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10th International Conference on Applied Energy (ICAE2018), 22-25 August 2018, Hong Kong,
China
10th International
TheConference on Applied
15th International Energy (ICAE2018),
Symposium 22-25 August
on District Heating 2018, Hong Kong,
and Cooling
Effect of potassium impregnation China on the emission of tar and soot
Assessing the feasibility
from biomass of using the heat demand-outdoor
gasification
Effect of potassium
temperature function impregnation
for a long-term ondistrict
the emission of tar and
heat demand soot
forecast
a* a,b a
Albert Bach-Oller
from ,Erik Fursujo
biomass , Kentaro Umeki
gasification
a,b,c a a b c c
I. Andrić *, A. Pina , P. Ferrão , J. Fournier ., B. Lacarrière , O. Le Corre
Division of Energy Science, Luleå University of Technology, Universitetsområdet Porsön, SE-971 87 Luleå, Sweden
a

a*Kristinas a,b Pais 1, a1049-001 Lisbon, Portugal

Albert Bach-Oller ,Erik Fursujo , Kentaro Umeki
RISE Bioeconomy, Drottning väg Superior
61, SE-114 86 Stockholm, Sweden
a b
IN+ Center for Innovation, Technology and Policy Research - Instituto Técnico, Av. Rovisco
b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
c
Département
a Systèmes
Division of Energy Énergétiques
Science, et Environnement
Luleå University - IMT Universitetsområdet
of Technology, Atlantique, 4 rue Alfred Kastler,
Porsön, 44300
SE-971 87Nantes, France
Luleå, Sweden
Abstract b
RISE Bioeconomy, Drottning Kristinas väg 61, SE-114 86 Stockholm, Sweden

Entrained flow gasification of biomass has the potential to generate synthesis gas as a source of renewable chemicals, electricity,
Abstract
andAbstract
heat. Nonetheless, formation of tar and soot is a major challenge for continuous operation due to the problems they cause at
downstream of the gasifier. Our previous studies showed the addition of alkali in the fuel can bring significant suppression of such
District heating networks are commonly addressed in the literature as one of the most effective solutions for decreasing the
Entrainedproducts.
undesirable
greenhouse flowemissions
gas gasification of biomass
from the building has the potential
sector. Thesetosystems
generaterequire
synthesishighgasinvestments
as a source which
of renewable chemicals,
are returned throughelectricity,
the heat
and heat.Due
The
sales. Nonetheless,
present to work formation
investigated,
the changed ofintaraconditions
climate and
dropsoot
tubeisand
a major
furnace, challenge
the effect
building for continuous
of potassium
renovation policies,on operation
heat and due
tar demandsootto the
theproblems
informationfuture they as
(ascould
well cause
on its
decrease,at
downstream
prolonging of
intermediates) the
thefor gasifier.
three
investment Our
different
returnprevious
types
period. ofstudies
fuels: showed
an ash leanthe addition
stemwood, of alkali in the rich
a calcium fuel bark
can bring
and asignificant
silicon rich suppression
straw. Theofstudy such
The main
undesirable
focused onscope
products.of this paper
an optimal method is tofor
assess the feasibility
impregnating the of using the
biomass heatpotassium.
with demand – outdoorExperimentstemperature function forfor
were conducted heatdifferent
demand
forecast.
impregnation Themethods;
The present district of Alvalade,
work investigated,
wet in located
impregnation, a drop in impregnation,
tube
spray Lisbon
furnace,(Portugal),
theand effect was used asto ainvestigate
of mixing
solid potassium case
on tarstudy. Theformation
anddifferent
soot district
levels ofis(as
consisted
well as
contact of
on 665
between its
buildings
fuel andthat
intermediates)
the theforvary in different
three
potassium. both construction
types of fuels:periodanand ashtypology.
lean stemwood,Three weather
a calcium scenarios
rich bark (low,
andmedium,
a siliconhigh) and three
rich straw. The district
study
renovation scenarios were developed (shallow, intermediate, deep). To estimate the error, obtained heat demand values were
focused on anwas
Potassium optimal
shownmethod
to catalyzefor impregnating
both homogenous the biomass with potassium.
and heterogeneous reactions. Experiments
Wet and spraywere impregnation
conducted for haddifferent
similar
compared with results from a dynamic heat demand model, previously developed and validated by the authors.
impregnation
effects on methods; wetreactions
heterogeneous impregnation,(in charspray impregnation,
conversion) and solid
indicating that mixing
there to investigate
was an different
efficient molecularlevelscontact
of contact between
between the
The results showed that when only weather change is considered, the margin of error could be acceptable for some applications
the fuel
potassium and
(the errorand the potassium.
the organic
in annual demandmatrixwaseven
lower if potassium
than 20% was in the
for all form of
weather precipitated
scenarios salts at aHowever,
considered). micrometer scale.
after On the other
introducing hand,
renovation
Potassium
potassium
scenarios, inthe was
the gasshown
error valueto
phase led catalyze
to muchup
increased both to homogenous
lower 59.5% and heterogeneous
of C2 hydrocarbons,
yields(depending heavyreactions.
on the weather tars
and and Wet These
soot.
renovation and spray
results
scenarios impregnation
revealed thathad
combination similar
potassium
considered).
effects
shifted on pathways
The value
the heterogeneous
of sloperelated reactions
coefficient
to tar and (in
sootchar
increased onconversion)
average
formation, indicating
within
reducing the that of
thelikelihood
range there
of3.8%wasupan
carbon efficient
totoend8%upper molecular
decade,
as soot contact
that
and heavy between
corresponds
tars by tothe
favouring the
decrease
potassium
the formationin the
and of number
thelighter
organic of heating
matrix
compounds even hours
such asofbenzene.
22-139h
if potassium wasAduring
in the heating
the form
moderate season
of precipitated
interaction (depending
betweensaltsthe on the
at aadded
micrometer combination
potassiumscale.andOnthe ofinherent
the weather
other hand, and
ash
renovation
potassium
forming in scenarios
the gas
elements were considered).
phase
alsoled to much
observed: OnPotassium
the other
lower yieldshand,
had function
ofaCsmaller
2 hydrocarbons,
intercept
effect when increased
heavy
the tars
fuel and
wasforsoot.
7.8-12.7%
Theserich
naturally perin decade
results revealed
silicon. (depending on the
that potassium
coupled
shifted
Thethe scenarios).
pathways
combined The
related
results values
to tar
open suggested
theand
doorsoot could
to formation, be
a gasification used
reducing
processto modify
thethat the
likelihood function
of carbon
incorporates parameters
to end upof
recirculation for the
asnaturally scenarios
soot and heavy considered,
tars potassium
occurring by favouring and
to
improve the accuracy of heat demand estimations.
the formation
improve of lighter
entrained compounds of
flow gasification such as benzene. A moderate interaction between the added potassium and the inherent ash
biomass.
forming elements were Published
also observed:ElsevierPotassium Ltd.had a smaller effect when the fuel was naturally rich in silicon.
©©2019
2017TheTheAuthors.
Authors. Published bybyElsevier Ltd.
The combined
Peer-review
This is an open under results
access open
responsibilitythe door
article underofthe to
theCC a gasification
Scientific
BY-NC-ND process
Committee that
Theincorporates recirculation of naturally
licenseof(http://creativecommons.org/licenses/by-nc-nd/4.0/)
15th International Symposium occurring
on District Heatingpotassium
and to
improve
Peer-reviewentrained flow gasification of biomass.
Cooling. under responsibility of the scientific committee of ICAE2018 – The 10th International Conference on Applied Energy.
*
Corresponding author. Tel.: +46 920493457
Keywords: Heat demand;
E-mail address: Forecast; Climate change
albert.bach.oller@ltu.se

1876-6102 Copyright © 2018 Elsevier Ltd. All rights reserved.

*
Corresponding author. Tel.: +46 920493457
Selection and peer-review under responsibility of the scientific committee of the 10th International Conference on Applied Energy (ICAE2018).
E-mail address: albert.bach.oller@ltu.se
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility
1876-6102 of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 Copyright
© 2019 The© 2018 Elsevier
Authors. Ltd.
PublishedAll by
rights reserved.
Elsevier Ltd.
Selection
This is anand peer-review
open under responsibility
access article under the CCofBY-NC-ND
the scientificlicense
committee of the 10th International Conference on Applied Energy (ICAE2018).
(http://creativecommons.org/licenses/by-nc-nd/4.0/)
Peer-review under responsibility of the scientific committee of ICAE2018 – The 10th International Conference on Applied Energy.
10.1016/j.egypro.2019.01.164
 Copyright © 2018 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 10th International Conference on Applied
620 Albert Bach-Oller et al. / Energy Procedia 158 (2019) 619–624
Energy (ICAE2018).

Keywords: Biomass; gasification; tar; soot, alkali catalyst, potassium

1. Introduction

Biomass is the only source of renewable carbon atoms. Gasification appears as a resource-flexible and product
flexible process of upgrading biomass into renewable chemicals, electricity, and heat. However, impurities in the
syngas such as tar and soot impose difficulties for continuous operation of the synthesis/power generation units
downstream of the gasifier.
These problems, however, as shown by the successful black liquor gasification experience[1], might be reduced to
great extent by the utilization of a fuel that has a high alkali content. There is general agreement in literature that alkali
metals have a catalytic activity on char gasification. Furthermore, there is also empirical evidences that alkali metals
also bring a notorious reduction of tar and soot in biomass gasification[2]. However, the multi physics and complex
nature of an industrial gasifier, makes it difficult to assess independent effects of alkali metals. At a more controlled
set-up, we showed that loading 4% of potassium in stemwood led to a reduction of tar in the order of 30% and a ten-
fold reduction of soot [3]. However, it is not understood how alkali affected the pathways of soot formation; for
example, whether alkali compounds are active in the solid, gas phase or as a combination of the both. It is therefore
important to design experiments that allow isolating the effect of the contact between the fuel and the alkali. In the
present work, three different impregnation methods have been studied with different level of contact between the alkali
and the biomass, namely: dry mixing, spray impregnation and wet impregnation. On the other hand, due to economic
reasons low-grade biomass is of interest as gasification feedstock. Yet, these types of feedstock are typically ash-rich,
and therefore the effect of K should be studied not only in isolation but also in the presence of other ash forming
elements; particularly Ca, the most common inorganic element in forest biomass, and Si, abundant in herbaceous
biomass and affine to react with alkali to form silicates melts that are thought to be undesirable both chemically (non-
catalytic species) and physically (a molten layer around the fuel particles might restrict oxygen transfer into the
reacting char). The empirical study of the interactions between alkali and Si and Ca is particularly relevant due to the
lack of reliable thermodynamic databases for K-saturated Si-Ca-K systems[4].
The present work is framed on the one hand as an attempt to address the lack of fundamental knowledge on the
interactions between the biomass and the alkali, and on the other hand as an assessment of the possibility to use alkali
impregnation of biomass as a method to improve entrained flow gasification. In practice, this study investigates
potassium in particular as its natural occurrence in biomass is much higher than that of Li or Na, and therefore K can
potentially be recirculated into the system thereby avoiding or reducing the need of an external supply of alkali metals.
In an earlier study it was found that both hydroxides and carbonates were catalytically active forms of alkali [5].
Combined with the fact that in industrial gasifiers most alkali metals would be recovered in the form of
carbonate/bicarbonate, K2CO3 makes the natural choice to carry out the impregnation of the biomass.
In summary, in this work we investigated experimentally the effect of various contact between the alkali and the
fuels (e.g. impregnation method) and its interaction with various ash compositions inherent in the fuel (e.g. the
chemistry of the K-Si-Ca system).
 Albert Bach-Oller et al. / Energy Procedia 158 (2019) 619–624 621
Author name / Energy Procedia 00 (2018) 000–000 3

2. Materials and method

Three different types of raw feedstock were used: Stemwood from Norway spruce, bark from Scots Pine and wheat
straw. The choice of the feedstock was done to have a typical low-ash biomass as a reference (stemwood) referred
simply as wood in this work, a Ca-rich biomass (bark) and a Si-rich biomass (straw). All the raw feedstock was sieved
to the fraction within the 200-300 µm of mesh size. The selected material was divided into a large number of
representative samples with a rotary sample divider and the subsequent divisions were further processed to obtain the
potassium impregnated samples.
Impregnation of biomass targeted potassium concentrations of ca. 4% (based on the mass of the K atom). The actual
measured concentrations of K can be seen in Table1.
Wet impregnation was carried out by mixing the biomass with an aqueous solution of K 2CO3 at a ratio of 15 ml g-
1
. A solution with a concentration of 0.2M was used for stemwood and 0.1M for bark and straw. These concentrations
were not arbitrary but decided on the basis of experience with preliminary tests. The mixing of the biomass and the
solution was conducted at 80 °C for 30 min, and the resulting slurry was subsequently vacuum-filtered and dried
overnight at 105 °C. It is expected that under this impregnation method part of the K would bond to the biomass
through ion exchange while the rest would precipitate as KHCO3 crystals on the internal and external surfaces of the
biomass particles.
Spray impregnation was carried out by spraying a calculated amount of K 2CO3 solution of 0.4M into the biomass
under continuous stirring. After spraying the samples were dried overnight at 105 °C analogously to the wet-
impregnated sample.
All the impregnated biomass batches were eventually divided into a set of representative samples for the
experimental runs as well as for the several fuel analyses.

Table 1 Elemetal analysis of the different fuels used in the experiments.

Fuel Imp. C H O Si Al Ca K Mg Na
Method (wt.%)a (wt.%)a (wt.%)b (mg/kg)c (mg/kg)c (mg/kg)c (mg/kg)c (mg/kg)c (mg/kg)c
Spruce none 47.6 6.1 42.5 n.a. 8.29 815 580 89.6 bdl
stemwood spray-4% 46.6 5.8 41.8 bdl 14.5 755 35100 97 bdl
wet-4% 46.3 5.9 41.1 bdl 10.9 628 31200 46.9 82.3
Pine Bark none 49.8 5.9 42.7 n.a. 530 4280 1990 420 93.6
spray-4% 48.4 5.6 38.6 520 777 3770 38700 460 190
wet-4% 46.8 5.5 39.5 416 783 3730 43300 448 198
Wheat none 40.4 5.6 40.6 n.a. 18.6 3240 7330 1030 bdl
straw spray-4% 40.5 5.4 38.8 7630 30.3 3050 42900 1110 94.9
wet-4% 40.0 5.3 38.6 5250 25.2 2710 45100 1120 153
a: By elemental analyser, EA3000 from Eurovector Srl.
b: by difference
c: By ISP-MS at ALS Scandinavia, Luleå
bdl: Below detection limit

All the experiments were conducted in an atmospheric laminar drop tube furnace (DTF). The reactor consists of an
alumina tube (internal diameter: 54 mm, heated length: 2.3 m) inside a furnace. The feedstock was fed by a syringe
pump that continuously displaces a volume of particles into the reactor. The fuel particles fell directly into the high
temperature zone in the reactor through a water-cooled probe, thus ensuring high heating rate (approx. 10 000 °C s-1).
Upon reaching a steady state in the tube both in temperature and gas environment the experiment was initiated by
feeding the fuel into the reactor at a rate of approximately 6 g h-1. A primary flow of N2 at 160 ml min-1 was injected
together with the fuel while a secondary flow composed by 4.64 l min-1 of N2 and 0.254 l min-1 of CO2 was
622 Albert Bach-Oller et al. / Energy Procedia 158 (2019) 619–624
4 Author name / Energy Procedia 00 (2018) 000–000

concentrically supplied to set the gas composition of the reactor at approximately 5% on volume basis. Gas volumes
are given at the reference conditions of T=0 °C and P=101.3 kPa. Feeding was maintained for 25 min but the
experiment was not considered completed until the reactor would recover the initial gas composition. The solid
residues from the gasification (char + ashes) were collected in a bin placed at the bottom of the reactor. The particles
suspended in the gas were captured first through a cyclone and subsequently through a glass filter. The combined mass
of the char bin and in the cyclone is referred as char residue. The exhaust gas line was heated to T=180 °C to avoid
the condensation of heavy tars before its collection. Condensable compounds were collected by bubbling through the
gas through methanol-filled washing bottles in a cold bath at -50 °C. Finally, a microGC measured gas species with a
measuring interval of 120 sec. At the end of each experiment a flow of oxygen (5% of O2 diluted in N2) was passed
through the tube to combust any carbon deposited on the tube, the CO2 that was formed under this process was
measured and used to calculate the amount of carbon deposited on the walls, referred as burnout carbon. It is believed
that it is the results of interaction of soot precursors that are allowed to take place on the surface of alumina. It is worth
noting that the existence of burnout carbon is due to the nature of the laboratory setup (high wall surface to gas flow
ratio, low gas velocity, etc…) and it is of interest mainly because it gives a hint on the concentration of intermediate
soot precursors. Ultimate analyses were performed for the biomass samples, char material and filter material in an
elemental analyser (EA3000, Eurovector). Methanol-dissolved tar were also analyzed with a GC-FID (model 7820A
by agilent).

3. Results and discussion

Figure 1 shows the amount of residual carbon in the different collections points. Unconverted carbon can be
grouped in two different categories; a) unconverted carbon in the char residue and b) carbon in products that are
relevant for the production of soot. These include: Black carbon in the filter, burnout carbon, C2 hydrocarbon gases
and condensable products (tar). Tar yield is presented in Figure 2.

Figure 1 Residual carbon as a mas fraction of the fuel carbon. Note that the scale of the different subplots is not the same. Error bars show one
standard deviation with N=3
 Albert Bach-Oller et al. / Energy Procedia 158 (2019) 619–624 623
Author name / Energy Procedia 00 (2018) 000–000 5

The presence of K2CO3 leads to a strong decrease of residual carbon in all the collection points. The three
impregnation methods have a similar effect, even when interactions between the organics and the potassium are limited
to gas phase reactions (as for dry mixing). These results suggest that it is the potassium in the gas phase that has an
active role in soot- suppression. Different phenomena may lead to varying concentrations of gaseous potassium (even
with a constant amount of potassium in the fuel) and therefore different yields of residual carbon: High inherent
contents of Si (as in the case of straw) tends to fixate K by forming potassium silicates. Besides, the release of gaseous
potassium is thermodynamically favored by reducing conditions, therefore an intimate contact between the organic
matrix and the potassium carbonate (as in wet and spray impregnation) tends to lead to higher concentration of
potassium in the gas phase.
The behavior of straw differs from that of bark and stemwood. There is a mixed effect between the added potassium
and the naturally occurring Si in straw. The results of such mixed effects are very clear in the yield of unconverted
carbon in the char residue. The hypothesis is that in straw a layer of potassium silicate forms around the char particles
that limits the transfer of oxidizing gases into the reacting char. This phenomenon is strongest for wet impregnation
as K and Si have a closer contact. The combined effect between Si and the added potassium can also be observed in
the yield of black carbon in the filter.

Figure 2 Tar yields classified by the number of aromatic rings. Note that the scale of the different subplots is not the same. Error bars show one
standard deviation with N=3

At the conditions in which the experiments were carried out the condensable volatiles (e.g. tar) consist of aromatic
hydrocarbons. Figure 2 shows the yields of tar for the different impregnation methods classified by the number of
aromatic rings. It can be seen that potassium-impregnated biomass yields lowered the amount of heavier tars (3-5
rings) while increasing, in exchange, the yields of lighter species (1-2 rings). This observation may be related to the
hypothesis that gaseous K inhibits the growth of light aromatics into larger PAH. This phenomenon is of particular
interest from a soot formation perspective. It indicates the mechanism through which alkali may suppress the formation
of soot. Reducing the likelihood in which light aromatic compounds to form larger PAH would indeed bring along a
reduction of soot, given the prevalent soot formation pathways[6].
624 Albert Bach-Oller et al. / Energy Procedia 158 (2019) 619–624
6 Author name / Energy Procedia 00 (2018) 000–000

4. Conclusions

This study was an experimental investigation on how gas impurities in biomass gasification were affected by
potassium, added into the biomass through various methods.
It was found that potassium has a very strong role not only in catalyzing char gasification but also in suppressing
the formation of gas impurities. However, it has been shown that there is a moderate interaction between the added K
and Si inherent in the biomass.
Furthermore, it has also been found that the impregnation methods and therefore the contact between the biomass
and the potassium were not essential because the interactions between potassium and soot precursors take place in the
gas phase. However, dry mixing releases less potassium in the gas phase and therefore the effect of potassium was
slightly less pronounced than spray and wet impregnation methods.
The combined results are of interest from a fundamental point of view but also for a development of a gasification
process that makes uses of the advantages of potassium in reducing gas impurities. That may be achieved by recovering
and recirculating the naturally occurring K and spraying it to biomass before the gasifier. For that matter, further work
focusing on spray impregnation is necessary. It would be of special interest varying the concentration of K in the fuel
to investigate a saturation threshold for the catalytic activity.

Acknowledgements

We thank the Swedish Energy Agency for supporting this work, and the Kempe Foundation for the financial support
to construct the equipment.

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