EPA REPORT NUMBER 74-KPM-4
CD
O
POLLUTIO
EMISSION TEST
ESCANABA PAPER COMPANY
Escanaba, Michigan
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Emission Measurement Branch
/ Research Triangle Park, North Carolina
-------
TABLE OF CONTENTS
Page
I. INTRODUCTION 1
II. SUMMARY OF RESULTS 4
III. PROCESS DESCRIPTION AND OPERATION 25
IV. LOCATION OF SAMPLING POINTS...., 53
V. SAMPLING AND ANALYTICAL PROCEDURES 56
APPENDIX
-------
I. INTRODUCTION
Under the Clean Air Act of 1970, as amended, the Environmental
Protection Agency is charged with the establishment of performance
standards for stationary sources which may contribute significantly
to air pollution. A performance'Standard is based on the best
emission reduction systems which have been shown to be technically and
economically feasible.
In order to set realistic performance standards, accurate data
on pollutant emissions must be gathered from the stationary source
category under consideration. .
The Escanaba Paper Company in Escanaba, Michigan was selected as
a stationary source in the kraft pulp mill industry for an emission
testing program in support of developing new source performance
standards. The tests were conducted during the period of September 17
to September 28, 1973.
The processes under consideration in this test series were the
smelt-dissolving tank and the lime kiln. Emissions from the smelt-
dissolving tank are controlled by a cyclonic scrubber followed by a
demister. Similarly, emissions from the lime kiln are controlled by
a venturi scrubber followed by a demister. A schematic diagram of the
simplified kraft process and the processes sampled is shown in Figure 1
-------
Three tests were conducted in the final exit stack of the smelt-
dissolving tank to determine total reduced sulfur compounds, and
filterable and total particulate emissions. Simultaneous determination
of moisture content and dry molecular weight were made of the flue gases,
A fourth test was made for moisture content and dry molecular weight
only.
Seven tests were conducted in the lime kiln exit stack to determine
total reduced sulfur compounds, flue gas moisture content and dry
molecular weight. During three of these tests, nitrogen oxides samples
were also collected.
All tests for reduced sulfur compounds were conducted by OAP
personnel.
-------
RECOVERY
FURNACE
DIRECT
CONTACT
EVAPORATOR
GREEN
LIQUOR
SMELT
DISSOLVING
TANK
SCRUBBER
PRECIPITATOR
SMELT-DISSOLVING
TANK TEST SITE
STACK
STACK
LIME KILN
TEST SITE
VENTURI
FUEL
DEMISTER STACK
Figure 1. Schematic diagram of simplified Kraft Process and processes sampled
-------
II. SUMMARY OF RESULTS
Smelt Tank
A summary of particulate emission data from the smelt
dissolving tank is presented in Table 1. Table 2 presents a
summary of flue gas conditions. The particulate test results
agree very well, indicating a fairly constant emission rate
which averaged 3.90 pounds per hour at a concentration of
0.0239 grains per DSCF.
Test 2-1 was run at too low a sampling rate because a higher
.iV-.
than actual moisture content was assumed to determine the
isokinetic sampling rate. Tests 2-2 and 2-3 were run at
essentially isokinetic conditions. The low sampling rate during
Test 2-1 did not apparently effect the measured emission rate.
Lime Kiln .
Nitrogen oxide concentrations and flue gas data from the
lime kiln are presented in Table 2. In all cases, nitrogen
oxides concentrations were low, ranging from 11.2 ppm to 24.0
ppm. The moisture content of the lime kiln stack gases varied
considerably ranging from 56.4% to 76.1% by volume. These
measurements were made during a four day period, indicating that
process changes could have accounted for some of this variation.
-------
Reduced Sulfur Results
A summary of the reduced sulfur emission data is presented in
Table 3. This summary includes daily total reduced sulfur average
concentrations for both the smelt tank vent and the lime kiln.'
Table 4 summarizes the daily average TRS concentrations 'for each
compound separately. The Tables are followed by the field gas
chromatograph data used to obtain the daily averages. A detailed
sampling and analytical method is included in Chapter V of this
report.
-------
.Table 1. SUMMARY OF PARTICULATE RESULTS
Smelt-Dissolving Tank
Run Number
2-1 2-2 2-3
Date, 1973 9-18 9-19 9-19
Volume of Gas Sampled-DSCF 65.763 76.592 75.025
Percent Moisture by Volume 23.8 25.8 26.5
Average Stack Temperature-°F , 150 151 15J :
Stack Volumetric Flow Rate-DSCFM 19,540 18,760 . 18,720
Stack Volumetric Flow Rate-ACFM 30,160 30,090 3Q,380
Percent Isokinetic 82.7 100.3 98.5
Particulates-probe, and filter catch
mg 101.2 126.7 110.1
gr/DSCF 0.0237 0.0255 0.0226
gr/ACF 0.0154 0.0159 0.0139
lb/hr 3.98 4.10 3.63
Ib/ton feed - -
Particulates-total catch
mg 156.6 } 180.1 168.9
gr/DSCF 0.0367 0.0363 0.0347
gr/ACF . 0.0238 0.0226 0.0214
lb/hr 6.15 5.83 5.57
Ib/ton feed
Percent impinger catch 35.4 29.6 34.8
a) Dry standard cubic feet at 70°F, 29.92 in. Hg.
b) Dry standard cubic feet per minute at 70°F, 29.92 in. Hg.
c) Actual cubic feet per minute.
d) Arithmetic average of individual tests.
25.4
151
19,007
30,210
0.0239
0.0151
3.90
0.0359
0.0226
5.85
33.3
-------
Table 2.
RUN NUMBER 6-1
Date 9-24
% Water Vapor - % Vol. 76.1
% C02 - Vol. % Dry 9.4
% O2 - Vol. % Dry 13.2
% CO - Vol. % Dry 0.2
SUMMARY OF
6-2
9-25
61.6
10.4
10.8
0.1
11.2'
19.2
RESULTS
6-3
9-25
61.1
10.1
11.1
0.2
13.7
12.7
.
6-4 ' 6-5 6-6 6-7 f
9-26 9-26 9-27 9-27
71.9 59.9 56.4 72.0
10.0 9.8 8.2 9.8
12.2 12.0 13.1 11. ft
0.1 0.3 0.1 0.2
24.0 -
13.2 - . . -
-------
TABLE 3
SUMMARY OF RESULTS
Escanaba, Michigan
Daily Average TRS
Daily Average SQ,
CO
Date
9-18-73
9-19-73
9-20-73
9-25-73
9-25-73
9-26-73
9-26-73
9-27-73
9-27-73
Location
Smelt Tank
Smelt Tank
Smelt Tank
Lime Kiln
Lime Kiln
Lime Kiln
Lime Kiln
Lime Kiln
Lime Kiln
ppm/dry
2.31
1.84
2.59
1.34
0.41
<.36
<.36
<.36
<.36
Ib/hr
0.30
0.23
0.35
0.10
0.03
<.03
<.03
<.03
<.03
Ib/ADTPD
1.08 x 10"2
8.35 x 10"3
1.25 x 10"2
3.63 x 10"3
1.09 x 10"3
<1 x 10"3
<1 x 10"3
<1 x 10"3 .
<1 x 10"3
ppm/dry
ND
ND
ND
ND
ND
ND
ND
ND
ND
Ib/hr fb/ADTPD
__ ___
___ ___
___
-------
TABLE 4
SUMMARY OF DAILY AVERAGES OF COMPOSITE ODORANTS
Escanaba, Michigan
Smelt Dissolving Tank Vent
Daily Average Daily Average
Date
9-18-73
9-19-73
9-20-73
Lime Kiln
9-25-73
(1st)
9-25-73
(2nd)
9-26-73
(1st)
9-26-73
(2nd)
9-27-73
(1st)
9-27-73
(2nd)
Compound
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
rirt J
2
H9S
2
H0S
2
n/} o
2
H5S
2
llr^O
2
(ppm, wet)
0.61
1.15
ND
0.53
0.83
ND
0.51
1.50
ND
0.32
0.16
<.13
<.13
<.13
<.13
(pprn, dry)
0.80
1.51
... '
0.72
1.12
0.66
1.93
1.34
0.41
<.36
<.36
<.36
<.36
Daily Average Daily Average
(Ibs/hr) (Ibs/ADTPD)
0.08
0.22
0.07
0.16
0.07
0.28
0.10
0.03
<0.07
<0.07
<0.03
<0.03
2.90 x 10
7.99 x 10
-3
-3
2.54 x 10
5.81 x 10
-3
-3
2.54 x 10
1.02 x 10
-3
-2
3.63 x 10
1.09 x 10
<1 x 10
<1 x 10
<1 x 10
<1 x 10
"3
-------
HEAD CORPORATION PAPER MILL
Escanaba, Michigan
Smelt Tank '
; Inject
Date . Time
9-18-73 1241
1257
1311
.-
1330
1345'
1400
1415
1430
Compound
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S '
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
' DMDS
H2S. .
CH3SH
- DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
Attenuation Peak
(Amps) Height (%)
4 x 10"8 17.9
3.2
n . ____
4 x 10"8 18.2
3.0
n
4 x 10"8. 11.3 .
2.0
n . .___
4 x 10"8 14.4
. . 2.0
n ____
4 x 10"8 9.8
" 3.0
n ____
4 x 10"8 9.9
2.6
II ... _
4 x 10"8 8.3
2.3
3.4
4 x 10"8 7.8
2.2
4.0
Concentration
(ppm, wet)
0.085
0.118
ND
0.086
0.115
ND
0.068
0.096
ND
0.077
. 0.096
ND
0.064
0,115
ND
0.064
0.108
ND
0.059
0.102
TR
0.058
0.100
TR
Dilution
Factor
10.3
II
II
10.3
II
II
10.3
II
II
10.3
"
II
id.3
n
n
10.3
"
;l!
10.3
11
n
10.3
I
"
Corrected Concentration
(ppm, wet)
. 0.88
1.22
ND
0.89
1.18
ND
0.70
0.99
ND
0.79
0.99
ND
0.66 ;
1.18
ND
0.66
1.11 . .
ND
0.61
1.05
TR
0.60
1.03
TR
-------
Inject
Dats_ Ting
9-18-73 1445
(continued)
1500
1515
1517
1530
1532
1545
1600
1617
1632
Compound
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS .
H2S
CH3SH
DMDS
Attenuation
(Amps)
4 x 10"8
ii
4 x 10"8
H
4 x 10"8
it
H
4 x 10"8
H
II
4 x 10'8
n
H
4 x 10'8
II
II
4 x 10"8
n
n
4 x 10"8
M
Peak
Height (*)
7.1
2.0
4.2
5.7
2.0
5.3
6.7
2.0
4.6
9.6
4.2
4.6
6.9
3.4
4.8
9.8
3.6
6.2
3.5
2.0
6.0
3.4
3.0
6.2
Concentration
(ppm, wet)
0.055
0.096
TR
0.050
0.096
TR
0.054
0.096
TR
0.064
0.133
TR
0.054
0.121
TR
0.064
0.120
0.005
0.039
0.096
0.005
0.038
0.115
0.005
Dilution
Factor
10.3
II
II
10.3
n
10.3
M
' II
10.3
n s. '
n
10.3
II
II
10.3
M
n
10.3
n
n
10.3
ii
n
Corrected Concentration
(ppm, wet)
0.57
0.99
TR
0.52
0.99
TR
0.56
0.99
TR
0.66
1.37
TR
0.56
1.25
TR
0.66
1.24
0.05
0.40
0.99
0.05
0.39
1.18
0.05
-------
ro
Inject
Date Time
9-18-73 1705
(continued)
1720
1735
1750
1805
t
1823
Compound
CH3SH
DMDS
. H2S
CH3SH
- DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
CH3SH
DMDS
.H2S
CH3SH
DMDS
Attenuation
(Amps)
4 x 10"8
II
II
4 x 10"8
II
II
4 x 10"8
11
4 x 10'8
II
II
4 x 10"8
n
4 x 10"8
n
Peak
Height (%)
8.2
4.5
4.6
7.1
2.7
5.0
8.0
4.1
. 6.4
6.2
3.6
6.5
6.9
3.0
7.1
5.8
3.0
6.7
Concentration
(ppm, wet)
0.059 .
0.137
0.055
0.110
TR
0.058
0.131
0.005
0.052
0.124
0.005
6.054
6.115
0.005
0.050
0.005
. Dilution
Factor
10.3
II
II
10.3
II
II
10.3
"
10.3
II
II
10.3
10.3
II
II
Corrected Concentration
(ppm, wet)
0.61
1.41
TR
: 0.57
1.13 "-/
TR
0.60
1.35
0.05
0.54
1.28
0.05
0.57
1.18
0.05
0.52
1.18
0.05
NOTE: TR = TRACE < 0.005 ppm after dilution.
ND = Not detected.
Those sulfur compounds not listed were not detected.
-------
V: Inject '.'.' , Attenuation
Bate' .',".: llroe '.-.' Corrpourid .; ..'"." (Amps)
9/19/73 1055 H2S 4 X 10"8
CH3SH ' .
.'.' . . HMDS - ';' "
mo : .'.-,- H2s .:- ; _':"/ 4 x io~8 .
; . .-. . CH3SH ':.". \
. DMDS . / . " - ;
1125 H2S 4 X 10"8
. CH3SH '..-".
:.; DMDS -.'I'".'
1140 H2S 4 X 10~8
CH3SH " .
DMDS ..
1165 H2S 4 X 10"8 '
CH3SH
DMDS . "
1210 H2S ' 4 X 10"8
CH3SH " .
DMDS "
Peak : ;: Concentration . Dilution . Corrected Concentration
' Height ' (%} '.:.: *' (ppm, wet)-- ; .'.;." Factor '-'':. (ppm, wet)
20.8
6.7
2.8
/.:' 24.9
5.9
5.0
12.6
'.'' 5.0
5.0
14.4
4.1
5.0
' 11.9
5.6
4.8
8.3
4.5
4.5
: 0.076
0.093
".-;_ '.: TR
.;. 5; 0.083 ;
'V:-'. '0.086 : '-.'
"f..^ .TR -;
0.059
:.'. 0.078
'._.; TR
0.063
V 0.069
. ' TR
0.058
0.084
' TR
. 0.048
0.073
1 TR
'''' /".\'-.' 10.4'
. '. . 10.4 . .
' '-'ki'-ii'--- 10-4. ' ' ;
'.'"' ' '' 'L .. V -' '' : '
;..'-;.".- .-VV 10'4 :'-.-
:-::.^ ''.' ->'.'. .10.4 :/.. ;
_ ;?;,-.- ': 10.4.'- ;.'' =-
' :. . 10.4 :
. . . 10.4 . '.-'.';;
:.. ;. .','.; '".. ' 10. 4 '. ,.
'-'.-' ..'..'..' . 10.4' .; /;
.''..' 10-4
' 10-4 -.-.';'
10.4
10.4
-'': 10.4
/."'. ' 10.4 , "
'. '.-,'. 10.4 .;
...'/' . . .- 10.4 ''/
0.79
0.97
:' TR
0.86
0.89
. TR
0.61
0.81 .
TR
0.66
; 0.72
'. TR
. 0.60
0.87
TR
0.50
0.76
TR
-------
inject
Date Time
9/19/73 1225
(continued)
1240
*
1255
'".'
1310
: 1,1325
. ' ' ' ": ^
,1340
Compound
H2S .
CH3SH
DMDS
H2S
CH3SH
DMDS
H2S
. CH3SH ..
DMDS
: H2S .
. CH3SH
DMDS
1
H2S
. , i CH3SH
* !,! DMDS
H0S
i.
,,|CH3SH
,,!, DMDS
Attenuation
(Amps) n ' !
' 4 X 10"8
II
M
4 X 10"8
"
.;- . M
4 X 10"8
" .' -:
" \
4 X 10 "8 .
.
M
I 4 X,10~8
ir .
: 4 xi o"8
1 4 X.,10'8
1 "
'.. . .: ;« '.,..'
Peak
Height (%)
5.3
4.3
5.4
10.3
5.9
5.0
10.4
5.7
' 5.8
9.1 "'.'.'
4.6 :,'.,'
5.6
i ' '.'
',,5.1 '.'.
:4.0 '" :.
|8.7 ' :. ,
,;7.3
,5.2
i7k8
Concentration "'
' '. "' (ppm, wet)
0.039
0.071
0.005 .
0.054
0.086
'.*:.-'. TR ;. ...-. _''.-./.'
.' .-'././ 0.054 '..:.' ";,'';
.;:,.; 0.084,. ;.;.; ;-;
': v 0.005 ;';'' /'.',-'
'.'.''.' 0.050 .-'.'.' ::
. .:::;.- : 0.074 ; -;.;'"'.".''
' .'-'-.' '.i 0005 ''.. ' '
. » | .
:;';.,'. 0.038 ; ;
'/ ' .,0.068 . ''. '*:..-'
, . .1,0.006 ' ;.
" :;. 0.045 " .' :'
' '' '/'li- 0.080 ,: .'",'
' « ' JU0.006 ;'''. :^..:/V:"
Dilution
Factor
10.4
10.4
10.4
10.4
10.4
'- 10.4
10.4 .
-. ;,..- 10.4
':-';.. 10'4
: ..'; 10.4 '
; .'..' 10.4
: 10.4
' '
,,10,4
I..10.4
. n.10.4
MlO.4
.' I..10.4
niI0.4
Corrected Concentration
(ppm, wet)
0.41
0.74
0.05
0.56
0.89
, TR -'^
0.56
'/. , 0.87 ''..'..
' : o.os
: 0.52
0.77
.;., 0.05 '<
, 0.40
., 0.71
i 0.06
,, 0.47
,, 0.83
. ': . ,,,0.05
-------
Date
9/19/73
(continued)
en
inject
Time
1355
i 1410 '
1425
14501"
1455 '
1510 '
' Compound
HS
: CH3SH
. DMDS
' H2S '..
CH-SH .
. DMDS
H2S
. CH3SH '
DMDS
H2S
i i'i
CH3SH
DMDS
H2S
CH3SH ': .
DMDS
H2S
CH3SH "
DMDS
RTtenuaTTOn ..
(Amps)
; '4 X 10"8
ii
..'" '
:: -4 X 10'8 .'- ':.'
" : '
ii "
! Q
4 X 10'8
" '''.." ...'..
;;: ':. ,. ..'.
4xio78; '';
"
.11
4 x iol8 ':
""'.,
» / Pi '°' '
4 X 1078 '
ii .-.
, " ..-.';'.'
Teak
Height ft
9.8
6.1 , .
- 6.5 .
8.1 ;
5.6 ;
5.5
4.7 '
.4.6 >
6.3 ';';
6.5 ; -:";
6.0
6.5
3.0 ' ;.
5.0 "
. 9.8 ' .
5.1 '
5.9
7.8
CoficenFraTSon ;-
) *' (ppm, wet)1
0.050 ->
. :.. 0.088 . . ';--'. . \_;; .
'-";,'' 0.005..' ;.' '' .::/7-V.
'.V-VV'--'' 0.048 ";':v;;:V.:-V'Jv.
-"'*.-' ,lt ' '. '
'.':;'.;. 0.084 ;.' x- -;:,, .v, .
... ,'v'V" o.oo5 ';:.v .;::. '-
'. '. .' : .' '0.036 '}.".. ',"' .;.:;
.-;: .0.074 '.-^'- .'' :'- -..";..
...''''.-.r.'.' 0. 005 ':-'i':.;-;;;J '..';-...
; ' ;;-' .'"o.o42 ;'>.'''.. ^\'.( /
.'',' t
- 0.088 . V
.'.'.'. 1 ' "'..'.'
..-.:'. 0.005 ; : .. ' ...
..:.' :'';'': 0.029" .";: ; ':;';; '".
'":.} 0.078 '[''.: ;'-'./:; .-.
' '.; .::; 0.007 .' '.'-. '"'.'.. V-1. '.'>
: .. . ; ; 0.038' '.;..''.'..'..
V. ';' ;. 0. 086 . : .'-.; -,;;.
; ':;../ 0.006^:: .' ;'.-: ;-v
WTTtlon
Factor
10.4
10.4 , .
: 10.4 ..:
10.4 ;
10.4
: 10.4 .,
;. 10.4 '
'.:' 10.4 :.
10.4 : ";
10.4. .!
1 .
10.4
. 10.4 '
.10.4 ''
10.4 I-
10.4 1
: 10.4
10.4
10.4 '
CoTPStod Tof!Seit?SnSn
(ppm, wet)
0.52
0.92
0.05
-:'; . 0.50
: 0.87
0.05
0.37
0.77 ,
',';':. 0.05
.''':'. 0.44- .
< t > /
0.92
. 0.05'
0.30;"
0.81'1
. 0.07 '
0.40
0.30
; ' 0.06
-------
TfTject
Date Time -Compound
9/20/73 1020 H2S
CH3SH
:;.. ' '. DMDS '
. : 1035 . H9S
. '. i . ' , £
. CH3SH
. '.'o,.',.; '-. : . -..: DMDS ,
1 ' ' ,
1050 , H5S
1 ' (
, : . ,. ./ CH3SH
' ': ' ': " , DMDS
,' lies . H2s ;
. so2 '
CH3SH
.- . . ' DMDS
1120 H2S
. so2
CH3SH
', DMDS
; ' 1135 H2S
so,
CH3SH
.DMDS
Attenuation Peax '''
: ; (Amps) : - Height (20 ;
,. , 4 X 10"8 5.1 '
r " " ""''.'/ 5-9 - ; '
V .' " "' ';;. 7.8 '.".;.; .
4 X 10l8, 33.9 ,
"';' ." " ";- ' .10.5 ': '-'';
:' , " ' ::--:i.:V- 3.9 .'''.- .:'.-.
4 X 10"8 51.7
; ";;'. 14.9
:;: '".-' '" '" '. -' : ' 4.o..--."'"-; :
.,' , 4 x lo"8. .:;.' 20.0; .
'-'' . " .'.''' 3-° '-.v
'.'; ' . " .:. -.... : 8.5 : .-.
. ,'' ' " ::;' ;' "'; 14-1 .'/:::
4 x 10"8 13.9 ;
'" : :v: ..''.. 3.0
; " 7.1
'..'' u ;. '''. 7-7 ' ''.''
4 x lo"8 ; ,11.2
" 1.8
' " 5.1
" 3.9 :
, Conc(Siri'r'at1oo
. v (ppm, wet)
;: 0.038
.; 0.086 '..'
;r:;, o.ooe : :
../: 0.086 .-;.,-
1 '^^ 'e.T85 :;"; '
;;^;-TR ^$t
. 0.109 .; .-_.-' ';.
V/; 0.215
;;';;V'.TR }:;...
.:.v:; .0.068 ;.:.;"
'': .'." 0.034
:;.' :> 0.170 :? '
'.; ^0.008 v;
;;'.'': 0.056 ...'. :.
V 0.034
0.156 '.;.
::.. 0.006 "' V'-.'.
0.050
.' 0.026
0.134
". TR
. PTlutrBTI .; Correct5im)nce7rt?a'tion
. . .' '.' Factor ':. ''
..'.,;. ;.. ..9.9- ',;:.
'>::;';v''' '9-9. :
;;-.;,^/;...V 9.9,. '.;... '
?ri'..;!r'V. <9-9v.'!..'V
'..' '.' :' "' ''" . i '
X;:;K ;{.',; :;,9.9 '^:-^\
.:;,;;-;:;:-'. -5^;;V::-'.' '
;'-.-.: ;,- ' -9.9"; _':-.: v,
,.'-/ :.., /.. 9.9 '!-.;: --. ,'
:;;rv;;:\:9.9-;,v-;:';''
'' ''A'''; :.'. 9.9, ' '
:; ';''..: ' * -9i ';.':'. ' .
:;.::...:..,'..\:: .9>9;,.'::-,":-!-'
.\P.;' ' ' 9-9 ''.'''' '
.:'''' :' '*:9 '':' '''.'
,' ''''.'"'.. 9«9 '...-'' ;
. : ': '-::v ' 9-9 . '
'".' ' .\ 9.9 ': '
9.9
- ; . . 9-9 "' .-
9.9 .
(ppm, wet)
0.40
0.89
0.06
0.85 .
1.83
,'TR '"- ' . 'V^-v..-1
1.08'
2.13 '. . -
TR
0.67 . '
0.34
1.68 X";
0.08
0.55
0.34
1.54
.06
0.50
0.26
1.33
TR
.;,-, i:y^i.»T.'*
-------
ijeci
Date Time
9/20/73 '"; 1150
(continued)
; . 1205
»'*''
,;'.'.' : 1220
',.,»; ;
1235
' 1250
/
1305
1335
-
Compound
' H2S ,
. ". CH3'SH . ....
DMDS . >
: ,;::'V ;V
. : CH,SH .'.;.,
-., ' 0 :'"'
.;.;. DMDS :,
'' H2S :;,;;.
: CH,SH ;
i - o . -'
. DMDS
'''. H2S *
CH,SH ,
. o . '
DMDS ;.:\.
. . H S
CH3SH
, DMDS
H S '"'
CH,SH
J
DMDS
. V
CH3SH
DMDS
AttMftlon
(Amps)
4 X 10"8 ;
,4 X 10"8
:'..'" '.".''
. 4X18"8.
;. "' . . ''.''
" i."'.'
4 x io"8 .:';'
II ',' .;
. . /
: "' ;;"
4 X 10"8
." . !': \
.'.'" " } ''
4 X 10"8-
4 X 10"8
"
4 X 10"8
4 X 10"8
"
4 X 10"8
Illl
II
He1ght.'.(%) -./'.. V
.'. i7.i /-,';-i.-;.
; 6.1 .;. ;:;,;^
: 3>5;' , ".: ' :?^.
.' 15-4 ' / fe
V 4-4..'.;' ;'.3;S:
;v.: 5.8 ;'.;\^-;'£G.-'
13.6 f .':" M'
:;'.' 8-4 .' :".;' ! ;?-';
:':' 3-1 ''.-'" T',;;,\;
''. 15,4 ./ ' ';>:'
'.. 9.4 ;'.>'';'': ^
; :;''.. 4-3." .v:":' '^:;'
' 3-° ':'---:''':--":'.-.
5.2 ;/v ' ;.;.
7.4 ' "' "' <:'.'-
3.3 .;';.'/'''''" ;
' . 5.5' ' '.-. .';;'
5.4 :
8.3 .,
: 7.0 , ';.'..
4.0 '
JonSlfW'atlW
(ppm, wet)
0.062
0.147
:'.TR '..','.;"
0.059 .;-.'':
8.127 : ;;;;
0.005 v:
0.055,''V-
o.ieg ";.;,;:
TR: \r*S
0.059 ' '
0.173 .-;- ':.
.TR '''"'::-.
0.026
0.136
o.ooe . -..';
0.026 '[
0.139
0.005
0.043 ;
0.155 ' :
TR
:': v.:/:1 Factof
.-''.;: ::;'; 9.9 .- "
. :::'''::'". 9-9 ;'"
.::\.r.r ;/;.' 9.9
'S&'-^ 9-9-:
V--'--'v;\:-V 9.9 ?:;'
>',;:.''V^;V-'.-. 9.9 ";:;
''^;;;- :''"' 9.9 '.'
':':;:.'V'.r. '9.9>i.-.
v:;": ";.:'' '. 9-9 '.:
. !/':: '' .' 9.9 ... !
:'-. ''-; .;.' .9.9 ' '.
...;>'..' '."'. ;''9.9.-':.
;:".-'' :: ..' -9.9 ...
:,'y'' ' '-9.9 . '..
--V '"'.' "''.' 9.9 .
' "''.'.:''':'-.' 9<9 "
9.9
9.9
.:..'"':':' ' .. . 9-93 '
,'.;. /: :;'' 899 .
." "".'' !\ 9.9 ,
CBTrecfCS ConcenEPStfon
(ppm, wet)
'"' : / 0.61
'";'/:.' 1<46 -.
V ;''' TR . . ' '
VV' ''-.''". 0.58 ''.''.'
',;;V\"'. 1.26 "' ' ^ -,-
' / ' : 0.05
'" i .-' .' . '
;: '. ..:\ ' 0.54 '; . '. . -. ;'.
';' .'' '1-67 ' '-.'
{':. :-:. TR '. ' '
..'.;' :., o.58 . ;
.-;';;. ';:-. 1.71 . .";' '. ' ; ' -
":' TR ' ; ' . '' "
".'...' °-26
...; 1.35
.'.'" ' .0.06
' .' . / 0.26 , ''
'v'.. 1.38
0.05
...; V 0.43 ,
; '"-1. 54 .
'''. TR
-------
Inject Attenuation ' Peak '".''' Concentration ' -: ''-"' Dilution '- Corrected Concentratl
Date Time Compound ../ (Amps) ' Height (%) .;' 1420 ;'- :{';' H2S ' '.''
: , ':'' CH3SH
. ' /.' -.- DMDS
1 * . ' . .
\ ',".-.. .'. 1435 .,.' ' H2S =' (
. CH3SH ^
";". ' ":''. .' ' ' ,DMDS ;: :
. . -;..: 1450_;;- '-...:' ;H2S. ;.
' '.''.- . -. CH3SH ;.;'
':'',, " 'i ''. '. 6-7 ;.:
;^:4 x io"8 h 2.1 '>;;
'' ' :';" f.-^';.3.4 ?.;;
. - ;.". }-.' -; 6.2 :
4 X 10"8 9.9 ;'
: ' '': .: '':"' 6-5
':" " _.' \ ': .,.";". 5. e '.'";
. :': ;4. X 10"8 :.;-:. 3.9 ;
'1:""' "'''.. '"'? "':;''4-8--'
' . ... ' ' ;' DMDS '.'';- -.;"'' ":/ ;.. :/.7.2
"; 0.029
: : . °-120
J ;.;., ?:£" 0.005 ^^'S^.-l
''I'H ' M-^0.021 ,;;. ^ -;:S'^ ;^;;--7 ':
':;; -v-. £;;:.; '0.113 V:v:v ::/.' ',-.. '-'^
^'::-'-:)'&^0.047^'1/';-£v^/y::
'; -. ..v." '.'O.i so .-.:. :'\_ ;;,;;:'': -:.;:
; : ^':';;: 0.005. ';,;'.''; - '';:v.;,;/
:; 'V-:^::./ 0.030 :::/-O\^;: ^';;:;.;-:>
. .:,.(:. 0.005 ':.;. 'X.': J.\ .
9.9
9.9 .',; :
9.9 :::: -'-;".'?
;;9.9y'^V;r-;
.9.9 f : '.:.;-".' '
9.9 "':f .:''.
9.9 : .:. =: ;:':-"-
9.9.;. ;;/ .
'9. 9..- ";;. .:':.;;
' I'.l : ^ ^
9.9 ' ';'' .."
0.29
1.19
0.05 . .
: °-21 ',.'" '.-..
1.12
. 0.05 "'
0.47 . :
,1.49 ' .
0.05
;. 0.30 '/.;:. .
1.30 .
0.05 '-,:
CO
-------
PAWW-1ILL
Escanaba, Michigan
Lime Kiln
Inject
Date Time
9-25-73 1015
1030
1200
1215
1230
1245
1300
1315
1330
1345
1400
1415
1430
1445
1500
Compound
V
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H0S
Attenuation, Peak
(Amps) Height (%)
4 x 10"8 7.0
<1.0
" 1.8
" 3.6
4.1
4.0
1.9
2.4
2.3
5.7
4.8
3.1
4.7
4.3
3.9
Concentration
(ppm, wet)
0.046
<0.017
0.023
0.033
0.035
0.035
0.024
0.027
0.026
01041
0.038
0.031
0.038
0.036
0.034
Dilution Corrected Concentration
Factor (ppm, wet)
10.0 0.46
<0.17 -/
" 0.23
11 0.33
11 0.35
" 0.35
" 0.24
" 0.27
" 0.26
" . 0.41
" 0.38
0.31
0.38
" . 0.36
" 0.34
Sample line and probe backflushed.
-------
Date
Beginning of
9-25-73
*
'
Inject
Time
Run #2
1515
1530
1545
1600
1615
1630
1645
1700
1715
1730
1745
1800
1815
' 1830
1845
Kiln no
1900
Attenuation
Compound (Amps)
H2S 4 x 10"8
; H2s ', . » .;...'
H2S
.; H2s
H2S . 7
H2S "
H2S-
H2S . " ....'
so2
so2
V H2S . " .
H2S '
H2S . » .
MS " '
H2S
longer on (no charging).
H2S
Peak ..-.'
Height (%)
10.0
3.8 .-"
2.3
3.3
2.1 .
2.8
2.9
2.0
-------
f\3
Inject Attenuation -Peak
'Date- .. Time Compound ' (Amos) ''Height ' (%) .
9-26-73 ; 1155 HgS - 4 x 10"8 2.1
1210 H2S " 1.6
1225 . H2S . ". . ; <1.0
1240 H2S " <1.0
1255 H2S " 1-8
1310 H2S " . <1.0
1325 H2S " <1.0
1340 H2S " Vl.O
1355 H2S . " <1.0
1410 H2S . " <1.0
1425 H2S " 1.0
1440 H2S " <1.0
1455 ' H2S " <1.0
1510 H2S " <1.0
1525 H2S " <1.0
1540 H,S " <1.0
Concentration "
" (ppm, wet)- . .
0.022
0.019 .
;.:.:'' <0.015 :". ;
T : ; <0.015 ;
0.020
<0.015 .
<0.015
<0.015
<0.015
<0.015
0.015
<0.015
<0.015
<0.015
<0.015
'.'.- <0.015
Dilution Corrected Concentration
Factor (ppm, wet)
9.0 0.20
0.17
: ; " ' <0-14
<0.14
" 0.18 '/
11 <0.14
. " <0.14
" <0.14
" . . <0.14
11 <0.14
11 . 0.14
" <0.14
<0.14
" <0.14
: "
-------
ro
Date
9-26-73
(continued)
Run # 2 ,
. » '
»
inject
Time
1555
1610
1625
1655
1710
1725
1740
1755
1810
1825
1855
1910
1925
1940
1955
2010
AtterlUaflon
Compound ' (Amps)
(
H9S 4 x 10"8
t.
'.' H2S '; ':' " i'-'
H2S
H S "
U C II
H2S
H2S .
H2S .
H2S '
H2S
H2S
H2S .
u c ii
H2S
H2S
H2S "
PeaK. concentration Dilution
' Height (?.) "' (ppm, wet) 'Factor
ND . . ND . ' . 9.0 '.
-------
CO
Inject
Date Time
9-27-73 1000
1015
1030
1045
1100
1115
1130
' 1145
1200
1215
1230
1245
1300
1315
1330
1345
Compound
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S
H2S .
H?S
H2S
H2S
H2S
H2S
H?S
Attenuation PeaK Concentration
' (Amps) ' Height (%) " (ppm, wet)
4 x 10"8 3.4 0.030
11 1.0 0.016
" " <1.0 <0.016
. *
<1.0 <0.016
" <1.0 ,.' <0.016
11 <1.0 <0.016
" -<1.0 <0.016
11 <1.0 <0.016
" <1.0 <0.016
<1.0 . . <0.016
" <1.0 <0.016
11 <1.0 .<0.016
" <1.0 . ' <0.016
11 ' <1.0 . <0.016
" <1.0 <0.016
" <1.0 / <0.016
DTlution Correctnd Conceotratii
Factor (ppm, wet)
8.4 0.25
".'.. 0.13
" ;.'. <0.13
" :'.;'' <0.13
<0.13 -..,./
" <0.13
; " ; <0.13.
' " :. . <0-13
" - <0.13
" . <0.13
" <0.13
'' <0.13
'' <0.13
" <0.13
'' <0.13
'» <0.13
-------
Inject Attenuation -Peak.- Concentration TJTTution Corrected Concentration
lite. Time Compound ' (Amps) ."Height (X) s (ppm. wet)- 'Factor (ppm. wet)
9-27-73. ' ; ' ' ; ' :' ' " ' '. ', '"' . ' '".
(continued) , .
Run n . 1400 H2S 4 x 10"8 . <1.0 ,- i/.'...' <0.016 , ;. :; 8.4 ; ; ^ : <0-
1415 H2S :: " .; <1.0 ;"'!' <0.016 T ; .: " ''/ c ..'v/ <0-13
1430 H2S " - 1.1 ; ;'" 0.017 "'.'' 0.14
' .", 1445 H2S " = ND ''.- . ND ; " : . NO
. .1500 H2S " ND ' ND ... ND
Started burning oil at 1505Plant Barton gave a quick peak, going up then coming back down after five minutes.
1515 H2S " 1.3 ' 0.018 " 0.15
1530 H2S ' " ND ND . " ' ND
1545 H£S ' " <1.0 , <0.016 " <0.13
1600 H?S " <1.0 <0.016 " <0.13
1615 H9S " . ND ND " ND
t C . "
1630 H2S " ' ND . ND " ' NO
1645 . H2S " . ND . ' ND .'."'" ND
1700 H2S . " ND . ND " ND
' 1715 H2S '".-. ND ..'..'. ND " - ND
1730 H2S " . ND ; ND " ND .
1745 H0S " ND NO .. ND '
-------
III. PROCESS DESCRIPTION AND OPERATION
The Escanaba Paper Company mill at Escanaba, Michigan, produces
about 650 tons of paper per day from its own bleached kraft pulp. The
paper mill began operating in 1917, and the kraft pulping operation
started in May 1972. .
The EPA test program conducted at this mill, included measure-
ments on the smelt dissolving tank (particulates and TRS emissions),
and the lime kiln (TRS emissions).
Process Description
A. General
.The process for making kraft pulp from wood is shown in Figure 2.
In the process, wood is chipped into small pieces and then cooked in a
continuous_digester at elevated pressure and temperature in "white liquor"
(a water solution of sodium hydroxide and -sodium sulfide). The white
liquor chemically dissolves lignin, leaving wood cellulose (pulp) which
is filtered from the spent liquor and washed. The pulp is bleached and'!
made into paper. .,,» - - /
" The"balance of the pulping process is designed to recover the cooking
-chemicals- Spent cooking liquor and the pulp wash water are combined for
treatment to recover cooking chemicals. The combined stream, called weak .
black liquor, is concentrated in steam heated multiple-effect evaporators,
including a special effect called a "concentrator." The strong black
liquor leaving the evaporators is fired in a recovery furnace.
Combustion of the organics in the black liquor provides most of the
heat needed to generate process steam. Inorganic chemicals from the black
25
-------
cr
2:
«
c.
MM
5!
c
L
«
c
L
_C
l-fonrl >
. . ' '
t
; * V'lvi to 1 i cuor 5
' (NaOH + Na2S)
f "...
(STACK 'LJ
(Naj
£
2 - --Water ~->
3 ' f .
J
J
< . ..,,....- ...
t.. ;-
v;;r.te liquor
(recycle- to'
digester)
"-."" . t .-..- . - ; . .
... _:.-__ ;":'.;_; /; . ...-.,. -.. ;.. .;.-.. " ...v. , \ : .'. :..'..''
^ " ^»^^ .
nTRFSTFR . D , ^ PH! P . ^ ri ' '
SYSTEM' " Pul|j - .WASHERS . PL|IP
3 s , '°' Water
- " -'. '. ..- -.- - '... . . '. -. : .. * - . .:.- ,
MULTIPLE
.RECOVERY Msavy EFFECT
Fl'Fl^TF t b'SCK EVAPOPATOP
CYCTFM liquor . SYSTEM < !
.Air
Smelt .'..:.. ' ' ' ' '"" ' .
ii fl ^ "! rJ^ioS i ' " " '
f V/ \J *. ' l\U S*J J . . -.--,.... ....
1 ' - - ,,;:,:::...; -.V^,;.-
SMELT - ,...;
.DISSOLVING -..-.- . : .....,....--. I.-UA. -. -.
TANK. '.'-."'.
-.-I'- : :: ?"<: ;
Green Liquor ^ "A ^^_^-
CAUSTICIZIHG . | ^.p \ \V^^^*
iAu,; ^".. . \>^-^ .
cnlcii;-:;
: ' ' ' - mud "x-
Figure 2 !'jV,FT rUi.Pi;^ ^'iOCLiiS, '
26 .,
-------
liquor are recovered as a molten smelt at the bottom of the furnace. The
smelt, consisting of sodium carbonate and sodium sulfide, is dissolved in
water and transferred to a causticizing tank.. Lime added to this tank
converts sodium carbonate to sodium hydroxide, completing the regeneration
of white liquor, which is then recycled to the digester. The calcium
carbonate mud that precipitates "from the causttcizing tank, is recycled
to a kiln to regenerate lime.
B. Recovery Furnace and Smelt Dissolving Tank
The recovery furnace was designed by Babcock and Wilcox to burn
100,000 pounds of black liquor solids per hour, which corresponds to a
pulp production rate of 800 air dried tons per day. This direct fired
.^"y
_ unit was installed in May 1972. -
Exhaust gases are treated in a Western Precipitation electrostatic
precipitator, backed up with four parallel low pressure drop scrubbers
manufactured by Chemical Construction Company. The precipitator and
scrubbers are located on the roof of the furnace. The precipitator was
"Installed with the furnace in 1972, and the scrubbers were added in 1973.
The molten smelt formed at the bottom of the recovery furnace is
-drawn into a water filled tank, called a smelt dissolving tank. The
reaction between the-hot smelt and the receiving water generates steam,
which is blown through a scrubber to remove entrained particulates.
The scrubber, shown in Figure 3 , was manufactured by Ducon and is
basically a wet fan cyclone. Scrubbing water is injected into the fan,
and the gas and water are swirled through the scrubber; additional water
is sprayed from above, and drains back to the dissolving tank. Before
27
-------
O
"ySampli
ing Ports
WIRE MESH
(DEMISTERS)
Pressure"
Relief
Valve
_. Smelt
(From recovery
furnace)
FAN
Loose Packing
WET FAN
SCRUBBER
\y
SMELT DISSOLVING TANK
Green Liquor
GREEN
LIQUOR
CLARIFIER
Water
.(From lime
mud washers)
-*- Clarified
Green Liquor
-> Dregs
FIGURE .3 SMELT DISSOLVING TANK AMD SCRUBBER. Escanaba Paper Company
Mill at Escanaba,- Michigan.
..28
-------
leaving the scrubber, the gases pass through e two foot section of loose
plastic packing for water removal. The gases then enter the stack and
pass through a conventional wire mesh demister before being discharged
to the atmosphere. The scrubbing water, called "weak wash", is'the
effluent from the lime mud washers. ,
C. Lime Kiln
The plant .operates a single rotary kiln to regenerate lime from the
calcium carbonate slurry precipitated from the causticizing tanks. The
slurry is washed and then dried on a rotary vacuum drum as shown in
'Figure -4 . The dried cake is removed from the drum by a knife edge and
conveyed to the kiln. The kiln is heated by burning oil or gas. In
the kiln, the calcium carbonate lime mud is roasted; carbon dioxide is .
driven off, leaving calcium oxide (lime) as product.
The kiln was built by All is Chalmers and installed in May of 1972.
The kiln is 275 feet long and has a diame.ter of 11 1/2 feet. It is
designed to produce 220 tons of calcium oxide (lime) per day. The design
feed rate of mud to the vacuum filter is 175 gallons per minute at 28
percent solids. No additional feed is used, makeup is supplied by
purchased-fresh lime. The-kiln is fired with either natural gas or #2
fuel oil. .-Dregs from the smelt dissolving tank are not burned in the
kiln.
The plant has installed an elaborate system for collecting noncondensabl.e
gas streams throughout the mill. Vent gases from the digesters, evaporators,
condensate stripping tower, and miscellaneous storage tanks are collected
and burned in the lime kiln. Foul oil, separated from the stripped.
condensate, is stored and burned in the kiln for about 12 hours every
4 or 5 days. ' v .
29 .
-------
co
o
Limestone-
Mud (feed)
Air
Fue
(oil or gas)
Lime (product)
Fresh Lime (makeup)
To Causticizing Tank
Fuel Gas
Air
STAND-BY
INCINERATOR
Combustion
Gas 1
Fresh Water
Sodium Hydroxiden ^ J,
Water
MIX
TANK
Sampling
Ports
Bleed
.''FIfiURE 4 LIME KILN AND VENTURI SCRUBBER. ESCANABA PAPER COMPANY MILL AT ESCANABA MICHIGAN.
-------
Exhaust gases from the kiln are cleaned in an adjustable throat
venturi scrubber. The scrubber was designed by Zurn with a 19 inch
water pressure drop, and installed with the kiln in 1972.
Water used in the scrubber is about 75 percent recycle and 25 percent
fresh water. A sodium hydroxide solution is added to the .scrubbing water
to reduce hydrogen sulfide emissions. The caustic is added at the rate
of about 4 gallons per minute of 8 percent sodium hydroxide. This
unusual practice is reportedly very effective in aiding control of hydrogen
sulfide. The water bled from the scrubber is used first to wash the mud
slurry charged to the kiln, and is then pumped to the smelt dissolving
tank. . "
The kiln gases exhaust through a 275 foot stack, which is exceptionally
high for kilns and protects against upsets. The same stack receives gases
from a standby incinerator used to burn the noncondensable gas streams
when the kiln is not operating. The incinerator is kept running continuously,
even when not burning the noncondensables; the hot gases heat the kiln
gases preventing excessive condensation and rain about the stack. During
all tests on the lime kiln, however, the incinerator was shut down to avoid
..diluting the kiln gases and lowering the TRS measurements.
Process Operation ' ...
A. General .
The purpose of the tests was to measure emission levels during normal
plant operation. Process conditions v/ere carefully observed and testing
was done only when the test facility appeared to be operating normally.
During the tests, important process conditions were monitored end
recorded on data sheets. Readinas were taken about once an hour. These
31
-------
data, and keys to the entries, are in the appendix. Entries shown in
the key with an asterisk, were obtained from continuous chart recorders,
and the readings are averages. The first reading is averaged over the
previous half hour, and .subsequent readings are averaged over the last
interval. Suppose, for example, the first readings were made at 1000
and 1100 hours; the 1000 reading is the average between 0930 to 1000
hours, and the 1100 reading is the .average between IQPO to 1100 hours.
Entries without an asterisk in the key are instantaneous readings.
The process data obtained are summarized below.
B. Smelt Dissolving Tank
The flow of smelt to the dissolving tank cannot be directly monitored.
The best indication of a normal smelt flow rate, is the operation of the
recovery furnace. When the furnace receives its usual charge of black
liquor and operates in its customary way, the production of smelt will be
normal. Accordingly, furnace operation .was monitored along with available
process indicators for the dissolving tank. The latter included the
dissolving tank level, the green liquor clarifier level, and the flow
rate of green liquor from the clarifier (refer to Figured ).
~~hs far as known from the process data and discussions with the
operators, the equipment operated normally during the tests. As shown on
the data sheets, the black liquor charging rate ranged between 225-275
gallons per minute (gpm); solids content, as fired, ranged from 64.9-65.8
percent.
A green liquor sample taken during the third particulate run (1400 hours,
Sept. 19, 1973) was analyzed by the plant. The reduction ratio was found
to be an acceptable 90.1 percent, showing.good conversion of sodium sulfate
to sodium sulfide in the recovery furnace.
32
-------
C. Lime Kiln
As far as known, the operation of the lime kiln was normal during
the tests. As shown on the process records (appendix), the mud charging
rate was about 175 gallons per minute. The noncondensable gases from the
digesters, etc. were burned in the kiln as usual. The caustic addition
rate to the venturi scrubber was also normal, at about 4 gallons a minute.
During the Vast test run, on September 27, the plant was asked to
burn the foul oil collected from the condensate stripper. When the oil
was introduced to the kiln at 1505 hours, the plant's Barton titrator
indicated a rise in TRS concentration from about 0.27 to 18.9 ppm. Air
flow to the kiln was quickly increased and the TRS reading soon dropped
below 1 ppm. The rise and fall in TRS occurred between sample injects on
the EPA gas chromatograph, and were not observed.
D. Equivalent Pulp Production Rates
In a kraft mill, recovery operations are closely related to pulp
production. A given feed rate of lime mud to the kiln, for'example, is
equivalent to a certain pulp production rate in the digesters. As a
result, pollutant emission rates can be expressed on the basis of equivalent
pulp production, as "shown below:
/^mission Rate\ -/Emission Rate\ , yEquivalent Pulp\ - . .. /,\
I Ib/ton-pulp } = ( Ib/hr } ' (Production Rate* Equation (1)
ton/hr
For calculating lime kiln emission rates, the equivalent pulp
production rate was assumed to be the average pulp production rate at
the mill, as determined the month preceding the tests. In that period,
plant-records for total production (hard and soft wood) indicate an average
of 27.5 tons of unbleached air dried pulp per hour.
33
-------
For calculating emission rates from the dissolving tank, increased
accuracy was desired. Equivalent pulp production was calculated from
the amount of black liquor fired during each test run, as shown below:
/EquivalentX /Black \ /Pulp to LiquorX /Actual % Solids\ Cniia4...n_
(Pulp I _[ Liquor ] [Ratio at Avg. \ lAvg. % Solids ]' tcluatlon
I Production / ~l Charged I 1% Solids /-
\tons / . \Gallons / \tons/gallon /
The last term in Equation 2 corrects for the actual percent solids (in
the black liquor charged), compared to the average percent solids on which
the pulp to liquor ratio is based.
/
The pulp to liquor ratio in the above equation was determined from
plant records for August 28 to September 26, 1973 (the 30 day period
ending with the test runs). The total production from hard and soft wood
during this time was 19,756 unbleached air dried tons of pulp. Integrator
readings show that 8,101,056 gallons of black liquor were charged during
the same period. By division, the pulp to liquor ratio is found to be
0.00244 tons per gallon.
The average solids content of the black liquor charged during the same
time period was determined from the furnace operator's hourly records of
solids content. The average of all the readings was found to be 63.8
percent.
Substitution of the above determined values into Equation 2 gives;
/EquivalentX /Black \ , . ,
Pulp .]_/ Liquor V /0-.00244 /Actual % Solids . rQ,,tion
I Production / ~l Charged Uon/gallonJ I SO I, tquation
\tons J ^Gallons/ x '
34
-------
Equation 3 was used to calculate the equivalent pulp production
during each day that tests were made on the dissolving tank. The gallons
of black liquor charged and the actual percent solids were obtained from
the process data in the appendix. Correction factors were needed for the
black liquor flowmeters, however, as explained below.
During the tests on the smelt dissolving tank a furnace operator
pointed out that the black liquor flowmeter and integrator were out of
calibration. Beginning September 16, the indicated flow rate had climbed
from 200 to 280 gpm; the actual charging rate, however, apparently did
not increase because: a) steam production did not increase; b) the oxygen
content of the exit gases did not decrease; c) the amount of air charged
did not increase; and d) the pressure in the charging guns remained about
constant. To develop a correction factor for the flowmeter readings, the
calculations described below were made.
The furnace operating log was examined for the period August 28 to
September 26, 1974 (the same period used to determine the pulp to liquor
ratio above). The daily production of steam in pounds (S), and the
-daily charge of black liquor in gallons (L), were calculated from integrator
readings. The.daily average of the liquor charging pressure in psig (P) was
calculated from the hourly readings. (To coincide with the log, each
"day" began and ended at 0700 hours). For each day, the ratios of L/S,
L/(p) > and S/(p)^/2 Were calculated, as summarized in Table 5.
35
-------
Table 5 Black Liquor, Steam, and Charging Pressure Ratios,'
And Percent Deviation from the Average
Aug 28-Sept. 26, 1973
Average Ratio
"% Deviation, Range
% Deviation; Avg.
Sept. 18, 1973
Ratio
% Deviation
Sept. 19, 1973 .
Ratio
% Deviation
Sept. 20, 1973
Ratio
% Deviation
L/S
4.114
+39.1 to-24.7
12.0
5.144
+25.0
4.756
+15.6'
4.565
+11.0
L/CP)1/2
32.4
+'43.9 to -25.9
13.2
41.9
+27.7
38.2
+16.5
. 36.7
+11.9
S/tP)1^
47.8
+5.0 to -5.2
2.1
48.8
+2.1.
48.2
+0.8
48.3
+1.0
36
-------
The calculated ratios should be nearly constant; steam production is
proportional to the amount of liquor fired, which in turn is proportional
to the square root of the charging pressure. (Some variations will
occur due to changes in the-heat content of black liquor, soot blowing,
and auxiliary fuel burning. The ratios were not calculated for September
11, because a large quantity of oil was burned.) The variations shown in
Table 5 support the conclusion that the black liquor flowmeter was
reading high during the emission tests. Both ratios involving L rose and
fell together from day to day^whereas the S/(P)^/ ratio was nearly
constant.
The amount of drift in the black liquor flowmeter during the tests
was estimated from the percentage deviations shown in Table 5 . On
September 18, for example, the black liquor flowmeter apparently read high
by 25.0 to 27.7 percent; averaging gives a correction factor of minus 26.4
percent. The similar correction factors for.September 19 and 20 are minus
16.0 and minus 11.4 percent, respectively.
Based on the above correction factors and Equation 3, equivalent pulp
.production was calculated for each test day. Dividing by the elasped
Jtime between black.liquor integrator readings gave the equivalent pulp
production rate. These calculations are summarized in Table- 6 .
In summary, emission rates, in units of pounds per ton of pulp,
are calculated from Equation 1. Equivalent pulp production rates to use
in this equation are shown in Table 7' .'
37
-------
Table 6 SUMMARY OF CALCULATIONS FOR EQUIVALENT PULP PRODUCTION RATE
Date
1973
Sept. 18
Sept. 19
Sept. 20
Elack Liquor Readings^ '
Hours
Start
1015
1010
0908
Finish
1826
1 546
1430
Integrator
Start
14131295
14504876
14821080
Finish
14255511
14593650
14895940
% Solids
Avg.
65.5
65.2
65.5
Black
Liquor
Measured
gal .
124216
88774
74860
Correction
factor
%
-26.4
-16.0
-11.4
V*
Black
Liquor
Charged
gal .
98272
76529
67199
(2)
Equivalent
Pulp
Production
tons
246.2
190.8
168.3
Elasped
Time
hr
8.18
"
5.60
5.37
Equivalent
Pulp
Production
Rate
tons/hr
30.1
34.1
-31.3
OJ
oo
(1) Items 11,12, and 14 on the process data sheets.
(2) Calculated from Equation 3
-------
Table 7 Summary Of Equivalent Pulp Production Rates To Be
Used with Equation 1
Day of Test
1973
Sept. 18
Sept. 19
Sept. 20
Sept. 24-27
Facility
Dissolving Tank
Dissolving Tank
Dissolving Tank
Lime Kiln
Equivalent Pulp Production Rate
ton/hr
30.1
34.1
31.3
27.5
39
-------
KEY TO INSTRUMENT READINGS ON RECOVERY FURNACE PROCESS DATA SHEETS
*1. Net rate of steam production (not Including steam used for soot blowing)
2. Running total of net steam production.
3. Time corresponding to item 2.
*4. Temperature of steam leaving the furnace.
*5. Pressure of steam leaving the furnace.
*6. Boiler feedwater flow rate.
7. Running total of boiler water fed. .
.8. Time corresponding to Item 7.
*9. Feedwater temperature.
*10. Feed rate of black liquor to the furnace.
11. - Running total of black liquor fed to the furnace.
12. Time corresponding to item 11. ;
*14. Percent solids in black liquor charged to the furnace.
*15. Temperature of black liquor charged to the furnace.
16. Pressure of black liquor charged to the furnace.
17. Number of spray guns charging black liquor to the furnace.
18. Diameter of spray gun nozzle.
19. Setting of damper to bypass black liquor around the furnace.
~~20. Feed rate of salt cake makeup.
24. Running total of auxiliary oil charged to the furnace with time of
reading in parentheses.
25. Number of auxiliary fuel burners.
*26. Temperature of gas leaving the furnace.
40
-------
27. Temperature of gas entering the precipitator.
*28. Temperature of gas in the stack. '
*30. Temperature of combustion air entering the furnace: primary air/secondary air.
31. Total flow rate of combustion air to the furnace.
*32. Flow rate of primary combustion air to the furnace.
*33. Flow rate of secondary combustion air to the furnace.
*34. Flow rate of tertiary combustion air to the furnace.
*35. Concentration of oxygen in combustion gases leaving the furnace.
*36. Concentration of combustible gases (CO, hydrocarbons) in combustion
gases leaving the furnace.
37. Furnace draft.
38. Induced draft fan. .
*39. Concentration of TRS in the stack (Company monitor}.
*40. Green liquor storage tank level.
41. Green liquor density; no units. A reading of 0.95 means 9.5 cc of
1.933 normal HC1 are required to titrate 50 cc of green liquor to
the methyl orange end point.
*42. Green liquor clarifier level. .
*43. F-low rate of clarified green liquor to causticizer.
*Readings are obtained from continuous chart recorders, and are averaged
over the previous time interval. Initial readings are averaged over the
previous half-hour.
41
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44
-------
KEY TO INSTRUMENT READINGS ON LIME KILN PROCESS DATA SHEETS
*1. Feed rate of lime mud to filter.
2. Solids content of lime mud to the filter. ' .
*3. Flow rate of oil to the kiln.
*4. Flow rate of natural gas to the kiln.
*5. Flow rate of combustion air to the kiln.
6. Total amount of gas burned in the kiln.
7. Total amount of oil burned in the kiln.
8. Time corresponding to items 6 and 7.
*9. Concentration of oxygen in kiln exit gases.
*10. Temperature of gases at the hot end.,of the kiln.
*11. Temperature of gases leaving the kiln.
12. Pressure drop across venturi scrubber.
13. Flow rate of caustic to scrubber mix tank. .
14. Flow rate of fresh make-up water to scrubber mix tank.
*15. TRS concentration in the stack (company -Barton).
*Readings are obtained from continuous chart recorders, and are averaged
over the previous time interval. Initial readings are averaged over the
previous half hour.
45
-------
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52
-------
IV. LOCATION OF SAMPLING POINTS
Figure 2 shows the sampling ports and the number of
sampling points at the smelt dissolving tank exit .vent. The
test site was located in a 47.6-inch round vertical duct.
Samples were collected at 20 points (10 along each diameter).
The distance from the sampling location to the nearest down-
stream disturbance was 7 duct diameters; the upstream distance
was 3 duct diameters. Twenty sampling points were chosen
as prescribed by the Federal Register; Method 1.
Figure 3 shows the sampling ports and the number of
velocity traverse points at the lime kiln exit 'vent. The
inside duct diameter was 48", eight diameters from the nearest
downstream disturbance and nearly 40 diameters from the nearest
upstream disturbance. The stack wall thickness was 25" at the
test site. Twelve velocity traverse points (6-along each
diameter) were determined from the Federal Register, Method 1.
1) Federal Register, .Vol. 36, No. 247, December 23, 1971,
53
-------
GREET!
LIQUOR
'
FROM
RECOVERY
. FURNACE
1
1
1
1
1
SHELT
DISSOLVING
TANK
1
DEf
^*"v.
0
us-
t
2
\
}-
4
^v
TE
^^
81
8'
D
-X^
SCRUBBER
47.587" I.D.
3.125" NIPPLES
h" W.T.
PORT A
PORT B
CROSS-SECTION
Figure 2. Smelt-dissolving tank sampling site.
54
-------
48" I.D.
25" W.T.
PORT B
PORT A
CROSS-SECTION
LIME
KILN
SCRUBBER
DEMISTER
150'
50
FigureS. Lime kiln sampling site
55
-------
V.. SAMPLING AND ANALYTICAL PROCEDURES
All sampling procedures were selected by EPA prior to
field sampling. All analyses of collected samples were
performed by PEDCo. Appendix E contains detailed sampling
and analytical procedures.
Velocity and Gas Temperature
All gas velocities were measured with a type S pitot
tube and inclined draft gage. In all cases velocities were
measured at each sampling point across the stack diameter to
determine an average value according to procedures described
in the Federal Register - Method 1. Temperatures were measured
with long stem dial thermometers.
Molecular Weight
A four hour integrated sample of the stack gases was
collected daily by pumping the gas into a Tedlar plastic bag at
the rate of approximately 0.015 CFM. This bag sample was then
analyzed with an Orsat analyzer for CO-, 0?, and CO as described
in the Federal Register, Method 3.
Particulates
2
Method 5 as described in Federal Register, was used to
measure particulate matter. A rigid train consisting of a
1) Federal Register, Vol. 36, No. 247, December 23, 1971.
2) Federal Register, Vol. 36, ...No. 247, August 17, 1971.
56
-------
heated .glass lined probe, a 3" glass fiber filter, and a series
of Greenburg-Smith impingers was employed in all particulate
tests as shown in Figure 4.
Sampling was conducted under isokinetic conditions by
monitoring the velocity with a pitot tube and adjusting the
sampling rate accordingly.
Sample recovery consisted of triple rinsing the nozzle,
probe, cyclone by-pass, and front half of the filter holder with
acetone into a glass container. The back half of the filter
holder, impingers, and connecting tubes were first rinsed with
distilled water, and placed into a glass container along with the
impinger contents. These components were then triple rinsed with
acetone and these washings placed into another glass container.
The filter was placed in a separate container.
N0x
Nitrogen oxides were collected in evacuated flasks containing
a dilute sulfuric acid-hydrogen peroxide absorbing solution. The
sampling and analytical procedure, as described in Method 7 of
the Federal Register, was used. The samples were analyzed using
PDSA method.
1) Federal.Register, Vol. 36, No. 247, December 23, 1971.
57
-------
Moisture
Method 4 of the Federal Register was used to determine stack
gas moisture content. A flue gas sample was drawn from the gas stream
through a heated probe, a series of midget impingers contained in an
ice bath, and a pump and dry gas meter assembly. The moisture was then
measured volumetrically and the proportion of water vapor in the gas
stream was determined by calculating the equivalent volume of the
condensate.
Total Reduced Sulfur
The following Method 16, "Semi-continuous Sulfur Emissions from
Stationary Sources", contains the procedures used for obtaining the
reduced sulfur concentrations.
1)Federal Register, Vol. 36, No. 247, December 23, 1971
58
-------
METHOD 16 - SEMICONTINUOUS DETERMINATION OF
SULFUR EMISSIONS FROM STATIONARY SOURCES
1. Principle and Applicability
.
1.1 Principle. A gas sample is extracted from the emission source
and diluted with clean dry air. An aliquot of the diluted sample is
then analyzed for gaseous sulfur compounds by gas chromatographic separa-
tion and flame photometric detection. Two GC/FPD analytical systems
equipped with suitable columns are used for resolution of both low and
high molecular weight sulfur compounds.
1.2 Applicability. This method is applicable for determination of
total reduced sulfur (TRS) in support of the New Source. Performance Stan-
dards for Kraft mills.
2. Range and Sensitivity
2.1 Range. The maximum range of the flame photometric detector for
each sulfur compound is about 1 ppm. This range is expanded by the a-
mount of sample gas dilution employed before analysis. Kraft mill gas
samples are normally diluted 10:1,and therefore the upper range is 10 ppm.
2.2 Sensitivity. The -minimum detectable concentration is less than
0.5 ppb.
3. Interferences
3.1 Moisture. Condensation in the analytical column and FPD burner
block may cause interferences. This potential is eliminated by condition-
ing the sample with dilution air to lower its dew point below the operating
Sulfide gases, hydrogen, and oxygen form toxic or flamab'le irixtures,
Work with these materials in a well-ventilated area.
-------
2
temperature of the GC/FPD analytical system prior to analysis.
3.2 Carbon Dioxide and Carbon Monoxide. The concentrations of CCL
and CO in Kraft mills have a substantial desensitizing effect on the
detector even after 10:1 dilution. The operating conditions described in
this procedure eliminate this interference because COp and CO are eluted
with the "air peak" prior to elution of any sulfur compound.
3.3 Particulate Matter. Particulate matter in gas samples causes
interference by eventual clogging of the analytical system. This inter-
ference is eliminated by use of a filtered probe described in Section 5.
4. Precision and Accuracy
«
4.1 Precision. Repeated analyses of the same standard sample, at any
dilution, should not exceed 5% relative standard deviation.
4.2 Accuracy. The accuracy is dependent on the accuracy of calibra- «
tion standards used and the sample dilution employed. Permeation tube
standards are considered primary standards. When the analytical systems
are calibrated as described in Section 8, the error in analysis of other
permeation tubes or compressed gas standards, at any required dilution,
should not exceed 10%.
5. Apparatus
5.1 Sampling (Figure 16-1)
5.1.1 Probe. Stainless steel or sheathed borosilicate glass
equipped with a glass v/ool filter to remove particulate matter. The ex-
posed portion of the probe between the sample line and sampling port should
be heated with heating tape.
-------
5,1.2 Sample Line. 3/16 inch inside diameter FEP Teflon"'
tubing, heated above 100°C.
5.1.3 Sample Pump. Leak-less Teflon coated diaphragm type or
»'
equivalent. The pump head should be heated above 100°C.
5.2 Dilution System. A schematic diagram of the dynamic dilution
system is given in Figure 16-1. Alternate dilution systems may be used
if they meet specifications shown in the addenda B ,
5.2.1 Pump. Model A-150 Komhyr^ ' Teflon positive displacement
type, non-adjustable 150 ml min j^l.5%, or equivalent, per dilution stage.
A 10/1 dilution of sample is accomplished by combining 150 cc of sample
with 1350 cc of clean dry air as shown in Figure 16-1.
5.2.2 Valves. Three-way Teflon solenoid or manual type.
5.2.3 Tubing. Sufficient Teflon fittings and tubing to assure
that all sample and calibration gas contacts are Teflon.
5.2.4 Box. Insulated box, heated and maintained above 100°C, of
sufficient dimensions to house dilution, apparatus.
5.2.5 Flowmeters. Rotameters or equivalent to measure flow from
0 to 1500 ml/min +_ 1.0% per dilution stage.
5.3 Kraft Mill Analysis. Tv/o types of columns are used for separation
of low and high molecular weight sulfur compounds.
5.3.1 Analytical system for measurement of low molecular weight
sulfur compounds (GC/FPD-1), (See Figure 16-2 and Addendum A). Separation
Column - 36 feet by 0.085 inch inside diameter Teflon tubing packed with
(1) Mention of trade names or specific products does not constitute an en-
dorsement by the Environmental Protection Agency.
-------
4
30/60 mesh Teflon coated with 5% polyphenyl ether .and 0.05% orthophos-
phoric acid, or equivalent.
5.3.2 Stripper or Precolumn. 2 feet by 0.085 inch inside diameter
Teflon tubing packed as in 5.3.1.
5.3.3 Sample Valve. Teflon ten-port gas sampling valve, equipped<
with a 10 ml sample loop, actuated by compressed air.
5.3.4 Oven. For containing sample valve, stripper column and
separation column. The oven should be capable of maintaining an elevated
temperature ranging from ambient to 100°C, constant within +_ 5°C.
5.3.5 Temperature Monitor. Thermocouple pyrometer to measure column
oven, detector, and exhaust temperature +_ 2%.
5.3.6 Flow System. Gas metering system to measure sample flow,
hydrogen flow, oxygen flow and nitrogen carrier gas flow.
«
5.3.7 Detector. Flame photometric detector as specified in Addendum A.
5.3.8 Electrometer. Capable of full scale amplification of linear
-9-4
ranges of 10 to 10 amperes full scale.
5.3.9 Power Supply. Capable of delivering up to 750 volts.
5.3.10 Recorder. Capable of full scale display of voltages from elec-
trometer amplifier in the 1 millivolt range.
5.3.11 Analytical System for Measurement of High-molecular Weight
Sulfur Compounds (GC/FPB-II). (See Figure 16-2 and Addendum A). Separation
Column - 10 feet by 0.085 inch inside diameter Teflon tubing packed with
. 30/60.mesh Teflon coated with 10 percent Triton X-305, or equivalent.
5.3.12 Sample Valve. Teflon six-port gas sampling valve equipped
-------
5
with a 10 ml sample loop, actuated by compressed air.
5.3.13 Other Components. All other components same as in
5.3.4 to 5.3.10.
'
5.4 Calibration. Permeation tube system (Figure 16-3).
5.4.1 Tube Chamber. Glass chamber of sufficient dimensions to
house permeation tubes.
5.4.2 Flowmeter. Rotameter or equivalent or measure flow range
from 0 to 10 1/min +_ 1.0%.
5.4.3 Constant Temperature Bath. Capable of maintaining permea-
tion tubes at certification temperature within j^0.1°C.
5.4.4 Temperature Monitor. Thermometer or equivalent or monitor
t
bath temperature within j^0.1°C.
6. Reagents
f
6.1 Fuel. Hydrogen (Hp) prepurified grade or better.
6.2 Combustion Gas. Oxygen (0^) research purity or better.
6.3 Carrier Gas. Nitrogen (N,,) prepurified grade or better.
6.4 Diluent. Air containing less than 0.5 ppb total sulfur compounds
> M}
and less than 10 ppm each of moisture and total hydrocarbons. MSAV ' fil-
ters are used to purify compressed air.
6.5 Compressed Air. 60 psig for GC valve.actuation.
6.6 Calibration Gases. Permeation tubes gravimetrically calibrated
and certified at 30.0°C + 0.1°C.
7. Procedure
7.1 Instruments may be assembled from the components described herein or
(T)Mention of trade names or specific products does not constitute an en-
dorsement by the Environmental Protection Agency.
-------
6
may be purchased commercially. If commercial instruments are used, follov/
the specific instructions given in the manufacturer's manual.
7.2 Sampling. Calibrate the dilution and analysis systems as de-
scribed in Section 8. Heat and maintain the sample line, pump and dilution
apparatus above 100°C. Check the sampling system for sample losses and leaks
by introducing a known concentration of hydrogen sulfide (H^S) into the
probe, approximating the TRS level anticipated to be present in the gas stream
analyzed. Monitor its response on GC/FPD-I. If sample losses are"less than
5%, insert the probe into the test port making certain that no dilution air
is entering the stack through the port. Begin sampling and dilute as re-
quired to maintain the sample below its ambient dew point. Usually, ten to
one will suffice. Condition the entire system with sample for approximately
15 minutes prior to commencing analyses.
«
7.3 Analysis of Kraft Mill Sulfur Compounds. ATiquots of diluted sam-
ple are injected simultaneously into both GC/FPD analyzers for analysis.
GC/FPD-I is used to measure the low-molecular weight reduced sulfur compounds.
The low molecular weight compounds are hydrogen sulfide, sulfur dioxide,
methyl mercaptan, ethyl mercaptan, and dimethyl sulfide. GC/FPD-II is used
to resolve the high-molecular weight compounds. The high molecular weight
compounds are propyl mercaptan, butyl mercaptan, dimethyl di.sulfide, dipropyl
sulfide, and dibutyl sulfide.
7.3.1 Analysis of Low-Molecular Weight Sulfur Compounds. The sample
valve is actuated for one to three minutes in which time an aliquot of
diluted sample is injected into the stripper column and analytical column.
-------
7
The valve is then de-actuated for approximately fifteen minutes in which
time, the analytical column continues to be foreflushed, the stripper
column is backflushed, and the sample loop is refilled. Monitor the
responses. The elution time for each compound will be determined during
calibration. The chromatographic and flame conditions will be as follows:
nitrogen carrier gas flow rate of 50 ml/min, exhaust temperature of 110°C,
detector temperature of 105°C, oven temperature of 40°C, hydrogen flow rate
of 80 ml/min,oxygen flow of 20 ml/min and sample flow rate between 20 and
80 ml/min.
7.3.2 Analysis of High-molecular Weight Sulfur Compounds. The proce-
dure is essentially the same as above except that no stripper column is
needed. The operating conditions are also the same with the exception of
an oven temperature of 70°C and nitrogen carrier gas flow of 100 ml/min.
*
8. Calibration
8.1 General Considerations. Accurately known concentrations (+_ 1%)
of a variety of sulfur compounds can be generated by passing clean dry air
or other diluent gas over permeation tubes, each containing a specific sul-
fur compound as a permeant.> These tubes consist of hermetically sealed FEP
Teflon tubing in which a liquefied .gaseous substance is enclosed. The en-
closed gas permeates through the tubing wall at a constant rate. When the
temperature is constant, a wide range of known concentrations can be generated
by varying and accurately measuring the flow rate of diluent gas passing over
the tubes.
8.2 Calibration Procedure. Assemble the permeation tube calibration
-------
8
apparatus as depicted in Figure 16-3. Insert the permeation tubes into
the glass tube chamber. Check the bath temperature to assure agreement
with the calibration temperature of the tubes within ^0.1°C. 30°C is
recommended for the.sulfur gas tubes. Allow several hours for the tubes
to equilibrate. When equilibrated, vary the flow rate of diluent air
flowing over the tubes to produce the desired concentrations for cali-
brating the analytical and dilution systems. The airflow across the tubes
must at all times exceed the flow requirements of the analytical systems.
The concentration in parts per million generated by a tube containing a
specific permeant can be. calculated as follows:
P
C = K -j^- Equation 16-1
Where: C = .concentration of permeant produced in ppm.
P = permeation rate of the tube in ug/min.
M = molecular weight of the permeant ( ^ , )
L = flow rate of air over permeant @ 20°C, 760 mm Hg.
K = gas constant at 20°C and 760 mm Hg = 24,04 1/g mole
8.3 Calibration of GC/FPD Analysis Systems. Generate a series of
known concentrations (usually three) spanning the linear range of the FPD
(approximately 0.01 to 1.0 ppm) for each sulfur compound anticipated to be
present in the gas stream analyzed. Inject these standards into the GC/FPD
analyzers and monitor their responses. Peak heights, rather than integrated
areas, have proven satisfactory.
-------
9. Calculations
9.1 Determine the concentrations of each reduced sulfur compound de-
tected directly from the calibration curves.
9.2 Calculation of TRS. Total'-reduced sulfur will be determined for
each analysis made by summing the concentrations of each reduced sulfur
compound resolved during a given analysis.
TRS = £ (H2S5 MeSH, DMS, 2DMDS, x ) d Equation 16-2.
Where:
TRS = total reduced sulfur in ppm, wet basis.
H?S = hydrogen sulfide, ppm.
MeSH = methyl meraptan, ppm.
DMS = dimethyl sulfide, ppm.
DMDS .= dimethyl disulfide, ppm.
x ,= other reduced sulfur compounds
d = dilution factor, dimensionless.
9.3 Average TRS. The average TRS will be determined as follows:
N - .
TDC
Ava TDC - 1 = 1 * Equation 16-3.
Avg< TRS ~ N (1 - Bwo)>
Where:
Avg. TRS = average total reduced sulfur in ppm, dry basis.
TRS. = total reduced sulfur in ppm as determined by Equation 16-2.
N = number of analysis performed.
Bwo = fraction by volume of water vapor in the gas stream as de-
termined by Method 4 - Determination of Moisture in Stack
Gases (36 FR 24887).
-------
10
10. Bibliography
a. O'Keeffe, A. E. and Ortman, G. C., "Primary Standards for
Trace Gas Analysis", Anal. Chem. 33,760 (1966). . - . '
b. Stevens, R. K., O'Keeffee, A. E., and Ortman, G. C., "Absolute
/
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels", Environmental Science and Technology,
3:7 (July, 1969).
c. Mulick, 0. D., Stevens, R. K., and Baumgardner, R., "An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to Kraft
Mill Activities", Presented at the 12th Conference on Methods in.Air Pol-
lution and Industrial Hygiene Studies, University of Southern California,
Los Angeles, Ca., April 6-8, 1971.
d. Devonald, R. H. Serenius, R. S., and Mclntyre, A. D., "Evaluation
of the Flame Photometric Detector for Analysis of Sulfur Compounds", Pulp
and Paper Magazine of Canada, 73, 3 (March, 1972).
e. 'Grimley, K. W., Smith, W. S., and Martin, R. M., "The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
>
Analysis by a Mobile Sampling Van", Presented at the 63rd Annual APCA Meeting
in St. Louis, Mo.,June 14-19, 1970..
-------
ADDENDA
'A. Performance Specifications for-Gas Chromatographic - Flame Photome-
tric Analyzers.
Range (linear) 0 to 1 ppm
Output (minimum) -0 to 1 MV full scale
at 1 K-ohm
Minimum Detectable Sensitivity 5 ppb
Precision (minimum) 5% relative standard devia-
tion
Noise (maximum) +1% of full scale
«
Oven Stability + 0.5°C
B. Specifications for Dynamic Dilution Systems.
Design The dilution system shall
be constructed such that
all sample contacts are
made of inert materials.
> Also, the dilution system
shall heat and maintain the
sample above 100°C both
prior and during dilution.
Range The dilution system shall be
capable of a minimum ten to
one dilution.
-------
Capacity
Drift
Precision
C. Definitions of Performance Specifications
Range
Output
Full Scale
Minimum Detectable Sensitivity
The capacity should be in
excess of that required for
analysis. The excess will be
vented to the atmosphere.
Output shall not change .more
than +_ 2% over a 24-hour unad-
justed continuous operation.
+_ 2% of dilution factor.
The minimum and maximum mea-
surement limits.
Electrical signal which is
proportional to the measure-
«
ment; intended for connection
to readout or data processing
devices. Usually expressed as
millivolts or mi Hi amps full
scale at a given impedance.
The maximum measuring limit
for a given range.
The smallest amount of input
V *
concentration that can be de-
tected as the concentration
approaches zero.
-------
Accuracy
Precision
Noise
Interference
The degree of agreement be-
tween a measured value and
the true value; usually ex-
pressed as +_ percent of full
scale.
The degree of agreement be-
tween repeated measurements of
the same concentration, ex-
pressed as the average devia-
tion of the single results
from the mean.
#
Spontaneous deviations from ?.
mean output not caused by in- *
put concentration changes.
An. undesired positive or nega-
tive output caused by a sub-
stance other than the one being
measured.
-------
To Instrur.cr.ts
and
Dilution System
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Constant
Temperature
Bath '
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FIGURE 16-3. APPARATUS FOR FIELD CALIBRATION
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Stripper
j-s- Vent
Sa-plinj» Valve for
Vacuun Ccrrler
Sample
Loop
Scrplc
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(r.-.C.'-,-
iSi(
Separation
Colusn
H2 "
Oven
Calibration
Gas
erce Photometric Detector
o- To GC/r?D-7.I .
FIGUr.F. 16-2. GAS CHR^ATOGRATHIC-FLAME piiOTOMZuRIC ANALYZERS
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'
1
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,
Stack
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Filter
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Permeation
Tube
Calibration
Gas
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.
TV *
j . V , V^ J
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1 ' , . *
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(Heated)
*
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r
To GC/FPD Analysers .
10:1 104:1 103:1 -,,,.. , . . '
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Positive
Displacement
1 X* Pump
) (150 cc/min) '
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Dilution ~Bo:< Heated
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3.250 cc/n:L-
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.
25 PSI
§
Clean
Dry Air
Vent
FIGURE 16-1. SAMPLING AND DILUTION APPARATUS.
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