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Biomass and Bioenergy 17 (1999) 389±403

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Biomass gasi®cation in atmospheric and bubbling ¯uidized


bed: E€ect of the type of gasifying agent on the product
distribution
Javier Gil a, Jose Corella b, 1, Marõ a P. Aznar a,*, Miguel A. Caballero a
a
Chemical and Environmental Engineering Department, University of Saragossa, 50009, Saragossa, Spain
b
Chemical Engineering Department, University ``Complutense'' of Madrid, 28040, Madrid, Spain
Received 11 November 1998; received in revised form 10 March 1999; accepted 2 June 1999

Abstract

The e€ect of the type of gasifying agent used in biomass gasi®cation on product distribution (gas, char and tar
yields) and gas quality (contents in H2, CO, CO2, CH4, . . . , tars) is analyzed. Gasifying agents taken into account
are: air, pure steam, and steam±O2 mixtures. Process considered is biomass gasi®cation in atmospheric and bubbling
¯uidized bed. Previous results got by Herguido et al. (Ind. Eng. Chem. Res. 1992; 31(2): 1274±82), Gil et al. (Energy
and Fuels 1997; 11(6): 1109±18) and NarvaÂez et al. (Ind. Eng. Chem. Res. 1996; 35(7): 2110±20) are compared.
Such authors carried their research on biomass gasi®cation under similar conditions but varying the gasifying agent.
Three di€erent gasifying agent-to-biomass ratios are needed and used to compare results. The relationships between
the H2, CO, . . . , tar contents in the ¯ue gas and the type and amount of gasifying agent used are shown after a
carefully analysis. # 1999 Elsevier Science Ltd. All rights reserved.

Keywords: Biomass gasi®cation; Pilot plant; Gasifying agents; Bubbling ¯uidized bed

1. Introduction It is very well known how the heating value


and the H2-content, for instance, of / in the ¯ue
This work concerns the gasi®er in biomass gas are higher when gasi®cation is made with
gasi®cation in atmospheric and bubbling ¯uidized steam than when it is made with air.
bed. The only variable here studied is the gasify- Nevertheless, there are doubts or contradictory
ing agent. Three gasifying agents are considered: papers about the e€ect of the gasifying agent on
air (with some moisture), pure steam, and steam± other results like tar content in the raw or pro-
O2 mixtures. duced gas. Since there have been a research in
biomass gasi®cation in ¯uidized bed using similar
gasi®ers, gasifying with pure steam [1], with
* Corresponding author. Fax: +34-976-76-21-42. steam±O2 mixtures [2] and with air [3], it was
1
Fax: +34-91-394-41-64 decided to deeply compare these results to clarify

0961-9534/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S 0 9 6 1 - 9 5 3 4 ( 9 9 ) 0 0 0 5 5 - 0
390 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 1. H/C and O/C atomic ratios in the feeding in biomass gasi®cation with di€erent gasifying agents.

Fig. 2. Values of S/B and ER ratios for the 3 processes here considered (in biomass gasi®cation with di€erent gasifying agents).
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 391

Table 1
Basic ratios used for comparison of results using di€erent gasifying agents

Gasifying agent Name of the ratio used Symbol

Air Equivalence ratio ER


Steam±O2 mixtures Gasifying ratio [(H2O+O2)/Biomass, (kg/h)/(kg daf/h)] GR
(pure) Steam Steam to biomass ratio [H2O/Biomass, (kg/h)/(kg daf/h)] SB

the e€ect of the gasifying agent on product distribution and produced gas quality.
At least 20 operation parameters concerning the gasi®er and feedstock have an in¯uence on product
distribution and gas quality. To compare results got by di€erent authors is very dicult thus.
Nevertheless, in the work made in Spain on biomass gasi®cation in ¯uidized bed in the last 16 years,
and here used for comparison purposes, several parameters were constant. It helps and allows to make
an useful or valuable comparison of product distributions. The operation parameters which have been the
same or very similar in the three studies under comparison were:

Gasi®er atmospheric and bubbling ¯uidized bed


bed only silica sand (without in-bed dolomite)
u0/umf 2±4
temperature (of the bed) 750±7808C (for steam), 780±8308C (for air or steam-O2 mixtures)
2nd air injection none (in all the three cases or processes)
Feedstock small chips of pine (Pinus pinaster ) wood
feedstock moisture 10±20 wt%
feeding point near the bed bottom, using two screws
Gas and Tar sampling similar in the 3 cases (shown in NavaÂez et al. [3]). They are deeply discussed
and analysis and compared with the ones used by other institutions in the recent paper
from Corella et al. [4]. According to the methods used in the analized papers,
the authors are speaking of a tar which will be called tar.
The main di€erence in the three works or studies here compared concerns perhaps of the gasi®er free-
board. Freeboard acts, in fact, as a 2nd reactor connected in series with the gasi®er bed, and in it several
reactions (like tar thermal cracking, CO-shift, etc . . .) occur. The size and temperature (400±7008C) of
the freeboard and the gas residence time in it have to be taken into account, thus. They have been not
the same in the three above said studies.
Other di€erent operation variables in the three studies here compared are:

Gasi®er

Gasifying agent Inner diameter Total height Feeding ¯ow rate For more details
(cm) (m) (kg biomass/h) see:

(pure) Steam 15 1.2 1.5±4.0 Herguido et al. [1]


Steam±O2 mixtures 15 3.2 5±12 Gil et al. [2]
Air 6 0.7 0.4±0.8 NarvaÂez et al. [3]
392 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 3. Equivalence between ER and GR (in biomass gasi®cation with steam and oxygen mixtures).

Table 2
Operating conditions, gas composition and yields

Air3 (pure) Steam1 Steam±O2 mixtures2

Operating conditions
ER 0.18±0.45 0 0.24±0.51
S/B (kg/kg daf) 0.08±0.66 0.53±1.10 0.48±1.11
T (8C) 780±830 750±780 785±830
Gas composition
H2 (vol %, dry basis) 5.0±16.3 38±56 13.8±31.7
CO (vol %, dry basis) 9.9±22.4 17±32 42.5±52.0
CO2 (vol %, dry basis) 9.0±19.4 13±17 14.4±36.3
CH4 (vol %, dry basis) 2.2±6.2 7±12 6.0±7.5
C2Hn (vol %, dry basis) 0.2±3.3 2.1±2.3 2.5±3.6
N2 (vol %, dry basis) 41.6±61.6 0 0
Steam (vol %, wet basis) 11±34 52±60 38±61
Yields
Tars g/kg daf 3.7±61.9 60±95 2.2±46
Char g/kg daf naa 95±110 5±20
Gas Nm3/kg daf 1.25±2.45 1.3±1.6 0.86±1.14
LHV MJ/Nm3 3.7±8.4 12.2±13.8 10.3±13.5

a
na Ð not available.
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 393

Fig. 4. Hydrogen contents in the raw gas at the gasi®er exit vs ER and S/B using di€erent gasifying agents.

2. Basis of comparison typical values of these ratios for the 3 processes


here considered (gasi®cation with air, steam, and
The gasifying agent-to-biomass fed ratio is steam±O2 mixtures). These ratios give a valuable
di€erent depending on the gasifying agent used. information but are not good enough. For
One way of comparing the gasifying agent used instance, one atom of O has not the same e€ect
could be by using the (H/C) and (O/C), at-g/at-g, if it is introduced as H2O, as O2 (air) or even as
ratios existing in the process. Fig. 1 shows the CO or CO2. These ratios do not help thus to
394 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 5. CO contents in the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

characterize and understand the e€ect of the gasi- using steam±O2 mixtures as gasifying agent is
fying agent. The ratios selected thus for compari- shown in Fig. 3 (for two di€erent values of the
son of results are shown in Table 1. H2O/O2 ratio in the steam±oxygen mixture).
The relative amount (and type) of gasifying The range or interval of operating conditions,
agent will be ER, GR and S/B thus. Fig. 2 shows gas composition and yields here compared are
the values of the S/B and ER ratios for the 3 shown in Table 2.
processes here considered. The value of the ER The produced gas in the three gasi®cation pro-
ratio which correspond to each value of GR cesses here compared would probably have a
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 395

Fig. 6. CO2 contents in the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

di€erent end-use. Electricity production seems to biomass/h) could be thus di€erent for these three
be the best end-use of the produced gas when gasi®cation processes. So, comparison of results,
gasifying with air, but other end-uses (fuel regarding gas composition, has to be made care-
cells?) could appear for the H2-rich gas gener- fully, taking into account that both, at least,
ated in gasi®cation with steam or steam±O2 mix- scale and end-use of the produced gas can not be
tures. The optimum scale of gasi®cation (Tn the same.
396 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 7. Methane contents in the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

3. E€ect of the gasifying agent on the composition CO-content Fig. 5


and heating value of the produced gas CO2-content Fig. 6
CH4-content Fig. 7
The main components in the produced raw gas C2 hydrocarbons Fig. 8
at the gasi®er exit for the three gasifying agents
are shown in the following ®gures:
The gas composition being known, the low
H2-content Fig. 4 heating value (LHV) of the produced gas is easily
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 397

Fig. 8. C2 hydrocarbons contents in the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

calculated. It is shown in Fig. 9 for the three (decrease of only 1±2 MJ/m3n, depending, of
gasi®cation processes. As it is well known, the course, of the amount of O2 fed).
LHV is very di€erent depending on whether the Although the authors consider that each ®gure
gasi®cation is made with air or with steam, but can be understood with the attached meaning of
Fig. 9 also shows how O2 addition to steam does symbols used, a short explanation of them is as
not lower very much the LHV of the gas follows:
398 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 9. Low heating value of the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

Gasifying with air, the nitrogen dilutes the pro- CH4 and C2-hydrocarbons, respectively, and in
duced gas and softens the increase (vs ER) of Fig. 9 for the LHV of the gas.
some parameters. So, although the trends are the Considering all data using di€erent gasifying
same, the magnitude of the variations in some agents, it is clearly shown (as it was expected)
parameters are di€erent using air or other gasify- how the H2 and CO2 contents in the gas at the
ing agents. The clearest examples of this beha- gasi®er exit increase (Figs. 4 and 6) and the CO
viour are shown in Figs. 6, 7 and 8 for the CO2, content decrease (Fig. 5), by the shift reaction, as
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 399

Fig. 10. Gas yields at the gasi®er exit vs ER and S/B with di€erent gasifying agents.

the S/B ratio is increased. In the same way, the behaviour is due to partial oxidation and steam
H2 and CO contents decrease and the CO2 con- reforming reactions.
tent increase as the ER is increased (Figs. 4, 5 One question that arises is which is the ``opti-
and 6). mum'' S/B ratio: Using air as gasifying agent
Methane and C2-hydrocarbons also follow the NarvaÂez et al. [3] found that an increase in the
expected trend (Figs. 7 and 8). Their contents in H/C ratio in the feeding (equivalent to an
the gas decrease as ER or S/B increases. This increase in the moisture content in the biomass)
400 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

Fig. 11. Tar content in the raw gas at the gasi®er exit vs ER and S/B with di€erent gasifying agents

improves the gas quality. They recommend H/C around 50 vol% (wet basis). This high steam
ratios around 2.2 which is equivalent to S/B content in the gas could be a waste of energy
ratios around 0.28 kg/kg daf. Higher values have but the steam addition doubles the H2 content
not an important e€ect on the gas quality and in the gas respect to the pyrolisis experiments
reduce the LHV of the gas (Fig. 9). (Fig. 4).
Using steam as gasifying agent, the H2-con- On the other hand, for several end-uses of the
tent in the gas is maximum (around 55 vol%) for gas it is necessary a secondary step or treatment
S/B ratios of 0.8±0.9 kg/kg daf (Fig. 4). For this after the gasi®er to clean up the hot gas by using
S/B ratio, the steam content in the gas is dolomites or steam reforming (Ni based) cata-
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 401

Fig. 12. Tar yield at the gasi®er exit for di€erent. ER and S/B values using di€erent gasifying agents.

lysts. A relatively high steam content in the ¯ue 4. E€ect of the type of gasifying agent on the gas
gas increases then steam reforming reactions of yield and the tar content in the raw produced gas
tars and light hydrocarbons in this catalytic stage
and avoids coke deposition and catalyst deactiva- 4.1. Gas yield
tion. So, the authors' recommendation for the
``optimum'' S/B ratio in gasi®cation with air Gas yields obtained with the 3 gasifying agents
would be 0.30, and in gasi®cation with steam of are shown in Fig. 10. Notice how important it is
0.8±0.9. to give the value of the gas yield as dry gas. With
402 J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403

this dry basis, gasi®cation with air produces a gas yield (1.4±2.4 m3n dry basis/kg biomass daf) quite
higher than gasifying with steam (0.8±1.1 m3n, dry basis/kg biomass daf).

4.2. Tar content

Tar content in the produced gas is shown in Fig. 11 for the 3 gasifying agents. Analysing in detail
results in this ®gure it is seen how tar contents follow this order:

4.3. Tar yield

Another way of indicating the tar generated is as tar yield (g tars/kg biomass daf). The values
obtained for the 3 gasifying agents are shown in Fig. 12. The same just mentioned conclusions for tar
content apply to tar yield.

4.4. Tar composition

Tar yield or tar content in the ¯ue gas is not enough to fully describe the tar problem. Tars produced
using the three mentioned gasifying agents are quite di€erent between themselves. According to recent
studies [4,5], tars generated in gasi®cation with steam are more ``easy-to-destroy'' with nickel-based cata-
lysts or with dolomites than tars generated in gasi®cation with air. These authors are determining how
such ``refractoriness'' to be catalytically destroyed also depends on the values of ER, GR or S/B used
but such study is not ready for publication yet (it will be published elsewhere).

5. Conclusions

Under the best and/or selected (indicated below) conditions (and without in-bed use of dolomite) the
representative main results for the three gasifying agents are:

Gasifying agent

Result/parameter (Air ER=0.30 H/C=2.2 Steam±O2 GR=0.90 H2O/O2=3 Steam S/B=0.90)1

H2 (vol %, dry basis) 8±10 25±30 53±54


CO (vol %, dry basis) 16±18 43±47 21±22
LHV (MJ/m3n, dry basis) 4.5±6.5 12.5±13.0 12.7±13.3
Ygas (m3n, dry basis/kg daf) 1.7±2.0 1.0±1.1 1.3±1.4
Ytar (g/kg daf) 6±30 8±40 70
Tar content (g/m3n) 2±20 4±30 30±80
1
These numbers explain themselves the e€ect of the gasifying agent.
J. Gil et al. / Biomass and Bioenergy 17 (1999) 389±403 403

Acknowledgements Biomass gasi®cation in ¯uidized bed at pilot scale with


steam±oxygen mixtures. Product distribution for very
di€erent operating conditions. Energy and Fuels
This work has been carried out thanks to the
1997;11(6):1109±18.
CAICYT Project No. PB96-0743 and also as an [3] NarvaÂez I, Orio A, Corella J, Aznar MP. Biomass gasi®-
addendum to the Project No. JOR3-CT95-0053 cation with air in a bubbling ¯uidized bed. E€ect of six
of the EU, DG-XII, JOULE III Program. operational variables on the quality of the produced raw
gas. Ind Eng Chem Res 1996;35(7):2110±20.
[4] Corella J, Orio A, Toledo JM, Biomass gasi®cation with
References air in a ¯uidized bed: Exhaustive tar elimination with
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of lignocellulosic residues in a ¯uidized bed at small pilot [5] Aznar MP, Caballero MA, Gil J, MartõÂ n JA, Corella J.
scale. E€ect of the type of feedstock. Ind Eng Chem Res Commercial steam reforming catalysts to improve biomass
1992;31(5):1274±82. gasi®cation with steam±oxygen mixtures. Part II. Catalytic
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