AN ABSTRACT OF THESIS OF
Diana Djokotoe for the degree of Master of Science in Chemical Engineering
presented on January 8, 2004.
Title: Burning Emulsified Sulfur to Stabilize Sodium Compounds in a Lime Kiln
Abstract approved:
Redacted for privacy
Willie B. Rochefort
Weyerhaeuser's Paper Mill in Albany, Oregon has been experiencing
frequent ring formation in the # 3 rotary lime kiln. Rings form when lime mud
(CaCO3) or product lime (CaO) particles adheres to the walls of the lime kiln and
become resistant to the abrasive action of the sliding motion of product lime
particles ( Notidis,1994). Ring formation has resulted in frequent shut downs to
remove (blast) the rings and caused a significant loss of productivity and revenue to
the company. A careful analysis of the production process in the mill revealed that
concentration of sodium was high and that of sulfur low in the lime mud.
The high sodium was due to the low sulfur input to the kiln resulting in high
sodium to sulfur ratio. The use of natural gas as a fuel source in the kiln partly
causes low sulfur levels in the mud.
This study examines the effects of burning emulsified sulfur in the # 3
rotary lime kiln to reduce sodium enrichment in the solids, and examine its effect
on kiln operation and SO2 emissions from the # 3 rotary lime kiln. A four day trial
of burning emulsified sulfur to reduce sodium concentration in the # 3 rotary lime
kiln was planned. Tote bins of 70% solution of emulsified sulfur was fed into the #
3 rotary lime kiln. The sulfur feed was controlled to ensure an excess of sulfur by
observing the SO2 concentration in the kiln stack and maintaining a concentration
above 100 ppm corrected to 10% oxygen.
The results show that while burning emulsified sulfur had no significant
effect on kiln operation, it resulted in a high reduction of sodium in the dust caught
in the electrostatic precipitator and an increase SO2 emission from the stack. The
reduction of sodium in the dust was 50%, which is an enrichment factor of 2.
Although lime can effectively remove
SO2,
the removal efficiency decreased from
96.0% to 73.0% when emulsified sulfur was burned in the # 3 rotary lime kiln.
The results of this trial are promising, since it demonstrates that burning
emulsified sulfur significantly lowers the sodium enrichment in the kiln. The
reduced levels of sodium can potentially lead to a reduction in ring formation in the
#3 rotary lime kiln in the Albany Paper Mill.
© Copyright by Diana Djokotoe
January 8, 2004
All Rights Reserved
Burning Emulsified Sulfur to Stabilize Sodium Compounds in a Lime Kiln
by
Diana Djokotoe
A THESIS
Submitted to
Oregon State University
in partial fulfillment of
the requirement for the
degree of
Master of Science
Presented January 8, 2004
Commencement June 2004
Master of Science thesis of Diana Djokotoe presented on January 8, 2004.
Redacted for privacy
Major Professor, representing
Engineering
Redacted for privacy
'ci
Head of Department of Chemical Engineering Department
Redacted for privacy
Dean of th Oi'a&'iate School
I understand that my thesis will become part of the permanent collection of Oregon
State University libraries. My signature below authorizes release of my thesis to
any reader upon request.
Redacted for privacy
Djokotoe, Author
ACKNOWLEDGEMENTS
I would like to acknowledge Dr. Skip Rocherfort, my major advisor, for his
interest in, and enthusiastic support for this study. I wish to express my sincere
gratitude to Dr. Honghi Tran for his immense contribution to the success of this
work. I must also thank the staff and people of the Chemical Engineering
Department for the support and encouragement I received during the time I spent in
the department. To all the members of my committee, I would like to express my
highest gratitude for your willingness to help my dream come true.
I will also like to thank Kweku Wilson for encouraging and putting up with
me throughout the challenging times. From the depths of my heart, I thank my
parents and the rest of my family for all the support given me throughout my life.
My effort would not have yielded much without the invaluable support from The
Parnell' s, Ralph and Wilma Hull. I owe my life to you all. I thank God for giving
me the grace to endure all that came my way to this end.
This work would not have taken place but for the help and support of the
entire staff of the Albany Paper Mill, Oregon, especially Jim Pruett, Chuck
Mihalko, Brian Brazil and Eric Hekkala I thank you with all of my heart.
TABLE OF CONTENTS
Page
Chapter 1. Introduction ....................................................................................... 1
1.1 Overview of kraft pulping process ...................................................... 1
1.2 Kraft recovery cycle ........................................................................... 3
1.3 Brief description of recausticizing process .......................................... 4
1.4 Lime kiln ............................................................................................ 5
1.5 Lime kiln ring formation ..................................................................... 7
1.6 Impurities in lime mud ..................................................................... 10
1.6 Role of sodium compounds to ring formation ................................... 12
Chapter 2. Background ..................................................................................... 15
Chapter3. Methodology .................................................................................... 17
Chapter 4. Results and Discussions .................................................................... 23
4.1 Effect of burning sulfur on solid composition ................................... 23
4-1.1 Sodium .............................................................................. 23
4-1.2Sulfur ................................................................................ 24
4-1.3 Phosphorous ...................................................................... 25
4-1.4 Silicon ............................................................................... 26
4-1.5 Aluminum ......................................................................... 27
TABLE OF CONTENTS (Continued)
4-1.6 Magnesium ........................................................................ 28
4-1.7 Carbon dioxide .................................................................. 29
4-1.8 Residual Carbonate ............................................................ 30
4.2. Effect of burning sulfur on gaseous emissions ................................. 31
Chapter 5. Conclusions ...................................................................................... 33
Chapter 6 Recommendations .............................................................................. 34
References ......................................................................................................... 35
Appendix ........................................................................................................... 36
LIST OF FIGURES
Figure
Pge
1.1
B lock diagram of kraft pulping process ........................................ 2
1.2
Kraft chemical recovery cycle ...................................................... 3
1.3
#3 Rotary lime kiln at Albany Paper Mill ...................................... 6
1.4
Ring formation in a lime kiln ........................................................ 7
1.5
Comparison of "major" impurities in lime mud ........................... 11
1.6
Sodium enrichment in a lime kiln ............................................... 13
2.1
Histogram showing kiln shut down due to ring blasting .............. 15
3.1
70% emulsified sulfur tote bin and emulsified sulfur input ......... 17
3.2
Diagram of #3 lime kiln showing sampling location ................... 19
3.3
Mud and solids flow data from 7/26/03 to 8/7/03 at Albany
PaperMill ................................................................................... 20
3.4
Front and backend temperature profile from 7/26/03 to
8/7/03 at Albany Paper Mill ........................................................ 21
3.5
Gas flow and ID fan speed from 7/26/03 to 8/7/03
at Albany Paper Mill................................................................... 21
3.6
Percent excess oxygen data from 7/26/03 to 8/7/03
atAlbany Paper Mill ................................................................... 22
4.1
Chart showing changes in sodium concentration before, during
and after sulfur trial .................................................................... 23
4.2
Chart showing changes in sulfur concentration before, during and
after sulfur trial .......................................................................... 24
LIST OF FIGURES (Continued)
Figure
4.3 Chart showing changes in phosphorous concentration before,
during and after sulfur trial ............................................................. 25
4.4 Chart showing changes in silicon concentration before, during and
after sulfur trial ............................................................................... 26
4.5 Chart showing changes in aluminum concentration before, during
and after sulfur trial ......................................................................... 27
4.6 Chart showing changes in magnesium concentration before, during
and after Sulfur trial ........................................................................ 28
4.7 Chart showing changes in carbon dioxide concentration before,
during and after sulfur trial ............................................................. 29
4.8 Chart showing changes in residual carbonate concentration before
and after sulfur trial ....................................................................... 30
4.9 SO2 emission and emulsified sulfur input before, during and after
trial ................................................................................................. 32
4.10 SO2 emission and mud flow before, during and after trial ............. 32
LIST OF APPENDIX FIGURES
Figure
Pg
A.1.1 Chart showing gas flow vs. kiln shut as blast marker ................. 37
A. 1.2 Chart showing back end or feed temperature vs. kiln
shut as blast marker ..................................................................... 38
A.1.3 Chart showing mud density vs. kiln shut as blast
marker ......................................................................................... 39
A.1.4 Chart showing percent oxygen vs. kiln shut as blast
marker .......................................................................................... 40
A.1.5 Chart showing fan speed vs. kiln shut as blast
marker .......................................................................................... 41
A. 1.6 Chart showing front end temperature vs. kiln shut as
blastMarker ................................................................................ 42
A. 1.7 Chart showing mud flow vs. kiln shut as blast
marker ......................................................................................... 43
A.l.8 Chart showing ambient temperature vs. kiln shut
asBlast Marker ............................................................................ 44
A. 1.9 Chart showing turbidity vs. kiln shut
as Blast Marker ............................................................................ 45
A.1.10 Lime production rate vs. ring blasting ........................................ 46
LIST OF APPENDIX TABLES
Appendix
Page
A.2. 1 Total material balance for solids before and after trial ................... 47
A.2.2 Process information data for solids during sulfur triall ................. 48
A.2.3 Process information data for solids during sulfur trial (cont.) ...... 49
A.2.4 Process information data for solids during sulfur trial (cont.) ....... 50
A.2.5 Process information data for solids during sulfur trial (cont.) ...... 51
A.2.6 ICP analysis data for solids during sulfur trial .............................. 52
A.2.7 ICP analysis data for solids during sulfur trial (cont.) ................... 53
A.2.8 ICP analysis data for solids during sulfur trial (cont.) ................... 54
A.2.9 ICP analysis data for solids during sulfur trial (cont.) ................... 55
Dedicated in memory of Cephas Kwaku Djokotoe and Ralph Hull
My heroes.
Burning Emulsified Sulfur to Stabilize Sodium Compounds in a Lime Kiln
Chapter 1.
Introduction.
1.1.
Overview of kraft pulping process
The kraft process is a pulp producing method in which wood chips are
treated with an aqueous solution of NaOH and Na2SO4 at temperatures above
170°C to remove lignin so that fibers can be separated from one another to
make pulp. The kraft chemical recovery process is shown schematically in
Figure 1.1 and is described below.
A mixture of wood chips and cooking liquor all heated in a large pressure
vessel called a digester; the pulp out of the digester contains fiber and black
liquor. The black liquor removed is sent to chemical recovery where it is
burned to form a molten smelt of sodium sulfide and sodium carbonate (green
liquor). During the combustion process, the organic component of the wood
contained in the black liquor is burned to generate heat and produce carbon
dioxide, which is subsequently absorbed by the alkaline residue to form
sodium carbonate.
The conversion of sodium carbonate to caustic soda is one of the oldest
chemical processes in kraft pulp mill and is carried out in the recausticizing
2
plant. Sodium carbonate in green liquor from the recovery smelt dissolving
tank, is reacted with quick lime, Ca(OH)2 to form sodium hydroxide (white
liquor) and calcium carbonate (lime mud). The white liquor is separated from
the mud and sent to a digester as cooking liquor. The mud is washed and sent
to the lime kiln where it is converted into lime, and recycled.(Boniface, 1992)
WASH WATER
l
11GESTER
I
BROWNSTOCK
WASHERS
HIGH
DENSITY
STORAGE
l
WOOD
CHIPS
PULP
WEAK
BLACK
LIQUOR
STEAM
RECOVERY
BOILER
EVAPORATORS
STRONG
BLACK
LIQUOR
I
STEAM
SMELT
SMELT
DISSOLVING
TANK
MAKEUP
LIME
I
I
I
i
WEAK LIQUOR
WHITE
LIQUOR
GREEN LIQUOR
STICIZI
PLANT
(SLAKER,
CAUSTICIZERS)
I
I
LIME
LIME MUD
FUEL
LIME KILN
Figure 1.1. Block flow diagram of the kraft pulping process.
CAUSTIC
up
3
1. 2
Kraft recovery cycle
The kraft recovery cycle consists of six main stages: pulping, washing,
evaporation, combustion, causticizing and calcining. The main objective of the
kraft recovery process is to minimize, as efficiently as possible, the loss and
subsequent makeup of chemicals used in the preparation of white liquor. The
process is illustrated in Figure 1.2. An in depth look at the calcination of CaCO3 to
produce GaO in the lime kiln will be discussed in section 1.3, as it is the central
point of this thesis work.
Wood
ninJCaO
NaOH
Na2S
CaCO3
(7&a,s
Causticizing
tuoJ
I
Na,S
Combustion
Figure
1.2.
Kraft recovery cycle.
4
1.3.
Brief description of the recausticizing process.
The recausticizing process is important to this thesis because the calcium
oxide (CaO) produced from the lime kiln is the main raw material used in the
recausticizing plant.
The recausticizing process produces white liquor from the digestion process
from the green liquor of the smelting process. This process consumes lime (CaO)
and produces lime mud, principally CaCO3, as a by-product. The lime mud is
washed to reduce its chemical content before it is fed into the lime kiln. The weak
wash, (filtrate) generated from washing off all the white liquor from the lime mud
is recycled to dissolve the smelt generated from the recovery boiler to produce
green liquor. Slaking, causticizing, and calcining form a closed ioop process for
converting the recovered green liquor into white liquor. (Sanchez, 2001) The major
reactions are as follows:
Slaking:
CaO +1120
- Ca(OH)2
Causticizing: Ca (OH)2 +Na2CO3
Calcining:
CaCO3 + heat
-* CaCO 2 NaOH
-* CaO + CO2
(2-1)
(2-2)
(2-3)
Calcining, the conversion of lime mud to lime in the lime kiln can be
performed in either a rotary kiln or a fluidized bed calciner. The rotary kiln is
predominantly used due its thermal efficiency. (Boniface, 1992)
5
1.4.
Lime kiln.
A rotary lime kiln is an important piece of equipment for the recausticing
process in a kraft pulp mill. It is a large steel tube lined with refractory bricks. The
kiln typically has a length of approximately 250 ft, and a diameter of 10 ft, it is
slightly inclined horizontally and slowly rotated on a set of riding rings. It is used
to convert lime mud (CaCO3) to product lime (CaO). Lime mud is introduced at
the uphill end (backend) and slowly, it makes its way to the discharge end aided by
the inclination and rotation of the kiln. Heat is introduced at the downhill side
(front end) of the kiln by a burner. Kilns are typically fueled by either natural gas or
low sulfur fuel oil. Impurities from these sources cause problems (e.g. ring
formation) with kiln operation and white liquor quality.
The gases exiting from the kiln must be treated to remove particulate matter
before they enter the atmosphere. This is done with either an electrostatic
precipitator, or wet scrubber or a combination of both. The precipitator is
particularly effective in reducing particulate, but the sulfur dioxide levels may be
above environmental standards without the use of a follow-up scrubber.
(Boniface,1992) Figure 1.3 is a picture of the #3 rotary lime kiln at the Albany
Paper Mill.
6
Figure 1.3. Picture of #3 Rotary lime kiln at Albany Paper Mill.
Ring formation in lime kilns is a persistent problem in many kraft mills. It
limits kiln production capacity and in severe cases, cause unscheduled shutdowns
for clean-up after less than a month of operation. Ringing may also cause severe
mechanical damage to the kiln, such as warping, and shell cracking associated with
massive mud buildup.(Notidis and Tran, 1993)
7
1.5.
Lime kiln ring formation
The production of reburned lime from lime mud is accomplished in the lime
kiln and can be classified into three stages: drying, heating and calcining. In the
drying stage, water evaporates essentially completely from the mud. The dry mud
then enters the heating stage where it is heated to the calcining teniperature of about
800°C. Calcining is the process of driving
CO2
from the CaCO3 to produce CaO
(reburned lime). During the production of lime, rings sometimes form on the
refractory surface of the kiln, and gradually decrease the cross-sectional area of the
kiln and thereby reducing the passage of lime mud through the kiln. (Tran, 2001)
Figure 1.4 shows the formation of rings in a lime kiln.
Figure 1.4. Ring firmation in a lime kiln.
8
The location of rings is believed to be a function of the specific mechanism
of ring formation. Rings form quickly near the cold-end of the kiln due to high
moisture content in the lime mud, while rings near the hot-end of the kiln, are
believed to form as a result of the flame impinging directly on the refractory
surface. Mid-kiln rings, the most difficult to clean, are very distinct and are
believed to form as a result of recarbonation of CaO particles to CaCO3. (Tran,
Mao and Baharm, 1992)
When a ring of sufficient diameter forms in the rotary lime kiln forms, the
kiln must be shut down and the rings literally "blasted" out. This can keep the
rotary lime kiln off line for about 24-48 hours.
Ring formation occurs when lime mud or product lime adheres to the kiln
wall. The ability of the particle to adhere is a function of particle size and the
amount of liquid phase that covers the particle surface. In general, small wet
particles tend to adhere more rapidly than large dry particles.
The stickiness of lime mud is dictated by the presence of a liquid phase that
is either water at low temperatures or molten material at high temperatures. Lime
mud containing low solids may not be completely dry after passing through the
chain section this situation contributes to mud ring formation.(Tran, 2001)
From the calcination zone onward, the melting of water-soluble sodium and
guarded sodium (bound sodium) compounds in the mud may contribute to
increases in the stickiness of the lime mud and/or product lime particles, and lead to
the formation of mid-kiln and front-end rings. The different zones of in the lime kin
mentioned above can be seen in Figure 1.6 below.
10
1.6.
Impurities in lime mud
Lime mud consists of about 95 wt% CaCO3, and 5 wt% of impurities, while
product lime consists of 82.7 wt% CaO and 17.3 wt% impurities. Ring deposits
composition lies between the lime mud and product lime and contains large
amounts of CaO and occasionally CaSO4. The composition of the rotary lime kiln
ring is a function of the mechanism of formation and it is the topic of this thesis
work.
In these studies the impurities (elements other than Ca) in all lime mud and
ring deposit
samples were quantified, they included: Na (sodium), Mg
(magnesium), S (sulfur), P (phosphorus), Si (silicon), Al (aluminum), K
(potassium), Fe (iron), Cl (chlorine), Mn (manganese, Sr (strontium), Ba (barium),
Cr (chromium), Ti (titanium), Y (yttrium), Zr (zirconium), Nb (niobium), and Rb
(rubidium). The elements of highest concentrations (>0.1 wt %) were found to be:
Na, Mg, S, Al, P, Si, Fe, and K.
Figure 1.5 shows the comparison between the concentrations of oxides of
the major impurities in the lime mud and ring deposits, expressed as percent of
CaO in the individual samples. In the lime mud, Na20, MgO, SO3 and P205, had
the highest concentrations (>0.8 wt %), followed by Si02, Al203, Fe203 and K20.
For ring deposits similar results were obtained, except that the Na20 content was
much lower and the SO3 content was much higher than in the lime mud. This can
11
be due to vaporization of Na compounds and the suiphation of CaO after ring
formation. (Tran, 2001)
1.2
1.0
0
CD
0.6
0
0.4
0.2
U
0
o
Figure 1.5. Comparison of "major" impurities in lime mud.
o
o
12
1.7.
Role of sodium compounds in ring formation.
The sodium enrichment process is illustrated in Figure 1.6. Sodium
compounds inside the kiln are likely to be in the form of Na2CO3. The melting
point of these sodium compounds when mixed is approximately 820°C. The
sodium content in the lime mud is usually less than 1 wt% Sodium may be enriched
in the kiln via a vaporization/condensation mechanism.
Due to the high temperature at the front-end of the kiln, sodium vaporizes
from the product lime, flows with the flue gas, and condenses on the mud particles
at the feed-end, where temperature is low. Sodium may also condense on the cooler
refractory brick surface beneath a thick layer of ring deposits. (Tran 2001)
This suggests that the sodium compounds in the kiln melts, makes the kiln
dust sticky and accelerates the rate and size of ring build-ups. (Notidis, 1994)
It is therefore important to be able to accurately determine and control the
sodium content in the lime.
13
Dust
Chains
Mid Kiln
Burner
Na
Na
Mud
Back
end
Lime
Front
Temperature
end
High
Na2CO3
'
NaO + CO2
Low
High
Na2CO3 + H20
2 NaOH + CO2
Low
Figure 1.6. Sodium enrichment in a lime kiln.
The Weyerhaeuser Albany Paper Mill is one of the few mills that burn
natural gas as fuel source for the kiln. Most Mills burn concentrated non
condensable gases (CNCG), #6 Diesel fuel and coal. Natural gas contains very low
levels of sulfur; as a result, the sodium to sulfur ratio becomes high in the mud. In
cases where there are low levels of sulfur in the lime mud, less thermally stable
sodium compounds in the form of Na2CO3, causing vaporization in the burning
zone. The vapor then recirculates to the feed end of the kiln. Compounds in the
vapor then condense, causing sticky buildups that form rings in specific areas of the
14
kiln. In an attempt to stabilize the sodium content in the kiln, emulsified sulfur is
burned to react with the sodium to form Na2SO4, which is more thermally stable
than Na2CO3 and can be purged from the kiln as a more stable compound. The
objectives of this thesis work, examine the effect of burning emulsified sulfur in the
kiln to stabilize the sodium enrichment in the solids and evaluate the effect of
sulfur addition on kiln chemistry and SO2 emission in the stack gas out of the #3
rotary lime kiln.
15
Chapter 2.
Background.
The burning of emulsified sulfur (sulfur trial) at the Weyerhaeuser Albany
Paper Mill was in response to a recurring problem of ring formation in the #3
Rotary lime kiln. The ring formation had resulted in periods of shut down to
remove (blast) the rings. Figure 2.1 shows the number of times kiln was shut down
to blast ring within a 15 month period.
Kiln Shut due to Ring Blast.
33
0
z
0
F (<1°''
s'
I
cF'
I F
Figure 2.1. Histogram showing kiln shut down due to Ring Blasting.
16
Typically ring formation in lime kilns is associated with high levels of
sodium in the lime mud due to poor mud washing. The problem of ring formation
at the Albany Paper Mill is different because of low sodium levels. The sodium
level in the lime mud is on the average less than 0.3 wt% water soluble sodium and
0.8 wt% total sodium, and is originally derived from NaOH, Na2CO3, Na2S and
Na2SO4, in the residual white liquor in the mud.
While the total sodium levels are not high it has been determined that the
sulfur levels are equally very low, resulting in a much higher sodium to sulfur ratio.
This may be contributing to ring formation because there is not enough sulfur
available to tie up the sodium as sodium sulfate (Na2SO4) which is a more
thermally stable compound.
17
Chapter 3.
Methodology.
A 4-day trial of emulsified sulfur addition was planned for July 29 through
August 1, 2003. Tote bins of 70% solution of emulsified sulfur were purchased
and a feed system consisting of a positive displacement pump, a filter to remove
any crystallized sulfur, and an atomizing spray nozzle (with pressurized air
atomization) was constructed for the trial.
The diesel burner was temporarily
removed from the kiln and the sulfur nozzle was installed in its place. Figure 3.1
shows a tote bin containing 70% solution of emulsified sulfur and the point at
which it was fed to the kiln.
Figure 3.1. 70% emulsified sulfur tote bin and emulsified sulfur input.
18
Sulfur feed was started on the morning of July 29 at rates from 44 to 50
quarts per hour or approximately 100 to 120 pounds of sulfur per hour. The sulfur
feed was controlled to assure an excess of sulfur by observing the SO2
concentration in the # 3 rotary lime kiln stack and maintaining a concentration
above 100 ppm corrected to 10% oxygen.
Several sets samples of the following; lime mud feed, pre-coat filter filtrate,
reburned lime, and precipitator dust were collected prior to the trial (4/7/03 through
7/29/03) and once following the trial (8/4/03). Samples were taken every 3 hours
during the emulsified sulfur trial.
Lime samples were also collected from 3
different locations: after the chain section, north sample port and south sample
ports across the length of the kiln for analysis three times prior to the trial (5/30/03,
7/2/03, 7/24/03), twice during the trial (7/31/03, 8/1/03), and once after the trial
(8/4/03). The trial was completed on the morning of August 1, 2003. Locations of
sample collection are shown in the Figure 3.2 below.
19
Dust
Figure 3.2. Picture of #3 Rotary lime kiln showing sampling locations
High production rates were planned for the trial period but could not be
maintained throughout the entire trial period. Production rates averaged from 100
to 165 TPD (tons per day) over the course of the 3-day trial, with 7/29/03 averaging
100 TPD, 7/30/03 averaging 150 TPD, and 8/31/03 at 165 TPD.
An ICP (inductively coupled plasma) optical emission was used to analyze
the samples. The basic technique involves the measurement of atomic emission by
optical spectroscopy. Samples in solution or fine particles suspended in solution
are nebulized and the resulting aerosol is transported to the plasma where element-
specific emission spectra is produced. A grating spectrometer then disperses the
resulting spectra. The spectral energy is measured at selected wavelengths and
20
compared with standards. The moisture content in the sample was accounted for
by drying the sample at 1050 for 24 hours before samples were analyzed.
The mud flow rate before and during the sulfur trial, ranged between 120 -
180 GMP (gallons per minute) as shown in Figure 3.3. The front and feed end
temperatures were very consistent throughout the period of this study, the front end
temperature was observed at about 2000°F while the feed end temperature was
about 550°F. This is shown in Figure 3.4.
II
1:iii
160
-hAOw
140
- &u Flow
120
.2 100
8O
6O
4o
20
0 L.....
7/26/03
7/28/03
7/30/03
8/1/03
8/3/03
8/5/03
8i7/03
Date
Figure 3.3. Mud and solid flow data from 7/26/03 to 8/7/03 at Albany Paper Mill.
21
2500
2000
1500
1000
I-
500
nv
7/26/03
Figure 3.4.
7/28/03
7/30/03
1/)3
8/5/03
8/3/03
8/7/03
Front and backend temperature profile from 7/26/03 to 8/7/03 at
Albany Paper Mill.
The flue gas flow and induced draft (ID) fan speed ranged between 20-40
and 20-60 thousand standard cubic feet hour (KSCFH) respectively.
70
-G Fb*
10
n
7/26
7/28
7/30
.B/1
uate
8/3
8/5
8/7
Figure 3.5. Gas flow and ID fan speed data from 7/26/03 to 8/7/03 at Albany Paper
Mill.
22
Excess oxygen was maintained below 10% during the duration of the study.
Figure 3-6 illustrates the excess oxygen levels during the trial.
12
10
2
0'
7/27/0 7/28/0 7/29/0 7/30/0 7/31/0 8/1/03 8/2/03 8/3/03 8/4/03 8/5/03 8/6/03
3
3
3
3
3
Date
Figure 3.6. Percent excess oxygen data from 7/26/03 to 8/7/03 at Albany Paper
Mill.
23
Chapter 4.
Results and Discussion.
4-1
Effect of burning sulfur on solid composition.
4-1.1 Sodium
The results show a decrease in the sodium concentration of the mud fed to
the kiln during the trial, compared to the baseline samples. There was a significant
reduction of sodium in the dust samples compared to the rest of the mud samples.
This result is illustrated in Figure 4.1.
Sodium
4.0
3.5
Mud
3.0
Dust
2.5
o Chain
2.0
o North
South
Lim
0.5
0.0
Before
During
After
Sulfur Trial
Figure 4.1. Changes in sodium concentration before, during and after sulfur trial.
24
4-1.2 Sulfur
As expected, the sulfur concentration
in
the product lime and the
precipitator dust was higher during the trial than it was in the samples collected
during the baseline sampling. It was also significantly higher than the sulfur content
in the mud fed to the kiln. Figure 4.2 shows the sulfur concentration before and
after the sulfur trial. Sulfur enrichment factor ranged from 7-12, the high sulfur
enrichment was caused by the sulphation of NaOH or Na2CO3. There was an
increase in the sulfur content in the solids as it moved through the kiln. Estimated
kiln stack SO2 emissions averaged 13 pounds per hour with SO2 for sulfur loss
averaging less than 7 pounds per hour. The remaining sulfur was bound to the
sodium and calcium of the lime produced during the trial.
Sulfur
1.2
1.0
0.8
0.6
IiiiiiiiiiiiiiiiiiIiiI.I [ZIZIZIZIiiiZIIJ
0.4
Mud
Dust
o Chain
o North
South
Lime
0.2
0.0
Before
During
After
Sulfur Trial
Figure 4.2. Changes in concentration of sulfur before, during and after sulfur trial.
25
The addition of sulfur did not have any effect on phosphorus, silicon, aluminum or
magnesium. As shown in the Figures 4.3, 4.4, 4.5 and 4.6 respectively.
4-1.3 Phosphorus
Phosphorus
5.0
IVk.id
Dust
o chain
a North
South
2.0
Lirre
1.0
Before
During
After
Sulfur Trial
Figure 4.3. Changes in concentration of phosphorus before, during and after sulfur
trial.
I
4-1.4 Silicon
Silicon
[1111
0
Mid
Dust
o Chain
D North
South
0.20
Lime
0.10
[111111
Before
During
After
Sulfur Trial
Figure 4.4. Changes in concentration of silicon before, during and after sulfur trial.
27
4-1.5 Aluminum
Aluminum
0.50
od
Co
0.40
0 Dust
0
0
o Chain
x
o North
0
0
South
Co
oLJ
0
0.10
Before
During
After
Sulfur Trial
Figure 4.5. Changes in concentration of aluminum before, during and after sulfur
trial.
4-1.6 Magnesium
Magnesium
2.5
0
[1ud
(
0 Dust
o Chain
o North
South
o Line
O.5
Before
During
After
Sulfur Trial
Figure 4.6. Changes in concentration of magnesium before, during and after sulfur
trial.
29
4-1.7 Carbon dioxide
The results obtained show there is no calcination occurring beyond the
south sample port. It appears that lime mud, chain section, north, and south samples
contain significant amounts of carbon dioxide in the kiln, this is an indication that
calcinations has not yet taken place. It also confirms that the two stages; drying
and heating, take place between the mud samples and the south samples at the
Albany Paper Mill. Figure 4.7 shows the concentration of carbon dioxide before
and after the sulfur trial.
Co2
80
60
R Mud
EXist
o chain
.4o
0 North
South
Lirre
20
0
Before
During
After
Sulfur Trial
Figure 4.7. Changes in concentration of carbon dioxide before, during and after
trial.
30
4-1.8 Residual Carbonate
Residual carbonate is a measure of the calcium carbonate in reburned lime,
it is used as a measure of the conversion efficiency of the calcium carbonate in lime
mud to calcium oxide in reburned lime. As shown in Figure 4.8, mud samples
analyzed from the chain section, north port, dust and south port all had residual
carbonate levels of more than 70%. This is an indication that recarbonation did not
occur until the south port.
Residual Carbonate
100
Md
I-
80
60
0 Chain
40
o North
20
South
C-)
C)
C5
Lime
U)
0
Before
During
After
Sulfur Trial
Figure 4.8. Changes in concentration of residual carbonate before, during and after
trial
31
4-2 Effect of burning sulfur on SO2 emission
Burning emulsified sulfur resulted in high SO2 emissions from the kiln
stack but this was within Department of Environmental Quality (DEQ) standard.
SO2 generated from adding emulsified sulfur to the #3 rotary lime kiln picked up
sodium inside the kiln and resulted in low levels of SO2 emission during the first 36
hours of the trial. Lime production rate and sodium concentration increased after 38
hours of the trial, when the shower water used in washing the mud was reduced.
This resulted in high levels of SO2 emission in the stack gas. This observation
indicates that lime mud had a shorter residence time in the kiln as the production
rate increased, as a result, suiphation reaction between CaO/ CaCO3 and SO2 could
not take place. This is shown in Figure 4.9. The rate of mud and SO2 input are
shown in Figure 4.10.
32
14
500
a
a.
a
400
j
300
a.
......
12
10#
- S02
8c1)
Emulsified_Sj
"
200
4-
100
2
0
7/29
7/30
7/31
8/1
Date
Figure 4.9. SO2 emission and emulsified sulfur input before, during and after trial.
500
500
-S02
400
400
-Mud Flow
300
300
200
Cl)
4fI -o
100
lULl
ti
0L
7/29
Cl)
7/30
7/31
Date
Figure 4.10. SO2 emission and mud flow before, during and after trial.
33
Chapter 5.
Conclusion.
This study has shown a valuable phenomeno logical review of the possibility
of reducing sodium concentration in the kiln by burning emulsified sulfur in the #
3 rotary lime kiln, as shown in the sulfur trial results.
The trial demonstrated a significant reduction of the sodium levels in the
precipitation dust samples. The reduction of sodium in the dust was 50% which is
an enrichment factor of 2 and a little less than 33% reduction or an enrichment
factor of 1.3 for the rest of the solids, as shown in Figure 4.1. Although lime can
effectively remove SO2, the removal efficiency decreased from 96.0% to 73.0%
when emulsified sulfur was burned in the # 3 rotary lime kiln. It also demonstrates
that recarbonation occurs right before calcination begins. This phenomenon is
shown in Figure 4.8.
A longitudinal study of all the variables related to the production of lime in
the # 3 rotary lime kiln at Albany Paper mill, Oregon was analyzed to determine
their relationships to ring formation, the results are shown in appendix A, Figures
A.1.1 to A.1.10.
34
Chapter 6.
Recommendations.
This study provides a first look at the effects of burning 70% emulsified
sulfur in the # 3 rotary lime kiln at the Albany Paper Mill in Oregon. However,
further work needs to be done.
A longer trial should be performed during periods when most of the rings
form, this will help to directly relate burning emulsified sulfur to ring formation.
During this next trial, fewer samples could be taken at greater time intervals to
analyze the following metals: Na, Ca and S. The rest of the impurities could be
ignored since they are inert in the production of lime.
A pilot scale could be set up in the laboratory for further experimentation on
a lime kiln proto type, where experiments could be performed at different
conditions in order to minimize all risks involved in adding too much sulfur to the
kiln while it is in operation. This will eliminate the possibility of forming sulfur
related rings which are very difficult to remove from the kiln.
Ring deposits may harden if too much sulfur is fed through the kiln to react
with lime. Lime reacts with SO2, SO3 and 02 to form CaSO4. (Tran and Mao, 2001)
This is shown in the following reactions:
CaO(s) + SO2 (g) + ½ 02 (g) -* CaSO4 (s)
6-1
CaO(s) + SO3 (g) -* CaSO4 (s)
6-2
35
References.
Boniface, A, "Introduction and Principals of Chemical Recovery",
Chemical Recovery in the Alkaline Pulping Processes, 3141 Edition, p.1 -4
(1992)
Doris, G. M. and Allen, L.H., Journal Pulp Paper Science 11(4): J89-98
(1985).
Gorog P. and Adams T.N., "Design and Performance of Rotary Lime Kilns
in the Pulp and Paper Industry - Parts 1 to 3". Kraft Recovery Operations
Seminar, TAPPI PRESS, p. 41-62 (1987).
Grace, T. M, Malcolm, E. W., "Pulp and Paper Manufacture", Canadian
Pulp and Paper Association, Vol. 5, p 3- 14.
Notidis, E. "The Formation of Guarded Sodium in Lime Mud", Masters
Thesis, Graduate Department of Chemical Engineering and Applied
Chemistry, University of Toronto, 1994.
NOTIDIS, E. and Tran, H.N., "Survey of Lime Kiln Operation and Ringing
Problems". TAPPI, Vol.76, No. 5, 1993, p.125.
Sanchez, D. R., "Recausticizing Principles and Practice", 2001 Kraft
Recovery Short Course, TAPPI PRESS, p. 2.1-1.
Tran, H. N, "Lime Kiln Chemistry", 2001 Kraft Recovery Short Course,
TAPPI PRESS, p. 2.3-1 2.3-8.
Tran, H. N, Mao, X., and Barharm, D., "Mechanism of Ring Formation in
Lime Kilns", International Conference on Chemical Recovery, June 7-11,
1992.
Tran, H. N, Barharm, D., "An Overview of Ring Formation in Lime Kilns",
TAPPI Pulping Conference, Toronto, October 1990, p. 2.
Appendix.
37
Appendix A.
Determination of correlation of variables with ring formation.
Al.
A longitudinal study was carried out to determine which variables are
correlated with ring formation in the # 3 rotary lime kiln. Selected correlation
variables include gas flow, back end temperature, front end temperature, mud
density, ID Fan speed, ambient temperature, percent oxygen, mud flow, turbidity
and lime production rate. Figures A. 1.1 through A. 1.10 illustrates the relationship
between these variables and the days the # 3 rotary lime kiln was shut due to ring
formation.
12
70
66
10
60
55
a
4
2
F
Figure A.1.1. Gas flow vs. kiln shut as blast marker
1
CD
1
3
0
rt;
CD
-
3
CD
CD
1
C
CD
N
>
CD
-t
.I1
1/11/03 100PM
1/27/03 900 PM
12/26/02 300AM
12/11/02 3:00AM
11/25/02 9:00 PM
11/9/02 3:00AM
10/26/02 9:00 AM
10/10/02 300 AM
9/24/02 5:00 PM
9/9/02 300 AM
8/28/02 1:00 PM
8/11/02 1:00AM
7/26/02 300 PM
7/9/02 3:00 AM
6/26/02 3:00 PM
6/16/02 9:00AM
6/4/02 100 PM
5/13/02530 PM
5/23/02 11:00PM
5/4/02 1:00 AM
4/19/02 7:00 AM
3/29/02 1 00 PM
3/12/02700 AM
2/23/02 3:00 AM
217/02 7:00 AM
1/18/02 7:00 PM
1/2102 7:00 AM
a
a
a
o
0
Feed Temp.
0
Blast Marker
0
0
0
-
00
-n
CD
t
t
B
ci)
cc)
CD
>
cJ
1/17/033 00 AM
1/4/03 900AM
12/20/027.00 PM
12/7/02 300PM
11/22/027:00 PM
11/8/02300 PM
10/26/02 900AM
10/11/02 3 00 AM
9/27/02 3 00 PM
9/13/02 11.00 AM
9/2/02 5 00 PM
8/19/02 1:00 PM
8/4/02 1 00 PM
7/19/02 3:00AM
7/5/02 5 00 PM
6/15/02 700PM
6/24/02 900 PM
6/4/02 1 00 PM
5/14/02 1:00AM
5/24/02 3.00 AM
5/7/02 900 PM
4/25/02 7:00 AM
4/5/02 700 PM
3121/02 1:00AM
3/6/02 100 PM
2119/02 7:00 AM
214/02 100 PM
1/17/02 9:00 AM
1/2/02700 AM
Mud Density
-
Blast Marker
-
0
11
12
10
10
9
8
8
7
4
4
3
2
0
Figure A. 1.4. Percent oxygen vs. kiln shut as blast marker
2
0
i
t
3
Cl')
Cl')
Cl')
ct
ri
>
r1
1/17/033:00 AM
1/4/03 9:00 AM
12/20/02 7:00 PM
1217/02 3:00 PM
11/22/027:00 PM
11/8/02 3:00 PM
10/26102 9:00 AM
10/11/02 3:00AM
9/27/02 3:00 PM
AM
9/2/02 5:00 PM
6/19/02 1:00 PM
814/02 1:00 PM
7/19/02 3:00 AM
7/5102 5:00 PM
6/24/02 9:00 PM
6/15/02 7:00 PM
6/4/021:00 PM
5/24/02 3 00 AM
5/14/02 1 00 AM
517/02 9:00 PM
4/25/02 700 AM
4/5/02 7:00 PM
3/21/02 1:00 AM
3/6/02 1:00 PM
2/19/02 7:00 AM
2/4/02 100 PM
1/17/02 9:00 AM
112/02 700 AM
Fan Speed
Blast Marker
U
U
I
U
U
U
U
U
U
U
U
C
4
a
t
t
B
CI
CD
t
CD
t
CD
CD
t
0
p.11
>
CD
t
1/25/03 300 PM
1/10/03 9.00 PM
12/27/02 9:00 AM
12/131027:00 PM
11/28/02 7:00 PM
11/13/021100
10/31/02 7.00 AM
10/16/02 3:00 AM
10/2102 3:00 PM
9/1 7102 3:00 PM
9/5/02 900 AM
8/23/02 7.00 PM
8/8/02 1.00 PM
7/23/02 3.00 AM
7/8102 300 AM
6/26/02 500 PM
6/16/02 1 00 AM
6/6/02 700 PM
5/26/02 1:00 AM
5/16/02 9:00AM
5/9/02 7:00 AM
4/26/02 1.00 AM
417/02 7 00 AM
3/23/02 700 AM
317/02 1 00 PM
2119/02 3:00 AM
214/02 3:00 AM
1/17102 1:00 PM
112102 7:00 AM
Front Temp
0)
Blast Marker
0)
0
t
t
çj
0
a;
I1
1/17/03 3:00AM
1/4/03 9:00AM
12120/02 7:00PM
1217/02 3:00 PM
11/221027:00 PM
1 1/02 3:00 PM
10/26/02 9:00 AM
10/11/023.00 AM
9,27/02 300 PM
9/13/02 11:00AM
9/2/02 5:00 PM
8/19/02 1 00 PM
814/02 1:00 PM
7/19/02 3:00AM
6/24/02 900 PM
7/5/02 5:00 PM
6/15/02 7 00 PM
6/4/02 1 00 PM
5,24/02 300 AM
5/14/02 1:00AM
5/7/02 9:00 PM
4125/02 7 00 AM
3/21/02 1:00AM
4/5/02 7:00 PM
3/6/02 1:00 PM
2119/02 7:00 AM
214102 1.00 PM
1/17/02 9:00 AM
1,2/02 7:00 AM
Mud Flow (gpm)
Blast Marker
0
44
It appears that there are fewer ringing events in summer than in winter,
which may be related to ambient temperatures. This is illustrated in Figure A.I.8.
12
140
120
10
100
80
I-.
80
40
2
20
0
r-c0coc'
.ocor-
r.
I()C0C0(W)
Figure A. 1.8. Ambient temperature vs. kiln shut as blast marker
45
River turbidity might contain certain impurities in the water used for mud
washing. Figure A. 1.9 shows the relationship between turbidity and days the #3
rotary lime kiln was shut to blast a ring.
Turbidity Vs. Blast
90
12
80
a... -
10
S
S
S
S
70
80
Blast Ma,lt.r
50
Turbidity
40
30
20
2
10
0
0
88888888888888888888888888888
(tOt Bit
B B
B
B
Figure A. 1.9. Turbidity vs. kiln shut as blast marker
01
B
B
46
Lime production rate, could be contributing to ring formation; this can be
seen on Figure A.1.1O, where production rate is plotted showing ringing events.
Ring formation increases during periods when lime production rates are sustained
over 150 tons per day (TPD) for extended periods, but ring formation has also
occurred at lower production rates.
200
180
160
I
i
100
'
01/01/02
04/11/02
07/20/02
I..
10/28/02
Figure A.1.10 Lime production vs. ring blasting
_80
02/05/03
05/18/03
08/24/03
I
47
A.2 Total material balance for solids during and after trial.
Table A.2. 1. Total material balance for solids before and after trial.
Sample
CaO
SO3
Na20
I(20
A1203
Fe203
S102
P205
MgO
CO2
Total
Name
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
LIME
Before
79.99
0.053
1.851
0.022
0.295
0.069
0.275
2.654
1.234
13.53
99.97
During
91.06
1.108
1.413
0.018
0.342
0.061
0.362
2.911
1.231
1.50
100.00
After
93.28
0.083
1.590
0.018
0.295
0.060
0.263
2.909
1.255
0.24
99.99
CHAIN SECTION
Before
55.23
0.035
1.099
0.012
0.142
0.038
0.135
1.649
0,769
40.91
100.02
During
59.52
0.333
0.939
0.012
0.191
0.037
0.201
1.687
0.752
40.94
99.97
After
54.32
0.045
0.822
0.020
0.157
0.031
0.173
1.672
0.498
41.53
99.97
Before
53.35
0.312
2.034
0.028
0,130
0.034
0.210
2.197
0.675
41.04
100.0
During
55.59
0.799
0.919
0.013
0.164
0.028
0.196
1.695
0.666
40.20
100.27
After
55.72
0.123
1.119
0.014
0.151
0.029
0.173
1.855
0.662
40,92
100.76
Before
53.74
0.027
1.007
0.010
0.125
0.031
0.141
1.453
0,677
42.79
100.00
During
55.23
0.051
0.832
0.012
0.173
0.029
0.197
1.683
0.653
41.14
100.(
After
59.26
0.030
0.849
0.010
0.153
0.029
0.218
1.672
0.580
37.19
99.98
Before
54.72
0.038
1.103
0.011
0.149
0.037
0.155
1.621
0.743
41.44
100.01
During
54.06
0.567
0.930
0.011
0.193
0.035
0.206
1.848
0.757
41.31
100.88
After
57.75
0.043
0.970
0.011
0.174
0.037
0.186
1.970
0.730
40.98
99.98
Before
55.79
0.038
1.130
0.012
0.157
0.037
0.157
1.686
0.772
40.23
100.01
During
58.94
0.675
0.997
0.013
0.191
0.036
0.204
1.893
0.791
38.71
101.22
After
56.11
0.053
1.065
0.011
0.151
0.031
0.154
1.626
0.726
39.66
99.59
DUST
MUD
NORTH
SOUTH
49
A.2.3. Process information data for solids during sulfur trial (cont.).
KILN BRN
LMPF
#3 KILN
MUD
CONVERSIO
ZONE TEMP
FEED
FEED TEMP
DENSITY %
N TO
SOLIDS
TONS/HR
FLOW
#3KIt.NFEED PRECIPIDFAN
END 02
SPD (POUT)
#3 KILN
River Water
MAIN GAS
Twtldlty
SOaData.
FLW
Dale and Irne
Units
DEG.F
GPM
DEG.F
%
tonThr(shor0
%02
IKSCFH
971J
I
P
7/30/0315:08
1824.71
75.31
260.36
24.97
147
1.58
27.08
2663
2.60
73.72
7/30/0316:08
1821.57
126.41
586.52
23.97
237
1.73
29.97
26.66
2.54
308.86
7/30/0317:08
1973.82
143.49
572.70
23.98
269
1.97
36.87
28.82
2.48
327.99
7/30/0318:08
2019.75
158.92
564.86
23.98
298
2.07
45.68
31.42
2.42
336.70
7/30/0319:08
1969.03
16423
572.41
23.98
308
2.16
51.79
34.21
2.38
318.59
7/30/0320:00
1870.43
164.79
605.22
23.99
309
2.59
55.44
2.30
303.93
7/30/0321:08
1805.34
165.18
596.81
23.99
310
2.18
54.05
2.22
344.70
7/30/032208
1775.69
165.07
597.87
23.99
309
1.94
53.27
2.15
351.75
7/301032308
1787.76
164.97
582.52
24.00
309
1.92
52.56
3666
2.07
35624
7/31/03060
177063
164.99
585.30
23.97
309
1.49
50.43
3661
1.99
382.67
7/31/031:00
1791.08
165.14
583.65
23.93
309
1.45
51.83
3850
1.91
360.78
7/31/032:00
180666
16529
591.76
23.88
308
1.51
53.62
39.93
1.83
350.32
7/31/033:00
1814.00
165.44
596.60
23.83
308
1.50
54.00
3975
1.76
352.33
7/311034:00
1826.41
165.59
599.39
23.79
308
1.50
53.55
3955
1.71
36620
7/31/035:00
1836.03
165.74
508.05
23.74
307
1.21
52.80
3931
1.85
318.36
7/31/036:00
185163
167.68
576.05
23.70
310
1.24
53.75
39.45
2.01
379.26
7/31/03 7:00
1862.78
177.51
590.63
23.65
328
1.55
58.59
41.04
2.18
284.22
7/31/038:00
1862.77
179.01
503.60
23.69
331
1.60
59.86
41.94
2.34
250.56
7/31/03 9:00
1869.37
179.06
595.37
23.80
333
1.59
60.58
4238
2.51
32063
7/31/031060
1848.98
179.11
597.75
23.90
334
1.59
60.70
4221
2.68
298.57
7/31/031160
1835.07
17924
600.12
24.01
336
1.62
60.82
42.07
2.84
286.55
7/31/031260
1817.85
179.90
600.09
24.11
339
1.61
60.93
4266
2.93
296.87
7/31/0313:08
1379.98
60.66
564.86
13.88
66
4.11
38.91
18.07
2.86
114.96
7/3110314:08
1792.09
130.79
574.79
22.02
225
1.15
41.87
3466
2.77
172.46
7/31/0315:08
1801.08
175.40
583.97
23.42
321
1.49
5525
39.42
2.69
287.77
7/3110316:08
1859.27
179.19
577.41
23.48
329
1.59
58.22
4079
2.61
321.33
7/31/0317:08
1914.93
17922
575.81
23.54
330
1.61
58.39
41.13
2.53
363.96
7/31/0318:08
1937.64
17925
57424
23.60
330
1.60
58.31
41.24
2.45
159.37
7/31/0319:00
1913.07
17929
578.98
23.66
331
1.60
5824
4t35
2.36
110.12
7/31/032060
1907.82
17932
582.16
23.72
332
1.60
58.64
4156
228
67.92
7/31/0321:08
1929.15
17935
586.07
23.78
333
1.61
58.48
4201
2.20
7.89
7/31/032260
195532
17938
592.04
23.84
334
1.61
58.30
4205
2.12
121
7/31/032360
1953.05
179.43
59321
23.88
335
1.61
58.17
4207
2.03
028
8/1/03 0:00
193363
179.57
55324
23.92
336
1.64
58.05
4203
1.95
0.21
8/1/03160
1915.20
179.71
594.05
23.97
336
1.61
57.92
41.81
1.88
0.14
8/1/03260
1899.27
179.81
595.18
24.01
337
1.60
57.80
41.59
1.78
0.07
8/1/033:08
189429
179.78
594.99
24.06
338
1.63
57.68
41.59
1.70
060
8/11034:00
1890.93
179.74
503.80
24.10
338
1.62
57.62
42.33
1.71
-0.07
8/1/03560
1887.56
179.65
598.43
24.15
339
1.58
57.86
4293
1.85
414
8/1/03660
1885.29
17950
601.57
24.15
339
1.59
58.14
4291
1.99
-0.19
8/1/03760
1892.07
17935
602,71
24.08
337
1.60
58.42
4290
2.14
8/1/038:00
189024
17922
605.52
24.01
336
1.60
58.69
4232
228
419
419
JJL
8/1/83960
1897.57
179.64
608.30
23.94
336
1.59
58.97
4296
2.42
-0.19
8/1/0310:00
1311.07
24.12
608.74
9.48
18
6.47
32.06
993
-0.19
8/110311:00
185332
120.45
599.58
22.66
213
0.43
3921
2.71
4.19
8/1/0312:00
1912.47
14054
572.90
24.35
267
1.51
44.00
j%
2.56
3528
2.74
-0.19
8/1/031360
1894.01
141.84
592.07
23.98
286
1.45
44.81
3562
2.69
4.19
8/1/0314:08
1912.53
145.10
598.86
23.66
268
1.50
46.67
J!...
2.63
4.19
8/1/0315:00
1924.37
14427
602.18
23.42
264
1.50
47.28
3719
2.58
-0.19
8/1/0316:08
1995.39
144.00
601.14
23.50
264
1.56
4651
3675
2.53
-0.19
8/1/0317:08
2029.97
143.75
585.37
23.62
265
1.57
44.06
3443
2.47
4.19
8/1/0318:00
2034.42
144.04
571.93
23.74
267
1.68
3397
2.42
-019
8/1/0319:00
2018.69
144.75
573.12
23.86
270
Ill
4353
43.59
3367
2.36
4.19
8/1/0320:00
2011.77
14469
575.05
23.99
271
1.74
43.73
3379
2.32
4.19
8/1/0321:08
2005.31
144.80
589.05
24.11
273
1.72
42.54
3373
8/1/032200
1995.62
144.70
581.95
24.23
274
1.62
42.52
3310
228
225
4.19
-020
50
A.2.4. Process information data for solids during sulfur trial (cont.).
KILNBRN
ZONE TEMP
Date a
#3 KILN
MUD
FEED TEMP
DENSITY %
N TO
SOLIDS
TONS/HR
FLOW
r
limis
FEED
DEG.F
GPM
DEGF
%
CONVERSIO #3KILNFEED
ton,1(shorO
EM) 02
PRECIPIDFAN
#3 KILN
River War
SPD (POW)
MAIN GAS
Turbidity
SO1DSI.
FLW
%02
KSCFH
Nih
PPM
8/1/0323:00
1981.97
I4461
572.48
24.32
275
1.65
43.10
33.88
221
.0.22
8/2/030:00
1961.67
144.76
566.88
24.29
275
1.61
45.10
3496
2.18
.0.24
8/2/031:00
1941.74
14494
571.15
2424
274
1.67
44.96
2.14
.027
8/2/032:00
1943.23
14494
576.86
24.20
274
1.64
44.82
3493
2.11
-0.29
8/2/033:00
1946.70
14474
584.55
24.15
273
1.65
44.97
35.13
2.07
431
8/21034:00
1947.45
14464
583.60
24.11
272
1.64
44.96
3533
2.05
034
8/2/035:00
1947.73
14455
585.89
24.07
272
1.67
44.76
3567
2.05
-036
812/036:00
1946.13
14451
581.48
24.02
271
1.68
44.62
2.04
-0.37
8/2/037:00
1948.18
2397
266
1.64
44.56
3526
2.04
-0.38
8/2/038:00
1923.78
583.32
23.91
261
1.66
43.55
3497
2.04
-038
8/21039:00
1919.40
596.83
23.85
242
1.74
42.45
2.03
-02
8/2/0310:00
1934.17
Jj
576.27
12520
602.18
2181
233
1.64
38.67
3310
2.03
0.38
8/210311:00
2399
235
1.66
39.21
3326
2.03
-038
1963.95
l2537
601.45
8/2/0312:00
1986.34
12481
598.30
24.00
234
1.67
38.79
3288
2.03
4.38
8/2/0313:00
2003.62
11536
594.76
24.00
216
1.72
3523
2.03
.036
8/2/0314:00
2020.90
11035
591.15
24.01
207
1.84
33.23
3113
3012
2.04
-0.37
8/2/0315:00
2038.18
10974
592.48
24.02
206
2.10
32.03
2871
2.05
-0.34
8/2/03 16:00
2055.46
10943
572.04
24.02
205
2.04
28.38
2630
2.64
-0.32
8/2/0317:00
2055.16
10994
56l.54
24.03
206
2.74
29.91
2626
2.90
-0.30
8/2/0318:00
2038.29
11048
571.98
24.04
207
2.79
30.38
2626
2.77
-0.27
8/2/03 19:00
2023.17
111.06
577.37
24.04
209
2.81
30.61
25.98
2.65
-0.25
8/2/032000
2024.32
11t80
578.69
24.03
210
2.83
30.44
2594
2.53
023
8i2/0321:00
2024.18
11000
587.32
24.03
206
2.76
29.51
25.88
2.41
-020
8/2/0322:00
2000.18
l0918
591.55
24.03
205
2.77
31.31
25.85
229
-0.19
8/2/0323:00
2009.41
10945
586.81
24.03
205
2.81
30.70
2520
2.17
-0.l9
8/3/030:00
1996.04
10979
580.92
24.03
206
2.82
31.05
2596
2.05
-0.19
8/3/031:00
1960.35
11013
584.53
24.03
207
280
31.16
26.19
2.00
-0.19
8/3/032:00
1954.99
11047
591.64
24.03
207
2.80
31.01
26A8
2.02
-0.19
8/3/033:00
1967.87
11081
591.47
24.03
208
2.79
31.96
26.73
2.04
-0.19
8/3/034:00
1965.86
11107
594.81
24.03
208
2.81
32.11
2692
2.06
-0.19
8/3/03500
1957.t5
03971
597.72
24.03
206
2.66
31.72
2711
2.06
-0.19
8/3/036:00
1955.02
109.80
594.66
24.04
206
2.47
31.02
27.30
2.10
-019
8/3/037:00
1954.71
11030
596.64
24.04
207
2.48
31.79
27.40
2.12
-0.19
8/3/038:00
l951.42
109.51
594,73
24.04
206
2.53
3l.34
27.47
2.14
-0.19
8/3/039:00
1950.62
11001
602.26
24.05
207
2.37
32.14
2.16
-0.19
8/3/0310:00
1965.61
11044
59002
JZA.
24.03
207
1.93
30.75
2786
2.17
-0.19
8/3/0311:00
1976.04
11074
591.02
23.87
206
225
32.76
2794
2.19
-0.19
81310312:00
1979.89
11074
59849
23.86
206
2.32
32.34
2807
2.56
-0.19
8/3/0313:00
1975.39
11073
600.32
2188
207
2.28
32.55
2820
3.43
-0.19
8/310314:00
197025
11085
603.53
2190
207
2.29
31.34
2811
3.30
-0.19
8/3/0315:00
1976.79
11052
599.84
2193
207
227
32.46
3.17
-0.19
8/3/0316:00
l963.16
11047
600.01
23.95
207
2.48
33.10
2795
2807
3.04
-0.19
8/3/0317:00
1985.91
11042
602.38
23.97
207
2.31
32.99
2804
291
-0.19
8/3/0318:00
1969.65
11037
603.72
24.00
207
228
32.43
2805
2.78
-0.19
8/3/0319:00
1994.05
111.78
599.76
24.02
210
228
32.94
2805
2.65
-0.19
2896
2807
253
-019
2.46
419
2817
2.41
-0.19
2826
236
-0.19
-0.l9
8/3/032000
1992.94
11555
589.77
24.02
217
2.36
33.70
8/3/0321:00
1985.38
11500
589.40
24.02
216
2.38
33.44
8/3/0322:00
I970.26
11123
591.02
24.02
209
2.39
33.56
8/3/0323:00
1948.44
11076
601.52
2402
208
2.42
3320
8/4/030:00
1931.82
11074
603.51
2402
208
239
33.35
8/4/03196
1928.59
11073
614.47
24.01
208
221
34.51
j.
29.81
232
227
8/4/032:00
l946.17
11071
616.08
240l
208
2.03
32.13
2887
222
-0.19
8/4/03396
1979.68
11069
607.11
24.01
208
2.00
31.71
-019
1988.81
11065
60721
24.01
208
2.00
31.56
2906
2927
2.18
8/4/034:00
2.13
.0.19
8/4/035:00
1992.35
I1055
608.76
24.01
207
2.01
31.80
2948
2.13
419
8/4/036:00
1995.36
11546
607.99
24.01
207
1.99
31.89
2873
2.14
-0.17
0.19
51
A.2.5. Process information data for solids during sulfur trial (cont.).
KILN BRN
IMPF
#3KLN
MUD
ZONETEMP
FEED
FEEDIEMP
DENSffY%
NT0
SOLIDS
TONSIHR
ftOW
I
CONVERSIO #3KLNFEED
ENDO2
PRECIPIDFAN
#3 KILN
SPDOUT)
YIAINGAS
RerWat
SO2Data.
Turhiddy
ftW
Dale aid Tine
L
linils
DEG.F
6PM
DEG.F
I
bMr(sho
%02
KSCFH
'
1998,92
11036
605,27
24.01
207
1.96
32.18
814/038:00
2002.34
11026
600.18
24.01
207
2.03
32.41
29.04
J
'
NTtJ
'
PPM
2.16
.0.11
2.17
.0.05
814/009:00
2007.27
110.16
596.85
24.01
207
127
31.73
29.00
2.59
0.01
814/03 10:00
1617.61
47.93
61025
1420
53
5.98
27.60
14.65
2.71
0.07
W431t00
842.71
aoo
502.14
7.35
0
4.30
23.00
415
2.87
0.12
814/0312:00
798.73
0
565.15
722
0
9.34
23.00
499
3.03
92.70
814/0313:00
798.73
0
587.11
7.28
0
9.36
23.00
482
3.18
265.07
8/4/0314:00
798.73
0
572.92
125
0
9.77
23.00
465
3.34
24.63
8/4/0315:00
798.73
0
575.11
721
0
10.20
23.00
448
3.58
.0.19
814/0316:00
1612.41
0
596.21
7.17
0
10.30
26,10
917
3.65
.0.19
8/4/0317:00
1788.24
591.14
8.75
7
5.37
30.85
2411
3.71
.0.19
814/0318:00
1838.15
11122
592.64
24.77
215
1.78
31.95
2539
3.49
.0.19
814/0319:00
1894.10
1105
593.20
24.70
224
2.04
38.07
293
326
.0.19
8/4/03200
1966.75
11917
500.74
24.62
229
226
32.75
2927
3.04
.0.19
814/0321.0
2001.03
11911
591.95
24.54
230
228
33.87
2926
2.81
0.19
W4/0322
202426
12022
588.93
24.47
220
2.30
33.03
29
2.58
.020
81410323:00
65
2002.81
12019
585.16
24.39
229
229
32.61
2918
2.35
.0.22
00
1979.00
119.94
500.77
24.31
228
2.30
33.55
29.23
2.13
.024
815/001:00
1952.85
11910
598.56
2424
227
2,31)
34.00
29.45
1.99
.0.27
815/002:00
1925.00
119A5
565.11
24.17
226
2.31
33.94
29.63
2.06
.0.29
8/5/003:00
1900.63
11L46
58827
24.12
221
2.30
34.98
29.62
2.13
.0.31
815/004:00
1881.87
11515
59623
24.07
217
2.31
34.53
29.57
220
.0.34
815/005:00
1880.41
11524
600.69
24.02
216
2.32
34.46
29.53
228
.0.36
8/5/006:00
1849.71
1154
600.77
23.97
216
227
34.65
2926
2.35
.0.37
8/5/03
52
A.2.6. ICP analysis data for solids during sulfur trial.
Date
Samp Name
Na
wV
S
K
jn .PE
S
Fe
M
I
Ca
ppm
ppm
ppm
ppm
ppm
wt
5/30/03
Lime
L4
211
18
150(
267
1556
10444
6478
57.
7/2/03
Lime
1.36
270
2
163(
220
155
11400
7760
56.8
7/24/03
Lime
_j
80
155
240
136
12500
7750
56.
Lime
1
190
1561
240
1401
12011
77
57.
_j/9
Lime
Li
330
7/29
Lime
1.1
2600
7/29
Lime
1.00
7129
Lime
i.0
7/30/03
Lime
7/30/03
Lime
7/30/03
_.224
if
1710
220
140
10600
6
66.
17
172
230
145'
12200
7
65.
5700
1
179
220
136
1141
64.
6300
1
170
21
139
i1
64.
0.9
6200
1
1750
240
138
130(
75
1.11
6000
11
1840
230
152
12000
7700
...j.
Lime
1.04
8000
i
17
220
145
12600
7700
65.
7/30/03
Lime
t02
4500
1
17
220
152
12800
7600
65.6
7/30/03
Lime
(19
6200
18
220
157
1300
74
7/30/03
Lime
0.99
5500
17
220
152
12500
6900
7/30)03
Lime
(19
4600
18
220
141
12800
76
7/30/03
Lime
_O.9
4000
18
220
157
1300
76
7/31/03
Lime
_l.14
5400
17
181
210
30C
13300
7500
7/31/03
Lime
_1.14
5400
17
181
210
30C
13300
7500
7/31)03
Lime
1.0
4000
141
187
200
204
13000
7
652
7/31/03
Lime
1,0
4400
161
17t
21
174
125(
7300
65.
7/31)03
Lime
1.1
5
221
18(
200
298
13000
7400
64.8
7/31)03
Lime
0.98
42
1
18f
220
U
12900
7400
65.5
7/31/03
Lime
0.9
4300
141
19
21
271
12900
7400
65.3
7/31/03
Lime
1.
350
1
19
21
13400
7300
65.6
7/31/03
Lime
1.
2200
1
19
2
2
13100
7800
66.
2
137C
740
65.3
13800
7000
65.
l
65.
_j.
62.5
_j
_jj4
j.4
1/03
Lime
1.1
1400
1
18
190
W1/03
Lime
1.05
1100
1
19
220
8/1/03
Lime
1.1
1100
1
1
200
3
14100
710
64.3
8/1/03
Lime
1.1
100
1
1
200
209
14300
710
65.
8/1/03
Lime
1.1
1000
1
1
200
209
14300
7100
8/4/03
Lime
1.1
33
1
156
210
1
12700
757
...j5
66.
53
A.2.7. ICP analysis data for solids during sulfur trial (cont.).
Date
Sample Name
Al
Fe
Si
_____P
ppm
ppm
ppm
ppm
S
Na
wjamj
M
Ca
m
7/24
Chain Section
0.82
142
9
751
132
72
7201
4
7/29
Chain Section
0.71
1600
75
99
130
970
77
4
_4
7/31
Chain Section
0.69
1200
110
102
130
112'
7200
4
_39
7/31
ChainSection
0.69
1200
110
102
130
112
7200
4
45
8/1
ChainSection
0.7
420
lii
1020
110
178
8
47
39
8/1
ChainSection
0.74
420
110
1020
110
178
81
4700
4
8/4/03 Chain Section
0.61
180
17
83
110
92
7300
39
8/4/03 Chain Section
0.61
180
17
83
110
92
7300
38
7054
37.
5/30/03
Dust
0.73
7/2103
Dust
2.4
7/24
Dust
7/24
7
215
946
39
1
667
2407
441
7
110
14
1.11
261
111
67
1
1055
Dust
1.79
2107
24
6
Dust
1,0
500
11
81
1
7
Dust
0.64
650
9
81
1
7
Dust
0.7230001
7
Dust
0.71
3000
7
Dust
0.61
2600
II
7
Dust
0.65
11
7
Dust
0.
7/30/03
Dust
0.
7/30/03
Dust
0.
7/30/03
Dust
0.
38
1
1
6600
7/30/03
Dust
0.
36
1
1
67
4
40.0
7/30/03
Dust
0.
35
1
71
3
39.
7/31/03
Dust
0.
35
4
38.4
7/31/03
Dust
0.
44
11
89
7/31/03
Dust
0.
38
1
96
7/31/03
Dust
0.
4600
7/31/03
Dust
0.
4
1
7/31/03
Dust
0.
33
1
7/31/03
Dust
0.
38
1
88
11
3
7/31/03
Dust
0.
1
1
86
117
3
1073
1
9429
37.
4
39.4
474
37.
890
39.
122
39.
7
40.
71
39.
1
7700
38.
1
7700
39.
11
1
8500
39.
1
1
81
1
1
13037
_j9.
7300
1
66
1
7
41.
39.6
3650
39.6
3
40.
40.4
90
9
40.
3680
__29
40.1
54
A.2.8. ICP analysis data for solids during sulfur trial (cont.).
Date
Sample Name
S
wt
_p
Al
Fe
ppm
ppm
I
JE11
___Si
jpm
Ca
I
ppm
ppm
wr
8/1)03
Dust
0.71
1200
120
900
87
11
8000
4020
39.6
8/1/03
Dust
0.72
1200
140
841
80
11
7600
3940
39.8
811/03
Dust
0.7
840
13
91(
90
ii
6900
811/03
Dust
0.7
780
13
8
80
104
6700
3890
39.4
490
120
801
100
92
8100
3990
39.8
40.8
8/4/03
Dust
0.6
5/30/03
Mud
0.
86
89
631
108
77
5679
2
38.
7/2/03
Mud
0.
143
99
792
117
88
7371
4892
38.
7/24/03
Mud
0.69
86
5
548
96
61
521
3
38.1
7/24)03
Mud
0.81
117
8
67t
11
796
7108
4
39.
7/29/03
Mud
0.65
_1i0
9
871
100
7100
3
j&
7/29/03
Mud
0.
110
92
840
100
108
6600
3400
38.3
7/29/03
Mud
0.
1
9
860
11
105
7700
3500
37.
7/29/03
Mud
0.54
120
86
100
108
7300
3200
37.
1/30/03
Mud
0.68
1
11
94
11
121
8200
4
42.6
7/30/03
Mud
0.6
1
10
94
10
111
8100
4200
38.9
7/30103
Mud
0.55
1
10
9f
12
8000
4400
382
7/30/03
Mud
0.64
1
11
94
114
7500
4400
382
7/30)03
Mud
0.6
1
16
9f
110
125
7800
4400.1
7/30/
Mud
0,
11
9
8
10
105
7700
3500
37.
7/30/03
Mud
0.
1
76
880
100
108
7300
3200
37,
7/30103
Mud
0.
1
8
&
100
881
6500
4000
39.0
7/31/03
Mud
0.68
230
1
97
120
113(
7 00
4300 __._
7/31)03
Mud
0.68
260
11
9
120
141(
8200
4400
39J
7/31/03
Mud
0.
290
_9
931
7000
3760
39.5
7I31/03
Mud
0.6
360
1
91
88
1011
7
387
39.
9
8
1051
3990
46.2
9
8
1051
85
1044
6500
40
8
1051
&
39
76
7/31
Mud
0.
340
11
7/31/03
Mud
0.65
340
11
7/31/03
Mud
0.59
320
7/31/03
Mud
0.
340
7/31/03
Mud
0.65
340
811/03
Mud
0.
360
9
8/1/03
Mud
0
350
10
10
92
_8
_9
_8
8&
_9
_1
3990
_j5
40.
_4
87
1101
7500
3990J2.
81
Ith
68
3940
39.5
78
1081
69
39
39.8
8/1/03
Mud
8/1/03
Mud
8/4/03
Mud
E/30/03
North
7/2103
North
7/24/03
North
7/24/03
North
7/30/03
North
7/31/03
North
7/31103
North
8/1/03
North
8/1/03
North
8/4/03
North
8/4/03
North
5/30/03
South
7/2/03
South
7/24103
South
7/24/03
South
7/30/03
South
7/31/03
South
7/31/03
South
8/1/03
South
8/1/03
South
8/4/03
South
8/4103
South