Sriniva Srinivasn

UNIVERSITY OF CINCINNATI
03/02/04
Date:___________________
Rangesh Srinivasan
I, _________________________________________________________,
hereby submit this work as part of the requirements for the degree of:
Master of Science
in:
Environmental Engineering
It is entitled:
Study of Trona (Sodium Sesquicarbonate) Reactivity with
Sulfur Dioxide in a Simulated Flue Gas
This work and its defense approved by:
Dr. Tim Keener

Chair: _______________________________
Dr. Soon-Jai Khang
_______________________________
Dr. Mingming Lu
_______________________________
_______________________________
_______________________________
Study of Trona ( Sodium Sesquicarbonate) Reactivity with

Sulfur Dioxide in a Simulated Flue Gas
A thesis submitted to the
Division of Research and Advanced Studies
of the University of Cincinnati
in partial fulfillment of the
requirements for the degree of
MASTER OF SCIENCE
In the Department of Civil and Environmental Engineering
of the College of Engineering
2003
by
Rangesh Srinivasan
B.E. Anna University, Madras, India 2000
Committee Chair: Dr. Tim C. Keener
Abstract
In the last few years, sulfur dioxide (SO2 ) has been under heavy scrutiny for reduction
and its emissions are being monitored very closely by both federal and state regulatory agencies.
Most of the conventional flue gas desulfurization techniques are able to meet the standards but
normally come with very high capital and maintenance costs and have other associated problems.
Dry injection of sodium-based sorbents has gained a lot of attention in the last few years. With
Dry injection, it is possible to achieve almost similar and in some cases even higher SO2 removal
efficiencies than with spray dry or wet scrubbing systems.
It is proposed to study the reactivity of Trona (Na2 CO3 .NaHCO3 .2H2 O) with SO2 in a
simulated flue gas stream by means of an entrained flow reactor coupled with a fabric filter
simulator. The objective of this study is to provide fundamental kinetic data on the effect of flue
gas variables including temperature, particle size, SO2 concentration and stoichiometric ratio on
removal of SO2 . A drop tube reactor with a fabric filter simulator was developed to simulate
sorbent injection and sorbent particle capture. Trona was found to remove SO2 from flue gas at
efficiencies that were comparable to those of sodium bicarbonate under certain conditions. It was
found that the different variables like temperature, SO2 concentration and especially trona
particle size have a very critical effect on removal efficiency.
ACKNOWLEDGEMENTS
I express my sincere thanks to my advisor Professor Tim Keener for providing me with
this wonderful research opportunity. Without his guidance and encouragement I wouldnt have
been able to complete my work.
I would also like to thank Dr. Soon Jai Khang and Dr. Mingming Lu for agreeing to serve
on my thesis committee.
I would like to thank Mr. John Mazuik at Solvay Minerals for funding this project and
providing all the trona samples.
Special thanks to all members of the air quality group for all their help in completing my
thesis. Finally, thanks to every one of my friends who made my stay at UC a wonderful and
unforgettable experience.
TABLE OF CONTENTS
LIST OF TABLES
ii
LIST OF FIGURES
iii
1. INTRODUCTION
1.1 Problem Statement
1.2 SO2 background information
1.3 Advantages of dry sodium-based sorbent injection
1.4 Project Objectives
2. LITERATURE REVIEW
2.1 Literature Overview
3. EXPERIMENTAL SETUP
18
3.1 Entrained Flow Reactor
18
3.2 Sorbent Feeder
21
3.3 Operating Conditions
22
3.4 Experimental Procedure
23
4. RESULTS
26
4.1 Effect of Particle Size on SO2 Removal
26
4.2 Effect of Temperature on SO2 Removal
31
4.3 Effect of Inlet Gas SO2 Concentration on Overall SO2 Removal

i
36
4.4 Effect of Stoichiometric Ratio on SO2 Removal
40
4.5 Model
42
5. CONCLUSIONS AND FUTURE WORK
49
6. REFERENCES
51
APPENDIX 1 EXPERIMENTAL DATA
53
APPENDIX 2 MODEL CALCULATIONS
63
APPENDIX 3 MODEL CALCULATIONS
66
ii
LIST OF TABLES
Table 1.
Flue gas composition
22
Table 2.
List of Equipment
23
Table 3.
T-200 particle size distribution
27
Table 4.
T-200 : Mean mass diameter of particles
28
iii
LIST OF FIGURES
Fig. 1.
Schematic of a dry sodium injection system in a coal fired

power plant.
Fig. 2.
Comparison of nahcolite and trona (200 mesh, A/C : 2.3).
10
Fig. 3.
Effect of trona particle size on SO2 removal (A/C : 2.3).
11
Fig. 4.
Variation of conversion with time (Temperature : 150 C,

SO2 concentration : 3500 ppm).
Fig. 5.
Variations of conversion of spray dried soda with time at

lower temperatures.
Fig. 6.
12
SO2 removal with trona (O : Pittsburgh seam coal(1.6 % S,

59 m sorbent) ; : West Virginia coal(3.1 % S, 32 m sorbent)).
Fig. 7.
12
13
Results of a pilot plant dry scrubbing demonstration study

using NaHCO3 .
15
Fig. 8.
Comparison of SO2 removal using trona and sodium bicarbonate.
16
Fig. 9.
Effect of stoichiometric ratio on SO2 removal.
17
Fig. 10.
Comparison of sorbent costs.
17
Fig. 11.
Drop tube reactor schematic.
19
Fig. 12.
Drop Tube Reactor.
19
Fig. 13.
Fabric Filter Simulator.
20
Fig. 14.
Sorbent Feeder System.
21
Fig. 15.
Conversion at different stoichiometric ratios (Temperature = 300 F ;

Inlet SO2 concentration = 500 ppm ; Particle Size = <38).
Fig. 16.
29
Effect of particle size on conversion at different stoichiometric ratios

(Temperature = 300 F ; Inlet SO2 concentration = 500 ppm).
iv
29
Fig. 17.
Comparison of conversion at a higher stoichiometric ratio.
30
Fig. 18.
Comparison of conversion at a lower stoichiometric ratio.
30
Fig. 19.
Conversion at different temperatures (Inlet SO2 concentration :

500 ppm; stoichiometric ratio : 2-4).
Fig. 20.

Fig. 21.
34

Fig. 25.
34

Fig. 24.
33

Fig. 23.
33

Fig. 22.
32
35

1500 ppm; stoichiometric ratio = 0-3).
35
Fig. 26.
Effect of S02 inlet concentration on conversion (T : 250F, SR : 2-4).
36
Fig. 27.
37
Fig. 28.
37
Fig. 29.
Comparison of utilization at two different inlet SO2 concentrations

(SR : 2-4).
38
Fig. 30.
Utilization versus Temperature (Inlet SO2 concentration : 500 ppm).
39
Fig. 31.
39
Fig. 32.
40
Fig. 33.
Effect of stoichiometry on conversion (Temperature : 275 F;

Inlet SO2 concentration : 500 ppm).
Fig. 34.

Inlet SO2 concentration : 500 ppm)
Fig. 35.
41
41

Inlet SO2 concentration : 1500 ppm).
42
Fig. 36.
Shrinking core of NaHCO3 and varying exposure times of Na2 CO3 .
43
Fig. 37.
Pore plugging model fit (Inlet SO2 concentration : 500 ppm).
46
Fig. 38.
Pore plugging model fit with actual data (Inlet SO2 concentration :
500 ppm).
Fig. 39.
46
X versus temperature at different stoichiometric ratios (Inlet SO2

concentration = 500 ppm).
Fig. 40.
47
X versus temperature at different stoichiometric ratios (Inlet SO2

concentration = 1500 ppm).
48
vi
1.
INTRODUCTION
1.1 Problem Statement

Sulfur dioxide (SO2 ) is arguably the most important pollutant on EPAs list of six criteria
pollutants and reduction in SO2 emissions remains the main focus of EPAs strategy for cleaner
air. SO2 has been associated with health effects ranging from respiratory illnesses to acute and
chronic heart and lung disorders. It is also a primary contributor to the formation of particulate
matter and acid rain. Ever since the 1990 amendments to the clean air act that revamped air
quality management in the United States, there has been a constant effort to research and
determine not only economical but more effective technologies for the control of the criteria
pollutants, especially SO2 . With an emphasis to build new power generation facilities, a majority
of which would use coal, this has become all the more pertinent.
FGD systems can be classified into wet limestone processes, semi-dry processes that include
spray dry lime/limestone injection and dry processes that use sodium or calcium based sorbents.
In the last few decades, dry flue gas desulfurization using sodium sorbents like sodium
carbonate, sodium bicarbonate and trona has been identified to be a highly efficient process. Dry
injection is advantageous because of the simplicity of the process and ease of retrofit with power
plants already equipped with bag house filters. At the same time, it also solves disposal problems
that are normally associated with wet FGD systems.
There has been a lot of research done on the removal of SO2 using sodium bicarbonate
(NaHCO3 ). Studies have shown that more than 90 % SO2 removal can be achieved with sodium
bicarbonate even at low stoichiometric ratios. On the contrary, very little work has been done to
study SO2 removal using trona. Trona is naturally occurring sodium sesquicarbonate with a
chemical compositon as shown.
Chemical Formula: (Na2 CO3 NaHCO 3 2H2O)
Composition: Molecular Weight = 226.03 gm
Sodium (Na) : 30.51 %
Hydrogen (H) : 2.23 %
Carbon (C)
: 10.63 %
Oxygen (O) : 56.63%
The largest pure deposit of trona in the United States lies underground near Green River,
Wyoming. T-200, which is a natural form of sodium sesquicarbonate, costs less than sodium
bicarbonate and has been found to have removal rates of upto 90% for SO2 [1]. It is currently
being used in a variety of industries including utilities, municipal waste, chemical and cement
plants. Selective research done on trona- SO2 reaction has shown that SO2 removal efficiencies
at slightly higher stoichiometric ratios for sodium bicarbonate and trona are very similar.
This is a potentially innovative and cost-effective method for desulfurization of flue gas.
The problem is the lack of consistent data on the kinetics of the trona- SO2 reaction. Without this
kind of data it would be very difficult to arrive at a model for this reaction and to compare it with
the sodium bicarbonate SO2 reaction.
1.2 SO2 Background information

Sulfur dioxide or SO2 , belongs to the family of sulfur oxide gases (SOx). All raw
materials, including crude oil, coal, and ore that contain common metals like aluminum, copper,
zinc, lead, and iron have sulfur in them. SO2 is formed as a result of combustion of fuel
containing sulfur, such as coal and oil, during distillation of crude oil, or metal during
2
extraction. SO2 dissolves in water vapor to form acid, and interacts with other gases and
particles in the air to form particulate matter that can result in serious health and environmental
problems [2].
Electric utilities, especially the ones using coal for combustion, are the primary sources
of SO2 releasing as much as 13 million tons every year, which is about 65 % of the total SO2
released into the air. Other sources of SO2 include industrial facilities that derive their products
from raw materials like metallic ore, coal, and crude oil, or that burn coal or oil to produce
process heat [3]. Petroleum refineries, cement manufacturing, and metal processing facilities,
locomotives, large ships, and other diesel equipment are known to burn high sulfur fuel and
release SO2 emissions to the air in large quantities.
SO2 has been associated with a wide variety of health and environmental effects because
of the manner in which it reacts with other gases and particles in the atmosphere. Effects range
from temporary breathing difficulties to severe heart and lung problems. SO2 contributes to the
formation of particulate matter, which in turn result in increased respiratory symptoms and also
reduce visibility. It also causes damage to crops and forests and aesthetic damage by formation
of acid rain.
The methodologies for SO2 control can be classified into pre-combustion and postcombustion control. Pre-combustion techniques would deal with either fuel switching or coal
pre-cleaning. Fuel switching is switching to a fuel with low sulfur content, from coal or oil to
natural gas or renewables like wind or solar. For power plants, this would correspond to using
low sulfur coal for the boilers. However the economics of availability and transportation of low
sulfur coal have to be considered. More recently, utilities have started focusing on coal cleaning
to remove sulfur to reduce acid-rain-related emissions. Coal-cleaning methods may be classified
into conventional physical cleaning and various advanced cleaning methods, including advanced
physical cleaning, aqueous phase pretreatment, selective agglomeration, and organic phase
3
pretreatment [4]. The total sulfur removal ranges 10 to 40 percent depending upon the method
used. However in order to make coal cleaning cost effective, the cost and energy requirements
involved have to properly balanced.
The post-combustion control would mainly deal with Flue Gas Desulfurization
technologies (FGD) [4]. FGD systems can be mainly classified into six broad categories.
1.
Wet Scrubbers
Wet scrubbers are the most widely used FGD technology for SO2 control
throughout the world. Calcium, sodium and ammonium-based sorbents are used in a
slurry mixture, which is injected into a specially designed vessel to react with the SO2 in
the flue gas. The reactions taking place in a wet scrubber are normally simple but the
resulting corrosion, congestion and waste disposal make them hard to handle in practical
situations. The preferred sorbent in the operation of wet scrubbers is limestone followed
by lime. These are favored because of their availability and relatively low cost. The
overall chemical reaction, which occurs with a limestone or lime sorbent, can be
expressed in a simple form as:
SO2 + CaCO3
CaSO3 + CO2
Ca(OH)2 + SO2
CaSO4 + H2 O
In Ammonia scrubbing the major reactions are :

NH3 + H2 O
NH4 OH
NH4 OH + SO2
NH4 HSO3
NH4 HSO3 + 1/2O2
(NH4 )2 SO2 + SO3 + H2 O
In this case ammonia bisulfite, which is a byproduct, presents disposal problems because
of its acidity and corrosiveness.
2. Spray dry scrubbers

Spray dry scrubbers are the second most widely used FGD technology. However,
their application is limited to small or medium sized coal- fired power plants. Spray dry
scrubbers in commercial use have achieved removal efficiency in excess of 90% with
some suppliers showing more than 95% SO2 removal efficiency as achievable.
Spray dry scrubbers require the use of an efficient particulate control device such
as an ESP or fabric filter. The sorbent usually used is lime or calcium oxide and is
atomized/sprayed into a reactor vessel in a cloud of fine droplets. The SO2 reacts with the
hydrated lime to form a dry mixture of calcium sulfate / sulfite. Wastewater treatment is
not required in spray dry scrubbers because the water is completely evaporated in the
spray dry absorber.
3. Sorbent Injection
Dry sorbent injection involves direct injection of the sorbent into the upper part of
the furnace or the flue gas stream to react with the SO2 forming sulfates of calcium or
sodium which are later captured in a fabric filter. Sodium based compounds or
commercially available limestone (CaCO3 ) or hydrated lime (Ca(OH)2 ) are used as
sorbents. It is important to have an even distribution of the sorbent in the flue gas for
higher removal efficiencies. Also, fine sorbent particle size (<5 m) has been found to
significantly improve the process performance. Typical reactions taking place in a
sodium bicarbonate based dry sorbent injection system are:
2 NaHCO3
Na2 CO3 + CO2 + H2O
2 NaHCO3 + SO 2
Na2 SO3 + 2CO2 + H2O
Na2 CO3 + SO2
Na2 SO3 + CO2
Na2 SO3 + O 2
Na2 SO4
5
4. Dry Scrubber
In this technology, a dry sorbent, mostly hydrated lime is injected into a circulated
fluid bed or a moving bed to react with the SO2 in the flue gas. The process achieves SO2
removal efficiency of 93-97% at a Ca/S molar ratio of 1.2-1.5.
5. Regenerable processes
In regenerable processes, the sorbent is regenerated chemically or thermally and
re-used. Regenerable processes generally require no waste disposal, produce little waste
water and have low sorbent make-up requirements. Although these processes can achieve
high SO2 removal efficiencies (>95%), they have in general high capital costs and power
consumption.
6. Combined SO2 /NOx removal
Combined SO2 /NOx removal processes are considered fairly complex and costly.
However, emerging technologies have the potential to reduce SO2 and NOx emissions for
less than the combined cost of conventional FGD for SO2 control and selective catalytic
reduction (SCR) for NOx control. Most processes are in the development stage, although
some processes are commercially used on low to medium- sulphur coal- fired plants.
1.3 Advantages of dry sodium-based sorbent injection

Some of the advantages associated with the use of dry sodium-based sorbents for flue gas
desulfurization are [5]:
Significantly lower capital costs because of the removal of SO2 and particulate matter in a
single device.
Lesser maintenance due to the simplicity of the process and ease of retrofit for utilities
already equipped with particulate control devices.
In most cases the byproduct is dry. Hence, ease of disposal and minimal scaling and
corrosion.
Lower operating and maintenance costs because of high conversion of the sorbents resulting
in a high-value byproduct.
Reasonably high NOx removal can be achieved simultaneously by the reaction of NO with
sodium bicarbonate to form solid products.
Unlike calcium based sorbents, sodium sorbents exhibit high removal efficiencies over a
wide range of temperatures (250 F- 900 F).
These advantages make sodium injection for FGD very attractive and the utility industry is
paying an increased attention to this technology. There are several small scale and a few fullscale commercial applications in practice. Among the various sodium-based sorbents, sodium
bicarbonate has been associated with the highest SO2 removal. Although the cost of sodium
bicarbonate is much higher when compared to lime/limestone, higher utilization still makes it
attractive. The only concern is the brown plume resulting from the formation of NO2, which can
be taken care of by addition of certain chemical additives. Fig. 1. shows a schematic of a typical
sodium based dry sorbent injection system in a coal fired power plant.
Fig. 1. Schematic of a dry sodium injection system in a coal fired power plant [5].
1.4 Project Objectives

The objective of this project was to identify and study the process parameters that
influence the SO2 removal ability of trona. An entrained flow reactor coupled with a fabric filter
simulator was used to study the effect of various variables like temperature, flue gas
concentrations and stoichiometric ratio on this reaction. Additional consideration was given for
future studies on the effect of moisture content, filter air-cloth ratio and trona particle size.
Kinetic data based on these variables could be used to model the reactions taking place between
trona and SO2 in a dry sorbent injection system.
2. LITERATURE REVIEW
2.1 Literature Overview
Studies performed over the last century have confirmed that materials containing sodium
are bound to be much more effective in removing SO2 from flue gas when used as sorbents in dry
injection when compared to materials containing calcium and magnesium. Most of this research
has been performed on sodium bicarbonate, and there is very little published information on the
reactivity of trona with SO2 . This can be attributed to the thought that the behavior of trona is
more or less similar to that of sodium bicarbonate stoichiometrically, because of the similarities
in their chemical composition.
In 1981, EPRI undertook an experimental study to characterize a process designed to
remove SO2 by injecting two dry sodium-based sorbents namely trona and nahcolite, which is
naturally occurring sodium bicarbonate [6]. The reactions took place in pulverized coal- fired
combustor that used a low-sulfur western coal at baghouse temperatures ranging from 200- 300
F, air to cloth ratio between 1 and 4, and inlet SO2 concentration between 350-750 ppm. They
studied the effect of nahcolite net stoichiometric ratio (NSR) on SO2 removal for both continuous
injection and batch feeding. For continuous injection the SO2 removal was 67% at a NSR of 1
and upto 90% when the NSR was increased above 1.5. Batch feeding also produced similar
results but the injection system was much more complex. They also observed that there was a
time lag between the injection of nahcolite and the drop in the outlet SO2 concentration. It was
also found that removal increased with decreasing particle size and was not influenced by
increase in air to cloth ratio. They found the behavior of trona to be different than that of
nahcolite. With trona, the SO2 removal was almost immediate with essentially no time la g until
the outlet SO2 reached a steady state concentration. Trona removed SO2 at an efficiency of 40%
at an NSR of 1 and about 57% at an NSR of 2. On the contrary, nahcolite had almost 90%
removal at an NSR of 2 as shown on Fig. 2.
9
Fig. 2. Comparison of nahcolite and trona (200 mesh, A/C : 2.3) [6].
Unlike nahcolite, the baghouse temperature did have an influence on SO2 removal with
trona. As with nahcolite, the variation in air to cloth ratio did not have any significant influence
on the reaction. It was also found that particle size had a very significant effect on SO2 removal
using trona. Fig. 3. compares SO2 removal efficiencies for three different trona particle sizes.
10
Fig. 3. Effect of trona particle size on SO2 removal (A/C : 2.3) [6].
In 1982, Keener and Davis performed a study to compare the reactivities of trona and
sodium bicarbonate in a differential fixed-bed reactor [7]. The results indicated that trona had
better reactivity than sodium bicarbonate on average. It was concluded that gas temperature and
particle size had a very significant impact on the utilization of the sorbent and the overall SO2
removal, especially for trona.
In 2000, Guldur and Dogu studied the reaction of activated soda, produced by
decomposition of trona, with SO2 [8]. The activated soda was generated by employing two
different procedures - spray drying of trona solution and direct calcinations of trona particles,
forming activated trona. A two-stage behavior was observed for both samples but was more
significant for the activated trona. This two-stage behavior was also found to be more significant
at lower temperatures as shown in Fig. 4. and 5. At low temperatures, adsorption of SO2 followed
by surface reaction becomes more significant than direct conversion of Na2 CO3 to Na2SO3 . This
11
along with textural variations of the solid are the two main reasons for the two-stage behavior.
The authors developed a deactivation model that gave satisfactory results in the prediction of
experimental results for this reaction.
Fig. 4. Variation of conversion with time
(Temperature : 150 C, SO2 concentration : 3500 ppm) [8].
Fig. 5. Variations of conversion of spray dried soda

with time at lower temperatures [8].
In 1985-86, the department of utilities at the City of Colorado Springs, FMC corporation
and EPRI conducted a full-scale demonstration of the injection of dry sodium sorbents, namely
sodium sesquicarbonate and sodium bicarbonate [9]. Sodium sorbents were injected upstream of
one of the fabric filters, side-by-side with an identical fabric filter operating without sorbent
injection. The objective of the study was to run the plant boiler continuously for 55 days with
sodium injection and to determine the SO2 removal and sodium utilization. The results showed
12
that the system averaged almost 74% SO2 removal with 56% sodium utilization over the entire
period of operation as seen in Fig. 6. At the same time, a NOX removal of about 23% was
achieved. The sodium sesquicarbonate injection also resulted in a significant reduction in the flue
gas pressure drop across the fabric filter. It was concluded that the distribution of the sorbent in
the flue gas stream was critical in achieving maximum sorbent utilization.
Fig. 6. SO2 removal with trona (O : Pittsburgh seam coal(1.6 % S, 59 m sorbent) ; :

West Virginia coal(3.1 % S, 32 m sorbent)) [9].
Thermal decomposition kinetics of sodium bicarbonate [16] is what governs the reaction
of SO2 with both trona and sodium bicarbonate. Keener and Khang developed a parallel reaction
path model to explain the reaction between sodium bicarbonate particles and SO2 [10]. They
concluded that the bicarbonate reacts directly with SO2 at temperatures below which thermal
decomposition occurs but at higher temperatures, it decomposes to form sodium carbonate,
which then reacts with SO2 to form the final product. The following chemical reactions could be
used to explain this parallel path reaction behavior in the trona SO2 reaction as well.
13
Na2 SO3
SO2
Kd1
NaHCO3
path1
K1
Na2 CO3
Kd3
SO2
{Na2 CO3 NaHCO3 2H2 O}

(trona)
+ CO 2 +H2O ---
K2
+ CO2 + H2 O
Na2 SO3 + CO 2 +H2O --- path 2

Kd2
Na2 CO3
CO2 + H2O
K3
Na2 SO3
SO2
+ CO2 + H2 O ---
path 3
The sodium carbonate micro-grains formed in this manner have very high specific
surface area and result in high level of conversion. Hence the overall reaction can be described as
a multipath reaction. For the development of the model, it was assumed that as the reaction
progresses, a shrinking boundary of sodium bicarbonate exists, and at this boundary, micrograins of the reaction products, namely sodium sulfite and sodium carbonate are produc ed. The
overall conversion is the summation of the conversions resulting from paths 1 and 2 and the
reaction kinetics of these 2 paths are derived separately. The model is developed based on the
assumption that the bicarbonate is almost non-porous, path 1 is a first order reaction and that a
semi-empirical pore plugging model can be used for path 2 which is a zero order reaction. The
model was found to be in agreement with kinetic data published earlier. The authors concluded
that this model could be used to give a reasonably good prediction of the behavior of sodium
bicarbonate particles during their reaction with SO2 in flue gas.
14
Fig. 7. Results of a pilot plant dry scrubbing demonstration

study using NaHCO3 [10].
Wu, Keener and Khang proposed a mathematical model for simulation of dry sodium
bicarbonate injection for SO2 removal across a fabric filter [10]. They found out that SO2 removal
took place in two stages- within the duct section and across the fabric filter and developed a twostage model on these lines. In the duct section, its was assumed that the particles were in a
monodisperse mode, axial diffusion was negligible when compared to the convective flow for
the flue gas and the solid particles. With a plug flow for both gas and solid and a mass balance
on the SO2 , a mathematical expression was arrived at for the duct section. For the fabric filter
section, a pseudo steady-state assumption is used for the height of the particle buildup on the
filter. By doing a mass balance on the sorbent, the height of the sorbent layer is calculated. A
final mathematical expression is derived by performing a mass balance on the SO2 . It was found
that SO2 removal predominantly occurs across the filter (95%) and only a small fraction (5%) is
15
removed in the duct section. The model has also been used to discuss the effects of operating
parameters like temperature, stoichiometric ratio, particle size and SO2 concentrations on
removal efficiency and these results were validated with published test data.
Experiments performed by Solvay Minerals at their Central Study and Research Center
[11] have shown that at temperatures over 250 F, trona is rapidly calcined to sodium carbonate
by means of the following reaction, resulting in a popcorn like crystal structure change that
creates a large and reactive surface for adsorption and neutralization of acidic gases like SO2 .
4{Na2 CO3 NaHCO3 2H2 O} 6 Na2 CO3 + 2 CO2 + 10 H2 O
This increase in surface area has been found to be as high as 20 times the original surface
area. At higher stoichiometries around 1.8-2, the behavior of trona and nahcolite is almost
similar as shown in Fig. 9.
Fig. 8. Comparison of SO2 removal using trona and sodium bicarbonate [11]
The effect of trona particle size on SO2 removal is shown in Fig. 10. with almost 90%
removal at a particle size of around 11 microns.
16
Fig. 9. Effect of stoichiometric ratio on SO2 removal [1]
The following figure shows how the economics of the various dry sorbents compare. Trona is
found to be significantly cheaper when compared to sodium bicarbonate.
Fig. 10. Comparison of sorbent costs [1]
17
3 EXPERIMENTAL SETUP
3.1 Entrained Flow Reactor
A drop tube reactor system (Fig. 13 and 14) was developed for the purpose of studying
the reaction between SO2 and trona. The actual test concentrations of SO2 , CO2 , NO2 , NO and
H2 O to be used for the baseline tests were first determined. These concentrations were based on
the combustion data for Colorado seam B coal. A known concentration of these gases was
injected by means of individual cylinders into a manifold where these constituent gases mixed to
simulate the flue/reactant gas. There are two streams of gases to the reactor system, the stream on
the right-hand-side is the flow of carrier gas whereas the other contains reactant gases. Sorbent
particles are fed into the carrier gas by means of a sorbent feeder system. The reactant gases
traveled a 10.5 feet long duct, 0.5 inches diameter before entering the reaction chamber. The
carrier gas duct was 6 feet long. All the ductwork was heated to simulate actual flue gas
conditions by means of band heaters, the temperatures on which could be easily adjusted. Steam
was fed at a known rate by injecting water by means of a calibrated syringe pump and by heating
the feed line with a furnace heater, the rate of heating on which could be manually controlled.
18
Fig 11. Drop tube reactor schematic
Fig. 12. Drop Tube Reactor
19
Fig. 13. Fabric Filter Simulator
The reactant gas and the sorbent particles come into contact inside the venturi where by
virtue of turbulence, they are well mixed with the gases before entering the reaction chamber.
The entrained flow reaction chamber is a stainless steel tube 3 ft in height and 2 inches in
diameter. A constant temperature can be maintained in this reaction chamber by means of a
Lindberg 3 zone-heating furnace by manually adjusting the three individual heating zones. This
first stage reaction chamber is used to simulate sorbent injection where the sorbent particles are
in a dispersed mode. Immediately below the entrained chamber is the fabric filter simulator that
is a cylindrical metallic container 1 ft high and 1 ft wide as sho wn in Fig. 15. A filter made of
NOMEX fiber, 9 diameter was used for collecting the reaction byproducts. The fabric filter
20
simulator also consists of thermocouples, static pressure taps, flanges for disassembly and clamp
heaters for maintaining the test temperatures.
3.2 Sorbent Feeder
The sorbent feeding system as shown in Fig. 15., runs on a variable speed DC motor, a
turning plate with three grooves, a hopper for loading the sorbent particles and an aspirator for
delivering the particles into the reactor. The turntable feeder had three grooves of different sizes
and had provisions for changing the speed of rotation. By setting the rotational speed and by
selecting the appropriate groove, a wide range of sorbent feeding rates could be maintained over
a long period of time
Fig. 14. Sorbent Feeder System
21
3.3 Operating Conditions

Once the desired temperature is reached inside the fabric filter simulator, known
concentrations of the reactant and carrier gases (Table 1.) are injected through calibrated
flowmeters. Sorbent injection takes place only after a steady state SO2 concentration is achieved.
Most of the SO2 in the reactant gas is converted to solid sodium sulfate, which is retained on the
filter. As a result, the flue gas coming out of the fabric filter simulator has a significantly lower
SO2 concentration. Table. 2. lists all the equipment utilized in this study. A gas conditioning unit
was used downstream of the fabric filter to remove any moisture from the gas before the gas
sample reaches the analyzers. A single component infrared gas analyzer was used to measure the
SO2 concentration coming out of the reactor. The analyzer was calibrated with appropriate span
and zero gas before each experiment. A portable Nova gas analyzer was used to measure the
percentage of CO2 and O2 in the outlet gas stream. All gas and temperature data was stored on a
computer through the data acquisition system. The data was then transferred to an excel
spreadsheet for plotting and comparison of results.
Table 1. Flue gas composition
Percentage
Flow rate(scfh)
N2
62.71
38.41
CO2
17.16
10.513
SO2
0.05
0.031
O2
16.82
10.304
H2 O
3.26
1.994
22
3.4 Experimental Procedure

A basic stepwise experimental procedure to run a test is shown below:
1. The data acquisition sys tem is turned on in order to view the inlet gas concentrations and
system temperatures at different points.
2. The reactor system is preheated to the required temperature by turning on the Lindberg 3zone heating furnace and by adjusting the settings on the controller.
3. The flue gas duct is preheated by turning on the two furnace heaters and setting the
controller to the required temperature. The controllers on the band heaters around the
duct are also adjusted to the right temperature.
4. A fresh filter cut out to the right dimensions is placed inside the fabric filter simulator.
5. The fabric filter section is also heated to the right temperature by turning on the
respective controller.
6. The SO2 analyzer is now calibrated by following the procedure shown below.
7. The gas conditioning unit along with the pumps upstream and downstream of the unit are
turned on.
8. The exhaust system is now turned on before injection of any gas takes place.
9. After approximately two hours of preheating, the different gases namely air, CO2 and
nitrogen are injected into the system at already determined flowrates.
10. Steam is injected into the system by turning on the syringe pump and adjusting to arrive
at the right settings.
11. The overall system temperature is adjusted again to account for the temp erature change
because of the gas flow.
12. Pure SO2 is now injected into the system at the predetermined rate.
23
13. The flow rate is adjusted on the flowmeter till the SO2 concentration reaches the required
test concentration.
14. The system temperature and SO2 flowrate are fine tuned to be as close to the required test
conditions as possible.
15. The data acquisition system is brought to the save mode thereby allowing the user to save
all the data till the end of the experimental run.
16. The system conditions are maintained till steady state conditions are reached.
17. The sorbent feeder system is checked for calibration by measuring the turn table
rotational speed. Trona is now injected through the sorbent feeder system by selecting the
appropriate groove and corresponding rotational speed.
18. The dilution effect due to pulling in of atmospheric air is taken into account.
19. The different system parameters like temperature at various points, sorbent feed rate are
monitored during the duration of the test and necessary adjustments made.
20. The pressure drop across the filter is monitored periodically.
21. The experimental run is continued until the outlet SO2 concentration decreases to a
constant value.
22. Once a steady state outlet concentration is achieved, logging of data on the system is
discontinued.
23. The system is now shut down systematically and is allowed to cool.
24. The filter cloth is now removed from the system for analysis.
Calibration of the Gas Analyzer

The SO2 analyzer that works on the non-destructive infra-red principle (NDIR), is calibrated
by following the simple procedure given below:
1. Power the unit on and adjust the knob to the correct range setting.
24
2. Turn on the supply of the zero gas (NO) and adjust the zero knob till the display shows 0
ppm and is steady.
3.
Cut the supply of the zero gas and open the regulator on the span gas.
4. Adjust the span knob till the display shows the right SO2 concentration.
5. Turn off the supply of span gas and turn on the supply of zero gas. Check if it the display
goes back to 0 ppm, otherwise adjust accordingly.
6. Repeat the above steps till the analyzer displays consistent concentration values.
Table 2. List of Equipment.
1.
Instrument
Manufacturer
Model Number
Serial Number
SO2 gas analyzer
California
100
1M12005
Analytical
Instruments
2.
Data Acquisition System
Superlogics Inc.
8017, 8018 input

modules
3.
Gas Dryer
IMR Inc.
IMR 400
H2507483
4.
Three zone heating furnace
Lindberg
55347-4
927585
5.
Reactor temperature
Lindberg
58434
919021
114797
controller
6.
Furnace heaters
Lindberg
70
7.
Turn table motor
Marathon electric
SJ92M68W
manufacturing co.
8.
Syringe pump
Sage instruments
9.
Trolley jack
Central Hydraulics
351
619S
Inc.
10.
Outlet gas pump
Thomas Industries
2107CA18TFEL-A
Inc.
11.
Sorbent feeder vibrator
Vibco Inc.
25
SPR-21
04760
4 RESULTS
Based on the results obtained from carrying out the reaction between SO2 and trona in the
entrained flow reactor, the effects of various operating conditions on SO2 removal are evaluated.
The major parameters in any dry FGD process are temperature, inlet SO2 concentration,
stoichiometric ratio of the sorbent to SO2 and sorbent particle size. For a better understanding of
the comparison of results at different operating conditions, the results have been presented as a
series of charts.
According to Keener et al [15], removal of SO2 takes place in two stages, one within the
duct section and the other in the bag house filter. In the duct section, the residence time of the
particles is very small and generally varies between 1 to 2 seconds. This does not give enough
time for the particles to decompose and hence contribution of the duct section towards SO2
removal is almost negligibly small when compared to the removal in the baghouse. Also within
the duct, smaller particles show higher removal efficiency. It was found that at higher
temperatures, the removal is increased for a short period of time. However, the final removal is a
combined result of both temperature and particle size. It is the baghouse filter where the primary
SO2 removal occurs, where the particles accumulate on the surface of the bag filter and react with
the SO2 in the flue gas in a continuous manner. The SO2 removal is considered to be a very
dynamic process and the reaction between SO2 and sorbent particles at different positions along
the particle layer is considered. However after a certain period of operation, the SO2 removal
reaches a steady state.
4.1 Effect of Particle size on SO2 removal
Previous studies dealing with SO2 removal using dry sorbent injection have demonstrated
that removal of SO2 increases with the decrease in particle size. This can be mainly attributed to
26
the fact that the active surface area for smaller particles is much larger in comparison to bigger
particle sizes under the same stoichiometric conditions. Also the time for smaller particles to
reach steady state is much shorter than for larger particles because the time required for particles
to decompose decreases with size. The diffusion of SO2 into the particles governs this reaction.
According to Keener and Khang [10], the initial sodium bicarbonate is considered to be a nonporous solid particle and pores are formed as a result of removal of CO2 and water vapor from
the solid matrix. This decomposition process not only provides a path for further reactions but
also results in a large amount of freshly formed active area. Hence, another possible reason for
high reactivity is that the diffusion resistance for SO2 is relatively smaller for particles with a
smaller size when compared to larger particle sizes where the pore structure becomes more
complex.
To study the effect of particle size on the trona- SO2 reaction, tests were run on two
different types of trona - one with particles passing through 38 micron sieve and the other being
the T-200 trona. Result s of sieve analysis showed that the mean mass diameter for T-200
particles was around 41 microns as shown in Table 2 and 3.
Table. 3. T-200 particle size distribution
Sieve Opening
Typical weight percent
< 70 m
75
< 28 m
50
< 6 m
10
On the smaller sized trona, tests were run at an inlet SO2 concentration of 500 ppm and a
temperature of 300F and at three different stoichiometric ratios. Fig. 15. shows the conversions
for the finer trona at three different stoichiometric ratios. It can also be observed that the
conversion is higher at higher stoichiometries.
27
From Fig. 16., it can be clearly seen that the conversion for the smaller particle size is
higher when compared to the conversion for T-200 at all three stoichiometric ratios. Figures 17.
and 18. compare conversions between T-200 and finer trona at a lower and a higher
stoichiometry. When compared to T-200, the conversion for the finer particle size trona is
significantly higher.
Table. 4. T-200 : Mean mass diameter of particles

Size range (m)
Weight %
Mean Diameter(m)
Wt % * MD
<6
10
0.3
6~28
40
17
6.8
28~70
25
49
12.25
>70
25
85
21.25
MMD (m)
40.6
28
Fig. 15. Conversion at different stoichiometric ratios

(Temperature = 300 F ; Inlet SO2 concentration = 500 ppm ; Particle Size = <38)
1
conversion
0.8
0.6
0.4
SR
6.2
0.2
2.9
1.5
0
0
1000
2000
time (s)
3000
Fig. 16. Effect of particle size on conversion at different stoichiometric ratios

(Temperature = 300 F ; Inlet SO2 concentration = 500 ppm)
1
Conversion
0.8
0.6
0.4
Particle Size
<38
T-200
0.2
0
0
Stoichiometric Ratio
29
10
Fig. 17. Comparison of conversion at a higher stoichiometric ratio

1
Conversion
0.8
0.6
0.4
Particle Size
<38 micron(SR:6.2)
T-200(SR:5.2)
0.2
0
0
1000
2000
3000
time (s)
4000
Fig. 18. Comparison of conversion at a lower stoichiometric ratio
0.8
Co nversio n
0.6
0.4
Particle size
0.2
<38 micron(SR : 2.9)

T-200(SR : 2.36)
0
0
1000
time (s)
30
2000
3000
4.2 Effect of Temperature on SO2 removal

Temperature has a very crucial effect on the overall desulfurization process. Fig. 19
through 25 show some of the typical results at different temperatures. The plots show the
variation in conversion with temperature within the first 600 seconds of trona injection. Tests
have been conducted at five different temperatures to study the effect of temperature on SO2
removal. The temperatures ranged from 250 F to 350 F. Generally, upto a certain temperature,
the conversion increases with temperature and then drops back and finally increases again.
However this trend is not true for all stoichiometric ratios and inlet gas concentrations as seen
from the plots. It can be seen from the plots that in most cases the conversion drops as the
temperature increases from 250 F to around 275 F and then starts to increase with temperature
upto 300 F. Conversion drops as the temperature reaches around 325 F followed by another
increase in most cases as the temperature reaches 350 F. At lower temperatures, the
desulfurization reaction proceeds during and after the sodium bicarbonate decomposition. Since
the reaction proceeds at a lower rate, there is more time for the reaction to occur and hence
higher removal of SO2 before pore closure occurs. Freshly formed sodium carbonate becomes
available at the right rate for the reaction to proceed. At higher temperatures, the reaction reaches
the final removal rate at a very short period of time due to the quick decomposition and quicker
build up of decomposition byproduct resulting in pore plugging and closure at outside surface of
the particle. As a result, it becomes very difficult for the SO2 to penetrate the unreacted core of
the decomposition product. The primary reason for pore plugging is the molar volume difference
between the initial sodium carbonate (42.25 cm3 /mol) and the final product sodium sulfate
(53.16 cm3 /mol). It can also be observed that the time to reach steady state reduces with increase
in temperature. According to Chungfa wu [5], the time to reach steady state depends on particle
size and system temperature instead of flue gas concentration.
31
It is observed that for this type of a system, which can be considered as a combined sytem
of duct and filter house, there exists a temperature at which the SO2 removal is the highest. This
effect is interestingly different from that of sodium carbonate, which always displays a higher
conversion with increasing temperature. According to Keener and Davis, there exists a
temperature at which the release of CO2 and water vapor from the decomposing particle is just at
the right rate to allow maximum counter-diffusion of SO2 into the inner particle for further
reaction. However studies have shown this optimum temperature to be a function of the particle
size and hence, the particle size has to be taken into consideration before making any
conclusions.
Fig. 19. Conversion at different temperatures

(Inlet SO2 concentration : 500 ppm; stoichiometric ratio : 2-4)
0.6
Conversion
0.4
Temperature
0.2
250 F
275 F
300 F
325 F
350 F
0
0
200
400
Time (s)
32
600
800

0.8
Conversion
0.6
0.4
Temperature
250 F
275 F
0.2
300 F
325 F
350 F
0
0
200
400
Time
600
800

0.8
Conversion
0.6
0.4
Temperature
250 F
0.2
275 F
300 F
325 F
325 F
0
0
200
400
Time (s)
33
600
800

0.5
Conversion
0.4
0.3
0.2
Temperature
250 F
275 F
300 F
0.1
325 F
350 F
0
0
200
400
Time (s)
600
800

0.8
Conversion
0.6
0.4
Temperature
250 F
275 F
0.2
300 F
325 F
350 F
0
0
200
400
Time (s)
34
600
800

0.3
Conversion
0.2
0.1
Temperature
250 F
300 F
325 F
0
0
200
400
Time (s)
600
800

0.6
Conversion
0.4
Temperature
0.2
250 F
275 F
300 F
325 F
350 F
0
0
200
400
Time (s)
35
600
800
4.3 Effect of Inlet Gas SO2 Concentration on overall SO2 removal

Apart from the temperature, SR and particle size, inlet SO2 Concentration also has an
influence on the overall SO2 removal. From the results, it can be seen that increase in the inlet
SO2 concentration enhances the reaction and hence increases the overall SO2 removal. Tests run
at three inlet SO2 Concentrations namely 500 ppm, 1000 ppm and 1500 ppm have shown that the
conversion is highest for 1500 ppm at the same temperature and SR. Figures 26. through 28.
show the effect of inlet SO2 concentration on conversion at different temperatures. Studies have
shown that the effect of inlet SO2 concentration is more pronounced for trona / sodium
sesquicarbonate than for sodium bicarbonate. According to Chungfa Wu [5], the concentration
has a direct effect on the pore plugging time constant which inturn has a critical effect on
conversion. Hence, inlet SO2 Concentration has an indirect effect on the overall desulfurization
process.
Fig. 26. Effect of S02 inlet concentration on conversion (T : 250F, SR : 2-4)

0.8
Conversion
0.6
0.4
Inlet SO2 concentration

500 ppm
0.2
1000 ppm
1500 ppm
0
0
1000
2000
Time (s)
36
3000
4000

0.6
Conversion
0.4
Inl et SO2 concentration
0.2
500 ppm
1000 ppm
1500 ppm
0
0
1000
2000
Time (s)
3000
4000
Fig 29. compares the sorbent utilization for two different inlet SO2 concentrations. It is
very clear that the sorbent utilization at the higher inlet gas concentration is higher.
0.8
Conversion
0.6
0.4
Inlet SO2 concentration

500 ppm
0.2
1000 ppm
1500 ppm
0
0
1000
2000
Time (s)
37
3000
4000
Fig. 29.Comparison of utilization at two different inlet SO2 concentrations (SR : 2-4)
50
Utilization (%)
40
30
20
Inlet SO2 concentrati on
10
500 ppm
1500 ppm
0
240
260
280
300
Temperature (F)
320
340
360
Figures 30. through 32. show the variation in utilization with temperature and
stoichiometry at three different inlet gas concentrations. It is very difficult to establish a trend for
utilization versus temperature and inlet SO2 concentration as it exhibits a sinusoidal behavior.
However it can be said with certainty that the utilization of trona increases with increase in
stoichiometry.
38
Fig. 30. Utilization versus Temperature (Inlet SO2 concentration : 500 ppm)
30
Utilization (%)
20
10
SR
2-4
4-6
8-10
0
240
260
280
300
Temperature (F)
320
340
360
40
Utilization (%)
30
20
10
SR
2-4
3-6
0
240
260
280
300
Temperature (F)
39
320
340
360
50
Utilization (%)
40
30
20
SR
10
0-2
2-4
0
240
260
280
300
Temperature (F)
320
340
360
4.4 Effect of Stoichiometric Ratio on SO2 removal

Stoichiometric ratio corresponds to the amount of trona injection at a certain inlet SO2
concentration at a given flue gas flow rate. The following plots show the results from tests run at
different stoichiometries for the same inlet SO2 concentration and temperature. It is easy to
conclude that as the stoichiometry increases, SO2 removal also increases, irrespective of the other
factors like temperature, particle size and inlet SO2 concentration. From Figures 33. through 35.,
it can be seen that this trend holds for different temperatures and inlet SO2 concentrations.
Theoretically at a net stoichiometric ratio (NSR) of 1, the removal or conversion should be 100
%. However this is not practically possible because of the reaction efficiency, particle behavior
and other factors.
40
Fig. 33. Effect of stoichiometry on conversion

(Temperature : 275 F; Inlet SO2 concentration : 500 ppm)
1
Conversion
0.8
0.6
0.4
SR
2-4
0.2
4-6
8-10
0
0
2000
Time (s)
4000
6000
Fig. 34. Effect of stoichiometry on conversion

(Temperature : 300 F; Inlet SO2 concentration : 500 ppm)
1
Conversion
0.8
0.6
0.4
SR
2-4
0.2
4-6
8-10
0
0
1000
2000
Time (s)
41
3000
4000
Fig. 35. Effect of stoichiometry on conversion (Temperature : 250 F; Inlet SO2

concentration : 1500 ppm)
0.8
0.6
0.4
0.2
SR
0-2
2-4
0
0
1000
2000
3000
4.5 Model
While selecting a model for the progress of any gas-solid reaction, it is important to
understand that every model comes with its own set of mathematical expressions and it should be
able to closely predict and describe the actual kinetics of the reaction. The two main types of
models used for prediction of gas-solid reactions are unreacted core and the pore plugging model
[12].
4.5.1 Unreacted core Model
According to the unreacted core model, the reaction first occurs at the outer skin of the
particle and the zone of reaction eventually moves into the solid leaving behind completely
converted material and inert solid. The gas first diffuses through the film surrounding the particle
to the surface of the solid which is followed by penetratio n through the blanket of ash to the
surface of the unreacted core.
42
Fig 36. Shrinking core of NaHCO3 and varying exposure times of Na2 CO3 [10]
This is when the actual gas solid reaction takes place followed by diffusion of gaseous
products through the ash back to the exterior surface of the solid and eventually through the gas
film back into the main gas stream. There are three major types of resistances to this reaction and
they have their own set of mathematical expressions.
1. Diffusion through gas film controls
3
t
rc
= 1 = XB
2. Diffusion through ash layer controls
t
r
= 1 c = 1 (1 XB )1/ 3
3. Chemical reaction controls
t
= 1 (1 XB )2 / 3
43
4.5.2 Pore Plugging Model

During any gas-solid reaction, the pore structure of the solid is altered during the reaction
with the gas and formation of solid product. Depending upon the molar volume of the product,
different pore structures result. If the molar volume of the product is less than that of the
reactant, a more open structure is formed. On the contrary, if the molar volume of the product is
greater than that of the reactant, a more dense pore structure is formed. Conversions of CaO to
CaSO4 and of Na2 CO3 to Na2 SO4 result in this kind of a structure.
In the past few years, a variety of pore plugging models have been developed to
demonstrate the various gas solid reactions. Chrostowsli and Georgakis [13] proposed a model
for the reaction of SO2 with CaO. Keener [14] modified this model to arrive at a mathematical
expression for the reaction of sodium bicarbonate with SO2 . The final simplified expression is
t
X
= ln 1
X
p =
X =
P*
CSO2
P*
( sf m )
X : Conversion at any time t

X : Conversion at infinite time
t : time
p : time for complete conversion
P* : Pore plugging constant
CSO2 : gas phase concentration of SO2
m : Molar density of the solid
Sp : Specific surface area of particle, gm/cm3
: particle density, gm/cm3
44
Keener [14] proposed a series of steps that need to be followed in order to arrive at the kinetic
parameters.
1.
Estimate X experimentally from conversion versus time data
2.
Plot versus reaction time to get the slope 1/p
3.
Calculate P* from p = P* / CSO2, where CSO2 is known
4.
Calculate sf from the expression X = (P* /sf )* m
5.
Calculate the kinetic rate term ko from the expression, sf = 1/(Sp ko )
Keener [14] used the pore plugging model to fit data from the reaction of sodium bicarbonate
with SO2 and obtained good results. Since trona behaves very similar to sodium bicarbonate
when reacting with SO2 , the pore plugging model would fit better than the unreacted core model
for trona. During the reaction with trona, SO2 diffuses through the outer layer of the freshly
formed sodium bicarbonate and reacts to from sodium sulfate. Since the molar volume of sodium
sulfate is higher than that of bicarbonate, as the reaction proceeds, more and more product is
formed which eventually plugs up all the pores in the solid thereby inhibiting the reaction.
The following plots (Fig. 37. and 38.) display a good fit with reasonably high r-squared values.
45
Fig. 37. Pore plugging model fit (Inlet SO2 concentration : 500 ppm)
6
-ln(1-(X/X4 ))
R-squared : 0.9682
Temperature : 250 F
SR : 2.36
X : 0.49
0
0
400
800
1200
Time (s)
1600
Fig. 38. Pore plugging model fit with actual data

(Inlet SO2 concentration : 500 ppm)
0.5
Conversion
0.4
0.3
0.2
Model
Actual Data
0.1
0
0
400
800
Time
46
1200
1600
2000
Figures 39. and 40. show the variation of Xwith temperature. It can be observed that in
most cases the value of X first increases, then reaches a maximum and then decreases followed
by another increase. These stepwise sinusoidal behaviors can be seen at all three inlet
concentrations. The first increase that is observed at 275 F can be attributed to the formation of
active sodium carbonate from the decomposition of trona resulting in very high conversion. The
decreasing trend that follows, could be because the rate of production of active bicarbonate is
very high resulting in pore plugging thereby resulting in a drop in the conversion. Increase in
temperature around the 325 350 F range causes the conversion to rise again.
Fig. 39. X versus temperature at different stoichiometric ratios
(Inlet SO2 concentration = 500 ppm)
30
X%
20
10
SR
2-4
4-6
8-10
0
240
260
280
300
Temperature (F)
47
320
340
360
Fig. 40. X versus temperature at different stoichiometric ratios

(Inlet SO2 concentration = 1500 ppm)
0.8
X%
0.6
0.4
0.2
SR
0-2
2-4
0
240
260
280
300
Temperature(F)
48
320
340
360
5. CONCLUSIONS AND FUTURE WORK
Use of trona could serve as a very good cost effective alternative for sodium bicarbonate
in dry sorbent injection for flue gas desulfurization. The cost of trona, which is significantly less
than that of sodium bicarbonate, would offset the enhanced removal efficiency of sodium
bicarbonate. It can also be very easily retrofitted into an already existing flue gas desulfurization
system. At higher stoichiometries, conversion and removal efficiency of trona is almost
comparable to that of sodium bicarbonate. Particle size appeared to be the most important factor
influencing the reaction of trona with sulfur dioxide. Results showed trona to achieve
considerably high conversions at small particle sizes. Temperature also seemed to have a
significant effect on the conversion but it was not as direct as the other parameters. There does
not seem to exist a steady trend for conversion with change in temperature, it exhibits a
sinusoidal pattern. It is a complex functio n of all the other parameters and they have to be taken
into consideration before arriving at any conclusions. Inlet SO2 concentration on the other hand
has a more direct effect. Conversion increases with increase in the inlet gas concentration as it
enhances the reaction. The other important factor considered in the reaction of SO2 with trona is
the stoichiometric ratio. As the stoichiometric ratio increases, there is more and more sorbent in
the system to react with the SO2 and hence higher conversion. Data from the trona-SO2 seem to
fit the pore plugging model more than the unreacted core model. However more data is required
to arrive at numerical values for the kinetic parameters like reaction rate, pore plugging constant,
etc.
For a direct comparison of trona and sodium bicarbonate, it would be ideal to conduct
experiments for both reactions in the same reactor under the same operating conditions. It would
give a very good idea of how they compare and what parameters need to be fine tuned to
49
optimize SO2 removal using trona. To make it commercially feasible it is also important to study
its behaviour as far as removal of other pollutants like mercury is concerned. Studies are also
being performed to test the viability of making a more reactive sorbent from trona by
carbonating the carbonate component to bicarbonate thereby making it similar to sodium
bicarbonate. There has been very little research on the kinetics of the trona SO2 reaction. More
data needs to be collected in order to arrive at the reactio n kinetics. A suitable model can then be
developed and used to predict and explain the reaction between trona and SO2 .
50
6. REFERENCES
1. http://www.solvayminerals.com/
2. Spriggs, L.S.,1999, Examination of the ammonia sulfur dioxide water system using
FTIR spectroscopy. MS thesis, The University of Cincinnati.
3. Wark, K., Warner, C.F. and Davis, W.T., 1998, Air pollution its origin and control.
Addison Wesley Longman, Inc.
4. Cooper, C.D. and Alley, F.C., 1994, Air pollution control a design approach. Waveland
Press, Inc.
5. Wu, C.,1997, A scrubbing model for dry sodium bicarbonate duct injection flue gas
desulfurization. MS thesis, The University of Cincinnati.
6. Murio, L.J. and Arand, J.K.,1981, Bench scale study of the dry removal of SO2 with
nahcolite and trona. EPRI final report, March 1981.
7. Keener, T.C. and Davis, W.T., 1984, Study of the reaction of SO2 with NaHCO3 and
Na2 CO3 . JAPCA 34, 651-654.
8. Guldur, C., Dogu, G. and Dogu, T.,2000, Kinetics of trona sulfur dioxide reaction.
Chemical engineering and processing. 40, 13-18.
9. Albin, D.W., Hammond, J. J., Watts, D. B., Ostop, R. L. and Hooper, R. G., Full scale
demonstration of dry sodium injection flue gas desulfurization at city of Colorado
Springs Ray D. Nixon power plant, Abstract, EPRI.
10. Keener, T.C. and Khang, S.J., 1993, Kinetics of the sodium bicarbonate-sulfur dioxide
reaction. Chemical Engineering Science 48, 2859-2865.
51
11. Ninane, L.,1993, Trona use in dry sodium injection for acid gas removal. Central study
and research center, Solvay S.A.
12. Levenspiel, O.,1972, Chemical Reaction Engineering. Wiley, New York.
13. Chrostowski, J.W. and Georgakis, C.,1978.Pore plugging model for gas-solid reactions.
ACS symposium series 65, 225-237.
14. Keener, T. C.,1982, Thermal decomposition of Sodium Bicarbonate and its effect on the
reaction of Sodium Bicarbonate and Sulfur Dioxide in a simulated flue gas. Ph.D.
dissertation, The University of Tennessee.
15. Keener, T. C. and Biswas, P., A dry scrubbing model for SO2 removal. Chemical
Engineering Commun. 81, 97-108.
16. Keener, T.C., Frazier, G.C. and Davis, W.T., 1985, Thermal decomposition of sodium
bicarbonate. Chemical Engineering Commun. 33, 93-105.
17. Ucar, C.,Guruz, G., C., Dogu, G. Durmaz, A., Ercan, Y. and Dogu, T, 1992, Scrubbing of
SO2 with trona solution in a spray drier. The Canadian journal of chemical engineering.
70, 808-812.
18. http://www.epa.gov
52
APPENDIX 1 EXPERIMENTAL DATA
The following tables show the experimental data that was used to arrive at the conve rsion
plots. Data on the temperature and outlet SO2 concentration is recorded every second by the data
acquisition system.
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200
3600
4000
Temperature : 275 F ; SR : 6.05

SO2 Concentration (ppm) Conversion (X)
472.28
0
219.062
0.537431
194.053
0.590385
142.261
0.700049
157.029
0.668779
153.098
0.677103
134.226
0.717062
134.274
0.71696
123.205
0.740398
123.03
0.740768
109.292
0.769857
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

SO2 Concentration (ppm) Conve rsion (X)
530.88
0
258.054
0.513913
209.998
0.604434
195.241
0.632231
184.042
0.653327
195.877
0.631033
165.122
0.688965
165.132
0.688947
181.904
0.657354
Time (s)
0
500
1000
1500
2000
2500
3000
3500

465.28
0
185.101
0.602173
149.165
0.679408
124.227
0.733006
123.257
0.735091
104.027
0.776421
96.989
0.791547
101.847
0.781106
53
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

1088.38
0
634.844
0.416707
557.448
0.487819
563.957
0.481838
575.206
0.471503
562.35
0.483315
555.866
0.489272
560.163
0.485324
593.449
0.454741
Time (s)
0
500
1000
1500
2000
2500

1013.91
0
683.821
0.32556
622.874
0.385671
550.869
0.456688
573.888
0.433985
600.794
0.407448
Time (s)
0
400
800
1200
1600
2000
2400
2800

474.4
0
170.527
0.640542
156.728
0.669629
133.459
0.718678
124.48
0.737605
161.841
0.658851
160.716
0.661223
124.42
0.737732
Time (s)
0
400
800
1200
1600
2000
2400

1018.6
0
553.228
0.456874
463.136
0.545321
478.213
0.530519
408.37
0.599087
461.041
0.547378
495.34
0.513705
54
Time (s)
0
500
1000
1500
2000
2500

1150.03
0
649.791
0.434979
620.651
0.460318
607.915
0.471392
588.18
0.488552
654.74
0.430676
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

489.67
0
205.015
0.58132
187.497
0.617095
189.046
0.613932
208.87
0.573447
183.041
0.626195
166.062
0.66087
171.725
0.649305
180.915
0.630537
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

494.51
0
138.209
0.720513
115.228
0.766986
107.335
0.782947
102.313
0.793102
105.185
0.787294
94.246
0.809415
102.277
0.793175
106.3
0.78504
Time (s)
0
400
800
1200
1600
2000

502.09
0
160.098
0.681137
97.341
0.806128
111.12
0.778685
96.425
0.807953
93.428
0.813922
55
Time (s)
0
400
800
1200
1600
2000

490.54
0.00
129.125
0.74
103.283
0.79
98.241
0.80
95.312
0.81
91.236
0.81
Time (s)
0
200
400
600
800
1000
1200
1400
1600
1800
2000

506.14
0
163.128
0.677702
115.241
0.772314
100.398
0.80164
97.239
0.807881
93.351
0.815563
92.305
0.81763
98.259
0.805866
96.909
0.808533
96.387
0.809565
94.234
0.813818
Time (s)
0
400
800
1200
1600
2000
2400
2800

499.6
0
148.095
0.703573
133.182
0.733423
122.405
0.754994
108.429
0.782968
105.249
0.789333
101.234
0.79737
100.363
0.799113
Time (s)
0
300
600
900
1200
1500
1800

495.52
0.00
130.359
0.74
87.224
0.82
79.389
0.84
76.255
0.85
76.27
0.85
75.413
0.85
56
Time (s)
0
300
600
900
1200
1500
1800

508.63
0.00
313.122
0.38
288.024
0.43
293.006
0.42
325.173
0.36
323.236
0.36
291.392
0.43
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200
3600
4000
4400

484.5
0.00
194.916
0.60
189.063
0.61
179.025
0.63
186.029
0.62
172.154
0.64
172.148
0.64
160.088
0.67
154.019
0.68
147.166
0.70
140.454
0.71
135.239
0.72
Time (s)
0
400
800
1200
1600
2000
2400
2800

479.7
0
201.05
0.580884
177.184
0.630636
183.104
0.618295
173.983
0.637309
191.159
0.601503
201.08
0.580821
191.097
0.601632
Time (s)
0
200
400
600
800
1000
1200

499.3
0
303.365
0.392419
290.162
0.418862
290.137
0.418912
292.089
0.415003
292.447
0.414286
292.26
0.414661
57
Time (s)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500

500
0
306.165
0.38767
302.37
0.39526
269.108
0.461784
268.313
0.463374
260.161
0.479678
248.791
0.502418
241.776
0.516448
243.7
0.5126
245.86
0.50828
231.923
0.536154
237.809
0.524382
Time (s)
0
500
1000
1500
2000
2500
3000

491.5
0
302.125
0.3853
267.277
0.456201
255.041
0.481097
245.862
0.499772
250.403
0.490533
264.314
0.46223
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

483.92
0
299
0.382129
270
0.442057
264
0.454455
245
0.493718
247
0.489585
238
0.508183
229
0.526781
220
0.545379
Time (s)
0
500
1000
1500
2000

981.44
0
671.5
0.315801
615.5
0.37286
577
0.412088
595.5
0.393239
58
Time (s)
0
400
800
1200
1600
2000
2400

SO2 Concentration (ppm) Convers ion (X)
999.7
0
519.5
0.480344
499
0.50085
401
0.59888
410
0.589877
411
0.588877
425.5
0.574372
Time (s)
0
500
1000
1500
2000
2500
3000
3500

993.34
0
554.5
0.441782
425
0.572151
403
0.594298
425
0.572151
385
0.612419
392
0.605372
374
0.623492
Time (s)
0
400
800
1200
1600
2000
2400

1021.5
0
398
0.604153
355
0.646921
299
0.702618
326
0.675764
313
0.688694
313
0.688694
Time (s)
0
500
1000
1500
2000
2500

987.53
0
379
0.616214
381
0.614189
423
0.571659
438
0.556469
450
0.544318
59
Time (s)
0
200
400
600
800
1000
1200
1400
1600
1800
2000

1000.64
0
540
0.460345379
448
0.552286537
401
0.599256476
375
0.625239846
332
0.668212344
323
0.677206588
319
0.681204029
307
0.693196354
322
0.678205948
337
0.663215542
Time (s)
0
500
1000
1500
2000
2500

1489.3
0
1205.5
0.190559
1152
0.226482
1171.5
0.213389
1153.5
0.225475
1214.5
0.184516
Time (s)
0
500
1000
1500
2000
2500

1471.52
0
1178.5
0.199127
969
0.341497
1027
0.302082
1006
0.316353
1064
0.276938
Time (s)
0
400
800
1200
1600
2000
2400

1500
0
1221.5
0.185667
1087
0.275333
1062.5
0.291667
1061
0.292667
1078
0.281333
1110.5
0.259667
60
Time (s)
0
400
800
1200
1600
2000
2400
2800
3200

1496
0
738.5
0.50635
625.5
0.581885
607.5
0.593917
619.5
0.585896
574.5
0.615976
545.5
0.635361
571.5
0.617981
564.5
0.62266
Time (s)
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200

1508.5
0
904
0.400729
816.5
0.458734
797.5
0.471329
750.5
0.502486
771.5
0.488565
784.5
0.479947
815.5
0.459397
782
0.481604
764.5
0.493205
753.5
0.500497
760.5
0.495857
Time (s)
0
500
1000
1500
2000
2500

1492.35
0
674.5
0.548028
644.5
0.568131
654.5
0.56143
654.5
0.56143
643.5
0.568801
Time (s)
0
400
800
1200
1600
2000
2400
2800

1487.95
0
848.5
0.429752
898
0.396485
776
0.478477
736.5
0.505024
726.5
0.511744
703.5
0.527202
706.5
0.525186
61
Time (s)
0
400
800
1200
1600
2000
2400

1495
0
812.5
0.456522
637.5
0.573579
595.5
0.601672
557.5
0.62709
544.5
0.635786
530.5
0.645151
62
APPENDIX 2 MODEL CALCULATION

The following fig. shows an example of pore plugging model fit. X is the conversion at
time t. The following mathematical expression represents the pore plugging model.
t
X
= ln 1
X
The technique for estimating the value of X is to maximize the correlation coefficient
for various assumed values of X. The initial value of X is assumed to be the final value of X
plus an incremental value. The final X is the one that gave the highest R-squared value for this
plot.
Fig. 38. Pore plugging model fit (Inlet SO2 concentration : 500 ppm)
5
-ln(1-(X/X4))
R-squared = 0.986
Temperature : 250 F
SR : 2-4
X =0.51
0
0
1000
2000
3000
4000
Time (s)
The following table gives the R-squared values for the different assumed values of X.
63
R-squared
-0.0045
0.986
0.8785
0.7553
0.7068
X
.5
.51
.52
.53
.54
From the table it can be clearly seen that the X value that has the highest correlation coefficient
is 0.51.
The following table displays the X values for all tests at different temperatures, inlet SO2
concentrations and stoichiometries.
SO2 conc
SR
range
2-4
500 ppm
4-6
8-10
2-4
1000 ppm
3-6
Temperatute
250
275
300
325
350
250
275
300
325
350
250
275
300
325
350
250
275
300
325
350
250
275
300
325
350
X
0.51
0.53
0.63
0.44
0.53
0.72
0.76
0.67
0.8
0.67
0.84
0.83
0.81
0.8
0.83
0.55
0.45
0.42
0.49
0.48
0.7
0.61
0.72
0.61
0.64
64
SR
2.36
2.26
2.36
2.1
2.53
5.8
6.05
5.24
5.93
5.2
9.33
9.35
8.97
9.39
9.15
2.82
2.73
2.24
2.49
2.48
3.77
3.63
4.07
3.58
3.88
t
714.28
1111.11
555.55
555.55
625
555.55
769.23
588.23
833.33
666.66
370.37
500
555.55
416.66
416.66
476.19
500
588.23
714.28
555.55
384.61
416.66
526.31
476.19
666.66
R-squared
0.9427
0.9329
0.6756
0.7729
0.9436
0.8363
0.9309
0.8396
0.84444
0.8488
0.8232
0.6978
0.8064
0.9411
0.8387
0.8974
0.9256
0.8232
0.635
0.7475
0.9457
0.6672
0.827
0.9097
0.8998
SO2 conc
SR
range
0-2
1500 ppm
2-4
<38
(500 ppm)
6.2
1.5
2.9
Temperatute
250
300
325
250
275
300
325
350
300
300
300
X
0.3
0.23
0.34
0.67
0.53
0.6
0.51
0.65
0.87
0.43
0.71
65
SR
0.75
0.77
0.79
2.06
1.98
2
2.04
2.01
6.21
1.5
2.9
t
526.31
476.19
714.28
555.55
526.31
500
454.54
666.66
333.33
476.19
1000
R-squared
0.4096
0.8993
0.9642
0.9519
0.8758
0.8155
0.8516
0.9169
0.8638
0.5841
0.7632
APPENDIX 3 MODEL CALCULATION
SO2 feed rate

Inlet SO2 concentration = 1000 ppm
Total gas flow rate = 82.52 scfh
1000 *10 6 * 28.3 * 82.52

moles/min
SO2 feed rate =
24.04 * 60
= 1.619 * 10-3 moles/min

Trona feed rate
Turn table revolution speed = 1.27 rev/min
Mass of trona/rev = 1.03 g
1.27 *1. 03
Feed rate =
moles/min
226
= 5.787 * 10-3 moles/min

Stoichiometric Ratio
SR = (moles of trona/ moles of SO2 )
= (5.787 * 10-3 moles/min) / (1.619 * 10-3 moles/min)
= 3.57
Conversion
SO 2 o - SO 2 t
X t =
SO 2 o
Xt : Conversion at time t
SO2o = inlet SO2 concentration
SO2t = SO 2 concentration at time t
66

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UNIVERSITY OF CINCINNATI

Sulfur Dioxide in a Simulated Flue Gas

This work and its defense approved by:

Dr. Tim Keener

Study of Trona ( Sodium Sesquicarbonate) Reactivity with

Committee Chair: Dr. Tim C. Keener

1.1 Problem Statement

1.2 SO2 background information

1.3 Advantages of dry sodium-based sorbent injection

1.4 Project Objectives

2.1 Literature Overview

3.1 Entrained Flow Reactor

3.2 Sorbent Feeder

3.3 Operating Conditions

3.4 Experimental Procedure

4.1 Effect of Particle Size on SO2 Removal

4.2 Effect of Temperature on SO2 Removal

4.3 Effect of Inlet Gas SO2 Concentration on Overall SO2 Removal

4.4 Effect of Stoichiometric Ratio on SO2 Removal

5. CONCLUSIONS AND FUTURE WORK

APPENDIX 1 EXPERIMENTAL DATA

APPENDIX 2 MODEL CALCULATIONS

APPENDIX 3 MODEL CALCULATIONS

Flue gas composition

T-200 particle size distribution

T-200 : Mean mass diameter of particles

Schematic of a dry sodium injection system in a coal fired

Comparison of nahcolite and trona (200 mesh, A/C : 2.3).

Effect of trona particle size on SO2 removal (A/C : 2.3).

Variation of conversion with time (Temperature : 150 C,

Variations of conversion of spray dried soda with time at

SO2 removal with trona (O : Pittsburgh seam coal(1.6 % S,

Results of a pilot plant dry scrubbing demonstration study

Comparison of SO2 removal using trona and sodium bicarbonate.

Effect of stoichiometric ratio on SO2 removal.

Comparison of sorbent costs.

Drop tube reactor schematic.

Drop Tube Reactor.

Fabric Filter Simulator.

Sorbent Feeder System.

Conversion at different stoichiometric ratios (Temperature = 300 F ;

Effect of particle size on conversion at different stoichiometric ratios

Comparison of conversion at a higher stoichiometric ratio.

Comparison of conversion at a lower stoichiometric ratio.

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Conversion at different temperatures (Inlet SO2 concentration :

Effect of S02 inlet concentration on conversion (T : 250F, SR : 2-4).

Effect of S02 inlet concentration on conversion (T : 325F, SR : 2-4).

Effect of S02 inlet concentration on conversion (T : 350F, SR : 2-4).

Comparison of utilization at two different inlet SO2 concentrations

Utilization versus Temperature (Inlet SO2 concentration : 500 ppm).

Utilization versus Temperature (Inlet SO2 concentration : 1000 ppm).

Utilization versus Temperature (Inlet SO2 concentration : 1500 ppm).

Effect of stoichiometry on conversion (Temperature : 275 F;

Effect of stoichiometry on conversion (Temperature : 300 F;

Effect of stoichiometry on conversion (Temperature : 250 F;

Shrinking core of NaHCO3 and varying exposure times of Na2 CO3 .