Biomass and Bioenergy 108 (2018) 345–370

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Biomass and Bioenergy

journal homepage: www.elsevier.com/locate/biombioe

Review

Reduction of tar generated during biomass gasification: A review T

a,∗ b b
Martha Lucia Valderrama Rios , Aldemar Martínez González , Electo Eduardo Silva Lora ,
Oscar Agustin Almazán del Olmoc
a
NEST–Excellence Group in Thermal Power and Distributed Generation, Institute of Energy Engineering, Federal University of Itajubá, Av. BPS 1303, Itajubá, MG, CEP:
37500-903, Brazil
b
NEST–Excellence Group in Thermal Power and Distributed Generation, Institute of Mechanical Engineering, Federal University of Itajubá, Av. BPS 1303, Itajubá, MG,
CEP: 37500-903, Brazil
c
ICIDCA – Instituto Cubano de Investigaciones de los Derivados de la Caña de Azúcar, Via Blanca y Carretera Central 804, San Miguel Del Padrón, A.P. 4036, La Habana,
Cuba

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

Keywords: One of the main problems that happen during biomass gasification is tar formation, which could make this
Biomass gasification technology unsuccessfully from a commercial point of view. Tar content present in syngas defines its application,
Tar formation considering that limits - according to desired application - can be very demanding. There are two ways to
Tar conversion overcome this problem: by optimizing gasification operation conditions and removal of tar from gas through in-
Catalytic cracking
situ (primary methods) or post-gasification (secondary methods) treatments. This way, multiple technologies
Tar cleaning systems
have been developed considering the balance between efficiency and economy of the process, besides being
(ecofriendly) environmentally acceptable. Some aspects related to tar formation, laboratory and industrial
methods and technologies for its reduction-removal, as well as research and development in this area are re-
viewed and evaluated in this paper.

1. Introduction In general, several options are available for tar reduction, which can
be divided into two groups: (1) tar reduction in situ, which avoids
At a time when mankind is facing to become a victim of its genius, (depletes) tar formation and (2) post-gasification reduction, which re-
and is not being able to get rid of its own residues, biomass is becoming moves tar from the product gas. In-situ reduction is achieved through
an ideal option to supply renewable and sustainable resources. an adequate control of process operation and use of additives/catalysts
Compared with fossil fuels, biomass has not a net CO2 emission because during operation, thus tar generation inside gasifier is decreased (lim-
it consumes atmospheric CO2 during its growth through photosynthesis, ited); when this process is performed in gasifier, quality of product gas
and therefore, emissions generated during its thermal conversion can be increases. Post-gasification reduction, on the other hand, does not in-
considered neutral [1,2]. Thus, it is observed that growing interest in terfere with process in the reactor; tar can be removed through physical
fossil fuel substitution and reduction of greenhouse gases in recent processes using cyclones, cooling towers/wash columns, electrostatic
decades, has promoted development a great number of research works precipitators among others, or can be chemically treated by thermal
about biomass use in energy conversion processes, of which gasification and catalytic processes, and partial oxidation. Sometimes it may not be
is a remarkable one [3,4]. possible to remove tar with the desired efficiency and maintaining the
One of the main problems in biomass gasification, whether it is used quality of product gas unchanged; in such cases, a combination of in-
for energy purposes or to produce a synthesis gas (syngas), is the issue situ and post-gasification reduction is more effective [6–9]. In this re-
of dealing with removal of tar formed during pyrolysis stage [5]. Pro- gard, this work presents a review on the different methods used for
duct gas typically leaves the gasifier along with a mist constituted by product gas cleaning obtained from biomass gasification and a broad
different tars components released in the form of aerosol, which can picture of the state-of-the-art of it.
condense and form sticky deposits by quenching downstream when This paper provides a comprehensive overview of definition, che-
they contact cold points of the gasification system. These deposits can mical composition and different but complementary tar classification
further evolve in other more complex molecular arrangements of tar by systems, as well as some of the possible mechanism and pathways of
polymerization, increasing the difficulty for its treatment. both tar formation and tar destruction by thermal cracking and

∗
Corresponding author.
E-mail address: marthalu80@gmail.com (M.L. Valderrama Rios).

https://doi.org/10.1016/j.biombioe.2017.12.002
Received 17 July 2017; Received in revised form 19 November 2017; Accepted 4 December 2017
0961-9534/ © 2017 Elsevier Ltd. All rights reserved.
M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

catalytic cracking, which has been proposed in literature. Likewise, low temperatures to generate liquid tars. Oxygen from air reacts with
different methods for destruction and tar removal have been discussed, present combustible substances (pyrolysis gases, produced tars and
including some primary tar reduction methods based on operational char) totally or partially oxidizing them, forming CO2 and steam. Hy-
conditions and gasifier design. In addition, this paper reviews the main drogen present in biomass is also oxidized generating water. As a
tar removal systems used in biomass gasification industrial plants consequence of oxidation reactions (exothermic reactions) process
around the world. temperature increases and reduction reactions (endothermic reactions)
are favored, allowing char gasification and obtaining a gas rich in H2,
CO, CH4, which leaves from the bottom of reactor [11].
2. Gasification of biomass On the other hand, when gasification process is carried out in a fixed
bed updraft gasifier, biomass is fed from the top and gasification agents
Gasification is the process of thermochemical conversion of a solid could be supplied from the reactor side. Gases produced leave from the
fuel into a mixture of combustible gases, through partial oxidation and gasifier top, consequently the reaction regions are different compared
high temperatures typically in the range of 800–1,000 °C, mainly when with downdraft gasifier as previously described, where thermal energy
air/oxygen is used as gasification agent [10]; nevertheless, biomass required for biomass drying is supplied by the total and partial com-
gasification can be carried out in presence of steam taking place en- bustion reaction as shown in Fig. 1, while in an updraft gasifier a part of
dothermic reactions (steam gasification) which encourage a producer pyrolysis gases are burnt in order to provide the thermal energy needed
gas with high H2/CO ratio as well as remarkable heating value, but with for drying process.
high energy requirements that must be supplied by external source, Both updraft and downdraft gasifier reach high gasification tem-
which is a drawback. For this reason, a steam/oxygen mixture is re- peratures (1,200–1,400 °C) and significant hot efficiencies (85–95%),
commended for biomass gasification in order to ensure autothermal nevertheless the mass and heat transfer along of reactor is very poor,
process. which makes it difficult to achieve uniform distribution of temperature
Thermochemical conversion of carbonaceous material contained in and gas composition in the gasifier cross section, so, undesirable hot
biomass, generating a mixture of non-condensable gases such as carbon spots are formed. When fluidized bed reactor (bubbling or circulating)
monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen is used for biomass gasification process, the mass and heat transfer is
(H2), volatile organic compounds (VOCs), tar, water vapor, H2S, as well improved due to suitable mixing between biomass and bed material
as solid residues, char (solid waste with high carbon content) and traces particles, therefore a homogeneous temperature distribution on both
of HCN, NH3 and HCl. Specific fractions of different species obtained axial and radial direction in the gasifier are expected, giving a higher
depend on the gasifier type (fixed bed and fluidized bed), process gas yield and higher carbon conversion than a fixed bed gasifier.
conditions and gasification agents used during gasification process (air, However, performance of gasification process in fluidized bed system is
steam, oxygen and/or mixtures between them). limited by ash melting temperature; therefore, if gasification tempera-
Biomass gasification involves a great number of complex and closely ture increases, a particle agglomeration could be generated, and a bed
interconnected thermochemical processes. Fig. 1 shows the stages ty- collapse could occur, so, the use of additives (CaO, MgO) to control the
pically found in gasification process whit air as gasification agent in a alkaline species responsible to bed agglomeration and a gasification
downdraft gasifier, this scheme begins with biomass drying through its temperature lower than ash melting temperature in fluidized bed ga-
heating until reaching 150 °C, where humidity is converted into steam. sifier are recommended.
Later, thermal decomposition of dry biomass takes place in absence of The potential mechanisms of biomass gasification and tar reforming
oxygen or air and their volatile material is vaporized as temperature could be expressed by the partial combustion reactions, heterogeneous
increases, generating a gas mixture composed mainly of H2, CO, CO2, reactions and homogeneous reactions shown as reactions (1–16) in
CH4, gaseous hydrocarbons and steam; as a result of these gases release, Table 1. Catalytic reforming reactions cleave the C–C bonds of the
biomass is reduced to char, while gaseous hydrocarbons condense at

Fig. 1. Stages typically found in biomass gasification in a downdraft

gasifier with air.

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Table 1
Main chemical reactions involved in biomass gasification process. Adapted from Ref. [13].

Stoichiometry Reaction heat ΔH° (kJ/mol) Name #

Biomass → char + tar + H2 O+ light gas (CO + CO2 + H2 + CH 4 + N2 + C x Hy Oz + …) Endothermic Biomass devolatilization 1
Char combustion reactions
C+ 1/2O2 → CO −111 Partial Combustion 2
C+ O2 → CO2 −394 Complete Combustion 3
Char Gasification reactions
C+ CO2 ⇆ 2CO +173 Boudouard reaction 4
C+ H2 O→ CO + H2 +131 Steam gasification 5
C+ 2H2 → CH 4 −75 Hydrogasification reaction 6
Homogeneous volatile reactions
CO + 1/2O2 → CO2 −283 CO Oxidation 7
H2 + 1/2O2 → H2 O −242 H2 Oxidation 8
CH 4 + 2O2 → CO2 + 2H2 O −802 CH4 Oxidation 9
CO + H2 O⇆ CO2 + H2 −41 WGS reaction 10
CO + 3H2 ⇆ CH 4 + H2 O −206 Methanation 11
Tar reactions
Cn Hm + (n/2)O2 → nCO + (m/2)H2 Between −715 and ≈ −2,538 Partial oxidation 12
Cn Hm + nH2 O→ (m/2+n)H2 + nCO Between +740 and ≈+2,302 Steam reforming 13
Cn Hm + nCO2 → 2nCO + (m/2)H2 Between +980 and ≈+3,112 Dry reforming 14
Cn Hm + (2 n− m/2)H2 → nCH 4 Between −498 and ≈ −1,815 Hydrogenation 15
Cn Hm → (m/4)CH 4 + ( n− m/4)C Between −161 and ≈ −505 Thermal cracking 16

carbohydrate backbone to yield a combination of carbon monoxide and pathways [19]. Myrén et al. [20] identified the main tar compounds
hydrogen (reactions 13 and 14). If H2O is present, CO2 can be generated present in product gas, considering three raw materials: birch, mis-
via the Water Gas Shift reaction (WGS) to produce more H2 (reaction canthus and straw, at temperatures of 700 °C, 850 °C and 900 °C, as
10). Aqueous-phase reforming by bimetallic catalysts can produce H2 shown in Table 2.
and CO2 starting with sugars and sugar alcohols (polyols). The se- Feng et al. [22] studied biomass tar evolution during homogeneous
lectivity towards H2 can be controlled using catalysts with different conversion at 500–900 °C through Gas Chromatography Mass Spec-
metal composites (e.g., Pt) and metal alloys. Steam reforming can re- trometry (GC-MS) analysis. In Fig. 3 and Table 3 it can be seen that at
generate CO and H2 from tars. It is an endothermic process, and an lower temperature (500–600 °C) the majority of the biomass tar still
external source of heat is needed. Steam reforming should be conducted comprises components based on the primary biomass tar containing
at high temperature, low pressure, and high steam to hydrocarbon ratio oxygen and substituent compounds, such as levoglucosan and di-
in order to achieve maximum conversions, based on Le Chatelier's methoxymethane. At higher temperatures (700–900 °C), most of the
principle. It is possible that increasing temperature could promote the primary pyrolyzed tar is gradually transformed and tar composition
endothermic reaction of hydrocarbons (reaction 13) occurred at the seems to be mainly composed of aromatic compounds, such as toluene,
steam reforming process, which result in remarkable tar removal effi- indene and naphthalene amongst others. Increasing the temperature
ciency and slight increase of CO and H2 concentration. The reactions resulted in either a gradual reduction or complete removal of tars
(11), (13) and (14) were based on the thermal catalytic cracking and containing branched or heteroatom compounds, and PAHs are pro-
reforming mechanisms, converting tars and light hydrocarbons into H2 gressively formed. Specific tar components decompose into small mo-
and CO. In addition to the above mechanisms, reactions (2–6) may also lecular gases and C1∼C5 hydrocarbons, while there is evidence for the
take place with the presence of char as the catalyst support [12]. promotion of aromatic rings as a function of increasing temperature. H-
abstraction, C2H2-addition and cyclodehydrogenation are the mechan-
3. Tar definition isms typically responsible for such processes. Thermal decomposition
and additional reactions convert short chain hydrocarbons (C1∼C5)
Tar can be defined as a mixture of condensable hydrocarbons, in- into compounds containing unsaturated double bonds and triple bonds
cluding aromatic compounds with up to five rings (which can be oxy- that gradually increase in concentration by the acetylene addition re-
genated) as well as Polycyclic Aromatic Hydrocarbons (PAHs) [8]. action. The aromatic components can also be polymerized by dehy-
However, according to the meeting about tar measurement protocol drogenation. Further, increasing the temperature to 900 °C, results in
carried out in Brussels in the Spring of 1998, between the International the relative content of PAHs, such as naphthalene, phenanthrene and
Energy Agency (IEA), the Directorate General for Energy of the Eur- anthracene, to increase by the above conversion pathway yielding
opean Commission (DG XVII) and the Energy Department of the United highly stable aromatic hydrocarbons.
States, has been agreed to define tars as all hydrocarbons with mole- In relation to tar classification, there are two ways of classifying it,
cular weight higher than benzene [14]. one refers to process conditions in which compounds are formed and
the other one was defined by physical tar properties: tar water solubi-
3.1. Tar chemical composition and classification lity and tar condensation, besides consider rings number of compo-
nents.
Biomass tar chemical composition depends on many factors such as Thus, Milne et al. [23] classified tar in four groups according to
reaction temperature, type of reactor and raw material used in the process conditions inside gasifier: primary, secondary, alkyl-tertiary
gasification. The typical composition is shown in Fig. 2. Studies carried and tertiary condensates. Primary tar compounds are formed during
out by Kosstrin [15], Sadakata et al. [16], Hanaoka et al. [17] and more pyrolysis by decomposition of biomass building blocks and consists of
recently Yu et al. [18] shown that the type of biomass influences the acids, sugars, alcohols, ketones, aldehydes, phenols, catechols, guaia-
thermal degradation kinetics, reactivity, and product characteristics in cols, syringols, furans and oxygenates. Secondary tar is formed as a
a gasification process. The amount and type of char as tar from gasifi- result of primary tar rearrangement due to temperature increase above
cation appear to be composed of different chemical species and these 500 °C, forming heavier molecules such as phenols and olefins. Tar-
ones are a function of feedstock used and the different cracking alkyl tertiary products include methyl derivatives of aromatic

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Fig. 2. Typical composition of biomass tars.

Adapted from Ref. [21].

Table 2
Tar compounds from birch, miscanthus and straw after thermal cracking (mg/g dry biomass) [20].

Compound Birch Miscanthus Straw

700 °C 850 °C 900 °C 700 °C 850 °C 900 °C 700 °C 850 °C 900 °C

Benzene 0.6 1.1 2.4 3.3 3.1 5.4 0.7 0.8 0.9
Toluene 1.5 1.5 1.7 3.2 2.7 2.2 1.1 1.1 0.7
p-Xylene 0.6 0.4 0.1 0.6 0.4 0.2 0.4 0.2 0.1
o-Xylene 1.2 1.2 0.7 1.5 1.2 0.7 1.3 1.0 0.6
Indene 0 0.1 0 1.3 1.4 0.6 0.2 1.0 0.4
Naphthalene 1.0 2.5 2.3 1.6 3.3 3.7 2.2 3.3 3.9
2- Methylnaphthalene 0.1 0 0 0.5 0.5 0.3 0.3 0.3 0.1
1- Methylnaphthalene 0.1 0 0 0.1 0.2 0.1 0.3 0.2 0.1
Biphenyl 0 0 0 0 0.1 0.1 0.2 0.2 0.1
Acenaphthylene 0 0 0 0.4 0.8 0.6 0.5 0.5 0.5
Fluorene 0.1 0 0 0 0 0 0.1 0.2 0.2
Phenanthrene 0 0 0 0.2 0.5 0.5 0.3 0.3 0.6
Anthracene 0 0.3 0.3 0.1 0.2 0.2 0.1 0.1 0.2
Fluoranthene 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2
Pyrene 0 0 0 0 0.1 0.1 0.1 0.1 0.3
Total light aromatics excluding benzene 4.6 6.1 5.2 9.6 11.5 9.4 7.2 8.6 8.0

compounds, such as methyl acenaphthylene, methyl naphthalene, to- real partial pressure of tar equals the tar saturation pressure. Hence, in
luene and indene, however, condensed tertiary aromatics form PAHs condensation related issues, tar dew point is a powerful parameter to
series without substituent atoms such as benzene, naphthalene, ace- evaluate the performance of gas cleaning systems. It is believed that,
naphthylene, anthracene, phenanthrene and pyrene. This type of ter- when the tar dew point is reduced to levels below the lowest expected
tiary tar is also produced from primary tar. temperature, fouling related problems by condensation or tar aerosols
Nevertheless, distinction between secondary and tertiary compounds are solved. To use this approach in design issues, a calculation tool has
is not always clear, with overlapping secondary and tertiary tar com- been developed to predict the tar dew point on basis of the con-
pounds, given by Milne et al. [23]. In this respect, a classification system centration of the individual tar components in the product gas. An il-
less ambiguous based on physical tar properties and rings number, was lustration of the relation between the tar dew point and tar con-
developed by the Energy Research Center of Netherlands (ECN), the centrations is provided by Fig. 4. Condensation curves are given for the
Applied Scientific Research Center of Netherlands (TNO of the Dutch individual tar classes (as defined in Table 3), e.g. the dew point curve
Toegepast Natuurwetenschappelijk Onderzoek) and the University of for class 5 is calculated including only class 5 tars. Furthermore, each
Twente- Netherlands, which jointly proposed a classification of tar based tar component contributes equally to the total concentration on mass
on the solubility and condensability of the different tar compounds [6]. basis. The dew point calculation excludes tar class 1, as the components
These two classification systems are equally important and com- are not known. Leaving out class 1 in this discussion, it can be derived
plemented each other. Table 4 presents this classification. from Fig. 2 that class 5 tars dominate tar dew point. Even for very low
Tar condensation behavior is an effect of all tar components present concentrations of class 5 tars (e.g. < 1 mg/Nm3) a dew point below
in the product gas and their individual contributions to the total tar 100 °C cannot be obtained. The graph clearly points out that, dependent
vapor pressure are therein decisive. When tar vapor pressure exceeds on the concentration in the product gas, classes 2 and 4 need to be
the tar saturation pressure, the gas becomes over saturated according partially removed for a proper tar dew point of about 25 °C. The class 3
Raoult's Law. Thermodynamically, this state leads to condensation of tar compounds do not condense at concentration as high as 10,000 mg/
the saturated vapor. The tar dew point is the temperature at which the Nm3 and play an unimportant role in this matter [24].

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Fig. 3. Gas Chromatography Mass Spectrometry (GC-MS) analysis of biomass tar during Ar (99.999%) homogeneous conversion at 500–900 °C. Adopted from Ref. [22].

Table 3 secondary tar; at higher temperatures, primary tar is completely de-

GC/MS peak assignment of biomass tar. Adapted from Ref. [22]. stroyed and tertiary tar is produced [23].
According to Amen-Chen et al. [25], Friderichsen et al. [26], Shin
No. R.T. (min) M.W. Formula Compounds name
et al. [27], Ledesma et al. [28], Palma [29], Nowakowska et al. [30],
1 4.626 102 C5H10O2 Butanoic acid, methyl ester Wang et al. [31], Shen et al. [32], Huang et al. [33] lignin can be as-
2 4.744 61 CH3NO2 Methane, nitro- sumed as the main tar precursor due to its aromatic nature. In these
3 5.210 132 C6H12O3 2-Butanone, 4,4-dimethoxy- studies, among the main components obtained from primary lignin
4 5.620 92 C7H8 Toluene
5 6.204 76 C3H8O2 Methane, dimethoxy-
pyrolysis, vanillin (4-hydroxy-3-methoxybenzaldehyde, C8H8O3),
6 7.366 90 C3H6O3 1,3,5-Trioxane guaiacol (2-methoxyphenol, C7H8O2), catechol (1,2-dihydroxybenzene,
7 7.703 106 C8H10 Ethylbenzene C6H6O2) and anisol (metoxibenzeno, C7H8O) are found; so, these
8 7.889 106 C8H10 p-Xylene compounds are the most used to simulate and study possible pathways
9 8.023 102 C8H6 Phenylethyne
for tar formation. A free radical mechanism has been suggested as a
10 8.332 104 C8H8 Styrene
11 9.528 142 C7H10O3 2-Furanethanol, a-methoxy-(S)- major route during the early lignin degradation stages followed by a
12 10.382 118 C8H6O Benzofuran combined free radical and concerted pathway at elevated temperatures.
13 11.263 116 C9H8 Indene Fig. 6 shows proposed reaction paths where lignin is pyrolyzed to
14 12.768 146 C8H18O2 Hexanal dimethyl acetal produce vanillin, guaiacol, catechol and anisole like model compounds,
15 13.672 128 C10H8 Naphthalene
16 15.334 142 C11H10 Naphthalene, 1-methyl-
including some volatiles such as CO, H2 and CO2, which are also pro-
17 15.570 142 C11H10 Naphthalene, 2-methyl- duced as result of model units unimolecular and bimolecular decom-
18 17.496 152 C12H8 Acenaphthylene position reactions through cleavage of bonds with the lowest dissocia-
19 17.766 162 C6H10O5 Levoglucosan tion energy, while temperature increases. The homolitic cleavage of O-
20 19.203 166 C13H10 Fluorene
CH3 bond could be the dominant initial step in pyrolysis of vanillin
21 21.539 178 C14H10 Phenanthrene
22 24.442 202 C16H10 Pyrene (R1a, R1b). In path R1b, vanillin decomposes to guaiacol and CO
23 24.987 202 C16H10 Fluoranthene through transfer the hydrogen atom of formyl group to the substituted
C(aromatic) and the cleavage of C(aromatic)-C bond. Guaiacol produces
catechol through demethylation (R2d) and can also generate o-cresol
3.2. Tar formation and 2-hydroxybenzaldehyde by homolysis of the O-H bond (R2a, R2b).
Likewise, carbon monoxide and phenol are produced by demethoxyla-
Tar formation is still not fully understood. As already mentioned, tion of guaiacol (R2c).
when the biomass fed to gasifier is previously dried and then pyrolysed According to paths R3a and R4, catechol and anisol can be con-
within a temperature range between 200 and 500 °C, then biomass verted into phenoxy radical through thermal unimolecular decom-
decomposes into primary tar, a mix of oxygenates and condensable position (phenol is also observed as a reaction product from guaiacol
organic molecules. As shown in Fig. 5, above 500 °C components of pyrolysis). In path R7a the hydrogen abstraction reaction between hy-
primary tar begin to reform into smaller molecules, non-condensable drogen radical and phenolic hydroxyl forms phenoxy that can decom-
light gases (CO2, CO, H2O) and a series of heavier molecules called pose into CO and cyclopentadiene radical. Thereby, these

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Table 4
Tar compounds classification according to chemical composition, solubility and condensability [6].

Tar class Class name Property Representative compounds

1 GC-undetectable tar Very heavy tars compounds that cannot be detected with a GC-FID or Determined by subtracting the gas chromatography-detectable tar
GC-MS equipped with a non-polar capillary column. fraction from the total gravimetric tar
2 Heterocyclic Tars containing heteroatoms; highly water-soluble compounds Pyridine, phenol, cresols, quinoline, isoquinoline, dibenzophenol
3 Light aromatic Usually light hydrocarbons with single ring; do not pose a problem Toluene, ethylbenzene, xylenes, styrene
(1 ring) regarding condensability and solubility
4 Light PAHs compounds 2 and 3 rings compounds; condense at low temperature even at very Indene, naphthalene, methylnaphthalene, biphenyl,
(2–3 rings) low concentration acenaphthalene, fluorene, phenanthrene, anthracene
5 Heavy PAHs Compound larger than 3 rings, these components condense at high- Fluoranthene, pyrene, chrysene, perylene, coronene
compounds temperatures at low concentrations
(4–7 rings)

formation is very high (825 kJ/mol).

The formation of toluene could occur through hydrogenolysis of o-
cresol like path R5a. Once the toluene is formed, the initiation reactions
dominating toluene pyrolysis are the formation of benzyl radicals and
hydrogen atoms and the formation of phenyl and methyl radicals. A
large number of reactions continue these initiations, with formation of
benzene and 2-methyl-1,1′-biphenyl as the main products (R8a, R8b).
The path R9 is one of the possible paths of fluorene formation, through
loss hydrogen from 2-methyl-1,1′-biphenyl formed during toluene
pyrolysis.

3.3. Tar reactivity

To further development of biomass gasification systems, the bio-

mass tars reactivity is very important, as tars are difficult to remove
from biomass product gas (fuel gas or syngas, depending on the use to
which it is put), so removal methods based on condensation, filtration
Fig. 4. Tar dewpoint of different tar classes in relation to the concentration. Adopted from or collecting tar droplets are at the very least in need of further de-
Ref. [24]. velopment. The equipment ultimately required is likely to be more
complicated and more expensive than standard gas cleaning devices.
cyclopentadiene radicals combine to form bigger compounds, e.g. Decomposition off the tars could therefore be an attractive alternative
aromatic compounds like naphthalene. Then, the naphthalene loses H that merits further study. Tars could decompose using plasma or in
radical form indenyl under severe condition and reacts with cyclo- catalytic or thermal tar cracking process: this would involve a separate
pentadiene into phenanthrene or successive condensation to larger tar cracking reactor downstream or using the fluid bed or the freeboard
PAHs (R10a-R13). In paths R3b and R7b, a formation of benzene is of the gasification reactor itself. Biomass tars undergo reactions when
considered to result from the hydrogen radical addition reaction to held at somewhat elevated temperatures at increased residence times.
hydroxyl substituted C(aromatic) and the release a hydroxyl radical, in the Reactions can even take place at room temperature if the tar is exposed
pyrolysis of phenol and catechol. An alternative path for the formation to air [34]. Various reactions can occur:
of benzene is the reaction between phenol and hydrogen radical in the
pyrolysis of vanillin (R1a-R5b-R7b). In path R6b, 2-hydro- 1. Reactions between liquid/gaseous tar compounds and carbonaceous
xybenzaldehyde could decarbonylate to form phenol and CO, never- ash/char
theless this path is unlikely to occur because the total energy barrier of 2. Reactions between liquid tar compounds

Fig. 5. Distribution of different tar types as

function of temperature (residence time of 0.3 s)
Adapted from Ref. [23], p.7.

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Fig. 6. Possible pathways for formation of primary, secondary and tertiary tar.

3. Decomposition reactions in the gas phase in an inert atmosphere on cool surfaces. If this happens in ducts, heat exchangers or filters, it
4. Reactions between gaseous tar compounds and gaseous reactants, produces deposition and blocking, which decreases process efficiency,
which usually also result in the decomposition of the tar com- increases emissions and consequently increasing system operational
pounds. costs [36].
Presence of tar in the product gas define its usefulness and de-
Reactions of types (1) and (2) are referred to as ‘tar polymerisation’ termine if it could be used in direct combustion systems, internal
and decomposition reactions of types (3) and (4) as ‘tar cracking’. The combustion engines, gas turbines, fuel cells or as raw material for
radical forming reaction is the step that determines the cracking reac- synthesis of methanol. Limits specified by application are shown in
tions rate of tar compounds and when an individual model compound is Table 5. In direct combustion systems, the product gas is burned di-
considered, these reactions depends on parameters like the strength of rectly while it remains hot, so there is little possibility for tar con-
the weakest bond in the model compound, the number of weak bonds densation; no restrictions on the amount of tar and particles, but the
and the size of the compound. Radical reactions play a vital role in flue gas produced must meet the emission requirements for this tech-
thermal cracking. The main reaction steps are: (1) radical-forming re- nology. In internal combustion engines, tar could condense in fuel in-
actions caused by the breaking of chemical bonds, (2) propagation re- jection systems; although these engines are more pollutant tolerant
actions through the formation of new chemical bonds, (3) hydrogen than gas turbines, where there are even stricter restrictions on gas
transfer, (4) isomerisation reactions, and (5) termination reactions in cleaning, because blades are more sensitive to deposits from hot gas
which two radicals react with each other [34]. passing through them after combustion [6,7,23].
Jess et al. [35] studied the mechanisms and kinetics of thermal
conversion of the naphthalene, benzene and toluene and the influence
of the presence of hydrogen and steam in order to understand the 3.5. Tar reduction
aromatics hydrocarbons thermal reactions. They compare the conver-
sion degrees of the aromatic hydrocarbons as a function of reaction Researches in this area seeks to develop efficient and economical
temperature at a constant residence time of 0.5s. Under the given re- methods for tar content reduction, having in mind that in addition to
action conditions, the following order of reactivity is obtained: to- these characteristics, the method must be ecofriendly, and even more
luene > naphthalene > benzene. These results are in concordance important, should not affect the formation of the main gaseous com-
with the energy activation of toluene, naphthalene and benzene pounds of gasification (CO2, CH4 and H2). All methods available for tar
thermal conversion, 247 kJ/mol, 350 kJ/mol and 443 kJ/mol, re- reduction could be classified in two groups, depending on where tar is
spectively. Therefore, for thermal conversion of soot and organic
cracking products into CO and H2 in the presence of steam, higher Table 5
temperatures are required (of at least 1,400 °C). They also indicated Tar limits in gas produced for various applications [6,23,37–39].

that benzene should be the key component of thermal decomposition of Application Tar (mg/Nm3)
aromatic hydrocarbons, and the carbonaceous residue (soot) formed
during the experiments is principally from the large hydrocarbon mo- Direct combustion No specified limit
lecules such as naphthalene. Internal combustion engine < 100
Gas turbine < 5.0
Synthesis of methanol < 0.1
Compressors 50–500
3.4. Acceptable limits for tar
Fuel Cells < 1.0
Fischer Tropsch Synthesis < 1.0 μL/L (class 2, BTX)
Tar remains vaporized until the product gas is cooled, condensing

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removed: in-situ methods, which are known as primary methods, and oxidizing medium which leads to a 75% of tar reduction when re-
post-gasification methods, known as secondary methods [40]. sidence time increases from one to 5 s. About ER ratio, it can be con-
cluded that with increase of oxygen available in the gasification agent,
3.5.1. Primary methods will ensure a total oxidation of tar compounds with one and two rings,
These are the actions taken during the gasification stage, to prevent as well as an increase in temperature encourage tar components for-
the formation or to convert the tar formed within gasifier; an ideal mation with three or more rings (tertiary tar).
primary method eliminates the need for secondary treatments. In order
to obtain optimum output product gas, it is mandatory to make an 3.5.1.2. Gasifier design. Gasifier type and design are also influential on
appropriate selection of operating conditions, also to use appropriate tar content in biomass gasification product gas [50]. Typical tar levels
additives and catalysts during gasification process and to get a properly according to the gasifier type are shown in Table 6. It was observed that
reactor design [8]. other variables like feedstock, gasification agent, bed material and
gasification temperature affecting the tar content, so, there is not a clear
3.5.1.1. Operating conditions. Operating conditions play an important trend when all this variable are taken into account. However, most of
role during biomass gasification in all respects, such as carbon the studies listed in Table 6 reached values lower than 20 g/Nm3 of tar
conversion, product gas composition and tar formation. The most in product gas, as shown in Fig. 9. For updraft gasifier, the product gas
influential operating parameters are: temperature, pressure, leaves from the top while solids leave from the bottom. Process
gasification agent, additives-catalysts used and the mass ratio temperature is increased as heat from char oxidation reaction is
between fuel and gasification agent [8]. released, providing the thermal energy required for endothermic
Several studies that evaluate the effect of gasification temperature pyrolysis and gasification reactions. Primary tar is produced at a low
on product gas tar content, showing that when decreasing gasification temperature (200–500 °C), which moves upward with other gasses
temperatures higher levels of tar content are observed in product gas, produced and heat exchanging with cooler regions of the reactor, so,
are presented in Table 6. Knight [41] studied the effect of pressurized primary tar conversion into gases and secondary tar is minimum,
systems for biomass gasification, finding that when pressure was in- producing a gas with high tar content (50 g/Nm3).
creased from 8.0 to 21.4 bar, almost a total elimination of phenols was In a downdraft gasifier, both gas and biomass move downward.
achieved, total amount of tar decreased and PAHs fraction increased High temperature in the combustion zone is reached and tar is pro-
with increasing pressure. Recently, Tuomi et al. [42] investigated the duced after drying at lower temperatures (200–500 °C). The pyrolysis
pressure effect (1–10 bar) on tar decomposition activity generated by product is forced to pass through the combustion zone before leaving
different bed materials (sand, dolomite, MgO and olivine), finding that the gasifier, where a primary tar conversion into non condensable gases
dolomite and MgO slightly decreased its catalytic activity at higher is observed as oxygen are available and temperature increase, ensuring
pressures, however, for sand and olivine this catalytic activity increase the oxidation or thermal cracking reaction of tar, respectively. Thus, the
with the pressure growth, therefore tar conversion increases. tar content (< 20 g/Nm3) obtained when a downdraft gasifier is used is
In the same way, tar content is influenced by gasification agent used lower than that from an updraft gasifier.
(air, steam and vapor-oxygen mixture), showing that a higher amount When fluidized bed gasifier (bubbling or circulating) is used as
of tar is produced when steam was used and the lowest when air was biomass thermal conversion system, a high level of mixing between
supplied [43]. This could be explained by reduction of gasification biomass and bed material is achieved. Thus, the hydrodynamic char-
temperature, as result of steam injection, particularly if it is saturated. acteristics encourage a high biomass conversion into fuel gases because
Nevertheless, pure O2 supply as a gasification agent could mitigate this the most carbon content from biomass is partially oxidized and lower
negative effect, and therefore tar thermal cracking reactions would be amounts of tar are generated, which moves up in the bed and leaves
guaranteed, reaching a lower tar concentration in product gas (59–64 along with the product gas. In a general way, tar concentration gen-
mg/Nm3) in comparison with the one obtained from mixture air + sa- erated are between 5 and 20 g/Nm3 and 1–5 g/Nm3 for bubbling and
turated steam (91–92 mg/Nm3) as shown by De Sales et al. [44]. Mass circulating fluidized bed, respectively. When entrained flow gasifier is
ratio between fuel and gasification agent is an important parameter that used, tar content is negligible and whatever is released passes through a
influences the gasification products quality including tar content; for air high temperature zone (> 1,000 °C), so, high tar reduction by thermal
gasification, the parameter is equivalence ratio (ER), for steam gasifi- cracking of tar compounds is observed.
cation is steam-biomass ratio (S/B) and for steam-oxygen gasification is Introducing modifications in gasifier design allows an efficient
gasifying ratio (GR) [45]. The ER ratio strongly influences the gasifi- production of clean product gas. Pan et al. [74] injected secondary air
cation products type, being more significant at elevated temperatures. above biomass feeding point in a fluidized bed, achieving an 88.7%
According to Wang and Kinoshita [46] tar content decreases as ER ratio reduction of total tar content, within gasification temperature range of
increases due to the greater availability of oxygen to react with volatile 840–880 °C. Likewise, two-stage gasifier design has been a relevant
compounds in pyrolysis zone, so tar concentration decreased about 30% strategy in production of clean product gas, the basic concept being to
when ER was increased from 0.22 to 0.32 at temperature of 700 °C. separate pyrolysis zone and reduction zone, in this way the tar formed
Narváez et al. [47] reported a decrease in tar content by 50% with the during pyrolysis (first phase) is decomposed in reduction zone (second
ER ratio increase of 0.20–0.45 at temperature of 800 °C using air as stage) [8].
gasification agent. Cao et al. [75] developed a combined two-region reactor for bio-
Residence time also influences tar concentration and significantly mass gasification with air, at laboratory-scale for product gas produc-
modifies tar composition. According to Wang and Kinoshita [46], the tion without tar and a high calorific value. Results showed an efficient
amounts of oxygen compounds tend to decrease with increasing re- control in tar production reaching 10 mg/Nm3 under optimal condi-
sidence time; one and two aromatic rings compounds (with the ex- tions and a LHV of 5 MJ/Nm3 approximately.
ception of benzene and naphthalene) decreased, while three and four Galindo et al. [57] evaluated product gas quality obtained in a two-
rings compounds increased in tar total fraction. Tregrossi et al. [48] stage downdraft gasifier using air as gasification agent and eucalyptus
evaluated the effect of residence time over tar oxidation as well as the as fuel, results confirm air supply in a second stage produce a tem-
effect of ER ratio: with increasing residence time the results agree with perature increase inside reactor, which favors thermal tar cracking,
those obtained by Wang and Kinoshita [46], one and two aromatic rings decreasing 87% its content in the product gas, achieving a tar final
compounds decrease significantly; however, as ER ratio increases, for- concentration of 54 mg/Nm3 and an average LHV of 4.74 MJ/Nm3.
mation of more PAHs occurs. Results are shown in Figs. 7 and 8. Re- Other gasification technologies separate the zones of drying, pyr-
sidence time increase allows greater exposure of tar compounds to olysis, gasification and combustion. These multi-stage processes

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Table 6
Typical tar levels according to the gasifier type and operational conditions.

Gasifier Type Feedstock Gasification Agent Bed Material Gasification Temperature (°C) Tar Content (g/Nm3) Reference

Fixed Bed
Updraft Wood n.a n.a 1,000 1.0 [19]
Updraft Straw Air n.a 400–500 50.0 [51]
Updraft Sawdust Air n.a n.a 8.6 [52]
Updraft Woodpellet Air/Steam n.a 650 90.3 [53]
Updraft Pine pellet Air n.a 1,000 132.4 [54]
Downdraft Wood n.a n.a 1,000–1,400 1.0 [19]
Downdraft Wood chip n.a n.a n.a 0.5 [51]
Downdraft Pine pellet Air n.a 900 32.3 [54]
Downdraft Hazelnut shell Air n.a 821–1,206 3.3 [55]
Downdraft Pine wood Steam/Oxygen n.a 774–934 2.9 [56]
Downdraft Pine wood Air n.a 870–1,108 12.3 [56]
Downdraft Pine wood Steam/Oxygen n.a 910–1,090 14.4 [56]
Downdraft Pine wood Air n.a 798–910 1.9 [56]
Downdraft Eucalyptus wood Air n.a 550–700 0.236 [57]
Downdraft eucalyptus spp Air/Steam n.a 500–700 0.0915 [58]
Downdraft eucalyptus spp Steam/Oxygen n.a 501–700 0.060 [58]
Fluidized Bed
Bubbling Pine wood chips Air Silica Sand 780–830 18.0 [45]
Bubbling Pine wood chips Steam Silica Sand 750–780 53.0 [45]
Bubbling Pine wood chips Steam/Oxygen Silica Sand 785–830 24.0 [45]
Bubbling Coal/Biomass Air Sand 700–900 2.0 [19]
Bubbling forestry residues Air n.a 700–900 3.0 [59]
Bubbling Pine wood chips Air Silica Sand + dolomite 700–850 2.0 [60]
Bubbling Pine wood chips Steam/Oxygen Silica Sand 780–890 5.0 [61]
Bubbling Spruce wood pellet Air/Steam Quartz, olivine, dolomite 780 7.6 [61]
Bubbling Radiata pine Steam Co/MgO 600 8.4 [62]
Bubbling Pine wood chips Steam/Oxygen Calcined dolomite 795–835 2.5 [63]
Bubbling Pine sawdust Air Calcined dolomite 800 13.9 [64]
Bubbling Bagasse Air n.a 800 14.8 [65]
Bubbling Wood sawdust Air Silica Sand 750 0.010 [65]
Bubbling Almond shell Steam Olivine, sand, dolomite 700 6.5 [66]
Bubbling Almond shell Steam Olivine, sand, dolomite 820 1.3 [66]
Bubbling Pine sawdust Air Silica Sand 790–810 10.0 [47]
Bubbling Pine sawdust Steam Silica sand + CaO, MgO 750 180.0 [67]
Bubbling Pine sawdust Steam Silica sand + CaO, MgO 780 40.0 [67]
Bubbling Sawdust Air n.a 780 2.0 [51]
Bubbling Sawdust Air n.a 857 0.3 [51]
Bubbling Rice husk Air n.a 750 6.0 [51]
Bubbling Rice husk Air n.a 940 0.8 [51]
Circulating Wood pellet Steam Olivine 841 3.5 [68]
Circulating Wood pellet Steam Calcite 645 1.4 [68]
Circulating Woody biomass Air Silica Sand 800–860 0.270 [69]
Circulating Sawdust Air Ni-alumina 700–850 2.4 [70]
Circulating Coal/Biomass Air Sand 800 0.7 [19]
Entrained flow
– Sawdust wastes Air n.a 750 0.001 [71]
– Sawdust Air n.a 700–1,000 0.001 [72]
– Coconut coir dust Air n.a 976 23.6 [73]
– Coconut coir dust Air n.a 1,100 4.8 [73]

n.a.: not available.

increase gasification efficiency and product gas quality through the methods are divided into two categories: dry cleaning methods and wet
combination of different reaction zones. Xiao et al. [76] designed and cleaning methods. Dry gas cleaning is usually carried out at
built an Internally Circulating Fluidized Bed Gasifier (ICFG) composed temperatures between 200–500 °C even at 600–800 °C, but when
of two chambers with different functions: one is the gasification using fabric filters product gas must be cooled, because high
chamber and the other one is the combustion chamber with bed ma- temperatures affect the resistance of bag material fabric [77,78]. Wet
terial circulating between two chambers. Tar content in gaseous pro- gas cleaning is performed after cooling in the range of 20–60 °C [6]. The
ducts was about 300 mg/Nm3. Burhenne et al. [36] developed an al- typical equipment of these cleaning systems is listed in Table 7.
ternative gasification process in the Fraunhofer Institute for Solar Physical cleaning systems are mainly used to capture particles, but
Energy Systems, where process is carried out in a fixed bed gasifier pilot they are also used to capture tar in a condensed form. The fabric filters
plant with four separate reaction zones, obtaining a fuel gas with an or the cyclonic separator alone will not be able to reduce the tar sig-
LHV of 5.8 MJ/Nm3 and a tar content of less than 50 mg/Nm3. nificantly, and additional tar reduction may be necessary. The concept
of cyclonic separator uses a rotating cylinder which is centered in a
3.5.2. Secondary methods single cyclone, so this device is more applicable for solid particulates
3.5.2.1. Tar removal through physical processes. Tar removal with than tar removal [6]. In recent years catalytic hot gas filters for tar
physical processes play an important role in commercialization of abatement have been developed as a cost-effective way to upgrade
gasification because its maintenance and operation costs (O&M) are biomass gasification gas. This method combines the filtration for par-
lower than for catalytic processes, also operation is more simple, and ticles removal and catalytic cracking of tar from producer gas in one
cost/benefit relation is acceptable [23]. Physical/mechanical cleaning step. A catalytic filter candle is normally placed in the freeboard of a

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Table 7
Physical/mechanical gas cleaning systems classification [6].

Cleaning type Equipment

Dry Cyclonic separator, electrostatic precipitators, bag filters,

ceramic filters, fabric/tube filters, sand bed filters, adsorbents,
activated carbon adsorbents, catalytic filters (recently
developed).
Wet Spray towers, packaged column scrubbers, scrubbers,
impingement, venturi scrubbers, wet electrostatic precipitators
(ESP), wet cyclones.

avoided. Therefore, a hot and clean gas is obtained at the outlet of the
gasifier with reduced investment costs. Experimental results demon-
strated that the method is also considerably efficient in removing tar
and particles like shown in Table 8. Three different types of manu-
facture processes for catalytic filters have been described in literature:
(1) incorporation of a catalytic component in the ceramic grain and
binder mixture during the ceramic filter manufacture process, (2)
Fig. 7. Residence time effect over tar compounds. Adapted from Ref. [49].
modification of the design of the ceramic filter by including a porous
inner tube fixed at the head of the filter candle to allow the integration
of a catalyst fixed bed, (3) catalytic coating on the porous support of a
conventional hot gas ceramic filter. The first process was early dis-
carded due to the low surface area of the catalytic filters produced. The
high temperatures used in the manufacturing process led to grain sin-
tering and therefore to losses in the active surface of the catalyst. Cat-
alytic filters produced under the other two processes have been opti-
mized and tested under different conditions [79]. Fig. 10 presents a
scheme of the different configurations of the two catalytic filters.
In another way, water scrubber is the existing technique commonly
used in many gasification plants to remove contaminants and tar.
Owing to the fact that tar is a mixture of several hundreds of organics
having low or no water-solubility characteristics (hydrophobic sub-
stances), water is not appropriate to be used as a scrubbing medium for
tar removal. Therefore, use of other kinds of absorbents, especially
hydrophobic absorbents, should be more effective for tar absorption
[80]. In this regard, Phuphuakrat et al. [81] investigated several kinds
of scrubbing liquids (water, diesel fuel, biodiesel fuel, vegetable oil, and
engine oil) for their absorption performances as a medium against real
Fig. 8. ER effect on tar oxidation. Adapted from Ref. [49]. biomass tar without augmentation of mass transfer operation such as
spray towers and packed columns. The results showed that only 31.8%
fluidized bed where gasification takes place. The incorporation of a of gravimetric tar was removed by the water scrubber and could reduce
catalytic filter inside the gasifier presents several advantages. On one this gravimetric tar down to 9.1 g/m3 (the product gas contained tar of
hand, it contributes to maintain the thermal efficiency of the biomass 13.3 g/m3), although most of tar components have less or no solubility
conversion process and on the other hand, particle entrainment is in water, the decrease in the gravimetric tar by water scrubber can be

Fig. 9. Tar content for different gasifier type.

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Table 8
Tar removal efficiency - dry cleaning methods (with various definitions of “tar”).

Technology Tar removal Comments Reference

Efficiency

Cyclonic Separator 30–70% Gas temperature at cyclone of 130 °C in this study. Typical operation temperature is between 100 and 900 °C. [37,82]
Fabric Filter 0–50% Gas temperature at filter of 130 °C. As filter material, Nextel® is used. This fiber tissue can be operated at least up to a
temperature of 600 °C.
Sand bed filter 50–97% Gas temperature at filter is between 10 °C and 20 °C.
Fixed bed tar adsorber 50%–65% Gas temperature at Fixed bed tar adsorber of 80 °C.
(activate carbon)
Ceramic quartz filter 76–94% Tar content before filter: 34 ± 2.4 g/Nm3. Gas temperature at filter is between 650 °C–700 °C. [83]
Ceramic glass filter 77–97.9%
Porous catalytic filter disk 96–98% Benzene/naphthalene were chosen as tar model compounds with a concentration respectively 15 g/Nm3 and 5 g/Nm3. [84]
(1%wt/0.5%wt Ni/ Operation temperature of 900 °C.
CaO)
Porous catalytic filter disk 77% Naphthalene was chosen as tar model compound. Three different feed naphthalene concentrations (1, 2.5, 5 g/Nm3) were [85]
(2.5%wt Al2O3; 1.0% (800 °C) used to study. A 77% reduction in tar is achieved at 800 °C, while a 99% reduction is achieved at 850 °C.
wt Ni; 0.5%wt MgO) 99%
(850 °C)
Catalytic layer candle 95% Tar content at filter inlet: 3.42 g/Nm3-dry. Operation temperature of 850 °C. [79]
filter integrated with a
catalytically activated
alumina foam tube
Adsorbent activated 81.5% Tar content at filter inlet: 1.3 g/Nm3. Gas temperature at filter inlet is 16 °C. The tar removal performance decreases to [86]
carbon filter 15.7% 10 h after the start of the operation.

Fig. 10. Scheme of configurations of catalytic filters: (A)

fixed bed and (B) catalytic layer. Adopted from Ref. [79].

attributed to condensation taking into account that the temperature of environmental and economic benefits. The OLGA system (a Dutch ac-
the water scrubber (28–28.5 °C) was lower than the temperature of the ronym for oil based gas washer) is one of these technologies that re-
entering gas stream (30.8–33.6 °C). Because of solubility of tar, the moves and reuses valuable tar components without costly waste re-
change of the absorption medium from water to an oily material can be mediation. The process is shown in Fig. 11 and the typical operating
expected to improve tar removal performance. According to this, the temperatures are between 60 and 450 °C. Oil as absorbent medium is
highest removal of gravimetric tar was obtained by a vegetable oil used instead water like in water scrubbers. Similar to water scrubbing,
scrubber with a removal efficiency of 60.4% and a gravimetric tar condensable tars (classes 1, 4, and 5) are recovered by condensation as
content of 5.3 g/m3 remained after passing through the vegetable oil. temperature is reduced below the tar dew point. Lighter tar compounds
When focusing on light PAHs tar removal (representing by naphtha- such as phenols and 1 or 2 ring aromatics (classes 2 and 3) are subse-
lene), was observed that diesel fuel shows the highest absorption effi- quently removed via absorption into a second liquid scrubbing medium.
ciency for naphthalene, but it has a distinct drawback of losing the The OLGA process offers several advantages compared to conven-
absorption medium due to easy evaporation. The absorption efficiency tional dry and wet techniques. This approach eliminates the operational
for these light PAHs can be ranked in the following order: diesel and economic challenges of catalytic and high temperature tar removal,
fuel > vegetable oil > biodiesel fuel > engine oil > water. On the besides eliminating waste water treatment. Highly toxic PAHs com-
contrary, an increase in gravimetric tar was observed for diesel fuel and pounds are always a concern, but these tars are generally easier to re-
biodiesel fuel scrubbers because of their easy evaporation. Therefore, move from water because of their volatility and low water solubility.
the vegetable oil is recommended as the best absorbent to be used in The greatest issue is highly soluble tar, particularly phenol. These small
gasification systems. polar compounds dissolve easily in water and are more difficult to re-
According to Woolcock et al. [39], a combination of dry and wet move. Costly waste water treatment is avoided by removing these tars
technologies is now being developed for tar removal, considering its with oil. The oil can then be easily regenerated or used as feedstock.

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Fig. 11. Simplified OLGA process diagram for tar removal. Adopted from Ref. [82].

The valued products of gasification also remain unaffected by OLGA. identified as carcinogens, mutagens and teratogens. For wet washing
Primary light components, such as C2H4, CH4, CO, and H2, remain re- systems, treatment and disposal of waste fluids and sludge must be
latively unchanged when are compared to the use of thermal and cat- done, which is a disadvantage, as it increases the operating costs of
alytic tar reduction methods. Valuable tar compounds that are ex- these systems. In addition, the calorific value of the product gas, and
tracted with the oils can also be utilized rather than discarded as they the net process energy efficiency are lower after the wet cleaning pro-
are during water scrubbing. The primary condensed tars can serve as cess. Also, in dry treatments it is necessary to make an adequate dis-
additional feedstock in many carbon conversion processes, such as posal of the residues generated during the process [6].
those in petroleum refineries [39].
A large number of experimental results have shown that product gas
3.5.2.2. Partial oxidation, thermal and plasma cracking. These methods
cleaning with these physical technologies, effectively removes tar as
can be applied only to reactors with high temperature zones.
shown in Tables 8 and 9. Likewise, Table 10 shows some product gas
Temperature range suitable for the process has to do with the
cleaning systems together with their efficiencies used in industrial
molecular weight of tar formed in gasification systems, and can vary
plants mainly for tar removal.
between 900 and 1,300 °C. For economic and operational reasons,
Operation of these cleaning systems requires very strict safety pro-
thermal cracking is not attractive for large-scale gasification systems
cedures, since solid and liquid waste generated are highly toxic due to
[91]. According to Bridgwater [92], tar produced from biomass is
presence mainly of aromatic hydrocarbons, compounds that have been
difficult to “crack” through heat treatment only and suggests the

Table 9
Tar removal efficiency - wet cleaning methods.

Technology Tar removal Efficiency Comments Reference

Impinger 70% The amounts of tar in the gas entering and leaving the gas impinger were determined in [87]
Three impingers in series > 95% terms of the total carbon content, since could indirectly quantify the amount of tar. The
temperature at impinge inlet is nearly to 50 °C.
Washing tower 10–25% Gas temperature at wash tower is between 50 °C and 60 °C. [37]
Wet electrostatic precipitator (ESP) 40–70% Tar content at ESP inlet between 920 and 2224 mg/Nm3. Temperature at ESP between [88]
20 °C–30 °C.
Venturi Scrubber 51–91% Operational temperature 20–100 °C [49,82]
Packed bed scrubber 75% Inlet gas tar + dust content is below about 600 mg/Nm3. Gas Temperature at scrubber [89]
inlet of 300 °C.
Bio-Oil Scrubber 51.6%–64.5% Tar content at scrubber inlet 6.3 g/Nm3. The tar removal performance was investigated [86]
at 40 °C, 50 °C and 60 °C. The optimal temperature of the bio-oil scrubber was 50 °C.
Water Scrubber 22% The amount of total tar content from the outlet of gasifier was 0.977 g/Nm3. [82,90]
Diesel scrubber 62% Operational temperature 20–100 °C.
Scrubber - waste oil from a restaurant 75%
Scrubber - Oil residue from a 98%
restaurant + activated carbon

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following alternatives to ensure an effective tar decomposition: (i)

It is suitable for small scale installations. High operating cost due to effluent

It simultaneously removes solid particles and tar. They have small size, but
Solids removal mainly. No data on efficiency was found on using centrifugal

They are the simplest, high cost of operation by the treatment of effluents
increase the residence time, (ii) increase the direct thermal contact with

Operates in conjunction with activated carbon absorbers. This device is

They are low capital investment and simple manufacturing. The cost of
a heat independent source (heated surface), which decreases overall
efficiency, (iii) promote partial oxidation through air or oxygen
addition in oxidation reactors, but this increases CO2 levels, reduces

It combines the solids filtration and catalytic cracking of tar

efficiency and increases costs when pure oxygen is used.

OLGA system, used by the ECN plant in the Netherlands.

devices for biomass tar removal but for coal gasification.

more applicable for solid particulates than tar removal

The thermal requirement varies depending upon process parameters

with a high operating cost due to effluent treatment

and the individual molecule. Simulations of thermal destruction of
Low cost. Requires activated carbon absorbers.

benzene, toluene and naphthalene showed that a very high destruction

operation is high by the disposal of effluents

requires significant residence time and high temperature according to
High complexity and high investment cost
Low investment cost. Frequent clogging

literature reviewed. To reach very significant tar decomposition in a

Large size and high investment cost
realistic residence time a temperature of 1,250 °C is required.
Unfortunately, utilizing this temperature for thermal decomposition has
the drawbacks of high cost and production of heavier products and
agglomerated soot particles; thus, conventional thermal decomposition
is not an ideal solution for tar removal and reforming [93]. In this re-
spect, Zhang et al. [2] studied partial oxidation over a wide tempera-
ture range of 600–1,400 °C, finding the temperature growth markedly
Comments

treatment

decreased tar yield. Thus, achieving complete decomposition of species

such as benzene and toluene requires temperatures above 1,200 °C in-
dependently of gasification agents used, although presence of catalysts
could possibly reduce the thermal cracking temperature.
Can reduce tar + solids from 600 mg/

Jess [35] studied mechanisms and kinetics of aromatic hydro-

carbons thermal conversions, using naphthalene, toluene and benzene
as the model compounds and proposed a simplified reaction scheme in
the presence of hydrogen and steam as shown in Fig. 12. He concluded
Efficiency & % Removal

that benzene should be the key component of thermal decomposition of

Nm3 to 150 mg/Nm3

aromatic hydrocarbons. Carbonaceous residue (soot) formed is princi-

96% naphthalene

70% tar + solids

pally from the large hydrocarbon molecules such as naphthalene. He

85–90% solids

70–95% solids

70–99% solids

60–98% solids
79% benzene

99% phenol
50–90% tar

30–70% tar

75–95% tar

50–97% tar

40–70% tar

10–25% tar

50–90% tar
99% solids

also indicated that the soot and organic cracking products can be
0–50% tar

97% tar

completely converted to CO and H2 in the presence of steam at a high

temperature of 1,400 °C.
Recently, plasma, which consists of highly excited atoms and mo-
Temperature: 130 °C and pressure: 1atm. Can decrease the tar content

Temperature: 50–60 °C and high pressures. High gas velocity to favor

Temperature: 200–500 °C, high pressure to compensate for sand-bed

lecules, ions, electrons, radicals, neutral particles and so on, is widely

Temperature: above 850 °C, gas velocity: 2.5 cm/s and injection of

Gas residence time: 4 s; precipitator voltage: 28–34 kV; operating

utilized for tar abatement. It can be divided into thermal and non-
Interacting with each other in an absorption-regeneration mode.
Higher percentages of tar removal (95%) could be achieved by

Temperature: 50–60 °C; low pressures to promote absorption.

thermal plasmas (or non-equilibrium plasma). For thermal plasma, such

as arc discharge and gliding arc discharge, the typical gas temperature
Fixed bed updraft coal gasifier pressurized (1 ton/day).

is higher than 1,730 °C and all charged and neutral species are in
Temperature 600–800 °C and atmospheric pressure
Temperature: 130 °C and pressures relatively low.

thermal equilibrium. But, for non-thermal plasma, like dielectric barrier

Temperature: 50–60 °C and atmospheric pressure

discharge, corona discharge or pulsed discharge, the temperature of the

Temperature: 80 °C and atmospheric pressure

electrons can reach 104–105 °C, while the gas temperature can remain
in the range of room temperature [94].
Nair et al. [95] compared tar removal efficiency of two plasma
connecting wet impingers in series

generation methods, a pulsed corona system and a DC/AC system, ob-

from 8 g/Nm3 to 4.5 g/Nm3.

taining a similar naphthalene conversion of 90–95% in both plasma

separation of solids and tar.

technologies. In addition, it could also be seen that for DC/AC system,

temperature: 40–50 °C
Operation conditions

complete tar removal requires higher levels of energy than pulsed

corona system. Thus, from an overall process point of view, a combi-
H2S (100 ppm)
pressure drop

nation of two systems would be ideal. In the same way, Van Heesch
et al. [96] achieved tar cracking up to 68% with use of plasma pulsed
corona system. Rabou et al. [97] tested the effectiveness of a glid-arc
plasma (low intensity plasma) for tar removal obtaining a reduction less
than 50%. Nunnally et al. [93] achieved over 90% naphthalene and
Tar removal efficiency in industrial systems [6].

(battery collector tubes)

Impingement Scrubber
Removal Technologies

Packed Bed Scrubber

Spray Towers (wash

Cyclone-Humidifier

Scrubbing Towers
Venturi Scrubber
Wet Electrostatic
Rotating Particle

Catalytic Filters
Sand Bed Filter
Ceramic Filter
Fabric Filter

Precipitator
Separator

column)
Removal Process

Wet Operation
Dry Operation
Table 10

Fig. 12. Simplified reaction scheme of thermal conversion of aromatic hydrocarbons in

the presence of hydrogen and steam. Adopted from Ref. [21].

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

toluene conversion in a gliding arc plasma reformer at low tar con- including OH and Ar metastable species. The ionization of Ar requires a
centration of 30 g/m3 and over 70% naphthalene and toluene conver- much higher electron energy (15.76 eV) compared to the excitation of
sion at a higher concentration of 75 g/m3, showing significant im- Ar to its metastable states Ar∗ (e.g. 11.55 eV). Therefore, in the Ar DBD,
provement over previous work in gliding arc for tar reforming. Ar is more likely to be excited to its metastable states rather than being
Good tar removal efficiency could be obtained using plasma tech- ionized. Previous studies have shown that metastable Ar species play an
nique, however, plasma along has many disadvantages for industrial important role in initiating chemical reactions. The presence of steam in
purposes, such as being expensive, having a limited lifetime for pulse the plasma could generate OH radicals from the dissociation of water by
power supplies and a high energy demand from overall process [6]. electrons and Ar∗. The generated OH radicals can oxidize toluene and
Nevertheless, plasma it seems to be a promising alternative method to its intermediates, opening a new reaction route for the conversion of
integrate catalyst in a plasma reactor to realize the efficient conversion toluene, resulting in the enhanced conversion and energy efficiency of
of tar to high value-added energy products, since catalysts can increase the plasma process.
the production of H2 and CO by promoting the steam reforming reac- According to Liu et al. [98] different bond energies of chemical
tion and water-gas shift reaction. A synergistic effect may be obtained bonds in toluene determine the reaction pathways involved in the
through combination of non-thermal plasma with a desirable catalyst. plasma conversion of toluene. The dissociation energy of C-H bond in
This catalysis-plasma process has simultaneously the advantage of high methyl is 3.7 eV, which is smaller than that of C-H bond in aromatic
product's selectivity from thermal catalysis and the fast startup from the ring (4.3 eV), C-C bond between aromatic ring and methyl group
plasma technique. As a new technology, the plasma-catalytic process (4.4 eV), C-C bond (5.0–5.3 eV) and C=C bond in aromatic ring
has been widely applied for volatile organic compounds (VOCs) re- (5.5 eV). Therefore, the primary reaction pathway of toluene decom-
moval and hydrocarbon reforming for hydrogen production. In this position could be the H-abstraction from methyl group by energetic
regard, Tao et al. [94] studied and compare the performance of direct electrons or reactive species such as Ar* and OH. The H-abstraction
thermal decomposition (DD), plasma-assisted decomposition (PD), from the methyl group forms a benzyl radical, which could further react
catalytic steam reforming (CR) and plasma enhanced catalytic steam with OH to generate benzyl alcohol. The formed benzyl alcohol can be
reforming (PCR) of biomass tar using toluene as a model compound, converted to benzaldehyde, followed by further reactions with elec-
finding that the PCR process have the best performance. For the ex- trons and reactive species to form a phenyl radical. In addition, the C-C
periments was used a non-thermal pulsed plasma generated by applying bond between methyl and aromatic ring and C-H bond in the aromatic
a negative high voltage with a direct current (DC) power supply, tem- ring can be broken through the reactions with energetic electrons and
perature of 500 °C, S/C ratio of 1 and for catalytic steam reforming metastable Ar species, generating phenyl, methyl, and toluene radicals.
processes, 0.5 g of the Ni/SiO2 catalyst. The results shown that the As shown in Fig. 13a, the recombination of phenyl with H and OH
toluene conversion increased in the following sequence: DD radicals could produce benzene and phenol, respectively, while adding
(5.4%) < CR (32.8%) < PD (34%) < PCR (57%). They concluded OH to the aromatic ring of toluene radicals produces 3-methyl phenol,
that introduction of a plasma prior to catalyst bed remarkably enhanced as identified by GC–MS. Moreover, ring opening and cracking of phenol
the conversion rate of toluene as plasma activated hydrocarbons to via electron impact dissociation forms butyl alcohol, which then reacts
radical state, while the co-existing Ni/SiO2 reforming catalyst, on the with benzyl to generate benzene, (butoxymethyl). These aromatic in-
other hand, guided the reaction towards formation of CO and H2, rea- termediates can be further ruptured by electrons and Ar∗ species to
lizing the highest toluene conversion, and the highest CO and H2 for- form ring-opening by-products and then oxidized by OH to end-pro-
mation rates simultaneously. The performance of plasma-catalyst ducts such as CO2 and H2O. Toluene can also be decomposed by the
system is better than that of plasma only or catalysis only reaction cleavage of benzene ring through collisions with reactive species, e.g.
mode, indicating its promising application in biomass tar model com- OH radicals, producing hydroxycyclohexadienyl type peroxy radicals
pound (toluene) removal, but the yield of tar remotion must been im- (Fig. 13b). This reactive compound is unstable and can form a peroxide
proved yet. The stabilities of CR and PCR were also investigated. Ni/ bridge radical, a precursor for the formation carbonyl and epoxide. The
SiO2 catalyst deactivated rapidly after 2 h of reaction in the case of CR, carbonyl reaction route opens the benzene ring of toluene via a step-
for PCR, toluene conversion kept almost unchanged during 6 h of re- wise oxidation by OH species to form a relatively stable epoxide, which
action. can be further decomposed by electrons or active species, forming small
The plasma-catalytic steam reforming of toluene as a biomass tar molecules, such as oxalic acid and acetic acid.
model compound in a coaxial dielectric barrier discharge (DBD) plasma The presence of the Ni catalysts in the plasma steam reforming of
reactor was studied by Liu et al. [98]. In this work, the effect of Ni/ toluene enhanced the production of most gas products, while sig-
Al2O3 catalysts with different nickel loadings (5–20 wt%) on the nificantly reduced the formation of condensed organic by-products.
plasma-catalytic gas cleaning process was evaluated in terms of toluene These findings suggest that the combination of the plasma with the Ni
conversion, gas yield, by-products formation and energy efficiency of catalysts shifted the primary reaction pathways of toluene destruction
the plasma-catalytic process. Compared to the plasma reaction without from dehydrogenation or oxygenation of methyl group to direct clea-
a catalyst, the combination of DBD with the Ni/Al2O3 catalysts sig- vage of toluene ring, which can be evidenced by the enhanced yield of
nificantly enhanced the toluene conversion, hydrogen yield and energy hydrogen and C2H2. Previous experimental and theoretical studies
efficiency of the hybrid plasma process, while significantly reduced the showed that acetylene was most likely formed by rupturing the toluene
production of organic by-products. Increasing Ni loading of the catalyst ring through the collisions with electrons and Ar∗ species [98].
improved the performance of the plasma-catalytic processing of to-
luene, with the highest toluene conversion of 52% and energy efficiency 3.5.3. Catalytic tar elimination
of 2.6 g/kWh when placing the 20 wt% Ni/Al2O3 catalyst in the plasma. Tar elimination through catalytic process can be classified de-
The possible reaction pathways in the hybrid plasma-catalytic pro- pending on experimental conditions into: reforming, cracking, hydro-
cess were proposed by Liu et al. [98] and are shown in Fig. 13. Only genation and selective oxidation [99]. The research on catalytic tar
gas-phase reactions are involved in the plasma reforming of toluene conversion involves two methods: one approach involves incorporating
without the Ni catalyst. However, placing the Ni catalyst in the DBD or mixing catalyst with the feed biomass to achieve so called catalytic
makes the reaction more complicated as plasma driven surface reac- gasification or pyrolysis (also called in situ). This method is a one of
tions occur in addition to the gas-phase reactions. The destruction of primary methods used for tar reduction, where the tar is removed in the
toluene as a tar model compound in the argon DBD can be initiated gasifier itself. In the second approach, the gasifier producer gas is
through two major reaction routes: (i) direct electron impact dissocia- treated downstream of the gasifier in a secondary reactor. This method
tion of toluene and (ii) reaction with chemically reactive species is a one of secondary methods used for tar reduction, where the tar is

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Fig. 13. Possible reaction pathways for toluene destruction initiated by (a) energetic electrons and Ar∗, and (b) OH radicals. Adopted from Ref. [98].

removed outside the gasifier. So, if the catalyst is used inside gasifier it below 650 °C.
is called primary catalyst, and when used in a secondary reactor it is Among the characteristics of an ideal catalyst the main are: (1) good
called secondary catalyst. Among hot gas conditioning systems, cata- activity and efficiency on tar conversion in environments that contain
lytic cracking and steam reforming of high molecular weight hydro- high concentrations of H2, CO, CO2, H2O and temperatures between
carbons offer several advantages, such as thermal integration and high 600 and 900 °C, (2) good activity for methane reforming reactions
tar conversion [80]. when the focus is the hydrogen production, (3) good stability to coke-
The primary catalysts such as dolomite, calcined dolomite, olivine, deactivation and H2S poisoning, (4) easy regeneration, (5) good re-
and Ni/Al2O3 promote several important chemical reactions such as sistance to friction, (6) commercial availability and low cost, (7) no
water gas shift and steam reforming. Thus, there is the possibility with environmental toxicity [101]. Tar cracking potential depends on com-
primary catalysts to minimize tars and increase both hydrogen and CO2, position and type of catalyst. In this regard, composition of hetero-
avoiding altogether complex downstream tar removal operations. geneous catalysts can be divided into: (1) a catalytic phase - the metal,
However, catalysts in the gasifier, particularly the Ni-based catalysts, (2) a promoter which increases the activity and/or stability of the
may be affected by deactivation due to carbon deposition on the cata- catalyst and (3) a support that facilitates the dispersion of the active
lyst surface. Furthermore, the addition of active materials to the bed phase [102]. Guan et al. [21] classified catalysts in six groups: (1)
also helps prevent solid agglomeration tendencies and subsequent nickel based catalyst, (2) transition metal catalysts, (3) alkali metal
choking of the bed. In spite of challenges, the use of primary catalysts, catalysts, (4) natural catalysts, (5) zeolites catalysts, (6) activated
in the context of biomass gasification, is gaining much attention carbon catalysts or char.
nowadays as they reduce the need for expensive downstream opera-
tions. Another possible alternative is to have a catalytic process in a 3.5.3.1. Nickel based catalysts. Among the transition metals (group
reactor placed downstream from the gasifier. In this reactor, product VIII), nickel is the most widely used in the industry for steam and dry
gases are further processed using secondary catalysts. Typical materials reforming reactions. Commercially available nickel reforming catalysts
that are used as secondary catalysts are dolomite and nickel-based have been used extensively for biomass gasification. Under the
formulations. These catalysts decrease the tar content of the product gas conditions of catalytic gasification, nickel catalysts are more active
in the 750–900 °C range. Secondary catalysts are effective for hot gas for heavy hydrocarbon steam reforming than for light hydrocarbon
cleaning with the overall gasification process cost increasing sig- steam reforming. These nickel catalysts also promote water gas shift
nificantly [19]. reaction and are very effective in tar conversion. As a result, these
The chemistry involved in catalytic tar decomposition of producer nickel-based catalysts reduce tars while increasing H2/CO ratio,
gas is a complex mix of hydrocarbon decomposition and equilibrium improving synthesis gas quality [19].
reactions. The tar reaction mechanisms have been investigated for Nickel is generally supported on various materials of which Al2O3,
Simell et al. [100] by using toluene as a tar component in hot catalytic olivine, ZrO2, TiO2, CeO2 and MgO are the most studied ones. The main
gas cleanup. They proposed a set of decomposition and equilibrium limitation is the rapid deactivation caused by formation of carbon on
reactions summarized in Table 1. In addition to the partial oxidation of catalyst surface, as well as poisoning by coke, sulfides, metal chlorides
tar components, studies have shown that steam and dry reforming re- and alkali oxides [21]. However, these catalysts are effective both for
actions (13 and 14) are catalyzed by metals from group VIII. This im- tar and ammonia removal in coal or biomass gasification [6]. Table 11
plies that the Fe content of the ilmenite for example, together with the shows tar removal efficiencies of some types of Ni-based catalysts.
water and carbon dioxide content in the product gas, will induce both Miyazawa et al. [105] studied the catalytic activity of Ni supported
steam and dry reforming. Furthermore, the WGS reaction (10) is re- on various materials (Al2O3, ZrO2, TiO2, CeO2 and MgO) like is shown
ported to be catalyzed by Fe-based catalysts [80]. Calculation per- in Table 11. Two types of catalytic activity tests were carried out in a
formed by Simell et al. [100] showed that dry reforming was more laboratory-scale continuous feeding dual-bed reactor. One was the
thermodynamically favored than steam reforming reactions at tem- partial oxidation of tar with O2, the other was the steam reforming of
peratures above 830 °C, while the Boudouard reaction (4) is favored tar. The reactor contained the primary bed for pyrolysis of biomass and

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Table 11
Nickel-based catalysts performance [6].

Catalyst Tar Cracking Temperature Comments Reference

Efficiency
Metal Promoter Support

Ni Mo Quartz wool ≈100% 550 °C Good anti-coke capability. [103]

This catalyst maintains more than 95% of tar removal conversion at 550 °C, during
168 h and with a space velocity of 3000 h−1.
Commercial viability must be verified. A fixed-bed reactor was used. In the
experiments, the catalyst
sample of 5 g was supported by quartz wool.
Ni – Al2O3 100% 730-850 °C They are not stable and are eventually disabled. [104]
SiO2 95-99% A fixed-bed reactor was used
15 wt% of catalyst load (Ni/Ni + Support).
Ni – Al2O3 80-100% 550-650 °C Ni/CeO2 Presented the lowest amount of coke in the reactor during the tar [105]
ZrO2 74-100% decomposition. This tar cracking efficiency corresponding to the performance in
TiO2 69-100% partial oxidation. In steam reforming conditions the efficiency is reduced in low
CeO2 60-100% temperatures.
MgO 31-97% A fluidized bed reactor was used
12 wt% of catalyst load (Ni/Support).
Ni – Ca12Al14O33 65-100% 550-850 °C Ni/mayenite showed excellent stability against coke formation and good resistance to [106]
(mayenite) H2S poisoning due to free oxygen in the catalyst.
A fixed-bed reactor was used and 1 to 7 wt% of catalyst load (Ni/Support) were
tested.
Ni – Dolomite 97% 750 °C No deactivation was observed in 60 h of test. [107]
A catalytic packed-bed
quartz reactor and a space velocity of 12000 h−1 were used.
NiO – MgO 75-100% 650-850 °C High and stable reduction capacity. No deactivation during 100 h of test. [108]
A catalytic of fuel gas reforming reactor and 15 wt% of catalyst load (Ni/
Ni + Support) were used. A space velocity of 15000 h−1 was considered.
Ni – Olivine 85-100% 750-900 °C The difference in surface area did not influence catalytic activity. [109]
A fluidized
bed reactor and 5 wt% of catalyst load (Ni/Support) were tested. A space velocity of
1166 h−1 was considered.
Ni CeO2 ZrO2 43.2–87.2% 550-700 °C 15 wt % of catalyst load (Ni/(75% CeO2 + 25% ZrO2)) was tested as the best [110]
performance.

accumulation of solid products in the pyrolysis reaction such as char oxidation was much smaller than that in steam reforming. This can be
and ash. The gaseous products at reaction temperature including tar due to the high performance in coke removal in the partial oxidation.
were introduced to the secondary catalyst bed. In the evaluation of
catalytic performance in the partial oxidation, oxygen was introduced 3.5.3.2. Transition metal catalysts. Metal catalysts such as Rh, Ru, Pd,
into the catalyst bed through a thin tube in the inner reactor and N2 was Pt, etc. were specifically developed to reduce tar produced in biomass
also fed from the bottom of the outer reactor. In this case, the reaction gasification mainly in steam reforming conditions. These catalysts have
between tar and O2 proceeds in the catalyst bed. In catalytic perfor- a high catalytic activity with a high resistance to sulphides and a long
mance evaluation in the steam reforming, no gas was introduced and N2 thermal stability in tar steam reforming [21]. On this matter, Tomishige
was also fed from the bottom of the outer reactor. At the same time, et al. [111] found that Rh/CeO2/SiO2 exhibit higher and more stable
steam was supplied to the reactor using a microsyringe. activity in the partial oxidation of tar derived from the pyrolysis of
In order to study the partial oxidation a fluidized bed reactor was cedar biomass even under the presence of high concentration H2S
used by Miyazawa et al. [106]. A model scheme of this catalytic process (280 ppm) than the steam reforming Ni catalyst at lower reaction
is illustrated in Fig. 14, and a further description of the reactor sche- temperature than conventional conditions. These transition metal
matic diagram is detailed in Ref. [105]. Tar from the pyrolysis of cedar catalysts can significantly reduce tar (almost complete abatement),
wood is supplied from the bottom of the reactor through the distributor, but they are more expensive than a conventional nickel catalyst and
and oxygen is introduced near the bottom of the catalyst bed through their high cost, difficult the implementation at large scales. Among
thin tube. The amount of O2 introduced is far from that for complete these catalysts, Rh catalysts have a better tar removal performance than
combustion of cedar wood and the tar. Therefore, O2 is present near the other commercial catalysts, with the following performance in
bottom of the catalyst bed, however, in the upper part, O2 is absent gasification: Rh > Pt > Pd > Ni = Ru [6]. Table 12 shows tar
after the consumption. In the presence of oxygen, Ni metal is easily removal efficiencies for some catalysts of this type.
oxidized to NiO, and this catalyzes the combustion reaction. On the Besides noble catalysts, other metal catalysts like Co, Fe, Zn, and Cu
other hand, in the absence of oxygen, Ni metal catalyzes tar reforming. have also been investigated in the steam reforming of tar, and some of
From the results in partial oxidation and steam reforming, the differ- them showed higher catalytic activity than Ni catalyst [21]. Furusawa
ence is coke yield. In the fluidized bed reactor for the partial oxidation, and Tsutsumi [116] reported that Co loaded MgO pre-calcined showed
it is suggested that coke deposition can proceed in the reforming zone better tar reforming performance and higher catalytic activity than Ni
and the upper part of the reactor. In the steam reforming using fixed loaded MgO with naphthalene as a model compound, with conversions
bed reactor, this coke can be removed only by the reaction with steam. of 23% and 12%, respectively. However, both catalysts showed lower
In contrast, in the fluidized bed reactor, catalysts with deposited carbon activity in this study due to low S/C ratio (0.6) and high concentration
have a chance to react with oxygen during the catalyst fluidization. This of fed naphthalene, corresponding to 100 times as much as that in real
can explain the smaller amount of coke in partial oxidation than that in biomass gasification tar. From these results, it was concluded that this
steam reforming. The removal of coke during reaction is very important catalyst based on Co is a promising system for the steam reforming of
in terms of self cleaning of catalyst surface because carbon deposition naphthalene derived from biomass gasification as a second fixed cata-
can cause catalyst deactivation. In addition, tar amount in the partial lytic bed. Noichi et al. [117] studied the effects of addition of copper

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Fig. 14. A model scheme of partial oxidation of

tar from the biomass in a fluidized bed reactor.
Adopted from Ref. [105].

species to the iron-based mixed metal oxides such as iron–alumina gas quality. However, the main disadvantages of these catalysts are
(Fe–Al) and iron–zirconia (Fe–Zr) catalysts on the catalytic activity in their evaporation during the reaction, their difficult recovery when are
steam reforming of naphthalene as model biomass tar at 850 °C in a added directly to the biomass by dry mixing or wet impregnation,
fixed bed reactor. They found that the addition of Cu increased the which is not always cost effective for the gasification process and their
activity and stability of the Fe-Al catalyst because the well dispersed tendency to react in the gasifier with silica forming silicates leaving a
copper in the compound oxide facilitated the reduction of iron oxide to sticky deposit and causing agglomeration at high temperatures.
metallic iron and prevent the catalytic deactivation due to decreased in Kuchonthara et al. [118] studied the catalytic activity of K2CO3 on
surface area of the catalysts during the reaction. The conversion of the steam gasification of lignin and found that K2CO3 had a good
naphthalene was between 60% and 90% with loadings of 1 wt%, 3 wt% catalytic activity for tar decomposition during pyrolysis and steam
and 5 wt% showing the highest activity with the lowest CuO loading. gasification. Particularly, almost all components in biomass were
Some possible reason for this CuO loading effects on naphthalene completely converted at 800 °C.
conversion could be the difficulty for impregnate CuO homogeneously On the other hand, alkaline species contained in biomass always
with higher loading and some portion of active sites of the Fe-Al cat- play a catalytic role in thermal conversion process and when released
alysts may be covered with CO at high loadings. On the other hand, for during gasification process, can also act as catalysts for tar steam re-
Fe-Zr catalysts the conversion of naphthalene was lower, between 30% forming but they are deactivated easily by sintering [21]. Monovalent
and 80% with addition of 1 wt% CuO. alkali metals of group 1A are all highly reactive and electropositive.
Alkali metals, principally K and to a lesser extent Na, exist naturally in
3.5.3.3. Alkaline catalysts. Several studies have proven that alkali metal biomass and accumulate in the gasifier ashes. These alkali metals can
catalysts are effective for tar steam reforming and improve the product have a significant impact during pyrolysis, forming a reactive char that

Table 12
Transition metal catalysts performance.

Catalyst Tar Cracking Temperature Comments Reference

Efficiency
Metal Promoter Support

Rh CeO2 SiO2 ≈100% 550-700 °C The formation of char and coke is very low. It does not present severe deactivation problems. [112]
The cost is higher than for conventional catalyst. Continuous feeding fluidized bed reactor.
1.2 wt % of catalyst load (Rh/(40% CeO2 + 60% SiO2)) was tested
Rh LaCoO3 Al2O3 ≈100% 700 °C This proposed catalyst exhibits better performance than conventional catalysts. It is able to [113]
completely convert tar and significantly decrease the formation of coke.
A laboratory scale dual fixed bed reactor and 20 wt % of catalyst load (Rh-LaCoO3/support)
were considered
Pt – CeO2 20% 800 °C Pt/Al2O3 and Pt/MgO presented stable performance. [114]
TiO2 20% An atmospheric catalytic reforming reactor and 1.0 wt % of catalyst load (Pt/support) were
MgO 50% tested. While, a space velocity of 19200 h−1 was used.
Al2O3 50%
Ru – (PPh3)3Cl2 62-80% 600 °C The results correspond to% conversion of toluene. An atmospheric conventional fixed bed [115]
– Cl3 nH2O 21.3–42.1% reactor and 1.0 wt % of catalyst load (Ru/support) were evaluated.
– Al2O3 11.8%

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enhances gasification performance. Furthermore, the use of ash itself as as catalysts at varying S/C ratios and temperatures between 805 and
a catalyst solves the problem of ash wastes handling and gives an added 875 °C. Tar conversion was 95% for Norte dolomite and the lowest
value to the gasification process by increasing the gasification rate and conversion was 77% for the Sevilla dolomite been the order of catalytic
reducing the tar content in the producer gases. However, the major activity: Norte > Chilches > Malaga > Sevilla. The higher activity
disadvantage of these ash-based catalysts is their potential activity of the Norte and Chilches dolomites may be accounted for by their
losses due to particle agglomeration [19]. Hognon et al. [119] studied higher Fe2O3 contents and, also by their larger pore diameters. Like-
the influence of inorganic elements in the biomass itself on the steam wise, was observed an increase in gas yield (10–20%), lower heating
gasification of biomass, comparing two species of algal biomass (Chla- value (15%) of the product gas and its hydrogen content (4%), while
mydomonas reinhardtii and Arthrospira platensis) and three species of the content of CO, CO2 and CH4 was relatively unchanged.
lignocellulosic biomass (miscanthus, beech and wheat straw). These Ekstrom et al. [124] studied different catalysts for refinement and
samples had very different contents in inorganic elements, which re- upgrading of product gas obtained under steam reforming conditions.
sulted in different reactivities, with about a factor of 5 between sam- Among the catalysts evaluated, the Malaga dolomite was used after
ples. For biomass with ratio between potassium content and phosphorus being calcined achieving a nearly complete conversion of tar at
and silicon content K/(Si + P) higher than one, the reaction rate was 700–800 °C. Likewise, was also observed the increased yields of CH4
constant during most of the reaction and then slightly increased at high and C2H4 together with the reduction of tar yields, which is an in-
conversion. On the contrary, for biomass with ratio K/(Si + P) lower dication of the cracking/reforming activity of the dolomite.
than one, the reaction rate decreased along conversion. Thus, they The catalytic activity of olivine for tar elimination can be related to
confirmed that the difference of the reactivity of various biomass de- the magnesite (MgO) and iron oxide (Fe2O3) contents, where the latter
pends on the inorganic elements in them. The high reactivity was ob- is much higher in olivine than in dolomite. On this basis, the reactions
served for the biomass samples contained high amount of potassium, involved in tar elimination with olivine should be similar to those in-
which is known to act as catalyst in char gasification as well as tar volved in the same process with calcined rocks. This catalyst is mainly
reforming. deactivated by the formation of coke, which covers the active sites and
Berguerand et al. [120] studied the possibility to use an alkali- reduces the surface area of the catalyst. The advantages of this catalyst
feldspar ore as a catalytic bed material to upgrade producer gas from are its low price (similarly to dolomite), its high attrition resistance
biomass gasification. Tests involved a bubbling bed batch reactor flui- compared to dolomite and its mechanical strength which is comparable
dized with a slipstream of raw gas generated by the Chalmers Uni- to that of sand, even at high temperatures. However, olivine shows a
versity indirect gasifier (2–4-MW). Experiments were carried out at slightly lower activity in biomass gasification and tar reforming. The
700, 800 and 900 °C, with focus on tar reforming and producer gas addition of some metals to olivine can help to increase its tar reforming
quality. The results showed that alkali-feldspar presented a high re- activity. In this sense, the tar abatement activity of a Ni/olivine catalyst
sistant and holds, being a promising alternative as a tar-abatement was successfully demonstrated in the 100 kWth Dual Fluidized Bed
catalyst. (DFB) pilot plant located in Vienna, with an order of magnitude re-
duction in the tar content of the product fuel gas [80]. Likewise, Vir-
3.5.3.4. Natural catalysts. Natural minerals such as dolomite and ginie et al. [125] studied the performance of Fe/olivine catalyst on tar
olivine can be used directly as catalysts or after receiving some removal during biomass gasification in a DFB as well as the catalyst
pretreatment, such as calcination. Dolomite is a calcium magnesium efficiency for the production of a rich product gas with low tar content.
ore with general chemical formula [Ca,Mg(CO3)2] and olivine They observed that Fe/olivine material has a double effect on tar de-
represented by the formula [(Mg,Fe)2SiO4] consists mainly of silicate struction. On the one hand, it acts as a catalyst for tar and hydrocarbon
mineral in which magnesium and irons cations are set in the silicate reforming; on the other hand, it can act as an oxygen carrier that
tetrahedral. These catalysts are cheap, abundant and present transfers oxygen from the combustor to the gasifier, and part of the
considerable activity for tar reforming [21]. A large number of oxygen is used to burn volatile compounds. Therefore, an inexpensive
investigations deal with biomass gasification in fluidized bed reactors and non-toxic Fe/olivine catalyst is a material suitable for use as a
utilizing nickel based catalysts, dolomite or olivine. Hu et al. [121] primary catalyst in a fluidized bed gasification of biomass and improves
shown that catalytic activity of dolomite and olivine is increased when the commonly used olivine catalytic activity.
calcined during the steam gasification of apricot stone and calcined Others comparatives studies of the dolomite and olivine perfor-
dolomite was the most effective catalyst for increasing the H2 content in mance have been carried out. In this regard, Corella et al. [126] com-
the product gas. Calcination of olivine causes the disappearance of the pared catalytic activity of calcined dolomite, natural olivine and sin-
phase (Mg, Fe)SiO3 and formation of Fe2O3, for dolomite the tered olivine in biomass gasification. Tar content in product gas when
elimination of CO2 and formation of CaO-MgO occurs in calcination; dolomite used was 60% of the tar content obtained when natural oli-
and this could be the cause of the difference in activity. Calcined vine was employed. This indicates that dolomite was 1.4 times more
dolomite becomes very fragile after calcination and reaction; however, catalytically active than olivine. The sintered olivine lost its porous
calcined olivine maintains good mechanical strength. This decrease of structure and was not catalytically active. Devi et al. [127] studied the
dolomite mechanical strength with time during catalytic runs is catalytic activity of pure sand, pre-calcined dolomite and olivine for tar
commonly exhibited and is more evident in fluidized beds; however, removal in a bubbling fluidized bed gasifier, with a second fixed bed
once the activity is significantly reduced, the catalysts could be reactor, where the catalysts were placed. They found that when using
replaced without great expense to the overall process. Deactivation pure sand there was a 48% decrease in PAHs; when adding 17% olivine
due to carbon deposition is another problem presented by dolomite in sand the PAHs decreased by 71%, while adding 17% pre-calcined
catalyst but relatively high amounts of steam used in gasification are dolomite gave a conversion of 90% of these compounds.
effective in maintaining the activities of these catalysts due to the steam
reforming of any carbon deposited [122]. 3.5.3.5. Zeolite catalysts. Zeolites materials referred to as ‘molecular
Orío et al. [123] studied the performance of four dolomites from sieves’, are microporous crystalline aluminosilicate earth metal
diverse quarries (Norte, Chilches, Malaga, Sevilla) and the influence of minerals based on a three-dimensional network of tetrahedral
type, origin and composition on the tar elimination activity during [SiO4]4- and [AlO4]5- whose framework are open structures with
oxygen/steam gasification of wood in a downstream catalytic reactor. cations positioned within the material's pores. The cation neutralizes
The main chemical difference between the samples was the Fe2O3 the negative charge on the lattice, thus the ion-exchange and the
content: the Malaga and Sevilla dolomites has low levels of Fe2O3 catalytic properties of zeolites and other similar materials is basically
compared to those from Norte and Chilches. These samples were tested the result of this cation mobility [128]. Both, naturally occurring and

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

synthetic zeolites (referred by the generic name of zeotypes) offer almost 100% of the tar at 550 °C, but observed deactivation as soon as
essential materials widely used for industrial application [129]. The 10 h of testing, using 1-methylnaphthalene as a model of tar compo-
discovery and application of zeolites has been strictly linked with the nent.
development of refinery and petrochemistry, but these materials will Buchireddy et al. [134] investigated catalytic activity of zeolites ZY
have a key role also in the restarting era of chemistry based on biomass (5.2, 30, 80), Zβ, ZSM5 without and with supported nickel for tar re-
conversion. In most of their applications, zeolites acidity and basicity moval. They found that zeolites ZY have the best catalytic activity for
are key properties. In spite of this very relevant practical role, still a lot naphthalene conversion compared to Zβ and ZSM5 due to their larger
of questions are open concerning the behavior of zeolites, in particular pore size. On the other hand, supported nickel zeolites had a much
as acid and basic materials [130]. higher naphthalene removal activity compared to zeolites without
Protonic zeolites represent today the most prominent class of en- nickel. Thus, Ni/ZY-80 zeolite showed the best activity among the
vironmentally friendly solid acid catalysts, largely used in industry for catalysts tested with conversions of more than 99.5%. This high activity
catalytic cracking, alkylations, skeletal isomerizations, etc. Some tran- of Ni/ZY-80 was attributed to nickel activity and the zeolite acid
sition metal-containing zeolites find application as redox catalysts, such nature.
as for catalytic reduction of NOx with ammonia and for the abatement Kaewpanha et al. [21] studied the application of low concentrations
of N2O by decomposition and reduction with methane. Likewise, of Ni, Fe and Rh metal catalysts, supported on commercial zeolite (F-9)
transition metal exchanged, or impregnated zeolite catalysts have been beads by incipient wetness impregnation method, and applied for the
applied for the partial and deep oxidation of hydrocarbons, showing steam reforming of tar derived from the steam pyrolysis of seaweed in a
that transition metal cations improved the zeolite activity for hydro- fixed bed reactor. It is found that the high hydrogen production yield
carbon conversion by increasing both the zeolite acidity (by cation can be obtained at a reaction temperature above 610 °C even in the case
hydrolysis), and oxygen chemisorption. The addition of copper in Y- when is using a low metal loading on zeolite. Among the metal catalysts
zeolites promoted the oxidation of toluene and accommodated the re- supported zeolite, Rh showed the most effective for the tar removal and
moval of coke formed in the course of reaction [21]. a lower concentration of Rh loaded on zeolite showed a higher catalytic
Alkali and alkali earth cationic zeolites are largely used as industrial activity, indicating a better dispersion of metal on the surface of zeolite
adsorbents for gas purification including CO2 capture, to produce beads. Furthermore, these catalysts had an excellent reusability for the
membranes for gas separations, and as ion exchangers for water soft- reforming of tar derived from steam pyrolysis of seaweed.
ening. The possible application of cationic zeolites as “basic catalysts” is Although, zeolites are a good catalyst supports due to its high
mentioned but actual industrial applications seem to be still absent. In thermal/hydrothermal stability, have a good catalytic activity as well as
the case of natural and “cationic” zeolites, the balancing cations high resistance to sulfide in the clean-up of gasification effluents and
(usually alkali or alkali earth ions) are located in relatively large cav- are easy to be regenerated [21], shown deactivation associated with
ities formed by the [Si1-xAlxO2]x− negatively charged framework, coke formation due to the complexities of the series of reactions oc-
where x ≤ 0.5, which means that the Si/Al atomic ratio never is lower curring during the pyrolysis and gasification processes, likewise the
than 1 (Lowensteins' rule). The cations are exchangeable, thus zeolites poisoning of the active Bronsted acid sites in the catalyst by the gen-
may also act as cationic exchangers. Today, protonic zeolites are mostly erated gases during the reactions. Coke deposits pose a major challenge
synthesized directly, by using templating agents. In this case the pro- to fast pyrolysis for example, by limiting the upgrades of biomass and
tons may be residual from the combustion or decomposition of the fossil fuels; they typically cause catalyst deactivation with the negative
templating agents [130]. consequence of reducing selectivity for the desired reaction products. In
According to the Structure Commission of International Zeolite principle, this reduces the final value of the process, so increasing the
Association [131], until now, there are 234 zeolite framework type lifetime of the catalyst by just 10–20% could increase a company's
codes that have been registered. When the first synthetic materials were revenues by hundreds of millions of dollars. In reactions involving
discovered by Milton, Breck and coworker at Union Carbide, they used zeolites, carbonaceous materials are produced from the undesired in-
the modern Latin alphabet such as zeolites A, B, X, Y, and L to name the teraction of the reaction feeds or the catalyzed side reactions. The hy-
zeolites. After that, Mobil and Union Carbide initiated the usage of the drogen-rich coking species can attack key active sites at zeolite surfaces
Greek alphabet, for example, zeolites alpha, beta, and omega. Synthetic with a net consequence of catalyst deactivation. Carbonaceous mate-
zeolites with a structural topology of mineral zeolites were allotted the rials could be deposited inside zeolite catalyst's pores and create dif-
name of mineral, for example chabazite, erionite, mordenite, and off- fusion difficulties, this phenomenon is common during fast pyrolysis
retite [132]. due to the production of char and polyaromatic coke precursors via
A three-letter code has been assigned according to the rules set up oligomerization, dehydrogenation and other related reactions. How-
by the IUPAC Commission on zeolite nomenclature, to be used for ever, coke could be removed using appropriate catalyst regeneration
known framework topology irrespective of composition, for example, strategies. Although this carbonaceous material can be deposited when
MFI code is given to ZSM-5 (Zeolite Socony Mobil-5), likewise LTA using any zeolite catalysts, their concentrations and overall effect on
(Linde Type A zeolite), FAU (molecular sieves with a faujasite to- catalyst stability are dependent on the zeolite's topology and associated
pology), MOR (mordenite topology), AFI (aluminophosphate AlPO4−5 acidic properties. According to Mihalcik and co-workers [135], the
topology) [128,132]. Depending on the structure type the zeolite fra- degree of coke formation is associated with the zeolite structure/to-
mework composition can be varied to different extents. Thus, the di- pology and acidity properties [136].
versity of zeolitic materials is extremely large, from both structural and
chemical points of view. The number, nature and distribution of the 3.5.3.6. Activated carbon and char catalysts. Activated carbon, char
active centers are of paramount importance for the efficiency of a derived from biomass (biochar) and mineral char, are widely used as
heterogeneous catalyst. Zeolite structures comprise channels and cages catalyst supports for tar cracking, due to its highly porous structure. Its
that make the crystalline frameworks accessible to foreign species. catalytic activity is related to surface area and its macro-pores and
Thus, they offer great advantages with respect to non-porous solids micro-pores size, which significantly improves the dispersion of metal
[133]. ions, as well as facilitates the transport of reactant molecules to catalyst
With respect to the application of zeolites on pyrolysis and gasifi- internal surfaces [6,21].
cation, Dou et al. [103] studied tar catalytic cracking from high-tem- The heterogeneous reforming of biomass tar in presence of a biochar
perature fuel gas in a fixed-bed reactor with five different types of catalyst and H2O and CO2 like reforming agents have been studied by
catalysts: Y-zeolite, Ni-Mo, silica, alumina and lime, and found that the Feng et al. [22] in order to better understand the transformation
most efficient catalysts were Y-zeolite and Ni-Mo, which removed pathway between tar and biochar. A mechanism proposed by Feng et al.

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Fig. 15. Heterogeneous reforming mechanism of biomass

tar over biochar in the presence of H2O and CO2. Adopted
from Ref. [22].

[22] is shown in Fig. 15, in which H2O and CO2 dissociate in space to bed in fir wood pyrolysis. Char samples were prepared from wood, rice
form a large number of H/O/OH radicals, which play an important role straw, palm kernel bark and activated carbon. With the presence of hot
in the tar-biochar reforming reaction. Biomass tar, through the biochar char particles, the amount of tar was reduced from 32% in the primary
layer, is adsorbed onto the acid-base active sites (oxygen-containing tar vapor to approximately 8% in terms of carbon yield (percentage of
functional groups, alkali and alkaline earth metallic (AAEM) catalysts). biomass carbon). In addition, they observed that tar decomposition was
The attraction effect of the carbon-rich biochar matrix invokes an not influenced by char type used despite its differences in microscopic
electron pair shift in the tar molecules (relatively small mass), which surface areas, pore size distributions and inorganic content.
promotes the tar molecules to break at high temperatures. According to Zhang et al. [1] studied the effects of inorganic substances on char
the free radical theory, the tar adsorbed on the catalyst surface will for catalytic tar reforming during gasification of malle wood, corn stalk
catalytically crack to form the corresponding free radicals. The che- and wheat straw. Char was prepared from pyrolysis of malle wood. The
mical reaction between these free radicals may permit new products. catalytic activities of char and washed char with sulfuric acid under
H2O and CO2 act as the reforming agents in the biochar carbon matrix, identical gasification conditions were evaluated. It was found that char
resulting in the fragmentation of the smaller aromatic rings. The empty catalysts were effective in tar reforming for all biomass tested, reaching
active sites, formed by bond cleavage, were gradually occupied by H/ a tar content in product gas close to 100 mg/Nm3 which is low com-
O/OH radicals, forming active groups such as O-containing functional pared to tar concentration obtained in a typical gasification process
groups. In the presence of H2O and CO2 a significant amount of H/O/ with different gasifying agents and without use of any catalysts, as
OH radicals in the vicinity ingress into the biochar carbon structure. shown in Table 6 (20–100 g/Nm3). Regarding to acid washed char, it
The catalytic elements, such as AAEM species migrate at different rates was shown, that high activity for tar reforming was presented although
and transformation from the carbon matrix onto the gas-solid interface its catalytic activity was lower than raw char. However, both catalysts
or the gas phase undergoes. As the AAEM species are bonded with the C can reform tar aromatic compounds. Unfortunately, char is unrecovered
element on the biochar surface by the O element H2O and CO2 react because is partially gasified after being used as a catalyst.
with these C elements on the biochar surface resulting in AAEM-O bond El Rub et al. [139] compared experimentally tar reduction using
cleavage followed by precipitation. The valence state of Ca results in a char produced in laboratory, biomass ash, commercial char, calcined
stronger bonding interaction with the biochar when compared with K. dolomite, olivine, used fluid catalytic cracking (FCC) catalyst, sand, and
Additionally, Ca migration and precipitation is more difficult than K. nickel catalysts; model tar compounds used for this research were
When tar is adsorbed, the AAEM-O bond is cleaved and functional naphthalene and phenol, which are the best model tar compounds,
group bond on the biochar surface, an aromatic fragmented radical is representing light polyaromatic hydrocarbons and heterocyclic tar
formed when other free radicals are encountered. At the same time, types, respectively. Experimental test was carried out separately for
active AAEM species in the vicinity will continue to occupy active sites each model compound in order to evaluate the catalytic activity of
on the tar fragment groups, thereby inhibiting their secondary poly- those bed materials. Regarding results, catalytic activity classification
merization. At the same time, the H/O/OH radicals are exchanged to of different catalysts tested for phenol conversion was as follows: nickel
the AAEM species, which increases the possibility for the reforming of (91%) > dolomite (90%) > FCC (87%) > commercial char
tar macromolecules. After the reaction, gas and light tars (CnHy/CO/H2) (82%) > olivine (42.7%) > sand (34.5%). On the other hand, for
were formed, thus realizing the H2O or CO2 heterogeneous reforming of naphthalene conversion, catalytic activity tested was as follows: nickel
biomass tar over the biochar catalyst. (100%) > commercial char (99.6%) > laboratory char (94.4%) > bio-
Likewise, the catalytic activity of this type of catalysts has been mass ash (73.7%) > FCC (60.3%) > dolomite (61%) > olivine
evaluated. Min et al. [137] investigated catalytic activity of limonite, (55%) > sand (2%). According to this, char promotes a high conversion
char and iron/nickel catalysts supported in char, in order to study tar of both model tar compounds evaluated and therefore, represents a
vapor reforming. Results indicated that catalysts supported in char good alternative for tar treatment considering its low cost and naturally
(iron/nickel) exhibits much higher activity for tar reforming than char production possibility within the gasifier; but with disadvantages of
itself. This way, the authors concluded that char not only disperses the pore blockage by coke, as well as loss of char by dry and steam re-
catalysts, it also interacts with them to increase their catalytic activity forming reactions [6].
in tar steam reforming. Activated carbon (AC) is a non-graphitic, microcrystalline form of
Park et al. [138] studied primary tar reduction using a char particles carbon. Its structure is more disordered than that of graphite, and

364
 Table 13
Main tar removal systems used in biomass gasification industrial plants.

Country Application Type of gasifier Products Feedstock Gasification gas cleaning system Reference
(Startup year)

Güssing plant from Austria Combined heat and power (CHP) Dual Fluidized Bed Power: 2 MWe Wood chips Heat exchanger, fabric filters and scrubber are used. [142,143]
(2002) production based on steam gasification (850–900 °C) Heat: 4.5 MWth (3 t/h, wet: 25–40%) For tar removal, rapeseed methyl ester is used in the
M.L. Valderrama Rios et al.

scrubber as solvent.
GoBiGas plant from Sweden Biomethane production by allothermal Circulating Fluidized Bed Power of Forest residues Cooler, fuel gas filter and wet scrubber are considered. [143]
(2014) gasification and steam injection (850 °C) Biomethane Rapeseed methyl ester and activated carbon are used
20 MWgas for tar removal.
Skive plant from Denmark Combined heat and power (CHP) Bubbling Fluidized Bed Power: 6 MWe Wood chips and pellets Catalytic Cracking Reactor, cooler, bag filter, wet [143,144]
(2008) production by using gasification with air (2 bar - 850 °C) Heat: 13 MWth (wet:10–30%) scrubber that uses water as solvent
and reciprocating engines
Lahti Energy's Kymijärvi II Combined heat and power (CHP) Circulating Fluidized Bed Power: 50 MWe Organic residues and waste streams Initially mechanical hot filtering is used like ceramic [143]
Finland (2012) production (850–950 °C) Heat: 90 MWth (31 t/h, wet:15–25%) filter. Bag filter filters, N2, and activated carbon are
used after gas cooling.
Harboøre plant from Denmark Combined heat and power (CHP) Updraft fixed bed gasifier Power: 1 MWe Wood chips A wet gas cleaning system with gas coolers and a wet [143]
(1996) production based on two gas engines Heat: 3.5 MWth electrostatic precipitator are used
The Bioliq® process - KIT Production of synthetic fuels and High pressure DME (608 t/y) Lignocellulosic crop straw (0.5 t/h) Hot filters, sorption system and catalytic reactor is [143]
Germany (2014) chemicals from biomass pyrolysis and entrained flow gasifier Gasoline: used to removal particle matter and tar compounds
bio-oil gasification (8 MPa) (360 t/y)
Burkhardt Nuernberger plant Combined heat and power (CHP) Fluidized bed gasifier in Power: 0.2 MWe Wood chips Cyclone and fabric filters [143]
Germany (2009) production integrated with a gas engine co-current flow, using air Heat: 0.3 MWth
CHP plant of Yamagata Combined heat and power (CHP) Updraft gasifier using air Power: 2 MWe Wood chips n.a. [143]
Japan (2003) production as gasification agent Heat: 8 MWth (60 t/d)
Senden plant from Germany Combined heat and power (CHP) Dual Fluidized Bed Power: n.a Wood shavings Heat exchanger, bag filter and scrubber that uses [142]
(2012) production Heat: 15 MWth rapeseed methyl ester as solvent
Villach plant from Austria (2009) Combined heat and power (CHP) Dual Fluidized Bed Power: n.a Wood shavings Heat exchanger, bag filter and scrubber that uses [142]

365
production Heat: 15 MWth rapeseed methyl ester as solvent
Oberwart plant from Austria Combined heat and power (CHP) Dual Fluidized Bed Power: n.a Wood shavings Heat exchanger, bag filter and scrubber that uses [142]
(2007) production Heat: 8.5 MWth rapeseed methyl ester as solvent
Tournai plant from Belgium (2009) Combined heat and power (CHP) Dual stage downdraft Power: 260 kWe Wood ships Cyclone, scrubbing, heat exchangers and bag filter [145]
production gasifier Heat: 475 kWth
Mont-Godinne Hospital from Combined heat and power (CHP) Dual stage downdraft Power: 700 kWe Wood shavings (recycled) Cyclone, scrubbing, heat exchangers and bag filter [145]
Belgium (2017) production gasifier Heat: 1.2 MWth
Glass bottle manufacturer from Gasification plant with direct use of Dual stage downdraft Heat: 950 kWth Woodchips from vineyards – Cyclone, scrubbing, heat exchangers and bag filter [145]
France (2015) product gas gasifier pruning branches and obsolete vine
stocks
Karlovo biomass plant from Electric cogeneration plant Bubbling fluidized bed Power: 1.5 MWe Straw pellets, composting and Cyclonic precipitator, thermal cracking reactor, gas [146]
Bulgaria (2015) gasifier Heat: n.a. wood chips cooler, particulate metal filter, ash evacuation system,
venturi scrubber, dynamic precipitators.
Movialsa plant from Spain (2011) Combined heat and power (CHP) Four bubbling fluidized Power: 6 MWe Dehydrated orujo and orujillo Gas cooler, particulate filter, ash evacuation system, [146]
production bed gasifier Heat: 6.6 MWth (olive or grape residues) venturi scrubber
Syngas plant from Italy (2015) Electric generation plant Bubbling fluidized bed Power: 1 MWe Straw pellets Cyclonic precipitator, thermal cracking reactor, gas [146]
gasifier cooler, particulate metal filter, ash evacuation system,
venturi scrubber, dynamic precipitators
University of Norhtern British Biomass gasification plant to provide heat Entrained flow gasifier Heat: 4.4 MWth Locally sourced wood waste (bark, Oxidation reactor and ESP (electrostatic precipitator) [147]
Columbia from Canada (2011) for campus – District heating wood chips, sawdust)
University of British Columbia Biomass gasification plant to generate Entrained flow gasifier Power: 2 MWe Locally sourced urban waste wood Thermal cracking reactor and bag filter [147]
from Canada (2012) heat and electric power Heat: 4.35 t/h of (bark, wood chips, sawdust)
steam
University of British Columbia Biomass gasification plant to generate Entrained flow gasifier Heat: 9.07 t/h of Locally sourced urban waste wood Oxidation reactor and ESP (electrostatic precipitator) [147]
from Canada (2012) steam (thermal mode) steam (bark, wood chips, sawdust)
Birmingham Bio Power Ltda from Biomass gasification plant to generate Four entrained flow Power: 10 MWe Locally sourced, class A – C Oxidation boiler [147]
United Kingdom (2016) electric power gasifier waste biomass fuel
Kruger products plant from Canada Biomass gasification plant – Process Two entrained flow Heat: 12 MWth Locally sourced wood residue and/ Does not apply because direct firing of the product gas [147]
(2009) steam fired directly into boiler gasifier (18.14 t/h steam) or clean construction debris in the boiler
(continued on next page)
Biomass and Bioenergy 108 (2018) 345–370
M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

Reference contains crystallites only a few layers thick and less than 10 nm wide.
Due to their highly porous textural structures, activated carbons have
[147]

[143]

[143]

[143]

[143]

[143]

[143]
also been widely used as catalyst supports for conversions of hydro-
carbons and tar cracking, not only because their macropores and me-

The raw gas is then separated of dust and tars through

Sulfur removal and tar reforming in a special filtering

Oxidation reactor and ESP (electrostatic precipitator)

sopores would greatly improve the dispersion of metal ions, but facil-
itate transport of reactant molecules (e.g., toluene, 0.68 nm molecular
size) into the internal surfaces of the catalyst. It has been demonstrated
that activated carbon has a high affinity and adsorption selectivity to
dust and tars through a filtering system.

hydrocarbon compounds such as asphaltenes. Particularly the meso-

Cyclone gasifier with gas cleaning

Cyclone gasifier with gas cleaning

Cyclone gasifier with gas filtering pores of the activated carbon was thought to play an important role for
The raw gas is then separated of
Gasification gas cleaning system

effective conversion of heavy hydrocarbon compounds into lighter

fractions, while restricting the carbon/coke formation. In addition,

system is accomplished
carbon-supported catalysts, due to their neutral or weak base proper-
a filtering system. ties, were found to be superior to the solid acid catalysts with respect to
the resistance to deactivation by deposition of coke and heavy metals
[80].
AC derived from coconut shells was used in a study by Lu et al.
[140] for toluene decomposition. The AC was used as a support for
three copper precursors, i.e., copper nitrate, copper acetate and copper
sulfate, and the effects of Cu loadings and reaction temperatures were
Locally sourced waste wood (bark,

Wood chips (dry, good quality)

examined. The tests were carried out using 200 ppm toluene in a N2 gas
Pellets, wood chips (24 t/d)

containing 10% O2. The copper nitrate precursor produced a catalyst

Woody biomass and bio-oil

with the highest toluene conversion at lower temperatures (270 °C).

wood chips, sawdust)

The activities of the copper catalysts AC-supported were in the order

copper nitrate (99%) > copper acetate (97%) > copper sulfate (80%)
for 1 wt% copper loading weight. This high toluene conversion was due
Wood chips

Wood chips

Wood chips
(133 kg/h)
Feedstock

to the good dispersion of the active phases and to the nanoscale di-
mensions of the copper particles.
According to Shahbaz et al. [141], coal bottom ash showed a good
potential to be used as catalyst and adsorbent in steam biomass gasi-
Woody Biomass: 0.5
superheated steam)

fication. The presence of Si, Ca, Mg, Fe and oxygen elements in coal
Gasoline: 94.5 L/d
Power: 0.14 MWe

Power: 0.30 MWe

Power: 0.05 MWe

Power: 0.20 MWe

Heat: 0.24 MWth

Heat: 0.80 MWth

Heat: 0.11 MWth

Heat: 0.34 MWth

Bio-Oil: 1 MWth
Heat: 12 MWth

bottom ash confirmed its ability to be used as a catalyst. With the

Heat: 5 MWth

presence of SiO, it can also be a bed catalyst. The iron oxide enhances
(10.89 t/h
Products

the tar reduction and CaO increases the gas yield by decreasing the CO2
MWth

content in the product gas while the alumina will resist sintering of
metal catalyst.
Finally, Table 13 presents a summary of the main technologies of
Entrained flow gasifier

Pressurized entrained

gas cleaning and tar removal used in some biomass gasification in-
Downdraft fixed bed

Downdraft fixed bed

Downdraft fixed bed

Downdraft fixed bed

And Fischer Tropsch

Biomass gasification

dustrial plants in the world. These systems represent a combination of

Type of gasifier

the technologies described above.

flow gasifier

Technology
gasifier

gasifier

gasifier

gasifier

process

4. Conclusions

Characteristics and performance of different reduction-removal

Biomass pyrolysis and bio-oil gasification

treatments of tar generated during biomass gasification were reviewed,

Biomass gasification plant to generate

making special considerations about its formation, composition, con-

Fuel synthesis and heat production
Combined heat and power (CHP)

Combined heat and power (CHP)

Combined heat and power (CHP)

Combined heat and power (CHP)

version, classification and potential removal.

An optimized gasification process, through appropriate selection of
operating parameters (temperature, gasification agent, equivalent air
heat and electric power

ratio or steam to biomass ratio and residence time), allow to produce a

to heat production

considerably clean product gas. There is not a clear trend about tar
content behavior in product gas (increasing/decreasing) when gasifier
Application

production

production

production

production

design is considered (fixed bed and fluidized bed gasifier); however, it

was observed the tar content in product gas from up draft fixed bed
gasifier is higher than downdraft fixed bed gasifier, giving a tar re-
duction between 30 and 90%. Likewise, when bubbling fluidized bed
(VA) Medical Center from USA

Urbas Terni plant from Italy (2015)

US Department of Veterans Affairs

GTI gasifier Des Plaines from USA

Holzgasanlage 1 Käser Gasel from

gasifier is compared with circulating fluidized bed gasifier, a tar re-

Steiner A. & Cie AG plant from
Kempele Ecovillage plant from

duction of 50% in the latter was noted. Modifications in gasifier design

MEVA VIPP Pilot Plant from

are complementary and could increase tar removal, but these should be
Switzerland (2015)

Switzerland (2013)

easy to implement and economically viable.

Sweden (2006)

Finland (2009)
Table 13 (continued)

Physical-mechanical treatments, which include dry and wet

n.a: not available.

cleaning processes have tar removal efficiencies up to 99%, but with

(Startup year)

disadvantages of potentially reducing energy conversion efficiency and

(−)
Country

generating highly hazardous waste. From this point of view, thermal

cracking methods are better because they can achieve removal effi-
ciencies up to 98% without generating toxic waste. However, these heat

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M.L. Valderrama Rios et al. Biomass and Bioenergy 108 (2018) 345–370

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