Bio Oil PDF

View Article Online
View Journal
Sustainable
Energy & Fuels
Interdisciplinary research for the development of sustainable energy technologies
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Zheng, Y. Zhu,
M. Zhu, K. Kang and R. Sun, Sustainable Energy Fuels, 2019, DOI: 10.1039/C8SE00553B.
Volume 1 Number 1 2017 Pages 1–100 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
Volume 1 | Number x | 2017
Sustainable accepted for publication.

Energy & Fuels Accepted Manuscripts are published online shortly after
Interdisciplinary research for the development of sustainable energy technologies
rsc.li/sustainable-energy
acceptance, before technical editing, formatting and proof reading.

Sustainable Energy & Fuels
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the

author guidelines.
Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
Pages 0000–0000
in our author and reviewer resource centre, still apply. In no

event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
rsc.li/sustainable-energy
Page 1 of 86 Sustainable Energy & Fuels
View Article Online
A review of gasification of bio-oil for gas production DOI: 10.1039/C8SE00553B
Sustainable Energy & Fuels Accepted Manuscript

Ji-Lu Zheng a, Ya-Hong Zhu a, Ming-Qiang Zhu a, b*, Kang Kang b, Run-Cang Sun c
a College of Forestry, Northwest A&F University, Yangling, Shaanxi 712100, China

Published on 04 March 2019. Downloaded by Drexel University on 3/23/2019 11:28:05 AM.
b College of Mechanical and Electronic Engineering, Northwest A&F University,
Yangling 712100, China.
c Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University,
Beijing, China.
*Corresponding authors. Address: Northwest A&F University, 712100, Yangling,
China. Tel.: +86-029-87092269; Fax: +86-029-87092269.
E-mail address: zmqsx@nwsuaf.edu.cn (M. Q. Zhu).
1
Sustainable Energy & Fuels Page 2 of 86
View Article Online

DOI: 10.1039/C8SE00553B
Abstract
The commercial production of advanced fuels based on bio-oil gasification could

be promising because the cost-effective transport of bio-oil could promote large-scale
implementation of this biomass technology. So far there has no specialized review of
bio-oil gasification processes, including non-catalytic partial oxidation of bio-oil for syngas
production and steam gasification of bio-oil for hydrogen production. A detailed and
comprehensive review of gasification of bio-oil for gas production is presented in this
paper. The background and significance of bio-oil research, the characteristics of
bio-oil suitable for gasification, bio-oil gasification theory, types and configurations
of bio-oil gasifiers, the quality of the product gas, parameter effects, and economic
evaluation of bio-oil gasification are discussed, and finally a summary and future
outlook is also delivered. Particular emphasis is placed to on the discussion regarding
the atomization of bio-oil, entrained flow gasifiers and their advantages, gas
composition and the economic feasibility of production of advanced fuels via bio-oil
gasification. Challenges for the future are identified as (1) make full use of the
experience accumulated in the area of petroleum refining; (2) practical demonstration
of bio-oil gasification on a scale of 500 to 1000 kg bio-oil per hour; (3) the
development of mathematical models for bio-oil gasification systems; and (4)
development of suitable catalysts and profoundly understand the catalysts deactivation
mechanism at different stages for steam gasification of bio-oil.
2
View Article Online

DOI: 10.1039/C8SE00553B
1. Introduction
In the research field of biofuel and biorefinery, when people start talking about

gasification, they often mean gasification of lignocellulosic biomass, which is
considered as one of the promising technologies for production of a producer gas used
as gaseous fuels or chemical feedstock because of its high conversion efficiency and
simplicity.1-6 A noteworthy feature of this thermochemical technology is that it must
be coupled with its utilization, such as combined heat and power generation,
Fischer-Tropsch synthesis for diesel or synthetic natural gas production.7-11 This leads
to the fact that biomass gasification plants are operated at rates equivalent to dozens
of megawatts of power at most because the quantity of biomass is not concentrated at
a site as fossil fuels are, and large-scale implementation of biomass gasification
technologies will seriously aggravate biomass delivery expenses.12, 13 Fuels, including
gaseous and liquid biofuels, are so-called commodity chemicals, where a bigger
production scale is usually better due to economies. Because large fuel plants can
produce a product more economically than small fuel plants due to economies of scale.
Since biomass gasification must be done on a small-scale and a local level to
eliminate the transportation cost, the economic feasibility of this technology
quantified by IRR (Internal rate of return) or NPV (Net present value), could be
constrained. Moreover, oil prices have shown a continued bleakness in recent years
and it is argued that a 25% IRR is necessary for advanced biofuels technology to be
attractive in capital markets, which is an serious challenge to all the conversion routes
from biomass to biofuels, including biomass gasification technologies.14
3
View Article Online

DOI: 10.1039/C8SE00553B
Large-scale implementation of biomass conversion technologies could be
achieved by distributed fast pyrolysis of biomass to bio-oil for subsequent production

of motor fuels or chemicals via bio-oil gasification.15-21 Namely, bio-oil can be
produced economically at small scales matching the size of cost-effective biomass
collection, stored until transport to the nearest harbor, and finally shipped together
with the production of many other pyrolysis plants to a central site for syngas
generation and use, such as the production of synthetic natural gas, diesel fuel,
dimethyl ether, ethanol and higher alcohols. In the above-mentioned overall
conversion chain, which is shown in Fig. 1, fast pyrolysis of biomass to bio-oil is at
early stage of commercialization with companies such as Biomass Technology Group
(BTG) and Ensyn although this technology also is confronted with some fundamental
research challenges.22-28 A 2 tones/hr fast pyrolysis plant has been designed,
constructed and delivered to Malaysia on the basis of BTG's fast pyrolysis technology.
In the factory - located closely to an existing palm oil mill - Empty Fruit Bunches
(EFB) are converted into bio-oil, which was used to replace expensive diesel for
start-up of a fluid bed combustor near Kuala Lumpur International Airport.17 In 2015
Ensyn signed a five year contract (with extension rights) with Youngstown Thermal
LLC for the supply of Ensyn's bio-oil for their district heating operations.
Youngstown Thermal is the owner and operator of the district energy system in
Youngstown, Ohio. Deliveries began in May of 2016. Catalytic conversion of the
syngas to motor fuels, such as Fisher-Tropsch synthesis, is a well-known and highly
practical process. Being petroleum-poor but coal-rich, Germany used the
4
View Article Online
Fischer-Tropsch process during World War II to produce alternativeDOI:fuels.

10.1039/C8SE00553B
Fischer-Tropsch production accounted for an estimated 9% of German war production

of fuels and 25% of the automobile fuel. The largest scale implementation of
Fischer-Tropsch technology are in a series of plants operated by Sasol in South Africa,
a country with large coal reserves, but little oil. The first commercial plant opened in
1952, 40 miles south of Johannesburg. Sasol uses coal and now natural gas as
feedstocks and produces a variety of synthetic petroleum products, including most of
the country's diesel fuel. If the syngas has been produced from bio-oil, the known
technology of the CTL (coal to liquid) and GTL (gas to liquid) plants can be applied
to the syngas to motor-fuels. However, bio-oil gasification is still at the experimental
stage and it hasn't been fully developed. Therefore, the most critical part is bio-oil
gasification for syngas generation in the overall conversion chain.
In comparison with solid biomass gasification, bio-oil gasification is a relatively
new and promising concept of thermochemical conversion technology. Moreover,
compared to catalytic hydrodeoxygenation or catalytic cracking of bio-oil for the
production hydrocarbons, gasification of bio-oil for further conversion to biosynfuels
is also a relatively new route.29-34 Generally speaking, bio-oil gasification processes
can be divided into two categories on the basis of gasifying agents used in these
processes. One can be called as non-catalytic partial oxidation processes, in which
oxygen is used as one of gasifying agents for production of syngas (CO+H2), another
can be named steam reforming or steam gasification processes, in which only steam is
5
View Article Online

DOI: 10.1039/C8SE00553B
used as the gasifying agent to produce hydrogen (H2). The latter is also known as
bio-oil steam reforming, which has been extensively studied under different operating

conditions including temperatures, catalysts and steam carbon ratios and is mainly
intended to convert bio-oil into H2 with a maximum rate. Water contained in bio-oil
can be completely utilized via this route. It is interesting that a delocalized strategy
can also be applied to this route.17, 35 Moreover, there has been recent research in
using two-stage biomass pyrolysis/reforming (catalytic or non-catalytic) processes for
hydrogen production or syngas production.35 This process has several advantages. For
example, this process can produce gas with minimum content of tar; Reaction
temperature optimization can be performed independently in the pyrolysis and
reforming steps, respectively; Catalyst deactivation by fouling or sintering can be
avoided; Volatiles from fast pyrolysis of biomass can be directly and high efficiently
utilized inline, and so on. Overall, although it is related to biomass fast pyrolysis, this
route is essentially a solid biomass gasification process and can be fit for a localized
strategy. Since bio-oil gasification is a relatively novelty and important technology for
biofuel production, a detailed overview, analysis and evaluation of bio-oil gasification
is necessary. In this paper, Bio-oil gasification theory, bio-oil gasifiers, the effects of
several process parameters on the quality and composition of the producer gas, the
advantages of bio-oil gasification, and the economic feasibility of biosynfuel
production via bio-oil gasification are presented and discussed.
2. What kinds of bio-oil is suitable for gasification
6
View Article Online

DOI: 10.1039/C8SE00553B
As a liquid product, bio-oil is totally different from solid biomass.29, 36-40 The
properties of bio-oil depends on their biomass precursors, such as wood or agricultural

residues, and the operating conditions, such as temperature or biomass particle size
and pyrolysis rate, including fast pyrolysis or slow pyrolysis. The properties of some
bio-oils obtained from different feedstocks under fast pyrolysis or slow pyrolysis
conditions are listed in Table 1.17, 36, 41-50
Fast pyrolysis bio-oils are suitable for the non-catalytic partial oxidation
processes because they are not readily prone to phase separation and have lower
viscosities. It is much more beneficial if these bio-oils can be produced with higher
heating values. In fact, Fast pyrolysis bio-oils are normally single-phase chemical
solution, in which water is an integral part, and has satisfactory heating value and
relatively low viscosity.17, 36 However, slow pyrolysis bio-oils could be readily prone
to phase separation, and often contains a viscous organic phase (like wood tar) and a
aqueous phase (like wood vinegar). Therefore, slow pyrolysis bio-oils are not suitable
for the non-catalytic partial oxidation processes, but can be applied to bio-oil steam
reforming processes.51-54 Of course, fast pyrolysis bio-oils can also be utilized in these
reforming processes, but phase separation of them are not easy in comparison with the
slow pyrolysis bio-oils. This separation can be performed by addition of water or by
molecular distillation.55, 56 However, an important criterion in this strategy of bio-oil
reforming is the efficiency in bio-oil production. In this sense, biomass fast pyrolysis
allows for higher bio-oil yields and has better perspectives for full scale development
7
View Article Online

DOI: 10.1039/C8SE00553B
than slow pyrolysis. Therefore, fast pyrolysis is more appropriate for bio-oil steam
reforming. The organic phase of slow pyrolysis bio-oils is normally too viscous to be

atomized to use in these non-catalytic partial oxidation processes, and it could also
lead to ../Downloads/A review of gasification of bio-oil for gas production.doc -
_ENREF_17#_ENREF_17catalyst deactivation due to pore blocking during catalytic

steam gasification processes. But it is fairly fit for production of commodity
chemicals and fine chemicals, such as acetic acid, adhesives, and pharmaceuticals.33
Finally, all the bio-oils used for gasification should be filtered to remove char
particles.
3. Bio-oil gasification theory
3.1 Bio-oil atomization
As solid biomass needs to be chopped and ground from hundreds of millimeters
to dozens of millimeters or several millimeters diameter prior to feeding into a
biomass gasifier such as an entrained flow gasifier or a fluidized bed gasifier, an
atomization process, by which bio-oil is split up into a large number of fine droplets,
is usually necessary before gasification. Atomizers are a very key factor in the
atomization process. The most common atomizers used for atomization of liquid fuels
include steam or air-blast atomizers, pressure swirl atomizers and rotating cup
atomizers. Air-blast atomizers, some of which are shown in Fig. 2, are usually suitable
for light fuel oils. By coincidence, it was found that bio-oil's combustion
characteristics are fairly similar to light fuel oil even if significant differences in
8
View Article Online

DOI: 10.1039/C8SE00553B
viscosity, pH, stability, ignition, heating value and emission levels have been
observed.17, 57-64 A typical bio-oil droplet diameter distribution which is produced by

an internal mixed air-blast atomizer nozzle is shown in Fig. 3(a), it is clear that the
bio-oil droplet size basically varies between 10 and 80 μm.65 Bio-oil droplet formation
is also related to its physical properties, such as viscosity and surface tension, and
temperature.65 The viscosity is peculiarly important for bio-oil atomization. The
viscosity for bio-oil atomization should normally be in the range of 5-30 cP (mPa.s).17,
57 Fig. 3(b) shows temperature effects on the viscosity of bio-oil and two fuel oils
(light fuel oil for heating and heavy fuel oil 180 cSt). It could be inferred from Fig.
3(b) that bio-oil should be preheated before it is fed into atomizers so as to reduce its
viscosity and surface tension and bio-oil could be more easily atomized than heavy
fuel oils. However, the atomizers used in bio-oil gasification processes should be
water-cooled or air-cooled to prevent any coking of the bio-oil in the atomizer nozzles.
Water is an integral part of bio-oil, which is a single-phase chemical solution, and has
important impacts in bio-oil atomization and gasification. The typical water content of
bio-oil ranges from 15-30wt.%.17, 57 Water can cause a decrease in viscosity of the
bio-oil and facilitate bio-oil atomization, as shown in Fig. 3(c). However, if the water
content of bio-oil exceeds 30wt.%, phase separation (oil phase and aqueous phase)
can occur. Phased separated bio-oil inevitably led to poor atomization. Moreover,
every kilogram of water in the bio-oil consumes at least 2.26MJ extra energy from
bio-oil gasifiers for vaporization of the water, and the energy is usually not
recoverable. In consideration of the substantial reduction in energy use in the bio-oil
9
View Article Online

DOI: 10.1039/C8SE00553B
gasifiers and improvement of bio-oil atomization, bio-oil with a water content of
20-25wt.% could be desirable. Finally, bio-oil droplets are easy to aggregate under

cold conditions because of surface tension but they tend to break into smaller droplets
in hot conditions.57, 66 In order to improve the atomization, a high temperature gasifier
favors formation of the finer bio-oil droplet.

3.2 Non-catalytic partial oxidation of bio-oil
3.2.1 Gasification stage
During gasification step, bio-oil droplets undergo four key stages, including
drying (i.e., the evaporation of water and light volatiles), pyrolysis (i.e., the thermal
cracking of unstable components), oxidation (i.e. CH4 + 2O2 → CO2 + 2H2O, H2 +
0.5O2 → H2O) and reduction (i.e. CnHmOk + (n - k) H2O → nCO + (n + m/2 - k) H2,
CO + H2O ↔ CO2 + H2). During these processes, the phenomenon of distortion
welling and micro-explosion will occur simultaneously. These peculiar behaviors help
to eliminate mass transfer restrictions and intensify gasification reactions during this
phase.67 To sum up, because bio-oil droplets have much smaller size than solid
biomass particles, bio-oil can be more easily gasified.
With very high heating rate and small size of the bio-oil droplets, all of the four
steps could occur simultaneously. Therefore, it is worthwhile noting that there is no
sharp boundary between the four key steps, which often overlap. In drying phase, the
loosely bound water in bio-oil starts bubbling and is irreversibly removed so the
10
View Article Online
bio-oil become more viscous above 100℃. Light volatiles starts volatilizingDOI:as10.1039/C8SE00553B
the
temperature rises. When the temperature exceeds 200℃, the bio-oil droplets undergo

swelling, shrinking, distortion and microexplosions, which results in the ejection of
mass from the bio-oil droplets. This phase continues till the temperature reaches
350-450℃. In the pyrolysis phase, thermal cracking of unstable components in the

bio-oil droplets occurs. Since the size of the bio-oil droplets is fairly fine, the
pyrolysis of the unstable components is a fast pyrolysis process with no major
chemical reactions with any gasifying agents. Two undesirable products during the
pyrolysis phase are soot and tar, respectively. The formation of soot will lead to a
decrease of cold gas efficiency and CCE in bio-oil gasification processes. Chhiti et al.
proposed a model to describe soot formation during bio-oil gasification (C2H2 → 2C
(soot) + H2, Soot formation).68 The soot is a mass of impure carbon particles and
sometimes referred to as cokes or char. The char or soot could be the results of some
form of pyrolysis because of lack of oxygen. In fact, bio-oil droplets undergo a
pyrolysis stage during gasification steps. Soot or char will be inevitably produced
during this route because of lack of oxygen. In comparison with combustion, soot or
char can also be more or less formed during combustion of all kind of fuels even
when oxygen is adequately supplied. Their study shows that soot yield has a strong
increase in the temperature range of 1000-1200℃, but the soot yield strongly
decreases above 1200℃ because of carbon dioxide and steam gasification of soot;
soot formation can occur under fuel-rich conditions and an increase of oxygen amount
can remarkably reduce the soot yield. Luckily, the soot normally makes 1-2wt.% on
11
View Article Online

DOI: 10.1039/C8SE00553B
the basis of bio-oil feed flow. Tar is a sticky liquid and creates a substantial amount of
difficulty in the industrial use of the product gas. Fortunately, tar amount in the

product gas derived from bio-oil gasification processes is fairly low. The phase which
follows the pyrolysis phase involves chemical reactions, including oxidation and
reduction reactions among the organic compounds in bio-oil, oxygen, char (viz. soot),
steam and evolved gases.
3.2.2 Gasification reactions
Table 2 lists important oxidation and reduction reactions take place in the
non-catalytic partial oxidation processes. Of these, the char reactions are very
important. The rate of the char reactions depends mainly on the reaction reactivity of
gasifying agents, such as oxygen, steam, carbon dioxide and hydrogen. The rates of
the char-oxygen reactions (R4 and R5) are the highest; the rate of the char-steam
reaction (R2) is 3 to 5 times lower in order than that of the char-oxygen reactions. The
Boudouard reaction (R1) is the 6 to 7 times lower in order. The rate of the water gas
reaction (R2) is 2 to 5 times higher than that of the Boudouard reaction. The
char-hydrogen reaction (R3) is the slowest of all. The relative rates of the four
reactions were estimated at 10000 for oxygen, 1000 for steam, 10 for carbon dioxide
and 0.003 for hydrogen at 10 Kpa pressure and 800 ℃ temperature by Walker et al.69
When char touches oxygen, the char-oxygen reactions (R4 and R5) can take
place. However, their reaction extents depend on temperature. If both R4 and R5 are
12
View Article Online

DOI: 10.1039/C8SE00553B
combined and written as "βC+O2 → 2(β-1)CO + (2-β)CO2", β, a partition coefficient,
can be defined to determine how O2 is partitioned between the two reactions. A

commonly used expression for β is "β=2400*exp(-6234/T)", where T is the kelvin
temperature of the char surface.70 Blasi proposed a reaction mechanism describing the
Boudouard reaction (R1) and found that below 1000K the rate of the reaction is
insignificant.71, 72 Blasi and Barrioand also revealed that the accumulation of H2 could
lead to a strong inhibiting effect on the water gas reaction (R2).71, 73 So continuous
removal of H2 from gasifiers could be an effective way to accelerating the reaction
(R2). The char-hydrogen reaction (R3) results in the production of CH4. Generally
speaking, CH4 is an undesirable constituent of the syngas for advanced liquid fuel
production, and it is important only for the production of synthetic natural gas (SNG).
Fortunately, the rate of this reaction (R3) is much lower than that of the other
reactions, and in entrained flow gasification processes, the gasification temperature is
usually sufficiently high to produce a low-methane syngas. R12 denotes those non
catalytic reforming reactions between the organic molecules which are present in
bio-oil and steam. Oxygenated organic molecules present in bio-oil are more reactive
than hydrocarbons present in bio-oil because the oxygenated organic molecules have
some carbon-oxygen bonds. R12 plays a very important role in hydrogen production
during bio-oil gasification processes. The reaction pathways which occurred in the
non catalytic reforming process were very complex and have still not been studied.
3.3 Steam reforming of bio-oil
13
View Article Online

DOI: 10.1039/C8SE00553B
3.3.1 Reforming stage
Steam gasification of bio-oil for production of hydrogen is a complex process, in

which catalysts are normally used. This process mainly includes reforming reactions,
cracking reactions and water-gas shift reactions. Firstly, bio-oil, whose formula is
designated as CnHmOk·xH2O, reacts with water and CO and H2 are produced via the
following reforming reactions.74-76
CnHmOk·xH2O + (n - k-x) H2O ↔ nCO + (n + m/2 - k) H2 (R13)
Secondly, CO is converted into CO2 and H2 via the water-gas reaction.
nCO + nH2O(g) ↔ nCO2 + nH2 (R14)
The above-mentioned two reactions can be amalgamated into an overall reaction.
CnHmOk·xH2O + (2n-k-x)H2O ↔ nCO2 + (2n + m/2 - k)H2 (R15)
Since this process is operated under high temperature, thermal cracking reactions
and catalytic cracking reaction also occur, which leads to the production of fragment
molecules, gas, and coke, which is expressed as the following reaction.
CnHmOk → CxHyOz + (H2, CO, CO2, CH4, …) +coke (R16)
Moreover, the disproportionation reaction of CO may also occur in this process.
2CO→CO2+C (R17)
Except for hydrogen, CO2 and CO, a small amount of CH4 and C2H4 are also
produced in this processes. There is two main pathways to production of CH4. One is
thermal cracking of oxygenated organics in bio-oil; another is the methanation
reactions of CO2 and CO. C2H4 could be derived from the decomposition of alcohols
in bio-oil. For example C2H4 and water can be produced via the decomposition of
14
View Article Online

DOI: 10.1039/C8SE00553B
ethanol.

3.3.2 The mechanism for steam reforming of representative compounds in bio-oil
Different compounds, such as acids, alcohols, phenols and their derivatives, have
been recognized in bio-oil. It is critical to understand the mechanism of steam

reforming of some representative compounds in bio-oil, which are also called as
bio-oil model compounds. Small molecules in bio-oil normally contain carbon,
hydrogen and oxygen, and these atoms are bonded by C-C, C-H, C-O, C=O or O-H
bond. These small molecules could have similar behavior as those typical compounds
during the steam reforming process. Therefore, the investigation in the mechanism of
steam reforming of the typical compounds could have much significance to the
exploration of the mechanism of steam reforming of bio-oil.
The reaction pathways that occurred in the catalytic steam reforming of acetic
acid, which is one of the major components in aqueous fractions of bio-oil, were fairly
complicated and many intermediate or potential products may form, depending on the
catalysts used and the reforming conditions. The first column of Table 3 presents
some major reactions in this reforming process.77-79 On the basis of these reactions, in
order for the increase of selectivity toward hydrogen production, the CH4 level must
be lowered. This reason is that CH4 is rich in the element hydrogen, which is
unfavorable for hydrogen production. Therefore, for the catalytic steam reforming of
acetic acid, it is important to select a high activity catalyst for CH4 reforming.
15
View Article Online

DOI: 10.1039/C8SE00553B
The mechanism for steam reforming of ethanol includes two main pathways.80-82

The first pathway is the dehydrogenation of ethanol, namely the dehydrogenation of
ethanol results in the production of acetaldehyde and hydrogen. And then the
acetaldehyde is cracked and CH4 and CO are produced. Finally, CO and hydrogen are
produced via the reforming of CH4. The second pathway is the dehydration of ethanol.
The dehydration of ethanol leads to the production of ethylene; the ethylene is
decomposed to produce hydrogen and coke, or hydrogen and CO are produced via
reforming of the ethylene; CO is converted into CO2 and hydrogen via the water-gas
reaction. The two pathways are shown in the second column of Table 3. On the basis
of thermodynamic analysis of the two pathways, it can be concluded that higher
temperatures, lower pressures and higher water to carbon feed ratios could increase
the hydrogen production.83
The mechanism of hydrogen production during steam reforming of phenol over
Rh and Fe catalysts supported on metal oxides have been examined.84-86 Firstly, steam
dissociatively adsorbs on the metal oxide surfaces. Secondly, OH and H species spill
over to the Rh surface. Thirdly, phenol decomposition on the Rh metal surface occurs
and the adsorbed intermediate OH and CHx species are produced. Finally, the
desorption of H, O and (CO) from the Rh surface occur and hydrogen and CO2 are
produced. The detailed mechanism is listed in the third column of Table 3. The
mechanism study shows that supported-metal catalysts with support which possesses
16
View Article Online

DOI: 10.1039/C8SE00553B
a large number of oxygen vacancies are expected to be significantly in favor of the
phenol steam reforming reaction.

4. Bio-oil gasifiers
4.1 Entrained flow gasifiers and the advantages

For the non-catalytic partial oxidation of bio-oil, pressurized entrained flow
gasifiers are the most suitable gasifiers.67, 87-89 Fig. 4(a) and (b) show two typical
entrained flow gasifiers equipped with direct quench cooling chambers and indirect
syngas coolers, respectively. The two gasifiers themselves are both vertically placed
cylindrical and refractory lined vessel. Bio-oil and gasifying agents, such as air,
oxygen, or steam, are fed together into a downward burner on the top of the vessels.
In the direct quench mode, the hot product gases leave the bottom of the vessel
(quench chamber) via a dip-tube. The quenched product gases are saturated with
water, which makes the product gases suitable for the water-gas shift reaction for
hydrogen-riched gas production. The bulk of soot and ash in the product gases can
also be removed by the quench, which helps to ease subsequent treatment in
downstream separation units. In the indirect cooler mode, the hot product gases are
cooled by the indirect cooler and meanwhile high pressure steam is generated. The
mode is suitable for the applications where a high carbon monoxide level is required.
Obviously, this mode also increase the burden of subsequent treatment in downstream
separation units compared to the direct quench mode. Geometrically the two gasifiers
are called so-called top-fed gasifiers and used top-fired reactor design. There are also
17
View Article Online

DOI: 10.1039/C8SE00553B
side-fed entrained flow gasifiers, of which feed and gasifying agents are injected into
the side-mounted horizontal burner and product gases leave from the top. Side-fed

entrained flow gasifiers are commonly used for coal gasification.12, 90, 91
Entrained flow gasifiers are easy to scale-up and have high conversion
efficiencies. Moreover they produce good-quality syngas, with low concentrations of
tar methane, due to the high temperatures applied (1200 to 1500°C, depending on
whether air or oxygen is used). Entrained flow gasifiers are quite common in large
scale oil gasification plants. Although entrained flow gasifiers have also been applied
for pulverized coal gasification and black liquor gasification, they have rarely been
considered for solid biomass gasification.92 For the following reasons, entrained flow
gasifiers are not preferred for solid biomass gasification. Firstly, because of short
residence time (a few seconds) in entrained flow gasifiers, carbonaceous materials fed
into them needs to be very fine. But pre-treatment of solid biomass to a dry pulverized
feed stock (<20 μm) is quite expensive and it cannot be crushed like coal; secondly,
feeding fine, fluffy, and low density biomass into a pressurized gasifiers is difficult
and expensive; Finally, the melting point of biomass ash is usually under high
temperature in entrained flow gasifiers, which leads to melting the ash to form a slag,
and molten biomass ash is highly aggressive, which greatly shortens the life of the
gasifier's refractory lining. One example of entrained-flow gasification of biomass is
the Chroren process.93, 94 However, it is char not solid biomass that is injected
downward into an entrained flow gasifier in this process. The other examples include
18
View Article Online
gasification of sawdust, grapevine pruning wastes, coconut coir dust, and riceDOI:
husk10.1039/C8SE00553B
in
an entrained flow gasifier for reduction of tar generated during biomass gasification,

but the entrained flow gasifiers were operated at atmospheric pressure.95-97 To sum up,
due to simplification of the feeding technology, improved gasification efficiency,
cheaper gasification equipment, less expensive gas cleaning, etc., utilization of

entrained flow gasifiers for bio-oil gasification is attractive.
4.2 Commercial-scale entrained flow processes
At present, three major entrained flow processes are commercially available,
developed by Texaco (The GEE gasification process), Shell (The SGP gasification
process) and Lurgi (The MPG gasification process).The key features of all the three
processes are similar. A top-fired gasifier design with a downward burner and a
refractory lined vessel is used. Operation temperatures are similar (in the range
1250-1450℃). When processing liquid feed ， all three processes produce a small
amount of residual carbon and which need to be removed from the syngas.
Differences between them are in inlet nozzles of the gasifiers, in syngas cooling
configurations and in syngas scrubber system. The Texaco nozzle followed a
water-cooled design, where oil and steam are fed together through an annular slit
surrounding a central oxygen pipe. The steam is used to atomize the oil, and mixing is
ensured by imparting counter-rotating vortex motion to the two streams. Two
different syngas cooling options, which are separately characterized by direct
quenching with water and using a syngas cooler to generate steam, are offered by the
19
View Article Online

DOI: 10.1039/C8SE00553B
GEE process. In the direct quench mode, the gas leaving the quench vessel is
scrubbed in a venturi scrubber and then in a packed column. The Shell nozzle is

specially designed so that the mixture of steam and oxidant can be intimately mixed
with fuel oil. It is a co-annular design using blast atomizing and can handle fuel oil of
up to 300cSt. A syngas cooler and a boiler are used to cool raw gas and for primary
and secondary heat recovery in the SGP process, respectively. The soot and ash are
removed from the gas in a two stage water wash. The Lurgi nozzle is a
multiple-nozzle design and can accept separate feed streams of otherwise
incompatible materials. The MPG process offers two alternative syngas cooling
configurations, which are a combination of a quench vessel and a cooler. In the first
configuration, gas is quenched by a quench vessel firstly, then, is washed by a venturi
scrubber, and is finally cooled by two syngas coolers. In the second configuration, gas
is cooled by a syngas cooler at first, then is quenched by a wash quench vessel, is
filtered by a soot separator and is scrubbed by a packed column finally.
Although there is no commercialization of bio-oil gasification via entrained flow
processes, commercial units or demonstration plants of bio-oil gasification via
entrained flow processes could be technically feasible. Besides bench-scale
experimental results from bio-oil gasification in an entrained flow gasifier,
commercialization of black liquor gasification via entrained flow processes can also
offer some support for this view. After all, the density, viscosity, heating value, and
elemental composition of bio-oil are fairly similar to those of the black liquor.
20
View Article Online

DOI: 10.1039/C8SE00553B
4.3 The gasifiers for bio-oil steam reforming

Fluidized bed reactors and fixed bed reactors have also been used as bio-oil
gasifiers for bio-oil steam reforming. Czernik and Wang investigated hydrogen
production by catalytic steam reforming of bio-oil in a bench-scale bubbling

fluidized-bed reactor.98-100 In this process, superheated steam was used as a fluidizing
gas and nitrogen as atomization gas. A horizontal water-cooled nozzle was used to
spray bio-oil into the reactor. A commercial nickel based naphtha reforming catalyst
was used as the bed material. Latifi et al. performed extensive researches of thermal
and catalytic gasification of bio-oils in fluidized bed reactors for syngas production,
and Wu et al. developed a CFD model for bio-oil steam gasification in a fluidized bed
reactor.101-105 Either steam or nitrogen was preheated and then used as fluidization and
atomization medium, but atomization nitrogen was not preheated. Bio-oil and
gasifying agents (steam or nitrogen) were injected into a side-mounted and horizontal
spray nozzle which was 0.18m above the wind-distribution plate. Fluidizing steam or
nitrogen passed through the plate to fluidize and heat bed material, which was silica
sand or catalyst particle. The fluidized bed can provide fairly good contact of bio-oil
droplets with hot solid particles to achieve high heat and mass transfer rates. When the
silica sand was used as the bed material, the gasification process was driven mainly by
thermal cracking of the bio-oil and non catalytic steam reforming of the bio-oil. When
the catalyst particle was used as the bed material, the gasification process was driven
mainly by catalytic cracking of the bio-oil and catalytic steam reforming of the bio-oil.
21
View Article Online
However, these researches were totally done on a commercial scale, and upDOI:
to 10.1039/C8SE00553B
now
the commercial application of fluidized bed reactors for oil gasification for gas

production has not yet been found except for so-called fluidized bed hydrogenation
processes. This may be caused by the fact that fluidized bed reactors are noted for
their excellent gas-solid mixing so as to peculiarly advantageous for gas-solid

reactions. Moreover, for a down-flow fluidized bed reactor, in the middle of which
quartz chips were placed to get enough good flow and temperature distribution, had
ever been used for thermal cracking of bio-oil for syngas or high-BTU fuel gas.
Nitrogen was used to carry bio-oil into the reactor, and an electric heater was
maintained around the reactor.106 Fixed bed reactors were also used for hydrogen
production via catalytic steam gasification or reforming of bio-oil. The reactors were
normally made of quartz or stainless steel, and housed in a resistive heater or a tubular
furnace, and were packed with catalyst. There are three modes of the introduction of
bio-oil and steam into the fixed bed reactors: bio-oil was atomized using N2 and
mixed with superheated steam in a top-fed nozzle;107 bio-oil and liquid water were
introduced into a fixed bed reactor drop by drop via a peristaltic pump;108 bio-oil was
fed into a fixed bed reactor using a syringe pump and steam was also simultaneously
fed into the reactor.78 It seems that the first mode is the best because fined bio-oil
droplets can provide the largest specific surface area to minimize the heat and mass
transport effects during the reforming processes. Similarly, the fixed bed reactors are
all a bench-scale fixed-bed unit, and up until now there has been not yet the
commercial application of fixed bed reactors for catalytic steam reforming of oil. This
22
View Article Online

DOI: 10.1039/C8SE00553B
is because carbon deposit and catalyst deactivation are particularly prone to occur in
these processes.

5. The quality of product gas and parameter effects
5.1 Gas composition

Table 4 lists several investigations performed on bio-oil gasification.18, 67, 87, 88, 99,
101, 108-114 Obviously, gasifying agents have a remarkably effect on the gas
composition. As mentioned before, based on gasifying agents used in bio-oil
gasification processes, bio-oil gasification processes can be divided into two major
types. One can be named as non-catalytic partial oxidation, in which oxygen is used
as one of the gasifying agents for the production of syngas (CO + H2), and another
can be named after steam reforming or gasification processes, in which only steam is
used as the gasifying agent for the production of hydrogen. There are also some
bio-oil gasification processes without using any gasifying agent. For example Latifi et
al. investigated thermal cracking of the bio-oils for syngas production and Chakinala
et al. studied hydrothermal gasification of the aqueous phase of bio-oil in supercritical
water.101, 114 However in consideration of that bio-oil contains a certain quantity of
water (15-30%), the two processes can be classified into steam reforming or
gasification processes. Based on the same reason, steam always participates in any
processes of non-catalytic partial oxidation of bio-oil.
When air is used as gasifying agents, the product gas obtained contains certain
23
View Article Online

DOI: 10.1039/C8SE00553B
quantity of nitrogen. Therefore, the product gas is not suitable for Fischer-Tropsch
Synthesis but can be used for heat or power generation. On the basis of decentralized

bio-oil production and transportation of the produced bio-oil to a central plant for
gasification, large scale production of fuel gas via bio-oil gasification can be
performed, which could perfectly meet the cooking requirement in areas with dense
population or the demand of fuel gas in large gas-fired power plants. However, the
German company, Choren Corporation, commercialized BTL technology on the basis
of their Carbo-V® biomass gasification process and built a second (Beta) plant with an
air blown gasifier in Freiberg in 2005 with a design capacity of 15 MW.98 Other than
the gasifying agents, the composition of the product gas derived from bio-oil
gasification processes is closely related to the source of the bio-oil, gasifiers, catalysts,
and operating conditions such as gasification temperature and equivalence ratio (ER).
For instance, catalysts are not required in the non-catalytic partial oxidation processes,
but they are very important in the bio-oil steam reforming processes and are normally
used to produce hydrogen-rich syngas with low amounts of tar and methane.
A box plot, Fig. 5, is plotted based on Table 4 to show the H2, CO, CH4, and CO2
concentration distributions, the H2/CO and CO/CO2 value distributions, and the lower
heating value and Wobbe Index distributions. It is apparent from Fig. 5a that the H2
and CO concentration distributions have larger variability or degree of dispersion.
This reflects that H2 and CO concentrations are more easily affected by all kinds of
gasification conditions, especially gasifying agents. CH4 concentration distribution
24
View Article Online
has an outlier. The outlier corresponds to the hydrothermal gasification of DOI: 10.1039/C8SE00553B
aqueous
phase of bio-oil. In fact, hydrothermal gasification processes (temperature > 374℃,

pressure > 22.1 MPa ) mimic the formation of natural gas.115 In order to produce
methane-riched gas, hydrothermal gasification of bio-oil can be considered. Except
for several outliers, the H2/CO and CO/CO2 value distributions display small variation
on the basis of Fig. 5b. Not surprisingly, the outliers in the H2/CO distribution
corresponds to the steam reforming processes. The H2/CO ratio is fairly important for
CO hydrogenation reactions, which include Fischer-Tropsch synthesis and can
produce fuels and accompanying organic chemicals from the product gas. Because the
1st Qu, median and 3rd Qu of the H2/CO value distribution are 0.85, 1.28, and 2.84
respectively, about half of these product gases could either be suitable for
Fe-catalyzed Fischer-Tropsch synthesis and higher alcohols (C>2) synthesis (1<the
required H2/CO ratio<1.4) or CO-catalyzed Fischer-Tropsch synthesis, methanol,
ethanol and dimethyl ether synthesis (the required H2/CO ratio≥2).116-118 The CO/CO2
ratio reflects how much proportion of carbon is converted to the effective gas
component (CO). There two outliers for the CO/CO2 value distribution in Fig. 5b.
This is because that steam to carbon ratio is relatively low so as to suppress the
water-gas-shift reaction. In fact, CO/CO2 value normally decreases with steam to
carbon ratio.87, 119-121 From syngas production standpoint, slightly higher H2/CO and
lower CO/CO2 ratio would be preferred. It can also be seen from Fig. 5(a) that a
substantial amount of CO2 will be produced during non-catalytic partial oxidation
bio-oil. Although the CO2 will not lead to net zero carbon emissions, Capture or
25
View Article Online

DOI: 10.1039/C8SE00553B
utilization of the CO2 would be preferable.122-124 For example, electrochemical
reduction of CO2 to fuels and chemicals is currently a focus of significant research

effort.125-129
It is very interesting to compare the composition of gas derived bio-oil

gasification with that of gases via solid biomass, coal, black liquor and heavy oil
gasification. To ensure the comparability of the collected data, only oxygen is used as
the gasifying agent, exogenous steam is not used as much as possible, gasification
reactions are performed under high pressures and mostly using entrained flow
gasifiers are selected as much as possible in all the gasification processes selected.
Table 5 presents some typical syngas compositions on the basis of gasification of
different feedstocks.88, 91, 93, 109, 130-132 Since H2 and CO content are very important for
application of the gases, a scatter plot (Fig. 6), which is based on Table 5 and whose
horizontal ordinate is CO content and vertical ordinate is H2 content, is plotted in
order for cluster analysis of the gases. Overall, the plot is divided into two parts by a
purple line on the basis of feedstock difference. The points over the purple line stand
for those gases via hydrocarbon or coal gasification. Obviously, the three points
which are light blue stand for the gases from gasification of bio-oil ， and lie at the
lower left corner of the plot. The points which are red and stand for the gases from
gasification of wood and the point which is deep blue and stands for the gas from
gasification of black liquor are basically located in the same location. This shows that
similar gas composition could be obtained via gasification of bio-oil, wood or black
26
View Article Online

DOI: 10.1039/C8SE00553B
liquor. This is mainly because that the element composition of the bio-oil is similar to
that of wood or black liquor. However the points which are deep green stand for the

gases from gasification of hydrocarbons，and are located at the top left corner of the
plot, which shows the composition of gas from gasification of bio-oil is completely
different from the composition of gas from gasification of hydrocarbons. There are
two deep green points, which are located at the top left corner of the plot. They stand
for the gases from gasification of natural gas. It is worth noting that five points which
are light green and stand for the gases from gasification of coal distribute in two areas
of the plot. Three of them are located in the lower right corner of the plot but two of
them at the lower left corner of the plot. In fact, the two points get mixed up with
those points which stand for the gases from gasification of bio-oil or wood. The main
reason is that the two points stand for the gases from gasification of coals whose
oxygen content is more than 20wt%. It seems that the element composition of
feedstocks has a fairly significant effect on the gas composition.
Except for gasification of pure bio-oil, some researchers performed non-catalytic
partial oxidation of bio-slurry, a mixture of bio-oil and bio-char.15, 21, 59 Firstly the
bio-char powder was mixed with the bio-oil to generate a dense bio-slurry with a
specific gravity of about 1.2 and a higher heat value from 18 to 25 GJ/m3. Then, the
bio-slurry was preheated to reduce the viscosity and transferred with plunger or screw
pumps into an entrained flow gasifier. The gasification conditions were a pressure of
2.6 MPa and a temperature of 1200 °C to 1600 °C. The volume composition of the
27
View Article Online
syngas exiting in the gasifier include 60 vol.% CO, around 30 vol.% H2, andDOI: 10.1039/C8SE00553B
almost
10 vol.% CO2. In comparison with gasification of pure bio-oil, more CO can be

produced by gasification of bio-slurry because the carbon content of bio-slurry is
remarkably higher than that of pure bio-oil. Overall, syngas composition for bio-slurry
gasification is similar to coal gasification.90 Solid biomass is converted into bio-oil,

bio-char and uncondensable gases via fast pyrolysis. The bio-oil and bio-char contains
about 90% of the initial energy contained in solid biomass. Therefore, this gasification
route can ensure fairly high CCE (from initial biomass to syngas). In fact, CCE at
higher temperatures has always been above 99% for this route.21 However, bio-slurry
gasification is a complex technology and a special nozzle system is required for
atomization of bio-slurry.
Up to now, bio-oil gasification or biomass gasification has been utilized to
produce low-to-medium energy fuel gases, synthesis gas (CO and hydrogen), and
hydrogen.133-138 In these gasification processes, it is also regrettable that only H2 and
CO for CO hydrogenation to fuels and accompanying organic chemicals were paid
very close attention to and nitrogen remains an underused resource or is considered to
be harmful. Dry air contains 78 vol% nitrogen. It might be a promising technology
pathway to utilize air as gasifying medium and make full use of nitrogen in the air for
the production of raw gas for ammonia synthesis via bio-oil gasification. This
pathway has the advantages of: ① ammonia has higher added value than the fuel
gases highly diluted by nitrogen with LHV of 4-6 MJ/m3. ②ammonia is an essential
28
View Article Online

DOI: 10.1039/C8SE00553B
and necessary chemical for the production of all kinds of nitrogenous compounds,
such as nitrogen fertilizer, nitric acid and potassium nitrate. However, it can also be

used as a practical alternative to fossil fuel for internal combustion engines. Its high
octane rating of 120 and low flame temperature allows the use of high compression
ratios without a penalty of high NOx production. Since ammonia contains no carbon,
its combustion cannot produce carbon monoxide, hydrocarbons or soot.139-143 ③air is
free of charge while the investment in air separation for production of pure oxygen is
quite high. ④ getting syngas with an appropriate H2/CO ratio and a high enough
purity for motor fuel synthesis is where the challenges lie. ⑤ ammonia can be
regarded as a promising hydrogen carrier for hydrogen storage. Namely, hydrogen
storage is widely known to be a limiting step for achieving a hydrogen-based
economy. Ammonia could be a reasonably promising hydrogen carrier because it
would be a much lower cost to produce, store, and deliver hydrogen as ammonia than
as compressed and/or cryogenic hydrogen.144-148 Therefore, bio-oil gasification for
production of the raw gas for ammonia synthesis could also be an attractive and
exciting field of study.
5.2 The lower heating value and Wobbe Index of the product gas
The heating value of product gas is closely related to its composition. In fact, the
heating value of product gas can be calculated by formula.120, 149 As seen from Fig. 5c,
the lower heating values of the product gases range from 8 to 18 MJ/Nm3. There is an
upper outlier in this distribution. This mainly is because the outlier stands for the gas
29
View Article Online

DOI: 10.1039/C8SE00553B
whose CH4 content is fairly high (15.6 vol%) and CO2 content is relatively low (5.6
vol%). These values are basically in agreement with those values reported in several

biomass gasification processes.10, 150-152 The gases can be suitable for power
generation in a power plant which uses gas turbines since a minimum heat value of
4.18 MJ/Nm3 of gases is required for application of them to gas engines. Furthermore,
some of the gases can be utilized as town gas. However, when fuel gas is used as a
substitute for another fuel gas, not only their heating value should be considered, but
also their Wobbe Index should be focused on. The Wobbe Index is an indicator of the
interchange ability of fuel gases such as natural gas, liquefied petroleum gas, and
town gas, and is frequently defined in the specifications of gas supply and transport
utilities.153 The Wobbe Index is used to compare the combustion energy output of
different composition fuel gases in an appliance (fire, cooker, etc.). If two fuels have
identical Wobbe Indices, then for given pressure and valve settings the energy output
will also be identical. On the basis of Fig. 5c, the degree of dispersion of the Wobbe
Index of the product gases is less than that of LHV of the product gases，except that
there are three outliers. Specifically, two lower outliers correspond to that air is used
as the gasifying agents and the obtained gases can replace producer gases. This upper
outlier in the Wobbe Index distribution corresponds to the gas which is marked as that
upper outlier in the lower heating value distribution. The gas could be substituted for
town gas based on its Wobbe Index (23.8). It seems that the rest of the gases could
replace CO according to their Wobbe Indices.106
30
View Article Online

DOI: 10.1039/C8SE00553B
5.3 Tar and particulate amount
Tar is produced during bio-oil gasification processes. It is a highly viscous, thick

and brown-black liquid, and is a complex mixture of condensable organics, such as
aromatic hydrocarbons, derivatives of phenol and oxygen-containing compounds,
which usually have a molecular weight larger than benzene.154 Tar is highly
undesirable because it can result in corrosion, plugging and fouling of pipelines and
downstream equipment and poison catalysts for syngas applications. Typical tar levels
in gases from entrain flow gasifiers or fluidized-bed gasifiers for bio-oil gasification
are between 50 mg/Nm3 and 2600 mg/Nm3.87, 88, 112 Overall, the levels are basically
lower than the typical tar levels in gases from biomass gasifiers, such as downdraft
gasifiers (average tar concentration ≈ 0.5~1 g/Nm3), updraft gasifiers (average tar
concentration ≈ 50 g/Nm3) and fluidized-bed gasifiers (average tar concentration ≈ 10
g/Nm3).10, 155-158 Tar concentration is normally low due to high temperature applied
when bio-oil is gasified in a entrain flow gasifier. In entrain flow gasifiers or
fluidized-bed gasifiers, bio-oil is atomized and split into a large number of micro
droplets, which can rapidly be pyrolyzed or evaporated to form vapor during the
pyrolysis stage. The vapor reacts with gasifying agents and then product gas is
produced. Therefore in the above-mentioned bio-oil gasification processes, the
pyrolysis stage is far shorter than in solid biomass gasification processes. This also
may explain why less tar is produced in the above-mentioned bio-oil gasification
processes. Moreover, water contained in bio-oil can react with tar via steam reforming
reactions so that tar is converted into hydrogen and CO. However, tar-free gas can be
31
View Article Online

DOI: 10.1039/C8SE00553B
produced via two-staged (pyrolysis/reforming) gasification or entrained flow
gasification of solid biomass.93, 95, 113, 159, 160 As for steam reforming or gasification of

bio-oil in fixed reactors, the reports on tar amount in product gas have not yet been
found.107, 161, 162 There could be two reasons. One reason is that only the aqueous
fractions of bio-oil are usually used in this process but tar normally originated from
those lignin-derived compounds in the viscous organic phase of bio-oil. Another
reason is that bio-oil is fed into the fixed reactors by pressure pumps and wet or cover
the surface of the catalyst in the fixed reactors. Steam reacts with the bio-oil, which is
a continuous fluid phase but not a disperse fine droplet phase, or the vaporized
aqueous fraction of it and hydrogen is produced. Tar could be formed on the surface
of the catalyst. In fact, carbon deposition and deactivation of catalyst often occur
because of coke-formation in this processes.79, 163
In general, the product gas from bio-oil gasification is free of particulate matter.
Bio-oil has a fairly low ash content and is relatively clean. The ash in the original
biomass will be largely concentrated in char, which is separated from bio-oil by
gas-solid separation equipment such as cyclones and filters during fast pyrolysis
processes for bio-oil production. Moreover, obvious carbon deposit or soot was hardly
observed during bio-oil gasification processes in entrained flow gasifiers and fluidized
bed gasifiers because fine bio-oil droplets can be fairly easily gasified.67, 87, 88, 110, 112
Similarly, particulate matters are not entrained by the hydrogen-riched gas during
steam gasification of bio-oil in fixed bed gasifiers.81, 99, 108, 164, 165 Therefore, the
32
View Article Online
restrictions on particulates in the application of the product gas derived fromDOI: 10.1039/C8SE00553B
bio-oil
gasification will not be considered.

On the basis of the amount of tar in the product gas derived from bio-oil
gasification, the product gas can directly be applied to direct combustion systems and
there is no need for cleaning because such systems usually have no limits for the
amount of tar, but the gas should not cool down below the tar dewpoint when it
travels from the gasifier exit to the burner inlet. Moreover, the product gas is also
suitable for use in Stirling engines, which have a high tolerance for tar, for power
generation.166 However, the product gas cannot be directly applied to
internal-combustion engines (the limits of tar: 50-100 mg/Nm3) or gas turbines (the
limiting level of tar: 0.05-5 mg/Nm3). The limits for tar in a fuel cell (the limiting
level of tar: <1.0 mg/Nm3) or syngas applications (the limiting level of tar: 0.1
mg/Nm3) are even more stringent. There are several methods for reducing tar content
in the product gas.167-169 However, gas cleaning would not remarkably increase the
total capital investment (TCI) of plants for production of the product gas, or the TCI
could not be sensitive to the cost of tar cleanup.
5.4 Soot and coke
Soot formation could be a problem within the non-catalytic partial oxidation and
steam reforming processes. In a bio-oil non-catalytic partial oxidation process, soot
formation results from some form of pyrolysis because of incomplete combustion and
33
View Article Online
usually occurs at bio-oil rich stoichiometries. Soot particles not only can causeDOI: 10.1039/C8SE00553B
serious
environmental contaminations but also is related to health risks because it could be

carcinogenic. Furthermore, soot formation lead to the decrease of CCE during bio-oil
non-catalytic partial oxidation process, and the result in clogging and fouling of
equipments. Reduction or control of soot formation is a crucial research topic for the
field of bio-oil non-catalytic partial oxidation research. However, the research of soot
formation during bio-oil non-catalytic partial oxidation is extremely limited. Zheng et
al. found no obvious soot formation arising from non-catalytic partial oxidation of
bio-oil.87, 88 Rossum et. al shown that about 20% of carbon in bio-oil could finally
form soot during their bio-oil non-catalytic partial oxidation process.112 Chhiti et al.
proposed a model to describe soot formation and oxidation during bio-oil
non-catalytic partial oxidation. These studies confirmed that high temperature and
addition of O2 or steam could reduces the soot yield.67, 68 Bio-oil steam reforming is
usually accompanied by coke formation. Coke have a high carbon content, and can
lead to catalyst deactivation. Therefore, it is undesirable during reforming. Garcia et.
al found that acetic acid in bio-oil was a compound with low coke formation but
furfural in bio-oil had high tendency to produce coke during bio-oil reforming process.
These results further concluded that the reactivity of coke formation of some species
followed this order: glucose > mxylene > acetone> ethyl acetate> ethylene glycol >
acetic acid. It is concluded that the amount of coke deposited on catalyst was
0.02~0.28 g per 100 g carbon fed and the coke, which did not included the coke
deposited on catalyst and resulted from an incomplete vaporization of the feed,
34
View Article Online

DOI: 10.1039/C8SE00553B
amounted to 3~59 g per 100 g carbon fed.79 Moreover, other cyclic oxygenated
compounds in bio-oil, such as saccharides and phenols, are also supposed to be

responsible for coke formation.35 Panigrahi et. al showed that the yield of coke, which
was defined as g coke/100 g bio-oil, was 20%~40% when steam carbon ratio
(mol/mol) was 0.32 and temperature was varied in a range of 650 to 800 ℃.106
Increase of reforming temperature and steam carbon ratio can lead to decrease of coke
formation. However, this will result in the increase of operating cost because bio-oil
steam reforming is an endothermic process and a lot of high temperature steam could
be also required at the same time. A special techno-economic analysis of this route
could be important to determine the optimum reforming temperature and water carbon
ratio and maximize the profit rate of this route.
5.5 Effect of Equivalence ratio (ER)
ER, which is an important gasifier design and operation parameter involved in
the non-catalytic partial oxidation processes, is defined as the ratio of actual air or
oxygen-fuel ratio to the stoichiometric air or oxygen-fuel ratio. The quality of gas
obtained from non-catalytic partial oxidation of bio-oil strongly depends on the ER.
The levels of CO, H2 and CH4 in the product gas usually decrease with the rise of ER
because higher ER means a more plentiful supply of oxygen and more CO, H2 and
CH4 are oxidized to yield CO2 and H2O. In fact, a too high ER value will lead to the
excessive formation of products resulting from perfect combustion, such as CO2 and
H2O, at the cost of desirable products, such as H2 and CO2.88, 110, 112, 113 In practical
35
View Article Online

DOI: 10.1039/C8SE00553B
gasifiers for non-catalytic partial oxidation of bio-oil, the ER value had better vary
from 0.2 to 0.3. When air is used as gasifying agents, the increase of ER can

undoubtedly lead to the increase of the N2 concentrations because the flow rate of N2
is enhanced at higher ER. Since N2 is always an undesirable product for any
application of product gas, the optimum ER value should be as low as possible for
bio-oil gasification using air as gasifying agents. The H2/CO ratio is an important
indicator for CO hydrogenation reactions such as Fischer-Tropsch synthesis. Zheng
et.al found that when ER varied from 0.1 to 0.5, the ratio showed a markedly
downward trend using air as the gasifying agent, gradually decreased using
oxygen-enriched air and basically kept constant using pure oxygen in bio-oil
gasification processes. The reasons for these variation tendencies were also explained
in their report.88 As for the lower heating value of the product gas, increasing ER will
obviously lead to reduce it whatever gasifying agents are used. It is also found that the
lower heating value of the product gas is lowest for using air as the gasifying agent
when ER is equal because of remarkable dilution effect by nitrogen. Moreover, the tar
content decreases as ER increases. Thus, when the limits for tar in gas applications are
significantly stringent, the greatest possible ER value could be preferable. Moreover,
if the same ER value is used, the tar concentration in the product gas for using air as
the gasifying agent is lower than for using pure oxygen as the gasifying agent because
of the effect of dilution with N2. During non-catalytic partial oxidation of bio-oil, the
cold gas efficiency increases with ER, and then decreases with ER being further
raised. A maximum cold gas efficiency of 0.75 was obtained at an ER value of 0.3
36
View Article Online

DOI: 10.1039/C8SE00553B
without the addition of steam by Zheng et.al.88 This efficiency is higher than that
obtained in solid biomass gasification processes. This could be because there is no

obvious carbon deposit in the non-catalytic partial oxidation of bio-oil but unburned
carbon is always observed in fly ash in solid biomass gasification processes. After all,
chemical energy in the unburned carbon can reach about 20% of the total chemical
energy of solid biomass.170 Moreover, Rossum et.al found that the CCE of a
fluidized-bed gasifier for bio-oil gasification increases with ER and then decreases.112
On the whole, the effect of ER on bio-oil gasification processes is similar to that on
solid biomass gasification processes.10, 171-173
5.6 Effect of steam to carbon ratio (SC)
SC is defined as the ratio of the total amount of moles of water, including the
water in the feed such as bio-oil, to the moles of carbon in the feed. It is also an
important to process parameter involved in bio-oil gasification, as the ER is.
Superheated steam, which contributes to the production of hydrogen, is used either
alone in bio-oil steam reforming or with air / oxygen in the non-catalytic partial
oxidation of bio-oil. In bio-oil air-steam gasification processes, increasing SC leads to
a lower CO and CH4 concentration, but a higher CO2 concentration. This is mainly
because more CO2 is produced via the water-gas shift reaction at the expense of CO
and CH4 is converted via steam reforming reactions.87, 111, 113, 174 Normally, methane
and CO2 are all inert materials in CO hydrogenation reactions, and thus a low
concentration of methane or CO2 is advantageous. However, a little carbon dioxide
37
View Article Online
(around 4 vol.%) can increase methanol yields for methanol synthesis viaDOI: 10.1039/C8SE00553B
carbon
dioxide hydrogenation using a Cu-Zn-based catalyst. The level of H2 usually shows a

gradual upward trend and then a gradual downward trend with the rise of SC, while
the N2 concentration shows an exactly the reverse variation trend. Guo et.al reported
that a maximum H2 concentration of 47 vol.% was obtained.111 The tar content

normally decreases considerably and increases slightly on increasing SC. Steam
reforming of tar can occur and the tar can be converted into hydrogen and CO.
However, excessive steam may intensify thermal cracking reactions for tar generation.
Generally speaking, higher SC can promote steam reforming reactions and the water
gas reaction, leading to higher yields of smaller gas molecules such as CO, H2 and
CO2. However, excessive steam could intensify thermal cracking reactions or lower
gasification temperature, resulting in the suppression of the above-mentioned
reactions. Therefore, the lower heating value of the product gas, gas yield (Nm3/kg
bio-oil), CCE and cold gas efficiency in bio-oil air-steam gasification processes will
reach their maximum values, respectively. For example, a maximum gas yield of 1.90
Nm3/kg bio-oil was observed at SC of 4.36, ER of 0.4 and 1000℃ by Zheng et al.87
SC is a significant operating parameter for steam reforming of bio-oil. Higher SC
favors greater conversion of bio-oil to hydrogen, prolonging of catalyst lifetime and
decreasing of carbon deposit. Therefore, increasing SC results in the increase of
hydrogen and CO2 concentrations and the decrease of CO and CH4 concentrations.
However, excessively high SC will raise the operating cost in the processes. SC
38
View Article Online

DOI: 10.1039/C8SE00553B
should normally be between 4 and 6. If 1.0 kg of bio-oil is consumed, around 0.15 kg of
hydrogen can be produced theoretically. This theoretical value depends on the

elemental composition of bio-oil. Chhiti reported that about 0.12 kg of hydrogen could
be obtained experimentally at 1400℃ and the corresponding hydrogen yield (the ratio of
moles of hydrogen obtained to moles of hydrogen in stoichiometric potential) was

84% when SC is more than 6.67 Generally speaking, the hydrogen yield is between
60% to 80%. Zhu et al. found that the hydrogen yield increased from 65% to 79% and
the CCE from 82% to 95% at 750℃ using C12A7-18%Mg catalysts when SC grown
from 1.5 to 4.74 And SC was higher than 6, the hydrogen yield and he CCE remain
basically unchanged. Li et al. reported that the hydrogen and CO2 concentrations
separately increased from 44 vol% to 62 vol% and from 27 vol% to 37 vol% but the
CO and CH4 concentrations separately decreased from 5 vol% to 2 vol% and from 10
vol% to 2 vol% when SC increased from 1.0 to 7.5.77 Therefore, the highest possible
SC can not only favor production of hydrogen and CO2, but also aid in reduction of
other gas impurities such as CO, CH4 and C2H4.
5.7 Effect of gasification temperature
Generally speaking, commercial-scale entrained flow gasifiers require a fixed
value for ER belonging to adiabatic operation at a certain temperature. Namely, the
gasification temperature is not independent and dependent on the ER. The variation of
the ER at a given gasification temperature is not impossible. However, small-scale
entrained flow gasifiers used in laboratory experiments are typically wrapped with an
39
View Article Online

DOI:113
10.1039/C8SE00553B
electric heating-jacket in order to adjust the gasification temperature.87, 112, A
lab-scale entrained flow gasifier with an electric heating-jacket can be used to

investigate the effect of gasification temperature in the non-catalytic partial oxidation
processes for bio-oil gasification. As for steam reforming of bio-oil in fixed bed
gasifiers or fluidized bed gasifiers, these processes are highly endothermic and the
temperature in steam reformers is usually no less than 800℃. The heat outside the
reaction system is absolutely necessary, and thus the temperature in bio-oil steam
reformers can be easily adjusted by an electric heating-jacket, whose output power
was regulated by a PID temperature controller.
In the processes of non-catalytic partial oxidation of bio-oil, the H2 content
normally increases with the temperature because hydrogen production reactions, such
as the water-gas reaction, steam reforming reactions, bio-oil and tar cracking reactions,
are all strengthened. However, the CO level could show a decreasing trend. This trend
is in agreement with those found in some biomass air-steam gasification processes,120,
132 while it is contrary to those investigated in other biomass air-steam gasification
processes.149, 175 The effect of the gasification temperature on CO concentration is
difficult to understand because exothermic and endothermic reactions are inseparably
intertwined. The CO level could show a decreasing trend. There might be two reasons
for this trend. One is that the water gas shift reaction is accelerated; another is that
there is competition between the productions of CO2 and CO. The decrease of CH4
concentration with the gasification temperature can be easily explained because of
40
View Article Online

DOI: 10.1039/C8SE00553B
CH4 steam reforming reactions. However, the increase of CO2 content could be
explained by carbon balance. Tar content shows a downward trend with the rise of

temperature because tar steam reforming reactions and tar cracking are strengthened
by higher temperature. The lower heating value of product gas increases with
temperature because of the enhancement of thermal cracking of tar and the increase of
the yields of H2. It should also be noted that the rise of gasification temperature under
this section results from external heat supply and not the rise of ER or oxygen supply.
In fact, more ER or oxygen supply will result in producing more CO2 and H2O and
reducing the lower heating value of product gas. The CCE will improve while
increasing the gasification temperature since all kinds of oxidation reactions are
strengthened. Similarly, higher gasification temperatures allow higher cold gas
efficiencies because of the external heat supply. For example, Zheng et al. reported
that cold gas efficiency reached 93% under 1000℃ in a bio-oil air-steam gasification
process.87 However, since commercial-scale entrained flow gasifiers are operated
without external heat supply, it is also necessary that an experimental study on
non-catalytic partial oxidation of bio-oil in a lab-scale adiabatic entrained flow
gasifier is performed.
Since bio-oil steam reforming reactions are highly endothermic and external heat
supply is necessary for bio-oil steam reforming processes, it is evident that increasing
gasification temperature usually results in the increase of hydrogen and CO2
concentrations and the decrease of CO and CH4 concentrations. Chhiti found that
41
View Article Online

DOI: 10.1039/C8SE00553B
hydrogen and CO2 concentrations separately increased from 38 vol% to 65 vol% and
from 10 vol% to 22 vol% while CO and CH4 concentrations decreased from 35 vol%

to 15 vol% and 5 vol% to 1 vol% when reforming temperature increased from 1000°C
to 1300°C. However, when the temperature continued to rise, CO2 and CO
concentrations slightly decreased and increased respectively.67 This can be because of

Boudouard reaction under high gasification temperature. However, excessively high
gasification temperature raises the operating cost and capital cost in the processes.
Thus, catalytic steam reforming of bio-oil usually occurs between 600°C and 900°C,
but non catalytic steam reforming of bio-oil is operated under the temperature range
1000 - 1400°C.67, 79, 101, 112 Since neither of excessively high SC and gasification
temperature is economically feasible, Xie et al. developed a sorption-enhanced steam
reforming process, in which CaO was in situ used as CO2 sorbent and CO2 was
removed via the reaction (CaO + CO2 → CaCO3), for improving hydrogen production.
the hydrogen concentration was raised as much as 90 vol% with CO2 sorption.108 The
water-gas shift reaction easily reaches equilibrium during bio-oil steam reforming
processes. Bell et al. provided a method for estimating gasification temperature based
on the water-gas shift gas equilibrium constant and gas composition.90 By making a
comparison between the calculated temperature and the measured temperature, the
extents of reactions in bio-oil steam reforming processes or whether the bio-oil steam
reforming processes reach equilibrium can be evaluated or judged.
5.8 Effect of catalysts
42
View Article Online

DOI: 10.1039/C8SE00553B
Catalysts used in catalytic steam gasification of bio-oil mainly include transition
metal catalysts, such as Ni, Co and Cu based catalysts, and noble metal based

catalysts, such as Rh, Pt, Ru and Pd. Although noble metals are normally more
expensive than transition metals, they have better catalytic activity and the power to
resist carbon deposition. Nickel-based catalysts and cobalt-based catalysts have higher
activity than copper-based catalysts while the activity of noble metal catalysts
followed the order of: Rh > Pd > Pt > Ru in the steam reforming of ethanol in bio-oil.
Fierro et al. reported that the Ni-Cu/SiO2 had higher activity and selectivity than
Ni/SiO2 in the steam reforming of ethanol in bio-oil.81 Nickel-based catalysts are the
most widely used for in the steam reforming of acetic acid in bio-oil. However, noble
metal catalysts, such as Rh, Pt, Ru and Pd, have much better catalytic activity and
power to resist carbon deposition than Nickel-based catalysts in the steam reforming
of acetic acid in bio-oil. Suzuki et al. found that the activity of some metal catalysts
followed the order of: Ru > Rh > Ni > Ir > Co > Pt > Pd > Fe when the carrier used is
the same, and Ru/Y2O3 shows best catalytic activity, selectivity and stability in the
steam reforming of glycerol in bio-oil.176 Fernando et al. investigated the effect of
fourteen different catalysts on the steam reforming of glycerol in bio-oil and found
that Ni/Al2O3 and Ru/Ce/Al2O3 shown good catalytic activity and selectively.177
Takanabe et al. found that Pt/ZrO2 had a significantly high catalytic activity and
hydrogen yield was nearly the theoretical yield when the catalyst was used in the
steam reforming of acetic acid in bio-oil.178 Polychronopoulou et al. found that natural
calcite showed good catalytic activity and stable in steam reforming of phenol in
43
View Article Online

DOI: 10.1039/C8SE00553B
bio-oil. Overall, Ru is apparently an excellent catalyst for steam reforming of
bio-oil.85

Catalyst supports used usually include Al2O3, CeO2, ZrO2, MgO, ZnO, TiO2,
SiO2 and cordierite in the steam reforming of bio-oil. The most widely used supports
is Al2O3 because it is relatively cheaper, easy to mold and stable. However, Lewis
acid centers on its surface can promote thermal cracking reactions and ketonization to
cause carbon deposition and catalyst deactivation in steam reforming of bio-oil.
Therefore, it could be preferable that basic oxide or neutral oxide is used as catalyst
carriers in steam reforming of bio-oil. Moreover, a certain amount of alkali metal,
alkaline earth metal or rare earth metal is added to Al2O3 can also restrain carbon
deposition. Fernando et al.， examined the effect of Ni/MgO, Ni/CeO2 and Ni/TiO2
on the steam reforming of glycerol in bio-oil and reported that Ni/MgO shown the
best catalytic activity. The reason is that MgO is alkaline and can improve the
adsorption of water.179 Polychronopoulou et al. found that the catalytic activity of
Rh/MgO was further improved after CeO2 or ZrO2 was added to MgO because
oxygen vacancies were formed on the catalyst' surface and the adsorption of reactants
was strengthened in steam reforming of phenol in bio-oil.85 Moreover, Ochoa et al.
found that the catalyst deactivation was mainly attributed to the encapsulating and
amorphous coke deposition and the oxygenates in bio-oil were the precursors of the
encapsulating coke.180
44
View Article Online

DOI: 10.1039/C8SE00553B
Normal catalytic steam reforming of bio-oil is performed under relatively high
temperature, which leads to high energy consumption. However electrochemical

catalytic reforming of bio-oil for hydrogen production can be performed under
medium temperature (400°C ~ 500°C) and the hydrogen yield can exceed 90%. Zhu
et al. used normal Ni/Al2O3 as the catalyst for electrochemical catalytic reforming of
bio-oil. They found that the electrochemical catalytic reforming temperature
decreased by about 300°C and carbon deposition or coke-formation were remarkably
depressed on the catalyst' surface in comparison with the processes of catalytic steam
reforming of bio-oil.74 The mechanism of electrochemical catalytic reforming of
bio-oil is mainly that an electrified wire provides a large number of thermal electrons,
whose concentration usually ranges from 109 to 1010 /cm3 in the reformers used, onto
the catalyst, and these thermal electrons can promote dissociation and degradation
reactions of all kinds of compounds in bio-oil. Moreover, many free radicals
(e.g.， ·OH, ·CH, ·CH2 ，etc.), which show high activity are produced and they can
induce radical chain reactions. All the factors significantly increase the reaction rate
of bio-oil steam reforming and decreases the reforming temperature.78 Although
electrochemical catalytic reforming of bio-oil seems cleaner and more cost-effective,
using rigorous LCA (Life cycle assessment) and TEA (Techno-economic analysis) for
comparison of the two reforming routes are necessary.181-186
6. Economic evaluation of bio-oil gasification
Advanced biofuel production based on non-catalytic partial oxidation of bio-oil
45
View Article Online

DOI: 10.1039/C8SE00553B
could have good economic feasibility. One of the reasons is because of the simplicity
of bio-oil production via fast pyrolysis. Technical and economic data on the basis of

NREL report by Ringer et al. showed that a plant capacity of 28 million gallons of
bio-oil per year could only have a production cost of $0.65 per gallon (2003 basis
year).187 Overall, bio-oil production costs could range from $0.41 to $1.21 per
gallon.188-190 The second reason is that bio-oil can be more easily stored and
transported than solid biomass.191, 192 As a liquid, the bio-oil which is produced on a
small scale fast pyrolysis plant can be economically transported by trucks, such as
liquid tank trucks and super B-train tank trailers, and the bio-oil which is produced on
a large scale fast pyrolysis plant (capacity > 1700 m3 bio-oil per day) can be
economically transported by pipeline (transportation distance ≥ 100 km.).20, 193-195
Another more important reason is decoupling bio-oil production (location, time, and
scale) from its utilization. On the basis of the two reasons, a so called BTL2 (biomass
to liquid in two steps, which means a regional bio-oil production and a central bio-oil
gasification and synthesis for Fischer Tropsch liquids and whose schematic diagram is
shown in Fig. 7) plant can have a fairly large size or capacity when its operating cost
per unit of production of Fischer Tropsch liquids reaches the minimum value.15-17, 19, 21,
196-198 In fact, operating costs per unit of production of motor fuels derived from fossil
fuels decreases monotonically with increasing plant size while operating costs per unit
of production of biofuels firstly went down and then went up with the rise of plant
size. Namely, different kinds of biofuel plants normally have a minimum operating
cost and a corresponding optimal size according to the type of processes used and the
46
View Article Online
nature of biomass processed. This is because biomass feedstocks are DOI: 10.1039/C8SE00553B
widely
distributed geographically and have a low energy density, which leads to a remarkable

increase of biomass transportation costs with the biofuel plant size, while fossil fuels
can be obtained from a single ‘mine mouth’ or ‘well head’ for petroleum-based motor
fuels industries and have high energy density. Distributed pyrolysis of biomass to
bio-oil on a small scale near the biomass source, transport of all the bio-oil to a central
site, and gasification of the bio-oil to syngas and catalytic conversion of the syngas to
Fischer Tropsch liquids in this site are expected to remarkably alleviate biomass
delivery expenses and increase the optimal size of BTL2 biofuel plants. Wright et al.
estimated the minimum operating costs of different kinds of biorefinery processes,
including grain ethanol, biochemical cellulosic ethanol, centralized gasification of
solid biomass to methanol, centralized gasification of solid biomass to hydrogen
(liquid), centralized gasification of solid biomass to mixed alcohols, centralized
gasification of solid biomass to Fischer Tropsch liquids, fast pyrolysis to bio-oil, and
BTL2, and established their corresponding optimal plant sizes, including annual
capacity and biomass input.16, 199 Here, the operating cost, which is also known as
total product cost, includes direct production cost, fixed charge and plant-overhead
cost.200, 201 The estimated and established data are shown in Fig. 8(a), (b) and (c). In
comparison with centralized gasification of solid biomass to Fischer Tropsch liquids,
BTL2 has a lower optimal operating cost but a remarkably higher corresponding
annual capacity and biomass input. This shows that BTL2 could be more profitable
than centralized gasification of solid biomass to Fischer Tropsch liquids. Moreover,
47
View Article Online
BTL2 has also a remarkably higher optimal annual capacity and biomass DOI:
input10.1039/C8SE00553B
in
comparison with the other biorefineriey processes except for centralized gasification

of solid biomass to Fischer Tropsch liquids. The optimal annual capacity of a BTL2
plant can reach up to 2500 million gge (gallon of gasoline equivalent, 1
gge=120.74MJ), which hints that a BTL2 plant reaching up to its optimal annual
capacity would have a good profit rate or internal rate of return. It is generally known
that fuels, including biofuels, belong to so-called bulk chemicals or commodity
chemicals. These chemicals must be produced on the greatest possible scale in order
for reasonable profit rates. Henrich et al. performed a cost estimate for production of
Fischer Tropsch liquids via BTL2. The Fischer Tropsch liquids can be produced at the
expense of 700 Mt/ an of biomass input in the BTL2 plant with a capacity >1 Mt/a
and the operating cost was estimated to be €0.8 per liter.15 An important prerequisite
for the above-mentioned conclusions is that biomass can nearly be supplied
unlimitedly exactly as fossil fuels. However, it seems that the prerequisite could be
met via distributed fast pyrolysis of biomass to bio-oil and then transport them to a
central site for further conversion.
Since the supply of biomass resource is limited, Li et al. investigated the
economic feasibility of centralized bio-oil production, bio-oil gasification and syngas
conversion to Fischer Tropsch liquids in a plant with a 2000 ton per day facility. On
the basis of an internal rate of return of 10%, a minimum fuel selling price of 5.59
$/gge was calculated in their study. Therefore, they believed that this pathway was
48
View Article Online
still at high risk with current technical and economic situation and a largerDOI: 10.1039/C8SE00553B
facility
capacity could be very necessary to make this pathway economically. Therefore,

biomass supply availability is crucial for biofuel industries, including BTL2.18 Li and
Hu found that the locations of distributed fast pyrolysis plants are more centralized
when biomass availability factor, which is defined as the ratio of the available
biomass to the collectable biomass, increased.197 A case study reported by them based
on Iowa State of U.S. shown that only 40 counties were required to supply the
biomass when the factor is 0.7 (rather than 71 when the factor was 0.4). If the
availability factor is less than 0.23, BTL2 would be not profitable. When the factor
ranged from 0.23 to 0.36, BTL2 is profitable but it could not satisfy the advanced
biofuel (Fischer Tropsch liquids) production target of the entire Iowa state. They also
found that farmers' participation or farmers' willingness to supply cellulosic biomass
could have a significant impact on biomass supply chain. Specifically, biomass
availability factor represents the average amount of the farmers who would participate
in cellulosic biomass collection. The operating cost breakdown for Fischer Tropsch
liquids production with BTL2 is interesting. Wright et al., Henrich et al., and Hu et al.
separately performed the breakdown (fraction) of the operating cost, which is shown
in Fig. 9. Overall, it can be seen from Fig. 9 that the proportion of the biomass cost in
the operating cost ranges from 18% to 48%. However as shown in Fig. 9, biomass
cost accounts for nearly half of the operating cost in the research of Wright et al. but
only 18% of that in the research of Hu et al. This could be attributed to the fact that
there is more biomass input in the research of Hu et al. (about 11.3 million tons/a)
49
View Article Online
than in the research of Wright et al., (about 8.7 million tons/a) so the estimatedDOI: 10.1039/C8SE00553B
capital
cost and conversion cost from Hu et al. are much more than the estimated ones from

Wright et al. Biomass input data from Henrich et al. was about 7 million tons/a and
thus the proportion of the biomass cost in the operating cost is closed to that from
Wright et al. Above all, the proportion of the biomass cost in the operating cost
mainly depends on biomass input and biomass price. In comparison with Wright_55
("55" stands for that the capacity level of distributed fast pyrolysis facilities is 55 tpd),
biomass transport cost in Wright_5.4 ("5.4" stands for that the capacity level of
distributed fast pyrolysis facilities is 5.4 tpd) accounts for a slightly lower proportion
in the operating cost. This shows that small scale distributed fast pyrolysis facilities
could be more advantageous in BTL2. In comparison with Hu_0.4 ("0.4" stands for
that biomass availability factor is 0.4), biomass transport cost in Hu_0.6 ("0.6" stands
for that biomass availability factor is 0.6) accounts for a slightly lower proportion in
the operating cost. This also shows that higher biomass availability factor is more
advantageous in BTL2. On the basis of Fig. 9, the proportion of the biomass transport
cost in the operating cost ranges from 5% to 19%. Notably, the proportion of the
biomass transport cost in the operating cost only was about 5% according to the data
from Wright et al. while they found that biomass transport cost accounts for 25% of
the operating cost of a plant for centralized gasification of solid biomass to Fischer
Tropsch liquids when the two kinds of plants (BTL2 and centralized gasification of
solid biomass to Fischer Tropsch liquids) have the same capacity (550 million gge).
50
View Article Online

DOI: 10.1039/C8SE00553B
As described before, steam gasification of bio-oil or bio-oil reforming focuses on
the hydrogen production. Sarkar et al. developed a techno-economic model to

estimate the operating costs of hydrogen production via steam gasification of bio-oil
via fast pyrolysis of whole trees, forest residues, and straw, respectively. The
operating costs are 2.40$ per kg H2 (2.41 $/gge), 3.00$ per kg H2 (3.01 $/gge) and
4.55$ per kg H2 (4.59 $/gge), respectively. In their study, bio-oil was produced at a
fast pyrolysis plant with a capacity of 2000 ton biomass per day, and transported to a
bio-oil reforming plant for hydrogen production which was 500 km away.202 The
operating costs are higher than that for hydrogen production via centralized
gasification of solid biomass (1.21 $/gge) reported by Wright et al.199 This is mainly
because that the plant for centralized gasification of solid biomass to hydrogen has a
much higher capacity on the based on biomass input data (5.11 million tons per year)
from the analysis by Wright et al. This shows again that biofuels should be produced
on a scale which is as large as possible. Zhang et al. performed a comparative
techno-economic analysis of bio-oil reforming and non-catalytic partial oxidation of
bio-oil for hydrogen production.174 The biomass input data are all 2000 tons per day
for the two pathways. On the basis of their analysis, hydrogen production capacity is
160 tons per day for bio-oil reforming pathway and 147 tons per day for bio-oil
non-catalytic partial oxidation pathway at the facility. Internal rates of return were
18.6% and 8.4% for facilities employing the bio-oil reforming pathway and bio-oil
non-catalytic partial oxidation pathways, respectively. Sensitivity analysis showed
that hydrogen price and hydrogen yield had the greatest impacts on facility internal
51
View Article Online
rates of return. Therefore, for hydrogen production, it was proved thatDOI: 10.1039/C8SE00553B
bio-oil
reforming is more advantageous and profitable than non-catalytic partial oxidation.

For hydrogen production, it can also be anticipated that higher internal rates of return
could be reached if bio-oil is produced locally and bio-oil reforming is performed
centrally in a central site.

7. Conclusion
The research of bio-oil gasification could be significant because high energy
density bio-oil can be easily transported from distributed fast pyrolysis plants to a
central plant for further conversion and gasification. As an end-of-pipe technique,
gasification can convert different bio-oils into a uniform, gas intermediate that is
named as syngas for further conversion to heat, electricity, hydrogen or motor fuels.
All results of techno-economic analyses have shown that bio-oil non-catalytic partial
oxidation for advanced biofuel production or for hydrogen bio-reforming would be
profitable. In the conversion chain of lignocelluloses biomass to gas, there is little
discharge of solid and liquid wastes; therefore, the conversion chain would be fairly
environment-friendly. Life cycle assessments of bio-oil gasification processes are still
necessary to quantitatively and rigorously evaluate their environmental protection
feasibility in the future.
The experimental results from bio-oil non-catalytic partial oxidation or bio-oil
reforming show that these two pathways are suitable for syngas production or
52
View Article Online
hydrogen production, respectively. However, only these lab-scale experimentalDOI: 10.1039/C8SE00553B

results
are not sufficient. Pilot scale studies of bio-oil gasification should be performed for

full-scale demonstrations, such as continuous operation (not less than 1000h per year)
preferably of multiple plants on the scales of 500 to 1000 kg bio-oil per hour. Here,
mature refining technologies applied to coal-liquid and petroleum conversions, such

as bio-oil gasifier design and bio-oil gasification process design, can be utilized as a
reference to bio-oil gasification. Considering that bio-oil is completely different from
petroleum feedstocks and has complex nature, it is necessary to improve the upstream
processes (for example, fast pyrolysis and bio-oil pretreatment), to make the resulting
bio-oil products more suitable to subsequent gasification processes. For bio-oil
reforming processes, new pretreatment of bio-oil and novelty design of bio-oil
reformers should be studied to prevent coke formation and catalyst deactivation.
Suitable catalysts need to be developed via testing different catalytic materials.
Catalyst deactivation and associated fundamental engineering issues should be
systematically investigated. Especially, catalysts deactivation at different stages the
process should be carefully characterized. For bio-oil non-catalytic partial oxidation
processes, it is necessary to modify the existing entrained flow gasifiers and
corresponding gas clean-up and shift system for gasification of hydrocarbon or coal to
make them applicable for bio-oil gasification processes. Except for experiments, all
kinds of mathematical models of bio-oil gasification, including thermodynamic
models, kinetic models, computational fluid dynamics models, artificial neural
network models, should be developed to predict product gas characteristics, parameter
53
View Article Online

DOI: 10.1039/C8SE00553B
effects and process performances. Moreover, analytical techniques should be
improved for the detection and quantification of syngas impurities with low contents.

While the intention of steam reforming of bio-oil is to produce H2 with maximum
quantity of, bio-oil non-catalytic partial oxidation is mainly intended to convert

bio-oil into CO and H2. Therefore, for syngas production, non-catalytic partial
oxidation of bio-oil is more attractive than steam reforming; On the other hand, it is
more appropriate for production of biohydrogen by steam reforming of bio-oil. It is
worth noting that bio-oil steam reforming is highly endothermic and heat outside the
reaction system needs to be provided for this route. In this regard, bio-oil can be
partially oxidized in autothermal regime without introducing extra energy supply as
long as enough bio-oil is fed into gasifiers. However, bio-oil steam reforming could
have higher cold gas efficiency or energy conversion efficiency than bio-oil
non-catalytic partial oxidation since a part of chemical energy contained in bio-oil
need to be release as heat. Biomass pyrolysis and in-line steam reforming has several
advantages and shown an excellent effect on minimization of tar production so that a
product gas with a extremely low tar content or a tar-free H2 or synthetic gas can be
produced in the route. This route is a fairly good solid biomass gasification
technology. Hence, a localized strategy can be applied to this technology, but a
delocalized strategy could be suitable for non-catalytic partial oxidation or bio-oil
steam reforming. Our observations suggest that non-catalytic partial oxidation and
steam reforming of bio-oil could have good economic feasibility.
54
View Article Online

DOI: 10.1039/C8SE00553B
Conflicts of interest

There is no conflict to declare.
Acknowledgment
The authors wish to express their gratitude for the financial supported by the
Fundamental Research Funds for the Central Universities (2452017198), the Natural
Science Basic Research Plan in Shaanxi Province of China (No. 2015JQ3067), the
program of International S&T Cooperation of China (2015 DFG31860), the Natural
Science Foundation of China (31430092).
Abbreviations
BTG Biomass Technology Group
BTL Biomass to liquid
BTL2 Biomass to Liquid in Two Steps
BTU British thermal unit
CCE Carbon conversion efficiency
CFD Computational fluid dynamics
CGE Cold gas efficiency
CTL Coal to liquid
EFB Empty Fruit Bunches
EFG Entrain flow gasifier
ER Equivalence ratio
ER Equivalence ratio
FIG Fixed bed gasifier
FLG Fluidized bed gasifier
GEE General Electric Energy
gge Gasoline gallon equivalent
GTL Gas to liquid
Hu_0.4 Biomass availability factor is 0.4
Hu_0.6 Biomass availability factor is 0.6
IRR Internal rate of return
55
LCA Life cycle assessment View Article Online

DOI: 10.1039/C8SE00553B
LHV Lower heating value
LLC limited liability company
MBG Moving bed gasifier
MPG Multi-Purpose Gasification process

NPV Net present value
OL A surface lattice oxygen of support
P Pressure
PID Proportional-integral-derivative
Qu Quantile
S1 A Rh atom
S2 A metal cation
SC Steam to carbon ratio
SC Steam to carbon ratio
SGP Shell gasification process
SNG Synthetic natural gas
T Temperature
TCI Total capital investment
TEA Techno-economic analysis
tpd Tonne per day
Wright_5.4 A 5.4 tpd of capacity level
Wright_55 A 55 tpd of capacity level
References
1 V. S. Sikarwar, M. Zhao, P. Clough, J. Yao, X. Zhong, M. Z. Memon, N. Shah, E.
Anthony and P. Fennell, Energy Environ. Sci., 2016, 9, 2927–3304.
2 V. S. Sikarwar, M. Zhao, P. S. Fennell, N. Shah and E. J. Anthony, Progress
Energy Combust. Sci., 2017, 61, 189-248.
3 A. A. Peterson, F. Vogel, R. P. Lachance, M. Fröling, J. M. J. Antal and J. W.
Tester, Energy Environ. Sci., 2008, 1, 32-65.
4 X. Zhao, H. Zhou, V. S. Sikarwar, M. Zhao, A.-H. A. Park, P. S. Fennell, L. Shen
and L.S. Fan, Energy Environ. Sci., 2017, 10, 1885-1910.
5 M. Juraščík, A. Sues and K. J. Ptasinski, Energy Environ. Sci., 2009, 2, 791-801.
56
View Article Online

DOI: 10.1039/C8SE00553B
6 X. Zhang, Green Chem., 2016, 18, 5086-5117.
7 G. Moreels, W. F. J. Evans, J. E. Blamont and A. V. Jones, Energy Environ. Sci.,

2012, 5, 5768-5789.
8 M. Gassner, F. Vogel, G. Heyen and F. Maréchal, Energy Environ. Sci., 2011, 4,
1726-1741.
9 M. Gassner, F. Vogel, G. Heyen and F. Maréchal, Energy Environ. Sci., 2011, 4,
1742-1758.
10 Z. A. B. Z. Alauddin, P. Lahijani, M. Mohammadi and A. R. Mohamed, Renew.
Sust. Energy Rev., 2010, 14, 2852-2862.
11 J. Fermoso, F. Rubiera and D. Chen, Energy Environ. Sci., 2012, 5, 6358-6367.
12 P. Basu, Biomass Gasification and Pyrolysis: Practical Design and Theory,
Elsevier Science, 2010.
13 Z. A. B. Z. Alauddin, P. Lahijani, M. Mohammadi and A. R. Mohamed, Renew.
Sust. Energy Rev., 2010, 14, 2852-2862.
14 Y. Zhang, T. R. Brown, G. Hu and R. C. Brown, Bioresour. Technol., 2013, 127,
358-365.
15 E. Henrich, N. Dahmen and E. Dinjus, Biofuels, Bioprod. Bioref., 2009, 3, 28-41.
16 M. M. Wright, R. C. Brown and A. A. Boateng, Biofuels, Bioprod. Bioref., 2008,
2, 229-238.
17 R. H. Venderbosch and W. Prins, Biofuels, Bioprod. Bioref., 2010, 4, 178-208.
18 Q. Li, Y. Zhang and G. Hu, Bioresour. Technol., 2015, 191, 88-96.
19 P. C. Badger, P. Fransham and J. Richardson, Biomass Bioenerg., 2006, 30,
57
View Article Online

DOI: 10.1039/C8SE00553B
321-325.
20 J. G. Rogers and J. G. Brammer, Biomass Bioenerg., 2009, 33, 1367-1375.

21 N. Dahmen, Energy Sustain. Soc., 2012, 2, 3.
22 M. S. Mettler, D. G. Vlachos and P. J. Dauenhauer, Energy Environ. Sci., 2012,
5, 7797-7809.
23 X. Zhou, W. Li, R. Mabon and L. J. Broadbelt, Energy Environ. Sci., 2018, 11,
1240-1260.
24 M. S. Mettler, S. H. Mushrif, A. D. Paulsen, A. D. Javadekar, D. G. Vlachos and
P. J. Dauenhauer, Energy Environ. Sci., 2012, 5, 5414-5424.
25 M. S. Mettler, A. D. Paulsen, D. G. Vlachos and P. J. Dauenhauer, Energy
Environ. Sci., 2012, 5, 7864-7868.
26 R. Vinu and L. J. Broadbelt, Energy Environ. Sci., 2012, 5, 9808-9826.
27 S. Wang, G. Dai, H. Yang and Z. Luo, Prog. Energy Combust. Sci., 2017, 62,
33-86.
28 A. Anca-Couce, Prog. Energy Combust. Sci., 2016, 53, 41-79.
29 M. Saidi, F. Samimi, D. Karimipourfard, T. Nimmanwudipong, B. C. Gates and
M. R. Rahimpour, Energy Environ. Sci., 2014, 7, 103-129.
30 H. Jahromi and F. A. Agblevor, Energy, 2017, 141, 2186-2195.
31 J. F. Peters, F. Petrakopoulou and J. Dufour, Energy, 2015, 79, 325-336.
32 M. S. Talmadge, R. M. Baldwin, M. J. Biddy, R. L. McCormick, G. T. Beckham,
G. A. Ferguson, S. Czernik, K. A. Magrini-Bair, T. D. Foust, P. D. Metelski, C.
Hetrick and M. R. Nimlos, Green Chem., 2014, 16, 407-453.
58
View Article Online

DOI: 10.1039/C8SE00553B
33 M. Saber, B. Nakhshiniev and K. Yoshikawa, Renew. Sust. Energy Rev., 2016,
58, 918-930.

34 X. Li, G. Chen, C. Liu, W. Ma, B. Yan and J. Zhang, Renew. Sust. Energy Rev.,
2017, 71, 296-308.
35 A. Arregi, M. Amutio, G. Lopez, J. Bilbao and M. Olazar. Energy Convers.

Manage., 2018, 165, 696-719.
36 S. Czernik and A. V. Bridgwater, Energy Fuel., 2004, 18, 590-598.
37 A. H. Zacher, M. V. Olarte, D. M. Santosa, D. C. Elliott and S. B. Jones, Green
Chem., 2014, 16, 491-515.
38 P. Duan and P. E. Savage, Energy Environ. Sci., 2011, 4, 1447-1456.39.
39 C. Hargus, R. Michalsky and A. A. Peterson, Energy Environ. Sci., 2014, 7,
3122-3134.
40 D. Neves, H. Thunman, A. Matos, L. Tarelho and A. Gómez-Barea, Progress in
Energy Combust. Sci., 2011, 37, 611-630.
41 R. G. Graham and D. R. Huffman, in Proceedings of Power Production from
Biomass Ⅱ conference, NewYork, 1997, p. 36.
42 D. S. Scott and P. Jan, Can. J. Chem. Eng., 2010, 62, 404-412.
43 J. Scahill, J. P. Diebold and C. Feik, Removal of Residual Char Fines from
Pyrolysis Vapors by Hot Gas Filtration. In: Bridgwater A.V., Boocock D.G.B.
(eds) Developments in Thermochemical Biomass Conversion. Springer, 1997,
253--256.
44 J. L. Zheng, J. Anal. Appl. Pyrol., 2008, 83, 205-212.
59
View Article Online

DOI: 10.1039/C8SE00553B
45 L. Qiang, X. L. Yang and X. F. Zhu, J. Anal. Appl. Pyrol., 2008, 82, 191-198.
46 X. Miao, Q. Wu and C. Yang, J. Anal. Appl. Pyrol., 2004, 71, 855-863.

47 M. S. W. Yang S.I. , Energy, 2018.
48 Z. M. Farooq MZ, Iqbal S, Ahmed N, Shah SAY, Energy, 2018.
49 V. Stamatov, D. Honnery and J. Soria, Renew. Energy, 2006, 31, 2108-2121.

50 http://www.btgworld.com/nl/rtd/technologies/fast-pyrolysis, (accessed July 31,
2018).
51 J. A. Medrano, M. Oliva, J. Ruiz, L. García and J. Arauzo, Energy, 2011, 36,
2215-2224.
52 S. Xiu and A. Shahbazi, Renew. Sust. Energy Rev., 2012, 16, 4406-4414.
53 L. Zhang, R. Liu, R. Yin and Y. Mei, Renew. Sust. Energy Rev., 2013, 24, 66-72.
54 A. R. K. Gollakota, M. Reddy, M. D. Subramanyam and N. Kishore, Renew. Sust.
Energy Rev., 2016, 58, 1543-1568.
55 S. Kai, E. Kuoppala, L. Fagernäs and A. Oasmaa, Biomass Bioenergy, 1998, 14,
103-113.
56 S. Wang, X. Li, F. Zhang, Q. Cai, Y. Wang and Z. Luo, Int. J. Hydrogen Energy,
2013, 38, 16038-16047.
57 J. Lehto, A. Oasmaa, Y. Solantausta, M. Kytö and D. Chiaramonti, Appl. Energy,
2014, 116, 178-190.
58 P. Feng, L. F. Hao, C. F. Huo, Z. Wang, W. G. Lin and W. L. Song, Energy,
2014, 66, 744-749.
59 H. Abdullah, D. Mourant, C. Z. Li and H. Wu, Energy Fuel., 2010, 24,
60
View Article Online

DOI: 10.1039/C8SE00553B
5669-5676.
60 D. Carpenter, T. L. Westover, S. Czernik and W. Jablonski, Green Chem., 2014,

16, 384-406.
61 L. Leng, H. Li, X. Yuan, W. Zhou and H. Huang, Energy, 2018, 161, 214-232.
62 J. Ábrego, D. Plaza, F. Luño, M. Atienza-Martínez and G. Gea, Energy, 2018,

158, 72-80.
63 S. I. Yang, M. S. Wu and T. C. Hsu, Energy, 2017, 119, 26-36.
64 S. I. Yang, T. C. Hsu and M. S. Wu, Energy, 2016, 115, 458-467.
65 J. L. Zheng and Y. P. Kong, Energy Convers. Manage., 2010, 51, 182-188.
66 X. Yuan, X. Ding, L. Leng, H. Li, J. Shao, Y. Qian, H. Huang, X. Chen and G.
Zeng, Energy, 2018, 154, 110-118.
67 Y. Chhiti, Institut National Polytechnique, Toulouse, 2011.
68 Y. Chhiti, M. Peyrot and S. Salvador, J. Energy Chem, 2013, 22, 701-709.
69 P. L. Walker, F. Rusinko, L. G. Austin, P. W. Selwood and P. B. W. D. D. Eley,
Adv. Catal., 1959, 11, 133--221.
70 J. R. Arthur, Transactions Faraday Soc., 1951, 47, 164-178.
71 C. D. Blasi, Prog. Energy Combust. Sci., 2009, 35, 121-140.
72 C. D. Blasi, Prog. Energy Combust. Sci., 2009, 35, 121-140.
73 M. Barrio, J. Landscape Ecol., 2000, 1, 5-21.
74 X. Zhu, Preparation and application of bio-oil, Chemical industry press, BeiJing,
2013.
75 W. Nabgan, T. A. Tuan Abdullah, R. Mat, B. Nabgan, Y. Gambo, M. Ibrahim, A.
61
View Article Online

DOI: 10.1039/C8SE00553B
Ahmad, A. A. Jalil, S. Triwahyono and I. Saeh, Renew. Sust. Energy Rev., 2017,
79, 347-357.

76 S. Ayalur Chattanathan, S. Adhikari and N. Abdoulmoumine, Renew. Sust.
Energy Rev., 2012, 16, 2366-2372.
77 S. Wang, Q. Cai, F. Zhang, X. Li, Z. Li and Z. Luo, Int. J. Hydrogen Energy,

2014, 39, 18675-18687.
78 Y. Chen, L. Yuan, T. Ye, S. Qiu, X. Zhu, Y. Torimoto, M. Yamamoto and Q. Li,
Int. J. Hydrogen Energy, 2009, 34, 1760-1770.
79 J. Remón, F. Broust, G. Volle, L. García and J. Arauzo, Int. J. Hydrogen Energy,
2015, 40, 5593-5608.
80 P. Y. Sheng, W. W. Chiu, A. Yee, S. J. Morrison and H. Idriss, Catal. Today,
2007, 129, 313-321.
81 V. Fierro, O. Akdim and C. Mirodatos, Green Chem., 2003, 5, 20-24.
82 Y. Yang, J. Ma and F. Wu, Int. J. Hydrogen Energy, 2006, 31, 877-882.
83 E. Y. García and M. A. Laborde, Int. J. Hydrogen Energy, 1991, 16, 307-312.
84 K. Polychronopoulou, C. N. Costa and A. M. Efstathiou, Catal. Today, 2006,
112, 89-93.
85 K. Polychronopoulou, J. L. G. Fierro and A. M. Efstathiou, J. Catal., 2004, 228,
417-432.
86 D. A. Constantinou, J. L. G. Fierro and A. M. Efstathiou, Appl. Catal. B Environ.,
2009, 90, 347-359.
87 J.L. Zheng, Y.H. Zhu, M.Q. Zhu, H.T. Wu and R.C. Sun, Energy, 2018, 142,
62
View Article Online

DOI: 10.1039/C8SE00553B
426-435.
88 J.L. Zheng, M.Q. Zhu, J.L. Wen and R.C. Sun, Bioresour. Technol., 2016, 211,

164-172.
89 R. Venderbosch, L. Van de Beld and W. Prins, in 12th European Conference and
technology Exhibition on biomass for energy, Industry and Climate Protection,

Amsterdam, The Netherlands, 2002, pp. 17-21.
90 D. A. Bell, B. F. Towler and M. Fan, Coal Gasification & Its Applications,
Elsevier Science, 2011.
91 C. Higman and M. V. D. Burgt, Gasification (Second Edition), Elsevier Science,
2008.
92 A. Gómez-Barea and B. Leckner, Prog. Energy Combust. Sci., 2010, 36,
444-509.
93 M. R. Tom Blades, in ISAF XV, San Diego, USA, 2005.
94 S. Heidenreich and P. U. Foscolo, Prog. Energ. Combust. Sci., 2015, 46, 72-95.
95 Y. Zhao, S. Sun, H. Zhou, R. Sun, H. Tian, J. Luan and J. Qian, Fuel Process
Technol., 2010, 91, 910-914.
96 J. J. Hernández, G. Aranda-Almansa and A. Bula, Fuel Process Technol., 2010,
91, 681-692.
97 P. K. Senapati and S. Behera, Bioresour. Technol., 2012, 117, 99-106.
98 D. Wang, S. Czernik, D. Montané, A. M. Mann and E. Chornet, Ind. Eng. Chem.
Res., 1997, 36, 1507-1518.
99 S. Czernik, R. French, A. Calvin Feik and E. Chornet, Ind. Eng. Chem. Res, 2002,
63
View Article Online

DOI: 10.1039/C8SE00553B
41, 4209-4215.
100 K. Jacobson, K. C. Maheria and A. Kumar Dalai, Renew. Sust. Energy Rev.,

2013, 23, 91-106.
101 M. Latifi, F. Berruti and C. Briens, Int. J. Hydrogen Energy, 2015, 40,
5856-5868.
102 M. Latifi, in In: ECI conference, bioenergy II, Rio de Janeiro, Brazil, 2009.
103 M. Latifi, Gasification of Bio-oils to Syngas in Fluidized Bed Reactors. Edited
by London, The University of Western Ontario, 2012.
104 M. H. Ghezelchi and H. Wu, Fuel, 2018, 220, 575-585.
105 T. P. Vispute and G. W. Huber, Green Chem., 2009, 11, 1433-1445.
106 S. Panigrahi, S. T. Chaudhari, N. N. B. And and A. K. Dalai, Energy Fuel.,
2002, 16, 1392-1397.
107 D. Wang, A. Stefan Czernik and E. Chornet, Energy Fuel., 1998, 12, 19-24.
108 H. Xie, Q. Yu, Z. Zuo, Z. Han, X. Yao and Q. Qin, Int. J. Hydrogen Energy,
2016, 41, 2345-2353.
109 L. W. Nicholas Creager, Song-Charng Kong, Robert Brown, In Tcbiomass
2013 Conference, Chicago, 2013.
110 J. R. Marda, J. Dibenedetto, S. Mckibben, R. J. Evans, S. Czernik, R. J. French
and A. M. Dean, Int. J. Hydrogen Energy, 2009, 34, 8519-8534.
111 H. Guo, F. Peng, H. Zhang, L. Xiong, S. Li, C. Wang, B. Wang, X. Chen and Y.
Chen, Int. J. Hydrogen Energy, 2014, 39, 9200-9211.
112 G. V. Rossum, S. R. A. Kersten and W. P. M. V. Swaaij, Ind. Eng. Chem. Res.,
64
View Article Online

DOI: 10.1039/C8SE00553B
2007, 46, 249-252.
113 P. Feng, W. Lin, P. A. Jensen, W. Song, L. Hao, K. Raffelt and K.

Dam-Johansen, Energy, 2016, 111, 793-802.
114 A. G. Chakinala, J. K. Chinthaginjala, K. Seshan, W. P. M. V. Swaaij, S. R. A.
Kersten and D. W. F. Brilman, Catal. Today, 2012, 195, 83-92.

115 C. Tian, B. Li, Z. Liu, Y. Zhang and H. Lu, Renew. Sust. Energy Rev., 2014, 38,
933-950.
116 E. V. Steen and M. Claeys, Chem. Eng. Technol., 2008, 31, 655-666.
117 M. Ding, Y. Yang, Y. Li, T. Wang, L. Ma and C. Wu, Appl. Energy, 2013, 112,
1241-1246.
118 T. P. Vispute and G. W. Huber, Int. Sugar J., 2008, 110, 138-149.
119 T. Chen, C. Wu and R. Liu, Bioresour. Technol., 2011, 102, 9236-9240.
120 P. M. Lv, Z. H. Xiong, J. Chang, C. Z. Wu, Y. Chen and J. X. Zhu, Bioresour.
Technol., 2004, 95, 95-101.
121 Y. N. Chun, S. C. Kim and K. Yoshikawa, Appl. Energy, 2011, 88, 1105-1112.
122 A. Otto, T. Grube, S. Schiebahn and D. Stolten, Energy Environ. Sci., 2015, 8,
3283-3297.
123 X. Huang, Q. Shen, J. Liu, N. Yang and G. Zhao, Energy Environ. Sci.,2016, 9,
3161-3171.
124 D. W. Keith, G. Holmes, D. St. Angelo and K. Heidel, Joule, 2018.
125 J. M. Spurgeon and B. Kumar, Energy Environ. Sci., 2018, 11, 1536-1551.
126 Gurudayal, J. Bullock, D. F. Srankó, C. M. Towle, Y. Lum, M. Hettick, M. C.
65
View Article Online
Scott, A. Javey and J. Ager, Energy Environ. Sci., 2017, 10, 2222-2230.DOI: 10.1039/C8SE00553B
127 Y. J. Jang, J.W. Jang, J. Lee, J. H. Kim, H. Kumagai, J. Lee, T. Minegishi, J.

Kubota, K. Domen and J. S. Lee, Energy Environ. Sci., 2015, 8, 3597-3604.
128 M. Alvarez-Guerra, J. Albo, E. Alvarez-Guerra and A. Irabien, Energy Environ.
Sci., 2015, 8, 2574-2599.

129 M. S. Xie, B. Y. Xia, Y. Li, Y. Yan, Y. Yang, Q. Sun, S. H. Chan, A. Fisher
and X. Wang, Energy Environ. Sci., 2016, 9, 1687-1695.
130 A. v. Heiningen, in International Conference on Biomass Energy Technologies,
Guangzhou, 2008.
131 C. A. Finch, Ullmann's Encyclopedia of Industrial Chemistry 5th Edn, Wiley
InterScience, 2010.
132 J. Gil, M. P. Aznar, M. A. Caballero, E. Francés and J. Corella, Energy Fuel.,
1997, 11, 1109-1118.
133 A. Olivares, M. P. Aznar, M. A. Caballero, J. Gil, A. Eva Francés and J.
Corella†, Ind. Eng. Chem. Res., 1997, 36, 5220-5226.
134 S. Cheah, W. S. Jablonski, J. L. Olstad, D. L. Carpenter, K. D. Barthelemy, D. J.
Robichaud, J. C. Andrews, S. K. Black, M. D. Oddo and T. L. Westover, Green
Chem., 2016, 18, 6291-6304.
135 P. Azadi, G. Brownbridge, S. Mosbach, O. Inderwildi and M. Kraft, Green
Chem., 2015, 17, 1793-1801.
136 G. Kumar, S. Shobana, W.H. Chen, Q.V. Bach, S.H. Kim, A. E. Atabani and
J.-S. Chang, Green Chem., 2017, 19, 44-67.
66
View Article Online
137 T. M. C. Hoang, E. R. H. van Eck, W. P. Bula, J. G. E. Gardeniers, L. DOI: 10.1039/C8SE00553B

Lefferts
and K. Seshan, Green Chem., 2015, 17, 959-972.

138 M. Asadullah, T. Miyazawa, S.I. Ito, K. Kunimori, M. Yamada and K.
Tomishige, Green Chem., 2002, 4, 385-389.
139 N. Olson, in NH3 Fuel Conference 2017, Minneapolis, USA, 2017.

140 P. V. Hans Vrijenhoef, in NH3 Fuel Conference 2017, Minneapolis, USA, 2017.
141 H. I. I. D. Greg Vezina, Yusuf Bicer, in NH3 Fuel Conference 2017,
Minneapolis, USA, 2017.
142 K. D. K. A. S. Akihiro Hayakawa, Ekenechukwu C. Okafor, Taku Kudo,
Osamu Kurata, Norihiko Iki, Hideaki Kobayashi, in NH3 Fuel Conference 2016,
Los Angeles, USA, 2016.
143 S. K. Shintaro Ito, Tsukasa Saito, Toshiro Fujimori, Hideaki Kobayashi, in NH3
Fuel Conference 2016, Los Angeles, USA, 2016.
144 G. Gideon S., E. Michael, D. Ayillath Kutteri, E. Oren, S. Gennady E. and M.
Bar, in NH3 Fuel Conference 2017, Minneapolis, USA, 2017.
145 W. C. Leighty, in NH3 Fuel Conference 2017, Minneapolis, USA, 2017.
146 S. Ian Wilkinson, in NH3 Fuel Conference 2017, Minneapolis, USA, 2017.
147 G. Soloveichik, in NH3 Fuel Conference 2016, Los Angeles, USA, 2016.
148 A. Lavine, in NH3 Fuel Conference 2016, Los Angeles, USA, 2016.
149 G. Y. Chen, J. G. Yao, H. J. Yang, B. B. Yan and H. Chen, Bioresour. Technol.,
2015, 179, 323-330.
150 A. A. P. Susastriawan, H. Saptoadi and Purnomo, Renew. Sust. Energy Rev.,
67
View Article Online

DOI: 10.1039/C8SE00553B
2017, 76, 989-1003.
151 S. K. Sansaniwal, K. Pal, M. A. Rosen and S. K. Tyagi, Renew. Sust. Energy

Rev., 2017, 72, 363-384.
152 S. S. Thanapal, K. Annamalai, J. M. Sweeten and G. Gordillo, Appl. Energy,
2012, 97, 525-531.

153 C. M. Benedict, Wobbe Index, Phon, 2011.
154 H. Knoef, Handbook biomass gasification, BTG Biomass Technology Group
BV, The Netherlands 2012.
155 S. Youngil, Y. Sangjun, K. Yongku and L. Jaegoo, Biomass Bioenergy, 2011,
35, 4215-4220.
156 M. Seggiani, S. Vitolo, M. Puccini and A. Bellini, Fuel, 2012, 93, 486-491.
157 E. R. Widjaya, G. Chen, L. Bowtell and C. Hills, Renew. Sustain. Energy Rev.,
2018, 89, 184-193.
158 M. L. Valderrama Rios, A. M. González, E. E. S. Lora and O. A. Almazán del
Olmo, Biomass Bioenergy, 2018, 108, 345-370.
159 Y. Wang, K. Yoshikawa, T. Namioka and Y. Hashimoto, Fuel Process.
Technol., 2007, 88, 243-250.
160 T. Phuphuakrat, T. Namioka and K. Yoshikawa, Appl. Energy, 2010, 87,
2203-2211.
161 L. García, M. L. Salvador, A. J. Arauzo and R. Bilbao, Energy Fuel., 1999, 13,
851--859.
162 T. Hou, L. Yuan, T. Ye, L. Gong, J. Tu, M. Yamamoto, Y. Torimoto and Q. Li,
68
View Article Online

DOI: 10.1039/C8SE00553B
Int. J. Hydrogen Energy, 2009, 34, 9095-9107.
163 K. Takanabe, K. I. Aika, K. Seshan and L. Lefferts, Chem. Eng. J., 2006, 120,

133-137.
164 S. Authayanun, D. Saebea, Y. Patcharavorachot, S. Assabumrungrat and A.
Arpornwichanop, Int. J. Hydrogen Energy, 2017, 42, 1977-1988.

165 H. Xie, Q. Yu, X. Yao, W. Duan, Z. Zuo and Q. Qin, J. Energy Chem., 2015,
24, 299-308.
166 N. Jensen, J. Werling, H. Carlsen and U. Henriksen, in Proceedings of 12th
European Biomass Conference, ETA-Florence & WIP-Munich, London, 2002.
167 Y. Richardson, J. Blin and A. Julbe, Prog. Energy Combust. Sci., 2012, 38,
765-781.
168 T. Damartzis and A. Zabaniotou, Renew. Sustain. Energy Rev., 2011, 15,
366-378.
169 E. G. Pereira, J. N. D. Silva, J. L. D. Oliveira and C. S. Machado, Renew.
Sustain. Energy Rev., 2012, 16, 4753-4762.
170 Y. Cao, Y. Wang, J. T. Riley and W. P. Pan, Fuel Process. Technol., 2006, 87,
343-353.
171 Y. D. Kim, C. W. Yang, B. J. Kim, K. S. Kim, J. W. Lee, H. M. Ji, W. Yang, T.
U. Yu and U. D. Lee, Appl. Energy, 2013, 112, 414-420.
172 J. Watson, Y. Zhang, B. Si, W.T. Chen and R. de Souza, Renew. Sust. Energy
Rev., 2018, 83, 1-17.
173 J. Amaro, A. Z. Mendiburu and I. Ávila, Energy, 2018, 152, 371-382.
69
View Article Online

DOI: 10.1039/C8SE00553B
174 Y. N. Zhang, T. R. Brown, G. P. Hu and R. C. Brown, Biomass Bioenergy,
2013, 51, 99-108.

175 A. C. C. Chang, H. F. Chang, F. J. Lin, K. H. Lin and C. H. Chen, Int. J.
Hydrogen Energy, 2011, 36, 14252-14260.
176 T. Hirai, N. Ikenaga, A. Takanori Miyake and T. Suzuki, Energy Fuel., 2005,
19, 1761-1762.
177 S. Adhikari, S. Fernando and A. Haryanto, Catal. Today, 2007, 129, 355-364.
178 K. Takanabe, K. I. Aika, K. Inazu, T. Baba, K. Seshan and L. Lefferts, J. Catal.,
2006, 243, 263-269.
179 S. Adhikari, S. D. Fernando and A. Haryanto, Renew. Energy, 2008, 33,
1097-1100.
180 A. Ochoa, B. Aramburu, B. Valle, D. E. Resasco, J. Bilbao, A. G. Gayubo and
P. Castaño, Green Chem., 2017, 19, 4315-4333.
181 N. V. D. Assen and A. Bardow, Green Chem., 2014, 16, 3272-3280.
182 M. J. Eckelman, Green Chem., 2016, 18, 3257-3264.
183 H. H. Khoo, W. L. Ee and V. Isoni, Green Chem., 2016, 18, 1912-1922.
184 D. Kralisch, D. Ott and D. Gericke, Green Chem., 2015, 46, 123-145.
185 G. Wernet, S. Papadokonstantakis, S. Hellweg and K. Hungerbühler, Green
Chem., 2009, 11, 1826-1831.
186 J.L. Zheng, Y.H. Zhu, M.Q. Zhu, G.T. Sun and R.C. Sun, Green Chem., 2018,
20, 3287-3301.
187 M. Ringer, V. Putsche and J. Scahill, Large-Scale Pyrolysis Oil Production: A
70
View Article Online

DOI: 10.1039/C8SE00553B
Technology Assessment and Economic Analysis, Technical Report
NREL/TP-510-37779, National Renewable Energy Laboratory: Golden, CO,

2006.
188 M. L. Cottam and A. V. Bridgwater, Biomass Bioenergy, 1994, 7, 267-273.
189 H. Mullaney, University of New Hampshire, Durham, Technical,

Environmental and Economic Feasibility of Bio-oil in New Hampshire's North
Country. Edited by Durham, University of New Hampshire, 2002.
190 T. M. H. Dabros, M. Z. Stummann, M. Høj, P. A. Jensen, J.D. Grunwaldt, J.
Gabrielsen, P. M. Mortensen and A. D. Jensen, Prog. Energy Combust. Sci.,
2018, 68, 268-309.
191 D. Chen, J. Zhou, Q. Zhang and X. Zhu, Renew. Sust. Energy Rev., 2014, 40,
69-79.
192 J. D. Nixon, P. K. Dey, P. A. Davies, S. Sagi and R. F. Berry, Energy, 2014, 68,
262-271.
193 T. Pootakham and A. Kumar, Bioresour. Technol., 2010, 101, 7148-7154.
194 Z. Yang, A. Kumar and R. L. Huhnke, Renew. Sust. Energy Rev., 2015, 50,
859-870.
195 A. Mirkouei, K. R. Haapala, J. Sessions and G. S. Murthy, Renew. Sust. Energy
Rev., 2017, 67, 15-35.
196 K. Raffelt, E. Henrich, A. Koegel, R. Stahl, J. Steinhardt and F. Weirich, Appl.
Biochem. Biotech., 2006, 129, 153-164.
197 N. Dahmen, E. Henrich, E. Dinjus and F. Weirich, Energy Sustain. Soc., 2012,
71
View Article Online

DOI: 10.1039/C8SE00553B
2, 1-44.
198 Q. Li and G. P. Hu, Energy, 2014, 74, 576-584.

199 K. Braimakis, K. Atsonios, K. D. Panopoulos, S. Karellas and E. Kakaras,
Renew. Sust. Energy Rev., 2014, 35, 57-72.
200 M. Wright and R. C. Brown, Biofuels, Bioprod. Bioref., 2010, 1, 191-200.

201 G. Towler and R. K. Sinnott, Chemical engineering design: principles, practice
and economics of plant and process design, Elsevier, 2012.
202 K. A. Kobe, Plant Design and Economics for Chemical Engineers,
McGraw-Hill, 1991.
203 S. Sarkar and A. Kumar, Bioresour. Technol., 2010, 101, 7350-7361.
72
View Article Online
DOI: 10.1039/C8SE00553B
Figure caption

Fig. 1. The overall conversion chain of biomass to Fischer-Tropsch liquids via bio-oil
gasification
Fig. 2. Typical air-blast atomizers which are suitable for light fuel oils
Fig. 3. (a) A typical bio-oil droplet diameter distribution.64 (b) Temperature effect on
the viscosity of bio-oil (BO), light fuel oil for heating (LFO heating) and heavy
fuel oil 180 cSt (HFO 180).56 (c) Typical air-blast atomizers suitable for light
fuel oils.56
Fig. 4. Entrain flow gasifiers with (a) a quench chamber (b) a syngas cooler.67, 87-89
Fig. 5. (a) Gas concentration distributions; (b) H2/CO and CO/CO2 value distributions;
(c) The lower heating value and the Wobbe Index distributions.18, 67, 87, 88, 99, 101,
108-114
Fig. 6. A comparison of H2 and CO content in gas produced from different
feedstocks.88, 91, 93, 109, 130-132
Fig. 7. A schematic diagram of biomass conversion into liquid products following the
two-step approach
Fig. 8. (a) Optimum operating costs, (b) Optimum plant annual capacity, and (c)
Optimum biomass input of different kinds of biofuel processes. 16, 199
Fig. 9. Operating cost breakdown (fraction) for different BTL2 process researches.15,
197, 199
DOI: 10.1039/C8SE00553B
View Article Online

Page 74 of 86
Page 75 of 86
Fig. 2.
DOI: 10.1039/C8SE00553B
View Article Online

Fig. 3.
(a)
(c)
(b)
DOI: 10.1039/C8SE00553B
View Article Online

Page 76 of 86
View Article Online
DOI: 10.1039/C8SE00553B

Fuel oil Fuel oil
HP steam
Gasifying agent Gasifying agent

Gasifier Gasifier
Gasifying Gasifying
chamber chamber
Quench water
Raw gas
Black water
Quench Raw gas
chamber
Water
(a) (b)
Fig. 4.
Fig. 5.
DOI: 10.1039/C8SE00553B
View Article Online

Page 78 of 86
Page 79 of 86
Fig. 6.
DOI: 10.1039/C8SE00553B
View Article Online

Fig. 7.
DOI: 10.1039/C8SE00553B
View Article Online

Page 80 of 86
Page 81 of 86
Fig. 8.
DOI: 10.1039/C8SE00553B
View Article Online

Fig. 9.
DOI: 10.1039/C8SE00553B
View Article Online

Page 82 of 86
Published on 04 March 2019. Downloaded by Drexel University on 3/23/2019 11:28:0
Table 1 Basic properties of typical bio-oils

Pyrolysis reactor C H O Water Ash Density Viscosity LHV
Ref Feedstock pH
Pyrolysis type (wt%) (wt%) (wt%) (wt%) (wt%) (kg/m3) (40℃) (MJ/kg)
Rotating cone reactor
50 Oak 46 7 47 25 2.9 0.02 1170 13 (cSt) 16
Fast
Circulating fluidized bed 17
41 Pine 56.4 6.2 37.1 22 2.5 0.1 1180 45 (cP)
Fast (HHV)
Bubbling fluidized bed 9.72 (cSt) 17.6
42 White spruce 54 6.8 39.2 22.4 2.1 0.0034 1220
Fast (50℃) (HHV)
Ablative reactor
43 Poplar 49.0 6.0 44.1 19.6 / 0.98 / 46.5 (cSt) 18.2
Fast
Bubbling fluidized bed 138 (cSt)
44 Maize stalk 44.3 6.3 47.5 22.5 3.2 / 1220 19.6
Fast (20℃)
Bubbling fluidized bed 16.5
45 Rice husk 38.7 5.4 / 28 3.2 0.25 1140 13.2 (cSt)
Fast (HHV)
Bubbling fluidized bed
46 Microalgae 61.52 8.50 20.19 / / / 1160 100 (cP) 29
Fast
Fixed bed reactor 7600 (cP)
47 Pinewood 52.1 6.6 / 8.1 3 / / 17.12
Slow (20℃)
Fixed bed reactor 23.3
48 Wheat straw 58 8.55 32.84 / 3.4 / 1022 9.92 (cP)
Slow (HHV)
Fixed bed reactor 100 (cP) 26.1
49 Red gum 63.7 6.9 29.3 7.7 / 0.05 1160
Slow (20℃) (HHV)
Representative values 1250 25-1000 16-19
17, 36 Wood 55-65 5-7 35-40 15-30 2.8-3.8 0.01-0.30 -
Fast or Slow 10500 (cP) (HHV)
Table 2 Important reactions in bio-oil gasification 1, 12, 66 View Article Online

DOI: 10.1039/C8SE00553B
Reaction type Reaction

Carbon reactions
R1 (Boudouard) C + CO2 ↔ 2CO + 172kJ/mol

R2 (Water-gas) C + H2O ↔ CO + H2 + 131kJ/mol
R3 (Hydrogasification) C + 2H2 ↔ CH4 - 74.8kJ/mol
R4 C + 0.5O2 → CO - 111kJ/mol
Oxidation reactions
R5 C + O2 → CO2 - 394kJ/mol
R6 CO + 0.5O2 → CO2 - 284kJ/mol
R7 CH4 + 2O2 ↔ CO2 + 2H2O - 803kJ/mol

R8 H2 + 0.5O2 → H2O - 242kJ/mol
Shift reaction
R9 CO + H2O(g) ↔ CO2 + H2 - 41.2kJ/mol
Methanation reactions
R10 2CO + 2H2 → CH4 + CO2 - 247kJ/mol
Steam-reforming reactions
R11 CH4 + H2O → CO + 3H2 + 206kJ/mol
R12 CnHmOk + (n - k) H2O → nCO + (n + m/2 - k) H2
Table 3 Reaction mechanism for steam reforming of representative compounds in bio-oil

Acetic acid 76-78 Ethanol 79-81 Phenol 83-85
CH3COOH + 2H2O ↔ 2CO2 + 4H2 C2H5OH ↔ CH3CHO + H2 H2O(g) + S2 + OL → HO-S2 + H-OL
CO + H2O ↔ CO2 + H2 CH3CHO ↔ CO + CH4 HO-S2 + S1 → HO-S1 + S2
CH3COOH ↔ 2CO + 2H2 CH4 + H2O ↔ CO + 3H2 H-OL + S1 → HO-S1 + OL
CH3COOH ↔ CH4 + 2CO2 C2H5OH ↔ C2H4 + H2O xHC-S1 + DO-S1 → x-1HC-S1 + HDO(g) + S1
2CH3COOH ↔ (CH3)2CO + H2O + CO2 C2H4 ↔ 2C + 2H2 x-1HC-S1 + DO-S1 → …… → CO-S1 + HD(g) + DO-S1
CO + 3H2 ↔ CH4 + H2O C2H4 + 2H2O ↔ 2CO + 2H2 CO-S1 + DO-S1 → CO2(g) + D-S1 + S1
CO2 + 4H2 ↔ CH4 + 2H2O 2H-S1 ↔ H2(g) +2S1
2CO ↔ C + CO2
Table 4 Basic properties of selected gas produced via bio-oil gasification

Gasifying T P ER SC H2 CO CH4 CO2 N2 CO/C Tar LHV
Ref. Gasifiers H2/CO CCE CGE
agents (℃) (atm) (kg/kg) (mol/mol) (vol%) (vol%) (vol%) (vol%) (vol%) O2 (mg/Nm ) (MJ/Nm3)
3
88 Air EFG 1000 1 0.3 0.40 25.0 22.3 3.4 5.6 41.6 1.12 3.96 1300 8.00 / 74.7%
88 Air-Oxyge EFG 1000 1 0.3 0.40 30.1 28.1 5.2 12.5 20.3 1.07 2.25 820 11.10 / 73.2%
88 n
Oxygen EFG 1000 1 0.3 0.40 37.3 32.5 6.7 18.3 / 1.15 1.78 490 13.80 / 74.9%
87 Air-steam EFG 1000 1 0.4 4.36 30.6 15.3 0.6 20.6 32.2 2.00 0.74 52 8.26 93% 90%
109 Oxygen EFG 850 1 0.25 0.36 23.4 44.6 8 21.2 / 0.52 2.10 / 12.50 / /
109 Oxygen EFG 850 6.8 0.25 0.36 31.3 40.6 9.2 18.2 / 0.77 2.23 / 12.10 / /
110 Oxygen EFG 725 1 0.27 0.023 48.3 42.6 5.3 3.8 / 1.13 11.20 / 12.48 80.0% /
111 Air-Steam FIG 1100 1 0.05 0.88 47.3 34.2 0.8 7.9 9.8 1.40 4.3 / 9.70 95.3% 96%
19 Oxygen EFG 875 27.6 0.25 0.45 21.3 40.0 7.50 25.0 / 0.50 1.6 / 13.90 / /
67 Steam EFG 1200 1 / 7.39 55.3 16.0 4.7 22.4 / 3.45 0.71 / 10.60 / /
108 Steam (c) FIG 800 1 / 34.6 75.3 2.9 0.27 20.3 / 25.6 0.14 / 9.40 48.9% /
99 Steam (c) FLG 850 1 / 7 62.0 7.5 2.5 26.8 / 8.30 0.28 / 9.30 94.7% /
112 Steam FLG 790 1 / 1.9 26.8 44.7 15.6 5.6 / 0.60 8.00 2600 18.75 65% /
112 Steam (c) FLG 805 1 / 1.5 62.6 23.9 0.0 11.9 / 2.61 2.00 200 9.80 85% /
101 Steam FLG 800 1 / 2.0 52.2 32.4 4.8 9.6 / 1.60 3.38 / 12.07 59% /
113 Steam EFG 1300 1 / 5.0 55.44 18.97 3.1 22.49 / 2.92 0.84 / 10.70 92.4% /
114 Steam Autoclav 500 296 / 3.0 9.00 25.71 21.99 38.49 / 0.35 0.67 / 15.29 31.9% /
e
114 Steam (c) Autoclav 500 296 / 3.0 30.8 4.7 13.5 43.7 / 6.5 0.11 / 13.34 50.5% /
e

Bio Oil PDF

Uploaded by

Copyright:

Available Formats

You might also like

Bio Oil PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Bio Oil PDF

Uploaded by

Copyright:

Available Formats

View Article Online

Sustainable accepted for publication.

acceptance, before technical editing, formatting and proof reading.

You can find more information about Accepted Manuscripts in the

Please note that technical editing may introduce minor changes

in our author and reviewer resource centre, still apply. In no

View Article Online

A review of gasification of bio-oil for gas production DOI: 10.1039/C8SE00553B

Sustainable Energy & Fuels Accepted Manuscript

a College of Forestry, Northwest A&F University, Yangling, Shaanxi 712100, China

b College of Mechanical and Electronic Engineering, Northwest A&F University,

Yangling 712100, China.

c Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University,

*Corresponding authors. Address: Northwest A&F University, 712100, Yangling,

China. Tel.: +86-029-87092269; Fax: +86-029-87092269.

E-mail address: zmqsx@nwsuaf.edu.cn (M. Q. Zhu).

View Article Online

The commercial production of advanced fuels based on bio-oil gasification could

Sustainable Energy & Fuels Accepted Manuscript

implementation of this biomass technology. So far there has no specialized review of

comprehensive review of gasification of bio-oil for gas production is presented in this

paper. The background and significance of bio-oil research, the characteristics of

outlook is also delivered. Particular emphasis is placed to on the discussion regarding

experience accumulated in the area of petroleum refining; (2) practical demonstration

development of mathematical models for bio-oil gasification systems; and (4)

development of suitable catalysts and profoundly understand the catalysts deactivation

mechanism at different stages for steam gasification of bio-oil.

View Article Online

Sustainable Energy & Fuels Accepted Manuscript

simplicity.1-6 A noteworthy feature of this thermochemical technology is that it must

of megawatts of power at most because the quantity of biomass is not concentrated at

a site as fossil fuels are, and large-scale implementation of biomass gasification

technologies will seriously aggravate biomass delivery expenses.12, 13 Fuels, including

Since biomass gasification must be done on a small-scale and a local level to

eliminate the transportation cost, the economic feasibility of this technology

from biomass to biofuels, including biomass gasification technologies.14

View Article Online

achieved by distributed fast pyrolysis of biomass to bio-oil for subsequent production

Sustainable Energy & Fuels Accepted Manuscript

produced economically at small scales matching the size of cost-effective biomass

dimethyl ether, ethanol and higher alcohols. In the above-mentioned overall

conversion chain, which is shown in Fig. 1, fast pyrolysis of biomass to bio-oil is at

early stage of commercialization with companies such as Biomass Technology Group

research challenges.22-28 A 2 tones/hr fast pyrolysis plant has been designed,

Youngstown, Ohio. Deliveries began in May of 2016. Catalytic conversion of the

syngas to motor fuels, such as Fisher-Tropsch synthesis, is a well-known and highly

practical process. Being petroleum-poor but coal-rich, Germany used the

View Article Online

Fischer-Tropsch process during World War II to produce alternativeDOI:fuels.

Fischer-Tropsch production accounted for an estimated 9% of German war production

Sustainable Energy & Fuels Accepted Manuscript

Fischer-Tropsch technology are in a series of plants operated by Sasol in South Africa,

feedstocks and produces a variety of synthetic petroleum products, including most of

to the syngas to motor-fuels. However, bio-oil gasification is still at the experimental

gasification for syngas generation in the overall conversion chain.

In comparison with solid biomass gasification, bio-oil gasification is a relatively

new and promising concept of thermochemical conversion technology. Moreover,

compared to catalytic hydrodeoxygenation or catalytic cracking of bio-oil for the