Yang J, Yu X, Yan J, Tu S-T. CO2 capture using amine solution mixed with ionic
liquid. Ind Eng Chem Res 2014;53(7):2790–9. https://doi.org/10.1021/
ie4040658.
[30] Xue N, Wang Z, Wu J, He T, Zhang J, Li J, et al. Effect of equivalence ratio on the
CO selectivity of Fe/Ca-based oxygen carriers in biomass char chemical looping
gasification. Fuel 2019;252:220–7. https://doi.org/10.1016/j.fuel.2019.04.103.
[31] Hossain MM, Lasa HID. Chemical-looping combustion (CLC) for inherent CO2
separations-a review. Chem Eng Sci 2008;63:4433–51. https://doi.org/10.1016/j.
ces.2008.05.028.
[32] Galvita VV, Poelman H, Detavernier C, Marin GB. Catalyst-assisted chemical
looping for CO2 conversion to CO. Appl Catal B 2015;164:184–91. https://doi.org/
10.1016/j.apcatb.2014.09.007.
[33] Haribal VP, Wang X, Dudek R, Paulus C, Turk B, Gupta R, et al. Modified ceria for
“low-temperature” CO2 utilization: a chemical looping route to exploit industrial
waste heat. Adv Energy Mater 2019;9(41):1901963. https://doi.org/10.1002/
aenm.201901963.
[34] Fan L-S, Zeng L, Wang W, Luo S. Chemical looping processes for CO2 capture and
carbonaceous fuel conversion – prospect and opportunity. Energy Environ Sci
2012;5:7254–80. https://doi.org/10.1039/c2ee03198a.
[35] Shen L, Wu J, Xiao J, Song Q, Xiao R. Chemical-looping combustion of biomass in a
10 kWth reactor with iron oxide as an oxygen carrier. Energy Fuel. 2009;23(5):
2498–505. https://doi.org/10.1021/ef900033n.
[36] Rousseau A, Vijayagopal R. Cost benefit analysis of technology improvements in
medium- and heavy-duty fuel cell vehicles 2019; https://www.hydrogen.energy.
gov/pdfs/progress19.
[37] Xiong J, Jiang G, Qian Yu, Mu L, Feng X, Lu X, et al. Cycling pressure-switching
process enriches micropores in activated carbon by accelerating reactive gas
internal diffusion in porous channels. Sustain Mater Technol 2021;28:e00248.
https://doi.org/10.1016/j.susmat.2021.e00248.
[38] Li X, Yang C, Liu M, Bai J, Li W. Influence of different biomass ash additive on
anthracite pyrolysis process and char gasification reactivity. Int J Coal Sci Technol
2020;7(3):464–75. https://doi.org/10.1007/s40789-020-00349-6.
[39] Peters JF, Banks SW, Bridgwater AV, Dufour J. A kinetic reaction model for
biomass pyrolysis processes in Aspen Plus. Appl Energy 2017;188:595–603.
https://doi.org/10.1016/j.apenergy.2016.12.030.
[40] AlNouss A, Parthasarathy P, Shahbaz M, Al-Ansari T, Mackey H, McKay G. Techno-
economic and sensitivity analysis of coconut coir pith-biomass gasification using
ASPEN PLUS. Appl Energy 2020;261:114350. https://doi.org/10.1016/j.
apenergy.2019.114350.
[41] Stocker TF, Qin D, Plattner G-K, Tignor M, Allen SK, et al.Intergovernmental Panel
on Climate Change (2013) Climate change 2013: the physical science basis.
Contribution of working group I to the fifth assessment report of the
iIntergovernmental pPanel on climate change. editors Cambridge, United Kingdom
and New York, NY, USA: Cambridge University Press. Available: http://www.cl
imatechange2013.org/images/uploads/WGI_AR5_SPM_brochure.pdf.
[42] Zhu T, Wang R, Yi N, Niu W, Wang L, Xue Z. CO2 and SO2 emission characteristics
of the whole process industry chain of coal processing and utilization in China. Int
J Coal Sci Technol 2020;7(1):19–25. https://doi.org/10.1007/s40789-020-00297-
1.
[43] Liao M, Kelley S, Yao Y. Generating energy and greenhouse gas inventory data of
activated carbon production using machine learning and kinetic based process
simulation. ACS Sustain Chem Eng 2020;8(2):1252–61. https://doi.org/10.1021/
acssuschemeng.9b0652210.1021/acssuschemeng.9b06522.s00110.1021/
acssuschemeng.9b06522.s002.
[44] Zhang Y, Brown TR, Hu G, Brown RC. Comparative techno-economic analysis of
biohydrogen production via bio-oil gasification and bio-oil reforming. Biomass
Bioenergy 2013;51:99–108. https://doi.org/10.1016/j.biombioe.2013.01.013.
[45] Ahmad AA, Zawawi NA, Kasim FH, Inayat A, Khasri A. Assessing the gasification
performance of biomass: a review on biomass gasification process conditions,
optimization and economic evaluation. Renew Sust Energy Rev 2016;53:1333–47.
https://doi.org/10.1016/j.rser.2015.09.030.