L I C E N T I AT E T H E S I S

Department of Engineering Sciences and Mathematics

Division of Energy Engineering

ISSN: 1402-1757 ISBN 978-91-7439-225-8 Black Liquor Gasification

Luleå University of Technology 2011 Burner Characteristics and Syngas Cooling

Mikael Risberg
 LICENTIATE THESIS
Black Liquor Gasification
Burner Characteristics and Syngas Cooling

Mikael Risberg

Division of Energy Engineering

Department of Engineering Sciences and Mathematics
Luleå University of Technology
SE-971 87 Luleå, Sweden

[Link]@[Link]

March 2011
Printed by Universitetstryckeriet, Luleå 2011

ISSN: 1402-1757
ISBN 978-91-7439-225-8
Luleå 2011
[Link]
Abstract
Black liquor gasification at high temperature is a promising alternative to the conventional recovery
boiler process used in chemical pulp mills today. Compared to a conventional recovery boiler a
black liquor gasifier can increase the total energy efficiency of a chemical pulp mill and produce a
synthesis gas that can be used for production of motor fuel. In Piteå, a 3 MW or 20 tons per day
entrained flow pressurized black liquor gasification development plant has been constructed by
Chemrec at Energy Technology Center. The plant has been run more than 12 000 h since 2005.

One of the key parts in the gasification process is the spray burner nozzle where the black liquor is
disintegrated into the hot gasifier as a spray of fine droplets. In this thesis the spray burner nozzle
was characterized with high speed photography in order to visualize the atomization process of
black liquor. The results showed that black liquor forms non-spherical and stretched ligaments and
droplets with the considered nozzle. Comparison of the results with atomization of a syrup/water
mixture showed that the results were qualitatively very similar which means that a syrup/water
mixture can be used instead of black liquor for burner optimization experiments. This is a
considerable experimental simplification.

Also spatially resolved measurements of the gas composition in the development plant with a water
cooled quench probe have been performed. From the gas composition measurement and the spray
visualization it has been showed that the preheating of black liquor has a significant influence on
the gas composition.

Another important part in the gasification plant is the counter-current condenser where the gas is
cooled and the water content in the gas is condensed away in vertical tubes that are cooled on the
outside by a counter-current flow of water or steam. In this thesis a computational fluid dynamics
model of the counter-current condenser have been developed. The model consists of a two-phase
fluid model on the tube-side of the condenser and a single phase model of the shell side. Predictions
from the model are in excellent agreement with temperature measurements from the condenser used
in the 3 MW Black Liquor Gasification development plant. However, more validation data is
necessary before a definite conclusion can be drawn about the predictive capability of the code, in
particular with respect to scale up with about two orders of magnitude for commercial size gas
coolers.
Preface
The author gratefully acknowledges the Swedish Energy Agency, Mistra, Smurfit Kappa Kraftliner
AB, SCA Packaging AB, Södra’s Research Foundation, Sveaskog AB, Chemrec AB and the
County Administrative Board of Norrbotten for funding this work through the BLG II research
program.

Partial funding has also been received through the Bio4Energy program funded by the Swedish
government through the Swedish Energy Agency.

I would like to thank my supervisors Rikard Gebart and Lars Westerlund for their guidance and
support throughout my work. Furthermore I would like to thank my colleagues at the division of
Energy Engineering and Energy Technology Centre for creating a good work environment and a
friendly atmosphere. A special thank to Magnus Marklund for the help with the work in paper A.
Introduction ................................................................................................................................................1

Black liquor recovery ............................................................................................................................. 1

Black liquor gasification ....................................................................................................................... 3

Burner characterization ....................................................................................................................... 4

Connection between burner spray characteristics

and syngas composition......................................................................................................................... 6

Counter-current condensation .......................................................................................................... 7

Conclusions ................................................................................................................................................10

References ..................................................................................................................................................11

APPENDED PAPERS

A. Risberg, M. Marklund, M. 2009 Visualization of gas-assisted atomization of black liquor

and syrup/water mixtures at elevated ambient pressures. Atomization and Sprays. 19 ,10,
p.957-967
B. Gebart, R., Carlsson, P. , Grönberg, C. Marklund, M. Risberg, M., Wiinikka, H. Öhrman, O.
2009 Spatially resolved measurement of gas composition in a pressurised black liquor
gasifier. Environmental Progress and Sustainable Energy. 28, 3, p.316-323. 8p.
C. Risberg, M. Gebart, R. 2010 Numerical modeling of counter-current condensation in a
Black Liquor Gasification plant. Manuscript
Introduction
Due to the increased energy demand in the world today and the alarming global warming it has
become very important to expand the use of renewable and climate neutral fuel such as wood or
biomass in general. From wood one can produce paper via e.g. chemical pulping and in Sweden
10.9 million tons of paper was produced in 2009 or about 2.8% of the total world paper production
(Skogsindustrierna 2010). In Sweden the total energy demand from the pulp and paper industry was
72.2 TWh, which corresponds to 12.7% of the total energy used in Sweden 2008
(Energimyndigheten 2010). At the same time the pulp and paper industry produces black liquor
with a total fuel value of about 40 TWh/year as a side stream from the pulping process. Because of
this, the pulp and paper industry play an important role for the energy system in Sweden both as a
consumer and producer of energy. By increasing the efficiency of the energy recovery systems in
the pulp and paper mills more energy can be recovered from the mills and this will greatly affect the
national energy balance. One technique is to replace the conventional black liquor recovery boiler
used in the mills today with a black liquor gasifier. Compared to today’s recovery boiler technique,
a black liquor gasifier can increase the total energy efficiency of the mill’s recovery cycle and
produce a synthesis gas for production of high value end products, e.g. methanol or dimethylether
(Lindblom, Landälv 2007). The potential for motor fuel production from black liquor in Sweden is to
replace about 25% of the current consumption of gasoline and diesel. For this to be possible the
mills need to import additional biomass. However the quality requirements on this biomass are low
and estimates have shown that felling residues that are unused today could fill this need.

Black liquor recovery

In figure 1, the kraft pulping process is schematically described. First wood chips are fed into a
digester where the cellulose fibers are separated from the wood immersion in hot white liquor.
White liquor is a strong aqueous solution consisting of sodium sulfate and sodium sulfide that
neutralizes the organic acid and the bounding lignin in wood and separates the fibers that later
become pulp. The pulp is used to produce paper and the remaining by-products (lignin, cooking
chemical, etc.) leave the digester as weak “black liquor”. The black liquor is then transformed back
to white liquor via a sequence of steps. First the black liquor is sent through a series of evaporators
to increase the solid content in order to make it suitable for combustion. In the evaporators the black
liquor solid content is increased from about 15%wt to about 70-75%wt. The black liquor is then
fired in a recovery boiler where it is thermochemically converted to an inorganic smelt and
combustion products. The smelt from the recovery boiler is then dissolved into water and forms
“green liquor”. The green liquor then goes through a causticising process to convert green liquor
back to white liquor. Then the resulting white liquor is recycled into the digester.

The concentrated black liquor that goes into the recovery boiler consists of about 30% water, 30%
valuable inorganic cooking chemicals and 40% lignin and other organic matter separated from the
wood. The higher heating value is about 14 MJ/kg solids. Typically, a large pulp mill will produce
about 2000 ton/day of black liquor corresponding to about 300 MWth.

1
Figure 1. Schematic drawing of a recovery cycle in a conventional chemical kraft pulping process.

It’s important to recover both chemicals and energy from the black liquor for economical and
environmental purposes. Therefore, the recovery cycle is one of the most important processes in a
kraft pulp mill. In a conventional kraft pulp mill the energy in the black liquor is recovered as steam
by combustion in a recovery boiler. In the recovery boiler chemicals are recovered as a smelt that is
converted to new white liquor.

Most of the recovery boilers used today is of the Tomlinson type (Adams et al. 1997). A recovery
boiler acts both as a type of high-pressure steam boiler and as a chemical reactor with reductive and
oxidative zones. In the recovery boiler black liquor is sprayed with a splash plate nozzle into the
boiler at a temperature around 120 °C. The drying and pyrolysis conversion stage occur quickly
before most droplets fall onto a bed of char where the final conversion takes place. The resulting
inorganic smelt exits via a channel through the wall and dissolves into a liquid solution to form
green liquor. The combustible gases released during the pyrolysis are completely burned by
different air registers along the main wall. Then steam is produced from the combustion heat in
surrounding water pipes of the boiler, superheaters and economiser. The Tomlinson boiler has
served the pulping industry for more then 70 years, mainly because of its high availability and
stable running. Also continuous efforts have been made to increase its efficiency, but still it has a
relative low overall efficiency for generation of electricity.

The black liquor droplets being sprayed into the recovery boiler are undergoing the following three
stages: drying, pyrolysis and char conversion (Hupa, Solin & Hyoty 1987). First the droplet dries
and evaporates its moisture. Then the droplet is pyrolysed and the organic matter in the liquor is
released as various gaseous compounds from the volatile substances. The rate of drying and
pyrolysis is controlled by the heat transfer rate to the droplet. The resulting pyrolysis gases are
mainly H2, CO, CO2, H2O and some heavier hydrocarbons (Bhattacharya, Parthiban & Kunzru

2
1986). The remaining droplet is a swollen porous char particle containing mainly carbon and
sodium salts. The last stage is char conversion, in which gas phase species react with the organic
content in the char particle and convert it into gaseous species. At the end of this stage the droplet
would ideally consist only of inorganic salts, primarily sodium carbonate (Whitty, Backman &
Hupa 1998).

Black liquor gasification

During the last decade, extensive efforts have been made to develop alternative recovery
technologies based on a black liquor gasification process to supplement or replace the conventional
recovery boiler. In Piteå, a 3 MW or 20 tons per day entrained flow pressurized black liquor
gasification development plant (DP1) has been constructed by Chemrec at Energy Technology
Center (ETC). The DP1 has been run more than 12,000 h since 2005. Figure 2 shows the schematics
of the development plant. At the top of the reactor black liquor is dispersed into the hot reactor
cavity together with an under-stoichiometric amount of oxygen by use of a spray burner nozzle. The
spray burner nozzle atomizes the black liquor into a spray of small black liquor droplets. The
residence time in the reactor where the gasification takes place is about 5 seconds. After the reactor
the products reach the quench where the gas is rapidly cooled with water sprays and the different
products are separated into a synthetic gas and a smelt. The synthetic gas then goes to the counter-
current condenser (CCC) where the gas is cooled and the water vapor in the gas is condensed and
pumped back to the quench. The synthetic gas consisting mainly of CO, CO2, H2O and H2 is then
further cleaned to be able to convert it to motor fuel or use it in gas turbines. The separated smelt in
the quench is recovered and goes back into the recovery cycle as green liquor.

BLACK LIQUOR SHORT TIME

CONTACTORS
COOLING
OXYGEN AND WATER
ATOMIZING MEDIA

WHITE
GAS COOLER
LIQUOR

REACTOR
RAW
GAS

QUENCH

CLEAN, COOL
SYNTHESIS
GREEN GAS
LIQUOR

WEAK CONDENSATE
WASH

Figure 2. Schematic drawing of the black liquor gasifier.

3
Burner characterization
One of the key component in the BLG process is the burner nozzle where the viscous black liquor is
disintegrated into a spray of fine droplets into the hot gasifier. For an optimal performance of the
BLG process it is crucial that the spray atomizer produce a spray with the right characteristics. A
too large fraction of large droplets in the spray will increase fraction of unconverted black liquor
char droplets. Moreover, a too large fraction of small droplets may lead to very long settling times
for the green liquor dregs (Marklund 2006). Additional problem is that too small droplets will
increase the carry-over of smelt droplets to the counter-current condenser.

Only a few experimental studies have been done on spray burner characterization of black liquor
atomization process (Farrington Jr., Kuusinen & Sweerus 1987, Helpiö, Kankkunen 1996, Loebker, Empie
2001, Loebker, Empie 2002, MacKrory, Baxter 2007). Most of the earlier studies have been made on
black liquor atomization with a splash plate nozzle used in a conventional recovery boiler. The
droplets produced from a splash plate nozzle are too large for being used in an entrained flow black
liquor gasifier. However some work has been done with gas-assisted nozzles, e.g. the work by
Mackrory and Baxter (MacKrory, Baxter 2007). They used a gas-assisted nozzle and visualized
with high speed photography and found that the black liquor forms long, thin ligaments rather than
droplets. Loebker and Empie (Loebker, Empie 2001) have also done some work based on
effervescent atomization in a vee-jet nozzle where they used a syrup/water mixture in order to try to
mimic the atomization of black liquor.

In order to complement earlier work by using higher momentum flux ratios, elevated ambient
pressures, and higher liquid flow rates, and also to investigate the possibility to use syrup/water
mixtures as a substitute for black liquor the study in paper A was performed. The work was based
on a standard coaxially convergent gas-assisted atomizer (figure 3) where a high speed photography
system was used to visualize the spray formation. The experiment was performed in a pressurized
spray test rig at ETC that was developed in a master thesis project (Karlsson, Westerlund 2006).

Figure 3. Schematic of the considered coaxial gas-assisted atomizer. The liquid flows in the centre
and the gas in the surrounding annulus.
4
The main result from this study is that black liquor forms nonspherical and stretched ligament-
shaped droplets. Comparison between black liquor and syrup/water mixture shows that the shapes
and sizes of the droplets are similar for this liquid as showed in figure 4. When the viscosity was
decreased the droplet sizes decreased for both black liquor and syrup/water but the syrup/water
appears to form more spherical droplets. Results also show that with lower momentum flux ratio the
size of the droplets increase. At elevated pressure the increased ambient pressure appears to contract
spray to a dense cloud of droplets compared to the atmospheric case as showed in figure 5.

Figure 4. Liquid breakup 0.2 m below the nozzle for black liquor (left) and for syrup/water mixture
(right).

Figure 5. Black liquor spray formation 0.2 m below the nozzle for an atmospheric pressure case
(left) and for a case at 10 bar absolute pressure (right).

5
Connection between burner spray characterization and syngas composition
To be able to produce a high quality synthetic gas it is important to understand the coupling
between the operating parameters and the syngas composition. From experimental measurement it
is concluded that the most significant process parameters for the syngas composition are the system
pressure, the black liquor preheat temperature, the fuel-to-oxygen mass flow ratio, and the flow rate
of black liquor (Carlsson et al. 2010). In paper B the effect of black liquor preheat temperature on
gasifier performance is investigated. The gas composition was measured with a high temperature
gas sampling system inside the reactor. For the main gas components CO2, H2, and CO, it is
believed that the change in concentration is caused by increased thermal input to the gasifier which
results in a temperature increase in the reactor. The change in gas composition for the main
components when the black liquor preheat temperature is changed is presented in figure 6. Take
notice of that the major components are only marginally affected by the change in preheat
temperature.

38

36
CO2, H2, and CO [%]

34

32

30

28
CO2
26 H2
CO

24
110 120 130 140 150 160

BL temperature [oC]
Figure 6. Dry gas composition (molar) for the bulk gases (CO2, H2 and CO) when investigating the
influence of black liquor temperature, gas samples taken with the high temperature gas sampling
system.

In figure 7, molar fractions of CH4, H2S, and COS for the same case are presented. For methane
there is a significant effect with lower methane concentration for a higher preheat temperature. As
shown in both paper A and B increasing the black liquor preheating temperature will result in
smaller droplet size distributions. Smaller droplets will be subjected to higher heating rates in the
gasifier which in turn can alter the composition of the volatile species released during pyrolysis.
Sricharoenchaikul et al. (Sricharoenchaikul, Frederick Jr. & Agrawal 2002) showed that higher
temperature, i.e. high heating rate, during conversion of small black liquor droplets promotes semi
volatile species at short residence time. It was also discovered that the semi-volatile species
decreased rapidly with increased residence time. Increased preheating of black liquor results in

6
higher heating rates which gives longer residence time at higher temperature for the volatile species
released during pyrolysis. Assuming that CH4 can be used as an indicator for heavier hydrocarbons
it seems likely that, increased black liquor preheat temperature promotes the conversion of
hydrocarbons into CO and H2.
A similar line of thought can be used to explain the reduction of H2S with elevated black liquor
preheating temperature (see figure 7). The higher heating rate will promote the binding of sulfur as
Na2S and Na2SO4 in the droplet (García-Labiano, Hampartsoumian & Williams 1995) instead of sulfur
being released as H2S and COS (Carlsson et al. 2010).

3,0 550

2,5
CH4, and H2S [%]

450

COS (ppm)
2,0
350
1,5

250
1,0 CH4
H2S
COS

0,5 150
110 120 130 140 150 160

BL temperature [oC]

Figure 7. Dry gas composition for CH4, H2S and COS (ppm) from the DP-1 gasification reactor gas
samples taken with the high temperature gas sampling system when investigating the influence of
black liquor temperature.

Counter-current condensation
Another key part in the PEHT-BLG process is the counter-current condenser where the synthetic
gas is both cooled and the water vapor in the gas is condensed away in vertical tubes. The heat
recovered from the gas is used to generate low/medium pressure steam that will be used in the pulp
and paper process. The condensed water that falls down in the condenser also scrubs off fine
particulate material and other condensable material from the raw syngas (Lindblom, Landälv 2007). It
has been showed in paper B that concentration of particulate matter in the syngas was varied from
0.02 to 0.10 mg/Nm3 after the condenser. This is approximately the level of particles concentration
in normal office air. The lower part of the condenser in the dp1 consists of a tube package with 189
tubes with a length of 2.4 m and an upper part consisting of a package with 101 tubes with a length
of 4.5 m. The outer diameter of each tube is 20 mm and the inner diameter is 18 mm. The space
outside the tubes is closed by end plates at both ends of each tube package.

In figure 8 the schematics of one tube in the CCC are showed. The synthetic gas with a high amount
of moisture is flowing upward and the moisture condenses on the condenser tube wall and forms a
downward flow of condensed water. On the shell side of the tube cooling water is cooling the tubes
and flowing from the top of the condenser to the bottom.
7
Figure 8. Schematics description of one tube in the counter-current condenser.

The objective with the work in paper C is to develop a computational fluid dynamics model of the
flow in the counter-current condenser. The model consists of a two-phase fluid flow in the tube-side
of the condenser and a single phase model on the shell side. The two-phase flow was treated using
an Euler-Euler formulation with different closure correlations for the heat flux, condensation rate
and pressure drop. The single phase model uses a closure correlation for the heat flux and pressure
drop. In the study predictions of the model are compared with results from experimental
measurement in the condenser used in the DP1 gasifier.

The results are in excellent agreement with the limited experimental data that has been collected in
the DP1 for both gas and cooling water temperature. In figure 9 the results from one case are shown
for the gas temperature and in figure 10 for the water cooling temperature along the axial direction
inside the condenser compared with experimental data. For the gas flow the temperature
measurement point is between the tube packages and at the gas outlet and for cooling water flow the
measurement point is between the tube packages and at the cooling water outlet. The model predicts
that gas temperature is dropped from 191.7 °C in the beginning (z = 0m) to 61.3 °C after the first
tube package (z= 2.6 m). The predicted gas temperature after the second tube package (z= 7.4 m) is
32.9 °C. The measured gas temperature is 61.0 °C and 31.1 °C after the first respectively second
tube package. It can be seen that cooling water temperature is increasing from 39.3 °C at cooling
water inlet at the top of the condenser (z= 7.4 m) to 81.2 °C when the water has flowed through the
condenser and exit at the bottom (z= 0 m). The measured temperature is 82.5 °C at the cooling
water outlet. Between the first and the second tube package the water temperature is predicted to
30.5 °C and measured to 30.8 °C. To be able to use the model for design calculation of a scaled up
condenser further validation of the model is needed. One interesting observation from the

8
computational results is that more than 80% of the condensation is done in the first half of
condenser indicating that the design is non-optimal. It would be relatively easy with the model in
paper C to optimize the design and reduce the size and cost of this component without loss of
performance.

200

Tg Calculated
150 T Experimentall
Gas Temperature, Tg (RC)

100

50

0
0 2 4 6 8

Axial Location, z(m)

Figure 9. Axial gas temperature distribution calculated compared with experimental measurement
from the development plant.

100
Cooling Water Temperature, Tw (RC)

80 Tw Calculated
T Experimentall
w

60

40

20

0
0 2 4 6 8

Axial Location, z(m)

Figure 10. Axial cooling water temperature distribution calculated compared with experimental
measurement from the development plant.
9
Conclusions
A spray visualization of gas-assisted atomization of water, black-liquor, and syrup/water mixtures
was performed. The study showed that the breakup and atomization of black liquor and syrup/water
mixture produces ligament shaped droplets. The size and shape was similar between black liquor
and syrup/water mixture when both liquids had the same physical properties. Therefore the
development of black liquor gasification can be enhanced, since the testing of burner spray nozzles
can be performed on simple syrup/water mixtures instead of black liquor, which will greatly
simplify the experiment and thus enable more experimental design iterations.

Also spatially resolved measurement of the gas composition in the development plant with a water
cooled quench probe has been performed. From the gas composition measurements and the spray
visualization it was found that the preheating of black liquor can alter the gas composition
significantly. In particular, the methane concentration was reduced by more than 25% when the
preheat temperature was increased from 115 to 150 °C. The composition change can come both
from increased thermal input to the gasifier and higher heating rates because of smaller black liquor
droplets with higher preheating temperature.

For counter-current condensation a condensation model was implemented in the computational

fluid dynamics code CFX. The model consists of a continuum model, where the flow is considered
flowing in a porous medium. The model is able to predict the temperature of the gas and of the
cooling water. Also the results are in excellent agreement with the limited experimental data that
has been collected in the DP1 gasification plant. Finally the model can be used for prediction of the
heat transfer coefficients, water vapor mass fraction in the gas, velocities and liquid volume fraction
in the condenser.

10
References

Adams, T.N., Frederick, W.J., Grace, T.M., Hupa, M., Lisa, K., Jones, A.K. & Tran, H. 1997, Kraft
Recovery Boilers, TAPPI PRESS.

Bhattacharya, P.K., Parthiban, V. & Kunzru, D. 1986, "Pyrolysis of black liquor solids", Industrial
& Engineering Chemistry Process Design and Development, vol. 25, no. 2, pp. 420-426.

Carlsson, P., Wiinikka, H., Marklund, M., Grönberg, C., Pettersson, E., Lidman, M. & Gebart, R.
2010, "Experimental investigation of an industrial scale black liquor gasifier. 1. the effect of
reactor operation parameters on product gas composition", Fuel, vol. 89, no. 12, pp. 4025-
4034.

Energimyndigheten 2010,
Energy in Sweden– facts and figures.

Farrington Jr., T.E., Kuusinen, T. & Sweerus, N. 1987, "Investigation of droplet size distribution
from commercial kraft black liquor spray nozzles", Papers Presented at the Summer National
Meeting of the American Institute of Chemical Engineers.

García-Labiano, F., Hampartsoumian, E. & Williams, A. 1995, "Determination of sulfur release and
its kinetics in rapid pyrolysis of coal", Fuel, vol. 74, no. 7, pp. 1072-1079.

Helpiö, T.E.J. & Kankkunen, A.E.P. 1996, "The effect of black liquor firing temperature on
atomization performance", Tappi Journal, vol. 79, no. 9, pp. 158-163.

Hupa, M., Solin, P. & Hyoty, P. 1987, "Combustion behaviour of black liquor droplets", Journal of
Pulp and Paper Science, vol. 13, no. 2, pp. 67-72.

Karlsson, D. & Westerlund, S. 2006, A unique pressurized spray test facility for optimization of
black liquor gasification, Department of Applied Physics and Mechanical Engineering, Luleå
University of Technology.

Lindblom, M. & Landälv, I. 2007, "Chemrec's atmospheric and pressurized BLG (black liquor
gasification) technology-Status and future plans", Proceeding of International Chemical
Recovery Conference.

Loebker, D.W. & Empie, H.J. 2002, "Independently controlled drop size in black liquor sprays
using effervescent atomization. Part II: Splashplate nozzles", Journal of Pulp and Paper
Science, vol. 28, no. 8, pp. 251-258.

Loebker, D.W. & Empie, H.J. 2001, "Independently controlled drop size in black liquor sprays into
the kraft recovery boiler using effervescent atomization", Journal of Pulp and Paper Science,
vol. 27, no. 1, pp. 18-25.

MacKrory, A.J. & Baxter, L.L. 2007, "Characteristics of black liquor sprays from gas-assisted
atomizers in high temperature environments", Proc. International Chemical Recovery
Conference, pp. 75.

11
Marklund, M. 2006, Pressurized entrained-flow high temperature black liquor gasification : CFD
based reactor scale-up method and spray burner characterization, Division of Fluid
Mechanics, Luleå University of Technology.

Skogsindustrierna 2010, Skogsindustrin - En faktasamling.

Sricharoenchaikul, V., Frederick Jr., J. & Agrawal, P. 2002, "Black liquor gasification
characteristics. 2. Measurement of condensable organic matter (tar) at rapid heating
conditions", Industrial and Engineering Chemistry Research, vol. 41, no. 23, pp. 5650-5658.

Whitty, K., Backman, R. & Hupa, M. 1998, "Influence of char formation conditions on pressurized
black liquor gasification rates", Carbon, vol. 36, no. 11, pp. 1683-1692.

12
Paper A
 Atomization and Sprays, 19(10):xxx–xxx, 2009

VISUALIZATIONS OF GAS-ASSISTED
ATOMIZATION OF BLACK LIQUOR AND
SYRUP/WATER MIXTURES AT ELEVATED
AMBIENT PRESSURES
Mikael Risberg
Luleå University of Technology, Division of Energy Engineering, SE-971 87 Luleå, Sweden

Magnus Marklund
Energy Technology Centre, Box 726, SE-941 28 Piteå, Sweden

Original Manuscript Submitted: 11/02/2009; Final Draft Received: 03/06/2009

Pressurized entrained flow high-temperature black liquor gasification (PEHT-BLG) is a novel technique to recover
the inorganic chemicals and available energy in black liquor originating from kraft pulping. One of the key parts
in the PEHT-BLG process is the spray atomizer where the viscous black liquor is disintegrated into a spray of
fine droplets into the hot gasifier. In this study a high-speed photography system was used in order to visualize the
spray formation of black liquor and syrup/water mixtures at elevated ambient pressures based on a conventional
coaxially convergent gas-assisted atomizer. The main conclusion is that the breakup and atomization of black
liquor by a gas-assisted atomizer is similar to that of a syrup/water mixture with similar physical properties. The
observed difference in sphericity between black liquor and syrup/water may be explained by rapid cooling of the
black liquor by the cool nitrogen gas at the nozzle exit, resulting in a sudden decrease in viscosity and possible
skinning of the black liquor. Furthermore, it was found that an increased ambient pressure appeared to contract
the spray to a more dense cloud of droplets compared to the corresponding atmospheric case.

INTRODUCTION production of high value added end products, e.g.,

methanol or dimethylether [1]. One of the key parts
In chemical kraft pulping, black liquor is formed as in the PEHT-BLG process is the spray atomizer
a byproduct in a digesting process where the cellu- where the viscous black liquor is disintegrated into
losic fibers are separated from the lignin in small a spray of fine droplets into the hot gasifier. In
wood chips to form pulp. Black liquor mainly order to fully understand and optimize the control
consists of equal parts of water, inorganic digest- of the process, it is of interest to visualize and
ing chemicals, and organic substances. A novel characterize the resulting spray.
technique to recover the inorganic chemicals and Loebker and Empie [2] used a syrup/water mix-
available energy in black liquor is pressurized en- ture in order to try to mimic the atomization of
trained flow high temperature black liquor gasifi- black liquor in a vee-jet nozzle by effervescent at-
cation (PEHT-BLG). Compared to today’s conven- omization. Most of the visualization work on black
tional recovery boiler technique, PEHT-BLG can liquor sprays has been made for different kinds
increase the total energy efficiency of the mill’s of splash plate nozzles used in the conventional
recovery cycle and produce a synthesis gas for recovery boiler process but not applicable to the
This work was made possible by funding from the Swedish BLG II program. This program is sponsored by the
Swedish Energy Agency, Mistra, Smurfit Kappa Kraftliner AB, SCA Packaging AB, Södra’s Research Foundation,
Sveaskog AB, Chemrec AB, and the County Administrative Board of Norrbotten. Correspondence concerning
this article should be addressed to M. Risberg, Luleå University of Technology, Division of Energy Engineering,
SE-971 87 Luleå, Sweden; e-mail: [Link]@[Link]
1
1044–5110/09/35.00
c 2009 by Begell House, Inc.
2 M. RISBERG AND M. MARKLUND

NOMENCLATURE

Ag fluid flow exit section area for gas (m2 ) Ul liquid velocity (m/s1 )
A fluid flow exit section area for liquid (m2 ) We aerodynamic Weber number
dl liquid nozzle diameter (m) Greek Symbols
ln /min gas flow rate per minute at 1 atm and 0◦ C μg gas dynamic viscosity (Pa)
m mass flux ratio μl liquid dynamic viscosity (Pa)
M momentum flux ratio ρg gas density (kg/m3 )
Oh Ohnesorge number ρl liquid density (kg/m3 )
Ug gas velocity (m/s1 ) σ interfacial surface tension (N/m)

current process. However, Mackrory and Baxter Spray Test Rig

[3] made a study of gas-assisted atomization of
black liquor at relatively low momentum flux ratios The pressurized spray test rig consists of a vertical
where they show that black liquor mainly forms pressure vessel with a diameter of 0.5 m and a
long stretched ligaments instead of droplets. total height of 5.6 m [4]. The vessel is designed
This study was performed in order to comple- for a maximum pressure of 15 bar (g) and has
ment earlier work by using higher momentum flux four optical access ports with a diameter of 0.25 m
ratios, elevated ambient pressures, and higher liq- located 0.7 m below the top end of the vessel.
uid flow rates, and also to investigate the possibil- The window glasses mounted in the optical access
ity to qualitatively mimic the gas-assisted atomiza- ports are made out of quartz glass with quality
tion process of black liquor by using syrup/water SILUX and with a thickness of 0.055 m. At the
mixtures. The main reason for comparing atomiza- top of the vessel a vertical spray lance is mounted
tion of black liquor with syrup/water mixtures is having the atomizer connected at the lower end
that testing and improving the nozzle performance (inside the vessel) and the feeding streams of gas
for atomization of black liquor would be more safe and liquid connected at the upper end (outside the
and easily performed if a simpler and nontoxic vessel). The spray lance can easily be traversed
synthetic fluid could be used. The work was based in the vertical direction in order to change the
on a conventional coaxially convergent gas-assisted vertical position of the atomizer. To avoid droplets
atomizer where a high-speed photography system ending up on the optical access windows, a purging
was used to visualize the spray formations. system consisting of nearly radial directed funnels
with an opening diameter of 0.1 m connected with
METHOD a supply of nitrogen gas was mounted on the inside
of the window glasses (see Fig. 1). Basically, a
The experimental setup used in the current work flow of nitrogen is introduced in the cavity formed
mainly consisted of a pressurized spray test rig by the funnel surrounding the inside of the window
and a high-speed photography system suitable for glass, which creates an outward gas flow away
spray visualizations. For the spray generation, a from the window that prevents spray droplets to
conventional coaxially convergent gas-assisted at- end up on the window. The purging gas velocity in
omizer was used for atomization of water, black the funnels was low compared to the axial spray
liquor, and two syrup/water mixtures. The details velocity and was not considered to affect the center
of the performed experiments are described in the core of the spray where the imaging equipment
different sections below. was focused.
 VISUALIZATIONS OF GAS-ASSISTED ATOMIZATION OF BLACK LIQUOR 3

Fig. 1 Schematic top-view figure showing the lighting heads (1), camera (2), and the placement of the optical access
windows with the window purging system (3)

The pressure inside the vessel was controlled by Visualization Technique

the flow rate of atomization gas and a valve at the
evacuation outlet to the open atmosphere. Nitrogen In order to enable visualizations of the atomization
at about 17◦ C delivered from a large reservoir tank process in the performed experiments, a digital
was used as the atomization gas. The flow rate of high-speed camera from Redlake (Motionpro X3+)
nitrogen was controlled by a mass flow controller was used. The camera is able to take pictures with
from Brooks (instrument 5853S) able to control a resolution up to 1280 × 1024 pixels at a frame
the gas flow rate within 0–2500 lpm (1 atm and rate of 2000 frames per sec and with a global
0◦ C). shutter time down to 1 μs. Two different lens
setups were used, a 55 mm Micronikkor lens for
The black liquor was fed to the atomizer by a case 1B (see below) and a 110 zoom lens together
specially designed delivery system [5] consisting with a 450 mm closeup lens for the other cases.
of a storage barrel (200 liters) that was heated to For case 1B the resolution was set to 800 × 240
100◦ C by a 2 kW heater, a 7 kW peak heater pixels and for the other cases the resolution was
where the temperature was increased to maximum 1280 × 1024 pixels. For the purpose of intensive
120◦ C, and an eccentric screw pump followed by backlighting, two Dedocool tungsten light heads
a lobe pump in series. The liquid flow rate was (COOLH) were used. In Fig. 2 the placement of
measured by an inductive flow meter from Elis the camera and lighting heads together with a
Plzen (FLONET FR 2014). Note that in the cases schematic top view of the placement of the optical
where water or syrup/water mixtures were used, access windows are presented.
the heaters were bypassed and the liquids were fed To measure the size of droplets the scale of
directly to the pump connection. The spray test the images was determined by taking pictures of
rig including the nitrogen and black liquor delivery a ruler placed straight beneath the atomizer. This
systems are schematically presented in Fig. 2. procedure also served the need of focusing the
4 M. RISBERG AND M. MARKLUND

Fig. 2 Schematic view of the experimental setup showing spray test rig, camera, lighting, and nitrogen and black
liquor delivery and heating systems

camera in the geometrical center region of the characteristics. The density will increase as the dry
atomizer. Furthermore, the mean velocity of the solids content is raised and decrease as the tem-
droplets was calculated based on a sequence of 10 perature is increased [6]. The surface tension of
images where droplets were identified and tracked. black liquor is dependent on the liquor composi-
tion, dry solids content, temperature [6], and the
Atomizer
The atomizer used in this study was a conventional
coaxially convergent gas-assisted atomizer where
the liquid is fed in a central jet stream and the
gas is introduced in a surrounding annular jet. The
nozzle was manufactured with high precision by
a commercial metal hardware manufacturer. The
schematics of the atomizer can be seen in Fig. 3.
The annular gas contraction ratio (ratio of entrance
to exit area of the contraction) in this case is 16.5.

Fluid Properties
Physical properties of black liquor, such as dry
solids content, viscosity, density, and surface ten-
sion, are difficult to obtain, as they are functions
of both the liquor composition and the process
conditions. However, these properties are very im-
portant for understanding the atomization process
of black liquor. Dry solids content is the mass
of a dried liquor sample as a percentage of the
original sample mass. This property is one of the Fig. 3 Schematics of the considered coaxial gas-
most significant factors to determine other proper- assisted atomizer. The liquid flows in the center and the
ties. Density is an important property for the flow gas in the surrounding annulus
 VISUALIZATIONS OF GAS-ASSISTED ATOMIZATION OF BLACK LIQUOR 5

time after surface formation. For example, surface gström and Marklund [10] in order to obtain the
tension generally decreases as the temperature in- desired viscosity.
creases and decreases with time after the surface
is formed [7]. The viscosity depends on a number Experimental Runs
of factors but is most affected by the dry solids
content and temperature. By increasing the temper- The results presented in this paper were obtained
ature the viscosity will decrease, but at higher dry by using the setup described above. Images of the
solids contents the viscosity will increase [8]. At center of the spray were taken 0.2 m below the
high dry solids content, black liquor can exhibit atomizer at a frame rate of 2000 frames per sec
non-Newtonian behavior, generally shear-thinning and with a global shutter time of 6 μs. In total,
[9]. In the current determination of the black liquor 11 different cases were considered in this study
viscosity, however, this effect was not considered. and are presented in Table 1 together with the
In practice for high-shear-rate nozzles, this non- following dimensionless flow parameters:
Newtonian behavior can increase the expected de-
• momentum flux ratio, M = ρg Ug2 /ρl Ul2
gree of secondary atomization due to a lowering of
the liquid viscosity at high shear rates and result in • mass flux ratio, m = ρl Ul Al /ρg Ug Ag
a decrease in final droplet sizes in the atomization
process. • liquid Reynolds number, Rel = ρl Ul dl /μl
The viscosity of black liquor in this work was
• gaseous Reynolds number, Reg = ρg Ug dg /μg
calculated based on the work by Soderhjälm [7]
and was not specifically measured in the individual • Ohnesorge number, Oh = μl /(ρl σdl )1/2
experimental runs. This viscosity model is based
on black liquor originating from a paper mill that • aerodynamic Weber number, We = ρg Ug2 dl /σ
uses only hardwood. In this work the black liquor
One case was run with water (case 1W) as a
was taken from a mill that uses a combination of
reference and five different conditions for black
70% hardwood and 30% softwood. Mixed black
liquor and syrup/water mixtures. All cases used
liquor with both hardwood and softwood will de-
in the present study give an aerodynamic Weber
crease the viscosity slightly compared to black
number in the order of 104 , indicating fiber type
liquor from a mill that only uses hardwood [8].
atomization according to Lasheras and Hopfinger
Since the current study is qualitative, this effect
[11].
was not considered in the estimation of the vis-
cosity. In this work black liquor was used with a
dry solids content of 75.2 wt % with a viscosity RESULTS
of 500 mPa at 105◦ C temperature and with a dry In this section the results from the experimental
solids content of 70.2 wt % with a viscosity of runs (see above) are presented in the form of snap
150 mPa at a temperature of 115◦ C. The density of images of the disintegrated liquid 0.2 m below the
the black liquor was estimated to be 1350 kg/m3 atomizer. First, the visualization of the water spray
(based on a standard analysis of the origin black is presented. Then, comparisons between the re-
liquor) for the black liquor samples used in this sulting sprays of black liquor and the syrup/water
study. mixtures at different operational conditions are pre-
Two different syrup/water mixtures at 20◦ C were sented.
used. The first mixture had 72.4 wt % syrup (vis-
cosity of 500 mPa and density of 1356 kg/m3 )
Water
and the second mixture had 66.82 wt % syrup
(viscosity 150 mPa and density 1321 kg/m3 ). The In Fig. 4 an image of the resulting spray of pure
mixtures were mixed according to measurements water (case 1W) from the considered nozzle is
of the Newtonian viscosity and density of the presented. It can be seen that the atomization
sucrose based syrup/water mixtures made by En- in this case consists of spherical droplets with
6 M. RISBERG AND M. MARKLUND

Table 1 Experimental Data for the Considered Cases. W, BL, and S/W Indicate Water, Black Liquor, and
Syrup/Water Mixture, Respectively

Case
Parameter Unit 1W 1B 1S 2B 2S 3B 3S 4B 4S
Absolute pressure bar 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Liquid – W BL S/W BL S/W BL S/W BL S/W
Dry solid content wt % 0 75.2 – 70.2 – 70.2 – 70.2 –
Liquid flow rate ln /min 4.9 4.9 4.9 4.9 4.9 4.9 4.9 7.3 7.3
Liquid temperature ◦C 20 105 20 115 20 115 20 115 20
Liquid viscosity mPa 1 500 500 150 150 150 150 150 150
N2 flow rate ln /min 735 735 735 735 735 441 441 1652 1652
N2 temperature ◦C 17 17 17 17 17 17 17 17 17
M – 90 100 100 100 102 60 61 100 103
m – 5.33 7.21 7.24 7.21 7.05 12.55 12.28 4.78 4.67
Rel – 11500 31 31 104 102 104 102 155 152
103 Reg – 463 463 463 463 463 266 266 1040 1040
10−2 Oh – 0.13 64 52 19 16 19 16 19 16
103 We – 28 40 27 40 28 22 15 90 63

High Viscosity

In Fig. 5 spray images for black liquor (case 1B)

and syrup/water (case 1S) at low liquid flow rate,
high viscosity (500 mPa), and high momentum flux
ratio are presented. The difference in illuminated
area between the images is due to the different
lens configurations used for these two cases (see
the Visualization technique section above). Note
that both the black liquor and syrup/water mixture
form stretched ligaments and few spherical shaped
droplets. The maximum length of the ligaments
was up to about 12 mm in both cases. The mean
velocity was calculated at 26 m/s for the black
liquor (case 1B) and 25 m/s for the syrup/water
(case 1S).

Low Viscosity
Fig. 4 Resulting water spray formation 0.2 m below
the nozzle for case 1W Figure 6 shows the typical shapes of the re-
sulting ligaments and droplets for black liquor
(case 2B) and syrup/water (case 2S) at low liq-
uid flow rate, low viscosity (150 mPa), and high
a typical diameter of the order of 102 μm. The momentum flux ratio. Note that the flow rates
maximum diameter is found to be around 3 mm. and momentum flux ratio were equal to the pre-
The observed mean velocity for the droplets in the vious cases above (cases 1B and 1S). However,
spray is about 26 m/s. when the viscosity is decreased, the sizes of lig-
 VISUALIZATIONS OF GAS-ASSISTED ATOMIZATION OF BLACK LIQUOR 7

Fig. 5 Liquid breakup 0.2 m below the nozzle for case 1B with black liquor (left) and for case 1S with syrup/water
(right)

Fig. 6 Liquid breakup 0.2 m below the nozzle for case 2B with black liquor (left) and for case 2S with syrup/water
(right)

aments and droplets decrease in both of the cur- Low Momentum Flux Ratio
rent cases. The maximum size of the ligaments
is observed to be around 8 mm for both black The ligament and droplet shapes for black liquor
liquor and the syrup/water mixture. Furthermore, (case 3B) and syrup/water (case 3S) at low liquid
it can be seen that the syrup/water mixture ap- flow rate, low viscosity (150 mPa), and low mo-
pears to generate more spherical-shaped droplets mentum flux ratio are presented in Fig. 7. The ni-
than the black liquor. The mean velocity was trogen gas flow and hence the momentum flux ratio
calculated at 25 m/s in both case 2B and case were decreased compared to the previous cases.
2S. The maximum ligament length increased to about
8 M. RISBERG AND M. MARKLUND

Fig. 7 Liquid breakup 0.2 m below the nozzle for case 3B with black liquor (left) and for case 3S with syrup/water
(right)

16 mm for black liquor (case 3B) and to about High Liquid Flow Rate and Elevated
10 mm for syrup/water (case 3S) compared to the Pressure
previous cases (cases 2B and 2S) with the same
viscosity but higher momentum flux ratio. Further- In Fig. 8 the resulting spray formation of black
more, the shape of the droplets for syrup/water liquor at high liquid flow rate is presented at atmo-
was observed to be more spherical than for black spheric pressure (case 4B) and at 10 bar absolute
liquor. The mean velocities for the black liquor pressure (case 5B). Compared to case 1B with the
and the syrup/water were 12 and 13 m/s, respec- same viscosity and momentum flux ratio as in the
tively. atmospheric case (case 4B), it can be seen that

Fig. 8 Black liquor spray formation 0.2 m below the nozzle for case 4B at atmospheric pressure (left) and for case
5B at 10 bar absolute pressure (right)
 VISUALIZATIONS OF GAS-ASSISTED ATOMIZATION OF BLACK LIQUOR 9

the ligaments are shorter and the droplets smaller, forms spherical-shaped droplets. Compared to wa-
but still nonspherical. Upon increasing the ambient ter, black liquor forms nonspherical and stretched
pressure to 10 bar (case 5B), the black liquor forms ligament-shaped droplets with the same atomizer
nonspherical droplets of the same size as in the and similar operational conditions. Formation of
atmospheric case 4B but with almost no ligaments. ligament shaped droplets from gas-assisted atom-
It was also observed that it was more difficult to il- ization of black liquor at low momentum flux
luminate the spray when the ambient pressure was ratios (M ≈ 3) was earlier shown by Markrory
increased. The mean velocities were calculated to and Baxter [3]. However, since a different nozzle
be 42 and 25 m/s at atmospheric pressure (case 4B) and different operational conditions were used in
and elevated pressure (case 5B), respectively. the current study, the size of the formed ligament
The resulting syrup/water spray formation at differs.
high liquid flow rate is presented in Fig. 9 at Comparison between black liquor and
both atmospheric pressure (case 4S) and 10 bar syrup/water mixture at high viscosity shows that
absolute pressure (case 5S). In the atmospheric the shapes and sizes of the droplets are similar.
case, case 4S, some of the droplets are in the form Compared to water the size of the droplets for the
of spherical droplets and some are in the form of high-viscosity cases is much larger for black liquor
ligaments. Compared to the earlier case with the and syrup/water. The velocities of the droplets are
same viscosity and momentum flux ratio (case 2S), approximately equal for the water, black liquor,
the typical droplet size is smaller and the ligament and syrup/water cases under the same operational
shorter when the flow rates are increased. In the conditions, since the density is nearly the same for
pressurized case 5S fewer ligament-shaped droplets the different liquids.
are observed compared to the atmospheric case For the cases where the viscosity was decreased,
4S. The mean velocities for the atmospheric and the droplet sizes decreased both for black liquor
pressurized cases were 42 and 25 m/s, respectively. and syrup/water. For the cases at lower viscos-
ity the syrup/water appears to form more spheri-
DISCUSSION cal shaped droplets compared to the black liquor.
An explanation of the nonspherical-shaped black
In general, the results showed that the atom- liquor droplets can be found in the cooling of
ization of water with the considered atomizer the black liquor by the nitrogen gas at the nozzle

Fig. 9 Syrup/water spray formation 0.2 m below the nozzle for case 4S at atmospheric pressure (left) and for case
5S at 10 bar absolute pressure (right)
10 M. RISBERG AND M. MARKLUND

exit, resulting in a sudden increase in viscosity The conclusion from this study is that the break-
and possible skinning of the black liquor, which up and atomization of black liquor is similar to
also affects the surface tension and, hence, the at- that of a syrup/water mixture with similar physical
omization. The syrup/water is not affected by this properties. The observed difference in sphericity
cooling, since the temperature of the syrup/water between black liquor and syrup/water may be ex-
mixture is about the same as for the nitrogen gas. plained by the cooling of the black liquor by
For the cases with lower momentum flux ratio the nitrogen gas at the nozzle exit, resulting in
the size of the droplets increases. The reason is a sudden increase in viscosity and possible skin-
that a lower flow rate of nitrogen gas results in a ning of the black liquor. However, for qualita-
lower amount of atomization energy available for tive characterizations of different nozzles in dif-
the breakup of the liquid. As found for the other ferent operational conditions, syrup/water mixtures
cases discussed above, the droplet shapes for the can be used as a synthetic substitute for black
syrup/water case are more spherical than for black liquor. For more quantitative characterizations of
liquor. the syrup/water sprays, the notable differences in
For the cases with the same flow rates of liquor drop sizes compared to black liquor should be
and nitrogen gas, the velocity of the droplets is verified and quantified before correlations for size
almost equal for the three different liquors (water, based on results obtained from syrup/water mix-
black liquor, and syrup/water mixture). This can be tures are determined.
explained by the densities being almost the same From a more quantitative point of view it was
for the three different liquors used in this study. found that the size of the ligament-shaped droplets
At elevated pressures the atomization behavior increased with increased viscosity and that the
of black liquor and syrup/water changes. An in- droplet sizes increased with decreased momentum
creased ambient pressure appears to contract the flux ratio. At elevated pressures the atomization of
spray to a dense cloud of droplets compared to black liquor and syrup/water changed behavior. An
the corresponding atmospheric case. As a conse- increased ambient pressure appeared to contract the
quence, it was more difficult to illuminate the spray spray to a more dense cloud of droplets compared
when the pressure was increased. A reason why to the corresponding atmospheric case.
the spray appears to be denser at elevated pressure Based on the results of this work, the develop-
may be a change in the recirculation pattern and ment of black liquor gasification can be enhanced,
entrainment of droplets inside the vessel. An in- since the testing of burner spray nozzles can be
crease in ambient gas density due to pressurization performed on simple syrup/water mixtures instead
will enhance entrainment of droplet and hence re- of black liquor.
sult in more droplets being recirculated to the top
of the vessel. Furthermore, the increase in ambient REFERENCES
pressure results in lower droplet velocities, which
1. M. Lindblom and I. Landälv, Chermec’s atmo-
also will enhance the entrainment of recirculated
spheric and pressurized BLG (black liquor gasifi-
droplets. cation) technology—Status and future plans, Proc.
of the Int. Chemical Recovery Conf., 2007
CONCLUSIONS 2. D. W. Loebker and H. J. Empie, Independently
controlled drop size in black liquor sprays to
Spray visualizations of gas-assisted atomization of the kraft recovery boiler using effervescent atom-
water, black liquor, and syrup/water mixtures were ization, J. Pulp Paper Sci., vol. 27, pp. 18–25,
performed in different operational conditions using 2001.
3. A. J. Mackrory and L. L. Baxter, Characteristics
high-speed photography. The qualitative character-
of black liquor sprays from gas-assisted atomiz-
izations of the resulting sprays were performed by ers in high temperature environments, Proc. of
observing the shapes of ligaments and droplets in the Int. Chemical Recovery Conf., pp. 75–79,
individual images and calculations of the droplet 2007.
velocities based on a series of sequential images. 4. D. Karlsson and S. Westerlund, A Unique Pres-
 VISUALIZATIONS OF GAS-ASSISTED ATOMIZATION OF BLACK LIQUOR 11

surized Spray Test Facility for Optimization of bustion, PhD thesis, The Finnish Pulp and Paper
Black Liquor Gasification, Masters Thesis, Luleå Research Institute, 1988.
University of Technology, 2006. 9. A. A. Zaman and A. L. Fricke, Newtonian vis-
5. M. Risberg, Spray Visualizations of Gas-Assisted cosity of high-solids kraft black liquors: Effects of
Atomization of Black Liquor, Masters thesis, temperature and solids concentrations, Ind. Eng.
Luleå University of Technology, 2008. Chem. Res., vol. 33, pp. 428–435, 1994.
6. T. N. Adams and W. J. Frederick, Kraft Recov- 10. T. F. Engström and M. Marklund, Deviations from
ery Boiler Physical and Chemical Process, The the log-normal distribution—Effects of viscosity,
American Paper Institute, 1988. Proc. of the 19th Annual ILASS-Americas Confer-
7. L. Soderhjelm and U. Koivuniemi, Recent devel- ence of Liquid Atomization and Spray Systems.,
opments in black liquor analysis, Proc. of the 2006.
Black Liquor Recovery Boiler Symposium, pp. 11. J. C. Lasheras and E. J. Hopfinger, Liquid jet in-
B2:1–12, 1982. stability and atomization in a coaxial gas stream,
8. L. Soderhjelm, Characterization of Kraft Black Annu. Rev. Fluid Mech., vol. 32, pp. 275–308,
Liquor with Respect to Evaporation and Com- 2000.
Paper B
Spatially Resolved
Measurements of Gas
Composition in a Pressurised
Black Liquor Gasifier
Per Carlsson,a Rikard Gebart,a Carola Grönberg,a Magnus Marklund,a Mikael Risberg,b
Henrik Wiinikka,a and Olov Öhrmana
a
Energy Technology Centre (ETC), Piteå S-941 28, Sweden; rikard@[Link] (for correspondence)
b
Department of Physics and Applied Mechanics, Luleå University of Technology, Luleå S-971 87, Sweden

Published online 17 August 2009 in Wiley InterScience ([Link]). DOI 10.1002/ep.10380

Black liquor gasification is a new process for re- black liquor sprays have been carried out. The results
covery of energy and chemicals in black liquor from from these experiments make it possible to explain
the Kraft pulping process. The process can be com- the effect of black liquor preheat temperature on the
bined with catalytic conversion of syngas into motor gasifier performance.
fuels. The potential for motor fuel production from Finally, the particle content in cooled syngas has
black liquor in Sweden is to replace about 25% of the been measured with a particle sizing impactor. The
current consumption of gasoline and diesel. For Fin- particle content is extremely low (0.1 mg/Nm3) and
land the figure is even higher while for Canada it is the major constituents in the particles were found to
about 14% and for the USA about 2%. Ó 2009 Ameri- be O, Na, Si, S, Cl, K, and Ca.
can Institute of Chemical Engineers Environ Prog, 28: 316– From the experimental results, it is concluded that
323, 2009 the most significant process parameters for the syngas
Keywords: black liquor gasification, syngas, par- composition are the system pressure, the black liquor
ticles, alkali salts, refractory oxides preheat temperature, the fuel-to-oxygen mass flow
ratio, and the flow rate of black liquor.
The large interest in the new process in Sweden INTRODUCTION
has made it possible to build a 3 MW or 20 tons per Chemrec AB:s technology for pressurized black
day of black liquor gasifier, based on the Chemrec liquor gasification together with a catalytic process
technology. It has been run more than 10,000 h since for synthetic motor fuel production, fully commercial-
2005. ized has a potential to globally produce green motor
In this article, recent results obtained by spatially fuels equivalent to over 45 billion L/year of gasoline
resolved measurements of the gas composition in the [1]. Black liquor is a by-product of the chemical kraft
DP-1 gasifier with a water cooled quench probe are pulping process, and it consists of roughly 30% water,
presented. The measurements have been done under 30% inorganic cooking chemicals (valuable for the
various process conditions that enable conclusions pulp mill), and 40% lignin and other organic substan-
about the general process characteristics. ces separated from the wood during chemical pulp-
In addition to the spatially resolved measurements, ing in a digester. To obtain proof of the concept, a
detailed experiments with high-speed photography of development gasifier (DP-1) with a capacity of gasifi-
cation of 20 ton dry solid of black liquor/24 h was
Ó 2009 American Institute of Chemical Engineers commissioned in 2005 in Piteå, Sweden.

316 October 2009 Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep
Figure 1. Schematic drawing of the black liquor gasifier.

A supporting research program funded by a con- Beneath the reactor is a quench cooler where the
sortium of public and private organizations (see syngas and the smelt are separated. The syngas
acknowledgements) is conducted with the aim to passes through a counter current condenser (CCC)
solve scientific problems that are perceived as slow- that cools the syngas. Water vapor and tar species, if
ing down the commercialization of the process. A there are any, will condense in the CCC. The heat
large part of the research program is aimed at using recovered from the gas is used to generate low/me-
the development plant for systematic experiments dium pressure steam that can be used in the pulp
that provide input to the modeling activities in the and paper process. A typical composition of the syn-
program. The goal with the modeling activities is to gas after the CCC is 34% CO2, 29% CO, 34% H2, 1.5%
develop models that can be used for scale up of the CH4, and 1.5% H2S.
gasification process to commercial size and that can
be used for trouble shooting. Black Liquor Composition
The experimental part of the research program Black liquor consists of roughly 30% water, 30%
also provides detailed information about the amounts inorganic cooking chemicals, and 40% lignin and
of impurities that can be used for sizing the gas other organic substances separated from the wood
cleaning unit in commercial processes based on black during chemical pulping in a digester. A typical ele-
liquor gasification. mental composition of dry black liquor is shown in
In this article, a summary of the results from recent Table 1.
experiments in the DP-1 are presented. The results Compared to other biomass [3] the black liquor
include the concentration of main components in the consists of significantly more inorganic elements
syngas, trace elements, and particles. In addition, (cooking chemicals) especially, Na, S, and K. The
some results are shown from burner experiments black liquor also consists of mineral impurities (e.g.
showing the effect of varying black liquor preheat Si and Ca) from the pulp wood. However, the con-
temperature. centration of these elements is significantly lower
than the concentration of the cooking chemicals. The
concentration of Cl is also significantly higher com-
EXPERIMENTAL PROCEDURES pared to other woody biomass because of the accu-
mulation of Cl in the pulping process. Unfortunately,
The Gasifier the concentration of Ni, Br, F, and I are not analyzed
The main part of the black liquor gasifier is shown in the standard black liquor chemical analysis
in Figure 1 [2]. The gasifier consists of a refractory because the concentration of these elements has
lined oxygen blown entrained-flow gasification reac- been regarded to be of no importance for the
tor, with a gas assisted burner that produces small pulping process.
black liquor droplets by atomization followed by a
direct quench. In the gasifier, pressurized (30 bar) Gas Sampling and Particle Measurements
high temperature (10008C) gasification takes place, A small part of the raw cooled synthesis gas was
mainly through reactions with oxygen, steam, and taken from the purified and cooled syngas and ana-
carbon dioxide producing a syngas and a liquid smelt lyzed [4, 5]. The same sampling point was used for
containing mainly Na2CO3 and Na2S. particle sampling and gas sampling. In five different

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep October 2009 317
Table 1. Chemical composition of black liquor. The experimental campaigns that took place in
May 2008 and October 2008 were focused on four
Moisture (wt % as received) 27.9 operating conditions: reactor pressure, reactor tem-
C (wt % dry) 32.5 perature, residence time, and spray burner perform-
Na (wt % dry) 20.4 ance (level of atomization). The operating conditions
S (wt % dry) 5.9 were varied systematically around designed base
H (wt % dry) 3.4 cases by changing process parameters: pressure, oxy-
K (wt % dry) 2.16 gen equivalence ratio, black liquor flow rate-pressure
Cl (wt % dry) 0.14 ratio (BLP), black liquor temperature, and oxygen
N (wt % dry) 0.08 temperature. In this work, the influence of black liq-
Si (mg/kg dry) 89 uor temperature on gas composition from the Octo-
Mg (mg/kg dry) 83 ber campaign is presented. In an ongoing work [7],
Ca (mg/kg dry) 78 the influence of process parameters on gas composi-
Mn (mg/kg dry) 40 tion will be described and discussed in greater detail.
Fe (mg/kg dry) 19 The preheat temperature of the black liquor was var-
Al (mg/kg dry) 12 ied systematically around normal operating condi-
Ni n.a. tions that corresponds to an oxygen equivalence ratio
Br n.a. of 0.41 and 27 bar of pressure. The black liquor pre-
F n.a. heat temperature was varied from 115 to 1508C. The
I n.a. normal preheat temperature is 1408C. In this tempera-
Lower heating value (MJ/kg dry) 12.00 ture range a significant viscosity decrease is expected
[8] as well as a decrease in surface tension [9]. The
n.a, not analyzed. extra heat input by the increased black liquor tem-
perature from 115 to 1508C was calculated to about
experiments, the syngas was sent to a 13-stage Dek- 30 kW, which corresponds to approximately one-
ati-type low-pressure impactor (LPI) that size-classi- third of the wall heat loss of the DP-1 gasification
fies particles according to their aerodynamic diameter reactor.
in the range of 0.03–10 lm. Thin aluminum films
(standard aluminum foil) were used as substrates in
the impactor. Selected impactor substrates with de- Pressurised Atomization Experiments with Black
posited particles were analyzed by scanning electron Liquor
microscopy (SEM) and energy dispersive X-ray spec- One of the key parts in the BLG process is the
troscopy (EDS). spray atomizer where the viscous black liquor is dis-
Gas sampling bags were used to collect gas sam- integrated into a spray of fine droplets into the hot
ples from the DP-1 plant that were analyzed by gas gasifier. To fully understand and optimize the control
chromatography (GC). A system of two GC CP-3800 of the process, it is of interest to visualize and charac-
(Varian Inc.) was used. Hydrocarbons were analyzed terize the resulting spray. This part of the current
with a FID detector, COS by a PFPD detector. CO, work, done by Risberg and Marklund [10], was per-
CO2, N2, O2, H2, CH4, and H2S were analyzed by formed to complement earlier black liquor spray
TCD detectors. characterization work [11–13] using high momentum
The method used to analyze the concentration flux ratios and elevated ambient pressures at high
of trace components (Fe, K, Li, Na, Ni, NH3, HCl, liquid flow rates.
HBr, HI, HCN, and HF) in gas phase in the syngas The experimental setup used in this study
after the gas cooler is based on wet chemistry anal- mainly consisted of a pressurized spray test rig and a
ysis of different absorption solutions through which high-speed photography system suitable for spray
synthesis gas was bubbled during three sampling visualizations. See Refs. [13] and [10] for further
periods [5]. Upstream the absorption solutions an details concerning the experimental setup. For the
absolute filter was used to separate particles from spray generation, a conventional coaxial convergent
the syngas. gas-assisted atomizer was used for atomization of
Several gas samples were taken from the hot part black liquor and syrup/water mixtures (Figure 3).
of the DP-1 gasification reactor using a high tempera- The physical properties and operational conditions
ture gas sampling system. In short, the system con- for the presented cases in the results later are sum-
sists of four parts: a water cooled gas sampling marized in Table 2. See Ref. [10] for further details
probe, a water cooling system, nitrogen purge sys- concerning the experiments.
tem, and a pressure vessel sampling system. The high
temperature gas sampling system fulfils ATEX and SIL
class 2 directives, and it is therefore complex with RESULTS
several back-up valves and monitoring systems
(Figure 2). A pressure vessel was filled with reactor Influence on Black Liquor Spray Characteristics
syngas and later on filled into sampling bags and an- from Black Liquor Preheating Temperature
alyzed according to the method described earlier. and Ambient Pressure
The high temperature gas sampling system is In this section, the results from the experimental
described in more detail by Wiinikka et al. [6]. runs presented in Table 2 are presented in the form

318 October 2009 Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep
Figure 2. Schematic drawing of the high temperature gas sampling system.

Table 2. Experimental data for the considered cases

in this article.

Case
Parameter 1B 2B 4B 5B
Absolute pressure (bar) 1.0 1.0 1.0 10.0
Liquid BL BL BL BL
Dry solid content (% wt) 75.2 70.2 70.2 70.2
Liquid flow rate (ln/min) 4.9 4.9 7.3 7.3
Liquid temperature (8C) 105 115 115 115
Liquid viscosity (mPas) 500 150 150 150
N2 flow rate (ln/min) 735 735 1652 1652
N2 temperature (8C) 17 17 17 17
M 100 100 100 36
m 7.21 7.21 4.78 4.78
Rel 31 104 155 155
103 Reg 463 463 1040 1040
1022 Oh 64 19 19 19
103 We 40 40 90 32
Figure 3. Schematics of the coaxial gas-assisted atom-
izer. The liquid flows in the center and the gas in the BL and S/W stands for black liquor and syrup/water
surrounding annulus. mixture, respectively.

Figure 5 shows the resulting ligaments and drop-

of instantaneous images of the disintegrated liquid lets for black liquor in Case 2B at moderate liquid
0.2 m below the atomizer. flow rate, low viscosity (150 mPas), and high momen-
Figure 4 shows the typical shapes of the resulting tum flux ratio (M). The maximum size of the liga-
ligaments and droplets for black liquor in Case 1B at ments was here observed to be around 8 mm, and
moderate liquid flow rate, high viscosity (500 mPas), the mean velocity was calculated to be 25 m/s.
and high momentum flux ratio (M). The maximum In Figure 6, the resulting spray formation of black
size of the ligaments was observed to be around 12 liquor at high liquid flow rate is presented at atmos-
mm, and the mean velocity was calculated to be 26 pheric pressure (Case 4B) and at 10 bar absolute
m/s. pressure (Case 5B). Note that, when the ambient

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep October 2009 319
Figure 4. Black liquor breakup 0.2 m below the noz- Figure 5. Black liquor breakup 0.2 m below the noz-
zle for Case 1B. zle for Case 2B.

Figure 6. Black liquor spray formation 0.2 m below the nozzle for Case 4B at atmospheric pressure (left) and
for Case 5B at 10 bar absolute pressure (right).

pressure is elevated to 10 bar the black liquor forms second immediately after the gas cooler where the
nonspherical droplets but almost no stretched liga- syngas temperature has decreased to about 408C.
ments. Furthermore, it was more difficult to illumi- Both samples were first transferred to a clean Tedlar
nate the spray when the ambient pressure was gas sample bag and then analyzed off-line with the
increased. The mean velocities were calculated to be same GC. In Figures 7 and 8, the effect on gas com-
42 m/s and 25 m/s at atmospheric pressure (Case 4B) position from three different black liquor preheat
and elevated pressure (Case 5B), respectively. temperatures can be seen. In Figure 7, the bulk gas
(CO2, H2, and CO) components are showed with a
Influence on Gas Composition from Black black liquor preheat temperature of 115, 140, and
Liquor Preheating Temperature 1508C, respectively.
The syngas was sampled in two different positions, In Figure 8, the molar fractions of CH4, H2S, and
the first in the hot reactor as described above and the COS are shown, notice that COS is in ppm.

320 October 2009 Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep
Figure 7. Dry gas composition (molar) for the bulk Figure 9. The particle mass size distribution and the
gases (CO2, H2, and CO) when investigating the influ- particle concentration in the syngas.
ence of black liquor temperature, gas samples taken
with the high temperature gas sampling system.

probably formed by sulfur-induced corrosion of the

stainless steel pipes downstream the black liquor gas-
ifier. The smaller particles were probably formed
when hot inorganic vapor compounds condensed in
the quench of the gasifier.
Table 3 shows the average trace element concen-
tration (kg/kg) in the raw cooled synthesis gas. For
nonsignificant trace elements (Fe, K, Li, Na, Ni, Br, I,
CN, and F), the gas concentration is calculated from
the concentration in the absorption solution of the
blank solution for the elements together with the
average syngas volume under the experiments. Only
for NH4-N and Cl were significant amounts detected
in the experiments. The average concentration of
NH4-N was 89.5 ppb and 1297 ppb for Cl.

Figure 8. Dry gas composition for CH4, H2S, and COS

(ppm) from the DP-1 gasification reactor gas samples DISCUSSION
taken with the high temperature gas sampling system
when investigating the influence of black liquor tem- Influence on Black Liquor Spray Characteristics
perature. from Black Liquor Preheating Temperature
and Ambient Pressure
When the black liquor viscosity was decreased, the
Trace Elements and Particles in the Syngas ligament and droplet sizes decreased as expected. An
The impactor measurements had to be carried out explanation for the large fractions of nonspherical
for a very long time (4–8 h) because the concentra- shaped black liquor droplets can be found in the
tion of particulate matter in the cooled synthesis gas cooling of the black liquor by the nitrogen gas at the
was very low. The concentration of particulate matter nozzle exit resulting in a sudden increase in viscosity
in the five different samples varied from 0.02 to 0.10 and possible skinning of the black liquor which
mg/Nm3. The particle size distribution shows no also affects the surface tension and, hence, the
distinct log-normal distribution that is common for atomization.
combustion particles, see Figure 9. For the cases with lower momentum flux ratio the
Impactor plates from the five experiments were size of the droplets increases. The reason is that a
analyzed by SEM-EDS analysis to determine the lower flow rate of nitrogen gas results in a lower
particle morphology and composition. Note that a amount of atomization energy available for the
thorough evaluation of the analysis results will be breakup of the black liquor.
reported elsewhere, in which XRD, ICP, and STEM At elevated pressures the atomization behavior of
measurements are included [4]. The composition in black liquor changes. An increased ambient pressure
the larger particles deposited on e.g. Plate 10–13 appears to contract the spray to a dense cloud of
differed significantly from the smaller particles depos- droplets compared to the corresponding atmospheric
ited on Plate 2–8 (see Figure 10). The large particles case. As a consequence, it was more difficult to illu-
contained S, Fe, and Ni while smaller particles con- minate the spray when the ambient pressure was
tain Na, Si, S, Cl, K, and Ca. The larger particles were increased. A reason why the spray appears to be

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep October 2009 321
Figure 10. Particles from plate 5 (a) and from plate (10) of sample 18 March 2008.

Table 3. Concentration of trace elements in the pressure and is therefore expected to be found in the
synthesis gas in ppb (kg/kg). synthesis gas after the absolute filter. Furthermore, Cl
can also be bound in a particle phase as alkali chlor-
Element Average gas concentration ides (NaCl and KCl) [4].
The low concentration of the halogens (Br, I, and
Fe <1.8
F) in the synthesis gas may indicate that the concen-
K <1.8
tration of these elements in the black liquor is very
Li <0.02
low. Possibly, Br, I, and F in the synthesis gas could
Na <17.4
also be bound in a particle phase with the alkali met-
Ni <0.05
als, Na and K in a similar manner as for Cl. However,
NH4-N 89.5
this appears not to be the case since no significant
Cl 1297
amounts of Br, I, and F were detected in synthesis
Br <1.0
gas particles [4].
I <4.6
The concentration of trace components can affect
CN total <0.5
the life time of the catalyst. The measured amounts
F <2.6
will therefore be a valuable input to the reactor de-
signer for the design of the gas cleaning needed
downstream of the reactor before the catalytic pro-
denser at elevated pressure may be a change in the cess.
recirculation pattern and entrainment of droplets
inside the vessel. An increase in ambient gas density Influence on Gas Composition from Black
due to pressurization will enhance entrainment of Liquor Preheating Temperature
droplets and hence result in more droplets being
For the bulk gas components CO2, H2, and CO, it
recirculated to the top of the vessel. Furthermore, the
is believed that the change in concentration is caused
increase in ambient pressure results in lower droplet
by the increased thermal input to the gasifier (rougly
velocities, which also will enhance the entrainment of
30 kW) which results in a temperature increase in the
recirculated droplets.
reactor.
As shown by Risberg and Marklund [10] increasing
Trace Elements and Particles in the Syngas the black liquor preheating temperature will result in
The low concentrations of metals that were found smaller droplet size distributions from gas assisted
in the synthesis gas can be explained by the fact that spray nozzles. Smaller droplets will be subjected to
these elements have a low saturated vapor pressure higher heating rates in the gasifier which in turn can
(except possible Ni and Fe carbonyls). Hence, should alter the composition of the volatile species released
a particular metallic element vaporize in the gasifier during pyrolysis. Sricharoenchaikul et al. [14] showed
flame, then due to the low saturation vapor pressure that higher temperature promotes semi-volatile spe-
the metal will quickly recondense on any nuclei that cies at short residence time. It was also discovered
are present when the temperature goes down in the that the semi-volatile species decreased rapidly with
quench or the gas cooler. As mentioned earlier, a fil- increased residence time. Assuming that CH4 can be
ter was installed to separate particles from the gas used as an indicator for heavier hydrocarbons it
phase and these components were probably sepa- seems likely that, increased black liquor preheat tem-
rated from the gas flow by the filter. The concentra- perature promotes the conversion of hydrocarbons
tions of Cl and NH4-N in the synthesis gas are higher into CO and H2.
which indicates that these elements are in the gas A similar line of thought can be used to explain
phase. A part of the Cl and the N is probably bound the reduction of H2S with elevated black liquor pre-
as HCl, NH3, or NH4Cl which have a significant vapor heating temperature. The higher heating rate will pro-

322 October 2009 Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep
mote that sulfur will be bound as Na2S and Na2SO4 5. Öhrman, O., Häggström, C., Wiinikka, H.,
in the droplet dictated by thermodynamic equilib- Hedlund, J., & Gebart, R. Methanol synthesis via
rium, instead of being released as H2S and COS. black liquor gasification. I. Synthesis gas impur-
ities, Manuscript in preparation.
CONCLUSIONS 6. Wiinikka, H., Carlsson, P., Granberg, F., Löfström,
The following conclusions could be drawn from J., Marklund, M, Tegman, R., Lindblom, M., &
this work: Gebart, R. System design and methodology for
• An increase in the black liquor temperature and high temperature gas sampling during pressur-
momentum flux ratio results in decreased ligament ized black liquor gasification, Submitted for
and droplet size. publication.
• An increase in ambient pressure results in a con- 7. Carlsson, P., Wiinikka, H., Marklund, M., Petter-
traction of the black liquor spray to a dense cloud son, E., Grönberg, C., Öhrman, O., & Lidman,
of droplets compared to the corresponding atmos- M. Experimental investigation of process parame-
pheric case. ter influence on gas composition in pressurized
• A high temperature gas sampling system has been entrained flow high temperature black liquor
designed, constructed, and tested with convincing gasification. I. Reactor parameters, Manuscript in
results. preparation.
• When changing the black liquor preheat tempera- 8. Soderhjelm, L., & Koivuniemi, U. (1982). Recent
ture in the DP-1 gasifier a significant change in developments in black liquor analysis, In Black
CH4 can be seen. Liquor Recovery Boiler Symposium, Technical
• The major syngas trace elements are NH4-N, Cl, report.
and S (bound as H2S and COS). 9. Soderhjelm, L. (1988). Characterization of kraft
black liquor with respect to evaporation and
ACKNOWLEDGMENTS combustion, The Finnish pulp and paper research
We thank the Swedish Energy Agency, Mistra, institute, Technical report.
Smurfit Kappa Kraftliner AB, SCA Packaging AB, 10. Risberg, M., & Marklund, M. Visualizations of
Södra Cell AB, Sveaskog AB, Chemrec AB, and the gas-assisted atomization of black liquor and
County Administrative Board of Norrbotten for fund- syrup/water mixtures at elevated ambient
ing this work through the BLG II research program. pressures, Atomization and Sprays, in press.
We also like to thank Rikard Öhman at ETC and the 11. Loebker, D.W., & Empie, H.J. (2001). Independ-
operators and process engineers at Chemrec for help ently controlled drop size in black liquor sprays
with the measurements. to the kraft recovery boiler using effervescent
atomization, Journal of Pulp and Paper Science,
LITERATURE CITED 27, 18–25.
1. [Link] 12. Mackrory, A.J., & Baxter, L.L. (2007). Characteris-
2. Lindblom, M., & Landälv, I. (2007). Chemrec’s tics of black liquor sprays from gas-assisted
atmospheric and pressurized BLG (black liquor gas- atomizers in high temperature environments. In
ification) technology—Status and future plants, In Proceedings of International Chemical Recovery
Proceedings of the International Chemical Recovery Conference (pp. 75–79), May 29-June 1.
Conference, May 29–June 1, Quebec, Canada. 13. Risberg, M. (2008). Spray visualizations of gas-
3. Nordin, A. (1994). Chemical elemental character- assisted atomization of black liquor, Master thesis,
isation of biomass fuels, Biomass and Bioenergy, Luleå University of Technology.
6, 339–347. 14. Sricharoenchaikul, V., Frederick, J., & Agrawal,
4. Wiinikka, H., Grönberg, C., Öhrman, O., & P. (2002). Black liquor gasification characteris-
Gebart, R. (2009). Characterisation of particles in tics. II. Measurement of condensable organic
the syngas during pressurised black liquor gasifi- matter (tar) at rapid heating conditions, Indus-
cation, In 10th Conference on Energy for a Clean trial Engineering & Chemical Research, 41,
Environment, 7–10 July, Lisbon, Portugal. 5650–5658.

Environmental Progress & Sustainable Energy (Vol.28, No.3) DOI 10.1002/ep October 2009 323
Paper C
 Numerical modeling of counter-current condensation in a Black Liquor Gasification
plant

Mikael Risberg1*, Rikard Gebart2+

1
Luleå University of Technology, Division of Energy Engineering, SE-971 87 Luleå, Sweden
2
Energy Technology Centre, Box 726, SE-941 28 Piteå, Sweden

*Corresponding author. E-mail address: [Link]@[Link]

+E-mail address: [Link]@[Link]
Abstract

Pressurized Entrained flow High Temperature Black Liquor Gasification is a novel technique
to recover the inorganic chemicals and available energy in black liquor originating from kraft
pulping. The gasifier has a direct quench that quickly cools the raw syngas when it leaves the
hot reactor by spraying the gas with a water solution. As a result, the raw syngas becomes
saturated with steam. Typically the gasifier operates at 30 bar which corresponds to a dew
point of about 220 °C and a steam concentration that is about 3 times higher than the total
concentration of the other species in the syngas. After the quench cooler the syngas is passed
through a counter-current condenser where the raw syngas is cooled and most of the steam is
condensed. The condenser consists of several vertical tubes where reflux condensation occurs
inside the tubes due to water cooling of the tubes on the shell-side. A large part of the
condensation takes place inside the tubes on the wall and results in a counterflow of water
driven by gravity through the counter current condenser. In this study a computational fluid
dynamics model is developed for the two-phase fluid flow on the tube-side of the condenser
and for the single phase flow of the shell-side. The two-phase flow was treated using an
Euler-Euler formulation with closure correlations for heat flux, condensation rate and pressure
drop inside the tubes. The single-phase model for the shell side uses closure correlation for
the heat flux and pressure drop. Predictions of the model are compared with results from
experimental measurements in a condenser used in a 3 MW Black Liquor Gasification
development plant. The results are in good agreement with the limited experimental data that
has been collected in the experimental gasifier. However, more validation data is necessary
before a definite conclusion can be drawn about the predictive capability of the code.

Key Words: Black Liquor, Computational Fluid Dynamics, Counter-current Condensation,

Non-condensable gases

1. Introduction

In chemical kraft pulping, black liquor is formed as a by-product in a digesting process where
the cellulosic fibers in small wood chips are separated from the lignin to form pulp. Black
liquor mainly consists of about 30%wt water, 30%wt inorganic digesting chemicals and
40%wt organic substances. A novel technique to recover the inorganic chemicals and
available energy in black liquor is Pressurized Entrained flow High Temperature Black
Liquor Gasification (PEHT-BLG). Compared to the conventional recovery boiler technique,
PEHT-BLG can increase the total energy efficiency of the mill’s recovery cycle and produce
a synthesis gas for production of high value added end products, e.g. methanol or
dimethylether [1]. The main parts of the PEHT-BLG recovery unit is (see figure 1); an
entrained-flow gasification reactor, a quench cooler and a counter current condenser (CCC).
In the reactor the black liquor is gasified at about 1000 °C and a synthetic gas is produced
together with a liquid smelt. After the reactor the synthetic gas and the smelt is rapidly cooled
by water sprays in the quench cooler. In the quench the smelt is dissolved in water and the
synthetic gas is going to the CCC. The CCC cools the synthetic gas and condenses water
vapor. The heat recovered from the gas in the CCC is used to generate low/medium pressure
steam.

2
 BLACK LIQUOR SHORT TIME
CONTACTORS
COOLING
OXYGEN AND WATER
ATOMIZING MEDIA

WHITE
GAS COOLER
LIQUOR

REACTOR
RAW
GAS

QUENCH

CLEAN, COOL
SYNTHESIS
GREEN GAS
LIQUOR

WEAK CONDENSATE
WASH
Figure 1. Schematic drawing of the black liquor gasifier.

One of the key parts in the PEHT-BLG process is the counter-current condenser where the
synthetic gas is cooled and the water is condensed in vertical tubes. Two distinct flow
domains exist in the CCC, the tube side and the shell side. The shell-side fluid is water which
cools the tubes on the outside. The tube-side fluid is a mixture of steam, liquid water, and
synthetic gas.
There are several mechanisms of heat and mass transfer in the CCC. On both the tube-side
and the shell side a complicated heat and mass transfer process with phase change and
counter-current flow of water takes place. The heat and mass transfer mechanism on the tube-
side is affected by the condensed water flowing downward and also by the high amount of
non-condensable gases (synthetic gas) inside the tubes. On the shell side only liquid water and
steam is present but the heat and mass transfer is still very complicated.

Only a few experimental studies have been done on counter-current condensation of flowing
vapor and non-condensable gases counter-current to the liquid film [2-5]. Several empirical
correlations for calculation counter-current condensation have been proposed [2,5-7].
The current work implements the empirical correlation proposed by Nagae et al [7] in a
continuum model, where the gas is considered flowing in a porous medium. The empirical
correlation proposed by Nagae et al depends mainly on the following parameters: condensate
film Reynolds number, steam-gas mixture Reynolds number, partial pressure of steam and
non-condensable gases and finally the gas and liquid density.

The objective with this work was to implement the above correlation in a computational fluid
dynamics code and to compare the results with experiments on a counter-current condenser in
a 3 MW black liquor gasification plant.

3
2. Method

In this section the model is described together with a description of two different operational
conditions for the counter-current condenser. The geometry of the CCC is schematically
illustrated in figure 2.

2.1 Experimental Details

The experimental set-up consisted of a counter current condenser used in a 3 MW black liquor
gasification development plant (see figure 2). The lower part of the condenser consists of a
tube package with 189 tubes with a length of 2.4 m and the upper part consists of a package
with 101 tubes with a length of 4.5 m. The space outside the tubes is closed by end plates at
both ends of each tube package. The outer diameter of each tube is 20 mm and the inner
diameter is 18 mm. The gas flow is going vertically upward inside the tubes and the cooling
water is flowing in the opposite direction outside the tubes (see figure 2). In and industrial
CCC the cooling flow is adjusted to maximize the production of steam at a useful pressure.
However, in the experiment the coolant flow rate was always so high that no steam was
formed on the shell side.

Figure 2. Schematic drawing of the counter-current condenser (left) and of the counter-
current condensation flow in one tube (right).

Two experimental measurements were carried out, one at an intermediate load and one at a
high load condition. The gas temperature is about 5°C higher and the gas flow rate is about
20% higher in the high load case. The boundary conditions for the two cases are presented in
table 1. The gas composition was measured using a Varian CP-3800 gas chromograph to get
the CO, CO2, H2, CH4, H2S and N2 mass fractions. The H2O content was calculated by
assuming that the gas is at saturated conditions at the inlet of the CCC which is likely since
the gas is cooled from about 1050°C to about 200°C by spraying with water in the quench.
The temperatures were measured with PT100 elements at the inlet, between the tube packages
and at the outlet both for gas and cooling water flow. The gas mass flow rate was measured

4
with an orifice meter and the cooling water mass flow rate was measured with an ultrasonic
flow meter.

Table 1 : Boundary conditions for the gas flow into the dp1 counter current condenser
Variable Case1 Case2 Unit
Gas inlet massflow 0.3312 0.4025 kg/s
Water inlet massflow 2.0628 2.1132 kg/s
Inlet gas temperature 191.7 196.3 °C
Inlet water temperature 29.3 29.8 °C
Operating pressure 27 27 Bar
Composition Case1 Case2 Unit
CO 18.3 13.8 %wt
CO2 28.0 26.1 %wt
H2 1.36 1.1 %wt
H2O 42 50.4 %wt
CH4 0.07 0.2 %wt
H2S 1.87 1.6 %wt
N2 8.4 6.8 %wt

2.2 Numerical Model

The detailed geometry of the CCC is very complicated and a computational mesh would have
to be very large in order to resolve all details and the turbulent boundary layers. Even if it was
possible to resolve all details, the problem remains to define a proper mathematical model of
the very complicated multi-phase and turbulent flow with both condensation and evaporation.
The approach adopted is in the present model instead to use a volume average and porosity to
represent the effect of the solids on the multi-phase fluid flow similar to the approach
described by Sha et al [8]. The multi-phase flow is modeled using the Euler-Euler method.
The interaction of the flow with the solids is represented with source term in the continuum
equation. Closure relations for the source terms are obtained from experimental correlation,
thus illuminating the need for complicated theoretical closure relations.

The two-phase flow inside the tubes was treated using an Euler-Euler formulation with
closure correlations for heat flux, condensation rate and pressure drop inside the tubes from
the literature. For the shell side a single-phase model with a closure correlation for the heat
flux was used since the experiment were done without boiling on the shell side. The two flow
domains were coupled via heat transfer through the tube walls. The different closure
correlations were implemented in the governing equations of the fluid flow as source or sink
terms. Both the tube- and shell-side was modeled using a porous medium concept to account
for the distributed solids in the flow domain. The model is implemented in the commercial
CFD code Ansys CFX.

The simulations were performed in a computational domain represented by a structured mesh

consisting of 9456 elements. The geometry consists of an axisymmetric 5 degree wedge of the
condenser around the vertical axis to reduce the model computational demand. The
discretization error was estimated to a relative error of 0.2% by Richardson extrapolation [9]
with two finer meshes (20130 and 40324 elements) for the gas temperature between the two

5
tube packages. The iteration error was estimated to less than 0.1% since the convergence
criterion was that the norm of the residuals must be reduced at least 3 orders of magnitude [9].

2.3 Governing Equations

The governing equations for the different phases can be expressed as following:

Continuity Equation

డ
ሺߚ௠ ߩ௠ ሻ ൅ ‫ ׏‬ή ሺߚ௠ ߩ௠ ࢁ௠ ሻ ൌ ܵெௌ௠ (1)
డ௧

where m is the phase, either l for liquid or g for gas phase, ߚ is the volume fraction of each
phase, ρ is the density, U is velocity and ܵெௌ is a mass source term. For cooling water side the
flow is only one phase and therefore ݉ is denoted cw for that model.

Momentum Equation

డ
ሺߚ௠ ߩ௠ ࢁ௠ ሻ ൅ ‫ ׏‬ή ൫ߚ௠ ሺߩ௠ ࢁ௠ ٔ ࢁ௠ ሻ൯ ൌ െߚ௠ ‫ߩ׏‬௠ ൅ ‫ ׏‬ή ߬௠ ൅ ܵெ௠ ൅ ࢁ௠ ܵெௌ௠ (2)
డ௧

ଶ
߬௠ ൌ ቀߚ௠ ߤ௘௠ ሺ‫ࢁ׏‬௠ ൅ ሺ‫ࢁ׏‬௠ ሻ் െ ଷ ߜ‫ ׏‬ή ࢁ௠ ሻቁ (3)

where ߬௠ is the stress tensor, ߤ௘௠ is the effective viscosity and ܵெ is a momentum source
term either from the second phase or from distributed flow resistance that are unresolved by
the mesh. In the above equation the turbulent-viscosity hypotheses is assumed. The effective
viscosity is:

ߤ௘௠ ൌ ߤ௠ ൅ ߤ௧௠ (4)

where ߤ௠ is the molecular viscosity and ߤ௧௠ is the turbulent viscosity.

Energy Equation

߲ ߲‫݌‬
൫ߚ ߩ ݄ ൯ െ ߚ௠ ൅ ‫ ׏‬ή ൫ߚ௠ ߩ௠ ࢁ௠ ݄௠ǡ௧௢௧ ൯ ൌ ‫ ׏‬ή ሺߚ௠ ߣ௘௠ ‫׏‬୫ ሻ ൅
߲‫ ݐ‬௠ ௠ ௠ǡ௧௢௧ ߲‫ݐ‬
ߚ௠ ‫ ׏‬ή ሺࢁ௠ ή ߬௠ ሻ ൅ ܵா௠ ൅ ࢁ௠ ‫ܵ כ‬ெ௠ ൅ ݄௠ǡ௧௢௧ ܵெௌ௠ (5)

where ݄௠ǡ௧௢௧ is total enthalpy, ߬௠ is the stress tensor, ߣ௘௠ is the effective thermal
conductivity and ܵா௠ is an energy source term. The source term is in this case a contribution
from the second phase and distributed heat sources or heat sinks.

Mass Fraction Equation

డ
డ௧
൫ߚ௚ ߩ௚ ܻுଶை௚ ൯ ൅ ‫ ׏‬ή ൫ߚ௚ ሺߩ௚ ࢁ௚ ܻுଶை௚ െ ߩ௚ ‫ܦ‬ுଶை௘௚ ሺ‫ܻ׏‬ுଶை௚ ሻ൯ ൌ ܵுଶை௚ (6)

ܻே஼௚ ൌ ͳ െ ܻுଶை௚ (7)

6
where ܻுଶை௚ , is the mass fraction of steam in the gas phase, ܻே஼௚ is the mass fraction of the
non-condensable gases in the gas phase, ‫ܦ‬ுଶை௚ is the effective kinematic diffusivity including
turbulent diffusion and ܵுଶை௚ is a multicomponent mass source. For the shell side this
equation is not solved since it is only one component there.

Gas and Liquid Volume Fraction

The porosity ߚ for the tube side depends on the inner tube diameter ݀௜ , number of tubes
ܰ௧௨௕௘௦ and diameter of the condenser ݀௖௢௡ௗ௘௡௦௘௥ that is,

ߚ ൌ ͳǡ ݂‫ ݊݋݊ݎ݋‬െ ‫ܽ݁ݎܽݏ݈݁݀݊ݑܾܾ݁ݑݐ‬
೏ మ
గቀ ೔ ቁ ே೟ೠ್೐ೞ (8)
మ
ߚ ൌ ͳെ ೏ మ ǡ ݂‫ܽ݁ݎܽݏ݈݁݀݊ݑܾܾ݁ݑݐݎ݋‬
గቀ ೎೚೙೏೐೙ೞ೐ೝ ቁ
మ

The summation of volume fraction for gas and liquid is equal to the porosity,

ߚ௚ ൅ ߚ௟ ൌ ߚ (9)

For the shell side the porosity ߚ depends on the outer diameter of tube and the number of
tubes.

೏ మ
గቀ ೚ ቁ ே೟ೠ್೐ೞ
మ
ߚൌ ೏ మ (10)
గቀ ೎೚೙೏೐೙ೞ೐ೝ ቁ
మ

The volume fraction for the cooling water side ߚ௖௪ is equal to the porosity on the shell side,

ߚ௖௪ ൌ ߚ (11)

2.4 Correlations for the Different Sink and Source Terms

Energy Sink Term for the Tube Side

If the gas temperature is above the saturation temperature heat is taken away from the gas by a
heat source term in the energy equation:
்೒ ି்೎ೢ ஺
ܵா௚ ൌ െ‫ݍ‬ሶ ൌ െ ோబ ௏
 (12)

where ܶ௚ is the gas temperature, ܶ௖௪ is the cooling water temperature, ܴ଴ is the overall
thermal resistance, ‫ ܣ‬is the average heat transfer area of a control volume inside the tube
package and ܸ is the average volume of a control volume inside the tube package.

7
Mass Source Term for the Tube Side

If the gas temperature is below the saturation temperature the water vapor condenses. The
condensation rate, ݉ሶ, is the mass condensate rate per unit volume, which is due to the heat
transfer between the vapor and cooling water. It can be obtained by overall energy balance:
்೒ ି்೎ೢ ஺
݉ሶ݄௟௩ ൌ ோబ ௏
 (13)

where ݄௟௩ is the latent heat of vaporization.

The condensation rate per unit volume is implemented as a sink term in the continuity
equation for the gas phase, ܵெௌ௚ , a source term in the continuity equation for the liquid phase,
ܵெௌ௟ and a sink term in the mass fraction equations, ܵுଶை௚ .

்೒ ି்೎ೢ ஺
ܵெௌ௟ ൌ െܵெௌ௚ ൌ െܵுଶை௚ ൌ ݉ሶ ൌ ோబ ௛೗ೡ ௏
 (14)

Energy Source Term for the Shell Side

To calculate the energy transferred to the cooling water a source term is added to the energy
equations for the cooling water. This source term ܵா௖௪ is equal in strength to the energy
transferred from the tube side to the shell side as,
்೒ ି்೎ೢ ஺
ܵா௖௪ ൌ ‫ݍ‬ሶ ൌ ோబ ௏
 (15)

Calculations of Heat Transfer Coefficients

The overall thermal resistance, ܴ଴ , is calculated as the sum of all individual resistances
calculated from semi-empirical heat transfer correlations.
ௗ
ܴ଴ ൌ ܴ௖௪ ೔ ൅ ܴ௧௪ ൅ ܴ௖ (16)
ௗ ೚

where ܴ௖௪ is the shell side thermal resistance, ܴ௧௪ the tube wall thermal resistance and ܴ௖ the
thermal resistance for condensation heat transfer.

The thermal resistance of the tube wall, ܴ௧௪ is obtained through the following expression for
conduction through tube walls [10]:
೏
ௗ೔ ୪୬ሺ ೚ ሻ
೏೔
ܴ௧௪ ൌ (17)
ଶఒ೟ೢ

where ߣ௧௪ is the thermal conductivity of the tube wall.

8
Thermal Resistance on the Shell Side

For forced convection dominant flow conditions on the shell side, the cooling water Nusselt
number (ܰ‫ݑ‬௖௪ ) was calculated using the following correlation [11]:

ͶͺΤͳͳ ǡܴ݁௖௪ ൏ ʹ͵ͲͲ

ܰ‫ݑ‬௖௪ ൌ ൜ ଴Ǥ଼ ଴Ǥଷହ (18)
ͲǤͲʹ͵ܴ݁௖௪ ܲ‫ݎ‬௖௪ ǡܴ݁௖௪ ൐ ͳͲͲͲͲ

The Nusselt number in the transition regime (ʹ͵ͲͲ ൏ ܴ݁௖௪ ൏ ͳͲͲͲͲሻ is calculated as linear
interpolation between the two limits.
The shell side thermal resistance ܴ௖௪ is obtained through the following expression:

ఒ ିଵ
ܴ௖௪ ൌ ቀ ௗ೎ೢ ܰ‫ݑ‬௖௪ ቁ (19)
೚

Thermal Resistance for Condensation

The condensation thermal resistance ܴ௖ is obtained through the following expression:

ܴ௖ ൌ ሺ݄௖ ሻିଵ (20)

The calculated condensation heat transfer coefficient ݄௖ by Nagae et al [7] consist of the heat
transfer coefficient of the liquid film, hf, and the heat transfer coefficient at the gas-liquid
interface, hi, which are separately evaluated since they are governed by two different heat
transfer mechanism.
ଵ ଵ ଵ
௛೎
ൌ௛ ൅௛ (21)
೑ ೔

The liquid film heat transfer coefficient was calculated by the following equation [7].
భ భ
ఘ೒ య భ ఘ೒ య
ସ ି
ܰ‫ݑ‬௙ ൌ ݉ܽ‫ ݔ‬൝൤ଷ ή ൬ͳ െ ఘ ൰൨ ܴ݁௙ ǡ ‫ ܥ‬൬ͳ െ ఘ ൰ ܴ݁௙ ௡ ൡǡ య (22)
೑ ೑

‫ ܥ݁ݎ݄݁ݓ‬ൌ ͲǤͺʹǡ ݊ ൌ െͳȀͶ

During the iterative solution of the CFD problem it is normal that the intermediate solutions
oscillate within a large interval and this may lead to divergence of the solution if the model is
ill conditioned. In order to prevent divergence when eq. 22 is used outside its valid range,
Nagae et al [7] suggested the following limits:

ଵȀଷ
௛೑ ௅ ଶ௅ ఔ೑ మ ௎೑ ௗೢǡ೔
ܰ‫ݑ‬௙ ൌ ఒ೑
൒ௗ ǡ‫ ܮ‬ൌ ቀ
௚
ቁ ǡ ܴ݁௙ ൌ
ఔ೑
൒ ͲǤͳ (23)
ೢǡ೔

9
The interfacial heat transfer coefficient was calculated by the following equation [7]:

௛೔ ௗ೔ ௉ೞ೟೐ೌ೘ ଴Ǥ଻ହ
ܰ‫ݑ‬௜ ൌ ൌ ͳʹͲ ቀ ቁ ƒš൫ͳǤͲǡ ܽ ή ܴ݁௚௕ ൯ (24)
ఒ೒ ௉ಿ಴

௎೒ ௗ೔
ܴ݁௚ ൌ ൑ ͳͲͲͲͲǡ ܽ ൌ ͲǤͲͲ͵ͷǡ ܾ ൌ ͲǤͺ (25)
ఔ೒

Pressure Drop

The source term ܵெ௚ in the momentum equations is used to account for the effect of the tube
bundles on the gas flow and it is written as:

௙
ܵெ௚௭ ൌ ߩ௚ ‫ כ‬ଶௗ ȁࢁȁܷ௭ (26)
೔

The following friction loss coefficient ݂ obtained by Wallis [12] was used:

ଵା଻ହሺଵିఉ೒ ሻ
݂ ൌ ͲǤͲʹ ‫כ‬ (27)
ఉ೒ మǤఱ

For the transverse direction the source term ܵெ௚௭ is multiplied by 10000 to prevent flow in the
other direction inside the tubes:

ܵெ௚௫ ൌ ܵெ௚௬ ൌ ͳͲͲͲͲ ‫ܵ כ‬ெ௚௭ (28)

For the liquid phase ܵெ௟ is set equal to ܵெ௚௭ .

On the shell side the source term ܵெ௖௪ in momentum equation is calculated according to eq.
26 with the friction loss coefficient from a polynomial fitted to a Moody chart [13].

2.5 Calculation Procedure

Since the simulation consists of a model of the tube side and a model of the shell side that are
unconnected, data have to been transferred between the two models. From the tube side to
shell side the energy source term for heating the water is transferred, ܵா௖௪ . For the shell side
to tube side the parameters waterside thermal resistance ܴ௪ and cooling water temperature ܶ௪
are transferred. The transfer of the parameters are done by a Perl script that takes the results
from the two different model for the above parameter and inject the parameter to the other
model every 20 iteration. The simulation is stopped when both models are converged to the
tolerance set at the start of iterations (typically the change in temperature between the
iterations was less than 0.001 degrees for a point between the tube packages).

2.6 Gas Properties

The pressure of the gas is 27 bar, which means that the ideal gas law becomes inaccurate.
Therefore the Peng-Robinson equation of state [14] was used since is it more accurate at
higher pressures.
One important parameter for calculating the heat transfer coefficient for condensation is the
thermal conductivity. For this variable the TRAPP method [15] for gas mixtures at high
pressures was used to calculate the thermal conductivity.
10
3. Results

In this section the results from the two different cases (see above) are presented. First the
result from case1 is presented.

3.1 Case 1

Figure 3 shows the calculated condensation heat transfer coefficient along the axial direction
of the condenser from the start of the first tube package to the end of the second. The
condensation heat transfer coefficient is found to range from 1140 W/m2K to 30 W/m2K. In
the beginning of the condenser the heat transfer coefficient is high since the gas flow rate and
thus the gas velocity is highest at this point. The heat transfer coefficient is reduced higher up
in the condenser where more of the water vapor is condensed away which leads to lower
velocity. In addition, the mass fraction of non-condensable gases increases with increasing
height which also leads to lower heat transfer coefficient.
The increase in heat transfer coefficient at about 3 m high comes from the velocity increase
when the flow enters the second tube package. The velocity increase comes from the decrease
in the number of the tubes in upper part.

1000
Heat Transfer Coefficient, hc (W/m2K)

100

10
0 2 4 6 8

Axial Location, z(m)

Figure 3. Axial distribution of calculated condensation heat transfer coefficients for case 1.

In figure 4 the temperature distribution along the axial direction of the condenser is compared
with experimental measurements in the dp1 gasification plan. The model predicts a
temperature decrease from 191.7 °C in the beginning to 61.3 °C after the first tube package.
The predicted temperature after the second tube package is 32.9 °C. The measured
temperature is 61.0 °C and 31.1 °C after the first respectively second tube package.

11
 200

Tg Calculated
150 T Experimentall
Gas Temperature, Tg (RC)

100

50

0
0 2 4 6 8

Axial Location, z(m)

Figure 4. Axial gas temperature distribution calculated for case 1.

Figure 5 shows the cooling water temperature variation in the condenser. The cooling water
temperature increases from 39.3 °C at the cooling water inlet at the top of the condenser (z=
7.4 m) to 81.2 °C when the water exits at the bottom (z= 0 m). The measured temperature is
82.5 °C at the cooling water outlet. Between the first and the second tube package the water
temperature is predicted to 30.5 °C and measured to 30.8 °C.

100
Cooling Water Temperature, Tw (RC)

80 Tw Calculated
T Experimentall
w

60

40

20

0
0 2 4 6 8

Axial Location, z(m)

Figure 5. Axial water temperature distribution calculated for case 1.

12
In figure 6 the mass fraction of water vapor along the axial direction of the condenser is
shown. The mass fraction decreases from about 42.0 %wt in the bottom of the condenser to
0.2 %wt after the second tube package.

0,4
Mass fraction of water vapour

0,3

0,2

0,1

0,0
0 2 4 6 8

Axial Location, z(m)

Figure 6. Mass fraction of water vapour distribution calculated for case 1.

13
3.2 Case 2

In figure 7 the heat transfer variations for condensation in the condenser is shown for case2.
The heat transfer coefficient for condensation is 1400 W/m2K in the beginning and decreases
to 20 W/m2K at the end of the first tube package. In the beginning of the second tube package
the heat transfer coefficient is 30.6 W/m2K and then decreases to 18.6 W/m2K.

1000
Heat Transfer Coefficient, hc (W/m2K)

100

10
0 2 4 6 8

Axial Location, z(m)

Figure 7. Axial distribution of calculated condensation heat transfer coefficients for case 2.

Figure 8 shows the temperature distribution for the condenser. The model predicts the
temperature after the first package to 56.2 °C and 30.1 °C after the second package. The
measured temperature is 59.6 °C after the first package and 33.8 °C after the second package.

200

Tg Calculated
150 T Experimentall
Gas Temperature, Tg (RC)

100

50

0
0 2 4 6 8

Axial Location, z(m)

Figure 8. Axial gas temperature distribution calculated for case 2.

Figure 9 shows the cooling water temperature variation in the condenser for case2. The
cooling water temperature increases from 29.8 °C at the cooling water inlet at the top of the
condenser (z= 7.4 m) to 97.0 °C when the water exits at the bottom (z= 0 m). The measured

14
temperature is 94.2 °C in the lowest part of the first tube package. Between the first and the
second tube package the water temperature is predicted to 31.1 °C and measured to 31.4 °C.

100
Cooling Water Temperature, Tw (RC)

80 Tw Calculated
T Experimentall
w

60

40

20

0
0 2 4 6 8

Axial Location, z(m)

Figure 9. Axial water temperature distribution calculated for case 2.

In figure 10 the mass fraction of water vapor along the axial direction of the condenser is
shown. The mass fraction is decreased from about 50.0 %wt in the bottom of the condenser to
0.2 %wt after the second tube package.

0,6

0,5
Mass fraction of water vapour

0,4

0,3

0,2

0,1

0,0
0 2 4 6 8

Axial Location, z(m)

Figure 10. Mass fraction of water vapor distribution calculated for case 2.

15
Figure 11 shows a comparison between simulation and measurement of gas temperature after
the first tube package for seven different cases. The seven different cases are the two
mentioned above plus five other cases. The additional cases had gas and water inlet
temperature and flow rates in-between these in case 1 and case 2. The figure shows that the
average error is about 2% and that only one prediction deviated by 5% from the measurement.
+5%
70

-5%
Gas Temperature Simulation [oC]

65

60

55

50
50 55 60 65 70

Gas Temperature Measurement [oC]

Figure 11. Comparison of gas temperature predicted by the CFD model with experimental
data from the DP1 counter-current condenser measured between the two tube packages. The
two dashed lines indicate plus and minus 5% discrepancy between measurements and
prediction.

4. Discussion

The decrease in heat transfer coefficient along the axial direction comes mainly from the
condensation of water vapor that leads to lower velocity and an associated reduction of the
turbulent heat transfer. The decrease also comes from the increased amount of non-
condensable gases along axial direction which also leads to lower heat transfer coefficient.
The jump in the heat transfer coefficient at the beginning of the second tube package comes
from the increase in velocity due to the flow area reduction with the lower number of tubes in
the second part of the condenser.

The higher condensation heat transfer coefficient at the gas inlet in the second case comes
from the increased inlet velocity associated with a higher mass flow rate compared to the first
case. Also the higher inlet gas temperature allows the gas to carry a higher mass fraction of
water vapor and therefore the mass fraction of non-condensable gases is lower which also
leads to an increase of the heat transfer coefficient for the second case.

Since the heat transfer coefficient at the gas-liquid interface is dependent on the thermal
conductivity for the gas it is important to have a proper description for it. Therefore the
TRAPP method for gas mixtures at high pressures was used. However, there are only a few
experimental data for gas mixtures at high pressures and, even here, most studies are limited
to simple gases and light hydrocarbons [16] which make the estimation uncertain.

16
The results are in good agreement with the limited experimental data that has been collected
in the experimental gasifier. However, since only seven different cases were considered and
temperature was measured only at certain locations for limited variations, more validation
data is necessary before a definite conclusion can be drawn about the predictive capability of
the code.

5. Conclusions

A multi-phase model for a counter current condenser used for syngas cooling has been
developed. The model combines an Euler-Euler multi-phase formulation with experimental
correlations for drag forces and heat and mass transfer from distributed solid surfaces in the
flow domain. The model was used to predict cooling and condensation in an experimental gas
cooler used in a 3 MW black liquor gasification development plant.

The main conclusions from this work are:

x The model is able to predict both the temperature on the gas and cooling water,
respectively.
x The results are in good agreement with the limited experimental data that has been
collected in the experimental black liquid gasification plant.
x The model can be used for prediction of the heat transfer coefficients, water vapour
mass fraction in the gas, velocities and liquid volume fraction in the condenser.

The model must be extended with a boiling heat transfer model and a multi-phase formulation
for the cooling water (shell side) before steam production from the CCC can be predicted.

6. Acknowledgements

The authors would like to thank the Swedish Energy Agency, Mistra, Smurfit Kappa
Kraftliner AB, SCA Packaging AB, Södra Cell AB, Sveaskog AB, Chemrec AB, and the
County Administrative Board of Norrbotten for partial funding of this work through the BLG
II research program. Additional funding has come from the thermo-chemical research
platform of the Bio4Energy program through Luleå University of Technology.

7. Nomenclature

Roman letters

‫ܣ‬ Average heat transfer area of a control volume inside the tube package (m2)
‫ܦ‬ுଶை௚ Effective diffusivity of steam into gas (m2/s)
݀௖௢௡ௗ௘௡௦௘௥ Inner diameter condenser (m)
݀௜ Tube inner diameter (m)
݀௢ Outer diameter of the tubes (m)
݃ Gravitational acceleration (m/s2)
݄௠ǡ௧௢௧ Total entalphy (J/kg)
݄௟௩ Latent heat of vaporization (J/kg)
݄௖ Heat transfer coefficient condensation (W/m2K)
݄௙ Film heat transfer coefficient (W/m2K)
݄௜ Interface heat transfer coefficient (W/m2K)

17
ܷ௙ Velocity film (m/s)
ܷ௚ Velocity gas (m/s)
‫ܮ‬ Length scale (m)
݉ሶ Condensation rate per unit volume (kg/m3s)
ܰ‫ݑ‬௖௪ Cooling water nusselt number
ܰ‫ݑ‬௖ Condensation nusselt number
ܰ௧௨௕௘௦ Number of tubes
ܲ௦௧௘௔௠ Partial pressure steam (Pa)
ܲே஼ Partial pressure non-condensable gases (Pa)
‫ݍ‬ሶ Heat transfer rate per unit volume (W/m^3)
ܴ଴ Overall thermal resistance (m2K/W)
ܴ௪ Waterside thermal resistance (m2K/W)
ܴ௧௪ Tube wall thermal resistance (m2K/W)
ܴ௖ Condensation thermal resistance (m2K/W)
ܴ݁௖௪ Cooling water Reynolds number
ܲ‫ݎ‬௖௪ Cooling water prandtl number
ܴ݁௙ Film Reynolds number
ܴ݁௚ Gas Reynolds Number
ܵெௌ Mass source term (kg/m3s)
ܵெ Momentum source term
ܵா Energy source term (kg/m3s)
ܵுଶை௚ Multicomponent mass source (kg/m3s)
V Average volume of a control volume inside the tube package (m3)
ܶ௚ Gas Temperature (°C)
ܶ௖௪ Cooling Water Temperature (°C)
ࢁ Velocity (m/s)
ܻுଶை௚ Mass fraction of steam in the gas phase
ܻே஼௚ Mass fraction of the non-condensable gases in the gas phase

Greek letters

ߚ Porosity
ߚ௚ Gas-phase volume fraction
ߚ௟ Liquid-phase volume fraction
ߜ Kronecker delta
ߣ௘  Effective thermal conductivity, W/mK
ߣ௚  Gas thermal conductivity, W/mK
ߣ௟  Liquid thermal conductivity, W/mK
ߣ௧௪ Tube wall thermal conductivity, W/mK
ߤ௘௠ Effective viscosity (Pas)
ߤ௠ Molecular viscosity (Pas)
ߤ௧௠ Turbulent viscosity (Pas)
ߥ௙ Liquid kinematic viscosity (m2/s)
ߥ௚ Gas kinematic viscosity (m2/s)
Ug Gas density (kg/m3)
Ul Liquid density (kg/m3)
߬௠  Stress tensor

18
7. References

[1] M. Lindblom, I. Landälv, Chemrec’s atmospheric & pressurized BLG (Black Liquor
Gasification) technology – Status and future plans, in: Proceeding International Chemical
Recovery Conference, Quebec City, QC, Canada, 2007

[2] Y. Moon, H. Park, Y. Bang, Assessment of RELAP5/MOD3.2 for reflux condensation

experiment (2000) KAIST Technical Report. NUREG/IA-0181

[3] K. Vierow, T. Nagae, T. Wu, Experimental investigation of reflux condensation heat

transfer in PWR steam generator tubes in the presence of noncondensable gases, in:
Proceedings of the tenth International Topic Meeting on Nuclear Reactor Thermal Hydraulics
(NURETH 10), Seoul, Korea, 2003

[4] S.B. Al-Shammari, D.R. Webb, P. Heggs, Condensation of steam with and without the
presence of non-condensable gases in a vertical tube, Desalination 169 (2004) 151–160.

[5] K. Lee, H. No, I. Chu, Y. Moon, M. Chun, Local heat transfer during reflux condensation
mode in a U-tube with and without noncondensable gases, International Journal of Heat and
Mass Transfer 49 (2006) 1813–1819.

[6] T. Nagae, M. Murase, T. W, K. Vierow, Evaluation of reflux condensation heat transfer of

steam-air mixtures and gas-liquid countercurrent flow in a vertical tube, Journal of Nuclear
Science and Technology 42 (2005) 50–57.

[7] T. Nagae, M. Murase, T. Chikusa, K. Vierow, T. Wu, Reflux condensation heat transfer of
steam-air mixture under turbulent flow conditions in a vertical tube
Journal of Nuclear Science and Technology 44 (2) (2007) 171-182.

[8] W.T. Sha, C.I. Yang, T.T. Kao, S.M. Cho, Multidimensional numerical modeling of heat
exchangers, Journal of Heat Transfer 104 (1982) 417-425.

[9] J. Ferziger, M. Peric, Computational Methods for Fluid Dynamics., second ed., Springer,
1999, pp. 314-318.

[10] F.P. Incropera, D.P. Dewitt, T.L. Bergman, A.S. Lavine, Fundamental of Heat and Mass
Transfer, 6th Edition, John Wiley and Sons, 2007

[11] [Link], S. Guentay, D. Suckow, A. Dehbi,

Reflux condensation of flowing vapor and non-condensable gases counter-current to laminar
liquid film in a vertical tube, Nuclear Engineering and Design 239 (11) (2009) 2409-2416.

[12] G.B. Wallis, One-dimensional Two-phase Flow, McGraw-Hill, 1969, pp.355-360

[13] L. F. Moody, Friction Factors for Pipe Flows, Transaction of the ASME 66, 1944, pp.
671-684

19
[14] D.Y. Peng, D.B. Robinson, A new two-constant equation of state, Industrial and
Engineering Chemistry Fundamentals 15 (1976) 59-64.

[15] M.L. Huber, Transport Properties of Fluids, Their Correlation, Prediction and Estimation,
J. Millar, J. H. Dymond and C. A. Nieto de Castro (eds.), IUPAC, Cambridge Univ. Press,
Cambridge, 1996, pp.283-295

[16] B.E. Poling, J.M. Prausnitz, J.P. O'Connell , Properties of Gases and Liquids, 5th Edition,
McGraw-Hill, 2001, pp. 10.35

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