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Frontiers in Energy

Front. Energy    2020, Vol. 14 Issue (3) : 545-569
Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: a review
Ru Shien TAN1, Tuan Amran TUAN ABDULLAH1(), Anwar JOHARI1, Khairuddin MD ISA2
1. Centre of Hydrogen Energy, Institute of Future Energy; School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia
2. School of Environmental Engineering, Universiti Malaysia Perlis, Kompleks Pusat Pengajian Jejawi 3, 02600 Arau, Perlis, Malaysia
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Presently, the global search for alternative renewable energy sources is rising due to the depletion of fossil fuel and rising greenhouse gas (GHG) emissions. Among alternatives, hydrogen (H2) produced from biomass gasification is considered a green energy sector, due to its environmentally friendly, sustainable, and renewable characteristics. However, tar formation along with syngas is a severe impediment to biomass conversion efficiency, which results in process-related problems. Typically, tar consists of various hydrocarbons (HCs), which are also sources for syngas. Hence, catalytic steam reforming is an effective technique to address tar formation and improve H2 production from biomass gasification. Of the various classes in existence, supported metal catalysts are considered the most promising. This paper focuses on the current researching status, prospects, and challenges of steam reforming of gasified biomass tar. Besides, it includes recent developments in tar compositional analysis, supported metal catalysts, along with the reactions and process conditions for catalytic steam reforming. Moreover, it discusses alternatives such as dry and autothermal reforming of tar.

Keywords hydrogen      biomass gasification      tar      steam reforming      catalyst     
Corresponding Author(s): Tuan Amran TUAN ABDULLAH   
Online First Date: 24 March 2020    Issue Date: 14 September 2020
 Cite this article:   
Ru Shien TAN,Tuan Amran TUAN ABDULLAH,Anwar JOHARI, et al. Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: a review[J]. Front. Energy, 2020, 14(3): 545-569.
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Ru Shien TAN
Khairuddin MD ISA
Fig.1  Comparison between (a) fuel cell vehicle and (b) conventional vehicle.
Fig.2  A possible route of biomass gasification and proposed technique for improvement of syngas production.
Fig.3  Composition of gasified biomass tar derived from various biomass feedstock.
Class Description Properties Example
1 GC-undetectable Heaviest tars, condensable at high temperature
2 Heterocyclic aromatic HC Highly water-soluble Pyridine, phenol, cresols, quinoline, isoquinoline and dibenzophenol
3 Light aromatic HC
(1 ring)
Do not pose a condensation and solubility related problem Toluene, ethylbenzene, xylenes, styrene
4 Light polycyclic aromatic HC
(2–3 rings)
Condensable at low temperature even with low concentration Indene, naphthalene, fluorine, phenanthrene and anthracene
5 Heavy polycyclic aromatic HC
(4–7 rings)
Condensable at high temperatures even with low concentration Fluoranthene, pyrene, chrysene, perylene and coronene
Tab.1  Tar classification based on molecular weight [53]
Reaction ΔH2980/(kJ·mol−1) Refs.
Steam reforming of hydrocarbon
C xHy+xH2O\hscale 50%?(x+12y)H2+CO
Steam reforming of oxygenated hydrocarbon
C xHyO z+( xz) H2O\hscale 50%?(x+ 12 yz)H 2+xCO
Water-gas shift
CO+H2O\hscale 50%?CO2 +H2
−41 [72,73]
Dry reforming
C xOy+xCO2\hscale 50%?12yH2+2xCO
>0 [48,74]
C xHy+H2Cx1Hy2 +CH4
<0 [74,75]
Methane steam reforming
CH 4+ H 2O?(g)\hscale 50%? CO+3H2
206.9 [74,75]
Carbon formation
C xHyxC+ 12 yH2
<0 [70,71]
Boudouard reaction
C+CO2\hscale 50%?2CO
172 [70,72]
Carbon gasification
C+H2O\hscale 50%?CO+ H 2
131 [70,71]
Tab.2  Possible reactions involved in gasified biomass tar steam reforming process
Fig.4  Possible reaction pathways for steam reforming of tar.
Active metals Supports Preparation methods Tar model compound Operating conditions Catalytic performance/% Remarks Ref.
Ni (10% (wt.)) Activated char Impregnation Toluene, naphthalene T = 800°C, S/C= 2, GHSV= 8000 h1 Tar conv. = 92–100, H2 comp. = 66–67 Structural damage and surface area deterioration were observed on spent catalyst [41]
Ni (10% (wt.)) Al2O3, MgO, CaO Toluene, phenol, naphthalene, pyrene T = 450°C, S/C= 5, GHSV= 1900 h1 Tar conv. = 80–100, H2 yield= 2–13 Ni/Al2O3 and Ni/CaO had an unstable behavior in H2 yield [79]
Ni (20% (wt.)) Al2O3 Impregnation Phenol, toluene, Furfural, methyl naphthalene, ndene, anisole T = 750°C, S/C= 3 C conv. = 90, H2 yield= 14.3 H2 yield is much lower than the potential H2 yield (63%) calculated from stoichiometry; O2 contributed the largest constitute of reformate followed by CO and H2 [24]
Cu (1% (wt.)) Calcined scallop shell Incipient wetness impregnation Tar derived from cedar wood gasification T = 700°C, Catalyst= 2 g, Water= 0.09 mL/min H2 yield= 60 mmol/gcarbon Existence of Ca(OH)2 on catalyst improved the basicity of catalyst and anti-coking ability [84]
Ru (1% (wt.)) 12SrO-7Al2O3 Physical mixing, impregnation Toluene T = 600°C, S/C= 2, W/F = 7 g h/mol Tar conv. = 80 Ru(PPh3)3Cl2 recognized as a better Ru precursor for a high catalytic activity as compared with RuCl3nH2O [87]
Pt (1.5% (wt.)) Al2O3, CeO2/Al2O3 Incipient wetness impregnation Toluene T = 700°C, Steam/toluene= 40 Tar conv. = 80–95, H2 comp. = 65–68, H2/CO= 6.5–8.5 Doping of CeO2 decreased the selectivity to CO but increased the selectivity to CO2; Pt/CeO2/Al2O3 produced a higher H2/CO [44]
Ba/Ni, Sr/Ni, Ca/Ni (2.28+ 5% (wt.)) LaAlO3 Pechini method /Impregnation Toluene T = 600°C, S/C= 2, WHSV= 27.1 h−1 C conv. = 28–44, H2 yield= 26–41 Toluene conversion and H2 yields increased drastically by the addition of alkaline-earth metals [97]
Ni/Ru-Mn (16+ 0.6+ 2.6% (wt.)) α-Al2O3 Incipient wetness impregnation Toluene T = 600°C, S/C= 25, GHSV= 10000 h−1 C conv. = 100, H2 comp. = 68.1 Formation of filamentous carbon which leads to reactor clogging and pressure drop was observed on spent catalyst surface [45]
Fe (10 wt.%)
Fe-Ni (5+ 5 wt.%)
Olivine Thermal fusion Toluene T = 850°C, S/C= 0.93, WHSV= 0.88 h1 Tar conv. = 98, H2 yield= 88-98 Tendency of carbon formation of Fe/olivine was slightly higher than Fe-Ni/olivine [42]
Pt/Ni (0.85+ 5 wt.%) La0.7Sr0.3AlO3−δ Pechini method/Impregnation Toluene T = 600°C, S/C= 8.9, GHSV= 12000 h−1 C conv. = 59.1, H2 yield= 52.7 Pt/Ni was the best impregnation order lead to a high H2 yield and a high tolerance to coking [111]
Ni, Co (10 wt.%)
Ni/Co (5+ 5 wt.%)
ZrO2 Impregnation Phenol T = 600°C, S/C= 9, WHSV= 115.56 h1 Tar conv. = 33–53, H2 yield= 24–51 Bimetallic catalyst exhibited better catalytic activity than monometallic catalysts [117]
Ni (20 wt.%) Lignite char, Al2O3 Ion exchange Toluene T = 650°C,
S/C= 2
H2 yield= 512–1125 mmol/g-Ni Lignite char is readily gasified and not suitable service as catalyst support for steam reforming [120]
Ni (10 wt.%) Activated carbon, olivine, Al2O3 Incipient wetness impregnation Toluene T = 600°C, S/C= 2, LHSV= 0.87 h1 C conv. = 18–100 The large surface area and microporous structure of activated carbon support contributed to a fine Ni particle distribution and consequently lead to a high catalytic activity [122]
LaNi0.5Mn0.5O3 Pechini method Toluene T = 700°C, S/C= 3, HSV= 20000 h1 Tar conv. = 100, H2 comp. = 42 Catalyst required high reduction temperature (up to 1000°C) [133]
V (3 wt.%) Mg/Al Co-precipitation /Impregnation Toluene T = 500°C, S/C= 2, WHSV= 16.6 h1 C conv. = 77.5, H2 comp. = 57 A higher V content presented a better activity in toluene conversion while a lower V content produced a higher H2 composition of reformate [138]
Tab.3  Summary of catalytic gasified biomass tar steam reforming processes
Catalyst Perovskite Hydrotalcite Conventional supported
General formula ABO3
where A= alkaline earth metal; B= transition metal
Mg6Al2CO3(OH)16·4(H2O) Metal oxide, oxides mineral, carbonaceous material
Examples of Ni based catalyst LaNi0.5Mn0.5O3, La0.9Ni0.2Mg0.1Al0.8O3 Ni/MgAl Ni/Al2O3, Ni/olivine, Ni/lignite char
Structure Crystal structure, nonstoichiometric oxygen Brucite-like structure, where Mg2+ attached with OH- ions to form octahedral structure
Synthesis method Complex, i.e., citrate method, solution combustion techniques Complex, i.e., urea hydrolysis, sol-gel method, microwave treatment Easier, i.e., impregnation, precipitation
Thermal stability Higher Higher Lower especially carbonaceous material
Resistance against coke deposition Stronger Stronger Weaker
Tab.4  Comparison of perovskite and hydrotalcite catalysts with conventional supported catalysts
Favored temp. /°C Tar model Catalyst Metal loading
/% (wt.)
Other operating condition Catalytic performance/% Remark Ref.
700–900 Toluene, toluene/naphthalene Ni/MgO/Al2O3 10.0 S/C= 1.5,
GHSV= 20000 h1
Tar conv. = 89–100, H2 comp. = 22–30 CO2 and CO are the main products at lower and higher temperatures, respectively;
large cyclic HCs have a higher thermal stability
800 Toluene Ru/α-Al2O3, Ni/α-Al2O3 2.0 S/C= 3.57, WHSV= 10000 h1 C conv. = 96–98, H2 comp. = 69–76 Ru is more stable and has a higher activity toward tar conversion than Ni [121]
800 Phenol Ni/g-Al2O3 10.0 S/C= 13, WHSV= 0.444 h1 C conv. = 57, H2 comp. = 14 The low conversion may be due to the use of the unreduced catalyst [31]
650–750 Toluene Ce0.4Ni0.6AlO3,
5.8 S/C= 1.5, WHSV= 23068 h1 Tar conv. = 100, H2 comp. = 25–30 The present of CeO2 allows the full conversion of toluene at a lower temperature [150]
Tab.5  Favored temperature for H2 production in steam reforming of gasified biomass tar
Favored S/C ratio Tar model Catalyst Metal loading
Other operating condition Catalytic performance (%) Remark Ref.
3.5–5.0 Toluene Ni/olivine, Ni/Ce/olivine, Ni/Ce/Mg/olivine 3.0 T = 790°C, GHSV= 782 C conv. = 59–93, H2 comp. = 60–66 Ni/Ce/Mg/olivine had a more stable performance at a low S/C ratio [158]
2.0 Benzene NiO/ceramic foam 3.5 T = 750°C, WHSV= 5.6 C conv. = 85.4, H2 comp. = 60 The H2 selectivity is not affected by S/C ratio in this case [156]
8.0 Phenol/ethanol Ni/Cu/sepiolite clay 20.0 T = 650°C, WHSV= 3.2 C conv. = 75, H2 yield= 73 The limit of S/C ratio is not achieved since carbon conversion showed an increased trend [159]
Tab.6  Favored S/C ratio for H2 production in the steam reforming of gasified biomass tar
Favored WHSV/h1 Tar model Catalyst Metal loading/% (wt.) Other operating condition Catalytic performance/% Remark Ref.
5000 Toluene Ru/α-Al2O3 2.0 T = 700°C, S/C= 1.43 Tar conv. = 87.4, H2 comp. = 61.5 Carbon conversion showed a decreased trend with space velocity, indicating that the adsorption-limited was not achieved [121]
10000 Toluene Ni/coal 10.6 T = 400°C, S/C= 15 H2 yield= 62 H2 yield was stabilized above 40000 h1, implying that the adsorption-limited was achieved [163]
0.1–0.4 Toluene, benzene, phenol Ni/Mg/Al, Ni-Fe/Mg/Al 12.0 T = 600°C, S/C= 1.67 Tar conv. = 100%,
H2/CO= 4.4–5.6
Ni-Fe alloy has a better performance than Ni-based catalyst although Ni based catalyst showed a higher H2/CO ratio of reformate [109]
Tab.7  Favored space velocity or space time for H2 production in steam reforming of gasified biomass tar
Fig.5  Mechanism of coke suppression by CeO2 support.
Fig.6  SEM images of (a) fresh NiO/ceramic catalyst (adapted with permission from Ref. 157]); (b) amorphous coked NiO/ceramic catalyst (adapted with permission from Ref.[157]); (c) filamentous coked Ni/α-Al2O3 catalyst (adapted with permission from Ref. [121]).
Fig.7  TPO profiles of spent Ni/Al2O3 and Fe-Ni/Al2O3 catalysts after steam reforming of toluene (adapted with permission from Ref. [102]).
Fig.8  Activity of LaNiO3 catalyst. Reaction condition: S/C 3.9; catalyst 0.03 g; temperature 650°C; He 120 mL/min (adpated with permission from Ref. [135]).
Fig.9  Schematic diagram.
Fig.10  Steam reforming of toluene in BBCN hollow fiber membrane reactor (adapted with permission from Ref. [202]).
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