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Review article

Recent advances in catalysts for hot-gas removal of tar and NH3 from biomass gasification
Chunbao (Charles) Xu a , Jaclyn Donald a b, Enkhsaruul Byambajav b, Yasuo Ohtsuka b

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Abstract

Biomass gasification produces a low to medium-BTU product gas (or syngas) containing primarily CO2, H2, CO, CH4 and (C2 +C3), as well as some contaminants such as tars, NH3, H2S and
SO2. In order to achieve better efficiencies of the syngas applications, these contaminants must be removed before the syngas is used for internal combustion, gas engines, and in particular
for fuel cells and methanol synthesis. Compared with the wet scrubbing technology, hot-gas cleanup technology to remove tar, ammonia and other contaminants at the “hot” state is more
advantageous with respect to energy efficiencies. This paper provides an overview on recent advances in catalysts for hot-gas removal of tar and ammonia from biomass gasification. The
review focuses on the recent development and applications of dolomite catalysts, iron-based catalysts, nickel and other metal supported catalysts, and the novel carbon-supported
catalysts for hot-gas tar removal and ammonia decomposition. The barriers in applications of hot-gas cleanup processes and catalysts for full-scale biomass gasification, and areas for
future research, are also discussed.

Introduction

In biomass gasification, the biomass fuel is partially oxidized/gasified in an oxidizing atmosphere of air, oxygen and/or steam to form a low to medium-BTU product gas (also called
producer gas or syngas) containing primarily CO2, H2, CO, CH4 and (C2 +C3), which can be used for heat and electricity generation, or for synthesis of liquid fuels and methanol [1], [2], [3],
[4], [5]. In oxygen- or steam-blown gasifiers, lower heating values (HHV) of 10–14 MJ/Nm3 can be attained for the product gas, compared with only 4–8 MJ/Nm3 in a typical air-blown
process [6], [7], as shown in Table 1.

In addition to syngas, biomass gasification also produces some contaminants in the product gas, such as tars, NH3, H2S, HCl and SO2 [1], [2], [3], [4], [5]. These contaminants must be
removed before the syngas is used for internal combustion, gas engines, and in particular for fuel cells and methanol synthesis, in order to achieve better efficiencies in syngas applications.
Tar, representing all organics with a molecular weight greater than that of benzene [8], is highly undesirable because of the detrimental problems associated with condensation of tar in

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the process equipment, pipe lines as well as in end use applications such as engines and turbines. The allowable limits for tar in the producer gas depend on the process and end use
applications. Milne and Evans [9] reported tar tolerance limits for various end use devices: for example, less than 50–500 mg/Nm3, 50–100 mg/Nm3 and 5 mg/Nm3 is recommended for
compressors, internal combustion systems, and direct-fired industrial gas turbines, respectively. For methanol synthesis, the contents of tar and ammonia are required to be <0.1mg/Nm3,
and <10 ppm, respectively [2], [4], [5]. The content of NH3 in the product gas, typically 1000–5000 ppm [10], is dependant on the type of biomass used, as well as the gasifier parameters
and operating conditions. Most of the nitrogen that is contained within biomass or coal would end up mainly as NH3, N2, and some HCN, HNCO, and NOx during the processes of
gasification and pyrolysis [11], [12], [13]. As much as 60–80% of the nitrogen in biomass would convert to NH3 during the gasification process [14], and as much as 50–90% of the NH3 would
form NO, through a complex radical mechanism illustrated in Fig. 1, in gas turbines when the gas is combusted to produce power [15]. A large number of studies were reported on the
formation of tar and ammonia during gasification. It has been generally shown that increasing the air to fuel ratio decreased the ammonia and tar in the product gas [6], [16], [17], a high
temperature decreased the formation of tar but a longer residence time could increase ammonia formation [10].

The tar, ammonia and other contaminants (e.g., HCl and H2S) in the product gas can be cleaned by the wet scrubbing technology, widely adopted in the existing biomass gasification
processes. Compared with the wet scrubbing technology, hot-gas cleanup technology, preferably employing catalysts, to remove these contaminants at the “hot” state is more
advantageous with respect to energy efficiencies as it eliminates the needs of cooling the product gas and re-heating again for the syngas applications (internal combustion, gas engines,
fuel cells and methanol synthesis, etc.). Very recently, Ohtsuka et al. [18] overviewed some recent progress in Japan on the hot-gas cleanup of HCI, H2S and NH3 in raw fuel gas for coal-
based, combined cycle power generation technologies.

The light hydrocarbons and tars formed during the gasification process could be removed through steam/dry reforming or cracking/hydro-cracking reactions as shown below [19]:

Without the use of catalyst, steam reforming of tars occur appreciably at >900 °C (due to the endothermic nature of these reactions and a high activation energy >250–350 kJ/mol). Steam
and dry reforming reactions with the use catalysts have shown to be a promising way to remove the tar components from the gasification gas at a lower temperature [20]. Dolomite and
VIII metals such as Ni, Fe, and Co, were the most common catalysts for the tar removing reactions [21]. For instance, the use of NiMo/Al2O3 and dolomite could significantly reduce the
activation energy of the steam reforming reaction of toluene from >250–350 kJ/mol to 56–123 kJ/mol at 650–850 °C [22]. The decomposition of benzene at 900 °C through steam reforming
without a catalyst led to only 2% conversion, while the addition of a dolomite catalyst increased the conversion significantly, reaching 40% at 950 °C and 80% at 1000 °C [23]. In addition,
dolomite catalysts were found to be active for tar cracking.

The ammonia in the producer gas can be reduced by hot-gas cleanup either through catalytic decomposition or selective oxidation, as shown in the following reactions (Eqs. (6), (7)) [24].
For some applications such as hydrogen fuel cells, complete decomposition of ammonia into H2 and N2 is desirable. In catalytic decomposition of ammonia, dehydrogenation occurs
forming some reaction intermediate or N and H on the surface of a catalyst, which subsequently form N2 and H2 through surface reactions on the catalyst. Other gas components (CO, CO2,
H2, etc.) present in the bio-syngas may have a negative effect on the decomposition of ammonia, as they would compete for the adsorption and active sites on the catalyst, and they could
also react with NH3 to form HCN [24]

The ammonia decomposition reaction (to form N2 and H2) over an iron-based catalyst was found to be first-order with respect to the partial pressure of ammonia whose rate expression
was shown as follows [25]: where Ea is the activation energy of ammonia decomposition. The value of Ea was found to be 96 kJ/mol for the Fe catalyst with
potassium as a promoter, and 87 kJ/mol for the catalyst without potassium. Chellappa et al. [26] investigated ammonia decomposition using Ni–Pt/Al2O3 catalyst, and the reaction proved to
be first-order reaction too, with the activation energy of about 200 kJ/mol.

From the above discussion, it is clear that development of effective and stable catalysts for tar and NH3 removal are extremely critical for the development of viable hot-gas cleanup
technologies. This is because the reactions for steam/dry reforming or cracking/hydro-cracking of tars and ammonia decomposition are highly endothermic and require high activation
energies in the absence of a suitable catalyst. As such, this review will focus on the recent developments and applications of catalysts for hot-gas removal of tar and ammonia from biomass

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gasification.

Section snippets

Catalysts for hot-gas tar removal

The biomass-derived tars consist of a wide range of condensable hydrocarbon and oxygen containing compounds, which are mostly aromatics and complex poly-aromatic hydrocarbons
(PAHs) [19]. The complex composition of biomass tars makes it difficult to understand the reaction mechanisms. Therefore, most studies used model tar compounds such as benzene,
toluene, phenol, and naphthalene in the research. The properties of these model compounds are shown in Table 2. It was observed that in the …

Catalysts for hot-gas ammonia decomposition

The activation energy required for ammonia decomposition is high, and the typical temperatures in fluidized-bed gasifiers, ranging from 800–900°C, is not effective for ammonia
decomposition without the presence of a suitable catalyst [11], [27]. A catalyst is required to reduce and even eliminate ammonia completely from the product gas at a relatively low
temperature, and secondary catalytic processes are most commonly used. Many of the same catalysts used for tar decomposition, such as …

Barriers to full-scale application of hot-gas cleanup for biomass gasification and areas for future research

Due to the increasing interest in alternate fuels (e.g., F–T diesel and methanol) and integrated combined cycle (IGCC) for heat/power generation, the worldwide gasification capacity in
synthesis gas generation has climbed rapidly in the recent years. The syngas production was projected to increase from 40,000 MWth syngas in 2000 to ∼70,000 MWth syngas in 2006 [93].
The major commercialized gasifiers include (a) the Lurgi gasifier – the moving bed gasifier introducing coarse solids at the top of …

Conclusions

(1) Biomass gasification produces a low to medium-BTU product gas (or syngas) containing primarily CO2, H2, CO, CH4 and (C2 +C3), as well as some contaminants
such as tars, NH3, H2S and SO2. In order to achieve better efficiencies of the syngas applications, these contaminants must be removed before the syngas is used
for heat and electricity generation, or in particular for synthesis of liquid fuels and methanol. …

(2) Tars and ammonia contaminants from the gasification processes could be removed by …

Acknowledgements
The present work was financially supported by Ontario Ministry of Energy and Ontario Centres of Excellence through the Atikokan Bioenergy Research Center (ABRC) Theme-1 Project, and
partly from the Natural Science and Engineering Research Council of Canada (NSERC) through the Discovery Grant awarded to one of the authors (C. Xu). One of the authors (Y. Ohtsuka)
also acknowledges the Grant-in-Aid for Scientific Research (B) from the Ministry of Education, Science, Sports, and Culture, Japan (No. …

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References (98)

X.T. Li et al.
Biomass gasification in a circulating fluidized bed
Biomass Bioenergy (����)

T. Bui et al.
Multi-stage reactor for thermal gasification of wood
Energy (����)

J. Gil et al.
Biomass gasification in atmospheric and bubbling fluidized bed: effect of the type of gasifying agent on the product distribution
Biomass Bioenergy (����)

G. Schuster et al.
Biomass steam gasification – an extensive parametric modeling study
Bioresour Technol (����)

J. Leppälahti
Formation of NH3 and HCN in slow-heating-rate inert pyrolysis of peat, coal and bark
Fuel (����)

J. Leppälahti et al.
Nitrogen evolution from coal, peat and wood during gasification: literature review
Fuel Process Technol (����)

W. Mojtahedi et al.
Catalytic decomposition of ammonia in fuel gas produced in pilot-scale pressurized fluidized-bed gasifier
Fuel Process Technol (����)

E. Kurkela
Air gasification of peat, wood and brown coal in a pressurized fluidized-bed reactor. I. Carbon conversion, gas yields and tar formation
Fuel Process Technol (����)

Y. Ohtsuka et al.
Recent progress in Japan on hot gas cleanup of hydrogen chloride, hydrogen sulphide and ammonia in coal-derived fuel gas
Powder Technol (����)

4 of 6 6/3/25, 07:08
Recent advances in catalysts for hot-gas removal of tar and NH3 from biomass gasification - ScienceDirect https://www.sciencedirect.com/science/article/abs/pii/S0016236110000633

L. Devi et al.
Pretreated olivine as tar removal catalyst for biomass gasifiers: investigation using naphthalene as model biomass tar
Fuel Process Technol (����)

View more references

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