9;"

‘ ..p‘n'.
gm“ '

?.’I

0".Q

17);? {4

My:
t “"'

1:3

 

 

 

 

 

 

 

 
   

 

 

     

    
    

   

 

   

 

  
 
     

,-. o.— Aoo-q'v-I -- .\.9—.--"r6-

 

 

 
   
  

.
I - v
o
‘ O .
o
' o
o .
.
I
I -
. I .
. .
.
. ' o
. .
. "I ‘ . .
n ' . Q
a o I t t
. . , _o
’ ' . ' ' -
I ‘ ED WLUM .- I 1 I
. - . I I_ _ \ (I ‘
V c v _ .
. V - I _ , u __
. . I ‘ . .
. I ' .
I ,0 . . S
. I I
I 0 . 0 ‘
. I . . . I ..
. .
u . ' ‘ .
- . . . . . . _
'. , . V
. . . . , . . 0 ~
. 'N ‘ . I ‘
. , _. . ... ' . a . ‘
. . ' I _ I . ‘ - ‘ I
' .» - a . . '
. O ' ~ ~ ‘ . o
o ' ' D - ‘ '
T - o . .
v - .
, . A . .
I‘ ' I I . I . . v .
I .. ' . - v .‘ ‘1 .- ' ’
II . 4 . - - , . ."
. ,. ‘ ': . y
I . ' . v
. V O ' I“ -
. I . . .
, . .
- . I . - . I
. - ~ . - . ' '~ . .
. . I _ ~I
.
I .
. ' “r v .
V . . . . o ' . ' _ - o -
. . . v. -
¢ I ~
. _ . a. '
o I . . I
.
. . . . ». ~ ‘ .
o . I ' . . a
. I ¢ .
v . ' . . -
. .
. . . . . <
I
- . n
3
I - . _ . .
. . .25 - _ *
o v I s V.
I I ..- .-
0 .
. . . _
l I ~
. ' .. n ' — , - ' u -
I .
. . . . . '
. I c
. .- .
o I I - . . .. ' o
c 1- " I - I
. ‘ - ' ‘ - . '
C . ' ' '
. . .
. - . .
. > . ‘ ’
n . '
I I , .0 , u ‘ -
I _ ‘. _ '
o . ' . .
. o ‘ '. _" ‘ ‘ '- ' ‘ ..r-
. . . . . v ‘I
‘ “..' ' a
,. - _ . ._.
I f . .
. . . .' . . -. .
. I.. - ~ .- .
. I ‘ ’_ - , ~ . .
o
. ' . O . ‘ n on .
v .. n. f I
' - ,. -.I 4 I '~
-. n I ‘ . I ' -
. . . . . .
' ‘ o . I ._.. _- ' . .I . .
. ' v . . - . * —> . - .
g. . ~ -" 1 - ’ .-
‘ " ' l' ‘ ' ‘
. I - - . . I , . . _ -A
“ ' " " . a rnlo ' 4' "I ‘ ' ~ ‘
o . "I I ‘ I' , .. -. - - co.
. .. . , , ., , .15» . ..- . . ~. . , .. - . -
-d g I ’ I‘ . O , . . -. - - ., .. _
. I . , . . -, I » .
~ I - v . o '
_ , . E; 3 . . , .
. , V - . . . .
o ‘ ' ' - .- . .7 I . l—‘- I‘ I ' ‘ ' I
I . . . . H... I . , _ a . - - »- ' ‘
I ' . - r. 0: -- ‘ I . ' I - .‘ ' -/
' ‘ ... O . ' " v o ‘ o . , o
I" . » , .~ . cu“ ‘ '
. I ., _ ‘ .~ _ . -‘ .I.
‘ ’ I ~ ' c, . ,I- , I . -, ' . r ' r" r
I I- . I ' ‘ - ‘ 4 ' . . f . . I -
- -~ 0 , . , I. - ' , _ - .. - o ' -
. - o .. .- . ,_ _ . ,.. I . - __ . . r I
I . . .,, , , .< 1 . .» ' '
‘ . . I ... O C .‘ I - ‘ .9 ’ -.c ' ' .
' .I , o , . . .o 7- -— .—- l - "I I ’
A ' -' Q ' . I - ‘ . I o n n «‘0'» ' .- , ‘ .<‘ ‘
I ~ ’ ‘ o . I, .. - _. - - - - a -
. . . I , I ’ .vo I . . .-- .. -: r-l .
. . . l I.- . . _ .. .I' . I . , - . - _ "r‘
' i V r.’ .4 - o - ,I r - , ~'.,.I ... . . .
. . . -. ' .. ._ . II ...-t , . , _ . . - ' -‘ .q . ' v -.-
. - ‘ . . - 'I . . , I
I — I. , . I ~. . . . ‘n. .- I ‘ , I - .
- . . ,. II . ,_. . I, . ... . n -" ’-
. 4 - . a ..I , ', . A o--- , . . I." II . ~ - - . ‘- - -—
. I I. O . , - . r I. - ., - .-. I ‘ '- ' ‘ a - "
I - I l . .I _ , -. r ..-. .. .. , - , .' 'o *. ~ » u
0 ° - - . o - - o o ., . v _, , . _ . . . . . -7." r '
. . , . . . - I _. — I. a , n -
I D - - a a . I . . 4 ’
I . . . . —
- . l o
o ' . - . , r .
,. - .
. . . y .
. I ... — I '0 ‘ a I
v .. I 0 I ' "
" " " 'no r0”. -
l o ... I"
. I 0 O u ‘ '
. . . . . .. . ,
I .. . I
o - 4 o I
' a - s - o
r .O' .
‘ . I - ' l I p o -
- . . r . .-
v -o u' .0 ‘ .-. I - o o
I I 'G Q
'~ .I . , . I . I .
I . , . . a -
I I, I . 1- 0‘ 09- I ' a
I ... . v.
.a . . . . uu- I > . '.
‘ a) I. ‘0 . '
. - . , . . . . o - . V
.. C a ,
c - ' - I . . - - III-v . I
I ' I av l o . ‘ ' o .
. . I . - 9.. . -~, . ~v -
- v I ' - ; o I a U ...
C an v ‘ I O - '- H n . . g
I . .. . . . a a . o _
- - I . - ... -- I".l . .
. . ~ I o ... . . a--. .- .-
V . n o 0 IA . _'
., I - l ... . I - . _.. ,. , I
- " . o o ' '
. - c v l t a .. ‘ 0 " ’ a a I.
. . D . I. . ' -O‘ ' ' v'unl.-.
I I 4... - ' v.5 ' . ... _ I
I . I- v . - . a ' v - I; ..
on I '0 oulr. . c .... ‘I‘ i - o I. .q.
. I . . o 1 . . l 1-. . ... . ’
0 ' I90 - I . .. v . .- .
' - - . , ‘0. o' I.. . .
U - I’ I ... v - -~o .
l ' 'l' .0 ' D'A- .- ‘ 0 1
. o . I .I I ‘ v .o .v . - .I- ‘9 I - :0
- ' ' 0; ~ I I »n.. -, .
. - . . . .I- 'I It - . - ~ - a - n-r-o. -: v
,, I . I . .o . o-I-- - I .
- .. . I., . t O I- I ' v. .I. , d
g . . . q -0 .. I II; . -. -., ,., , I
- g I. . .. ,, . - . u 'l ,.-,.. .. r '
, I .I', ‘ n . v: 11- I. I ,. . _
0 ~" ; O¢‘« ~ .. .- . . a ) .- x...» . O
. . 00 . I .¢ .- . a -. ,v . p -
. . I . o I. r ‘ ‘D.I - a" ' -'
4 o . o - l , ..c 90"-_v.- 0' , -
I. I . , ..I ..... ...
. 1-. ' - . o- \. "-- . - a. -‘
v I I . .- o I -' I~"‘ - . . “f
_ ,. .. .I- , . 0". - . a
. l - - or» . .. I“! ' '0‘: ’- co
. v , ,. A - 1|. , . ---. .... ., I
l N ' “ ' . - - ...
I . . . v II . - .. .
I l H - ‘1: ,I '- - -.. .I
. I I ~ '5 -- , " ' - ‘ I
. . . ... - v - o “ ’r- ‘0.0) \.. o.
0 . . . I . o '00.: « 4. . ,.V 1'...
. . . I. I-l. "‘ " to: — u."¢.ll"'fifil"ti
6 - - ' I' . . ‘1 ' I -- A 3 l' '14.o.', c m.,
0'. ‘ - .1 - a, V 'rUI ll. .' - . . , ..‘v'¢... q. ... I"
u I. I ooh - ‘ -o‘ 4.1-.v. . .... . I b ' °' ""
I" an- I c . ' a. . . . -. I . -. I ' '.
.. . . I I. a I ~ oglu.‘ “I ' 0‘ v .v-‘V 9“. .I
I . In t: ..- ..l .,o I. ...o- . '. o”r"t-'
. a. I- -. I.- I.. .I .. Ion o ”no. .. a O-pu-‘o .v-o "'00‘1-
' .. “ " ' ‘ . - l-O-ooo'>u-->--..¢ernbo
, . . . . . I . A. . .. ... . , .. voc'I-v.-.¢- _ ..«- ~vv'lov
" - " ’ I ' ‘I'. ‘ 9’ -' '4 .' .t-I vol 0H1...-. .,,...lsru-“
. . l" I ‘.- . . ' .IL' a ... < ... .‘I‘ CV." ~‘— I..."
n '. - I. . Or.‘ .' .. .. .’ " . 5" .a-. A ‘—
‘ ' ' 'v. t I v l<
I 'I‘D. . I r C '
I ., . v .. “1.....- _
.. ..-o o a

 

 

 

K _‘ fl’- I

r Liszt Y

9
3 [Viking-an State *
" Ufi'. ' ¢
’ "ALIJCI'SIE

 

f a»

g om‘omc a;
HMS 8. SUNS' W 3.

  

 

800K BINDERY INB. '

LIBRARY BINDERS

.I-“" - nun-unn—

 

ABSTRACT
OPERATION OF A PACKED COLUMN FOR THE
ABSORPTION OF SULFUR DIOXIDE BY

AN AMMONIACAL SOLUTION IN AN
INDUSTRIAL SITUATION

BY

Thomas R. Gilson

Previously, a study1 was made of the absorption of
sulfur dioxide by a solution of ammonium bisulfite and
ammonium sulfite in a packed column. That work used a
synthetic mixture of gases similar to the effluent of a
power plant. The purpose of the present work was to Operate
the same absorption column using real stack gas as the gas
feed.w Operations under actual and ideal conditions could
then be compared.

The column used was four feet tall by 3.75 inches
inner diameter and was packed with 1/2 inch Rashig rings.
The inlet gas to the column was water-saturated at 50°C
with the sulfur dioxide concentration varying from 1500 to
2400 parts per million. The liquid was fed at 57 to 60°C.
The S/Ceff ratios of the solutions were between 0.70 and
0.73. The liquid mass velocity was varied between 290 and
480 pounds per hour per square foot. That of the gas ranged

between 360 and 500 pounds per hour per square foot. Two

Thomas R. Gilson

series of runs were made, one at constant gas rate and one
at constant liquid rate.

The column did indeed Operate with stack gas as
feed. However, it was discovered that the equilibrium
partial pressure of sulfur dioxide in the stack gas over the
ammoniacal solutions used in the experiments was apparently
much different than the equilibrium partial pressure
observed in the lab by Johnstone.2 The column absorbed
much more sulfur dioxide than would have been possible if
Johnstone's equilibrium data applied. Because there was no
applicable equilibrium data it was not possible to write an
equation to describe the absorption of sulfur dioxide (or
the desorption of ammonia) as a function of the liquid and

gas flowrates.

 

1S. R. Auvil, "An Investigation of the Absorption of
Sulfur Dioxide by an Ammoniacal Solution in a Packed Column"
(unpublished Master's thesis, Michigan State University,
1971).
2H. F. Johnstone, "Recovery of 802 from Waste Gases,"
Ind. Eng. Chem. 31 (5), 587-93 (May 1935).

OPERATION OF A PACKED COLUMN FOR THE
ABSORPTION OF SULFUR DIOXIDE BY
AN AMMONIACAL SOLUTION IN AN

INDUSTRIAL SITUATION

BY

Thomas R. Gilson

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Chemical Engineering

1972

ACKNOWLEDGMENTS

The author expresses his deep gratitude to Dr. Bruce
W. Wilkinson, Department of Chemical Engineering, for his
guidance and encouragement during this work. The author is
deeply indebted to Mr. Steven R. Auvil for his advice on
many aspects of the project. Mr. Auvil's work with the
computer program used for data analysis was especially
appreciated. The financial support of the Lansing Board
of water and Light is noted with appreciation.

Thanks are extended to the personnel at the Eckert
Power Station for their cooperation and to Joseph Strahan
of the Board of Water and Light for his assistance in

operating the equipment during the early experiments.

ii

INTRODUCTI

THEORY .

EXPERIMENT

The
The

TABLE OF CONTENTS

ON 0 O O O O O O O O O O O O O O O O 0

AL EQUIPMENT . . . . . . . . . . . . .

Path of the Gas Stream . . . . . . . .
Path of the Liquid Stream . . . . . . .

EXPERIMENTAL METHODS . . . . . . . . . . . . . .

DATA . .
DISCUSSION
CONCLUSION
Obse
Reco
BIBLIOGRAP
Appendices
A.
B.
C.
D.
E.
F.
G.

S O O O O O O O O O O O O O O O O O C O

rvations O O O O O O O O O O O O O O O
mmendations . . . . . . . . . . . . . .

HY O I O O O O O O O O O O O O O O O O

ANALYTICAL CHEMISTRY . . . . . . . . .

Determination of (NH4)2SO3 . . . .
Determination of NH4HSO3 . . . . .
Determination of Total NH4+ . . . .
Determination of $04= . . . . . . .

ROTAMETER CALIBRATION . . . . . . . . .
INFRARED ANALYSIS FOR SULFUR DIOXIDE .
DETERMINATION OF FLOWRATES . . . . . .

PHYSICAL PROPERTIES OF THE SOLUTIONS .

LISTING OF TIME VERSUS CONCENTRATION DATA

COMPUTER PROGRAM FOR DATA ANALYSIS . .

iii

Page

11
13

18
21

30

30
32

33

34

34
35
36
38

39
42
45
48
49

53

L IST OF TABLES

Table Page
1. Experimental Data . . . . . . . . . . . . . . . 20
2. $02 and NH3 Exit Gas Concentrations . . . . . . 22

3. Effect of Varying Water Mole Fraction on 802
Mole Fraction in the Exit Gas at 50°C--
Run 7.26 o o o o o o o o o o o o o o o o o o o 24

4. Effect of Converting All Sulfate to Sulfite
and Bisulfite O O O O O O I O O O O C O O O O O 27

5. PrOperties of the Experimental Solutions . . . 48

iv

LIST OF F IGURES

Figure Page

1. Equilibrium partial pressure of SO and
NH3 over ammoniacal solutions . . . . . . . . 6

2. Flowchart of experimental apparatus . . . . . 10

INTRODUCTION

The Lansing Board of Water and Light, because of
size and location factors, burns coal to generate elec-
tricity. Since this coal generally runs 2 to 3 percent
sulfur, sulfur dioxide is one of the by-products of the
power plants. The concentration of sulfur dioxide in the
stack gas approximates 2000 parts per million (ppm). This
constitutes an air pollution problem which the Board of
Water and Light is interested in correcting. With this end
in mind,.the Board of Water and Light sponsored a project in
the 1970-71 academic year at Michigan State University to

study a means of SO removal.

2

After several alternatives were investigated, an
absorption system using a solution of NH4HSO3, (NH4)ZSO3 and
(NH4)ZSO4 was chosen as the most feasible for use by the
Board of Water and Light.

The first phase of the research was conducted in
1970 and 1971 at Michigan State University. A packed bed
absorption column and the associated equipment were built.
The system was Operated in the lab using a mixture of

nitrogen, air and sulfur dioxide to simulate flue gas.

The work was quite successful, and from it an equation

to determine the rate of absorption of sulfur dioxide as

a function of liquid and gas flowrates was developed (1).

A similar equation was developed for ammonia losses from
the solution. This project was an extension of that work.
The column was moved to a power plant so that it could be
Operated using actual stack gas. The first purpose of this
project was to see if the column worked using stack gas.
The second purpose was to derive equations similar to those
of Auvil that would describe sulfur dioxide absorption and
ammonia losses in the column. A comparison between Opera-
tion in the plant and in the lab could then be made. The
ultimate hope was that the data taken for this work could

be the basis for design of a pilot plant.

THEORY

The absorption—desorption reactions of $02 and NH3

gas with a solution of NH4HSO3, (NH 803, and (NH4)ZSO4

4)2
were studied by Johnstone (5) who developed the following

equilibrium equations:

SO()+SO +HO+
2g 3 2 3

1.
N
:r:
U)
Q
I

... + ._
NH3(g) + H803 +H20 + NH4 + so3 + H20

and H 0 above the

The partial pressure of 802,

solution can be written as:

_ 2
(ZS/Ceff 1)

eff (l-S/C (1)

PSO =MC

eff)

(l- S/C )
P = N c eff

NH (zs/ceff - I) (2)

 

_ 100
PHO'Pw IOO+C+S+A (3)

The variables have the following definitions:

P = partial pressure of SO over solution
SO 2
2 (mm Hg)
PNH = partial pressure of NH3 over solution

3 (mm Hg)

Log M

Log N

eff

S/Ceff

Ceff (ZS/Geff-l)

Ceff (l‘S/Ceff)

It is noted that

0 over solution

partial pressure of H2

(mm Hg)

vapor pressure of H20 over solution
(mm Hg) '

5.865 - 2369/T
13.680 - 4987/T
temperature (°C)

moles H 0

moles 2

so4=/100

moles H 0

moles 2

NH4+/1OO

C -2A

moles reactive NH4+/100 moles H O

2

of H50 - and 80 =

moles 3 3

moles of H80 - and SO = per mole of re-

active NH4+ 3 3

moles HSO3—/100 moles H20

moles SO3=/100 moles H20

Johnstone's work was done in the lab with

uncontaminated solutions.

Chertkov (2) made an additional correction to

Johnstone's equation for the partial pressure of SO
account for the effect of SO =

oxidation of sulfite in solution.

2 to

4 which is the product of the

His data indicated that:

Ceff+A
eff

_ I
P802(true) — Psoz(calc d)

where P (calc'd) is the so
802

Johnstone's work.

2 partial pressure derived from

3 and H803 per mole

absorption and NH

The ratio S/Ceff (moles SO

reactive NH4+) describes the SO2 3

desorption characteristics of a solution. The range of
S/Ceff 13 from 0.5 (pure SO3 ) to 1.0 (pure HSO3 ). By

looking at the equilibrium equations presented earlier, it

eff 3
promote both 802 absorption and NH3 desorption while high

can be seen that low S/C values (SO rich solution)

eff 3
It is not possible therefore, to have high 802 recovery

S/C values (HSO rich solution) have the reverse effect.

without considerable NH3 loss. A compromise must be made,

and in general, a value of S/C approximately 0.7 is

eff
desirable for a single column absorber. Figure 1 shows a

plot of the partial pressures of SO and NH3 predicted by

2
Equations 4 and 2 as a function of the S/Ceff ratio of the
liquid. The NH4+ and 804: concentrations were typical of

those in the experimental work of this project.

 

 

 

0.4 '
I
Temperature = 50°C
,. +
m C = 10 moles NH /100 moles H 0
m 4 2
E A = 0.3 moles so4=/1oo moles
0 H20
5
U)
m
H
m
H
m
-H
4.)
n
m
m
0 0 l 1 1 l J_ l
0.60 0.65 0.70 0.75 0.80 0.85 0.90

S/Ceff moles SO in liquid/mole reactive NH

2 4

Figure l. Equilibrium partial pressures of 802 and NH3 over
ammoniacal solutions.

EXPERIMENTAL EQUIPMENT

The experimental equipment was designed and built by
Steven R. Auvil. Several of the important design criteria
should be reviewed. The column was divided into two, four-
foot sections so that a column height of either four feet
or eight feet could be used. The first four foot section
of column was used in this work. The columns were made of
3.75 inch diameter plexiglass and packed with one-half inch
Rashig rings. The design operating temperature for the
absorption column was 50°C with gas velocities Of two to
three feet per second. The design L/G ratio was one.
The column and its associated equipment were mounted in a
portable framework so that the system could be moved to a
power plant for use with actual stack gas. Further design
conditions can be found in Auvil's M.S. thesis (1:33-39).
Auvil's operation of the equipment in the laboratory using
a synthetic stack gas showed that the column performed as
expected. After several preliminary runs had been made in
the laboratory, the column was moved to the Eckert Power
Station of the Board of Water and Light. During the runs
in the lab and early runs at the power plant, several

modifications to the apparatus were made. A pump that

had been used to recirculate liquid in the feed tank was
replaced by a propeller stirrer. It had been observed that
the pump was returning tiny air bubbles to the tank. In the
lab experiments, three gas rotameters had been required
since the inlet gas was made up of nitrogen, air, and 802'
At the power plant only one was needed. The 802 rotameter
was disconnected, and the air rotameter was removed. The
nitrogen rotameter which had the largest capacity was used
to measure the flow of the stack gas. It had been expected
that the gas heater that had been used in the lab would not
be required at the power plant. However, because of the
heat loss in the long run (50 feet) of pipe from the stack,
it was necessary to use the gas heater. A pressure tap was
added just before the gas rotameter, and another was added
at the tOp of the first column. This second pressure tap
was also used to measure the temperatures of the exit gas
and to bleed off a stream for analysis by the infrared
spectrophotometer. Thermometers were inserted in the
tubing carrying the liquids to and from the column.

In the lab the humidifying column had been supplied
from a hot water tap. On the tOp floor of the power plant
where Operations were set up, hot water was not available.
The problem was solved by pumping water from a collection
bucket at the bottom of the humidifying column back to the

tOp of the column. The water then trickled down through

the column and back into the collection bucket. Recycling

the water in this way allowed the gas to heat it up to about
50°C as required. Another advantage of the scheme was that
the buildup of flyash in the humidifying water could be
observed. A

The gas was delivered to the column by two small
blowers piped in a parallel arrangement. The delivery line
and the stack sampler were 1.5 inch iron pipe. The sampler
had two sets of one inch by four inch slots opposite each
other spaced at four-inch intervals along its length. The
probe extended about half way across the stack. The end of
the probe in the stack was left open to facilitate back-
flushing with pressurized air. One air hose fitting was
placed at the exposed end of the probe, and another just
before the blowers. A gate value was used to throttle the
air to the rotameter.

Figure 2 is a schematic diagram of the system used
at the power plant. The path of the gas and liquid streams

are described below.

The Path of the Gas Stream

 

l. The two blowers delivered gas from the stack to the
gas rotameter.

2. The gas passed through an iron pipe with a heating
element and then entered the humidifying column.
This column was two feet tall by 3.75 inches in

diameter and was packed with 1/2 inch Rashig rings.

10

.msumummmm Hmucofiwummxm mo unmnozoam .N wusmwm

:--—§m

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

mmmu OHQEMm
Emeuw cucuom

Smmuum nonpoum
Emmflm comm
umumo: paw mewfi nufl3 xsmu comm

 

 

 

xcmu wmusm
masm mcfiumasouflomu kumx

...IIY m gaoo Goaumnomnd

GEOHOO mcfimmwpwfibm
Hounds mow

 

% mum3oHn mam

.m
..n
A
.n
.m
.m
.0
6
.0
.n
.M

11

The water circulated through the column at 50°C.
The gas left the column water-saturated at 50°C.

A variac connected to the gas heating element was
used to hold this temperature.

The gas next entered the absorption column through
a crowned riser. The riser kept the liquid out of
the gas line.

After leaving the column, the gas was vented to the
room and a roof fan exhausted it to the atmosphere.

Sample ports for SO analysis of the gas were

2

located just before and just after the absorption

column.

The Path of the Liquid Stream

1.

Liquid in the feed tank was mixed by a propeller
stirrer and heated to 50°C by a glass encased
heating element controlled by a variac.

Liquid was pumped through a rotameter and delivered
to the tOp of the column through a sprinkler head.
The liquid trickled through the packing to a small
pool in the bottom of the column. This pool sealed
the liquid piping system from gas and acted as a
reservoir for the return pump.

The liquid was then pumped back to the mixing tank.
A valve on this line was used to keep a constant

liquid level at the bottom of the column.

5.

12

A small product stream was taken off from the
return liquid. This stream removed an amount of
sulfur equivalent to that absorbed as the liquid
passed down the column.

Water was added to the mixing tank to replace that
lost in the product stream.

Ammonia was sparged into the feed tank to react the
the HSO3- formed in the column back to 803:, to

replace NH4+ lost in the product stream and to

replace NH4+ that was lost as NH3 in the column.

EXPERIMENTAL METHOD S

The rotameters had been calibrated in earlier work.
Those calibrations for the feed, product, water and ammonia
streams were used in this work. The gas rotameter had been
calibrated with air at 70°F and one atmosphere. This cali-
bration was corrected to the condition of the stack gas as
it entered the rotameter. Appendix B presents the details
of these calculations. The details of the calibrations of
the infrared cells are given in Appendix C.

Feed was made in the lab in six liter amounts. Four
liters of distilled water and two liters of 15 molar NH4OH
were mixed in a jug and cooled in an ice bath. ,Sulfur
dioxide was then bubbled into the solution until the pH
had fallen to 6.4. The process took about two hours. An
attempt was made to use the feed within a few days. This
kept the 804= concentration fairly low.

The start-up procedure in the power plant was as
follows:

1. The pipe from the stack to the blowers was back-
flushed with compressed air. Then the blowers were
disconnected from the column and turned on momen-

tarily. These two steps removed any flyash that

had settled in the gas delivery system.

13

14

The blowers were then connected to the column and
turned on. The heater was also turned on.

The pump supplying the humidifying column was turned
on and the liquid level in the bOttom of the column
established. This liquid pool prevented the hot gas
from deforming the crowned riser and the bottom
section of the humidifying column.

Feed was added to the tank at the top of the column.
Both the mixer and heater in the feed tank were
turned on. When the liquid had reached 50°C (about
20 minutes), the heater was turned off.

After 30 to 45 minutes the gas leaving the humidi-
fying column was at 50°C. The gas leaving the
absorption column was between 48 and 50°C at this
time. The system was now ready for the.final steps
of the start-up.

The feed pump was turned on with the rotameter wide
open until about 500 ml of feed had entered the
column flushing out the condensate that had formed
in the packing during warmup. When the column had
been flushed, the feed rotameter was set at the
desired flow rate. The feed that had been used to
flush the column was drained off and thrown away.
When a pool of liquid had formed-in the bottom of

the absorption column, the recycle pump was turned

15

on and set at a rate that kept the liquid level
in the column steady.

8. The product stream and the water stream were
turned on at the desired settings.

9. The ammonia was turned on at an initial setting

of 40 cubic inches per minute.

At this point the column was in full operation and
the run itself began. During the run the pH of the feed
tank was measured periodically, and, if necessary, the
ammonia flowrate was adjusted to keep the pH constant.

The inlet-gas sample line was run to a drying bottle
packed with calcium sulfate and then to the inlet-gas sample
cell for analysis by the infrared spectrOphotometer. It
took from 30 to 45 minutes for the line, the trap and the
cell to be purged. The exit-gas sample was bubbled through
a flask half full of concentrated sulfuric acid and then
passed through a drying chamber and on to the infrared gas
cell. It was necessary to add a suction blower just before
the acid trap in order to get enough flow to purge the acid
flask, the drying chamber, and the gas cell. The function
of the acid flask was to remove most of the water from the
gas. It also absorbed NH3 from the gas so that the SO2
concentrations derived from the gas cell were on an ammonia

and water-free basis. The flowrate to the gas cell was such

that the capacity of the drying chamber was too low to

16

completely dry the gas passing through it. Details of the
work done with the infrared cells can be found in Appendix C.

Samples of the inlet liquid were taken twenty and
forty minutes into the run. After sixty minutes both the
inlet and exit streams were sampled. The three inlet liquid
samples were used to observe how the system was approaching
steady state. The inlet and exit samples taken at the end
of the run were used to observe the degree to which SO2 was
absorbed and NH4+ lost as the liquid passed through the
column.

It was necessary to monitor the inlet and exit
liquid temperatures and the inlet and exit gas temperatures
(both dry and wet bulb). The pressures at the gas rotameter,
the bottom of the column and the tOp of the column were also
Observed. When the final liquid samples had been taken, the
wet and dry bulb temperatures just prior to the absorption
column and just after the blowers were measured.

Shutdown of the column was fairly rapid. All valves
were closed and the heaters and pumps shut off. The feed
remaining in the tank was drained and replaced with dis-
tilled water which was used to rinse the packing. This
distilled water was removed at the bottom of the column

and thrown away. An air line was connected to the column

for a few minutes to blow the stack gas out of the system.

17

+, HSO ’,

The liquid solutions were analyzed for NH 3

4
and 803:, while SO4= was determined by a charge balance.

3 4 , the

determination of $03: was started within two hours of

shutdown. That analysis took about three hours. The other

Because the SO = had a tendency to oxidize to SO =

analyses were done as soon as possible. The reagents used

in the titrations (KOH, H2804,

standardized for each run. Analytical procedures can be

and KI/I2 solutions) were

found in Appendix A.

DATA

The gas entered the absorption column at 50°C. It
was not possible to keep the liquid temperature at 50°C due
to the heating effect of the return pump. The inlet liquid
temperatures ranged between 57 and 60°C. The exit liquid
temperature was between 50 and 52°C. The gas left the
column at about 53°C. Pressure readings were taken at the
gas rotameter and the bottom and tOp of the column. The

concentration of SO in the inlet and the exit gas was

2
measured using an infrared spectrOphotometer. The cell

used for the inlet gas had a path length of 7.6 cm, and

the gas cell used for the exit gas had a path length of

one meter. The inlet gas SO2 concentration varied from

1500 to 2400 parts per million. The exit gas concentrations
were measured for three runs. The results were very low,
one at two hundred parts per million and the others about
fifty parts per million. The exit gas 802 concentration was

also calculated by a material balance, but the results were

unsatisfactory. The liquid solutions were analyzed for
+ - =

NH4 , H803 and SO3 . A charge balance was used to deter-
mine SO4=. The NH4+ concentration was approximately 4 molar
while the H503- and 803- both varied between 1 and 2 molar.

18

19

The 804: concentration was very low in all cases (about
0.2 moles per liter).

The physical properties of the liquid, viscosity,
density, and molecular weight, for each run are given in
Appendix B. These prOperties were calculated using methods
presented by Auvil (1:101-102).

Two series of runs were planned, one at a constant
gas rate and one at a constant liquid rate. The constant
gas runs were made at a gas velocity of 500 lb/hr/ft2 with
the liquid varying from 290 to 480 lb/hr/ftz. The constant
liquid runs were made at 360 lb/hr/ftz. The gas rates were
to have varied from 360 to 700 lb/hr/ftz. However, the runs
at the highest gas rate were not made since they would have
produced no new information. The gas and liquid rates were
similar to those Auvil (1) used.

Table 1 presents the data for the nine runs made.

A more complete listing including the analyses of the twenty

and forty minute liquid samples is given in Appendix F.

20

.Num memo.0|lcesaoo mo comm Hmcofluomm mmouu
.Oooonhm musumummsmu pfisvfla umHGH .Ooom wunumuwmswu mom DOHQHM

.HOOHH
mom moaofilfimum OH chHumuucoocoo

 

 

 

 

 

o.mmv m.mov m.mmv m.mmm 5.8mm m.nmm m.em~ m.mm~ m.omm Aflumann\nav mpmuzoam
mme.o vmn.o mmn.o mmn.o «mn.o mmn.o mom.o «we.o mm>.o mumO\m
mnma.o mmmH.o mmam.o mmma.o NFHH.o mmom.o meoa.o ammo.o mmma.o uvom
Ommo.a mHHH.H mmmo.a Heca.a ovoa.H «OHH.H some.o memo.H Homa.a "mom
oomo.a mmom.H mmam.m voom.a qvvm.a omvm.a «Hov.m meo.m mamo.~ -mOmm
namm.m mmvv.v Hmmh.v mmma.s momm.v mmmm.s Hmma.v mmnw.v Roam.s +vmz
mGOflHMHuEQUGOU
canvas uflxm
m.mmv m.ows m.oev m.mmm m.nmm H.mmm H.mmm m.omm m.mmm Awpunug\nav wumuzoam
moo.o vHe.o mmn.o woe.o mon.o Hae.o He~.o man.o mae.o LLmO\m
mmoa.o mmmH.o mmma.o sema.o ooaa.o Homfl.o mnmo.o Nome.o emaa.o uvom
ammo.H emmH.H Han.H vvoa.a ooqm.a Hoom.a mmom.o vva.H mmmm.a "mom
memv.a neme.a mmoo.m «moo.a mmmo.a mmme.a emma.m 40mm.a Hamm.a -momm
mmmm.m mmmv.q mman.v nmma.v mamm.v namm.v Hmva.v emsv.v ooam.v +vmz
mCOHHMHUGwUCOU
assess uchH
mam- mam vow mma- ms: ma man was- Ham- Afimn H.0mev mmm uflxm
om -u com om I. u- I: I- nu Aamu.mxmc mum ufixm
omma omoa mmam omma coma owed omoa onva ovma mam umacH
Asmmv oaoo mom
H.mm¢ v.oom o.mmq m.mmv o.mpv o.mms o.vm¢ m.mew m.vhm Auumuun\nac mum“ mmo
momum balm Hmnn momnm Baum owns maum moum mm-»
ucmsflummxm
mmuma Hmucmsflummxm .H manna

DISCUSSION

In the Theory section of this thesis, the equation
for the partial pressures, and hence the mole fractions, of
SO2 and NH3 were developed. Since, in the experiments, SO2
was being absorbed from the gas, its equilibrium mole frac-
tion over the gas was the lower limit on the exit gas SO2
concentration. Ammonia was being desorbed from the liquid
so its equilibrium mole fraction over the solution was the

upper limit for the concentration of NH in the exit gas.

3

Table 2 compares concentrations of 802 and NH3 in
the exit gas with their equilibrium concentrations over the
inlet liquid, which was in contact with the exit gas. In
every case, both by material balance and by direct measure-
ment using the infrared gas cell (in three experiments), the
SO2 equilibrium was violated. All exit-gas concentrations
of 502 were substantially below equilibrium concentrations.
Except for two cases, the concentration of NH3 in the exit
gas was greater than equilibrium allowed.

During most of the early runs, the flow of gas to
the gas cell was too low to flush it. It was not known why

the cell was flushed satisfactorily during Run 7-31. In

the early runs the analysis of the data depended on a

21

22

Table 2. $02 and NH3 Exit Gas Concentrations

 

 

NH3 Exit Gas

 

 

 

502 Exit Gas Concentration (ppm) Concentration (ppm)

Material Measured by Equilibrium Material Equilibrium

Balance Gas Cell Value Balance Value
7-25 -291 - 439 923 415
7-26 15 — 402 262 383
7—31 204 200 537 819 320
8-3 -l94 - 438 566 429
8-16 -45 - 350 810 391
8-17 316 — 470 1024 473
8-18 -79 - 839 169 254
8-3OA -125 50 344 514 385
8-30B -348 36 300 472 376

 

material balance. The flowrates and concentrations for the
inlet gas and the inlet liquid were known. Although the
exit liquid concentrations were known, the flowrate of the
exit liquid was not known due to evaporation losses in the
absorption column. The concentration of 502’ NH3, oxygen,
and water in the exit gas were unknowns. Also, because
these concentrations were unknown, the total exit gas flow-
rate was unknown. By means of a convergence technique (see
Appendix D) the material balance was closed. After some
study it was seen that the mole fraction of water in the

exit gas, or equivalently, the flowrate of liquid out of

23

the column (since the two were directly related), had a
tremendous effect on the material balance. Table 3 shows
the effect for Run 7-26. A very small change in the con-
centration of water in the exit gas caused a tremendous

change in the exit-gas SO concentrations. The NH3 con-

2
centration was not nearly as sensitive to variation of the
water mole fraction. It was not possible to measure either
the mole fraction of water in the exit gas or the exit
liquid flowrate with the accuracy required. The mole
fraction of water is generally calculated from the wet

and dry bulb temperature. The mole fractions shown in
Table 3 (except the equilibrium value) have wet bulbs
within 0.1°C at a constant dry bulb. After these obser-
vations had been made the material balance was considered
to be of little use for analysis. The calculations were
still made for comparison with the gas cell results.

When the material balance was shown to be unreli-
able, efforts to increase the flow to the gas cell were
redoubled. The solution was to insert a suction pump in
the exit-gas delivery system so gas was drawn from the
exit-gas sample taps and blown through the acid flask and
the drying chamber to the gas cell. NeOprene vacuum tubing
was used for the delivery lines. Runs 8-30A and 8-30B were
made back-to-back with the gas cell Operating in this manner.
The two runs were made at the same gas flowrate, but Run

8-30B had a higher liquid flowrate than Run 8-30A. The

24

Table 3. Effect of Varying Water Mole Fraction on SO Mole Fraction in

 

 

 

Exit Gas at 50°C--Run 7-26 2
802 Mole NH3 Mole
Water Mole 'Fraction Fraction
Fraction (ppm) (ppm)
Equilibrium values .151651 402 383
Mat'l bal. results .127963 15 262
.128069 -150 284
.127961 16 262
.127877 150 244
.127813 250 231
.127748 350 218
.127684 450 205
.127620 550 191
.127556 650 178

 

inlet gas for the two runs had the same mole fraction of 502'
Run 8-30B, made at the higher liquid flowrate, had a lower
concentration of 802 in the exit gas. This was as it should
have been according to Auvil's work (1:67-77). He had shown
that as the liquid rate increases, the absorption of 502
increases. The results of these two runs were evidence that
the absorption characteristics of the column were as expected,
and the equilibrium was different. After these two runs the
gas cell was calibrated again. Table 2 indicates that the
concentrations were 50 and 36 parts per million, respectively,
for Runs 8-30A and 8-30B. Both of these were very much

below equilibrium.

25

These results lead to the conclusion that equilibrium
over ammoniacal solutions in contact with actual stack gas
is radically different from that of solutions in contact
with uncontaminated gas. Apparently some trace material in
the stack gas (perhaps nitrates or nitrites formed by absorp-
tion of nitrogen oxides or even some component of fly ash)
have a great effect on the equilibrium partial pressures of
SO2 and NH3 over these solutions.

The possibility that nitrates or nitrites inter-

3 and H803 in the

liquid solutions would substantially affect the equilibrium

fering with the chemical analysis of SO

values of 802 and NH3 over the solutions was investigated.

Solid nitrates and nitrites were added to separate portions
of unused feed to make their concentration about 0.2 moles
per liter. Both anions interfered with the titrations. The

interferences were such that, if there were N03= or N02- in

3 and H803 would

be greater than the values determined. The sulfate calcu-

the liquid, the true concentrations of SO

lated by a charge balance on the NH4+ (which presumably

would not be affected) and the HSO3- and 803:, would then

be less than the value originally determined. Sulfate

concentrations for the runs were already quite low, 0.2

molar or less. By decreasing the SO4 concentrations to

3 and then the H503- to

balance charges, the maximum effects on the equilibrium

zero and increasing first the SO

26

was observed. Table 4 presents these changes and the
resultant change in S/Ceff ratios for two runs. The effect
on S/Ceff was small. By referring back to Figure 1 it can

be seen that such changes in S/Ce would cause little

ff
change in the equilibrium of the solutions. The indication
was that the effect of nitrates and nitrites, if present,
on the analyses for HSOB_ and 803: was not large enough to
allow the resultant changes in H80

3 , 803‘, and 504: to
change the equilibrium greatly. However, the direct effect
of dissolved nitrates or nitrites on the equilibrium could
not be speculated upon. It was apparently a direct effect
of the nitrates or nitrites or some other trace constituent
that was causing the equilibrium to shift.

The column was located on the tenth floor of the
power plant, so that the tap into the stack was above the
precipitator. Precipitators remove most Of the flyash in
the stack gas, but removal efficiency decreases as particle
size decreases. Consequently, the ash that reached the
column was the fines that had passed through the precip-
itator.

Two distinct periods of flyash loading were observed.
The loading was moderate in May and June and very heavy

during late July and August. This difference corresponded

to the plant's switch to a higher ash coal.

27

Table 4. Effect of Converting All Sulfate to Sulfite and Bisulfite

 

 

Concentration of Inlet Liquid (moles/l)

 

 

Original All 804: All SO4=
Run Specie Data Converted to $03= Converted to HSO3’
+
7-28 NH4 4.55169 4.55169 4.55169
8803' 1.75853 1.75853 2.13939
803: 1.20605 1.39658 1.20615
$04: 0.19043 0 0
.7 . .7
S/ceff 0 11 0 693 0 35
8-17 NH4+ 4.43365 4 43376 4.43376
Hso3' 1.78769 1.78769 2.04634
so3= 1.19371 1.32304 1.19371
s04- 0.12933 0 0
S/C 0.714 0.702 0.731

eff

 

28

Under moderate loadings the system was affected very
little. After a total of about fifteen hours of operation a
slimy layer of flyash had formed on the Rashig rings at the
bottom of the humidifying column. This slime caused no
problem whatever. Several times the humidifying column was
disassembled and the slime, while it was wet or after it had
dried, could easily be wiped off. There was no hardening
and apparently the buildup stopped after the initial layer
had formed.

Under heavy flyash loading the layer of slime
remained unchanged. However, the water recirculating in the
humidifying column became heavily loaded with flyash during
a run. The liquid was Opaque black. This heavy loading in
itself caused no change in the basic operation of the humid-
ifying column. The only problem was that the spray nozzle
on the inlet line to the column occasionally got blocked and
had to be blown out.

Toward the end of the experiments, after about forty
hours of operation, a very small amount of flyash was noted
in the feed solution. Several times bits of flyash were
found in the liquid samples. Two or three times late in
the project flyash was caught in the needle valve control-
ling the feed flowrate. After Opening and closing the valve
several times, the flyash was carried through the rotameter
and on to the column. When flyash was caught in this valve

it was difficult to keep the liquid flowrate from dropping,

29

but after the flyash had worked loose, the rotameter held
steady.

The humidifying column was very effective in
removing the flyash carried in the gas.. No buildup at all
was Observed in the absorption column, and only a few bits
of flyash were seen in the absorption liquid. When there
were only a few runs left to be made, the delivery pipes
from the stack and the blowers were disassembled to see if
there had been any buildup of flyash in them. There was a
definite coating in both, perhaps 1/8 inch thick. There
was no indication of blockage, and it was felt that the
coating would not continue to build up to block the pipe
or the blower.

During runs made in May and June, a phenomenon later
named blue haze, was observed. This was a blue smoke or
haze that was present at the final outlet of the system.

A blue plume up to two feet tall was observed at times. At
other times the blue haze would have the characteristics of
a heavy rolling smoke. The blue haze was not present during
the late July or August runs. There was no correlation
between the amount or type of blue haze and the liquid
solutions. Work done at TVA (3:5) indicates that the blue
haze is made up of fine ammonium sulfate particles. During
some of the runs qualitative tests to determine the compo-

sition of blue haze were made, but they were inconclusive.

CONCLUSIONS

Observations

 

The major result of this work was to demonstrate
that the absorption column worked using actual stack gas.
There were several components in stack gas whose effects
were unknown at the outset of this work. For instance,
many of the impurities in coal go up the stack in some form.
The presence of flyash was also a new factor. The effect of
the components of flyash on the liquid solutions was unknown.
There had been concern that the SO3= might have been oxi-
dized to 804: by catalytic action of some trace component.
However, these possible interferences to operation of the
column were shown to be nonexistent in practice. The column
did absorb SO2 in a way somewhat similar to that expected.

In fact, experimental measurements showed that the
column absorbed much more SO2 than theoretically possible.
It was apparent that the equilibrium partial pressure of
$02 was much lower than was predicted from laboratory
studies. The equilibrium studies made by Johnstone and
discussed in the Theory section of this thesis apparently

do not apply for ammoniacal solutions in contact with con-

taminated stack gas.

30

31

The lack of applicable equilibrium data made it
impossible to predict the operation of the column. Since
the equilibrium concentration of SO2

the driving force, that is, the difference between actual

(or NH3) was unknown,

and equilibrium concentrations, was unknown. The equations
for the height of a gas transfer unit which are used to
predict operation of an absorption column are based on this
driving force.

It had been anticipated that flyash might cause
considerable problems in the operation of the absorption
column. However, this was not the case. The humidifying
column removed virtually all of the flyash in the gas.
Because of this, the absorption column was unaffected by
flyash. The main problem associated with flyash removal in
a humidifying column in a plant operation would be that the
liquid would become loaded with flyash. A clarifier which
would allow the flyash to settle out would take care of that
problem.

The occurrence of blue haze was noted but not
explained. It was possible that weather conditions were
responsible for the phenomenon. Blue haze is certainly one
of the things to be reckoned with before an ammoniacal
scrubbing system is built into a power plant. A thick blue

plume pouring out of a stack would be unacceptable.

32

Recommendations

 

It is necessary to know the equilibrium character-
istics of ammoniacal solutions in contact with stack gas.
This suggests a very time-consuming and difficult study.
However, at present, without the equilibrium data, design
of a pilot plant or large-scale facility for removal of
sulfur dioxide by this method is guesswork.

On the other hand, if scheduling is such that a
pilot plant must be built, it could be done using Auvil's

work secure in the knowledge that SO absorption from flue

2
gas was greater than that from synthetic stack gas in all
eXperiments. This would lead to an over-designed process
whose Operation was not understood and hence could not be
predicted. It would seem that a very reasonable path would
be to design the pilot plant, and at the same time proceed

with work to determine the equilibrium characteristics of

the liquid in contact with stack gas.

BI BL IOGRAP HY

Auvil, S. R. "An Investigation of the Absorption of
Sulfur Dioxide by an Ammoniacal Solution in a
Packed Column." Unpublished Master's thesis,
Department of Chemical Engineering, Michigan State
University, 1971.

Chertkov, B. A., and N. S. Dobromyslova. "The Influence
of Traces of Sulfate on the Partial Pressure of 802
Over Ammonium Sulfite—Ammonium Bisulfite Solutions."
J. Appl. Chem. U.S.S.R. ‘31(8), 1707-11, Aug. 1964.

Falkenberry, H. L., A. V. Slack, and F. E. Gartrell.
"Control of Fossil Fuel Power Plant Stack Gas
Effluents." Presentation to The American Power
Conference, 34th Annual Meeting, Chicago, 111.,
April 20, 1972.

Fischer, K. "How to Predict Calibration of Variable-
Area Flow Meters." Chem. Eng., 5246), 180-184,
June 1952.

Johnstone, H. F. "Recovery of SO from WaSte Gases."
Ind. Eng. Chem., 21(5), 587-9 , May 1935.

Perry, J. H., C. H. Chilton, and S. D. Kirkpatrick.
Chemical Engineers' Handbook. New York: McGraw-
HiII Book Company, 1963. Third Edition.

 

33

APPENDICES

APPENDIX A

ANALYTICAL CHEMISTRY

The procedures used to determine concentrations of

+ =
(NH4)2803' NH4HSO3, total NH4 and SO4 are presented here.

They are adapted slightly from standard analytical tech-

niques. The amount of each solution used was based on the

expected concentrations of SO3 (less than two molar), H803-

(also less than two molar) and total NH4+ (less than five

molar). Standard KOH and H2804 were used. Their approx-

imate concentrations were 2 and 1 molar, respectively.
Potassium phthalate was used to standardize the base.
4)ZSO3 deter-

A standard solution

The standard KI/I2 solution used in the (NH
mination was about 0.3 molar in 12.
of sodium thiosulfate was_used to standardize this solution.
Potassium iodate was used to standardize the thiosulfate.
The determination of (NH4)ZSO3 was done first because the
sulfite was easily oxidized to sulfate. The other titra-

tions were done within twelve hours of the experimental run.

Determination of (NH4)ZSO3

 

1. Pipet 100 ml of standard KI/I2 solution (0.3 molar
in I2) into a 300 m1 Erylenmyer flask and dilute to

200 ml with distilled water.

34

35

Titrate the KI/I2 solution with sample until it
turns pale yellow. The flask must be swirled
constantly to avoid the production of 802°
Add five drops of starch indicator. This turns the
solution a dark blue-black.

Titrate the solution with standard KI/I2 to a clear

endpoint. This endpoint is very sharp, and the

slightest excess turns the solution pale yellow.

Reactions: (NH4)HSO -+I -+H O-+(NH4)HSO -+2HI

 

3 2 2 4
(NH4) 2803 + 12 + H20 + (NH4)ZSO4 + 2HI
(m1 KI/IZ)(Izconc) (NH4)HSO3

 

((NH4)2SO3) = (m1 sample)

Determination of NH4HSO3

 

l.

Pipet 25 ml of sample into a flask and add 150 ml of
distilled water. Cool the solution in an ice bath.
Add quickly 25 m1 of 30% H202 which is also ice
cold. Stopper the flask and swirl in the ice bath
until the bottom of the flask does not warm to the
touch when taken out of the ice bath. This proce-

dure is done in the ice bath because the reactions

are quite exothermic.

Reactions: (NH

 

‘1)280:3 + H202 + (NH4) 2804 + H20

(NH4)HSO3 + H202 + (NH4)HSO4 + H20

 

36

Let the flask sit in the ice bath a few minutes and
then set it out of the bath for ten minutes to
insure that the reactions are complete.

Add methyl red indicator (5 to 10 drops) and titrate
with standard KOH (two molar) to a bright yellow

endpoint.

-+K SO -+2H 0

Reaction: 2KOH-+ 2(NH4)HSO4-+(NH4)ZSO4 2 4 2

 

_ (ml KOH to titrate)(conc KOH)
(NH4)HSO3 _ m1 sample

Determination of Total NH4+

 

The sample is then boiled, releasing NH

In this procedure excess KOH is added to a sample.

3. The NH3 15 passed

through a condenser and bubbled into standardized sulfuric

acid which reacts with it. The acid is then titrated with

KOH and the concentrations of NH + in the sample back-

4

calculated.

1.

Place 100 ml of standardized H2804

flask or other receiving vessel. Add distilled

(one molar) in a

water so that when the delivery line from the con-
denser is put in the acid, the NH3 will have to
bubble through a fair height (at least four inches)
of acid.

Place the delivery tip in the acid container. Ready

the condenser so that the boiling flask containing

37

the sample can be attached quickly. Turn on the
water.

Pipet 25 ml of sample into a 500 ml boiling flask.
Add 100 ml distilled water and some boiling chips.
Add 100 ml KOH and quickly attach to the condenser.
Boil the solution until about half of it has passed
over. Most of the NH3 is produced when the solution
starts boiling. Care should be taken at this point
so that boiling is gentle. This allows the first

surges of NH to be trapped by the acid before

3
reaching the liquid surface. After a few minutes
of boiling, acid is drawn up into the delivery tip
of the condenser. When this happens the joint
between the condenser and the delivery tip must be

cracked for an instant to allow the liquid to fall

back into the acid container.

Reactions in the boiling flask:

 

2 KOH-+2(NH4)HSOB-+KZSO3-+(NH4)ZSO3-+2HZO

A
Then 2 KOH + (NH4) 2803 -> KZSO3 + ZNH3 + ZHZO

Reactions in the collecting flask:

 

ZNH +H SO + (NH4)ZSO

3 2 4 4

The sample may be boiled vigorously from this point
on. After about half of the solution has boiled

over, check the gas for NH by momentarily dis-

3
connecting the boiling flask and putting wetted

 

 

38

pH paper in the neck of the flask. If NH3 is
present, quickly reconnect the flask and continue
boiling. Recheck periodically until the test is
negative. I

7. Titrate the excess acid with standard KOH using

methyl red as an indicator.

Reaction: HZSO4-+2KOH-+KZSO4-+2HZO

2 [ (ml H 804) (conc H2804)--§ (ml KOH) (conc KOH)]

ml sampIe

+

_ 2

Determination of SO4=

 

A charge balance was used to calculate the SO4

present in the liquid.

= + - =
so4 — 1/2 [NH4 -Hso3 —2(so3 )J

APPENDIX B

ROTAMETER CALIBRATION

The gas rotameter had been calibrated with air at
70°F and 760 mm Hg. The rotameter was used under different
conditions with a different mixture of gases so the calibra-
tion had to be corrected. The differences were the tempera-
ture, the pressure and the constituents of the gas. These
differences all affected the density. The following
equation adapted from Perry (6:3-43) was used:
= KS 32 (5)

Ka p

leuQ
01

DJ

q = volumetric flowrate (cu ft/min)
p = density (lb/fta)
K = flow parameter

The subscript "a" referred to air while 5
referred to the stack gas. The flow parameter "K" was

a complex function of viscosity and density. It was not
easily solved for, but a graph by Fischer (4) indicated

that the values of Ka and KS were identical. The equation

for the corrected flowrate could then be written as:

39

4O

0
qs=qa /;—3 <6)

The density of air was its density at 70°F and 760 mm Hg.
The value used for the density of stack gas was a weighted-
mean density based on the percentages and densities of its
components. The stack—gas density was that at the tempera-
ture and pressure at the rotameter. Since these conditions
varied from run to run, the rotameter calibration was cor-
rected for each run.

Between the rotameter and absorption column water
vapor was added to the gas. The humidity correction was
made in the computer program used for data analysis. To
make the correction, the wet and dry bulb temperatures,
which were measured at the rotameter and the absorption
column, were used to find the two dewpoints. IA subroutine
calculated the partial pressure of water in the gas at the
tWo locations. Dividing by total pressure at each point,
the mole fraction of water was calculated. Then the gas

was put on a dry basis:

qdry = qwet (l-yr) (7)

where yr was the mole fraction of water at the rotameter.
The gas was put back on a wet basis by using the same

equation in a transposed form:

41

q = qdrY/(l-yc) (8)

wet

with yC being the mole fraction of water in the absorption

column.

APPENDIX C

INFRARED ANALYSIS FOR SULFUR DIOXIDE

Sulfur dioxide has a quantitative peak in the
infrared frequency range between 1400 and 1500 cm-1. This
peak was used to measure the $02 concentration in the inlet
and exit gases. Two sample cells were used, one for the
inlet gas and one for the exit gas. The cell used for the
exit gas had a longer path length (1 meter compared to 7.6
cm) because it was measuring lower concentrations.

Before the cells were calibrated it was necessary

to calibrate the SO rotameter in the experimental apparatus.

2
Air and 802 were then metered through their respective rota-
meters and run to a hood. A small portion of this gas was
bled Off to the infrared sample cells for the calibrations.
The short cell used for inlet gas was calibrated between

1600 and 2800 parts per million SO The gas cell was

2.
calibrated between 510 and 1800 ppm 802 and then extended
to zero by a smooth curve.

As has been mentioned, early attempts to use the gas
cell met with poor results. Use of the suction blower on

the exit-gas sample line was the solution, but the first

time it was tried, the gas cell was damaged. The acid flask

42

43

was not used that time, and water got into the cell. It
fogged the sodium chloride windows and spotted the mirrors
in the cell. The windows were repolished, but the mirror
damage was permanent. Recalibration was necessary. This
was done by using standard 802 rated at 510 parts per
million. The calibration plot could then be adjusted
downward using the old and the new peak heights at that
concentration. The new peak was just about half as tall
as the original peak at 510 ppm. The calibration plot was
decreased by the ratio of the new peak height to the old.

The first attempt at recalibration was unsuccessful
because the windows had not been tightened down enough after
they had been taken out and polished. This allowed 502 to
leak. The second attempt gave satisfactory results. The
cell was evacuated and the windows tightened until the cell
would hold a vacuum of ten inches Hg. The cell was filled
with standard SO2 and then evacuated again. This procedure
was repeated several times to insure that all the air in the
cell had been removed.

The concentrations of 802 in the exit gas, as
measured by the gas cell after recalibration, were quite low.
Although it was thought to be very doubtful, the possibility
that the concentrated sulfuric acid might be absorbing some
SO2 was checked. The peak heights using the delivery system

with the acid flask included and with it bypassed were

compared. The short cell and inlet gas were used in this

44

experiment to avoid the possibility of damaging the gas
cell a second time. This was felt to be acceptable since
the delivery system and not the cell itself was being
checked. The peak obtained with the acid flask in this
system was actually slightly higher than the peak obtained
when the flask was left out.

This brings out the possibility that water in the
drying chamber used for the inlet gas might have actually
absorbed some SO2 going to the infrared spectrophotometer
for analysis. A check of the effect of increasing the SO2
inlet concentrations was made, but the change in the results

were small. However, in future experiments, it would be

sensible to incorporate an acid flask in both drying systems.

APPENDIX D

DETERMINATION OF FLOWRATES

A material balance on the column was used in the
computer analysis to determine the flows of those species
not measured experimentally. The inlet flows of all com-
ponents were known. The fraction of oxygen in the inlet
gas was assigned at 6 percent based on information from the
Board of Water and Light. The concentrations of the solutes
in the exit liquid were known, but the total liquid flowrate
was not. The NH

SO oxygen and water vapor leaving the

3! 2!
column were not known. The material balance was based on
the water in the system.

Using data from Perry (6:3-43) an expression for

the vapor pressure of water as a function of temperature

was written:

Pvp = exp (-29.8799 +0.1632T- 0.0017547T2) (9)

where Pvp is the vapor pressure of water in mm Hg and T is
the Kelvin temperature. The constants in Equation 9 were
temperature-sensitive making it accurate only between 60

and 40°C. Equation (3) in the Theory section of this work

45

46

expressed the equilibrium partial pressure of water over

an ammoniacal solution in terms of the solute concentrations
and the vapor pressure of water over the solution. The
vapor pressure was calculated by Equation 9 using the liquid
temperature.

The mole fraction of water in the inlet gas was
known from the wet and dry bulb temperature measurements.
Since the gas was saturated, the partial pressure of water
in it was equivalent to the vapor pressure of water at that
temperature. This partial pressure was related to the
liquid temperature leaving the column by Equations (3)
and (9).

The unknown flowrates could then be calculated using
material and heat balances. The mole fraction of water in
the exit gas was guessed, and then the material and heat
balances were used to calculate an exit liquid temperature.
This value was compared with the temperature derived from
the inlet gas conditions. If the temperatures did not match,
the mole fraction of water in the exit gas was adjusted
which in turn affected the 802, NH3 and oxygen mole frac-
tions. This gave a new exit liquid temperature which was
again checked against the liquid temperature derived from
the inlet gas conditions. The convergence was complete when
the two temperatures matched. When experimental measure-

ments of exit-gas SO were used, the procedure was the same

2

except that the mole fraction of SO was fixed.

2

47

The weak point in this technique was the measurement
of the gas temperatures. The vapor pressure of water is
very sensitive to temperature. Hence, it was not possible
to fix the partial pressure of water in the inlet gas with
enough accuracy for this procedure to work satisfactorily.
The material and heat balances are incorporated in the data

analysis program (Appendix F) as Subroutine TCALC.

APPENDIX E

PHYSICAL PROPERTIES OF THE SOLUTIONS

The physical prOperties in Table 5 were used in the

analysis of the data. The average of inlet and exit liquid

prOperties was taken. Auvil (1:101-102) presented the

methods for the calculations.

Table 5. Properties of the Experimental Solutions

 

 

Specific Viscosity Molecular Moles Water per

 

Run No. Gravity (Op) Weight Mole Solution
7-25 1.15 1.20 24.20 0.932
7-26 1.15 1.19 24.31 0.932
7-31 1.17 1.23 24.49 0.924
8-03 1.15 1.19 23.88 0.933
8-16 1.14 1.19 23.69 0.936
8—17 1.15 1.19 23.80 0.934
8-18 1.14 1.19 23.79 0.933
8-30A 1.14 1.18 23.38 0.939
8-30B 1.13 1.16 23.04 0.944

 

48

 

APPENDIX F

LISTING OF TIME VERSUS CONCENTRATION DATA

Herein is contained a complete list of the
concentration versus time data for the runs. The solution
concentrations are in gram-moles per liter. Twenty and
forty minute samples were not taken for runs 8-3OA and

8-30B.

Experiment 7-25

 

Feed = 184.0 nl/min

 

Gas = 7.55 cfm
33:3 NH4+ HSO3- 503- $04? S/Ceff
20 4.5774 2.0537 1.1773 0.0846 0.733
40 4.5463 1.9496 1.2059 0.0925 0.724
60 4.5100 1.8221 1.2282 0.1157 0.713
60 Out 4.5197 2.0319 1.1201 0.1238 0.738

Experiment 7-26

 

Feed = 184.0 ml/min

Gas = 9.86 cfm

49

Time

+

 

50

 

(min) NH4 HSO3 SO3 SO4 S/Ceff
20 4.7268 2.0124 1.1881 0.1691 0.729
40 4.6405 1.8583 1.2030. 0.1881 0.718
60 4.5517 1.7585 1.2061 0.1904 0.711
60 Out 4.5893 1.9450 1.1164 0.2058 0.733

Experiment 7-31
Feed = 239.7 ml/min
Gas = 9.56 cfm

{mar-“5 NH 4+ HSO3- $03= so 4' S/ceff
20 4.9361 2.1446 1.2203 0.1754 0.734
40 4.8372 2.0833 1.1986 0.1783 0.732
60 4.7138 2.0059 1.1571 0.1969 0.732
60 Out 4.7291 2.2129 1.0385 0.2166 0.758

Experiment 8-03
Feed = 149.1 ml/min
Gas = 9.35 cfm

Fugue) NH4+ HSO3- SO3= SO4— S/Ceff
20 4.6499 2.0499 1.2657 0.0343 0.724
40 4.5202 1.9447 1.2166 0.0411 0.713
60 4.4497 1.8204 1.2344 0.0802 0.712
60 Out 4.4725 2.0941 1.0969 0.0922 0.744

51

Egperiment 8-16

 

 

 

Feed = 184.0 ml/min
Gas = 9.46 cfm
affine) NH 4+ Hso3‘ so 3: so 4: S/Ceff
20 4.4937 1.9286 1.1905 0.0920 0.724
40 4.4438 1.8345 1.1925 0.1121 0.717
60 4.3922 1.6896 1.2406 0.1106 0.703
60 Out 4.3869 1.9444 1.1040 0.1172 0.734
Egperiment 8-17
Feed = 239.7 ml/min
Gas = 10.09 cfm
Eff) NH4+ Hso3' SO3— SO4— S/Ceff
20 4.5725 1.9173 1.2277 0.1000 0.719
40 4.4972 1.8498 1.1924 0.1313 0.718
60 4.4338 1.7877 1.1937 0.1293 0.714
60 Out 4.4438 1.9623 1.1113 0.1295 0.734
Experiment 8-18
Feed = 149.1 ml/min
Gas = 10.01 cfm
3:11?) NH4+ H803- 803— SO4- S/ceff
20 4.3747 2.5655 0.8466 0.0580 0.801
40 4.2687 2.3152 0.9078 0.0690 0.780
60 4.1431 2.1357 0.9058 0.0979 0.771
60 Out 4.1891 2.4014 0.7867 0.1072 0.802

52

Experiment 8-30A

 

Feed = 184.0 ml/min

Gas = 9.91 cfm

Time + - = =
(min) NH4 50 S/Ceff

60 4.1827 1.6052 1.1644 0.1244 0.704

60 Out 4.1983 1.8094 1.1071 0.1238 0.738

Experiment 8—30B

 

Feed = 239.7 ml/min

Gas = 10.00 cfm

Time + — = =
(min) NH4 HSO3 SO3 SO4 S/C

eff
60 3.9835 1.4579 1.0999 0.1629 0.699

60 Out 3.9917 1.6300 1.0230 0.1579 0.722

APPENDIX G

COMPUTER PROGRAM FOR DATA ANALYSIS

The computer program presented below was written by
Steven R. Auvil during the fall of 1971. Modifications to
account for some of the unexpected phenomena (evaporation
primarily) were made in the early summer of 1972. The
program was designed to do two things. First, it made a
material balance on the absorption column to fix all flows.
Its second function was to calculate the height of a gas
transfer unit by the log mean approach and by integrating
up the column. This program was used to analyze the
experimental data taken. The material balance section was
useful, but the height of a gas transfer unit calculations
had no meaning in this work. The complete program is

presented for reference.

53

54

.¢.—I¥..x.ou.o04b .A—.GOVO(U¢
Acoo—bo.h<xmck «—
4ut)..¢.qnxoaxeuuvouah .u—ooo.o<u¢
.0<~.N~oOoo—bo .thCOk o—
anvouu
h<o o.~.Uh<o ohaoz .momtamu .mocouozuaohommoNomzmu .zmuaomooo.6(u¢
000 or ow .ooOoou64h.L~
.ZIDJOO
uzh th~ m<¢ Nth LG .04:- hu) mt» boz- thOaruo uzh mu hunk
ocuhu:<hom
wzh ohzu m¢a wt» 50 ..430 bus nth box. hz—OQJNO U!» nu buzbmoh
accouuh.h<x¢ou o

u<auxo.hu)»¢oh .hmoh .o<h .purp .(hao.oo.o<u¢ 000
o I xuua
.onm\om~¢~ont~to<~ou<mm< a oe-\nh.¢.¢louo a muonu<uo
.uonovupucz

\ men: onmoo oo—oo .mNoc omNoo \ . m an I x oaxvau . (FCO
\¢:\4080410\an—.MF~23 <h<o

\ ¢I\OJ to. 8&0 to. ahxvtmmro..Jo>-8a&10\.Nuoalfia.fiumh~23.<h(o
\ Unoummxoo¢x\JOthIQo ¢2\.Jtm.omzx\46810\.oomlfi.“fivmh—za.<h(o
\ J\u4010:oo u<¢L brzoou<au 40:10. u—ownm1¢\.¢.~lfio.fivmhuzavdhto
\ ONIIm. fizzrm. Nomzm. Norm. NZZM\.mo~I$oafieuuuamo.(h<o

\ omztm.llcom1m.Olnowzm.onomztm. ¢¢121m\.m¢~lfio.fivuulm.<hta
\oon.ohnoo¢0.o~n.oo~\.monlfio.5.)t0.<b<a
\oo~.o00ooom.o—m.oo«\.monlfio.sztm.<h¢o
PDOJutlohtOZ.am.O>.~omtnauoJuxzomomoaaz~a.04po~4h.0<h.<h~
o.mvuooam.ou.awe—U..m.<m..m.m..m.oxz».Amy—Izhpamuoxh.Amen!» zoxzco
.m.au..m~38moamvrxe zo—mzuxno
.meuzoamunmh..m.~tmu..m.~c>..m.n>..nom.o zoumzuz—o

.m.ou< zo—mzux—o

.maaz..m.02ho.m.utho.m.omh..m.ozk0o.mvoa> zo—mzuxno
.m.~oumm¢..n~.Mh~z:.«b.0Uhdaoahewb<o zommzwxno
.mvcuabaam.cmo.mvomuroamvomk zo—mzutuo
amonmaboam.nmuro.m.~mhoamvuuam zo—mzuxno
a~ceoom..chnzz>o-¢.N0m>..~¢vamuz>oamcocuum> zcnmzuxno
.hzuzulooum<hob3¢h30l~0UQ<h.baahaoabaazu.<b<o t<¢occa

0000

55

 

¢z\Jox ma A<h°h I maoxh
Nhk\¢I\-J I A) o¢:\OJ J<bcb I tank .h) 401 oJom hUJZn I 4083

oQ—\ON10I.m.~0
0200 3(408 auh<3 hudzn mt» 02—haatou

AtmoludzNOIooco~IONx0
own—taevu0ooonntan.~0oooo¢aweu0IJtce

. zmxdh m—
4: 900‘ no mum<o < I mtmcu .0200 mmzho Nth Oh abuzz «<40: tout
.0200 .40m hudzn uzh h¢u>zo0 Oh cum: mu .48\0. >b~mzuo huazu Nth

n¢vouthmuoo.o.6000tnGmmcoo.N.O0¢oonoo¢o—Inazuo
ace—UtmeOOooan.nucnommcooaN.~0ooon°ooo~I042uo
.Iuovh<t¢ou

mx<u¢hm buxu 92¢ hudzu 0:» k0 >h~mzuo 01h 0Z~h<4304<0

.\\\oo<¢~.xm.h<:¢0u
.h.~Ix..¥.00h<ao.x~Uh<o. .e«.~o.uh—¢3
auo0uh<OIaxeuup<o

.uvuhdclaxeuh<o

howl! n— on

h) 40: unouum I 3:0 .¢I\ch m4 I I»
.¢1\GJ I up .z~x\hu:0 I 8&0 .0<¢m h) I a» .04CLJO: I >
huahao I O ohuazn I n m<o .0
ON: I m .022 I c .Nom I n oNo I N .Nz I u
h) 40: u—uucm I 310 .mz\JOt 04 I I!» .mz\ma I nub
oONI AOI\JO! I o oc<AOt I 0 .0<¢u #3 I at) o0<mk do: I an
ON: I m .com I o onom I n anon: I N ocxz I u ohzuzomxou I uuuuam
hUJhao I O .huaz— I n Guacaa o<
0104400 m4 mu uo00 ZOnh<¢hzw0zou NI»

@—

n—

000 000

00000

000

00000000000

56

4NQ>ohuth0h0¢mh43 4440
.m<0 x0<hm 24 «Uh<) «Oh huumcou

.0204hd4004tu uh<¢304u m<0 24000

b \ .xvstm t .2000 I 42.0153

2» \ .2000 I .x-0mk a £200 t .2000 I 42.00
m .4 I 2 40m 00

402N2 \ 44200 \ 0.0004 \ 0402) I m200

2p \ .m000 I 402~z a 2» \ h I 04021

.2000 0 2» I 2»

420320 I 42000 9 h I h

m .4 I x 04 00

0.0 I 2b a 0.0 I h

02:03 auxh0 02b 24 0200 040044 b4xu uzh 0242w44¢(bmu

.04\0~20 I 4m000 n 4220044zuoo.0004I0~20
.~n402¢000¢.o440.0.000.0004N000I42¢0

0200 24402 mub() b4xu u!» 024h0¢200

0u242¢uhuo zuun u><2 m0200 040044 #0424 44¢

420415.45402hl420422h

420430104KQApI4¥04ath

4.00040042u00\4x.)2m¢42040I4xv42L)

2b\.¥040I4204¢u a u20004¥040I42040

m.4I2 m4 00

402~2\042u0\.0004\44023IL200

2h\4m040l402~2 n 44021\4haahI4u402h

<u¢<\4umuhl443 n .¢m¢\.00.4423804200I4uaah
2b\.0004t04200I44023 a 4m04004004004044094~040.44040I2h

400

04

m4

00000

000

000000

57

~¢.N I 4 0¢ht0¢ht00IN¢¢4om o 0¢hIO0INm44¢0.m . N0h40.0 0 I 0¢m4>
N¢.N04¢ht¢hIO0IN¢¢4.mo¢hIO0INm44&0.mo~0h40.0l¢m4>

h4xN 02¢
hN424 Nth h¢ mN4h400004> 44mn>0040044 02¢ 4¢m4>0m¢0 Nh00200

0Ntm440¢th 2NNO N>¢t mN04¢> m¢0 hN424 44¢
thI4m¢02h a hI40¢0nh a th\hI44020 a ¢N¢¢\hI40

tt\402 04 4¢h0h I m¢0th
Nhu\¢t\04 I 0 .¢t\04 4¢h0h I m¢0mh .h) 402 I 4020

hx4x04uhI4x04m>

zhx4x04th4x04>

m.4Ix 04 00

4204:».1hIxh

4x04u» . p I h a 4x031004x04th4x04mh
.0004204xu004020zNOI4x04xh

m.4Ix 04 00

0.0 I x» n 0.0 I h
nh.04\4e.omc.<h.\Nh.4m\24m Iaoxozua
4m04xuoI4¢04xuoI4n04xuun4~04zuuu4th0I4404:50
.m.4> I 4hxuu I 4m04zuu a 0.0 I 40.4:50
000.4\~omzaaoxuu I 400—240

u<¢uxot4 ha» I .4. \ :40 I 4~04zuu

0Ntmu40¢th Nm¢ MNh¢¢ 3045 02¢ 0200 m¢0 hN424 Nth $0 tha Nth

4 4004» I 0.4 0 \ 200 I 4htku 9 24¢ \ Nu) I 4004»
0.004 I 40> \ Na) I t:t4N¢
4 N0) .hNth etNh¢3 44¢0 a 4 40) .¢h 0¢Nh¢t 44¢0

.m4m¢0 NNKhItNh¢t ¢ 20 102 m4 240
4 huh I .4 0.250 I 250
h0¢0\~¢> I ht»

04

04

0000 0000000

000

58

.N>00¢ 0Nh¢4004¢0 0» Nth 0h
m0zoamN¢¢00 h¢th 4 h00 040.44 Nth 00 thh0 004h Nth 20 N0¢N>200

40.00 I 40000 I 4~000 0 44.00 9 .4 I >2t00
.N0¢t 04 N0» I 0» h¢th 204hmtamm¢ Nth

.204h04om Nth 0h h0N¢0N¢ th4t
m¢0 Nth 24 ¢Nh¢t 50 0204h0¢¢u N402 2042044400N Nm¢ N0» 02¢ Nh»

>2200.\ 4 00¢0Q I 240 0 \ 40> I Nhh
40040 . 46040 I 4~040 0 44040 I 0.4 I htta0
4 40) .44h 0¢Nh¢3 44¢0

NmNt 240N0 0204h¢0hu400t 003¢t Nh mNtttm

4\0000h 0N1» 00¢

xh. Inch ntz». .xh. taoh ~00». .xh. omoh 0Nt>t .xo. I00h aNomtht 0
.x0. Ih00 ONONtht .xo. Ih00 0Ntht .Ko. Ih00 atNh 044$ .x¢4 .\\. ~

.QtNh 040.44 h4KN Nth 20L m04¢0 N02N0¢N>200 Nth 024130 0Nh00200 m4

N40¢4¢¢> >N2 No hm44 ¢ 04 024:04400 Nth. .Km4 .\\\ 0h¢ttok 4000

44000.40 0Nh4¢t
0» I N0» 0 4004» I 0»

N¢IN I 0.~ \ 4 404) o 404) 0 I 404)

4 4M4) 0an I 4m4> a 44m4>0axNI4m4>

4NIm44
0.0.4.0400000400.94Nto40.o.40I4n0ootm00.o4NI4...40I4~00000n0.I4mu>
4&00094n00094N000IN

4Ntm44
0.0.40t4c040.400..4Nto40...40¢4n0400m00..4NI4.o.40I4~040.000.I4m4>
4&04004004004N040IN

0.N \ 4 0¢m4> I ¢m~> 0 I ¢m~>

000000 000

00000

0
0

59

4204h I Nh I omNN
44204h.h>004¢0h 44¢0

.N02NO0N>200 N00h¢¢NutNh 04th mt¢0L¢Nm 04¢0h N24h00¢000
.204h 04¢:0N
Nh 44h2: hmnfi0¢ .0N02N0200 00 0Nh¢¢00¢>N ¢Nh¢3 Nth 02¢ mN40Nam
44¢ 00 01040 hN4h00 tm440¢th 0h mN02¢4¢0 h¢Nt 02¢ 4¢4¢Nh¢t Nm:
.204h0¢¢k N402 mNh¢t m¢0 h4KNIIIh> Nh¢4004¢0

4 I 024

0» I h»
004h I Nh

.204h04om Nth 0h h0NamN¢ th4t 0Nh¢¢0h¢m
04 220400 Nth 024¢Nh2N m¢0 h¢th om 0Ntm440¢th 2NNO 302 m¢t
024>¢N4 040.44 Nth 00 N¢0h¢¢NutNh Nth .N02N0¢N>200 004h Lo 02N

0040.00004 024004
4¢.m4k.x040h¢2005
004h44000.400Nh4¢2

4 024 .omNN .004h0>200h 44¢0
0.0004o4htt:0\24a\0> I 0». I omNN
4 a) .004h00Nh¢t 44¢0

4 024 .0¢NN.004h0>200h 44¢0
0.0004I4h2200\240\0> I 0». I 0¢NN
40> .004h00Nh¢t 44¢0

4 o.m4un .¢.m4u .x04 0h¢t¢0h
Nhh .N0> .0» .004h 40000.400Nh403
.04 o ¢h I 004h

4 024 .OCNN .hNth0>200h 44¢0
0.0004¢4>2130\240\a> I a». I 0¢NN
40>.hNth00Nh¢t 44¢0

4 I 024

0040

4000

0000

0000

0 000000

00000

60

 

 

4t0000h . h

a 420320 I 4xvotth I 4x0oamh
0.4 I x 4N0 00
0.0 I 2h 0 0.0 I h

0.004INO>\0> I 04N¢
0.004.Nh>\h> I 44N¢
.004I4a>\h>0400100 I 2400 I 4t0t4N¢

0204h¢04m400t «00¢! Nh «Nttam no 02NIIII2¢¢00¢0 th4) N024h200

.23021 04 h0044t)

mt\40t.0Ntm440¢hMN 2NNO N>¢t ¢ .m¢0 02¢ 040044 .mt¢thm h4XN 44¢

.0Ntm424h Nm¢ 04h 20 mN02NO0N>200

44a> .0¢h00Nh¢3 44¢0
h004421 I 0448)

0040 .00004 024 054

4 024 .omNN .hh 0>200h 44¢0
h>.204h4~000.400Nh4¢t
0.04.4204h I thI omNN

4 204h .h>004¢0h 44¢0

4com4k.xm¢.¢.m4k.x040h¢t¢0L
h>.204h4~000.4o0Nh4¢t
4024.00NN.h>0>200h 44¢0

0000.004¢.00004 0¢NN \ 4 4204h I Nh00k4
0040 0h 00 4 40.0.h4.40¢NN000¢054

204h I Nh I OKNN

4204h .h>004¢0h 44¢0

Nhh I h»
4024 .omNN .h>0>200h 44¢0

0040 0h 00 440.0.h4. 40¢NN000¢0K4

0040

000m
N000
0000

0000000.

0

61

40000 I 40000 9 4~000 I htta0

00N0.4 I 4 4000» I 4000» I 0.4 0 \ 4n00> I h00~00

Nomtma I 24N0m
0.0000 \ 02N0 \ 0 I 4N>0

0.~\4 0402) o 4402) 0 I 402) n .N\4040t09440t00I40t0

0IN \ 4 40 0

0h) 402 Nth N0¢¢N>¢

00 0 I 0 a 0IN \ 4 44) o 04) 0 I 4)
IINO I 0.~ \ 4 442N0 I 042N0 0 I 42N0

0.~ \ 44 400000I2400\2400I40t02N0In4020 . 40t02NOI04020 0 I 02N0

th I om¢0th

0.00. I .m..:» \ m0<~om I ~0m¢ua

0.000 I mo<~om \ zu¢>xo . 0.~ I onxoaua

.~.oxp I .~._z» I zuo>x0

.n.ox» I .n.~zp I mm<~0m

. .Iom<0.. . :pprogoze . ¢u¢<pr00
. \ .x.oap I .x.o.> -n

z. \ .x.o:» I .x.0»

.x.0:uu . 00:00 I 0.3.0

0.00 \ Jozozuo \ .x.0x. I .x.0zuu

m .0 I x -n 00

0.0 I 0.:Iu

20. x . .000. I 2.. . . 4020200 I aoxozuo
.x.oxp.szxp 0~

.x.0.. . p I p a .x.axo..x.oz.I.x.oap

m._Iz 0~ 00

0.0 I x. a 0.0 I .

mNh¢c )04L 02¢ 00200 m¢0 h4xN 44¢ 024tm440¢th 240N0

th I

0N24t¢NhN0 2NNO N>¢t 0200 040044 h4XN 44¢

442N0 \ 0.00 \ 0.000 I h I 04423
0h40th n h I Okamh n (Nm¢ \ h I 04)
42002th 0 th I th 4N0

000

000000

62

00402h00LQah 4mo040.Uh~¢)
4200xzh04300cah04x00004:00004X001k304800mu04xeuunm 4¢00400uh~m3
m04Ix 00 00

4I0~0044 huwa0xm0\\\0h<:¢0L

400040.0huml
44xn0mIN—k.N0K000\0IIIIIIIIIIIXh0IIIIIIIIII0x¢ovh<x¢0k
~k402h0ukanh 4m004000h~m3

44xn0mIN4u000xm0m<0x0N0h<x¢0L
420~xxh04xvunmh04x0~00480—0.4¥0~1L30480~muI4xvomum 4¢oonovuh~83
m04Ix no 00

4I0—00ua hUJZhonm0\04xh00<0n

N O x°~ O \\\ 0 .-------'-'-------------'---:---'-------'--------------~

----------------------------. 0 xMN 0 \ 0 .m,°I-J°h m‘ “3‘ Wt‘wmhm 0 Mg h I— n

0.xu 02¢ 0u420 ux» 00 00000 0040 020 mz0_»_moaz00 u:~..xm~.»¢x¢00
.0._Ix..x.mp_za. .~0..0.up~¢:

.xxxxxxxxxx.Ȣxaou

.0m0.~0.upuza

....0.u»~¢a

mx<umhm 0400~J hmxu 02¢ thzn uzh to hbahao z~0mm

IomhannhN\o44MIoomnII00\00<< I ~0000<<
I¢m¢I004I000\00<1 I 4~100<3
I004I4¥0412h\4x000< I 4x0004

monlx can 00

4m00xthI 00(19 :00I4m0011h I 4m000<
4¢0~38hI :00I400081h I 40000(

460~82h I 00<< o :00I4n0021h I 4n000¢
4N0~tth I 00<<I :00I4N0012h I 4~000<
440~th I 004< I 200I440018h I 44.00(
04~tl\uJU>0u¢ I :00

4¢0~xh I 4¢00th o 1:0I440081h I 00C¢
4m0uxh I 4m001h I x00I4m0012h I 00¢)
040!)\00¢¢ I :00

00mm I 04~83 I machuua

00000~ I >8t00 \ 0I¢m¢ I 0000 \ mo<~0m I 00mm

00
00
mo

co
no

No
0m0

Inn

000

63

4—
4xOIMIOh000x000\0IIIIIIIIII0KhIIIIIIIIIIonh0IIIIIIIIII0X0~0hdxmcb 00
~m<08h0~m(0ah0~htk0 4000400wh—83
44K00mIGk.HIKOIM-NIX~omCIXNN0h¢x¢Ok 00
4¥0~2h0480uah04¥0~2k004¥0Q204¥v~20410nuuam0 4000~000h~¢3 NO
00NIAI4¥vnk> I 420ml 0 00No—I4¥0~> I 410~2
Monlx #0 OO
4Im<0 hW42~I0Km0\04XF00<000KWN0\H
\\ 0 0 ............................'.....................~
IIIIIIOIIIIIIIIIIIIIOIIIIIIIIOIKWNI\IOWIOJJOK m< 01¢ I‘NRPW m10 bud
KU 02¢ hUJZu 02h $0 mwh<¢ 104k 02¢ mZO—hnmcmtou wxhlome0\\0h<x¢0k 50
4fi—00I20410mh~230 4NOIAOVUP—83
40m00—00wh—33
4~Inovmh~33

tau m< 0<¢u h) 024
0<¢L 40! ozuhhauhao I mu04<> m<0 hu42~ 44¢ 50 hnahao z~0u¢

4~o0hoImn uaahdmNQIUh 0~0044 hnxu 4N
(hzutncuuxu uth ome0\0No0u0 Inn U¢0h(¢uuxuh 0400—4 huxu ouh44004—
<0 NthI 0xm~0\0NI000Im4 u¢0h<¢untuh 040044 hu4z— wth0me0\0h<xa0k 0nnh
04h ouh 0~4h40nnh0400uh4¢3
4 4 \ 0¢Imum 0m( 0x00 0m 0\\0 Inn 004 mus—h w~0u0
mm 10(U L0 304K hu424 280400 Nth >- 000—>~0 hz~0t 0znx~z uxh h¢ u—h
0uam 20¢“ $0 20~h<401000< thI oxa— 0\\. I2—t\zu 00 I 0nI0k0 Inn 00
h 00h<4004¢0 0(1 0 0n.02< th< 4 h( (420!t< anuz<x no 20—h4004 no um
htm uthI 0me 0\0 Iz~:\4t I 0nook0 Ium 0h owh<4004<0 m<3 awhtr a: I
m¥<x $0 20~h400< 30 uh<m urhI 0me 0\0 Iz—t\4x I 0~00k0 I00 0h ouhn
<4004<0 m<z uh<¢ 040044 u40>0u¢ uth ome 0\0 Iz~:\4x I 0NI0L0 IwO~
0h 00h<4004<0 m4) uh<¢ 304k 0~00~4 hnxu uth 0me .\0 Iz~:\4t I u
0~0050 Ih< hum m<3 Uh<¢ 304k 0~00~4 hu424 uth 0me 0\\\\ 0h“x¢“k non
m0 I4
x04¥000<04x00uam.0~0000<<04~t00<nou40>0wm004~x3044:) 4n¢n0400uhuar

hbnhao Idwmhm 040044 ozm

0000

000

64

 

4 a) 0N02Nh(3 44¢0 044m
I0N I 04h I N a 4024 00¢NN 0N 0>200h 44¢0
0.0004I44 cocoa I 24n0\n> I h». I 0¢NN
4Q>IN0¢Nh() 44¢0
0Im4 I 0<h I N n 4 I 024

I0Nm0 N¢< >200h 02¢ ¢Nh<t MN24h00m00m
IN02N0¢N>200 < mN¢40ONm 204h<4004<0 m4th
h00hNth II N¢0h(¢N¢tNh 0400 hNt m<0 h4xN Nth Nh<4004<0

. 4 NeckoIa
04 220400 024>h404t0t Nth 024¢Nh2N m<0 Nth 24 mtht $0 204h0<¢m N40
02 NthI 0 me 0 \\ 0 Noon. Im4 040044 hN424 Nth 0h h0NmmN¢ th4t hhh
40410t N>4h<4N¢ 0‘0 h4xN NthI ome 0\0~Ioua I04 040044 h4x0
N Nth 0h hoNamNm th4t >h404t0t N>4h<4N¢ 0(0 hN424 NthI 0me 0\ 0 Nm
Ion. Im4 out Oh h0NamN¢ th4t >h404t0t N>4h<4N¢ m<0 h4XN NthI oxmu I
0\0 0~o0u0 I04 0~t 0h h0NamN¢ th4t >h404t0t N>4h<4Nm 0(0 hN424 n
NthI 0xm~0\\0 I40) tam I 00.04L0 I04 m4m<u NN¢L 0N1 02¢ ntz < 20 mN
40 h4XN Nth 24 0200 ~0m NthI 0xm~ 0\0 I40) 2am I 00.04L0 I04 m4m<04
Numb 0Nt 02¢ ntz < 20 m<0 hN424 Nth 24 0200 N0m NthI ome 0h<t¢0k IIn
huh.44N¢004N¢04t0t4N¢0t0t4N¢0h00N0m024N0m 4¢¢00400Nh4¢3
4Nohu0Im4 0Nn
N404x0 m4) t04tt ~00 0N0¢000< Nth £0 h2N0aNa Nthonm~0\oNohmoIm4 0N
N02000< 0‘) h¢th ~00 024:0024 Nth 50 h2N0¢Na NthIIKmN0\0I0NM\hh I04
NIOLoIm4 220400 Nth 24 hh4004N> 0(0 024h40mNm NthI0xmm.\\\\.h<t¢0u 0N0
04x0¢Naomom¢NQ04N>0 40~00400Nh4¢t

Om¢0th00m<0uh00htk0 4000400Nh4¢t
42002h041001h04!.0tk00420Q2o42442042.40Nam0 4000400Nh4¢3 Nh

00NI4I4240Q> I 42002 a 00NI4I4x00> I 42.42

m04I¥ Nh 00

h0ah00 tdumhm m<0 hN424 02N

4Im<0 h4xNI0xm0\\\0h<t¢0L 4h
44h0400Nh4¢t

00000

000

65

02400040 00 hZNumNa I 0004L
mIII4NIII4N¢IN\4m4)0\Ic44\nIInmII00N004I€I02N0I42N0I4t00Iu0
4<hN0I<hN0I000m00II<hN0I~040moII044mo.nI0&XNI4ta
4mIII442N0\02N0.I0\430004<I<hN0

204h0¢¢th 02¢ 204ha¢000< I 0momo4a 02¢ 00011Ntm 24
h04c 0NN44<¢N2N0 < 201k )h4004N) mmdt 02400040 Nth 024h0mt00

44¢-4tthIINI4404tth0\44no4ttho4N04tth0Ihm
44&00tthIINI4400tth0\44n00tth04N00tth0I0m

th0\m 50 N044) 4Imeh4xN 02¢ 4hm.hN424 Nth 024h0at00

N024h200
000 0h00

4I<h<0 to th 3N24

0240<N¢ IIII mNh<m 304k N>4h<0uz cumuhznouzu N><1I0x0~.\\\.h<:mou
44000.4o0uh403

0000 ch 0040.0.u0.4x.ox:h.oz¢.0.0.uo.4x0oxh0u4

m.4Ix 0000 00

44.40.0h4ax

0000

4000

000

0000

000

4~I0m0Im4 40Nh<4004400 N¢0hdn

athNh 0400 hNt 040 h4XN NthI0me0\0N00k0 Im4 N¢0h<mNQtNh 0400 haw

0 010 h4xN NthI0xm~0\0~oou0Im4 N¢0h<mNatNh .400 hN) m<0 hN424 NthI4
0me0\0N00&0Im4 N¢0h<CNatNh 0400 >10 m<0 hN424 Nthonm~0\0h<tm0m 4nnh

h00hNth00<h0hNth0<h44nnh0400Nh4¢t

IMNm0h<mNatNh m<0 44¢ h0ah00
Ih00hNth no N02N0¢N>200 00 02N

N I h00hNth 0NNm
0N~m0044m4024054
402400¢NN0N0)200h 44¢0
000004I44 cocoa I 2400\u) I h). I 0¢NN

0000

66

40¢noom4\N.004<Im0

200002<t m)¢¢Nm 24 0Nh2NmN¢n <h<0 tomb 0Ntm440<th 0204h<00N
<4) 0Nh0¢t00 N0 002 4443 ntz 02¢ Now 00 mN4h4)4m0Lm40 Nth

44N\Ihoo¢I00In4vInonomvaxNIZh
4 4N\ooon~Imooom4In0nIN uuxN I 2L 0 004\4I0O¢044h0IN

0204mmNCQXN t04¢044400N nt2 02¢ N00 Nth
mom mh2<hmzo0 Nth 024h0&200 02¢ x mNN¢0N0 0h utNh Nth 024h¢N)200

0.0 I ht0u0 I htoao 0 00¢ \ £0300 I taco

0Nm0 No 4443
>44<h2Nt4¢NQXN 0N)¢N000 m< 280400 £0 h00k 1N0 coco N¢0mmN¢1 Nth

~hI4mI.¢¢4\.c~Ioou0o4.I\02N0\~II0I4<I0<I3<I000I.~Ih1000
4NINIohIo~IINIoooun.nIooc¢.04.0xuu4< 4.00thoI43054
4430004<IN

.4I4< 4.00mIN4I43054

mn.Im<

~II.<40\m..I.oo4(40\m.0Io.nI.4I3< 4.00.00.omou¢.u4
~II4<40\m.0Im~.co4(40\m.0om~4.~I.4I3< 4.0coh4.0aoum.u4
4m4ho.no~thmnhm4.I00xNIaau 4.0¢.N0.0uomm.u4
4no-h.oINIhcoo0.I.uxulmmu 4.0c.h4.000Nm0u4

4 0000a .004< I u a (m4>\.~4\m.toIoaoum

¢0h0<k h0NLk< 040044 I 4< In

mNhNt<¢(Q 0242040 I 04 IN

mNhNt(m<a h0thN 444) < I )4 I4
0204h<00N 0010 Nm0mmN¢a Nth a0L 0N24KNO
mc 002 00402)N¢ 010 Nth m4 000Nm IIII 0100040 02¢ 0001mutm 24
0Nh2NMN¢1 0204h<4N¢¢00 02¢ mh04a tomb coco Nm0mmN¢a Nth 024h0at00

I004IL0\0I0004k

0000

0000 00000

00000000

67

4 I204h<404) Nth 20 02402NON0 NMch 0. I mt2h ¢0\02( N~4
00) N.4 I N00) th4) N024h200 4443 0204h<4004<0I 0x0N .\\\\ 0h(t¢0u 0¢h
40ch0400Nh4¢t
(XUNt0 I 0.0 I 4c40) 4 0.0 .N4. 4040) 4&4
<80Nt0 I 0. I 4:40) 4 <¥0Nt0 .h0. 4000) 454
x0Nt0 I N.4 I 40.0) 4 20Nt0 .h4. 4n00) 4L4
40.N4L.II 0N nt2)I.xm¢.N
\00.~4u.II 0N N00)I0xmc .\\\.IIII<h(0 80Nt0III0Nh¢404) 2NNO N)<t 24
80400 Nth 50 u0h Nth h< 0204h40200 204¢04440QNI0KmN.\\\\\\\0h<t¢0k omo
¢¥0Nt0080Nt0 40m004O—Nh4ct
hmo 0h 00 4(80Nt0I00..h4.40.0).02<.80Nt0I40.4.h0.4000)0u4
4mv4tth\440488hI4~0488h\4n0488hI4.¢It000I 24au\.004I2uI(80Nt0
44¢0488hI.~I4404tth0\44&04t8hI4404
48th0I4m0488h\400488h\4N0488hI4~04t8hI4.¢It010I 24&.\.004ItkI80Nt0

<h<0 k0 th 3N2 < 0h moNN00¢& 8(m00mm Nth 02¢ 0Nh24¢¢ m4 NodmmNt
Nth mN00 h4 54 .2t0400 Nth 50 u0h Nth h< 804m044400N Nth mNh<404)
<h<0 4<h2N84¢Nth Nth k4 N248¢NhN0 0h N0<8 N0 002 4443 80Nt0 (

02N0\<hh40\<m4) I (8t00 n 02N0\mkh40\¢m4)Im8tum
404)\0.¢44\40I0.I I 4N: a (m4)\.¢44\0I.¢I0N¢

.02 h048t0m nt2 I <8tum 0.02 h04tt0m N00 I mttum
0.02 00402)Nm 040044 I 4N1 0.02 m0402>u¢ m<0 I 0Nm

.~\44.¢I1010I24a .\24a I<ku40.<uk400I<uk40
.N\44.¢It0a0I24a .\24a Imkh40.mkh400Imuh40

N02<t0 N¢0mmNta Nth 0h N00 0N0<¢N>< N¢< 280400
Nth £0 80hh0- Nth 02¢ 00h Nth h< ntz 024 Now 00 mN4h4)4m0kL40 Nth

.00hI24c \040\¢0IN00h0N.4Im.4IINI<uk40
400I00Inhn04..00I0c~o¢.lnhomn.I0axNI040

4000h.¢h4\N0004<I00
.00hI24a \040\m0INooo40.mIm.4IINImmu40
400I00Inhn04..mOI0¢~0¢.InhONn.I.QxNI040

0000 00000

0000

68

 

4x0uth4x0<m
0.4Ix 4n 00
4x04zhu4xvuxh
4x0oxth420uth
0.4.: on on

8th4¢004<
<hh0¥I<020¢ Nth 24 0N00 0N40<4¢<) h8t00 N¢< <0 02¢ 00.0th00t8h

4 I N¢0h04 0 240 I a
4 . h20004 I h20004

00
00

0.0I: 0h

0.0 I 040<N 0 0.0 I 040N

0 I h20004

0.00 I N000¥K 0 ~0.0 I 0008!

4 I 024 0 0.00 I N<00xx 0 N0.0 I (008x

4000. 0h240c NONth 50 t0<N 00k haNz 004< 04 khN0\0 £0 N04<> Nth
0N244 8040044400N Nth 02¢ 024h<¢Na0 Nth 80L 4h4N)4h0Na0Nm
nt2)00NN2).~00>00NN0h4 00<¢u 408 nt2 024 N00 Nth to 0N04<> 4(0h0<
02¢ 8041.44400N Nth 00 0N04<> Nth hm4m00000 0h 0N00 04 Nm0h04
0204h(4004<0 Nth 240N0 0h 400N¢000N¢a 02¢ 4t0ht04Nt NN444h424

4.It0

0204h<00N «Nb02<¢h 0018 Nth 00 204h0400 <hh0x I (020m CNO¢0
can Nth 24 0N00 N0 4440 02480(m $0 h00k th2Nh N20 00 4()¢Nh24 Nth

4\.Int2 00¥I0x00I~00 001I.xo.Iht04NtI.x0.I¢N4
QXN nt2)I.x0.Int2) 04<0I0x00I¢NuxN N00)I.X0.IN00) 04<0I0x440h<t¢Ou ~40

4~400400Nh4¢t

4\\\.I0h2N404huN00 N
cNh02<¢h 00¢: Nth 0245 0hI0x0N.\.I>¢<00N0N2 04) h¢th 204h<¢Nh4 t0<4
N COL 0N4md4¢<) )Nx Nth k0 h044 < 04 02430440L NthI0x0~.\\\0h<800k 440
4440.400Nh4at hmo

44.400Nh4at

0000

0000 0000000

69

 

4000:»..ox4.n.~0o.4~.~0o..¢.44.~000I4¢.<m
4n0oxh..o\44n.4.o.4~.40o..0.44.4.o.n4n0(m

00 ch 00

4.0zamxnozaax

00¢: 44¢0

44.000I4~.~0o..~.4¢0uzhu4c0<m a 44.40ou4~.400..~.4n0uuhumn.mm
. 0 h o
4 . umohm4 I ucohm4 a 4.0zamxuezaax

00¢: 44¢0

. 0Nh0u800 024N0 204h0N0
280400 Nth 20 N02¢4¢0 00¢: ¢ tmOKmNQ 0h N24h00¢000 ¢ 04 00¢8

0.~\44.~.0 . 400¢0 I 4I0¢0 0 .~\44.400.4n.¢0I4n.¢0
440.0..NI44000x44n.m.4~0m.u4umohm40000

N\4¢.¢0 I 4N¢0h0400t2h 0 N\400¢0I4N¢0h040N00>
N2hI4N¢0h0400NN2> 0 N0hI4Nm0h0400NN0>
ozzmx.4nn.~n.00o0 0h 00
t0I¢N¢¢I¢0oxxI4N\4¢0¢0INZ>.I4020¢80~00
t0I¢Na¢I0002xI4N\4n.¢0IN0>.I4020¢x.4.0
40.40.4¢.<0.4n0<0.4~0<0.440<0IN
4000\4400.4w.mx4n0m.0\.004.20302>
44000I.~I44000\44000I44000I4000\4n0mx4~00.4N0m.0\.004.:unu0>
44~\o.ho0¢ I 00.n4 0.n0n.~ 00x0 I an

44N\0.oon~ I 000.0 .In0MIN0QXN I 85

0.4 x 4 0.000 . 0.o4\zoxI4 uh I 44h. . uh. I N

tth4¢004¢ ¢hh08 I ¢020¢ Nth 24 ntz 02¢ N00 00 3040 Nth 24 N02¢t0
Nth h2NON¢aN¢ 4020m80N40 02¢ 402038.400 0N40¢4¢¢) Nth 02¢ .0¢0

40 ¢t\408 4¢h0h I N 0804:044400N 012 I N2) 0804104440ON N00 I N0)
4I020C8

¢hh08 I (0201 ¢N0¢0 014th Nth 240N0

484088hI4240

00

N0

000

0c

40

0000

000 00000

70

44004

0I.~I44000\44000I44.00I4040\4n.0\4~00I4N00Iu\.004ItkI4N¢0h04.0NN0)
0N244 2040044400N 08¢ 024h¢¢Nu0 Nth «on h240m h0¢4 Nth Nh0ut00

44.400Nh4ct
0.NI2N0)X0I2N0>X0 0 4080\¢002X\0I¢00t 0 4080\000¥x\0I000t

002000.000 020.000000
202 200000 0000020) 020 .0020 00002000 022 00 020002 I 0002
.0020 00002000 ~00 00 020002 I 0002 .02000 2000 002 20000000 020

:40 0h 00

4 I 024

_ 0h0000440 4 024 054

400 0h 00 4 00 .h0. h20004 0&4

4 024 .~¢00¥x .012N 0¢00¥x .N000xx 0~00N .0008x .240aNN 44¢0
00N.4I4 4000>I¢N 0 I 0t2N 0 00N.4I4 4000)IN 0 I ~00N
¢N I 040¢H 0 N I 040N

00 0h 00440IN0.4 .h4.
00N0.4I4040¢N I ¢N00O¢ .02¢. N0IN0.4 .h4. 00N0.4I4040N I N 000¢0b4

00

000

00000

440

I40

4h.04Lh.x00h¢t¢0k 000

¢008x00008x0t040.0)0¢N04nv0).N 4000.400Nh4at
th\4¢008h I ¢N 0 th\4000th I N
00 0h 00 4 00.0 .h4. t 0&4

4¢)¢Nh24 Nth mom 0NhN4u800 2NNO 0¢t NKO0NN00¢¢ ¢hh08 I (020m Nth

4800th.thIth

4x0¢0 I 4x00th 0 4800I420088h

0.4Ix 00 00

0.0I8h

00¢t 44¢0

t0It0¢0InIa

.¢\tI0II4h0\44e00I.~I44000\440.0.4N00.0 I.~I2N0>x0I4¢0088hI4¢00
tcotIt

000

71

o..420uom . :00 I :00 nnnn
4.~Ix nnnn 00
0.~\ o..4u¢ohm4.uom . 0.~\o..400uom I :00
0 I umohm0 I 4

x00N¢ .204h¢00N 0)08h¢Nt0 ¢4) Nh¢¢ 204h¢04x0 Nth 024h0at00

4\\\.Ict\h500 I.¢.hk.I0
>h4)400bu40 ntz .hI.x0n.\.Iut\hLO0 I.I.hu.Ihh4>400mu4o ~00 .0I0xonc
.\.I¢t\hm\04 I.¢.hu.I>h400004) .0I0x0n.\.4.0L.Ihn «(400N408 .eI0x0n
n.\.Ihu00\n4 I.I.hL.I>h402N0 .nI0x0n.\.Ihbo0\at\m4 I.~.hL.Ihh4004NN
) 00¢8 .NI0x0n.\.Ib I04.0m.INm0h¢¢Nu8Nh .4I.X000\\0I000440& 0¢ N¢¢4
204h¢4004¢0 04th 24 0N00 0¢0 Nth L0 0N4h¢NQOmn NthonmN.\\4h¢8¢0L nh
¢Lb4000uu40.¢04)040:0.02N000.¢h 40h04o0Nh4¢r

0N40¢4¢¢) 0N24bN0 )40004)N¢u 44¢ 024hh0ah00 240N0

44.400Nh4m)

0..:I: 400

44x0400.0k0c0x0400.050104.4.00980~0h¢t¢0fi N00
44.nt2h04400NN2>.440~00h04400NN0h0440000.: 4N000400Nh4mx
00N.4I4400t2> I 440nt2> 0 009NI4I440~00hI440~00)
00N.4I4400NN2> I 4400NN2> 0 00.N.4I4400NN0>I4400NN0>
N¢0h0404I4 400 00
0.0It
. 4\\.Int2>I.x4n
4.INnt2>I.x44.I~00>I.x04.INN00hI.x0.IkLN0\0I.Xh.Iht04NtI.Xh~.\\.I4N
40>0tua 24 Nm¢ 0204h¢¢h2N0200 44¢I.X00.\.I0N244 8041044400N 02¢ 024

4h¢¢N00 ntz 02¢ N00 Nth 20 0h240c N¢¢ 02430440k NthI.K0~.\\0h¢8m0h hmo
4h000400Nh4¢t

8mm 24 0200 44¢ I ¢h¢0 N244 8043044400N 02¢ 024h¢mNa0 h0lh00
44¢00I.~I4400.\440.0.4N000I4N10h040000

¢N I 4N¢0h0400t2> 0 NI4N60h040~00)
4000\4400I4N00\40.0It\.004I2LI4N¢0h04.0NN2)

000

000

000

72

u<o¢z.umaor .QOI4O.Uh4¢)
.Aoocvcuw2>l.o¢.nzz>.\.44.0wwz>024vn12>..664(4
\.acceowU2>ogoevn22>l24.0uuz>l.4vnzz>.t.Actunzz>l.4vnzz>.\oelu¢ooz
a4.ecuflmumhl.o¢.~omhv\.24.0uwm>044.Nomho.00444
\.aaevauumho.cchomhl.4.0uumhla4emomhvt..e¢.~om>l.4.Nom>.\o¢IUWOOI

auumz<a» nzz uz» oz« won uz» mom p_z:
mugmz¢cp < no pro—u: us» upaaxou o» zu¢oaua¢ z<ux co; mt» oz—m:

.Ihk I.nohhoch42: cub02<¢h 022 hzo4u2 ooc.xen.\.IhL I.nohh.m
Ih4z: ¢ummz<¢h N00 h204u2 oho.xon.\II huDU\mx\402¢4 Io~ohupth2u¢
4o4uuuoo cuumzdch n22 coo.xon.\oc hu30\az\aozm4 IINohuIIhzu4o4un
muco cuumzdch ~90 .mIIxon.\o~ookoIoz 0¢4¢2>u¢ 043044 I¢IIxono\oNoh~
L.Ioz moJozhum 040 onooxon.\onoomotoz ha42200 n22 .Nouxon.\.noou.t4
oz ho42200 ~o0 .4I.xcno\\.omzo4h<4:ua<u uth no 0h430umt.xm~.h<xucu 0h
(602.0002o4002xo0ooxx.Ju¢.ou¢.<2200.02200 .OhI4o.uh4muo
\\.062 22 I.~ohuoofio¢o u2300u¢¢ ouhtaauadu oao.xon.\.toz 22 I.~ohkm
ooaoca wmammmca 4(hzut4mwmxu chooxcno\o001 I: 0.4IhkaIwaammwcm hUJQ
24 223400 ooooxon.\.4omh.toz4oOOJu hzwuauc Imo.xon.\o~omh.oxm h4xun
oco.xono\o~omu.oza hu424 onIIxon.\.Iu c.4oou.ou2Uh 043044 h4xu INN
oncno\.022\OU2¢Ou #00 462.4 I.ooou.ouh<¢ 204h<o4xo .4toxon.\\ocxu4
hmhm ”1h mom mmuhwttmca OUh(t4hmw U2¢ 024IOJJOk uzhtoxmmo\\.h<xmck mh
hzoaao2060024AIOOOJLIOIQI42QIUhoxoow¢ .MhI4OVUh433
ooctzocclzata 0 .0I~0.¢Io~.ocht 0 h0I~oIIIONIOI42u
.Imzxouxzou #00 402.4 Ioooouotuh<¢ zo4h<a4m
xo ooogxon.\.noou.cuuw0\0 h4xu .hIIxcno\on.03.quu0\0 hN424 Io..xoc
n.\.I¢2\hu\na I.¢ohuoohh400004> omI.xon.\.~.ou.Ih) «(Jaumaoz oct.xn
ano\othu30\nd IINIOLII>h4mzuo ont.xono\othu00\mz\md IINohuoI>h4UOJN
w) 00¢: INI.xan.\oIL c.4oouoou23h41waxmh o4IIxon.\.omaoaaou 04 Mad—
zo4h¢4304(u 04th 24 cum: 043044 mzh no 0m4hmmaomu uzht.x0~.h¢2ack oh
zuchxo..0.h0.404>o4023o42uo.A).44h .Qha4ovwh4ca
.ommmnotoco\x 4
.IIQINIh.4II42ua\404>\o¢44I~II.IN4\<4Q.IhIIIJJInooum4hmoc.meooum
con\44h o oon\oo~twh I x
mNooottam I N

0000

73

OzN
achm 000
090 Oh 00
.I<h<o kc th 3N2 < o<N¢ oNhh 02¢ Nah 2NN3hNu hoz 04 h» Ivhtxmck @000
Aeoooo4oeNh4¢2 come
:90 Ch 00
a I hum ¢h¢0 IN! 4

< 24 @24OCNK III 0N20(N¢ N. hoz 2(0 N02N02N>200I oxen I\\\\.h<xmos Noo
.Neao4oeuh4cr 4¢o

000 ch 00

ONh<242¢Nh 04 2¢¢Go¢u N2h .mtuh m<o~<h N40<4a¢> Nth 20L o<N¢ m4
O¢NN 4 04 02¢ 2‘20023 Nth no @24240No Nxh Oh aszDhNa m4 40¢hzou

4ou4xm4la4¥n4
44.404Nh4mz
.h.4l¥..2.uuh<oo.z.Nh<o. 404.404Nh4wjuomo
\
\\oIhu Ionohuotxu<ocmm< 2<N2 004 Nxh 024m: n12 mom cc: IOIIan.\oI4
hm I’m-hm .320101LQ4 2<N2 964 Nth 0240: Nam mom ooz odIIxm04h<2¢ou to

0000

74

02N

2¢OhN¢

oN\..¢.0I.cOOtth.I.N~4thI4N4<0
a.n.<0I.n.4th4¢4040t2hI4040
.c.¢0¢..cv0I.¢~Otth.o4404(0IAH.4th40404OtthI4040
4¢4<0IIN04.n.<0I.n.4thOI4NVOtthI4N40
4¢4(0¢.4.0t2hla440

com I NO~\4 o 000 on
nO0t¢t2 o 012 I nomuaetzv IN
nOth I 000 o ONt I NO0 o4
0204hO<N¢
ONZ4NNO >40004>N¢n NuNth Oh Oz4oaouu< tOhhom Nth tomb ZtO4OU
Nth u: 0204h4003 h< NOZ<4<I 0042 d mtmOtha h4 ot<¢ooma 24¢!
Nth 24 NCOONNOOtt (thx I (@233 Nth th4) 6N0: 04 Nz4h302030 04th

hOO44ttohaOZ..meOh.NO0tmmN.44ttoaoaOQIZ4m.O4ho44h.O<h.(h4

o.mv4ooameooaamv4uoamvdmo40.0..meOttho2004ttho4040th..mv4th ZOItOO
00¢t Nz4hDO¢ma0

000000000

7S

02N

2¢0hN¢

0 I 024

zmnhNa

ntzn I NN>(0 0 NO0N I 4N>¢0

N I 024 0 N<0O22 I (0022 0 N00022 I 00022
ZCOhNC

4 nt2~u I flttuz .\4 (00220 I (00222 .ontZNm I (0022& I (0022
4 NO0N1 I NO0N2 .\4 000220 I 000222 .INO0N5 I 00022a I 00022
04 I 024

zmsth

0.N\N<0022 I (0022

0Noom4o.m4o 4 nt2N\NN>¢0 .54
_ 2¢0hN¢
04 I I 024 0 ¢0022I0IN I N<0O22

0.N\N00022 I 00022

040.000.000 4 024 .54

c Oh O0 4 0 choc 024 o02<o 0I0 oh4o ntZN\NN><0 .54
04 I I 024 0 00022I0IN I N00O22

0 0h 00 4 0.0 oh4o NO0N\4N><0 .54

«onoN 4 N I 024 .54

0 0h 00 4 0 oh0o 024 .54
(00220 0 ntZN I MtZNa
4N 0h 00

(0022 I (00222 0 ntZN I ntZNZ
onomNomN 4 nt2N .54

(0022

4N 0h 00 4 nolNo4 oh4I 4 MtZN .00< .54
00022 I 000220 0 NO0N I NO0Nm

0N 0h 00

00022 I 000222 0 NO0N I NO0Nz

04.04.04 4 NO0N .54

0N 0h 00 4 GOINI4 oh4o 4 NO0N .004 .54

4 0h 00 4 40INI4 oh4o 4nt2N.0O( I02<I N0INI4 .h4. 4NO0N.0m< .54
(00222 .000222 .ntZNz .NO0Nz 4<Nc

4 024.N<0022o022N.¢0022.N00022.NO0N.00022 .2401NN Nz4h002000

040
000

0N0
04o

4N
on

0N

0N
04

04

76

02N

2¢0hN¢

0 I 024

2¢0hN¢

N I 024

2¢0hN¢

42N I AN. \4 z» I m>.ImN I a» I h»
00 0h 00 44.0No024.54

OaNN I 5N

h» I a»

0: 0h 00

OKNN I 2N

h» I 2»

00.04.0N 4 0¢NN .54

04 0h 00 44o0oh4o40¢NN.0m¢.54

4 024 IOCNN .hh .>200h Nz4h002000

04
em

0:
on

0N

4n.Oth o 4n.4thI 40.02hI 40.4th o 40.4tth
0INI44N.Oth I4N.4th. o 40.4tth

o 4*.OthIINI44N.02h I 4N.4th.I 4n.Oth o4n.4th I 4n.4tth I
40.42hI 4Q.Oth o 440.02h I4n.4th.IoN o 4N.4tth I
4¢.4th o 40.02h I 44.4tth

40.022h
4¢.Otth
40.4th4
40.022h
4N.Otth
44.0tth nho

0.0Ih020020444tto4¢.40 Ih0044tto4¢.00. I 4N.4th I 4N.02h
h0200¢I4h0044ttc44.0u I 4423.44.40. I 40.42h I 40.02h 440
h0200<044423024N00 I h0044ttth00N00. I 4n.4th.I 40.02h 0N0

440 0h 00

_00N0o4\N00200NIO0<0th I 40.02h

0N0 0h 0044IN0oh002.54

4¢.40 I 40.40 9 4N.4U I 24N00

40.00 I 40.00 I 4N.Oo I h00N00

h0200nI44n.02h o 4n.4th I 40.02h I 40.42h. o 4423 I h004423

0000 Oh 00 400IN0I4 oh4o 440.02h I20NtUh.00<.54

h>000<0th I 40.02h

40.0th I 20Nt0h

77

40.045nI200.h(t¢05 4ho
40.0>o4¢.0>.4n.0> 44hoo4o.Nh4¢2

00<0th\42.02h I 42.0» 0000
0.4I2 0000 00

42.02h 9 00<0th.I 00¢02h Nho
0.4 I 2 Nho 00

0.0 I 00<0th «ho

42.4tth I

42.4th I

42.02th 0000
42.02h

0 .4 I 2 0000 00

.04II0O\I¢0¢ I hmzouo 0 I¢0¢\00o I h0200¢ Ohm
\ 00.0 onmo0 .04o0 .0No0 .0NI0 \ 4 0 .4 I 2 .42.00 . ¢h¢0
\o04ooh4II¢OIINM.I0N\40I4I0.45.220.<h<0
\004oo00oo00.o40.o04\40.4Ifi.40.220.4h20

h004422.h002o40.0h.N00200N.4422.00000.z4ao04h.44h.0<h.<h4

940.40.40.00.40.40.40.<0.40.0.40.Ottho40.4ttho40.02h.40.4th ZOttOO
40.00.40.320.40.320 20402Nt40
4 204h .h>.04<0h Nz4h00¢mam

78

h00h<Nt I O¢h I

h0h¢Nt \ 4 hO0h<Qt
I ONtt I N002 I 0222 I 202 I 244h4Nt I 240h<wt .

4 40.42h I 40.0th . I 0.00004 I

4 4n.Oth I 4n.4th . I homhnNN

4 40.42h I 4I.Oth . I 0oh0hnn I

4 40.422h I 4¢.Otth . I OIM0¢¢N4 I 202

42.320 I 42.0tth I h0h<Nt
44h I 42.320 I 42.4tth I 244h<Nt
42.00 I 42.220 I 42.02h
240h(Nt I (h I 42.00 I 42.320 I 42.4th

h0h<Nt
hO0h<Nt

0 .4 I
0.0
0.0

III...

02N
2¢0hN¢

204h
ONtt
N002
0:22

I h0h<Nt
244h<Nt
h00h<Nt
240h<Nt
0400 00
244h<Nt
240h<Nt

¢h0 0h 00

4

0400

0000

00

79

02N
2¢0hN¢ n

40N00hI0N00hI00044000I0 I 0N00hI000¢0N4I0 I N40400INNI .amN I a) N
0 0h 00

4 0N00hI0N00hIh¢0h4000. I 0N00hI~o~no4oa I 4ooho.0~I .a2u I a>
~ 0h 004 o.ncn .hoo 0000h.54

0.4 \ 4I.00I I h . I 0N00h

4;) .h .muh<) uz4h000000