-------
  TABLE B3-7.   CALCULATION OF  AVERAGE HYDROCARBON CONCENTRATION
                DIFFERENCE  (A PPM)  FOR TOC ANALYSIS AND PURGE
                ANALYSIS SAMPLES
Tower
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Total Number Analysis
of Analyses Method
5
4
5
12
16
6
7
7
12
5
14 .
7
14
7
7
11
7
1
7
6
10
1
5
7
4
5
1
1
1
18
7
Purge
Purge
Purge
TOC
TOC
TOC
TOC
TOC
TOC
Purge
TOC
TOC
TOC
Purge
Purge
TOC
TOC
Purge
TOC
Purge
TOC
Purge
Purge
TOC
Purge
Purge
Purge
Purge
Purge
TOC
TOC
Weighting Factor
A PPM W±
0.002
0.018
0.061
2.14
1.25
-1.17
1.61
0.61
0.38
-0.008
10.09
0.29
3.94
0.015
0.034
-0.14
0.83
0.013
-0.03
-0.131
1.45
0.019
-0.155
-0.80
-0.025
0.016
0.006
0.011
0.024
-2.09
-0.24
357.14
285.71
357.14
.923
1.23
.46
.54
.54
.92
357.14
1.08
.54
1.08
500.00
500.00
.85
.54
71.43
.54
428.57
.77
71.43
357.14
.54
285.71
357.14
71.43
71.43
71.43
1.38
.54
(A PPM)(W.)
.71
5.14
21.78
1.98
1.54
-.54
.87
-33
.35
-2.86
10.90
.16
4.26
7.50
17.00
-.12
.45
0.93
.02
56.14
1.12
1.36
-55.36
-.43
-7.14
5.71
.43
.79
1.71
-2.88
-.13
                                           4155.31
71.72
       PPM)(Wj)    71.72  _
       ZW        4155.31
Average Weighted A PPM for All Towers = 0.0173 ± .0585
                               312

-------
    TABLE  B3-8.   CALCULATION OF EMITTING  TOWER  EMISSION RATE
Tower
Number
4
5
7
11
13
15
20
21
Analysis
Method
TOC
TOG
TOC
TOC
TOC
Purge
Purge
TOC
A PPM
2.14
1.25
1.61
10.09
3.94
0.034
0.131
1.45
lb/1000 gal
0.0213
0.0124
0.0160
0.1004
0.0392
0.00028
0.00110
0.0144
X = Weighted A PPM for emitting towers = 0.101  =0.19  PPM





     r- •   •           ,-^£(A PPM)(Wj)  for TQC  samples \ /TOC Conversion \ a
Mean Emission Rate = (X)?>. P'^'/T, (	r,	 i	       17   _
                        \Z(A PPM)(Wjj  ror all  samples/ V   .Factor     /





                       /£(A__P_PM) (Wj)  for purge  samples\/Purge Conversion'


                       VI(A PPM)(Wi)  for all samples   A     Factor







                   => (0.101 ± 0.19)(|^||)(9.946)  +  (0.101 r 0.19)






                     (Z3 ».!_ \ (Q 33F-3)

                     ^94.06M       ;






                   = 0.000878 ± .00165 lb/1000  gal
  TOC Conversion Factor = (8.33)(1.194)(10~3)  =  9.946E-3



  Purge Conversion Factor = (8.33)(10~3)  =  8.33E-3
                                   313

-------
      TABLE  B3-9
CALCULATION OF EMISSION RATE FOR  TOC
ANALYSIS  SAMPLES
Tower
Number
3
4
5
6
7
8
9
10
11
12
13
16
17
19
20
21
23
24
25
30
31
X = Weighted A PPM
Mean Emission Rate


A PPM
0.35
2.14
1.25
-1.17
1.61
0.61
0.38
-5.03
10.09
0.29
3.94
-0.14
0.83
-0.03
2.22
1.45
1.46
-0.80
3.45
-2.09
-0.24
for TOC Analysis Samples = 1.25 ± 1.24
= (X) (TOC Conversion Factor)3
= (1.25 ± 1.24)(9.946E-3)
= .0124 ± .0123 lb/1000 gal
Emission Rate
(lb/1000 gal)
0.0035
0.0213
0.0124
-0.0116
0.0160
0.0061
0.0038
-0.0500
0.1004
0.0028
0.0392
-0.0014
0.0083
-0.0003
0.0221
0.0144
0.0145
-0.0080
0.0343
-0.0208
-0.0024




3 TOC Conversion Factor =  (8.33)(1.194)(10~3) = 9.946E-3
                                314

-------
      TABLE  53-10.  CALCULATION OF EMISSION RATE FOR  PURGE
                     ANALYSIS  SAMPLES
Tower
Number
1
2
3
10
14
15
18
20
22
23
25
26
27
28
29
A PPM
0.002
0.018
0.061
-0.008
0.015
0.034
0.013
0.131
0.019
-0.155
-0.025
0.016
0.006
0.011
0.024
Emission Rate
(lb/1000 gal)
0.000017
0.00015
0.00051
0.000067
0.00013
0.00028
0.00011
0.00110
0.00016
-0.00130
-0.00021
0.00013
0.00005
0.000092
0.00020
X = Weighted A PPM for Purge Analysis Samples =» 0.0198 ±  0.000219

Mean Emission Rate = (X)(Purge Conversion  Factor)3

                  = (0.0130 ± 0.0299)(8.33E-3)

                  = 0.000108 ± 0.00025  lb/1000 gal
                                 315

-------
  TABLE B3-11.
                  CALCULATION OF  EMISSION RATE  FOR TOG ANALYSIS
                  AND PURGE ANALYSIS SAMPLES
Tower Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Analysis Method
Purge
Purge
Purge
TOC
TOC
TOC
TOC
TOC
TOC
Purge
TOC
TOC
TOC
Purge
Purge
TOC
TOC
Purge
TOC
Purge
TOC
Purge
Purge
TOC
Purge
Purge
Purge
Purge
Purge
TOC
TOC
A PPM
0.002
0.018
0.061
2.14
1.25
-1.17
1.61
0.61
0.38
-0.008
10.09
0.29
3.94
0.015
0.034
-0.14
0.83
0.013
-0.03
0.131
1.45
0.019
-0.155
-0.80
-0.025
0.016
0.006
0.011
0.024
-2.09
-0.24
lb/1000 sal
0.000017
0.00015
0.00051
0.0213
0.0124
-0.0116
0.0160
0.0061
0.0038
0.000067
0.1004
0.0028
0.0392
0.00013
0.00028
-0.0014
0.0083
0.00011
-0.0003
0.00110
0.0144
0.00016
-0.00130
-0.0080
-0.00021
0.00013
0.00005
0.000092
0.00020
-0.0208
-0.0024
X = Weighted  A PPM for All Towers = 0.0207  r 0.325
     „ .       „  _     /^
Mean Emission Rate =  (X)
,
(A
                            PPM)(Wj)  for  TOC samples\ /TOC Conversion
                                     - -  --
.-           i
for all  samples
\  /
  I
/  \
                                                          ^
                                                          Factor
                                                                    /
                       /I(A PPM)(Wj) for purge  samples\ /Purge
                       \I(A PPMKWi) for all  samples  / (
                                                             Conversion\
                                                            Factor      /
                     (0.0173 ± .00585)(.^-SS)(9.946E-3) + (0.0173 ±  0.0585)

                     (|p||)(8.33E-3)  - 0.000151 ± 0.00051 lb/1000 gal
* TOC Conversion Factor = (8.33)(1.194)(10~3) = 9.946E-3
b Purge Conversion Factor =  (8.33)(10~3)  =  8.33E-3
                                  316

-------
Analytical       Number of       Towers with Negative Estimate
  Method           Towers            Number        Percent
TOC                  21                 7           33.3
Purge                15                 2           13.3
Combined             31                 8           25.8

          The negative estimates are due primarily to the ana-
lytical variation.  In order not to bias the average emission
calculation for cooling towers,  these negative values have been
used rather than setting the estimate to zero.

          The mean emissions for the 16 towers analyzed by TOC
only and the 15 analyzed by purge were 0.00015 lb/1000 gal with
957, confidence interval of = 0.00051 (negligible, 0.00066 lb/
1000 gal).  Mean emissions for the eight towers with statistic-
ally significant emissions were 0.00088 ± 0.0016 lb/1000 gal.
(negligible, 0.0025 lb/1000 gal).  Mean emissions for the 21
towers analyzed by TOC were 0.0124 ± 0.0123 lb/1000 gal (0.0001,
0.025 lb/1000 gal).  For the 15 towers analyzed by the purge
method, mean emissions were 0.000108 ± 0.00025 lb/1000 gal
(negligible, 0.00026 lb/1000 gal).

          Values  obtained by the purge method were much more
precise  than those obtained from TOC measurements.  This fact
is  illustrated in Figures B3-2 through B3-4.  Figure B3-2 is a
graph of the results of the TOC analyses; Figure B3-3, the
results  of  the purge analyses.  When the results are combined
on  Figure B3-4, the difference in precision of the two methods
is  apparent.
                               317

-------
A PPM
      10.0 - 10.49
      8.50 - 8.99
      6.50 - 6.99
4.SO - 4.99

3.50 - 3.99


2.50 - 2.99

1.50 - 1.99
      -5.0 - -5.49
                                      56   7   8   9   10

                                      Number of Cooling Towers.
                                                      i
                                                      11
12   13
-I
 14
                                                                 02-5210-1
  Figure  B3-2.   Display of  A ppm hydrocarbon  concentration
                   from TOC analyses.
                                   318

-------
        0.150 - 0.159





        0.100 - 0.109





        0.050 - 0.059


        0.020 - 0.029

        0.000 - 0.009

        0.020 - 0.029

        0.040 - 0.049
      -0.090 -  -0.099 —
      -0.140 -  -0.149
      -0.190 -  -0.999 	
                         I    I    I    111*1*    I

                         123456   7   8   9   10
                                Number of Cooling Towers
                                                                 02-5209-1
Figure  B3-3.   Display  of  A  ppm hydrocarbon concentration
                  from purge  analyses.
                                  TI O

-------
A PPM
10.50 -  10.99  	




  8.50 - 8.99  	




  6.50 - 6.99  	




  4.50 - 4.99

  3.50 - 3.99


  2.50 - 2.99

  1.50 - 1.99


  3.50 - 0.99


 0.00 - -0.49


 -1.0 - -1.49

 -2.0 - -2.49


 -3.0 - -3.49




 -5.0 - -5.49  	
                                                            Key
                                                        T.O.C.  Sampling Method

                                                        Purge Sampling Method
                      1   I   3   4   5   6   7   8   9   10   11  12   13   14  15

                                    Number of Cooling Towers


                                                                       02-5211-1
   Figure  B3-4.   Display of A  ppm hydrocarbon  concentration
                     from  all  analyses.
                                      320

-------
          Because of the varying precision of  the methods,  the
upper confidence limit for each estimate may be a more useful
value than the estimated average for many purposes.  These
values which give a "worst-case" estimate for  the magnitude
of hydrocarbon emissions from cooling towers are as follows:

       Analytical        "Worst-case" Estimate of Average
      Method Used          Emissions from Cooling Towers
      TOG  '                     0.025 lb/1000 gal
      Purge                     0.0003 lb/1000 gal
      Combined                  0.0007 lb/1000 gal

          We recommend the use of the combined emission factor
(0.0007 lb/1000 gal) for estimating cooling tower hydrocarbon
emissions.  Thus, a cooling tower with a circulation rate of
50,000 GPM would have the following emissions rate.
          O.OOOTlb)  f50,000_gal]  f60_min]   , ,
           lOOQ  galj  I - min*  J  iTr" j = 2'1

This emissions rate is relatively  small compared to other
sources of emissions from refineries .

3.2       WASTEWATER SYSTEMS

          Wastewater treatment is usually accomplished in three
stages:  primary, secondary, and tertiary treatment.  Primary
treatment facilities are principally involved in physically
upgrading the wastewater by removal of oil, oily sludge, and
grit.  Thus, primary treatment facilities will be the principal
sources of fugitive hydrocarbon emissions from the waste treat-
ment plant.  Oil removal equipment includes API separators,
corrugated plate interceptors, flocculation units, and dissolved
                               321

-------
air flotation units.  The latter are also used for suspended
solids removal.

          API separators, corrugated plate interceptors, and
dissolved sir flotation (DAF) units were sampled to determine
atmospheric emissions of hydrocarbon.  The emissions were esti-
mated from a hydrocarbon material balance around each unit.
There is a great deal of scatter and uncertainty in the data
and results, particularly in the determination of emissions
from the oil phase.  Negative values are even indicated for
some emissions.  The one conclusion that can be made regarding
these results is that the material balance approach, as imple-
mented in this program, is inadequate for defining emission
rates.  The composition of the incoming stream varies widely,
and grab samples are not generally representative.  For this
reason,  emission factors for oil-water separators and DAF units
were not developed from experimental results.

          Table B3-12 summarizes the average emissions per
gallon of material throughput for all sampled devices by
refinery.  Tables B3-13 through B3-20 show daily emissions
for each device sampled at individual refineries.
                              322

-------
               TABLE  B3-12.   DESCRIPTION OF SAMPLED  DEVICES  - WASTE OIL/WATER SYSTEMS
ho
Average Hydrocarbon Emissions
Refinery
1
2
3
it
5
6
7
8
Device
Rectangular API Separator
Circular DAF
Rectangular API Separator
Corrugated Plate Interceptor
Corrugated Plate Interceptor
Rectangular API Separator
Forebay Covered
Surge Tank
Two Rectangular Separators
Rectangular DAF
Rectangular API Separator
Rectangular API Separator
Rectangular DAF
Circular Separator
Circular DAF
Refinery
Size1
Large
Large
Large
Large
Large
Small
Large
Small
Covered/
Uncovered
C
U
C
C
C
U
U
U
U
U
U
U
U
U
Losses from
Oil Phase,
Ib/gal slop oil
1.6 + 2
0.073 1 0.4
1.84 + 1.11
-1.5 + 0.08
-0.11 + 0.06
0.12 + 1.3
0.45
-1.1 + 0.74
0.14 + 0.4
0.48 + 0.61
Losses from
Water Phase,
Ib/gal water
2,7x10"" +
8.2xlO~5 +
-3.0LxlO~6
—
2.2xlO~" +
1.6xlO"s +
-2.4xlO~5 H
' 1.5xlO~" +
6.5x10"" +
1.1x10"" +
3.4x10"" +
1.4xlO"5 +
1.8x10""
1.5xlO~"
+ lxlO~s

2.7x10""
3xlO~6
h 2.7x10 s
2.4xlO~"
1.9xlO~"
1.3x10 "
1.8x10""
1.7xlO~5
          'Small refinery £ 50,000 bbl/day capacity.  Large refinery > 50,000 bbl/day capacity.

-------
                  TABLE  B3-13.  WASTEWATER SYSTEM HYDROCARBON  EMISSIONS AT  REFINERY 1
u>
ISJ
•p-

Day
Sampled
1
2
3
4
5
Separator
Oil Phase,
Ib/gal slop oil
0.20
0.36
-0.34
a
	 b
Emissions
Water Phase,
Ib/gal water
2.6xlO~"
4.2x10 "
1.2x10 "
c
c
DAF Emissions
Water Phase
Ib/gal
-l.OxlO^14
2,7x10 5
2.0x10 "
2.0x10 "
__b
            Bay not sampled
            Points eliminated by Dixon's Outlier Criteria.

            Invalid samples.
                  TABLE  B3-14.  WASTEWATER SYSTEM  HYDROCARBON EMISSIONS AT  REFINERY 2
Day
Sampled
1
2
3
4
5
Separator
Oil Phase,
Ib/gal slop oil
0.75
2.23
2.54
0.59
3.07

Water Phase,
Ib/gal water
-3.4xlO~7
2.6x10 6
-1.8x10 5
3,7x10 6
a
           L)ay not sampled.

-------
       TABLE B3-15.   WASTEWATER SYSTEM HYDROCARBON EMISSIONS AT  REFINERY  3
    Day
  Sampled
  Corrugated Plate  Interceptor Emissions from Oil Phase	
CPI A (Ib/gal slop  oil)	CPI B (Ib/gal slop oil)
    1
    2
    3
         -1.5
         -1.46
         -1.52
-0.05
-0.15
-0.12
Average of  two analyses.
       TABLE B3-16.   WASTEWATER SYSTEM HYDROCARBON EMISSIONS AT  REFINERY 4


Day
Sampled
1
2
3
6
7


Oil Phase,
Ib/gal slop oil
-0.05,6

-1.27
1.84
-0.04
a
Separator
Water Phase,
Ib/gal water
-1.8xlO~5
4.6x10 "
5.4x10 "
9.9x10 5
2.3x10 5
.Average of multiple analyses.
 Points eliminated  by Dixon's Outlier Criteria.

-------
                  TABLE B3-17.   WASTEWATER SYSTEM  HYDROCARBON  EMISSIONS AT  REFINERY  5
Day
Sampled
1
2
5
6
7
8
16
Surge Tank
Emissions,
Ib/gal slop oil
b
b
b
b
b
b
0.45
Separator Water3
Phase Emissions
Ib/gal
1


1
1
1

.9xlO~5
	 "
c
.6xlO~5
.2x10 5
.6x10 5

DAK Water
Phase Emissions
Ib/gal
5
-2
-1
-6
-6
1

.2x10 6
.1x10 5
.7x10 5
.5x10 5
.2x10 5
.3x10 b

          .Sum of two separators.
           Day not sampled.
           Points eliminated by Dixon's Outlier  Criteria.
to
                  TABLE B3-18.   WASTEWATER SYSTEM HYDROCARBON EMISSIONS AT  REFINERY 6

Day
Sampled
1
2
3
4
5
6
16
17
18
19
Separator Emissions
Oil Phase3
Ib/gal slop oil
b
b
b
b
b
b
-1.3
0.24
-0.93
-2.4

Water Phase3
Ib/gal water
7.6x10""
1.04x10""
2.6x10 5
5.9x10 5
-1.6x10 5
-8.0x10 6
5
b

b
b

           Average of two analyses.
           Day not sampled.

-------
              TABLE  B3-19.   WASTEWATER  SYSTEM HYDROCARBON EMISSIONS AT  REFINERY 7

Day
Sampled
1
3
4
5
6
19
22
Separator
Oil Phase,
Ib/gal slop oil
b
0.5
-0.22
	 b
0.13
__b
b
Emissions
Water Phase,
Ib/gal water
-3. 4x10'"
__b
1.2xlO~ 5
8,4x10 5
-1.6x10 5
_b
b
DAF Water3
Phase Emissions
Ib/gal
5.27xlO~5
2.37x10 5
-6.6x10 5
-1.3x10 5
2,2x10 "
4,32x10 *
1.2x10 *
          Average of multiple analyses.
          Day not sampled.
OJ
TABLE B3-20.  WASTEWATER SYSTEM HYDROCARBON  EMISSIONS AT REFINERY  8
Day
Sampled
1
3
4
5
6
Separator Emissions
Oil Phase,
Ib/gal slop oil
-0.22
1.58
0.5
0.11
0.4

Water Phase,
Ib/gal water
8.9xlO~ 5
3.3x10 *
2.3x10 *
3.9x10 "
6.4x10 "
DAF Water
Phase Emissions
Ib/gal
3.5xlO~5
3.5x10 5
5.8x10 6
-5.8x10 6
1.9x10 6

-------
                             SECTION 4

                         STACK EMISSIONS
           Table  B4-1 lists  the stacks  sampled  during this
prograrr. along with a brief  description of the  associated  refin-
ery process or unit.  Tables  B4-2 through B4-56  contain the
detailed results  of analyses  for specific components in the gas
streams.   These  are grouped according  to the kind of processing
units  the stacks  are associated with.
             TABLE B4-1.   SUMMARY OF  SAMPLED STACKS
        Stack Number
        Description
            1
            2
            3
            4
            5
            6
            7
            8
            9
            10
            11
            12
            13
            14
            15
            16
            17
            18
            19
            20
Resin  Fume Oxidation Unit Stack
Crude  Process Heater Stack
Crude  Process Heater Stack
Crude  Process Heater Stack
Crude  Process Heater Stack
Crude  Process Heater Stack
Tail Gas Treating Unit (SRU)  Stack
Sulfur Recovery Unit Stack
TCC CO Boiler Stack
Fluid  Coker CO Boiler Stack
FCCU CO Boiler Stack
FCCU CO Boiler Scrubber Stack
FCCU CO Boiler Stack
FCCU CO Boiler Stack
FCCU CO Boiler Stack
FCCU CO Boiler Stack
FCCU CO Boiler Scrubber Stack
FCCU CO Boiler Stack
Fluid  Coker Scrubber
FCCU Compressor Exhaust Stack
                                 328

-------
          Tables B4-2 through B4-5 include the sampling results
of emissions from a resin fume oxidation unit.

          The sampling results for five heater stacks are given
in Tables B4-6 through B4-11.  These units were fired with mixed
refinery fuel gas and fuel oil.  No external emission controls
were in use during any of the sampling activities.

          The stack gases from the tail gas treating processes
of two sulfur recovery units were sampled and analyzed.  And,
the results are given in Tables B4-12 through B4-17.  The
accuracy of the hydrocarbon and S0y analyses of the gas from
Stack No. 7 is uncertain.  The concentration of hydrocarbons
in the gas is very high.  At the same time, almost no S02 was
found.   No satisfactory explanation of these results has been
put forward.

          Tables B4-18 through B4-23 give the sampling results
for emissions from the CO boiler stack of a Thermofor Catalytic
Cracking (TCC) unit.

          Tables B4-24 through B4-29 show the sampling results
from the CO boiler of a fluid coking unit.  This unit was also
equipped with a scrubber upstream of the CO boiler.  And,
sampling results for the inlet and outlet of the scrubber are
given in Tables B4-30 through B4-35.   Hydrocarbon samples were
the only results obtained at the scrubber outlet.   Hence, the
effect of the scrubber or the CO boiler alone cannot be evalu-
ated for any speciescexcept hydrocarbons.  A comparison of data
from these tables does, however, show the combined effect of the
scrubber and the CO boiler on reducing emissions of particulates,
methane and nonmethane hydrocarbons,  aldehydes,  HCN, and NH3.
N0x emissions, however, were higher at the CO boiler outlet.
                              329

-------
                     TABLE  B4-2.   STACK  GAS AND  PARTICULATES01  - RESIN  FUME  OXIDATION  UNIT
           Stack  Time
  Total Gaa     Avg   Avg
   Sampleb	 Meter  Stack Avg
Meter   STP  .  Temp  Temp  Dry
(ft1)  
-------
                               TABLE  B4-4.   SULFUR SPECIES  -  RESIN  FUME OXIDATION  UNIT
LO
LO


Stack
1








Time
1907-2007
1930
2103-2203
2150
2246
1443
1610
SOs8
ppn lb/SCFC
(Vol)
0.29 6.11x10"'
	 	
0.56 1.15x10"'
—
	 —
—
—
so,b
ppm Ib/SCF^
(Vol)
27.97 4.63x10"'

19.44 3.22x10"'
	 	
	
—
—

PP"
(Vol)

23.99

19.05
12.59
10.47
15.14
S02d H2S
Ib/SCF" ppn Ib/SCF"
(Vol)

3.97x10 '
	 	 ' 	
3.15x10"'
2.09x10"'
1.74x10"'
2.51x10"'
COS CS,
ppn lb/SCFC ppa lb/SCFC
(Vol) (Vol)

	 	 	 	
	 	 	 	
	
	
	
	
           bIPA Iraplnger, Ba(C10Oz Tltrallon.
           61 ll?0 Traplngera, Ba(C10<.)z TlLratlon.
           dCorrcctcd to 70°F and 29.92 Inches Hg, dry baale.
           CC analysis of grab samples yielded comparable results for SOi; other species not detected.
-------
                           TABLE  B4-5.  ALDEHYDES*  - RESIN FUME OXIDATION  UNIT
LO
LO
Gas Sample
Volume (£)
Stack Time (55°F)
1 2016-2116 12.0
2215-2240 12.0
2305-2340
(STP)R
11.82
11.82

Aldehyde
Collected
(us)
1275
300

Gaseous Aid. Conc.entration.sc
Volume Cd STP By Weight @ STP
(yJi) ppm(Vol.) (yg/Ji) (Ib/SCF)
1025.5 86.76 107.86 6.74x10"
241.3 20.41 25.38 1.59x10"


6
6

           Sample Rate - 200 mJi/min.  Bisulfite method used.

          Corrected to 70°F and 29.92 inches Hg.
          "Dry basis.
-------
   TABLE B4-6.    STACK  GAS  AND  PARTICULATES   -  CRUDE  UNIT  PROCESS  HEATERS
Total Can
Sample n






OJ
OJ
OJ
Stack Time
4 1119-1446
1742-1916
5 1255-1730
1155-1433
2 1142-1512
2 1230-1424
3 1929-1943°
Meter
(ft1)
36.68
35.42
39.17
54.17
31.21
24.14
5.83
AVR
Meter
STP Temp
(SCF)C (°F)
36 . 1 3
35.12
17.82
52.74
13. 18
24. 57
5.83
84
81
100. 1
95.4
89
78
80
Avg
Stack
Temp
418
420
492
490
345
344
350
Partlculaten
Avg
Dry
(HU)
27.56
26.04
28.06
28.87
27.59
27.92
30.11
Moisture
Collected
87.
78
719.
271.
139.
96.
74,
7
5
.6
.9
.3
.5
,8
Fract Ion
o . i n \
0.094
0.714
0. 196
0.166
0.157
0. 168
Filter Probe
0.0491 0
0.0807 0.
0.0247 (1
0.0181 0
0.0049 0.
0.0049 0
0.0016 0
.0374
.0490
.1092
.3925
.0790
.0165
.0127
Imp. fl
0.077?
0 . 0000
0.0182
0.0090
0.0592
0.0'. 70
0.0002
Crnln
Loading
Total (gr/SCF)
0.
0,
0,
0
0,
0,
0
,1639 0.070
1297 0.057
.1521 --d
.4196 --A
.0911 0.0411
,0634 0.0398
.0143 0.0378
Avg
Stnck
Velocity
(ft/sec)
58.01
58.03
17.70
76.39
16.63
11.05
10. 19
I
I.sokln.
102.6
99.0
19.6
30.1
9/.6
107.5
114.6
 Sampled with LSI EPA-5 train.
 Total gas flow rates:  Stack No. 2 - 3.26 x 10* SCKM; Stack No. 3 - 2.34  x 10e SCFM; Stack No.  4 - 7.03 x 10* SCKH; Stack No. 5 -
 2.78 x 10s SCFM; Stack No. 6 - Undetermined.
CCorrccted to 70°F and 1'9.92 Inches Hg.
 Partlculate sampling done under nonisokinetir  conditions.  Oraln loading  not reported.
 F.lectrlcol problems curtailed sampling.
-------
                    TABLE B4-7.
u>
METHANE/NONMETHANE HYDROCARBONS3 AND FIXED
GASESb - CRUDE UNIT PROCESS HEATERS
No nme thane ('one en t rat Jons
M r-l r r l c '^s H*-'xanc)

Stack
4
6
6
Amblrnt
5



1

:)
Ambient
2
a
Byron
«y
Time (ppm)
1458
1730 0.08
1955
1957 0.10
1439 0.47
1453 0./.4
1803 0.25
1813
2127 --£
2130
2130 3.6/i

1145 2.60
1520 0.90
1100 1.80
1230 0.59
1612 0.038
1921 0.0
1927 0.867

1608 0.0
Uclcht B>
(lb/SCF)J
5.55x10''
6.94x10-'
3.26x10'"
3.05x10'°
1.9 xl()'e
2.73x10''

1.92x10''
6.68x10'"
1 .33x10''
4.37x10'"
2.37x10-'
0.0
5.41x10'"

0.0
' Volume By UMp.ht
(ppm)
0.13
0.17
0.78
0.7/1
0.45
6.59

/, .7
1.63
3.26
1.07
0.057
0.0
1.31

0.0
hydrocarbon analyzer using flame
(ppm)
3.55
0.51
5.30
4.33
5.78
5.50
8.11

21.0
24.6
10.0
18.8
4 . 74
1.54
0.305

2.76
tont7al Ion
c
By Volume CO-
(Ib/SCF)11 (ppm)
2.46x10''
3. 54x10'"
3.68x10"'
3.00x10''
3.91x10''
4.07x10"'
6.0flxlO~'

1.55x10''
1.82x10'*
7.40x10''
1.39x10''
2.96xlO~'
9.61x10'"
1.90x10-'

1.72x10''
detector .
Fl.qchcr Model 1200 gas part 1C loner.
1.11
0.16
1.65
1.35
1.76
1.83
2.73

7.07
8.28
3.37
6. 33
1 . 33
0.432
0.086

0.774
m (
7.6 9
5.5 9
10.0 5
10.3 4

12.0 2
8.3 5
14.5 2
11.2 3
11.7 6
11.7 6


11.1 6
Corrected to 70°F and
^Results
quest lonable .
Flxrd C.isrs
(Dry Basis)
07
Z)
.2
.5
.3
.8

.0
.8
r.
.5
.2
.0
_

.3
29.
not
N2
(*)
76.0
73.5
80.1
80.7

79.4
80.2
79.5
79.5
82.1
82.0
	

82.6
CO 11 2
m m
0.0 --"'
0.0 --
0.0
o.o — e

e



0.0 0.0
0.0 0.0
	

0.0 0.0
Mol . lit.
(Dry)
27.56
26.04
28.53
28.67

28.15
27.96
29.44
28.31
10.12
—
	

28.29
92 Inches MC.
reported.
-------
                     TABLE  B4-8.    SULFUR  SPECIES -  CRUDE  UNIT  PROCESS  HEATERS


Stack Time
2 1342-1532
1230-1424
3 1923-1943

6 1637
1918
2000
5 1255-1730
1520
1155-1433
4 1319-1446
1510
1742-1916
1959
1310
1445
SO,'
ppm In/SCF*-
(Vol)
0.51 1.063x10-'
0.70 1. '.36x10-'
0.146 3.03 xlO-'




34.14 7.06 xlO-'

8.25 1.68 xlO-«
0.93 1.93 xlO-'
—
0.51
1.05 xlO-'
—
—
S02b (EPA-5) S02 (HP)6 H2S6 COS* CS2°
ppm Ih/SCF1- ppra lb/SCFf ppm lh/SCFC ppm lb/SCFC ppm lb/SCFC
(Vol) (Vol) (Vol) (Vol) (Vol)
2.33 3.854x10-'
1.97 3.248x10-'
2.11 3.479x10-'

0.2 3.0x10- -' - -A - -\
O.O/. 7.0 xlO-' —A - -° - -A
0.3 5.0x10-' -A - -A - -''
82.62 1.4 xlO-'

108.84 1.8 xlO-5
328.3 5.4 xlO-'
302.0 5.01x10-'
314.1 5.2 xlO-'
302.0 5.01x10-'
251.2 4.17x10-'
275.4 4.-J6xlO-5
*IPA IraplnRpr, Ba(C10«)2 Tltratlon.
 67. Ilj02 Iroplnger Ba(C10,)l Tltratlon.
dSTP = 70°F and 79.92 Inches Hf>.
 No Rprclea detected.
 Caseous SOj determined using a Heulltt Packard Gas Chronatograph equipped with a flame photonetrlc detector.
-------
                          TABLE B4-9.   ALDEHYDES - CRUDE UNIT  PROCESS HEATERS
U)
U)
Stack
2a
3a
6a

4d


5d


Time
1453-1553
1620-1723
1646-1746
2021-2121
1149-1255
1326-1426
1524-1624
1620-1720
1223-1328
1400-1500
Gas Volume i_!g
(£) 0 SIP Aldehyde
12
12
12
12
12
11
11
10
12
11
.0
.0
.0
.0
.88
.70
.68
.55
.47
.51
98.
102.
120.
145.
0.
0.
0.
1.
2.
0.
7
0
79
66
79
385
94
84
95
0
Q
Concentration
ppm(Vol . )
6
6
8
9
0
0
0
0
0
0
.62
.84
.10
.76
.049
.026
.065
.14
.19
.0
5.
5.
6.
7.
3.
2.
5.
1.
1.
0.
Ib/SCF
12
29
29
58
83
06
03
xlO
xlO~
xlO~
xlO~
xlO~
xlO~
xlO~
7
7
7
7
9
9
9
086xlO~8
480xlO~
0

8

          Bisulfite method.
          STP = 70°F and 29.92  inches Hg.
          Dry Basis.  Calculated as formaldehyde.
              method.
-------
            TABLE  B4-10.  OXIDES OF  NITROGEN  - CRUDE  UNIT PROCESS HEATERS
                                                         NOX (as N02) Concentration3
    Stack                Time                          ppm (Vol.)
                        1825                              98.0               1.17xlO~5

                        2136                              87.7               1.04xlO~5
.Dry basis.
 STP =  70°F and 29.92  inches Hg.
-------
                      TABLE  B4-11.   HCN  AND NH3  -  CRUDE UNIT PROCESS HEATERS
00
-1
Stack Time





a
b
c
d
e
5° 1630
1000
2d'e 0951-1112
1452-1621
3d'e 1541-1825
HCN
ppra (Vol
0.8
0.9
<1 xlO~
4.16x10"
<1 xlO~
Dry basis.
STP = 70°F and 29.92 inches Hg.
Infrared analysis at 3.01u(HCN)
NHs sampling performed using LSI
Concentration3
.) Ib/SCF"
5.49xlO~8
6.18xlO~8
3 6.5x10.""
2 2.91xlO~9
3 6.5xlO~n
and 10.4u(NH3). Path
train with impingers
NHs Concentration3
ppm (Vol.) Ib/SCF b
0.95 4.12xlO~8
1.5 6.49xlO~8
<0.3 <1 xlO~8
<0.3 <1 xlO~8
<0.3 <1 xlO~8
length = 20.25m; cell temperature = 75°C.
containing 0.1N foSOu.
„_ 	 4 — -: _ -: .~ ~ 1 Q n 1 ~ £ OM M«r*u nAAu
-------
u>
                                   TABLE  B4-12.
METHANE/NONMETHANE  HYDROCARBONS3  AND
FIXED  GASESb  - SULFUR RECOVERY UNITS


Methane Concentration



By Welgtu Ib/SCF" By Volume
Stack
8


Ambient


7
Ambient
Time
1455
11*0
1515
1505
1556
1613
1645
1908
(wm)
.213
1.30
0.062
0.822

3135
4120
0.43

1.33x10"'
8.11x10 "
3.87x10"'
5.13x10 '

2.10x10 "
2.76x10""
3.22x10 '
(ppm)
.321
1.96
0.094
1.24

5075
6669
0.78
Nonmc thane Co
(As He

By Welgl
(ppm)
4.745
51.065
4.87
1.155

7170
6650
1.40

it

7
3.
3
7,

*
*
1.

Ih/SCF

.96x11)"
.19x10
.04x10
.21x10

.81x10
.46x10"
.05x10
nc<
xar


7
C
7
•

<<
ii
7
jnt rat ton
ie)

By Volume
(ppm)
1.35
14.32
1.37
0.32*

2159
2003
0.47
Fixed Cases
(Dry Basla)
CO 0
tt> (%)
5.1 8.7
4.9 9.3
5.1 8.6

14.0 1.4



N
U>
86.2
85.8
86.3

83.2



CO 11 Mol. Wt.
(X) (%) (Dry)
0.0 0.0 27.03
0.0 0.0
0.0 0.0

1-4 -- 30.30



                       NOTE:  Gas flow rate from Stark No. 8 = 2.02 x 10* SCFH; this value provided hy plant personnel.
                       "hyron hydrocarbon analyzer using flame lolziitlon detector.
                       hFlschcr Model 1200 gas partltloner.
                        Dry basis.
                        STP = 70°F and 29.92 Inches Hg.
                        CResultfl qurstlonable, not reported.
                        Nor detectable, less than 0.01 ppm hy weight.
-------
                      TABLE  B4-13.    SULFUR  SPECIES -  SULFUR RECOVERY  UNITS
so,"
ppm Ib/SCF^
Stack Time (Vol)
8 1005-1035 0.61 1.263xlO"7
1115-1145 0.72 1.481x10-'
1318
1452
1553
1020
1055
1238
7 1644
1700
1540
S02b
S02
ppm Ib/SCK1" ppm
(Vol) (Vol)
319.72 5.282x10-'
315.18 5.207x10-'
444
491
528
582
509
510
_
0
0


.0
.0
.0
.0
.0
.Q

.2
.2


7.
8.
8.
•).
R.
8.

1.
3.

lb/SCFc


34xlO"5
llxlO-5
72x10-'
62xlO-5
41x10"'
42x10-'
	
0x10"°
0x10 "

ppm
(Vol)


- Not
- Not
- Not
- Not
- Not
- Not


—
HjS
Ib/SCF1-


Dotected -
Detected -
Detected -
Detected -
Detected -
Detected -
	
	
—
COS
ppm
(Vol)


0.6
0.5
0.4
0.45
Not Run
0.5
8.6
3.0
7.7
lb/SCFl


9.30x10"'
7.75x10-"
6.0 xlO-8
7.0 xlO-"
Not Run
8.0 xlO-9
1.3x10" s
5.0x10 '
1.2x10 6
CSj
PP"
(Vol)


1.
2.
2.
1.
Not
1.
15.
0
12,


3
9
6
1
Run
4
0
.04
.0
Ib/SCF1-


2.55x10"'
5.69x10-'
5.1 xlO-'
2.2 xlO-'
Not Run
2.7 xlO-'
2.91x10"'
8.0x10 '
2.36x10 k
"iPA Implnger, Ba(C10i,)2 Tltratlon.
 61 11,02 Implnger, Ba(C10»)2 Tltratlon
^STP -  70°F and 29.92 Inches Hg,  dry basis.
 No species detected.
 Rmultfl questionable, not reported.
-------
                 TABLE B4-14.   ALDEHYDES3 -  SULFUR  RECOVERY UNITS
                             Gas Sample         Aldehyde             Concentratiotf

                             Volume (£)         Collected
<-_  i           v                                                                  - .  ,„-„
Stack          Time             @ STp£             ^  .         ppm(Vol.)           Ib/SCF







  8         1525-1625            12.0              59.7           4.01             3.11xlO~7






            1120-1220            12.0              61.5           4.13             3.20xlO~7






            1315-1415            12.0              57.0           3.83             2.97xlO~7
aSample Rate  =  200 m£/min.  Bisulfite Method




bSTP = 70°F and 29.92  inches Hg.




CDry basis.   Calculated as formaldehyde.
-------
                       TABLE  4-15.   OXIDES OF NITROGEN - SULFUR RECOVERY UNITS
                                                                  NOX (as N02) Concentration3
                                                                                           "
Stack
Time
ppm (Vol.)
                                                                                    lb/SCFb
   8

   7
1732

1626
   16.7

   15.0
                                                                                    1.98xlO~6
                                                                                    1.70xlO
                                                                                           ~6
S3
         Dry basis.
         STP = 70°F and 29.92 inches Hg.
-------
UJ
•p-
UJ
                                TABLE B4-16.  HCNa -  SULFUR  RECOVERY UNITS
              „                          _.                                    HCN  Concentrations
              Stack                      Time
                                                                     ppm (Vol.)           lb/SCFc
                                       1551-1625                     <1 x 10  3          <6.5 x 10
                                       1305-1340                    <1 x 10  3          <6.5 x 10
          a
           Sampling performed  using LSI train with 3  impingers containing 250 ml  of  2N NaOH each.

           Dry basis.

          CSTP = 70°F  and 29.92  inches Hg.
-------
                        TABLE  B4-17.   NH33  -  SULFUR RECOVERY UNITS
                                                                   NH3  Concentration
   Stack
                                                           ppm(vol.)
                           1505-1540                        <0.3                    <1 x 10
                           1405-1440                        <0.3                    <1 x 10  8
 Sampling performed  using LSI train with impingers containing 0.1 N  HjSOi,.
 Dry Basis.
CSTP = 70°F and 29.92  inches Hg.
-------
                   TABLE B4-18.
STACK  GAS AND  PARTICULATES'
- TCCU CO BOILER STACK
Total Cns
Sample
Stack Time
9 1118-1450
1011-1125
1018-1 110
1503-1615
Meter
(ft1)
40.38
40. 32
27. 14
11.90
(SCF)C
19.27
38.80
26.73
31.25
Avg
Meter
Temp
82
81
76
79
Avg
Stack
Temp
446
458
474
458
Partlculntca
Avg
Dry
(MV)
78.47
28.38
28.56
28.17
Hot nture
Collected
106
107.
78
68
.0
9
.3
.9
Fraction
0.113
0.116
0.122
0.095
Filter
0.0363
0.0402
0.0305
0.028?
Probe
0.0484
0.0028
0.0457
0.0099
Imp. 11
0.0000
o.oooo
0.0220
0.0284
Total
0.0847
0.0430
0.098?
0.0665
Grain
Loading
(gr/SCF)
0.0333
0.0171
0.0567
0.0328
Avg
Stack
Velocity
(ft/sec)
51.67
Vt .77
36.69
40.%
I
Isokln.
105.6
101. 3
1115. 1
10V 9
 Sampled with LSI EPA-5 train.

bTotal gas flow - 3.10 x 10* SCFM

'corrected to 70°F and 29.92 Inches Hg.
-------
                  TABLE  B4-19.
METHANE/NONMETHANE  HYDROCARBONS'
GASESb  - TCCU CO BOILER STACK
AND FIXED



Stack Time
9 1345
1405
1525
1535
Ambient
UJ 9 1710
-P-
0^ 9 1415
1425
1535
1545
0930
1050
1410
1415
1520
1525
Ambient
9 1530

Methane
By Volume
(ppm)

4.6

2.32

6.22


0.24
0.0




0.0

0.0

0.87

Concent rat ion
lb/SCFa


3.4x10 '

1.71xlO~7

4.66xlO~7


1.8x10""
0.0




0.0

0.0

6.5xlO~8


By Volume
(ppm)

8.2

4.13

11.3


0.43
0.00




0.00

0.00

1.6
Noruae thane
(As
By Weight
(ppm)

30.7

27.83

9.36


1.38
0.0




1.96

0.85

0.99
Concentration
Hexane)
lb/SCFd By


2.26xlO~6

2.05xlO~6

7.01x10"'


1.01x10"'
0.0




1.44x10"'

6.2x10 "

7.4x10"'
c

Volume
(ppm)

10.2

9.21

3.15


0.455
0.0




0.646

0.28

0.33


C02
(Z)
10.8

11.4




10.5


11.5
11.3
10.8
10.0

11.4





02
(Z)
7.0

6.6




7.4


6.6
6.9
7.3
6.7

6.5




Fl_xed Canes
N2
(Z)
76.3

76.6




75.7


76.4
76.7
76.3
76.3

76.2





CO
(Z)
0.0

0.0




0.0


0.0
0.0
0.0
0.0

0.0





H2
U)
0.0

0.0




0.0


0.0
0.0
0.0
0.0

0.0





Mol. Wt.
(Dry)
28.35

28.58




28.19


28.56
28.66
28.45
27.90

28.44



rByron hydrocarbon analyzer using flame lonization detector.
 Fischer Model 1200 gas partitloner.
 Dry basis.
 STP - 70' and 29.92 inches Hg.
-------
LO
                                     TABLE  B4-20.    SULFUR  SPECIES  -  TCCU  CO  BOILER  STACK
so,a

Stark
9




Time
1338-1450
1013-1125
1018-1130
1503-1615
ppm
(Vol)
	
0.66
1.5
0.48
lb/SCFc

	
1.4x10-'
3.1x10"'
9.9x10-"
S0ib S02d H2S COS CSj
pp«
(Vol)
603.5
923.6
670.4
464.3
lb/SCFc ppm lb/SCFc ppm Ib/SCF c ppn lb/SCFc ppm ]b/SCFc
(Vol) (Vol) (Vol) (Vol)
9.99x10-'
1.53x10-"
1.11x10-*
7.68x10-'
            IPA  Iraptnp.er, Ba(C10»)2 Tltratlon.   S02 not reported on Run II  (2/6/78) due  to transfer of In^lnger contents yielding higher thnn expected SO?  results.
           bResults calculated as SO2.
                   ___________________ _
               H20j Implnger, Ba(C10«)2 Tltrntlon.
            STP - 70°F and 29.92 Inches Hg.
            Sulfur species (S02 , H2S, COS, and CS2) not reported due to problems with Hewlett Packard GC.
-------
                  TABLE  B4-21.  ALDEHYDES3 - TCCU CO BOILER STACK
Gas Sample Aldehyde „ c
v i,,m- rn r-llP-i-Pi Concentration
_ , _. Volume (Jc) Collected , .
Stack Time @ ^ (yg) ppm(Vol..)
9 1415-1515 12.0 121.9 8.17
1605-1705 12.0 121.8 8.16
1430-1530 12.0 117.0 7.84
0940-1040 12.0 129.0 8.65
UJ
-P-
°° 1120-1220 12.0 204.0 13.70
1415-1515 12.0 231.0 15.50
lb/SCFD
6.34xlO~7
6.34xlO~7
6.08xlO~7
6.71xlO"7
1.06xlO~6
1.20xlO~6
 Sample rate = 200 mH/min.  Bisulfite Method Used.




DSTP = 70°F and 29.92  inches Hg.




"Dry basis.  Calculated as formaldehyde.
-------
                        TABLE  B4-22.   OXIDES  OF NITROGEN -  TCCU CO  BOILER  STACK
            Stack
Time
                                                                  NOX (as NOz)  Concentration3
ppm (Vol.)
lb/SCF°
                                  1543
                                120
                      1.43x10
                                  1308
                                123
                      1.46x10
LO
                                  1405
                                  1555
                                121
                                125
                      1.44x10  5
                      1.48x10
                                                                                            -5
                                  1137
                                126
                      1.51x10  5
          Dry basis.
         bSTP = 70°F and 29.92 inches Hg.
-------
                  TABLE  B4-23.   HCNa AND  NH3a - TCCU CO BOILER STACK
HCNb Concentration
Stack Time ppm (Vol.)
1645-1715 d—
9 1431-1502
1336-1406
1112-1142
Ul
o a
Sampling performed using LSI Method
b~ , .
Dry basis.
lb/SCFc Time
1603-1634
1330-1440
1251-1322
1155-1225
5 train and acidic or basic impinger
NHs Concentration
ppm (Vol.)
1.96
2.75
2.21
2.70
solutions, as
lb/SCFc
8.61 x 10~8
1.21 x 10~7
9.72 x 10~8
1.19 x 10~7
required .
Corrected to 70°F  and 29.92 inches Hg.
 Not  detectable,  less than 0.005  ppm in solution.
-------
       TABLE B4-24.    STACK  GAS AND PARTICULATES*  -  FLUID COKER  CO BOILER  STACK
                                                                          PnrtlculHten
                                                                                                   Avg
                                                                                                  Stack
              Total Gas     Avg   Avg	
               Sample"	 Mctet  Stuck  Avg   Moloture                                      Crnln
             Meter  STP    Temp  Temp   Dry   Collected                                    Loading   Velocity     Z
Stack  Time    (ft1)  (SCF)C  (°F)  (°F)   (HV)     (g)    Fraction  Filter  Probe   Imp. Jl  Totol  (gr/SCF)  (ft/sec)   laokln
     10  2035-2145  38.33  37.16   115

        1135-1245  18.99  38.41   109
                               57?   29.61    207.0

                               570   30.17    206.4
0.208   0.0242 0.6500  0.0187  0.6929   0.2862

0.701   0.0263 0.1511  0.0000  0.179'.   0.0/21
/2.47     108.^

72.11     10').9
      Sampled with LSI F.PA-5 train.

     Notal gas  flow - 2.4'. x 10s SCFN.

     CCorrected  to 70"F and 29.92 Inches Hg.
                 TABLE  B4-25.
                                 METHANE/NONMETHANE  HYDROCARBONS3 -  AND  FIXED
                                 GASESb -  FLUID  COKER  CO  BOILER STACK
Methane

Stack Tlmr.
10 1255
1600
1820
1330
1515
1630

(ppm)
7.78
3.7
1.62
—
2.7
24.0
B
Concent rat lonsc
y Weight
A
(lb/SCF)"
6
2
I

2
1
.02x10 '
-9x10 '
.25x10
—
.1x10"'
.84x10-*
By Volume
(ppm)
I/.. 5
6.9
3.01
—
5.0
44.4
Nonmothane
(As
Concentrations rl . ,,
,, . Fixed Cases
Hexane) ,_ _ . >
By Weight
(ppm)
73.9
19.5
32.9
—
6.04
3.93
(Ib/SCF)
•i.
1.
2.
-
4.
3.
72x10 *
51x10 6
55xlO"s
-
63xlO~'
OlxlO-7
Ky Volume C02 0? Nj CO H2
(ppm) (I) (Z) (X) (Z) (Z)
25
6
11
_
2

.7
.78 11.5 5.49 81.4 0.0
.4
11.7 4.79 83.9 0.00
.08
.35 12.2 4.9 81.0 0.0
Mo I.
. Ut.
(Dry)

29

30,

29

.61

.17

.62
 Byron hydrocarbon analyzer unlng flame lonlzatlon detector.
cFlscher Model 1200 gas partltloner.
.Dry banlg.
 STP - 70* and 29.92 inches Hg.
-------
                              TABLE  B4-26.    SULFUR  SPECIES  -  FLUID  COKER  CO  BOILER  STACK
          Stack
             10
        Time

        1400
        1605
       2035-2145
       1135-1245
                                SO,"
                           ppm
                          (Vol)
                          0.31
                          1.9
                                  Ih/SCF '
6.5xlO_
4.0x10


ppm
(Vol)
_.
	
233
229
h
S02
Ib/SCF c

._
	
3.86xlO"5
3.79x10 5


ppm
(Vol)
106
314



S02
Ib/SCF c

5.07xl(f 5
5.20x10 5



HjS
ppm Ib/SCF c
(Vol)
d
d


                                                                                                           COS
                                                                                                                               CS2_
ppm
(Vol)
d
d
Ib/SCF c
—
ppm Ib/Sl
(Vol)
d
d
LO
Ln
to
.IPA Implngvr, Ba(C10»)2 Tltratlon.
C6Z H20  Implngcre, Ba(C10,)2 Tltratlon.
dCorrected to 70°F and  29.92 Inches Hg, dry bonls.
 No species detected.
-------
                          TABLE B4-27.  ALDEHYDES -  FLUID  COKER  CO BOILER STACK
LO

Ln

LO
                                          Gas  Sample        Aldehyde               _,            c
                                          tr  i     /n\a       „ , ,  '   ,               Concentration     _
           c..  ,            „.              Volume  (£)        Collected       - rn— : — r ---   .
           Stack           Time                   g            ^  .          ppm(Vol.)           lb/SCF
            10         1500-1600             25.0             91.4           2.94             2.28xlO~7





                       1610-1710             25.0             70.4           2.27             1.76xlO~7





                       1710-1810             25.0            106.5           3.43             2.66xlO'7
            CO Boiler  Stack samples flow = 417 mJ,/min.   Bisulfite

            method  used.




          bSTP = 70°F and 29.92 inches Hg.


          Q

           Dry basis.   Calculated as  formaldehyde.
-------
                      TABLE B4-28.   OXIDES OF NITROGEN  -  FLUID COKER CO  BOILER
                                                                  NOX  (as N02)  Concentration3

             Stack                 Time                          ppra  (Vol.)              lb/SCFb
               10                  1515                             209                2.49x10 5





                                   1630                             239                2.85xlO~5
LO
         a
          Dry basis.


         bSTP = 70°F and 29.92 inches Hg.
-------
                      TABLE B4-29.   HCN  AND NH3  - FLUID COKER  CO BOILER STACK
HCN Concentration 3'
Stack
10
Time
1515-1545
1540-1610
ppm (Vol.)
3.15
2.56
lb/SCFc
2.20 x 10~7
7
1.78 x 10"
Time
1701-1733
1705-1735
a ,b
NHa Concentration
ppm (Vol.)
<0.05
1.79
lb/SCFc
<2.3 x 10~9
8
7.85 x 10
££     3Sampling performed using LSI Method 5 train and  acidic or basic impinger solutions, as  required.
Cn     fj
       Dry basis.
      c
        orrected to  70°F and 29.92 inches Hg.
-------
                             TABLE B4-30.
STACK GAS AND PARTICIPATES   - FLUID  COKER
SCRUBBER -  INLET AND OUTLET
Total Can Avg


Stack
19

B


Time
2015-2)15

1 130-1210
Sara]
Meier
(ft1)
24.2'>

37.59
pic Meter
STP 1' Temp
(SCF)C (°F)
71.% 86

37.53 /9
Avg
Stack Avg
Temp Dry
(°F) (MTJ)
10R9 29.09

109R 79.09
Par t iculates
Moisture
Collected

115.9

199. 1


Fraction
0.1 87

0.201


Filter
O.RI65

1.0r,2H


Probe
0. 1013

0.1972


Imp. Hi
0.0401

0.6/70


Total
0.9601

1 .9220
Grain
Loading
(gr/SCF)
O.C.209

0.7902
Avg
Stack
Velocity
(Ft/sec)
113.10

174. 19


Z
Isnkln
102.0

I0h. 7
                Sampled wUh LSI F.PA-5 train.

                "Total gas flow • (scrubber inlet) - 1.77 x 10s SCFH

                CCorrected to 70"F and 29.92  Inches Hg.
LO
                     TABLE  B4-31.   METHANE/NONMETHANE HYDROCARBONS  AND  FIXED GASES
                                       - FLUID  COKER SCRUBBER -  INLET AND OUTLET
Nonnethane Concentrations '
Methane Concentrations"^
Source
19 - Inlet A

19 - Outlet A

19 - Inlet B





(ppm)
3360
3310
3400
3350
—
2050
3292
—
—
3250
By Weight
(lh/SCF)a
2.53xlO~"
2.49x10 *
2.56xlO~'1
2.52x10 '
—
1. 54x10""
2.48x10 "
—
—
2.45xlO~"
By Volume
(PP")
6110
6020
6180
6090
__
3730
5985
—
—
5910
(ppm)
394
402
382
3nf,
—
285
31B
—
—
636
(An llexanc)
By Weight
(Ib/SCF)
2.54xlO~5
3.03x10 b
2.88xlO~'1
2. 76x10 5
__
2.15x10 5
2.39x10 5
—
—
4.79x!0"5

By Volume CO?
(|>pra)
113
136
129
124
9.5
96.4
108
9.46
10.05
215
Fixed
(Dry
Oj
(Z)




2.11


2.45
2.13

Cases
Basis)
N, CO
(T) (%)




81.6 6.9


78.9 7.22
76. fl 7.06



1I2 Hoi. Wt. .
(7.) (Ory)




7.9.64


29.05
28.58

          .Byron hydrocarbon analyzer using flnmo lonlzatlon detector.
           Fischer Model 1200 gas partltloner.
           Dry basis.
           STP - 70"F and 29.92 Inches Hg.
-------
LO
                  TABLE B4-32.   SULFUR  SPECIES -  FLUID  COKER SCRUBBER -  INLET  AND OUTLET


Source

19
Inlet
B

«> • en b
SO] SO2
ppm Ib/SCF ppn Ib/SCF
Tine (Vol) e STP (Vol) ? STP
2015-2115
1130-1230
1633
1824
2018
S02 HjS COS CS2
ppm Ib/SCF ppa Ib/SCF ppa Ib/SCF ppn Ih/SCF
(Vol) (3 STP (Vol) £ STP (Vol) g STP (Vol) g STP


	 	 	 	 	 	 	
— 	 __ 	 	 	 	
— — __ —
         ||lPA lapinger. Bo(C10.)i Tltration.
         ^61 H;O; luplngers, Ba(C10>)2 Titration.
         ^Corrected to 70*F and 29.92 Inches Kg, dry basis.
          No species delected.
-------
                  TABLE B4-33.   ALDEHYDES -  FLUID COKER SCRUBBER -  INLET AND OUTLET
.CO
Ln
Co
Gas Sample
c, , T- ' Volume (£)a
Stack Time @ STpb
19- Inlet B 1644-1744 12.0
1838-1938 12.0
Aldehyde „ . c
_ , , , Concentration
LoJ locted /T. -i \ T i_ /r*/-n-.
/ , ppm(Vol.) Ib/SCF
(Mg)
180.0 12.10 9.37xlO~7
102.0 6.84 5.31xlO~7
          Gas flow through  impingers = 200 mfc/min.  Bisulfite method used.


         DSTP = 70°F and 29.92 inches Hg.


         'Dry basis.  Calculated as formaldehyde.
-------
               TABLE B4-34.   OXIDES  OF NITROGEN - FLUID COKER SCRUBBER - INLET  AND OUTLET
U)
Ul
                                                                    NOX  (as NOz) Concentration3
               Stack                 Time                         ppm (Vol.)            Ib/SCF @ STPb
            19  -  Inlet B             1645                             4.8                5.70x10 7


                                    1650                            22.6                2.69xlO~6
            Dry basis

           bSTP = 70°F and 29.92  inches Hg.
-------
         TABLE  B4-35.   HCN  AND NH3  - FLUID COKER SCRUBBER  -  INLET AND  OUTLET

                             HCN Concentration3'15                          NH3 Concentration a •b
Stack        Time        ppra (Vol.)    Ib/SCF @ STPC         Time        ppm (Vol.)    Ih/SCF @  STPC

  19         1530-1600       141.3       9.87 x 10~6        1700-1730       175.4        7.71  x 10~6
 Inlet                                            6                                             _6
  B         1530-1600       102.5       7.16 x 10~         1700-1730       195.8        8.61  x 10
3Sampling  performed using LSI Method  5  train and acidic or basic  impinger solutions, as required.
b.
 Dry Basis.
Corrected  to  70°F, and 29.92 inches Hg.
-------
          Sampling results from six stacks in five different
Fluid Catalytic Cracking  (FCC) units are given in Tables B4-36
through B4-<'-l.  The units were all equipped with electrostatic
precipitatiors and CO boilers.  Stack No.'s 13 and 18 were from
separate CO boilers on the same FCC unit.

          Tables B4-42 through B4-46 give the sampling results
obtained from an FCC unit whose flue gases passed through a CO
boiler and then through a scrubber.  Two scrubber units were
utilized, each handling one-half of the flue gas.  Both
particulates and S0y were removed in the scrubbers.

          The results for FCC unit CO boiler Stack No. 15 were
given in Tables B4-36 through B4-41.  However, grab samples were
obtained from this unit upstream of the ESP-CO boiler control
devices.  These results are listed, together with the results
from the CO boiler stack, in Tables B4-47 through B4-52.  These
results show the CO boiler is effective in removing carbon
monoxide, aldehydes, and HCN.

          Tables B4-53 through B4-56 show the sampling results
for a FCC unit compressor exhaust stack.  The emissions from
these internal combustion engines were relatively low compaired
to other refinery process emissions sources.

          Many of the sampling results listed in this section
compare favorably with published emission factors.  However,
these results should not be used in updating or developing
new emission factors due to the low number  of samples obtained
from each stack.
                              361
-------
         TABLE  B4-36.    STACK GAS AND  PARTICIPATES3  -  FCCU  CO BOILER  STACKS
Total Gas
Samplcb
Stack Time
13 1477-1854
0859-1230
18 1110-1536
14 1000-1100
1945-7.111
If) 1605-1755
1415- 1625
15 1745-1857
1015-112/
11 1045-1245
1500-1700
Meter
(ft1)
70.99
28.96
29.1 3
46.60
57.50
37.41
35.69
31.68
32.71
36.61
30.97
Avg
Meter
STP Temp
(SCF)C <°F)
73. /y
29.16
30.55
40.10
51.25
37.14
34.92
31.81
32.03
36.56
30.20
/8
94
75
1 I/
97
90
98
96
107
81 .4
93.6
Avg
Stack Avf>
Temp Dry
("F) (HW)
391
392
386
585
577
719
727
518
540
460
460
29.95
28.65
29.46
30.94
30.94
28.47
28.21
30.58
30.58
29.11
10. 39
Partlculates
Moisture
Collected
(B)
293
103
126
88
106
213
218.
185
186.
112.
85.
.3
.3
.4
.4
.8
.3
.21
.0
2
. 7
1
Frac t ion
0. J 59
0.144
0.161
0.09/.4
0.0897
0.214
0.278
0.216
0.216
0.127
0. 117
Filter
0.1296
0.0654
0.0728
0.1H64
0.1767
0.0714
0.0154
0 . 04 2 5
0.0372
0.0624
O.OR80
Probe
0.0679
0.0122
0.0174
0. 1001
0.37.19
0.0166
O.U127
0.0282
0.0384
0.0773
0. S007
Imp. 11
0.0110
0.0027
0.0075
__H
--
0.0060
0.0020
0. 1290
0.0081
0.0113
0.0071
Total
0.7035
0.0803
0.0977
0.4865
0.5006
0.0440
0.0781
0.1997
0.0837
0.510
0.5958
Avg
Grain Stack
Loading Velocity
(gr/SCF) (fl/nec)
0
0
0


0
0
0
0
0
0
.0/76
.0425
.0493
c
--
.0181
.0174
. OP69
.0403
.064
.10/1
47.57
44.21
43.1?
49. 7/i
52. 17
49.97
49.74
48.98
51.93
66.29
68.94
I
Tnok In .
105. 3
90.4
98.8
59. 1
50.8
106.8
104. 5
112.0
10/.1
115.4
90.6
'Sampled with LSI F.PA-5 train.
bTotal gas flow rates;  Stack No. 11 -  7.70 * 106 SCFH;  Slack No. 13 - 9.15 x 10* SCFM: Stack No.  14 - 1.26 x 10* SCFH;
 Stack No. 15 - 6.53 x 10'  SCFM; Stack  No. 16 - 8.97 x 10* SCFH; Sl.irk No.  18 - 8.58 x 106 SCFH
CCorrnrtcd to 70°F nnd 29.92 Inches HG.
 Not determined.
 Partlculate sampling conducted under nontsokinerIc conditions.  Grain loading not required.
-------
                       TABLE B4-37.
METHANE/NONMETHANE HYDROCARBONS'
GASESb - FCCU CO BOILER STACKS
AND FIXED
LO
•T>
LO
Hotliane Concent laL tony
By Weight

Stack
13
Ambient
13
18
14

*


Ambient
14
16


Ambient
16
16



Time
1440
1711
1335
1614
1500
1508
0844
0936
1042
1533
1035
1150
1373
1559
2000
2020
0900
1000
1030

1030
1034
1323
1531

1537
177?
2150
1950

(ppm)
f
__£
3.98
0.49
_ f
£
..
4.10
0.22
0.50
0.15

1.15
0
0
0

0.898
0.248
0
0
lb/SCFd By Volume

2.98x10"'
3.7x10"°
__
3.22x10"'
1.73x10 "
3.9x10""
1.18x10 '

8.62x10""
0
0
0

5.6x10"'
1.55x10"'
0
0
(ppra)
7.20
0.89
..
7.78
0.42
0.95
0.28

2.08
0
0
0

1.35
0. 374
0
0
Nonmetlmne Concentrations
(As Hexane)
By Wei glit
(ppm)
1.94
19.95
19.92
19.73
10.63
0.83
_.
66.00
32.62
4.20
4.87

13. 5T
23.7/5
2.655
1.446

1.986
8.065
13.9
10.58
lb/SCFd By Volume

1.50xlO~'
1.54x10"'
1.49x10"'
1.48x10 '
7.88xlO~'
6.3x10"°
._
5.19x10"'
2.56x10 '
3.30x10 '
3.83x10"'

1.01x10"'
1.48x10""
1.6frxlO
9.02x10"'

1.24xlO~'
5.03x10"'
8.67x10 7
6.60x10 '
(ppm)
0.68
6.92
6.71
6.64
3.54
0.28
..
23.31
11.52
1.48
1.72

5.45
6.67
0.745
0.406

0.557
2.26
3.90
2.97
C02 " "
(Z)
15.1
14.8
14.3
14.4
15.0
15.6
15.5
13.5
14.1
16.1
14.1
14.2



14.5
13.6
14.9

14.9



Fixed (Ja.ses

(Z)
3.5
3.8
3.5
3.3
5.0
3.7
3.5
3.'.
7.0
6.7
6.3
6.3



4.2
5,0
3.7

3.3



(%)
79.2
79.0
73.9
73.8
77.1
77.4
77.7
78.4
77.0
77.5
77.3
77.5



81.4
SI. 4
81.9

81.7



CO II Mol. Wt.
(Z) (7.) (Dry)
0.0 — ° 29.95
0.0 — e 29.85
0.0 --e 28.10
0.0 --e 28.06
0.0 --e 29.79
0.0 — e 29.71
0.0 — e 29.70
0.0 — ° 28.98
1.0 — C 30.24
0.0 --f 30.94
0.0 --' 29.76
0.0 --e 29.93



0.0 0.0 2B.47
0.0 0.0
0.0 0.0

0.0 0.0



                                                                                    Cnnr inued
-------
                                             TABLE B4-37.    Continued


Stack Time
15 1615
1915
1030
1215
11 1530
1615
1740
1100
1230
1625
Amb irnl
11 1 7 30







0
0
0
0
0
0

3
Methane Concen
3y Weight


(ppm)




30
30
98
10
70
12

20

lb/SCFd

-



2.25x10"
2.7.5x10
7.24x10
7.49x10
1.50x10
8.74x10

2.37xlO~'
t rations
By Volume
(ppm)




0.54
0.54
1.77
0.18
0.36
0.2?

5.79
Nonmethanc Concentrations
(Ar, Hexano)

By Weight
(ppm)




75.0
17.0
1H.O
31.5
23.4
25.5

37.1

Ib/SCF"





5.55xlO~6
1.26x10" n
8.43x10"'
2.33x10 '
1.73x10 '
1.89x10 f

2.74xlO~f'

By





75
5
38
10
7
8

12

Volume
ppm)




.25
.72
.38
.60
.88
.58

.49
Fixed Cases
(Dry Basis)
CO,

14.89
15.23
13.52
14.01

16.0
15.0
15.5
15. 0
15. 0


0
(
3
3
4
3

4
4
7
6
6


2
%)
53
39
35
75

0
0
0
5
7


Nj CO II
«) U) U)
81.98 0.0 0.0
81.21 0.0 0.0
82.67 0.0 0.0
81.63 0.0 0.0

75.0
75.5
77.0
77.0
77.0


Mol Wt .
(Dry)





29.32
28.88
30.62
30.24
30 . 30


 Byron hvdrocflrbon analyzer using flame ionization detector.
 Fischer Hodpl 1200 gas parrlrloncr.
LDry basis.
RTP = 70°F and 29.92  Inches Hg.
Results questionable, not reported.
Hot detectable, less  than 0.01 ppm by weight.
-------
                         TABLE  B4-38.    SULFUR  SPECIES  -  FCCU  CO  BOILER  STACKS


Stack Time
13 1427-1854
1720
1346
1622
0859-1230
18 1130-1536
1210
1341
1515
16 1605-1755
1415-1625
1045
1340
1550
15 1745-1857
1015-1127
1040
1115
14 1000-1300
1945-2133
2020
11 1045-1245
1500-1700



ppm
SO,"
Ib/SCF'
(Vol)
0



I
1



1
1



0
1


13
1

9
7
.65



.62
.B9



.18
.11



.781
.126


.46
.07

.71
.39
1.34 xlO"'



3.36 xlO-'
3.90 xlQ-'



2.434x10-'
2.298x10"'



1.61 xlO"7
2.32 xlO"7


2.78 xlO-6
2.51 xlO'7

1.87 ilO-'
1.52 xlO"'



ppm
S07h


lb/SCFc
(Vol)
368



528
605



14
20



289
708


644
606

92
101
.5



. 7
.0



.4
.9



.0
.0


.09
, 76

.11
.42
6.



8.
1.



2.
3.



4.
1.


1.
1.

1.
1.
10 xlO"*



75 xlO"5
00 xlO"*



374x10"'
446x10"'



78 xlO"'
17 xlO"°


06 xlO"'
00 xlO"'

5 xlO"'
654xlO-5

ppm
(Vol)

416.0
330.0
390.0


314.0
145.0
245.0


<0.5
17.0
14.0


841.0
871.0
..
	
251.0°


SO 2



6
5
6


5
2
4


-------
                              TABLE  B4-39.   ALDEHYDES3 -  FCCU CO  BOILER STACKS
(-0
Stack
15

13


18

16

14

11



Time
1050-1150
1245-1345
1558-1658
1504-1604
1627-1727
1544-1644
0920-1020
1049-1149
1552-1652
2045-2130
0855-0955
1137-1237
1540-1640
1035-1135
1330-1430
1550-1650
Gas Sample
Volume (£)
@ STPb
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
12.0
8.42
10.92
11.51
11.51
11.51
11.51
11.51
Aldehyde
Collected
(us)
220.5
292.5
111.91
113.68
101.25
83.48
81.72
147.0
52.5
76.88
172.2
1.58
1.18
0.1§
d
Concentration
ppm(Vol . )
14.77
19.60
7.50
7.62
6.79
5.60
5.48
9.87
3.52
7.34
12.68
0.11
0.08
o.ogs
d
lb/SCFb
1.144xlO~6
1.517x10 6
5.82 xlO~7
5.92 xlO~7
5.27 xlO 7
4.34 xlO"7
4.25 xlO 7
7.65 xlO~7
2.73 xlO 7
5.70 xlO~7
9.85 xlO 7
8.52 xlO~9
6.43 xlO 9
6.243x10 10
d
          Sample rate = 200 m  /min.  Bisulfite method used.
          ^Corrected to 70°F and 29.92 inches Hg.
          'Dry basis.
          Blue color  developed during sample collection; interference(s)  unknown.
-------
                     TABLE 40.  OXIDES  OF NITROGEN  -  FCCU CO BOILER STACKS
UJ

Stack Time
13 1823
1406
1755
18 1659
10A7
15 1125
1130
16 1410
1517
1640
14 2020
0900
1000
NOX (as N02
ppm (Vol.)
306
297
170
181
269
94.1
105.8
453
378
415
164.3
190.0
200.4
) Concentration3
lb/SCFb
3.64 xlO~
3.53 xlO~
2.00 xlO~
2.16 xlO~
3.20 xlO~
1.12 xlO~
1.26 xlO~
5.38 xlO~
4.49 xlO~
4.93 xlO~
1.395x10"
1.514xlO~
1.66 xlO~


5
5
5
5
5
5
5
5
5
5
5
5
5
          Dry basis.
         DSTP = 70°F  and 29.92 inches Hg.
-------
                            TABLE B4-41.   HCN AND  NH3  -  FCCU  CO BOILER STACKS
cr>
oo
NH3 Concentrations
Stack Time
15a

1305-1336
1515-1545
1315-1345
1215-1247
i/f iiio°
' (1300

13a


1257-1331
1425-1455
1613-1643
1750-1820
1Ra (0952-1052
(1706-1736

16a



lla

1345-1420
1115-1145
1455-1525
1015-1045
12:40 PM
14:10 PM
16:40 PM
ppm (Vol . )
15.36
6.64

0.75
0.70
0.511

—

d
<0.3
8.2


1.0
0.6
1.0
lb/SCFc
6
2

5
4
2





3


43
2
4
.76 x
.92 x

.24 x
.89 x
.25 x

—

—
<1 x
. 6 x


.7 x
.62 x
.37 x
10'7
10"'

ID' 8
10 8
10~8




10~8
10~7


10'8
10 8
10~8
HCN Concentrations13
ppm (Vol.)
19
19
1
1

0

-
0


< 1
0
0
0
0
.0
.1
.00
.05

.023

e
.005


x 10~3
.406
.9
.6
.9
lb/SCFc
1
1
6
7

1


4


6
2
6
4
6
.33
.33
.96
.31

.6


.0


.5
.84
.18
.12
.18
x
x
X
X

X

—
X


X
X
X
X
X
IO"6
l(f5
10~8
10 fl

10~9


10" 10


10'11
10~8
10~b
10~8
10~e
          Sampling  performed using LSI Method 5 train and  acidic  or  basic impinger solutions,  as  required.
          Dry Basis.
         CCorrected to  70°F and 29.92 inches Hg.
          Not detectable,  less than 0.01 ppm in solution.
         eNot detectable,  less than 0.005 ppm in solution.
         f Infrared  Analysis at 3.01 y (HCN) and 10.4 \i (NH3)
-------
               TABLE  B4-42.
STACK  GAS  AND PARTICULATESa -  FCCU
CO  BOILER  SCRUBBER  STACKS
Total Cas
Sample0
Stack Time
1? 1516-1641
1811-19??
17 1612-1741
1821-1929
Meter
(ft1)
41.67
4?. 08
40.55
40.24
STP
(SCF)'
41.09
41 .77
39.2?
39.45
Avg Avg
Meter Stack Avg
Temp
78
75
93
87
Temp
185
185
180
180
Dry
(HW)
29.11
29.19
29.71
29.81
PnrllculBtes
Molnture
Collected
(g)
751 .2
261.1
260.3
266.3
Fraction
0.22r-
0.229
0.239
0.247
Filter Probe Imp. 11
n.nv.2 0
0.0348 0.0111 0
0.0112 0.0084 0
0.0300 0.0145 0
.OlflO
. 0000
,0230
.OlO;
Crnln
Loading
Total (gr/SCF)
0.0522 0.020
0.0479 0.018
0.0676 0.025
0.0552 0.022
Avg
Stnck
Velocity
(ft/ser)
55.32
55.88
52.57
52.15
I
look In.
107.6
103.6
100.7
103. 1
'Sampled with LSI F.PA-5 train.

 Tot.il p.ns flow rates:  Stack No.  12 - 9.08 x 10' SCFM; Stack No. 17 - 8.53 x 10s SfFH

 Corrected to 70'F nnd 29.92 Inches Hg.
-------
              TABLE B4-43.   METHANE/NONMETHANE HYDROCARBONS3  AND  FIXED
                                GASESb  - FCCU  CO BOILER SCRUBBER  STACKS


St.ick Time
12 1547
1556
1818
1825
1212
1' 1803
1810
2049
2057
2339
2348
1732
1740
1930
1937
1943
1949


By
(ppm)
—
40.75
—
39.40
67.00
	
4.26
—
15.42
—
12.10
__
5.59
__
5.20
__
3.65

Hu thane
Weight
(Ug/D
—
49.24
—
47.61
80.97
	
5.25
—
19.01
_-
14.92
__
6.89
__
6.41
—
4.50



Concent rations
Ub/SCF)
__
3.08x10
--
2.97x10
5.06x10
	
3.28x10
—
1.19x10
—
9.32x10
	
4.30x10
__
4.00x10
__
2.81x10
d Bj> Volume
Tppm)
	
' 74.27
—
s 71.81
* 122.11
	
' 7.92
—
6 28.67
—
7 22.50
	
7 10.39
	
' 9.67
__
' 6.79
By
(ppm)
__
75.80
—
68.40
106.00
__
9.78
—
39.60
__
145.84
	
10.12
__
8.50
__
6.90
Nonnu! thane
(As
Weight
(l'B/1)
„
91.60
--
R2.66
128.10
..
12.06
—
48.82
__
179.81
	
12.48
__
10.48
__ •
8.51
Concentrations
Hexane)
(lh/SCF)d
__
5.72x10 '
—
5.16x10"*
8.00x10 *
..
7.53x10"'
__
3.05x10"*
__
1.12x10"'
__
7. 79x10"'
__
6.5xlO~'
_-
5.31x10 '

By Volume
(ppm)
	
25.70
—
23.19
35.94
._
3.38
__
13.70
._
50.45
__
3.50
	
2.94
__
2.39

CO,
CO
12.')

13.0


17.0

16.0

15.8

16.2

16.3

16.2


02
CO
6.0

5.5


2.5

3.0

3.0

2.5

2.1

2.5

Fixed
(Dry
Nj
76.0

76.0


76.0

78.0

77.5

77.4

77.3

77.2

Gases
Basis)
CO
00
1.5

1.5


0.1

0.2

0.4

0.4

0.5

0.6



11
(*)
0.5

0.5


0.4

0.4

0.2

0.2

0.2

0.2



Hoi. Wt.
(riry)
29.13

29.19


29.60

29.90

29.73

29.7]

29.81

29. 72

Byron hydrocarbon annlyzer using fljme ioniration detector.
Ftocher Model 1200 gas partltloner.
Dry basin.
Corrected to 70°F and 29.92 Inches Hg.
-------
                TABLE B4-44.    SULFUR SPECIES -  FCCU  CO  BOILER  SCRUBBER STACKS
so,"
St.'ick
12



17


Time
1516-16/.3
1609
1811-1922
1832
1219
1612-1741
1MO
1821-1929
1949
ppm
(Vol)
0. 19
0.13
—
—
0.23
0.'.7
—
Ih/SCFC
«.01xJO~"
2.6SxlO~"
—
—
«.67xlO~"
9.77x10""
—
S0jh SO/ MiS COS
ppm
(Vol)
0.73
9.53
—
—
11.98
13.10
—
Ib/SCF ppm Ib/SCF ppm Ib/SCF ppm Jh/SCF
(Vol) (Vol) (Vol)
1.20x10"'
I.b8xl0"s
—
--
1.98x10""
2.17x10''
—
CSj
ppm ]h/SCF
(Vol)

—
—
—

—
—
"rPA rmp(nf>er, BaCClOi.h Titratton.
 67. HjO? Tmplngcrn, Ba(C10»)z Tltratlon.
'corrected to 70°  and 29.92 Inches Hg. , d
                             dry hanle.
SO? onjy detected In samples from heater duct.  Due to Mfih moisture content in rep,ener,it or sLnck, no appreciable concentration of sulfur ypccles deterred
in samples.
                    TABLE  B4-45.   ALDEHYDES3  - FCCU CO  BOILER SCRUBBER  STACKS
Stack
12


17


Time
1438-1538
1707-1807
1229-1329
1614-1714
1816-1916
Cas
Volu
(ST
12
11
12
11
12
Sample
me (I)
t')fb
.04
.97
.??
.87
.25
Aldehyde Caseous Aid.
Collected Volume 9 STP
(Ug) (Hi)
635
691
761
582
497
.0
.25
.75
.5
.5
510
556
612
468
400
.8
.0
.7
.5
.2
Concentr.itionsc
ppm(Vol. )
42.42
46.45
50.14
39.47
32.67
By Wclg
(ug/JU
52.74
57.75
62.34
49.07
40.61
llit
@ STP
(lb/SCK)l'
3
3
3
3
2
.29xlO"6
.61xlO~6
.89xlO-6
.06xlO-6
.54x10"'
                Corrected to 70°F and 29.92  Indies llg.
                Dry basis.
-------
                 TABLE B4-46.   OXIDES  OF NITROGEN*  - FCCU CO BOILER SCRUBBER STACKS
         Stack
Time
                                                 NO Concentration
                                                     N02 Concentration
                                             Volume
                                                           B  Weiht
                                                  Volume
                                            By Weight
(ppm)     (yg/1)  (lb/SCF)c       (ppm)     (yg/1)  (lb/SCF)c
          12
1830
                                11.34     21.62  1.35x10 6
                           1158
                           1359
                                                   70.89    135.14   8.44x10
LO
          17
                           1845
                                                   77.98    148.65   9.28x10 G
                           1929
                                                  283.55    540.54   3.38x10
          A modified Phenoldisulfonic  Acid method was used for analysis of NOX as N02.



          Dry basis.




         "Corrected to 70°F and  29.92  inches Hg.




          Not detected.
-------
U)
^1
U)
                          TABLE B4-47.    STACK GAS AND  PARTICIPATES3  -  FCCU CO  BOILER
                                              STACK -  INLET  AND  OUTLET

                              Totnl Gas    Avg   Avg	Participates	    Avg
                               Sample**  _ Metier  Stock  Avg    Moisture                                     Cr.iln    Stark
                             Meier  STP    Temp  Temp   Dry    Collected                                    Loading  Velocity     X
                St.ick   Time   Ut') (SCF)C  (°K)  (°F)   (HU)      (g)    Fraction   Filter  Probe  Imp.  J]  Totnl  (gr/SCF)  (ft/sec)   Isokln.
                 IS  1745-1857  31.68  31.81   96   538   30.38    185.0      .216    0.0425  0.0282  0.1290 0.1997  0.09C.9   48.98     IK'.O

                     1015-1127  32.71  32.03   107   ViO   30.58    186.2      .216    0.0372  0.038'.  0.0081 U.083/  O.O'iOl   M.9J     107.1



                ^Sampled ulth LSI EPA-5 train.

                 Total gas flow rates:  CO Boiler Outlet (St.ick No.  15) - 6.53 x 106 SCFM; Prpcipl tator Tnlet - Undetei mined

                CCorrected to 70CF
                    TABLE  B4-48.   FIXED  GASES3  -  FCCU  CO BOILER STACK  -  INLET AND OUTLET
% Composition
Stack
15



Precipitator Inlet

Time
1615
1915
1030
1215
1600
1945
C02
14.89
15.23
13.52
14.01
10.88
10.11
H2
0.00
0.00
0.00
0.00
0.49
0.69
02
3.55
3.39
4.35
3.75
3.21
3.31
N2
81.98
81.21
82.67
81.63
77.64
78.14
CO
0,00
0.00
0.00
0.00
7.78
7.74
                    ^Fisher  Model  1200  gas  partitioner.
                     Dry basis.
-------
              TABLE  B4-49.   SULFUR  SPECIES  -  FCCU  CO  BOILER -  INLET  AND OUTLET

Stark
SO,"
ppra lb/SCFc
Time (Vol)
15 1745-1B57 0.781 1.61x10"'
1015-1127 1.1?6 .2.31x10-'
10'.0

Prrr Ipl
t.itor
Inlet
1215
1525
1530

S0,h SO, tt,S d COS CSj
ppm Ib/SCF ppm Ih/SCF ppm Ib/SCF ppm Ib/SCF ppm Ih/SCK
(Vol) (Vol) (Vol) (Vol) (Vol)
289 4.7flxlO~5
708 1.17x10'"
841 1.39x10"" n.d. n.d. n.d. n.d. n.H. n.d.
871 1.44xlO~" n.d. n.d. n.H. n.d. n.d. n.H.
321 5.30x10"^ n.H. n.d. n.H. n.d. n.d. n.H.
344 5.68x10"'' n.H. n.d. n.d. n.d. n.d. n.H.

 II'A ImvtnKcr. B,i(C10«)2 Tttrntton.
 61. IbO; Implngci, BnCClO,,)! Tltratlon.
^SIT - 70"F «nd 29.92 Inches HR.
 n.d. •= not detecltd.
-------
                    TABLE B4-50.   ALDEHYDES*
FCCU  CO BOILER - INLET AND OUTLET
U1

otcicK lime
15 1050-1150
1245-1345
Precipitator 1720-1820
Inlet
Gas Sample Aldehyde
Volume (£) Collected Concentration
@ STPb (jag) ppm(Vol.) lb/SCFh
12.0 220.5 14.77 1.144x10-
12.0 292.5 19.60 1-517x10"
12.0 3105 208.0 1.611xlO~


.6
6
•5
          Sample rate = 200 m£/min.  Bisulfite method used.




         bSTP = 70°F and 29.92  inches Hg..




         cDry basis.  Calculated as formaldehyde.
-------
                  TABLE B4-51.   OXIDES OF  NITROGEN - FCCU CO BOILER -  INLET AND OUTLET
               Stack
                                                                     NOX  (a.s N02) Concentration3
Time
ppm (Vol.)
 lb/SCFb
                 15
1125
   94.1
1.12x10 5
u>
           Precipitator
               Inlet
                                     1130
1700
                               105.8
   36.4
                      1.26x10
4.32x10"
                                    1700
                                46.5
                      5.52x10
            Dry basis.
           DSTP = 70°F and 29.92  inches Hg.
-------
  TABLE B4-52.  HCNa AND  NH3b  - FCCU CO BOILER  CO  BOILER STACK - INLET  AND OUTLET
HCN Concentration0
Stack Time ppra (Vol.)
15 1515-1545 19.0
1215-1247 19.1
Precipitator
Inlet 1617-1645 109.5
Sampling performed using LSI Method
Sampling performed using LSI Method
c
Dry basis.
lb/SCFd
1.33 x 10~6
1.33 x 10~6
7.65 x 10~6
5 train and 2 N H2SOi,
5 train and O.IN NaOH
Time
1305-1336
1315-1345
1530-1603
NHa Concentration0
ppm (Vol.)
15.36
6.64
3.99
lb/SCFd
6.76 x 10~7
2.92 x 10~7
1.76 x 10~7
irapinger solutions.
impinger solutions.
Corrected to 70°F and 29.92" Hg.
-------
LO
--J
OO
                 TABLE B4-53.   STACK GAS AND PARTICIPATES3  -  FCCU COMPRESSOR EXHAUST STACK
Total Gas
Sample ^

Stnck Time
10/.f|-t2'.8
20
1100-1700
Meter
(ft')
62.92

66.81
STP
(SCF)C
59.18

62.76
Avg
Heter
Temp
(*F)
114.9

115.6
Avg
Stack Avg
Temp Dry
("F) (HM)
600 78.39

660 27.42
Purtleulatea
Moisture
Collected
(R) Fraction
1B5.8 0.129

190.'- 0.125


Filter Probe
O.O020 0.2674

0.0011 0.02R7


Imp. {1
0.0173

0 . 004 7


Total
0.2867

0.0367
Grain
Loading
(gr/SCF)
0.075

0.009
Avg
Stnck
Velocity
(ft/sec)
89. 17

91.11


Z
Inokln.
105

9H
                 Sampled uLth I,S1 F.PA-5 train.

                ''Total BBS flow - 0.055 x 10* SCFH

                r«np = ?0°F and 29.92 Inchon Hg.
                       TABLE B4-54.   METHANE/NONMETHANE HYDROCARBONS3  - AND FIXED GASESb
                                        -  FCCU  COMPRESSOR EXHAUST STACK



Methane
Concent rat ions
By Height
Stack.
20





Tine
0930
1145
1530
0810
0945
1045
(ppm)
™..
..
—
NC
NC

(Pg/1)

—
—
NC
NC
"-
(Ih/SCF)
	
--
—
NC
NC
~~
j!y Voliiffle
(ppm)
~-
—
—
4.00
4.00
~-
Nonmethane Concentrations
(As Hexane)
By Weight
(l'l"») (Mg/1) (Ib/SCF)
	 	 	
—
—
NC NC NC
NC NC NC
--
By Volume
(ppm)
...
—
—
75
68
"-
Fined Cases
(Dry Basis)
CO;
(%>
4.0
'..0
6.8
9.0
9.0
8.0
Oj
(X)
10.3
12.5
10.0
7.0
6.5
8.0
NI
«)
76.5
77.0
75.3
76.5
76.0
77.0
CO
(X)
0.5
0.5
0.5
0.5
0.5
0.4
Hoi . Wt
(Dry)
26.62
27.46
27.42
27.76
27.46
27.75
            Byron hydrocarbon analyzer using flume lontzation detector.

            Fisclmr Modul 1700 gas port It loner.

           rNC - Hot Calculated.
-------
(^)
                    TABLE  B4-55.  SULFUR SPECIES - FCCU  COMPRESSOR  EXHAUST  STACK

Stack Time
20 0930
1048-1248
1145
1500-1.700
1530
SO
ppm
(Vol)
0.69
0.523

a
3
Ib/SCF
@ STP
1.4 xlO~7
1.04xlO~7

S
ppm
(Vol)
0.66
0.33

o2b
Ib/SCF
@ STP
1.08xlO~
5.29xlO~



7
8

             flPA Impinger, BaC10^  Titration.
             b.
              6% H20  Impinger,  BaClOi* Titration.
-------
                         TABLE B4-56.   HCN  AND NH3   - FCCU  COMPRESSOR EXHAUST STACK
00
o
Source Time

20 1200
1515
1710

20 1200
1515
1710
Baseline
(A)

0.
0.
0.

0.
0.
0.

0058
0065
0068

0060
0075
0074
Measured Net
Absorb Absorb
(A) (A)

0.
0.
0.

0.
0.
0.

0600
0720
0850

0320
0550
0310
HCN
0
0
0
NH3
0
0
0

.0542
.0655
.0782

.0260
.0475
.0236
. Concentration
Volume
(ppra)

1.8
2.1
2.5

1.0
2.4
0.9
By Weight @
(Mg/D

1
2
2

0
1
0

.99
.32
.76

.70
.39
.63
STP
(lb/SCF)u

1
1
1

4
8
3

.24x10 7
.45xlO~7
.72xlO~7

.37xlO~8
.68xlO~°
.93xlO~B
           .Infrared analysis at 3.01)J(HCN)  and 10.4y(NH3).  Path length =  20.25m; cell temperature = 75°C.
            STP  =  70°F and 29.92 inches Hg.
-------
                          SECTION 5
                   SPECIES CHARACTERIZATION


5.1       ORGANIC AND INORGANIC SPECIES CHARACTERIZATION

          The characterization and measurement of organic
emissions from controlled and uncontrolled sources were con-
ducted at several petroleum refineries.  The controlled sources
under study included the flue gas from carbon monoxide (CO)
boilers (that are charged with flue gas from fluidized catalytic
cracking regenerators) and from a fluidized coking unit.   The
uncontrolled sources included wastewater treatment systems,
valves, pumps, flanges, compressors, and drains.

          Tables  B5-1  through  B5-12  and Tables  B5-60  and  B5-61
 list  the  aromatic species  and  inorganics  contained  in emissions
 from  controlled  sources.

          Tables  B5-13  through B5-59 present  the  species  identi-
 fied  in various  refinery process  streams  and/or  the fugitive
 emissions from fittings  in service  on  those process streams.
 Each  of these sources  is identified by the process unit name
 followed  by the  stream name.   An  effort was made  to generalize
 these stream names  so  that similar  streams from  different
 refineries could  be  compared.

          Each process source  was sampled in  two  ways  when
 possible.  A  sample  of the material in the line was taken
 directly  for analysis by GC-MS.   For liquid streams,  a small
                               381
-------
  TABLE  B5-1.
ORGANIC  SPECIES Hi  FCCU CO BOILER
FLUE GAS (STACK NO.11)
Compound
           XAD-2
                                  Concentration (ppb)
Particulates
Total
Ace naphthalene
Anthracene/Phenanthrene
GS - Benzene
Benzo (a)pyrcnc
Benzo(ghi)perylene
Chrysene
Fluoranthene
Fluorene
Methyl Anthracene/Phenanthrene
Methyl-2,4-dichlorobenzoic acid
Methyl Fluorene
Methyl naphthalene
Naphthalene
C^ - Naphthalene
Pyrene
0.06
0.1
0.0
0.005
0.01
0.005
0.02
0.05
0.1
0.0
0.05
0.08
0.1
0.1
0.04
0.0
0.0
0.009
0.0
0.0
0.0
0.0
0.0009
0.0
0.04
0.0
0.03
0.03
0.0
0.001
0.06
0.1
0.009
0.005
0.01
0.005
0.02
0.05
0.1
0.04
0.05
0.1
0.1
0.1
0.04
                          382
-------
TABLE B5-2.
ORGANIC SPECIES IN FCCU CO BOILER
FLUE GAS (STACK NO. 14)
Concentration (ppb)
Compound
Acenaphthene
Acetophenone
Cz-Alkyl acetophenone
Cz-Alkyl anisole
Cz-Alkylbenzaldehyde
C3-Alkylbenzene
C2-Alkylnaphthalene
Benzaldehyde
Benzole acid
Biphenyl
Cresol
Cyclohexane diol
Cyclohexanol
Cyclohexanone
Cyclohexene oxide
Cyanobenzene
Diphenyl oxide
Fluoranthene
FLuorene
1-Methoxy naphthalene
Methyl cyclohexanone
1-Methylnaphthalene
2-Methylnaphthalene
Naphthalene
Phenanthrene/ Anthracene
Phenol
Phenyl benzoate
XAD-2
0.048
0.028
0.015
0.009
0.002
0.013
0.13
0.034
3.5
0.34
0.22
0.13
0.12
0.18
0.80
0.001
0.018
0.011
0.041
0.063
0.0
0.15
0.16
0.43
0.061
0.038
0.013
Particulates
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.61
0.0
0.0
0.0
0.0
0.0
0.0
Total
0.048
0.028
0.015
0.009
0.002
0.013
0.13
0.034
3.5
0.34
0.22
0.13
0.12
0.18
0.80
0.001
0.018
0.011
0.041
0.063
0.61
0.15
0.16
0.43
0.061
0.038
0.013
                    333
-------
         TABLE B5-3.   ORGANIC SPECIES IN  FCCU CO  BOILER
                        FLUE  GAS  (STACK NO.  15)

                                  	Concentration (pph)
          Compound                 XAD-2       Particulates       Total
Benzaldehyde
Cyclohexanone
Ethyl toluene
Naphthalene
Phthaldehyde3
Phenanthrane/ Anthracene
0.2
0.0
0.0
0.04
0.01
0.01
0.0
0.13
0.01
0.006
0.0
0.0
0.2
0.13
0.01
0.046
0.01
0.01
Q
 Sun of two or more isomeric species.
         TABLE B5-4.   ORGANIC SPECIES IN  FCCU CO  BOILER
                        FLUE  GAS  (STACK NO.  16)
                                           Concentration (ppb)
          Compound                XAD-2        Particulates       Total

           a.
Benzoic  acid                        1.5            0.0           1.5
Naphthalene                         0.02           0.0           0.02
PhenolJ                             0.003          0.0           0.003
a
 Rased  on  idor.rif ication of corresponding  nethyl oster.

 Based  on  identification of corresponding  phenol ether.
                                  384
-------
            TABLE B5.5.
ORGANIC SPECIES  IN FCCU  CO  BOILER
FLUE  GAS (STACK  NO.13)
      Compound
                                       Concentration  (ppb)
    XAD-2
Particulate
Total
Acenaphthene
Biphenyl
Chrysene
Dibenzofuran
g
Dimethyl naphthalene
Fluoranthene
Fluorene
Methyl dimethoxybenzoate
Naphthalene
Phenanthrene/ Anthracene
Pyrene
<0.001
0.003
0.0
0.0
0.02
0.006
0.008

0.02
0.025
0.02
0.0
0.0
0.002
0.008
0.0
0.006
0.009

0.08
0.05
0.003
<0.001
0.003
0.002
0.008
0.02
0.012
0.017
0.54
0.10
0.075
0.023
Sum of two or more isomeric species.
                               385
-------
TABLE B5-6.
ORGANIC SPECIES IN FCCU CO  BOILER
FLUE GAS FROM SCRUBBER  (STACK  NO.  12)
Concentration (ppb)
Compound
Acenaphthene
Acenaphthylene
Anthracene/Phenanthrene
Benzo(a)pyrene
Benzo(g,h, i)perylene
Benzof luorene
Benz (a) anthracene/Chrysene
C2-Alkylnaphthalene
C2-Alkyl phenols
Ca-Alkyl phenols
Dibenzof uran
Fluorene
Fluoranthene
Indanol
Methnaphthalene
Methyl phenols
Methyl indanol
Methyl epoxyoctadecanoate
Methyl hexadecanoate
Methyl octadecanoate
Methyl oleate
Naphthalene
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Heptadecane
n-Octadecane
n-Nonadecane
n-Eicosane
n-Uncosane
n-Docosane
n-Tricoscane
n-Tetracosane
n-Pentacosane
n-Hexacosane
n-Heptacosane
n-Octacosane
n-Nonacosane
n-Triacontane
n-Untriacontane
n-Dotriacontane
XAD-2
0.20
0.42
0.46
0.07
0.03
0.08
0.10
1.25
0.29
1.65
0.29
0.18
0.25
0.16
1.14
0.20
0.07
2.68
3.20
2.23
1.25
1.43
0.09
0.17
0.19
0.23
0.44
0.56
0.61
0.71
0.65
0.63
0.59
0.60
0.46
0.38
0.35
0.30
0.28
0.18
0.10
0.05
Particulates
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Total
0.20
0.42
0.46
0.07
0.03
0.08
0.10
1.2
0.29
1.6
0.29
0.18
0.25
0.16
1.1
0.20
0.07
2.7
3.2
2.2
1.2
1.4
0.09
0.17
0.19
0.23
0.44
0.56
0.61
0.71
0.65
0.63
0.59
0.60
0.46
0,38
0.35
0.30
0.28
0.18
0.10
0.05
                                                 Continued
                      386
-------
           TABLE B5-6.   CONTINUED
                                  Concentration (ppb)
Compound                    XAD-2      Particulates      Total
n-Tritriacontane
Ncnyl phenol
Octyl Phenol
Pyrene
0.03
0.66
0.21
0.11
0.0
0.0
0.0
0.0
0.03
0.66
0.21
0.11
                         387
-------
         TABLE B5-7.
ORGANIC SPECIES IN TCC CO BOILER
FLUE  GAS (STACK NO.  9)
Concentration (ppb)
Compound
C2-Alkyl biphenyl
C2-Alkyl naphthalene
Cs-Alkyl naphthalene
Cz-Alkyl phenanthrene
C3-Alkyl phenol
Azulene
Benz (a) anthracene
Benzaldehyde
Benzofluoranthene
Benzo(g,h, i)perylene
Benzole acid
Benzopyrene
Biphenyl
Carbazole
Chlorocresol
Chloroxylenol
Chrysene
Cresol
Ethyl phenol
Ethyl toluene
Ethyl xylene
Fluoranthene
Fluorene
Indeo (1, 2 , 3-c , d)pyrene
Methyl fluoranthene
Methyl naphthalene
Methyl phenanthrene
Methyl pyrene
Naphthalene
Phenanthrene/ Anthracene
Phenol
Phthaldehyde3
Phthalic acid°
Pyrene
Xylenol
XAD-2
0.02
0.03
0.02
0.09
0.56
0.01
0.003
1.2
07 02
0.005
15.0
0.02
0.01
0.01
0.07
0.02
0.03
0.02
1.7
0.036
0.054
0.09
0.008
0.007
0.01
0.02
0.15
0.07
0.08
0.17
0.11
0.26
0.20
0.06
1.3
Particulates
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Total
0.02
0.03
0.02
0.09
0.56
0.01
0.003
1.2
0.02
0.005
15.0
0.02
0.01
0.01
0.07
0.02
0.03
0.02
1.7
0.036
0.054
0.09
0.008
0.007
0.01
0.02
0.15
0.07
0.08
0.17
0.11
0.26
0.20
0.06
1.3
 SUID  of two or more isomeric species.
 Based on identification of corresponding phenol ether.
"Based on identification of corresponding methyl ester.
                                 388
-------
  TABLE  B5-8.
ORGANIC  SPECIES  IN  FLUID  COKER
SCRUBBER INLET  (1),  (STACK NO.  19)
Concentration (ppb)
Compound
Jt
Ci-Alltyl naphthalene
Azuleae
Benzaldehyde
Benzamlde
Benzofuran
Bcnzoic acid
Benzoaitrile
Benzothiophene
Bipheayl
Butyl benzene
Cyanobenzochiophene
Cyanothiophene
Cyclone xanone
n-Decane
Dibenzofuran
Dibenzothiophene
Diethyl benzene
Diiaethyl ethyl benzene
n-Dodecane
Dodeceae
Ethyl quiniline
Ethyl toluene
Ethyl xylene
Hydroxymethyl quinoline
Methoxy dipehnyl ether
Methyl benzonitrile
Methyl Indan
Methyl naphthalene
Methyl phenyl pyridine
Methyl quinoline
Naphthalene
Naphthonitrile
n-Sonane
Phenaruihrene/ Anthracene
Phenol6
Phthaldehydea
Phthalic acid
Phthalonitrile3
Propyl benzene
Quinoline
Styrene
n-Tridecane
Trideceny
n-Undecane
Undeeene
Xylene3
XAD-2
0.1
5.0
9.0
0.36
9.8
21.08
107.7
5.5
4.5
0.0
7.28
4.2
1.3
0.0
3.0
0.51
0.0
0.0
0.0
0.0
0.0
0.03
0.0
1.8
0.24
3.5
0.0
0.37
0.0
1.1
4.1
10.5
0.0
0.83
6.0
0.10
1.5
10.85
0.0
1.7
0.40
0.03
0.0
0.0
0.0
0.34
Partlculates
0.0
0.0
0.0
0.0
0.0
0.007
8.5
0.16
0.35
0.02
0.03
0.0
0.0
1.1
0.17
0.0
0.11
0.04
0.54
0.31
0.12
1.46
0.28
0.0
0.0
0.0
0.02
0.02
0.06
0.0
0.62
0.29
2.0
0.08
0.0
0.0
0.0
0.0
0.30
0.0
0.0
0.24
0.09
0.87
0.77
0.17
Total
0.1
5.0
9.0
0.39
9.8
21.0
116.
5.7
4.8
0.02
7.3
4.2
1.3
1.1
3.2
0.51
0.11
0.04
0.54
0.31
0.12
1.5
0.28
1.8
0.24
3.5
0.02
0.39
0.06
1.1
4.7
11.
2.0
0.91
6.0
0.10
1.5
11.
0.30
1.7
0.40
0.27
0.09
0.87
0.77
0.51
Sum of two or more isomeric species.
Based on identification of corresponding phenol ether.
Based on identification of corresponding methyl ester.
Baaed on identification of corresponding dimethyl diestei.
                           389
-------
          TABLE B5-9
ORGANIC SPECIES IN FLUID COKER
SCRUBBER OUTLET (2)  (STACK NO.  19)

Compound
Azulene
Benzofuran
c
Benzole acid
Benzonitrile
Benzothiophene
Biphenyl
Cresol
Cyanobenzothiophene
Cyanothiophene
Cyclohexane
n-Decane
Dibenzofuran
Dibenzothiophene
Dimethyl naphthalene
Ethyl toluene
Indan
Methyl benzonitrile
Methyl indan
Methyl naphthalene
Naphthalene
Naphthonitrile
Pnenaiiihrene/ Anthracene
Phenol
Phthaldehyde
Quinoline
Xylene
Styrene

XAD-2
3.2
3.4
21.0
110.0
5.5
3.4
0.11
0.06
2.26
0.12
0.0
1.0
0.03
0.02
0.20
0.02
1.6
0.05
0.33
3.6
0.36
0.03
3.04
0.59
0.40
0.93
0.61
Concentration (p
Particulates
0.0
0.0
0.11
-0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.02
0.0
0.0
0.0
0.06
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
pb)
Total
3.2
3.4
21.0
110.0
5.5
3.4
0.11
0.06
2.3
0.12
0.02
1.0
0.03
0.02
0.26
0.02
1.6
0.05
0.33
3.6
0.36
0.03
3.0
0.59
0.40
0.93
0.61
 Sum of two or more isomeric species.
 Based on identification of corresponding phenol ether.
"Based on identification of corresponding methyl ester.
                                 390
-------
         TABLE B5-10
ORGANIC SPECIES IN  FLUID  COKER
SCRUBBER OUTLET (2)   (STACK NO.  19)
                                          Concentration (ppb)
Compound
C2-Alkyl benzole acid
C2- Alkyl naphthalene
Azulene
Benzaldehyde
Benzofuran
Q
Benzole acid
Benzonitrile
Benzothiophene
Biphenyl
Butyl benzene
Cresol
Cyanobenzothiophene
Cyanothiophene
Cyclohexanone
Dibenzofuran
Dibenzothiophene
Ethyl toluene
Ethyl xylene
Indan
Isoquinoline
Methyl benzonitrile
Methyl indan
Methyl napthalene
Methyl quinoline
Naphthalene
Naphthonitrile
Pehnanlhrene/ Anthracene
Phenol
Phthaldehyde3
Phthalic acid
Propyl benzene
Quinoline
Styrene
Xylene
XAD-2
1.2
0.03
0.68
2.3
1.1
11.0
37.0
1.87
0.54
0.0
0.02
0.067
1.57
0.19
0.41
0.0
0.13
0.02
0.033
0.01
0.21
0.03
0.18
0.13
1.75
0.16
0.01
1.11
0.009
0.05
0.02
0.27
0.16
0.16
Particulates
0.0
0.0
0.0
0.0
0.0
0.0
0.65
0.02
0.07
0.003
0.0
0.0
0.0
0.0
0.07
0.008
0.11
0.02
0.0
0.0
0.21
0.03
0.008
0.0
0.37
0.06
0.02
0.0
0.0
0.0
0.02
0.0
0.0
0.02
Total
1.2
0.03
0.68
2.3
1.1
11.0
37.6
1.9
0.61
0-003
0.02
0.067
1.57
0.19
0.48
0.008
0.24
0.04
0.033
0.01
0.42
0.06
0.188
0.13
2.12
0.22
0.03
1.11
0.009
0.05
0.04
0.27
0.16
0.18
 Sum of two or more isomeric species.
 Based on identification of corresponding  phenol ether.
"Based on identification of corresponding  methyl ester.
 Based on identification of corresponding  dimethyl diester.
                                 391
-------
            TABLE B5-11.
        ORGANIC  SPECIES IN FLUID COKER
        CO BOILER  FLUE GAS (2)  (STACK NO.  10)
Concentration (ppb)
Compound
Benzaldehyde
Benzofuran
Q
Benzole acid
Benzonitrile
Benzothiophene
Biphenyl
Chrysene
Cyclohexanone
Dibenzofuran
Fluoranthcnc
Fluorene
Q
Methyl naphthalene
Naphthalene
Naphthonitrile
Phenanthrene/ Anthracene
Phenol
Phthaldehyde3
Pyrene
XAD-2
9.8
0.03
58.0
3.2
0.04
0.02
0.0
0.11
0.04
0.01
0.01
0.05
0.44
0.0
0.03
0.009
0.02
0.008
Particulates
0.0
0.0
0.0
0.55
0.0
0.16
0.003
0.22
0.15
0.002
0.0
0.006
0.03
0.07
0.02
0.0
0.0
0.005
Total
9.8
0.03
58.1
3.8
0.04
0.18
0.003
0.33
0.19
0.012
0.01
0.011
0.47
0.07
0.05
0.009
0.02
0.013
 Sura of two  or nore isomeric species.

 Based on identification of corresponding phenol ether.

"Based on identification of corresponding methyl ester.
    TABLE B5-12.
ORGANIC  SPECIES IN  RESIN FUME  OXIDATION
FLUE GAS,  (STACK NO.  1)
Compound
Biphenyl
Methyl naphthalene
Naphthalene
Phenanthrene /Anthracene
Pyrene
Concentration (ppb)
XAD-2
0.017
0.0011
0.0059
0.0097
0.011
Particulates
0.0066
0.0
0.0
0.0
0.0
Total
0.024
0.001
0.006
0.010
0.011
                               392
-------
TABLE B-13.  CRUDE DISTILLATION UNIT:  FLASHED CRUDE
Compound
Benzene
Toluene
Echylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzene
n-Propyl benzene
3 or 4-Ethyl toluene
1,3, 5-Tr imetnylbenzene
2-Ethyl toluene
1,2, 4-Trimethylbenzene
Isobutylbenzene
1,2, 3-Tr imethylbenzene
Me thylpropyl benzene
Methylpropylbenzene
Diethvlbenzene
Die thylbenzene
Dimethylethylbenzene
Methyl indan
Dimethylethylbenzene
Tetramethylbenzene
Methyl indan
Cs-Alkylbenzene
Naphthalene
Cs-Alkylbenzene
Cs-Alkylbenzene
2-Methylnaphthalene
1-Methy] naphthalene
Biphenyl
C2~Alkylnaphchalene
C2-Alkylnaphthalene
Cz-Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
C?. -Naphthalene
Cs-Naphthalene
C 3 -Naphthalene
C 3 -Naphthalene
Fluorene
Phenanthrene/ Anthracene
Bulk Liquid
ppm
60
680
220
640
240
60
—
580
400
310
680
80
280
240
160
120
200
290
18
80
120
21
90
860
40
30
1000
860
320
160
1100
1700
540
160
320
860
710
390
80
140
Vapor on
XAD, Mg
78
600
160
460
110
42
130
370)
220)
160
320
18
84
54
154
440
66
78
—
36
32
—
—
120
—
—
50
25
—

—
T--
	
	
	
	
—
	
	
	
Vapor on
Tcnax, Ug
0.10
0.47
0.09
0.24
0.11
0.34
—

0.15
0.14
0.13
0.08
0.08
—
0.05
0.06
—
0.05
—
0.02
0.15
—
—
0.01
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
                         393
-------
       TABLE B5-14.
CRUDE DISTILLATION  UNIT:
ACCUMULATOR GAS
ATMOSPHERIC TOWER  OVERHEAD
Peak
Number
1
(is)a
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
(IS)
Compounds
(In Retention Order)
Benzene
de-Benzene
CsHioO, possibly Tetrahydropyran
CeHizO, possibly a Dimethyl tetrahydrof uran
CeHizO, possibly a Methyl pentanol
C5Hi202, or C6Hi20
Toluene
CyHiaO, possibly a Trimethyl dihydrofuran
Ethylbenzene
m- + p- Xylene
o-Xylene
3- + 4- Ethyltoluene
1,3, 5-Trimethylbenzene
1 , 2 ,4 -Trimethyl benzene
Isobutylbenzene
Indan
Ci»-Alkylbenzene
Ci»-Alkylbenzene
Ci, -Alky Ibenzene
Cs-Alkylbenzene
Naphthalene
di o-Anthracene
Vapor on XAD
(ug)
606.0
—
—
230.0
210.0
770.0
1,220.0
690.0
70.2)
430.0)
120.0
7.5}
18.0)
28.5
—
—
—
—
—
—
—
(600.0)
Vapor on Tenax
(Mg)
0.100
(0.035)
0.010
—
—
—
0.036
—
0.054

0.032
0 065

' 0.068
0.031
0.010
0.052
0.050
0.046
0.021
0.140

IS = Internal Standard
-------
     TABLE  B5-15.   CRUDE DISTILLATION  UNIT:   INTERMEDIATE
                      NAPHTHA PRODUCT,  BULK LIQUID
        Compound                                                ppm

Benzene                                                        26.3
Toluene                                                        64.0
Ethylbenzene                                                  153.0
ir./p-xy]enes                                                   204.0
o-xylenes                                                      40.3
i-propylbenzene                                                 3.74
n-propylbenzene.                                                45.9
m/p-ethyltoluene                                              236.0
o-ethyltoluenc                                                 47.6
1,2,4-Trimethylbenzene                                        105.0
1,2,3-Trimethylbenzene                                          9.52
Cn-Alkylbenzene                                                 3.42
Cn- Alkylbenzene                                               70.0
n-butylbenzene                                                 88.0
Cii-Alkylbenzene                                               '24.0
Ci,-A1.kylbenzene                                                2^.0.
Methylindan                                                    10.8
Methylindan                                                    94.0
Cn-Alkylbenzene                                                60.0
Ci4-Alkylbenzene                                                36.0
Ct-Alkylbenzene                                                 3.04
Cs-Alkylbenzene                                                 8.05
Cu-Alkylbeuzene                                                13.6
Cs-Alkylbenzene                                                 6.56
Cs-Alkylbenzcne                                                20.8
Cb-A.lkyl benzene                                                ^^-O
Cs-Alkylbenzene                                                70.0
Tetralin                                                       74.0
Cj-Alkylbcnzene                                                27.5
Naphthalene                                                    24.2
Cz-Alkyl Tndan/Methyltetralin                                 140.0
C2-Alkyl Indan/Methyltetralin                                 115.0
2-Methyl te.tralir.                                               96.1
Cz-Alkyl Tndan/Mothyltetralin                                 102.0
C2-Alkyl Indan/Methyltetralin                                 112.0
C2-Alkyl Indan/Methyltetralin                                  52.7
2-MethyInaphthalcne                                            32.3
1-Methylnaphthalene                                            16-°
C2-Alky! naphthalene                                            5-25
C2-Alkyl naphthalene                                           25-°
B.Phenyl                                                        7.70
C2-Alkyl naphthalene                                           23-8
Cz-Alkyl naphthalene                                           12.3

                                                      Continued
                                   395
-------
                        TABLE B5-15.   Continued

        Compound                                                 ppni
Methylbiphenyls                                                 13.6
Cj-Alkyl naphthalene                                             2.67
Cj-Alkyl naphthalene                                             9.28
Cs-Alkyl naphthalene                                            13.1
C3-Alkyl naphthalene                                             9.86
Cs-Alkyl naphthalene                                             5.80
C2-Alkyl biphenyls                                              36.0
Phenanthrene/anthracene                                          5.50
Methyl phenanthrene/anthracene                                   14.0
C?-Alkyl phenanthrene/anthracene                                 14.8
Fluorenthene                                                     3.10
Pyrene                                                           7.50
Methyl fluoranthene/pyrene                                       10.8
Methyl fluoranthene/pyrene                                       15.6
Ci-Alkyl fluoranthene/pyrene                                     26.0
Ci-Alkyl chrysenes/Benzointhracines                               0.533
                                   396
-------
      TABLE B5-16.   CRUDE  DISTILLATION UNIT:  FULL RANGE
                       STRAIGHT RUN rtAPHTHA,  5ULK  LIQUID

        Compound                                                 PPM


Benzene                                                         57.5
Toluene                                                        139.0
Ethylbenzene                           '                        300.0
Tn/p-xylenes                                                    229.0
o-xylene                                                       228.0
i-propylbenzene                                                 21.6
n-propylbenzene                                                 63.8
m/p-ethyltoluene                                               284.0
1 , 3, 5-Triniethylbenzene                                          74.8
o-ethyltoluene                                                  49.3
1,2,4-Trimethylbenzene                                         257.0
sec-Butylbenzene                                                26.0
1,2,3-Trimethylbenzene                                          21.B
C^-Alkylbenzene                                                 28.8
Inden                                                            4.38
C4-Alkylbcnzene                                                 68.0
n-Butylbenzene                                                  28.0
CVAl.kylhenzene                                                 72.0
C4-Alkylbenzene                                                 90.0
Methylindan                                                     30.0
Methylindan                                                     18.4
CM-Alkylbenzene                                                 26.0
C,,-Alkylbenzene                                                  8.40
Cs-Alkylbenzene                                                 47.31
C5-Alkylbenzene                                                  7.00
(VAlkylbenzene                                                 24.0
Cs-Alkylbensjene                                                 17.4
Methylindan                                                      7.00
Cs-Alkylbenzene                                                  8.25
C5-Alkylbenzene                                                 15.0
C5-Alkylbenzene                                                 37.5
Methylindan                                                      9.10
Cj-Alkylbenzena                                                 45.0
Cs-Alkylbenzene                                                 11.5
Cs-Alkylbenzene                                                  6.00
Naphthalene                                                     12.1
Cz-Alkylincene/methyltetralin                                    17.4
                                   397
-------
        TABLE B5-17.
CRUDE DISTILLATION UNIT:   VIRGIN
MIDDLE DISTILLATE PRODUCT,  BULK  LIQUID
      Compound
                                        ppm
To lu e ne
ELhylbenzene
m/p-xylenes
o-xylene
n-propylbenzene
m/p-ethyltoluene
1,3,5-Trimethylbenzcne
o-ethyltoluene
1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene
Indan
C^-Alkylbenzene
Ci+-Alkylbenzene
Cu-Alkylbenzene
Methylindan
C^-Alkylbenzene
Ci+-Alkylbenzene
Methylindan
C5-Alky!benzene
Cs-Alkylbenzene
Methylindan
Cs-Alkylbenzenc
Cs-Alkylbenzene
Naphthalene
Benzothiophene
Cs-Alkylbenzene
Mcthylbenzothiophene
2-Methylnaphthelene
Me thylbenzothiophene
1-Methylnaph thalene
Cz-Alkylbcnzothiophene
Cz-Alkylbenzothiophenc
C2-AlkyInaphthalene
Cz-Alkylbenzothiophene
C2~Alkylnaphthalene
Cj-Alkylbtnzothiophene
C2-Alkylnaphthalene
C2-Alkylbenzothiophene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
Acenaphthcne
C 3-Alkylbenzothiophene
C3-Alkylnaphthalene
                                      4.48
                                      9.10
                                     40.3
                                     11.7
                                      7.80
                                     27.3
                                     22.1
                                      5.85
                                     89.8
                                     14.0
                                     11.4
                                     48.0
                                     38.0
                                     106.0
                                     28.0
                                     70.0
                                     80.0
                                     26.0
                                     27.5
                                     65.0
                                     29.9
                                     80.0
                                     32.5
                                     100.0
                                     38.0
                                     25.0
                                     129.0
                                     760.0
                                     114.0
                                     89.9
                                     80.0
                                     36.0
                                     62.5
                                     205.0
                                     400.0
                                     64.0
                                     700.0
                                     54.0
                                     143.0
                                     32.5
                                     19.6
                                     215.0
                                     241.0
                                                      Continued
                                   398
-------
            TABLE B5-17.  Continued
Compound
C3-Alkylnaphthalene
Cq -Alky Inaph thalene
Ca-Alkylnaphthalene
Fluorene
C 3-Alkylnaph thalene
Methylacenaphthene
Cu-Alkylbenzothiophene
Cu-Alkylnaph thalene
Me thy If luorene
Ca-Alkylacenapthene
Methylfluorene
Methylfluorene
Dibenzothiophene
Phenanthrene./ Anthracene
C?- Alky If lucrene
Methyldibenzothiophcne
Methyl dibenzothiophene
Methyl phenanthrene/anthracene
Methyl phenanthrene/anthracene
C 2- Alky Idibenzothiophene
Cz-Alkyl phenan threne /anthracene
Cz- Alky Idi hen znthiophene
Cz-Alkyl phenanthrene/anthracene
C2-Alkyl p lie nan threne /anthracene
Cz-Alky] dihenxothiophene
Cn- Alky Idi ben zothiophene
C2~Alkyl phenanthrene/anthracene
Fluoranthene
C3-Alkyldibenzothlophcne
Ca-Alkyl plienan threne /anthracene
C s-Alkyl phenanthrene/anthracene
Cs-Alkyl phenanthrene/anthracene
Pyrene
Cs-Alkyl phenanthrene/anthracene
C 4- Alky! dibenzothiophene
C 3-A1 kyJ phenanthrene/anthracene
Methyl f luoranthen/pyrene
Methyl f ] uoran then/pyrene
249.0
235.0
171.0
34.5
69.6
86.0
100.0
348.0
18.7
126.0
30.6
10.4
32.0
56.1
62.0
27.2
51.0
51.8
40.6
12.6
4.75
4.60
18.0
40.0
36.3
22.0
92.5
3.30
65.0
5.22
4.93
10.73
4.80
24.9
13.3
8.41
2.99
3.51
                     399
-------
       TABLE B5-18.   CRUDE  DISTILLATION UNIT:
                      ATMOSPHERIC GAS OIL,  BULK LIQUID
Compound
Toluene
Ethylbenzcne
m/p-xylenes
c-xylene
m/ p- e thy 1 to lu ene
1, 3, 5-Trimetnylbenzene
o-ethyltoluene
Ci»- Alky Ibenz ene
Ci,- Alky Ibenz ene
C^-Alkylbenzene
C 5- Alky "Ibenz ene
Naphthalene
2-Methylnapnthaiene
1-Methylnaphthplenc
GJJ_ Alky Inaph thai ene
Cj-Alkylnaphthalene
C?-Alkylnaphthalene
C^-Alkylnaphthalene
Cj-Alkylnaphthalene
Phenanthr ene /anthracene
Methyl phenanthrene/anthracene
Methyl phenanthrene/anthracene
C ? - Alk y 1 ph en a n th r ene / an t hr ac en e
C3~Alkyl phenanthrene/anthracene
7.60
5.46
11.1
4.68
15.1
5.27
18.7
4.40
7.20
4.80
5.25
3.52
4.75
3.48
9.75
0.750
13.8
8.25
14.5
3.30
10.6
14.0
80.0
60.9
                          400
-------
          TABLE B5-19.   CRUDE DISTILLATION UNIT:   LIGHT
                           VACUUM GAS  OIL,  BULK  LIQUID


    Compound                                                   ppm


Toluene                                                        5.04
Ethylbenzene                                                   5.85
m/p-xylene                                                     9.88
o-xylene                                                      11.6
n-propylbenzene                                                3.22
m/p-ethyltoluene                                              17.0
1,3,5-Trimethylbenzene                                         7.48
o-ethy1toluene                                                 9.01
1,2,4-Trimethylbenzene                                        12.4
Indan                                                          4.50
Cu-Alkylbenzene                                               10.2
C^-Alkylbenzene                                               16.0
C4-Alkylbenzene                                                6.80
Methylindan                                                    5.20
Methylindan                                                    5.00
C,,-Alkylbenzene                                                8.80
C^-Alkylbenzene                                               80.0
Methylindan                                                    4.20
C5-Alkylbenzene                                               45.0
C5-Alkylbenzene                                                3.5
C5-Alkylbenzene                                                3.25
Methylindan                                                   11.3
C5-Alkylbenzene                                                5.00
Cs-Alkylbenzene                                                5.00
Tetralin                                                       1.60
Naphthalene                                                   27.5
C2-Alkylindan/methyltetralin                                  27.3
C5-Alkylbenzene                                               14.0
C2-Alkylindan/methyltetralin                                  19.2
C5-Alkylbcnzene                                               15.3
C2-Alkylindan/methyltetralin                                  15.2
C2-Alkylindan/tnethyltetralin                                  18.3
2-Methylnaphthalene                                           68.4
1-Methylnaphthalene                                           18.9
C2-Alkylnaphthalene                                           25.0
C2~Alkylnaphthalene                                           72.5
Biphenyl                                                       8.80
C2-Alkylnaphthalene                                          113.0
C2-Alkylnaphthalene                                           70.0
C2-Alkylnaphthalene                                           18.0
Methylbiphenyls                                               13.6
Cj-Alkylnaphthalene                                           34.8
C3-Alkylnaphthalene                                           43.5
                                 401
-------
             TABLE B5-19.  Continued
Compound                                           ppm
C 3- Alky 1 naphthalene
Cs-Alkylnaphthalene
Fluorene
C3-Alkylnaph thai ene
Methyl acenaphthalene
Cz -Alkylbiphenyls
Methylfluorene
Paenanthr ene/ anthracene
C2 -Alkylf luorene
Methyl phenanthrene/anthracene
Methyl phenanthrene/anthracene
Cg-Alkyl phenanthrene/anthracene
C3-Alkyl phenanthrene/anthracene
55.1
31.9
9.36
4.93
13.6
28.0
9.35
12.1
9.40
6.30
5.18
9.50
2.9
  TABLE Bb-20.   CRUDE DISTILLATION UNIT:  VACUUM
                 GAS OIL, BULK  LIQUID
             No Aromatic  Species Detected.
                         402
-------
    TABLL  B5-21.   CRUDE  DISTILLATION  UNIT;   VACUUM  GAS OIL
Compound
Benzene
Toluene
Ethylbenzene
T., p-Xylene
o-Xylene
Isopropylbenzene
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Trimethylbenzene
2-Ethyl toluene
sec-Buty Ibenzene
1, 2 , 4-TriTr.ethylbenzene
Di ethyl benzene
Methylisopropylbenzene
Methylpropylbenzene
.Methylpropylbenzene
Methylpropylbenzene
Diethylbenzene
Die thy]. benzene
Diir.ethyle thy Ibenzene
Dimethylethy Ibenzene
Dimethyl ethy Ibenzene
Diir.ethylethylbenzene
C 5 -Alky Ibenzene
Dime thy le thy Ibenzene
Tetramethy] benzene
Tetrame thy Ibenzene
Tetramethy Ibenzene
Cs -Alky Ibenzene
Cs-Alky Ibenzene
Naphthalene
Cs-Alky Ibenzene
Cs-Alky Ibenzene
Ci -Alky Ibenzene
Bulk Liquid, Vapor on
ppm XAD,yg
1.5
29.0
8.9
42.0
34.0
11.0
49.0
38-0
30.0
73.0
17.0
55.0
13.0
10.0
4.2
25.0
14.0
19.0
17-0
20.0
11.0
10.0
5.6
10.0
4.7
7.0
17.0
4.9
31.0
5.8
59.0
6.7
2.8
2.6
Vapor on
Tenax,pg
0.00046
0.0070
0.0030
0.0099
0.0046
0.0017
0.0096
0.0052
0.0039
0.0099
0.0029
0.0062
0.0031
—
O.OOU49
0.0068
—
0.0029
0.0039
0.0044
—
—
—
0.0034


0.0034
0.0024
0.0065
0.0018
0.014
0.0016
—
—
aNone of  the listed vapor species were found in the  bulk liquid.  The vapor
 species,  therefore, must have been adsorbed from the ambient air or resulted
 from cross-contamination with other samples due to  residue in the sampling
 train.
                                   403
-------
 TABLE B5-22.   CRUDE DISTILLATION UNIT:   HEAVY
                VACUUM GAS OIL, BULK  LIQUID
             No Aromatic Species Detected
TABLE B5-23.   CRUDE DISTILLATION  UNIT:   VACUUM
               RESIDUE, BULK LIQUID
             No Aromatic Species Detected.
                       404
-------
TABLE B5-24,
API SEPARATOR: SURFACE OIL SKIMMED
FROM INLET BAY, BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3 or 4-Ethyl toluene
1,3 ,5-Trimethy Ibenzene
2-Ethyl toluene
1, 2 ,4-Trimethy Ibenzene
Isobutylbenzene
1,2, 3-Trimethylbenzene
Methylpropylbenzene
Indan
Methylpropylbenzene
Diethylbenzene
Diethylbenzene
Dime thyle thy Ibenzene
Methyl indan
Dime thyle thy Ibenzene
Tetrame thy Ibenzene
Tetramethylbenzene
Methyl indan
€5 -Alky Ibenzene
Cs -Alky Ibenzene
Naphthalene
C 5 -Alky Ibenzene
Cs -Alky Ibenzene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Ca-Alkylnaphthalene
C2-Alkylnaphthalene
Ca-Alkylnaphthalene
C2-Alkylnaphthalene
C2~Alkylnaphthalene
C2 -Biphenyl
C 3 -Naphthalene
C$ -Naphthalene
C3 -Naphthalene
C 3 -Naphthalene
Fluorene
Phenanthrene/Athracene
di c -Anthracene
Concentration
(ppm)
230
1800
480
1300
390
100
240
1000
500
460
1000
60
330
180
60
470
130
300
370
120
130
140
60
150
50
160
2000
100
80
2200
1700
620
390
1800
3000
700
240
840
390
1200
860
470
160
220
—
                       405
-------
TABLE B5-25.  API SEPARATOR:  SURFACE  OIL SKIMMED
                FROM  INLET  BAY, BULK LIQUID
                                               Concentration
       Compound                                    (ppm)

 Benzene                                             24
 Toluene                                            460
 Ethylbenzenc                                        30
 ro,p-Xylene                                         350
 o-Xylene                                           210
 Isopropylbenzene                                    72
 n-Propylbenzene                                    160
 3 or 4-Ethyl toluene                               710
 1,3,5-Trimethylbenzene                              490
 2-Ethyl toluene                                    145
 1,2,4-Trimethylbenzene                              730
 1,2,3-Trimethylbenzene                              160
 Methylpropylbenzene                                 79
 Methylpropylbenzene                                 14
 Diethylbenzene                                      31
 Dimethylethylbenzene                               170
 Dimethylethylbenzene                                78
 Diethylbenzene                                     190
 Dimethylethylbenzene                                25
 Dimethylethylbenzene                               180
 Cs-Alkylbenzene                                    140
 Cs-Alkylbenzene                                     65
 Cs-Alkylbenzene                                     90
 Cs-Alkylbenzene                                     20
 Dimethylethylbenzene                               145
 Tetramethylbenzene                                 250
 Cs-Alkylbenzene                                     35
 Tetramethylbenzene                                 260
 Cs-Alkylbenzene                                     80
 Cs-Alkylbenzene                                    100
 Cs-Alkylbenzene                                    165
 Cs-Alkylbenzene                                    120
 Cs-Alkylbenzene                                    190
 Cs-Alkylbenzene                                     55
 Cs-Alkylbenzene                                     55
 Cs-Alkylbenzene                                    165
 Cs-Alkylbenzene                                     70
 dio-Anthracene
                           406
-------
TABLE B5-26
API SEPARATOR: SURFACE  OIL  SKIMMED
FROM OUTLET END, BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42 .
43
44
Compound
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropylbcnzenc
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Trimethy Ibenzene
2-Ethyl toluene
see-But ylbenzene
1,2, 4-Trimethy Ibenzene
Diethylbenzene
Me thy lisop ropy Ibenzene
Me thylpropy Ibenzene
Diethylbenzene
Dimethylethylbenzene
Dime Chyle thy Ibenzene
Tetramethy Ibenz ene
Tetrame thy Ibenzene
Cs -Alky Ibenzene
Naphthalene
Cs-Alkylbenzene
Cs-Alkylbenzene
Cs-Alkylbenzene
Cs-Alkylbenzene
Cs-Alkylbenzene
Cs-Alkylnaphthalene
2-Methylnaphthalene
C -Alkylbenzene
1-Methylnaphthalene
Cs-Alkylnaphthalene
Biphenyl
C2-Alkylnaphthalene
C2-Alkylnaphthalene
Cz-Alkylnaphthalene
C2-Alkylnaphthalene
Ca-Alkylnaphthalene
Acenaphthene
C 3 -Alky Inapht ha lene
Ca-Alkylnaphthalene
C? -Alkylnaphthalene
Cs-Alkylnaphthalene
Fluorene
C 3 -Alkylnaphthalene
Concentration
(ppm)
280
200
2,400
950
250
2,500
1,200
950
3,800
280
1,600
210
85
700
600
900
850
1,100
120
6,500
1,200
210
430
180
120
140
160
23,000
140
14,000
70
380
4,100
18,000
22,000
4,500
1,100
600
6,000
10,000
11,000
3,200
1,200
240
                                            Continued
                        407
-------
TABLE B5-26.  Continued
Peak.
No.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
Compound
03 -Alkylnaphthalene
Methylbiphenyl
Ci» -Alkylnaphthalene
Cu -Alkylnaphthalene
Ci4 -Alkylnaphthalene
Cu -Alkylnaphthalene
Ci* -Alkylnaphthalene
C ^-Alky Inaphthalene
Methyl fluorene
Methyl fluorene
Ci>-Alky 1 naphthalene
Ci* -Alkylnaphthalene
Phenanthrene /Anthracene
di o-Anthracene
Concentration
(ppm)
500
4,600
1,700
1,600
220
800
1,300
850
1,300
240
1,300
380
1,800

           408
-------
TABLE B5-27
API SEPARATOR: OIL FROM THE SKIM
OIL SUMP, BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3 or 4-Ethyl toluene
1 , 3 ,5-Trimethylbenzene
2-Ethyl toluene
1 , 2 ,4-Triraethylbenzene
Isobutylbenzene
1,2, 3-Trimethylbenzene
Methylpropylbenzene
Indan
Methylpropylbenzene
Diethylbenzene
Dicthylbenzene
Dime thy lethylbenzene
Methyl indane
Dime thy lethylbenzene
Tetraraethylbenzene
Tetramethylbenzene
Methyl indan
C5-Alkylbenzene
Cs-Alkylbenzene
Naphthalene
Cs-Alkylbenzene
C5-Alkylbenzene
2-Methylnaphthalene
1-Methylnaph thalene
Biphenyl
C2 -Alky Inaph thalene
C2 -Alky Inaph thalene
C2 -Alkylnaphthalene
C 2 -Alky Inaph thalene
C2 -Alky Inaph thalene
C 3 -Naphthalene
C3-Naphthalene
C 3 -Naphthalene
C3-Naphthalene
Fluorene
Phenanthrene/ Anthracene
d j c-Anthracene
Concentration
(ppm)
70
1400
540
1600
450
130
480
1700
720
630
1600
100
480
240
120
740
220
320
520
220
240
320
60
260
280
240
690
120
130
4000
2700
840
390
2400
4500
1200
390
760
2000
1400
700
250
260
—
                     409
-------
TABLE B5-28.   CRUDE DESALTER: EFFLUENT
              WATER, BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Compound
Benzene
Toluene
Ethylbenzene
m.p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3 or 4-Ethyl toluene
1, 3,5-Trimethylbenzene
2-Ethyl toluene
1,2, 4-Tr imethylbenzene
1,2, 3-Trimethylbenzene
Diethylbenzene
Naphthalene
Carbazole
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
Ci-Alkylnaphthalene
C2-Alkylnaphthalene
Cz-Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
C 3 -Naphthalene
C3-Naphthalene
Ca-Naphthalene
Fluorene
Phenanthrene/ Anthracene
di o-Anthracene
Acenaphthene
Concentration
(ppb)
6.6
3.4
7.3
2.2
9.9
1.4
4.8
15.0
1.2
5.9
18 0
12.0
3.8
450.0
51.0
150.0
140.0
100.0
20.0
67-0
120.0
36-0
10.0
48-0
37.0
23-0
22.0
50.0
—
100.0
                   410
-------
TABLE B-29.  CRUDE  DESALTER:   EFFLUENT
             WATER,  BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Compound
Benzene
Toluene
Ethylbenzene
m-Xylene/p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
1 ,3,5-Trimethylbenzene
2-Ethyl toluene
1 ,2,4-Trimethylbenzene
(\-Alkylbenzene
Indan
Ci, -Alkylbenzene
Ci, -Alkylbenzene
Ct, -Alkylbenzene
Ci, -Alkylbenzene
C4 -Alkylbenzene
Methyl indan
C4 -Alkylbenzene
Methyl indan
C 5 -Alkylbenzene
C^ -Alkylbenzene
C,, -Alkylbenzene
C^ -Alkylbenzene
C 5 -Alkylbenzene
C5-Alkylbenzene
Naphthalene
Ci, -Alkylbenzene
2-Methylnaphthalene
1-Me thy Inaph thai ene
Biphenyl
Dime thylnaphthalene
Dime thy Inaph thalene
Dime thylnaphthalene
Dime thylnaphthalene
Dime thylnaphthalene
C3-Alkylnaphthalene
Methyl biphenyl
Methyl biphenyl
C 3-Alkylnaphthalene
Methyl biphenyl
C 3 -Alky Inaph thalene
C 3 -Alky Inaph thalene
Concentration
(ppb)
3.1
11.0
1.1
6.9
2.4
0.10
0.12
0.62
0.44
0.25
0.14
0.06
0.19
0.05
0.03
0.14
0.23
0.14
0.07
0.14
0.11
0.15
0.13
0.04
0.07
0.10
0.05
8.1
0.17
0.49
0.32
0.02
0.02
0.07
0.15
0.05
0.01
0.01
0.14
0.04
0.03
0.03
0.03
0.03
                                     Continued
                  411
-------
TABLE B5-29.  Continued
Peak
No.
45
46
47
48
49
50
51
52
Compound
Cs -Alkylnaphthalene
C-j -Alkylnaphthalene
GS -Alkylnaphthalene
Fluorene
Methyl fluorene
Methyl fluorene
Dibenzothiophene
Phenanthrene
Concentration
(ppb)
0.04
0.04
0.01
0.004
0.006
0.006
0.03
0.01
          412
-------
     TABLE B5-30.  CRUDE  DESALTER:   EFFLUENT
                   WATER,  BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzene
1,3, 5-Trimethylbenzene
Methylethylbenzene
1,2, 4-Tr inte thylbenzene
sec-Butylbenzene
Methylpropylbenzene
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
C2-Alkylnaphthalene
Fluorene
di o -Anthracene
Concentration
(ppb)
36
2600
290
250
130
24
120
110
60
56
100
1200
220
210
40
140
21
—
       TABLE B5-31.  SOUR  WATER STRIPPER: SOUR
                     WATER FEED,  BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
Compound
Dime thy Id isul fide
Phenol
Methylphenol3
Methylphenol
Methylquinoline
Dimethylphenol3
Dimethylphenol
Dimethylphenol
Methylquinoline
di o-Anthracene
Concentration
(ppm)
100.0
120.0
14.0
46.0
4.8
5.6
3.6
2.1
3.3

Identification based on corresponding methyl ether.
                       413
-------
TABLE B5-32
FLUID CATALYTIC CRACKER:
(GAS TO THE ABSORBERS)
COMPRESSOR DISCHARGE
Compound
Benzene
Toluene
Ethylbenzene
ra,p-Xylene
o-Xylene
Isopropylbenzene
n-Propyl benzene
3 or 4-Ethyl toluene
1,3, 5-Trimethylbenzenc
2-Ethvl toluene
1, 2 , 4 -Tr ime thy 1 benzene
1 , 2,3-Trimethylbenzene
Methylpropylbenzene
Diethylbenzene
Dime thy Ibenzene
Dime thy let hylbenzcne
Tetranethylbenzene
Tetranethylbenzene
C 5 -Alky Ibenz ene
C5-Aklybenzene
Naphthalene
2-Methylnaph thai ene
1-Methylnaphthalene
Vapor on XAD
Resin (]-g)
21.0
93-0
13.0
46.0
14-0
—
—
12.0
6.0
2.4
13-0
2.3
3.8
1.6
4.1}
0.4)
—
2.0
—
—
23.0
1.9
.0.3
Vapor on
Tenax (Ug)
0.54
2.5
0.68
1.6
0.58
0.05
0.30
0.74
0.55
0.31
0.94
0.28
0.40
0.22

0.48
0.08
0.26
0.16
0.13
0.01
—
—
                            414
-------
TABLE B5-33.
FLUID CATALYTIC CRACKER: LOW PRESSURE
SEPARATOR GAS (COMPRKSSOP. SUCTION)
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
u-Xylene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Trimethylbenzene
2-Ethyl toluene
see-But ylbenzene
1 , 2 , 4-Trimethylbenzene
Methylpropylbenzene
Dime thy lethly benzene
Diethylbenzene .
C5-Alkylbenzene
Tetramethylbenzene
Cs-Alkylbenzene
Naphthalene
Vapor on
XAD, ug
— _
8.5
—
—
—
0.55
—
—
—
—
—
—
—
—
—
—
—
—
—
—
Vapor on
Tenax, ug
0.028
0.054
0.0085
0.019
0.059
0.0010
0.0049
0.014
0.0096
0.0065
0.022
0.0086
0.0052
0.013
0.018
0-0083
0.0049
0.014
0.011
0.059
-------
TABLE B5-34.
FLUID CATALYTIC CRACKER:   LOW PRESSURE
SEPARATOR LIQUID, BULK  LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Compound
Benzene
Toluene
Ethylbenzene
m-Xylene /p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
1 ,3 ,5-Triniethylbenzene
2-Ethyl toluene
Ci^-Alkylbenzene
1 , 2,4-Trimethylbenzene
C^-Alkylbenzene
Indan
Ci^-Alkylbenzene
Ci^-Alkylbenzene
Ci^-Alkylbenzene
Ci^-Alkylbenzene
Ci,-Alkylbenzene
Methyl indan
(\-Alkylbenzene
Methyl indan
C5-Alkylbenzene
Cit-Alkylbenzene
Ci,-Alkylbenzene
Cc-Alkylbenzene
Cs-Alkylbenzene
Methyl indan
Methyl indan
C L -Alky Ib en 2 en e
Cs-Alkylbenzene
Cs-Alkylbenzene
Naphthalene
Cs-Alkylbenzene
C2-Alkyl indan
Cz-Alkyl indan
C.»-Alkylbenzene
C2-Alkyl indan
Cs-Alkylbenzene
C 5 -Alky 1 benzene
Cs-Alkylbenzene
Cs-Alkylbenxene
Cj-Alkylbenzene
Cs-Alkylbenzene
Concentration
(P?b)
4,300
5,000
7,300
55,000
32,000
5,600
44,000
66,000
14,000
82,000
1,300
20,000
2,000
15,000
15,000
14,000
19,000
4,600
24,000
7,000
24,000
1,200
2,200
4,000
20,000
18,000
4,700
16,000
16,000
7,000
14,000
16,000
15,000
3,000
21,000
28,000
13,000
15,000
15,000
4,300
1,200
2,100
2,500
8,800
                                                   Continued
                         416
-------
TABLE B5-34.  Continued
Peak
No.
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
Compound
Cs-Alkylbenzene
Cs-Alkylbenzene
Cs-Alkylbenzene
C2-Alkyl indan
Cs-Alkylbenzene
CG-Alkylbenzene
Cz-Alkyl indan
Cs-Alkylbenzene
C2-Alkyl indan
Cs-Alkylbenzene
Ce-Alkylbenzene
C s -Alky Ibenzene
C2-Alkyl indan
Methyl benzothiophene
Ce -Alky Ibenzene
C2-Alkyl indan
Methyl benzothiophene
2-Me Chylnaphthalene
Methyl benzothiophene
Methyl benzothiophene
1-Methylnaphthalene
Methyl benzothiophene
Ca-Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
Ca-Alkylnaphthalene
Concentration
(ppb)
5,200
4,800
1,300
11,000
7,500
8,100
11,000
7,500
14,000
3,900
7,500
5,000
9,700
500
2,500
5,000
1,400
16,000
1,400
1,200
15,000
1,600
700
1,400
1,100
300
        417
-------
TABLE B5-35.
FLUID CATALYTIC CRACKER:  LOW
PRESSURE SEPARATOR LIQUID
Peak
Number
1
(IS)
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
• 22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
(IS)
Compounds
(In Retention Order)
Benzene
dg-Benzene
Toluene
Ethylbenzene
n— f-p-Xylene
o-Xylene
Isopropylbenzene
n-Propyl benzene
3- + 4-Ethyltoluene
1,3, 5-Trimethylbenzene
2-Ethyltoluene
1, 2 ,4-Trimethylbenzene
1,2, 3-Trimcthylbenzene
C i, -Alkylbenzene
Indan
Ci, -Alkylbenzene
Cu -Alkylbenzene
Cu -Alkylbenzene
C i, -Alkylbenzene
Ci, -Alkylbenzene
2- +- Methylindan
Cu- Alkylbenzene
dt -Alkylbenzene
Methyl indan
Methylindan
Ci,- Alkylbenzene
C 5 -Alkylbenzene
C 5 -Alkylbenzene
Naphthalene
C^-Alkylbenzene
C2-Alkylindane
C^-Alkylbenzene
Cs-Alkylbenzene
C 5 -Alkylbenzene
C2-Alkylindan
C2-Alkylindan
C2-Alkylindan
C2 -Alkylbenzene
C5- Alkylbenzene
2-Methylnaphthalene
1-Methylnaphthalene
d i o-Anthracene (IS)
Bulk Liquid Vapor on XAD Vapor
(ppm) (wg)
6,600 260
—
47,700 8,100
10,600 4,400
57,200 8,000
21,300 7,500
130
3,000 850
32,500 7,100
15,100 2,800
7,100 1,280
46,000 6,150
9,600 880
72
4,000 250
17,200 1,000
19,600 960
2,400 210
13,200 520
13,600 480
2,500 85
2,000 32
19,600 340
2,500 10
2,800 30
2,800
27,000
2,700
15,600 66
1,200
2,400
600
4,000
1,700
400
600
400
100
1,000
8,700
3,600
0
(o'.
25
4
21
8
0

19


13
3
0
1

7

4

0
0
2
0
0
0
1
0
0

0

1
0





0
0
on Tenax
(yg)
.72
035)
.3
.0
.3
.7
.21

.8


.3
.2
.33
.2

.8

.1

.41
. 74
.3
.22
.24
.49
.2
.44
.03
—
.11
—
.2
.46
—
—
—
—
—
,03
.01
(100) (1000)
                       418
-------
TABLE B5-36.   FLUID CATALYTIC CRACKER:  LOW PRESSURE SEPARATOR LIQUID
Compound
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
1, 3 ,5-Trimethylbenzene
Methylethylbenzene
1,2 ,4-Trimethylbenzene
sec-Butylbenzene
Methylisopropylbenzene
Ci.-Alkylbenzene
Cij-Alkylbenzene
Ci, -Alkylbenzene
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Bulk
Fraction 1
160,000
39,000
250,000
68,000
150,000
6,700
24,000
84,000
22,000
—
—
—
6,000
320
170
Liquid, ppm
Fraction 2
2,400
380
7,800
8,200
3,300
3,100
3,400
11,000
5,600
1,300
620
1,100
8,600
3,600
590

Total
160,000
39,000
260,000
76,000
150,000
10,000
27,000
95,000
28,000
1,300
620
1,100
15,000
3,900
760

Fraction 1
300
91
220
26
99
—
—
—
—
—
—
—
—
—
—
Vapor, ug
Fraction 2
19
5
93
32
60
27
18
42
—
—
—
—
—
—
—

Total
320
96
310
58
160
27
18
42
— .
—
—
—
—
—
—
-------
          TABLE B5-37.   FLUID  CATALYTIC  CRACKER:  LIGHT
                           CYCLE  oAS OIL, BULK LIQUID


     Compound                                                    ppra


Benzene                                                         1.75
Toluene                                                        13.6
F.thylbenzene                                                    8.97
m/p-xylenes                                                    19.5
o-xylene                                                        8.58
i-propylbenzene                                                 0.578
n-propylbenzene                                                11.9.
n/p-ethyltoluene                                               76.5.
1,3, 5-Trimethylbenzene                                         22. L
o-ethyitoluene                                                  A.08
1,2,4-Trimethylbfcazene                                         30.1.
Sec-Butylbenzene                                               18.4
Indan                                                          15.0
Cit-Alkylbenzenc                                                46.0
d.-Alkylbenzene                                                34.0
Ci»-Alkylbenzene                                                26.0
Methylindan                                                    28.0
Ci,-Alkylbenzcne                                                32.0
Ci,-Alky] benzene                                                 8.00
Cs-Alkylbenzcne                                                Al.5
Metliylindan                                                    30.0
C5-Alkylben^ene                                                10.8
Cs-Alkylbcnzene                                                20.0
Methylindan                                                    32.5
Cs-Alkylbenzene                                                22.0
C^-Alkylbenzene                                                27.5
Tetralin                                                        1.6
Naphthalene                                                    96.8
C2-A]kylindan/methyltetralin                                   58.9
Cj-Alkylbenzene                                                45.0
Cz-Alkylindan/methyltetralin                                   55.8
C2-Alkylindan/me.thyltetralin                                   96.1
C2-Alkylindan/nethyltatralin                                   19.2
Methylbenzothiophene                                            2.89
Methylbenzothiophene                                           25.5
2-Methylnaphthalene                                           616.0
Methylbenzothiophene                                           37.4
1-Methylnaplithalene                     .                       71,1
C?-Alkylbenzothiophene                                         28.0
Ca-Alkylnapbthalene                                           485.0
Cz-Alkylbenzothiophene                                         65.0

                                                       Continued
                                    420
-------
                       TABLE B5-37.   Continued
      Compound                                                     ppm

 C2-Alkylnaphthalene                                            825.0
 Biphenyl                                                         5.72
 C?-Alkylbenzothiophene                                          28.0
 Cz-Alkylnaphthalene                                            550.0
 C2-Alkylbenzothiophene                                          17.3
 Cj-Alkylnaphthalene                                            185.0
 C2-Alkylnaphthalcne                                             87.5
 Acenaphthene                                                     8.40
 Methylbiphenyl s                                                 15.5
 Cs-Alkylbenzothiophene                                          92.5
 C3-Alkylnaphthalene                                             43.5
 Ca-Alkylnaphthnlene                                            218.0
 Cs-Alkylnaphthalene                                            203.0
 C3-Alkylnaphthalene                                            249.0
 Fluorene                                                        18.2
 C2-Alkylnaphthalene                                            148.0
 Methylacenaphthenes                                             62.0
 C2-Alkylbiphenyls                                               48.0
 C^-Alkylnaphthalene                                            328.0
 Methylfluorene                                                  17.0
 Methylfluorene                                                  23.8
 Methylf1uorene                                                   7.14
 Phenanthrene/anthracene                                         97.9
 Cz-Alkylfluorenes                                               52.0
 Methyldibenzothiophene                                          74.8
 Kethyldibenzothiophene                                          51.0
 Methyl phenanthrene/anthracene                                  71.4
 Methyl phenanthrene/anthracene                                  42.0
 Cz-Alkyl dibenzothiophene                                       10.8
 C2-Alkyl Dhenanthrene/anthracene                                 2.35
 C2-Alkyl diben?.othinphene                                       70.0
 C2-Alkyl phenanthrene/anthracene                                96.3
 C2-Alkyl dihenzothiophene                                       44.0
 C2-Alkyl dibenzothiophene                                       72.5
 C?-Alkyl dibensothiophene                                       30.0
 C2-Alkyl phenanthrene/anthracene                                20.0
 Fluorarithene                                                     3.50
 C3-Alkyl dibenzothiophene                                       65.0
 C3-Alkyl phenanthrene/anthracene                                 1.45
 C3-Alkyl phenanthrene/anthracene                                 4.64
C3-Alkyl phenanthrene/anthracene                                11.6
Pyrene                                                           4.30
C3-Alkyl phenanthrene/anthracene                                37.7
                                                        Continued
                                    421
-------
                     TABLE B5-3.7.   Continued
       Compound                                                 ppm


Ct»-Dibenzothiophene                                             13-. 0
C3-Alkyl phenanthrene/anthracene                                15.4
Cs-Alkyl phenanthrene/anthracene                                6.67
Methyl fluorenthene/pyrene                                      0.429
Methyl fluorenthene/pyrene                                      0.871
Methyl fluorenthene/pyrene                                      1.82
Methyl fluorenthene/pyrene                                      1.82
Ci,-Alkyl phenanthrene/anthracene                                13.1
                                  422
-------
                     TALBE B5-38.  FLUID CATALYTIC CRACKER:  LIGHT  CYCLE  GAS  OIL
ro
OJ

Bulk
Compound Fraction 1
Benzene
Toluene
Ethylbenzene
p ,m-Xyle.ne
o-Xylene
Methylethylbenzene
1, 3 , 5 -Trimethyl benzene
Methylethylbenzene
1,2 ,4 -Trimethyl benzene
see-But yl benzene
Methylisopropylbenzene
Diethylbenzene
Dime thylc thy Ibenzene
C^-Mkylbenzene
Ci,- Alky Ibenzene
0.,-Alky Ibenzene
Ci,- Alky Ibenzene
1,2 , 3, 5-Tetrame thy Ibenzene
1,2,3 , 4-Te trarae thy Ibenzene
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
Biphenyl
C2~Naphthalene
C2-Naphthalene
Ca-Naphthalene
Cz-Naphthalene
C[ -Biphenyl
Ca-Naphthalene
Cs-Naphthalene
C3-Naphthalene
Ca-Naphthalene
Ca-Naphthalene
Phenanthrcne/ Anthracene

40
—
360
270
1,400
950
470
—
14,000
950
1,800
1,100
1,100
1,500
2,400
940
—
—
40,000
52,000
44,000
—
9,900
20,000
27,000
8,100
—
—
—
—
—
—
—
Liquid, ppm
Fraction 2

—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
12,000
90,000
39,000
4,600
3,500
69,000
78,000
28,000
2,100
8,800
2,400
19,000
28,000
18,000
7,400
Vapor, pg
Total

40
—
360
270
1,400
950
470
—
14,000
950
1,800
1,100
1,100
1,500
2,400
940
—
—
52,000
140,000
83,000
4,600
13,000
89,000
110,000
36,000
2,100
8,800
2,400
19,000
28,000
18,000
7,400
Fraction 1

230
250
840
270
—
800
210
68
220
15
22
63
64
—
—
—
180
8
31
—
—
—
—
—
—
—
—
—
—
—
—
—
—
Fraction 2
2
1
—
19
24
7
22
9
68
16
4
11
6
2
2
—
—
22
—
50
4
—
—
—
—
—
—
—
—
—
—
—
—
—
Total
2
230
250
860
290
7
820
220
140
240
19
33
69
66
2
—
—
200
8
81
4
—
—
—
—
—
—
—
—
—
—
—
—
—
-------
   TABLE B5-39.   FLUID CATALYTIC CRACKER:   HEAVY
                  CYCLE GAS OIL, BULK LIQUID
Compound                                            ppm
Benzene
Toluene
Ethylbenzcne
Wp-xylenes
o-xylcne
n-propylbonzene
m/p-ethyltoluene
o-ethyltol uene
1, 2, 4-Trimethylbenzene
Sec-Butylbenzene
Tndan
n-Butyl benzene
Ci,-Alkylbenzene
C^-Alkylbenzenc
Methylindan
Csi-Alkylbenzene
Cu-Alkylbenzene
Methylin dan
Cj-Alkylbenzene
Cs-Alkylbenzcne
Methylindan
Cs-Alkylbenzene
Naphthalene
Cz-Alkylindan/methyltetralin
Benzothiophene
Cs-Alkylbenzene
Ca-Alkylindan/methyltetralin
Cs-Alkylbenzene
C2-Alkylindan /methyl tetralin
C2-Alkylindan/inethyltetralin
Methylbenzothiophene
Cs-Alkylbenzene
Methylbenzothiophene
2-Methylnaphthalene
Methylbenzothiophene
1-Methylnaphthalene
Ca-Alkylnaphthalene
Cz-Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
Cz-Alkylnaphthalene
Acenaphthene
C3-Alkylnaphthalene
4.75
15/4
4/29
27.0
13.1
3.91
21.8
2.72
38.3
4.80
6.13
3.60
6.80
11.2
11.4
16.2
8.80
6.40
4.00
3.25
4.81
15. ;5
19/0
20.2
2. -70
5/50
10.2
3.75
7.44
13.6
6.29
8.25
6.29
45.4
13.6
30.7
25.0
73.3
82.0
57.8
21.8
3.08
36.5
                                           Continued
                          424
-------
                      TABLE  B5-39.   Continued
     Compound                                                   ppra

C3-Alkylnaphthalene                                           115.0
Cj-Alkylnaphthalene                                            52.2
C3-Alkylnaphthalene                                            49.3
G 3-Alk.ylnaphthnlene                                            10.4
Fluorene                                                        8.97
C3-Alkylnaphthalene.                                             4.93
Methylacenaphthenes                                            51.0
C^-Alkylnaphthalene                                           151.0
Methylfluorene                                                 18.7
Methylfluorene                                 .                27.2
Methylfluorene                                                 14.3
Diben7.othiophene                                               55.0
Phenanthrene/anthracene                                       143.0
C?-Alkylfluorene                                              107.0
Methyldibenzothiophene                                        126.0
Methyldibenzothiophene                                        258.0
Methyl phenanthrene/anthracene                                333.0
Methyl phenanthrene/anthracene                                256.0
C2~Alkyl dibenzothiophene                                     127.0
C?.-Alkyl phenanthrene/anthracene                               25.0
C2-Alkyl dibenzothiophene                                     306.0
Ca-Alkyl phenanthrene/anthracene                              510.0
C2-Alkyl phenanthrene/anthracene                              943.0
Cz-Alkyl dibenzothiophene                                     232.0
C2-Alkyl dibenzothiophene                                     173.0
C2-Alkyl dibenzothiophene                                      49.0
C2-Alkyl phenanthrenK/anthracene                               37.5
C2-Alkyl phenanthrene/anthracene                               35.0
Cs-Alkyl dibenzothiophene                                     818.0
Ca-Alkyl phenanthrene/anthracene                               21.2
Cj-Alkyl phenanthrene/anthracene                               26".4
Pyrene                                                          5.60
Cs-Alkyl phenanthrene/anthracene                              409.0
Cn-Alkyl dibenzothiophene                                     370.0
Cs-Alkyl phenanthrene/anthracene                               87.0
Ca-Alkyl phenanthrene/anthracene                               87.0
Methyl fluorenthene/pyrene                                     18.2
Methyl fluorenthene/pyrene                                     32.5
Methyl fluorenthene/pyrene                                     68.9
Methyl f]uorenthene/pyrene                                    107.0
Cs-Alkyl dibenzothiophene                   '                   90.0
Ci4-Alkyl phenanthrene/anthracene                              334.0


                                                      Continued
                                  425
-------
                     TABLE  B5-39.   Continued
     Compound                                                   ppm
C2-Alkyl fluorenthene/pyrene                                    7g Q
C'2-Alkyl fluorenthene/pyrene                                    45 Q
C?-Alkyl fluorenthene/pyrene                                    64.0
Natphthabenzothiophene                                         JQ Q
C2-Alkyl fluorenthene/pyrene                                    g^ Q
Cz-Alkyl fluorenthene/pyrene                                    5g Q
Ca-Alkyl fluorenthene/pyrene                                   215*0
C5-Phenant"riTene/anthracene                                    128. C
C^-Alkyl fluorenthene/pyrene                                    78.3
C2-Alkyl chrysenes/benzanthracenes                               2.0
C,-Alkyl chrysenes/benzanthracenes                              25.8
                                   426
-------
TABLE B5-40.   FLUID CATALYTIC CRACKER:   HEAVY CYCLE GAS OIL
Compound
Benzene
Toluene
Echylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Trinethylbenzene
2-Ethyl toluene
1 ,2 , 4-Trimethylbenzene
Diethylbenzene
Methylisopropylbenzene
Methylpropylbenzene
Diethylbenzene
Diethylbenzene
Dime thyle thy Ib en zene
Dime thyle thy Ibenzene
Dime thy lethylbenzene
Dime thyle thy Iben zene
Cs-Alkylbenzene
Tetraaiethylbenzene
Tetrame thy Ibenzene
Cs-Alkylbenzene
Cs-Alkylbenzene
Naphthalene
Cs-Alkylbenzene
Cs-Alkylbenzene
Cj-Alkylbenzene
Cs-Alkylbenzene
2-Methylnaphthalene
1-Methylnaphthalene
Cz-Alkylnaphthalene
Bulk Liquid,
ppm
740
10,000
1,200
8,800
3,000
120
900
6,900
2,700
1,500
7,200
1,800
320
—
2,100
1,800
440
2,300
2,000
320
1,700
2,000
390
200
1,400
360
14,000
500
840
200
210
12,000
5,500
5,000
Vapor on
XAD, ug
15.0
34.0
66-0
190.0
120.0
7.6
59-0
250-0
42.0
24.0
140-0
34.0
23-0
17.0
9.8
17.0
7.6
20.0
14.0
—
—
—
1.4
—
9.2
—
13.0
—
—
—
—
—
—
—
Vapor on
Tenax, pg
0.10
0.83
0.16
0.54
0.15
—
—
0.25
0.10
—
0.057
0.19
—
—
0.036
0.017
—
—
—
—
—
—
0.0058
0.016
0.015
—
—
—
—
—
—
—
—
—
                            427
-------
TABLE B5-41,
THERMOFOR CATALYTIC CRACKER:
CYCLE GAS OIL, BULK LIQUID
HEAVY
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
Compound
Benzene
Toluene
Ethylbenzene
m-Xylene/o-Xylene
3-Ethyl toluene
1 , 3 ,5-Trimethylbenzene
2-Ethyl toluene
1,2, 4-Tr imethylbenzene
Indan
C it- Alkyl benzene
C^-Alkylbenzene
Ci^-Alkylbenzene
Methyl indan
Methyl indan
Methyl indan
Naphthalene
2-Methylnaphthalene
1-Methylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
C2~Alkylnaphthalene
Ca-Alkylnaphthalene
Acenaphthylene
C2-Alkylnaphthalene
C2~Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
C 3-Alkylnaphthalene
C2-Alkylnaphthalene
C2- Alky 1 naphthalene
Fluorene
C2-Alkylnaphthalene
Methyl fluorene
Methyl fluorene
Methyl fluorene
Dibenzothiophene
Anthracene
Methyl anthracene
Methyl anthracene
Methyl anthracene
Pyrene
Methyl pyrene
Methyl pyrene
Methyl fluoranthene
Concentration
(ppb)
80
540
200
1,100
940
500
200
200
350
350
500
400
250
150
250
920
2,200
1,400
2,700
4,200
1,700
740
200
390
1,300
1,700
1,900
2,300
1,600
200
150
500
250
250
200
650
180
4,800
4,900
5,200
5,200
420
2,900
2,100
                                              Continued
                        423
-------
               TABLE B5-41.   Continued
Peak                                        Concentration
 Ko.                      Compound                (ppb)

 45              Methyl  fluoranthene               260
 46              Chrysene                       2,400
 47              Methyl  chrysene                   200
 48              Methyl  chrysene                 1,400
 49              Methyl  chrysene                 1,600
 50              Methyl  chrysene                   600
 51              Methyl  chrysene                   900
 52              Methyl  chrysene                   480
 53              Dimethyl chrysene                 190
 54              Dimethyl chrysene               1,000
 55              Dimethyl chrysene                 900
 56              Dimethyl chrysene               1,100
 57              Dimethyl chrysene                 620
 58              Dimethyl chrysene                 880
 59              Dimethyl chrysene               1,100
                           429
-------
TABLE B-5-42.   CATALYTIC  REFORMER: HYDROGEN (H2) RECYCLE  GAS
  Compound
Vapor on
XAD, pg
Vapor on
Tenax  Ug
Benzene 130.0
Toluene 350.0
Kthylbenzene 25.0)
m.p-Xylene 100.0)
o-Xylene 36.0
I sopropylbenzene 4.8
n-Propylbenzene 18.3
3 or 4-Ethvl toluene 61.0
1,3
, 5-Trimethylbenzene 42.0
2-Ethvl toluene 11.0
1,2
1,2
,4-Trimethylbenzene 63-0
, 3-Trimethylbenzene 11-0
Diniethylethylbenzene 5.0
Tetranethylbenzene 6.6
0.010
0.34

0. 38
0.38
0.38
0.38


0.88


0.88
0.88
                             430
-------
        TABLE B5-43.   CATALYTIC  REFORMER:   NAPHTHA  FLED

                          Bulk Liquid       Vapor on        Vapor on
Compound                      (ppm)          XAD, Ug         Tenax, p
Benzene
Toluene
Ethylbenzene
m, p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3 or 4-Ethyl toluene
1,3, 5-TTitnethylbenzene
2-Ethyl toluene
1 , 2,4-Triinethylbenzene
1,2, 3-Trimethylbenzene
Methylpropylbenzene
Diethylbenzene
1040
1800
. 550
4500
1700
420
690
3200
2600
520
2600
190
65
19
59
670
88
640
260
48
90
330
200
33
180
11
-
-
0.098
2.9
0.55
2.6
1.6
0.38
0.52
2.70
1.9
0.24
1.19
0.077
-
0.013
                                431
-------
TABLE B5-44.   CATALYTIC REFORMER:  NAPHTHA FEED

Compound
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropylbenzenc
1, 3 ,5-Trimethylbenzene
Mechylethylbenzene
1,2, 4-Trimethylbenzene
sec-BuLylbenzcnc
Methylpropylbcnzene
Cj-Alkylbcnzcnc
Ci-Alkylbenccne
Ci.-Alkylbcn:cnc
Ci.-Alkylbenzcne
C".-Alkylbcnzene
Ci.-Alkylbcnzcnc
Ci«- Alky Iben zone
Naphthalene
2 -Methyl naphthalene
1-Me thy] naphthalene
Biphenyl
C2-Alkylnaphthalene
C2-Alkylnaphtlialene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
C2-Alkylnaphthalene
Methylblphenyl
Methylbiphenyl
Methylbiphenyl
Anthracene/phenanthrene
Cs-Alkyl naphthalene
C j-Alky Inaphthalene
C 3-Alkylnaphthalene
C 3-Alky Inaphthalene
Cz-Alkylbiphenyl
Cj-Alkylbiphenyl
Ci. -Alky Inaphthalene
Ci, -Alky Inaphthalene
Bulk.
Fraction 1
2,400
2,500
6,600
3,000
900
2,700
7,500
2,200
8,300
5,900
4,000
3,500
—
—
—
5,000
2,600
43,000
30,000
36,000
—
—
6,400
12,000
27,000
3,700
—
—
—
—
—
—
—
—
—
—
—
—
Liquid, ppm
Fraction 2
4.8
—
3.9
7.2
—
11
—
—
58
18
—
—
—
—
—
—
—
800
4,000
1,800
1,300
230
1,600
2,500
920
130
1,200
460
290
19
500
1,500
260
260
740
410
300
110

Total
2,400
i, 500
6,600
3,000
900
2,700
7,500
2,200
8,400
5,900
4,000
3,500
—
—
—
5,000
2,600
44,000
34,000
38,000
1,300
230
4,000
14,000
28,000
3,800
1,200
460
290
19
500
1,500
260
260
740
410
300
110

Fraction 1
95
120
280
38
—
—
110
—
19
70
—
—
—
—
—
—
00
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
Vapor, ug
Fraction 2
2
—
3
18
—
10
45
6
58
28
7
20
8
3
5
22
7
31
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—

Total
97
120
280
56
—
10
160
6
77
98
7
20
8
3
5
22
7
31
—
—
—
—

—
—
—
—
—
—
—
—
—
—
—
—
—
—
— —
-------
TABLE B5-45.
CATALYTIC REFORMER:  PRODUCT
NAPHTHA (DEPENTANIZER BOTTOMS)
Compound
Benzene
Toluene
Ethylbenzene
o, p-Xylene
o-Xyiene
I nop ropy 1'nenzene
Propylbcnzcne
ttethylethyl benzene
Mechylechylbenzene
Tr i me Uiyl benzene
Mechy let'.iy] bt-nzenc
Tritoc thylbenzene
Dtaetnyl benzene
Dlethylbenzcne
Indane
Dine chyle thy Ibcntene
Dine thylechy Ibtnzene
Dime chyle thyl benzene
Dine thyle thy Ibenzene
Te traracthyLbenzene
TetratneUr/1 benzene
Mcchy Id tc thyl benzene
Dt-iaopropylbenzen€
Methyl Indane
Methyl InJjne
Dl-lsnpropyl benzene
TK t ramc thyl bent ene
Cs-AJitylbenzcne
Cs-Al'Kylbfnzcne
C»-Al'ny 1 benzene
Naphi tinier i!
2-MeLliylm.v)hthfller.e
1 -Methyl naphthalene
Ca-Alkyln.iphtlinlene
Ci -Al*yln..phthalene
C;-AlltylnnphthAlenc
Cz-AIkyln.iphthfllene
C:-Alkylmphthalene
d-Alkyl naphthalene
Blphcnyl
Fluorene
Anthracene
Bulk
Fraction 1
„
85,000
15,000
74, COO
30,000
—
—
18,000
11,000
3,600
15,000
5,900
—
—
220
—
—
51
--
230
180
—
—
50
70
—
59
14
10
20
410
81
J7
6
34
40
22
13
)
—
—
—
Liquid, PFB
Fraction 2
_
480
49
8CO
570
—
—
78
78
45
440
140
14
—
33
<1
9
14
11
30
15
23
14
—
B
14
9
—
—
—
28D
120
62
—
31
41
18
14
--
54
54
4

Total
_—
85,000
15,000
75,000
30,000
—
—
18,000
11,000
3,630
15.000
6,000
14
— . •
250
—
60
65
11
260
300
23
14
50
80
14
68
—
—
—
720
200
100
6
65
81
40
27
3
54
54
4

Fraction 1
21
190
140
160
95
5
20
82
22
16
24
—
—
—
4
1
—
—
—
3
—
2
—
—
1
—
—
—
—
—
—
—
—
—
—
--
--
—
—
—
—
—
Vapor, v-g
Fraction 2
0.3
68
4
130
72
—
—
15
19
10
55
—
—
15
5
3
—
5
3
1
6
6
—
—
2
—
4
—
—
—
10
—
—
—
—
—
—
—
—
—
—
—

Total
21
260
140
290
170
5
20
97
41
26
79
—
—
15
9
4
-- -
—
—
6
a
8
—
—
3
—
—
—
—
—
10
—
—
--
—
—
— -
—
—
—
—
--
                  433
-------
TABLE B5-46
CATALYTIC REFORMER:   PRODUCT
NAPHTHA,  BULK LIQUID
Compound
Benzene
Toluene
Ethylbenzene
m, p-Xylene
o-Xyiene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Tr imethylbenzene
1,3, 5-Triraethylbenzene
2-Ethyl toluene
see-But ylbenzene
1, 2, 4-Tr imethylbenzene
Diethylbenzene
Methylisopropylbenzane
Methylpropylbenzene
Methylpropylbenxene
Methylpropylbenzene
Diethylbenzene
Diethylbenzene
Dixethylethylbenzene
Diirethylechylbenzene
Dime thy lethylbenzene
Dime Chyle thy Ibenzene
Cs-Alkylbenzene
Tetramethylbenzene
Tctramethylbenzene
Tetramethylbenzene
Cs-Alkylbenzene
C j-Alkylbenzene
Naphthalene
C 5-Alkylbenzene
Cs-Alkylbenzcne
2-MethylnaphLhalene
1-Methylnaphthalene
C2~Alkylnaphthalenc
C2-Alkylnaphthalene
Bulk Liquid
(ppm)
440
4,900
2,000
7,000
2,000
310
1,400
5,500
2,400
1,600
260
6,500
300
1,400
95
120
1,600
1,300
450
960
360
1,100
140
—
60
330
1,200
1,100
900
350
400
2,800
460
310
2,200
2,600
700
1,300
Vapor on XAD
(yg)
8.4
74.0
32.0
120-0
50.0
2.3
20-0
48-0
38-0
22.0
—
74-0
5.2
20-0
1.6
2.2
15-0
10-0
9.1
11.0
4.0
12.0
11.0
1.6
2.2
0.8
7.6
7.4
1.6
3.2
1.6
7.4
1.6
1.0
—
•
—
—
Vapor on Tenax
(Mg)
0.22
1.0
1.1
0.81
0.81
0.11
0.78
2.4
.
—
—
1.1
—
0.52
--
—
0.76
—
—
0.52
0.21
0.71
—
—
—
—
—
0.35
—
—
—
0.65
—
—
—
—
—
—
                    434
-------
TABLE B5-47.  CATALYTIC REFORMER:  PRODUCT
              NAPHTHA, BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Compound
Benzene
Toluene
Ethylbenzene
m-Xylene/p-Xylene
o-Xylene
Isopropylbenzene
n-Propylbenzene
3-Ethyl toluene
1, 3,5-Trimethylbenzene
2-Ethyl toluene
Ci4-Alkylbenzene
1,2, 4-Trimethylbenzene
Indan
C 4. -Alky 1 benzene
Cu.-Alkylbenzene
Concentration
(ppb)
80
2,100
440
4,100
1,200
200
780
620
180
80
140
230
86
320
69
                    435
-------
       TABLE B5-48.  CATALYTIC  REFORMER:   PRODUCT
                     NAPHTHA, BULK LIQUID


Compound                                             ppm
Benzer.e
Toluene
Ethylbenzene
r/p-xyl er.es
o-xvlene
i-propyl benzene
n-propyl berzene
T./p-e thy 1 toluene
1, 3, 5-Triir.ethylbenzcnc
o- ethyl toluene
1,2, 4-Trrnethylbenzene
sec-Butylbcnzene
i-Butylbenzene
Tncton
C L, - Alky 1 benzene
Ci^-Alkylbenzene
C^-Alkylbenzene
Methylindan
Mcthylindar.
Ci^-Alkyl benzene
C\-Alkyl benzene
Methylind.Tn
C^-Alkylbenzene
C^-Alkylbenzene
Cs-Alkylbenzene
Methylindan
Tetralin
Naphthalene
C 2-Alky lind an/me thy Itetral in
Cs-Alkylbcnzene
83.8
840.0
142.0
632.0
31.2
35.7
210.8
207.0
71.4
64.6
184.0
46.0
56.0
17.5
98.0
11.8
104.0
28.0
8.00
11.2
20.0
6.00
18.3
6.50
13.0
5.20
4.60
9.02
11.2
2.50
                           436
-------
           TABLE B5-49
CATALYTIC REFORMER:   PRODUCT
NAPHTHA,  BULK  LIQUID
    Compound
                                                                ppra
Benzene
Toluene
Ethylbe.nzene
m/p-xylenes
o-xylene
i-propylbenzene
n-propylbenzene
tn/p-ethyl toluene
1,3,5-Trimethylbcnzene
o-ethyl tol nene.
1,2,4-Triine thylbenzene
sec-Butylbenzene
Indan
Ci,-Alkylbenzene
n-Butylbenzene
Ci^-Alkylbenzene
Ci,-Alkylbenzene
Ci4-Alkylbenzene
Ci,- Alky 1 benzene
05-AlkyIbenzene
Cs-Alkylbenzene
Methylindan
C5-Alkylbenzene
C5-AlkyIbenzone
Cs-Alkylbenzene
Methylindan
Naphthalene
C5-Alky1benzene
Cs-Alky1benzene
2-McthyInaphthaiene
1-Methylnaphthalene
C'/-Alkylnaphthalene
Cj-Alkylnaphth,Tlene
Biphcnyls
Ca-Alkylnaphthalene
C?-Alkylnaphthalene
C2-AlkyInaph tha1en e
Methylbiphenyls
C a-AlkyInaphthalene
C3-Alkylnaphthalene
C3-Alky]naphthalene
C3-AlkyInaphthalene
Fluorene
                                   826.0
                                   445.0
                                   581.0
                                  1160.0
                                   315.0
                                    44.2
                                   182.0
                                  1560.0
                                   493.0
                                   168.0
                                   952.0
                                    32.0
                                    58.8
                                   548.0
                                   144.0
                                   322.0
                                   336.0
                                   284.C
                                   400.0
                                   166.0
                                    41.5
                                    76.0
                                    90.0
                                    22.
                                    92.
                                   107.0
                                    82.5
                                    87.5
                                    17.5
                                   277.0
                                    47.9
                                     5.25
                                    23.8
                                     0.660
                                    45.0
                                    15.75
                                       .00
                                       ,04
                                       .74
                                       .93
                                       .48
                                       .32
                                       .13
7,
2,
1
4,
3
2.
                                  437
-------
           TABLE B5-50.   CATALYTIC  REFORMER:   PRODUCT
                            NAPHTHA, liULK LIQUID
    Compound
   ppm
Benzene
Toluene
Ethylbenzene
m/p-xylenes
o-xylene
i-propyIbenzene
n-propylbenzene
m/p-ethyltoluene
1,3,5-Trimethylbenzene
o-ethyl toluene
1,2, 4-Trinethylbenzene
sec-Butylbenzene
I- B u ty 1 b en 7. en e
1,2,3-Trimethylbenzene
Ci,-Alkylbenzene
Indan
Ct4-AJ kylbenzene
n-Butylbenzene
Cu-Alkylbenzene
Cu-Alkylbenzene
Cu-Alkylbenzene
Methylinuan
Methylindan
C\-A1 kylbenzene
Cu-AIkylbenzene
d.-Alkylbenzene
C5-Al.kyI benx.ene
C14-Alkyl benzene
Methylindan
C5-Alkylbenzene
C 5-Alkyl benzene
Methylindan
C5-A1kylbenzene
C5-Alkylbenzene
Cs-Alkylbenzene
C5-AIkylbenze.ne
C5-Alkylbenzcne
Cs-Alkylbenzene
Naphthalene
Cz-Alkylindan/methyltetralin
C 5- Al kylb enz ene.
C2-Alkyl indan/inethyltetralin
Cs-Alky1 benzene
 150.0
 396.0
 451.0
1950.0
  85.8
  59.5
 204.0
1020.0
 340.0
  42.5
1390.0
  32.0
  30.0
 143.0
  56.3
  36.3
 280.0
 220.0
 300.0
  68.0
 300.0
  70.0
  44.0
 340.0
  32.0
  40.0
  83.0
 200.0
  58.0
 100.0
 160.0
  94.9
  75.0
  27.5
 100.0
  45.0
 125.0
  12.5
 228.0
   7.13
  40.0
  34.1
  27.5
                                                       Continued
                                    438
-------
                      'TABLE B5-50.  Continued
      Compound                                                  ppm
C:.-Alkylindan/mechyltetralin                                     12. 4
C?-Alkylindan/nethyitetralin                                     55. 8
Co-Alkylbenzene                                                 21.0
2-Methylnap'nthalene                                            106. A
1-Methylnaphthaiene                                             81-2
C -Alkylnaphthalene                                              7-°°
C -Alkylnaphthalene                                             32-5
C -Alkylnaphthalcne                                             ^5.0
C -Alkylnaphthalene                                             21-°
Phenanthrene/Anthracene                                           0.924
Methyl ohenanthrene/anthracene                                    1.18
                                  439
-------
TABLE B5-51.  ALKYLATION UNIT:  CRUDE ALKYLATE,
              ORGANIC SPECIES ON TENAX
         No Aromatic Species Detected.
    TABLE B5-52.  ALKYLATION UNIT:  ALKYLATE
                  GASOLINE, BULK LIQUID
         No Aromatic Species Detected
                      440
-------
        TABLE B5-53.   ALKYLATION UNIT:   CRUDE ALKYLATE
Compound
Benzene
Toluene
Ethylbenzene
n,p-Xylene
o-Xylene
n-Propyl benzene
3-Ethyl toluene
1,2,3-Trimethylbenzene
1.3, 5-Trimethylbenzene
2-Ethyl toluene
1,2, 4-Tr imethylbenzene
Diethylbenzene
Methylisopropylbenzene
Methylpropylbenzene
Methylpropylbenzene
Methylpropylbenzene
Diethylbenzene
Diethylbenzene
Dimethylethylbenzene
Dimethylethylbenzene.
Dimethylethylbenzene
Tetramethylbenzene
Tetramethyl benzene
Tetramethylbenzene
Cs-Alkylbenzene
C 5 -Alkyl benzene
Naphthalene
Cs-Alkylbenzene
2-Methylnaphthalene
Hulk Liquid, V;ipor on
ppm XAD, ng
0.69
3.3
5.2
42.0
22.0
48.0
36.0
96.0
54 -0
230-0
72-0
6.0
2.6
26-0
72-0
47-0
65-0
22-0
72-0
66.0
17.0
32.0
48.0
30.0
10.0
12.0
140.0
14.0
36.0
Vnpor on
Ten ax, MP,
0.0044
0.067
0.064
0.20
0.094
—
0.86
--
—
0.73
0.22
0.14
0.0088
0.35
—
—
0.083
—
0.15
0.11
—
0.12
0.15
—
—
—
0.57
—
0.12
None of the  vapor species were found in  the bulk liquid.   The  vapor  species,
therefore, must have been adsorbed from  the ambient air or from cross-
contamination with other samples from residue in the sampling  train.
-------
     TABLE  B5-54.   ALKYLATION  UNIT:   CRUDE
                      ALKYLATE,  BULK  LIQUID
Peak                                        Concentration
 No.                     Compound                (ppb)
  1              Benzene                          120
  2              Toluene                          200
  3              Ethylbenzene                      77
  4              m-Xylene/p-Xylene                370
  5              o-Xylene                         370
  6              Isopropylbenzene                 280
  7              n-Propylbenzene                  160
  8              3-Ethyl toluene                  100
  9              1,3,5-Trimethylbenzene           420
 10              1,2,4-Trimethylbenzene           300
 11              Indan                            100
 12              C^-Alkylbenzene                  100
 13              Cu-Alkylbenzene                  300
 14              Methyl indan                     100
 15              Methyl indan                     200
 16              d.-Alkylbenzene                  450
 17              Naphthalene                      200
 18              2-Methylnaphthalene              300
 19              1-Methylnaphthalenc              250
 20              C2-Alkylnaphthalene               50
 21              C2-Alkylnaphthalene              200
 22              Cj-Alkylnaphthalene              450
 23              C2-Alkylnaphthalene              250
                          442
-------
   TABLE  B5-55.   NAPHTHA  KYDRODESULFURIZATIOX:   DESULFURIZED
                   NAPHTHA  PRODUCT, BULK LIQUID
    Compound                                                     ppm


Benzene                                                         18.8
Tulue.ne                                                       5836.0
Ethylbenzene                                                   299.0
m/p-xylenes                                                    260.0
o-xylenes                                                      195.0
±-propylbenzene                                                 49.3
n-propylbcnzene                                                 51.0
m/p-ethyltolucnc                                               272.C
i, 3, .b-Trimethvlbenzenc                                         150.0
o-ethyltoluene                                                 170.0
1  , 2, 4-TriTr.ethy 1 benzene                                         136.0
i-Butylbenzene                                                  24.0
1  , 2, 3-Tr'i^iethyl.benzene                                          98.0
C^-Alkylbenzene                                                 80.4
Indan                                                           15.0
(\-Alkylbenzene                                                174.0
C^-Alkylbcnzene                                  .               70.0
C..-A1 rcyLhen/.ene.                                                 42.0
Methylindan                                                     24.0
Methylindan                                                     22.0
C^-Alkylhenzene                                                 10.0
C.s-Alkylbenzene                                                 55.6
Ci,-Alkylbenzenc                                                  16.8
Cr-Alkylbenzcnc                                                 23.2
Methylindan                                                     J3.4
C^-Alkylbenzene.                                                  7.50
Cs-Alkylbenzenc                                                 27.5
Methylindan                                                     16.9
Cs-Alkylbenzene                                                  40.0
Cj-Alkylbenzene                                                  42.5
Tetralin                                                        44.0
C5-Alky1benzene                                                  12.5
C2-Alkv1 indan/methyl tetralin                                   34.1
C2-Alkyl indan/mcthyl tetralin                                   31.0
C7-Alkyl indan/methyt tetralin                                    4.96
Cj-Alkyl indan/methyl tetralin                                    1.71
                                   443
-------
TABLE B5-56.  HYDRODESULFURIZATION UNIT:   DESULFURIZED
              GAS .'OIL,  BULK LIQUID
 Compound                                              PPm
Toluene
Ethyl benzene
m/p-xylenes
o-xylene
n-propylbenzene
m/p-ethyltol-iiene
1, 3, 5-Trimethylbenzene
o- ethyl toluene
1,2, 4- Tr ime thy 1 benzene
C^-AIkylbenzene
C 1,-Alkylbenzenc
Cn-Alkylbenzene
Ci|-Al!
-------
TABLE B5-57.  GASOLINE SWEETENING UNIT:   MIXED
              NAPHTHA FEED,  BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
Compound
Benzene
Toluene
Ethylbenzene
m,p-Xylene
o-Xylene
Isopropy Ibenzene
n-Propylbenzene
3-Ethyl toluene
4-Ethyl toluene
1,2, 3-Trimethylbenzene
2-Ethyl toluene
sec-Butylbenzene
1, 2, 4-Trime thy Ibenzene
Diethylbenzene
Methylisopropylbenzene
Methylpropylbenzene
Methylpropylbenzene
Diethylbenzene
Diethylbenzene
Dime thy le thy Ibenzene
Dime thyle thy Ibenzene
Dine thy le thy Ibenzene
C 5 -Alky 1 benzene
Dime thyle thy Ibenzene
Tetrame thy Ibenzene
Tetrame thy Ibenzene
Tetrame thy Ibenzene
C 5 -Alky Ibenzene
C 5 -Alky Ibenzene
Naphthalene
C 5 -Alky Ibenzene
Cs-Alkyl benzene
C 5 -Alky Ibenzene
Methylnaphthalene
C2-Alky 1 naphthalene
C2-Alkylnaphthalene
d i a -Anthracene
Concentration
(ppm)
130
8,500
1,100
7,000
1,700
1,100
1,800
4,200
2,900
1,800
5,000
650
2,000
800
130
1,100
550
900
230
900
650
340
290
150
600
600
600
80
200
1,600
200
120
160
300
300
190

                      445
-------
TABLE B5-58.
GAS ABSORB!ION UNIT:  LEAN
OIL (NAPHTHA),  BULK LIQUID
Peak
No.
1
2
3
4
5
6
7
8
9
.'10
11
12
.13
.14
-.15
16
17
:is
..19
.20
21
.22
"23
24
25
26
27
28
Compound
Benzene
Toluene
ELhylbenzene
m-Xylene/p-Xylene
o-Xylene
I sopropyl benzene
•n-Eropylbenzene
3-Ethyl toluene
1 , 3 ,5-TriTnethylben2ene
2, Ethyl toluene
Cu-Alkylbenzene
1 ,2 ,4-Trimethylbenzene
.Indan
C^-Alkylbenzene
C^-Alky'lbenzene
CM-Alkylbenzene
.Ci4-Alkylbenzene
C4-Alkylbenzene
Methyl indan
Methyl indan
Ci«^Alkylhenzene
Ci«-Alkylbenzene
Cv-Alkylbenzene
Cj-Alkylbenzene
-Methyl indan
'.Methyl indan
C 5— Alkylbenzene
Naphthalene
Concentration
(ppb)
1,600
10,000
2,200
:22,000
.5,000
980
9,500
•9,300
1,400
3,500
300
2,400
2,100
1,200
1,800
400
.1,300
1,300
560
1,100
450
600
840
250
400
500
800
100
                   446
-------
          TABLE B5-59.   SOLVENT DEWAXING  UNIT:   SLACK WAX
     Compound
 Bulk Gas
Liquid,  ppm
Vapor on
 XAD-.Ug
Benzene
Toluene
Ethylbenzene/n or  p-Xylenc
o-Xylene
3 or 4-Ethy.l  toluene

1,3, 5-Tri:nethylbenzene
2-Ethyl toluene
1,2,4-Trimcthylbenzene
1,2,3-Trimethylbenzene
Di-ethylbenzene

Di-methyl ethylbenzene
Di-niethylethylbenzene
Tetramethylbenzene
Tetramethylbenzene
    73
 17000
 4100
Vapor on
Tenax.yg
  0.022
 23.8
  0.033
  0.064
  0.059

  0.035
  0.013
  0.071
  0.024
  0.033

  0.014
  0.034
  0.020
  0.024
                                     447
-------
                           TABLE B5-60.   ELEMENTAL ANALYSIS OF FCCU CO BOILER
                                          FLUE  GAS PARTICUiATES (STACK NO.  14)
co
Element
Uranium
Thorium
Bismuth b
Lead
Thallium
Mercury
Gold
Platinum
Ir idium
Osmium
Rhenium
Tungsten
Ta n t a 1 um
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
Cone ."
5
6

54







5
<1
3
1
5
0.9
22
24
230
Element
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
B a r i um
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmi um
Silver
Palladium
Rhodium

Cone .
29
150
14
490
MCC
MC
MC
MC
790
0.2


0.9
5
STD
<0.5
0.5



Element
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gal 1 ium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium

Cone .

66
15
48
240
120
<0.5
<3
36
4
<0.7
10
260
40
300
50
MC
300
840

Element
Vanadium
Titanium
Scandium
Ca.l c ium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
Cone .
150
MC
17
MC
MC
22
MC
MC
MC
MC
MC
MCC
MC
NRd
NR
NR
69
1
280
NR
                 a,.
                 Concentration  in
                 Al 1 elements not
ppra by weight.
reported £0.3 ppm
by weight.
'"MC - major component.
 NR - not reported.
-------
         TABLE  B5-61.   ELEMENTAL  ANALYSIS OF  FCCU CO  BOILER
                         FLUE GAS PARTICULATES  (STACK NO.  11)
Element
Uranium
Thorium
Bismuth b
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
a_
a
Cone.
5
19
—
29
—
NR
—
—
—
—
—
2
1
4
0.4
2
0.6
.12
10
30

Element
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymium
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodium


Cone .
7
94
9
930
MC -
MC ~
MC -
MC -
860
1
0.4
--
3
4
ST1)
<0.3
-------
amber bottle was filled, sealed, and kept refrigerated until
analyzed.  The results of this type of sampling/analysis are
labeled "Bulk Liquid."  An attempt was made to get line material
samples for vapor phase streams, but no reliable results were
obtained because of leakage (glass bombs) or contamination
(metal bombs).   The fugitive emissions from fittings on these
streams were also analyzed by adsorbing the organics on a solid
resin.  The resin packed tubed were then capped, refrigerated,
and transported to Austin under refrigeration.  The adsorbed
organics were then extracted from the resin and analyzed by
GC-MS.  The results of this type of sampling/analysis are
labeled either "Vapor on XAD" or "Vapor on Tenax," depending
on which type of resin was used.

5.2       EXPERIMENTAL COMPARISON OF COMPOSITION OF LEAKING
          VAPOR WITH COMPOSITION OF LIQUID IN PIPES

          The scope of the refinery program included the deter-
mination of the location and concentration of hazardous materials
contained in fugitive hydrocarbon emissions.  To meet this
objective, corresponding liquid and fugitive vapor samples were  -
obtained during the field portion of the program.

          The liquid samples were obtained from selected process
streams at locations such as sample lines, drain lines, or other
appropriate equipment.

          Corresponding fugitive vapor samples were obtained
from  leaking valves on the process line in question.  The vapors
were  collected using either activated charcoal, Tenax resin, or
XAD-2 resin adsorption medias,  These materials were contained
in packed tubes.
                              450
-------
          Both the liquid and the vapor samples were analyzed
by Radian.  The analysis procedures are discussed in detail in
Appendix A.

          The sampling and analyses of vapor samples is time-
consuming .  The analysis of liquid hydrocarbons is considerably
simpler.  Corresponding vapor and liquid samples were analyzed
to compare their compositions.  The results were inconclusive
in defining the relationship between the liquid in the pipe and
the leaking vapor.

5.2.1     Experimental System

          An experiment was conducted to determine the relation-
ship between the liquid and fugitive vapor compositions.

5.2.1.1   Exp er iment a1 Equ ipmen t--

          In the experiment, a valve, similar to those used in
refineries,  was installed in a system designed to duplicate
conditions found within refinery process streams.  The system
consisted of equipment which circulated hydrocarbon liquid
through the valve at elevated temperature and pressure.  The
valve packing material was adjusted to produce a relatively low
vapor leak.   Samples of this vapor were analyzed and compared
to the liquid in the system.

          Two different hydrocarbon mixtures were used during
the experiment.  The first consisted of roughly equivalent
amounts of hexane and toluene.  The selection of these materials
was based on the following factors:

          •    Both materials are relatively volatile and
               would remain in the vapor phase.  That is, as
                              451
-------
               these hydrocarbons leave the seal,  they do
               not condense on cooler surfaces at  the low
               concentrations involved.

          •    There are considerable differences  between
               the physical and chemical properties  of
               hexane and toluene.   And, separation  of the
               materials by GC is not difficult.

          •    Both materials are available in bulk  quantities
               at low cost.

          The second hydrocarbon mixture used consisted of
hexane,  toluene, and naphthalene.  This system was selected
after the results of earlier testing indicated that  the compo-
sitions  of the liquid and vapor were identical.  The boiling
point of naphthalene (218"C) is considerably higher  than either
hexane or toluene.  And, the presence of significant quantities
of naphthalene in the vapor leak would provide additional
evidence for a conclusion of identical composition.

          A simplified  diagram of the  valve assembly used in
this experiment  is given in Figure B5-1.  This diagram indicates
important equipment and gives other  information on the operation
of the  system.

          Pressure within  the system was maintained with a small
gear pump.  The  pump was capable of  producing  pressures  in
excess  of 100 psig at flow rates of  approximately 5 GPM.

          From  the pump, the hydrocarbon liquid circulated
through a section of 1" pipe wrapped with electrical heating
tape.   The heating tape was used to  raise the  hydrocarbon tem-
perature of the  pump.   The  liquid then entered a  section of 6"
                              452
-------
              Liquid  Fill Lino

             O* Pressure Gauge
               - Liquid Level  indicator
                Vapor Space
            -*  * Elevated Surge Vesse
Liquid  Flow  Indicator
                                                     Temperature Gauge
                                                   Pressure Gauge
                                Safety Relief
                                   Valve
                                                            o
                                                         Tl
                                                     6"  Crane Gate Valve
                          Ice-Water
                          Cooled
                          Sample Line
1" Line  Wrapped in Electrical
  Heating Tape
                           Positive Displacement
                                 Gear  Pump
                   Figure B5-1.  Diagram of  experimental  set-up.
-------
pipe which contained the valve from which fugitive emission
samples were obtained.   Temperature and pressure indicators were
also located on this section of pipe.

          Liquid samples were obtained from a sample line
located after the 6" valve assembly.  Following the liquid
sample line was a. flow control ylobe valve.  This valve was
used to regulate the pressure within the 6" valve assembly.
From the control valve, liquid passed to a small elevated surge
tank from which the pump took suction.

5.2.1.2   Collection and Analysis of Vapor Samples--

          The fugitive emission vapor samples were obtained from
the 6" Crane gate valve.  The packing gland was adjusted to
give a leak rate of approximately 0.015 Ib/hr.  The leak rate
was determined by measuring the gas concentration at the seal
with a Bacharach "TLV Sniffer".  The leak rate was estimated
from the correlations presented in Section 2.4 of this appendix.

          The packing gland and valve stem were enclosed within
a  small Mylar plastic  shroud  (or tent).   Zero  air  (air with  an
extremely  low concentration of hydrocarbons) was  injected  into  the
tent to keep the hydrocarbon  concentration at  low  levels.

          Vapor samples for the hexane-toluene system were taken
from within the tent using a 1 ml gas-tight syringe.  The sample
was immediately injected into the sample port of an AID portable
gas chromatograph.

          Analysis of vapor samples for the hexane-toluene-
naphthalene system was accomplished using a Hewlett-Packard
temperature programmable gas chromatograph.
                               454
-------
5.2.1.3   Collection and Analysis of Liquid Samples--

          Liquid samples were taken from an ice-water cooled
sample line.  The sample line was cooled to prevent flashing
of the liquid.

          Liquid samples from the hexane-toluene system were
analyzed on the portable AID gas chromatograph while samples
from the hexane-toluene-naphthalenc system were analyzed on the
Hewlett-Packard temperature programmable gas chromatograph.

5.2.2     Testing Results

          The following tests were conducted:

          1)   The response time of the system was determined,
               that is, the time required for  the vapor
               composition to equilibrate after a change in
               the liquid composition.

          2)   Vapor and liquid compositions were determined
               for the hexane-toluene systems.

          3)   Vapor and liquid compositions were determined
               for the hexane-toluene-naphthalene system.

          4)   The effect of temperature and pressure on the
               vapor composition of the hexane-toluene system
               was investigated.
                              455
-------
5.2.2.1   Equilibration Test Results

          The response Lime of the system was determined to
insure that adequate time was allowed for the system to reach
equilibrium before testing was initiated.

          The results of this test are shown graphically in
Figure B5-2,  The concentration of toluene in the vapor as a
function of time in response to a step change in the concentra-
tion of toluene in the liquid is shown.   The concentration
values have been normalized to show the percentage of the total
required concentration change.  The actual toluene concentration
was changed from 43.1 percent to 57.2 percent.   These results
indicated that at least eight hours were required after a change
in the system composition before steady state operation was
achieved.

5.2.2.2   Vapor-LLquid Compositions:  Hexane-Toluene System--

          After completion of the equilibration test, numerous
vapor and liquid samples were taken.  The results of this test
are given in Table B5-62.  Operating conditions for the test
were :

                     Temperature =  200°F
                     Pressure    =  80 psig
                              456
-------
Final Toluene
Liquid Concentration
           100
Initial Toluene    °
Liquid Concentration
 4        5
Time (hours)
Figure 135-2.   Change in  the vapor toluene concentration versus  time for
                a  step change in  liquid  toluene concentration.
-------
  TABLE B5-62.  COMPARISON Or VAPOR AND LIQUID  COMPOSITIONS:
                HEXANE-TOLUENE SYSTEM
                        Concentration of Toluene
 Sample Type                      (%)               Number of  Samples
   Vapor                     56.9 ± 0.8                     7
   Liquid                    57.2 ± 1.2                    15
5.2.2.3   Vapor-Liquid Compositions :   Hexane-Toluene-Naphthalene
          Systcm--

          Naphthalene was added  to  the hexane-toluene  system to
determine the emission characteristics of  a  much  heavier com-
ponent.  A mixture of hexane and toluene containing  8  percent
naphthalene was used.  The naphthalene vapor concentrations
obtained ranged from 2-6 percent, somewhat lower  than  the liquid
concentration.  It was observed,  however,  that  small amounts of
solid naphthalene had accumulated within the sampling  syringe.

5.2.2.4   Effect: of Temperature  and Pressure--

          Vapor and liquid concentrations  were  measured for the
hexane-toluene system at the following operating  conditions:
          1)
          2)
          3)
          4)
T = 130°F, P =  40 psig
T = 130°F, P = 100 psig
T = 200°F, P =  40 psig
T = 200°F, P = 100 psig
           In  all  cases,  the vapor and liquid concentrations
remained  constant at  the levels given in Table B5-63.
                              458
-------
5.2.3     Conclusions

          Based on the results obtained during the course of
this experiment,  the following conclusions  are offered:

          1)    The composition of fugitive  emissions from
               refinery process equipment appears  to be
               identical to the composition of the liquid
               within the leaking equipment.

          2)    The temperature and pressure of the process
               stream have no effect on the composition  of
               the leak.

          3)    Heavier components within the liquid process
               stream may leak at concentrations  equivalent
               to that of the line concentration.   However,
               they may condense on cooler  external surfaces.
               Hence, only a portion of these heavier components
               will constitute air emissions.
                              459
-------
                          SECTION 6
                     MAINTENANCE STUDIES
          To evaluate control technologies for valves and to
develop parameters for "off-set" analyses using valve mainte-
nance programs,  data on the effectiveness of various types of
maintenance activities are needed.   In this section of the
report, the short-term effects of maintenance are described.
No long-term effects are available.  However, an ongoing program
is described.

6.1       SHORT-TERM MAINTENANCE RESULTS

          A short-term maintenance study was performed on 86
valves at four refineries.  Three variables were considered in
selecting valves for the study: leak rate, process stream, and
valve type.  A selective experimental design based on categories
of the above variables was used to minimize the number of
required valves in the study.

          Eligible valves were first located by screening with
a TLV Sniffer.  Variable information was recorded.  Each valve
was then rescreened and sampled.  Routine maintenance, such as
tightening the packing gland or adding grease, was performed on
the valve.  Maintenance was described as directed or undirected.
Directed maintenance involved simultaneous maintenance and
screening of the valve until no further reduction in TLV Sniffer
reading could be obtained.  Undirected maintenance was not
                              460
-------
monitored with the TLV Sniffer.  Finally,  the valve was
rescreened or resampled after  the maintenance had been per-
formed.  Table B6-1 summarizes all maintenance and leak  rate
information.

          The effect of the type of maintenance  performed,
either directed or undirected, can be seen in Figures B6-1 and
36-2.  The leak rate of the valve before maintenance is  plotted
against the leak rate for the valve after maintenance for both
the directed and the undirected maintenance efforts.  Valves
that exhibited a reduction in  leak rate are indicated by those
points that fall below Lhe diagonal line drawn in each figure.
Those valves whose leak rate increased are shown as the  points
plotted above the line.  Valves whose leak rates show no change
after maintenance are represented by points on the line.  It
appears that the directed maintenance produces a greater reduc-
tion in leak rate in a larger  percentage of valves.  This indi-
cates that the directed maintenance method is more effective
than undirected maintenance in reducing emissions from valves.

          The percentage reduction in leak rates after mainte-
nance was calculated using the following equation:
         _  ,        Leak Rate Before Maint. - Leaf. Rate Alter haint.
Percentage Reduction = 	;	:—	—;	*7~.	
       6                      Leak Rate Before Maint.
Negative percentage reductions are possible  in  cases where  the
leak rate increases after maintenance.  The  highest potential
reduction in emissions is 100 percent.  However,  it is  possible
to get negative percentage reductions that are  much greater
than 100 percent, particularly if the original  leak rate  is
very low.
                              461
-------
         TABLE B6-1.  SUMMARY OF MAINTENANCE AND LEAK RATE INFORMATION
          The data in this table are first sorted into directed and undirected
maintenance groups.  Within the type of maintenance group, the valves are  first
sorted by valve function (block or control) and then in descending order by percent
reduction due to maintenance.  The valves selected as "control sources"  (no main-
tenance performed) are the last valves listed in each valve type group.

          The following is a description of the variables listed on the  printouts:

ID  - Unit code and source number for each valve (refinery ID is not included so
      there may be some replication of ID).
BLK - B - Block valve
      C - Control valve
PRSI- Process stream code (see below for description).
TLV - Maximum screening value when source was first located.
DATE- Date (month, day, year) when valve was sampled and/or screened.
SAMP- Sample type:  BC - Sample for source selected as control.
                    BS - Sample before maintenance.
                    MI - Sample after maintenance
                    BQ - Quality control sample - before or after maintenance.
                    ES - Estimated leak rate based on maximum rescreening  value.

Screening information:

      MEAN STEM - Average of four screening values at the valve stem.
      MAX STEM  - Maximum of four screening values at the valve stem.
      MEAN GLAND- Average of four screening values at the valve gland.
      MAX GLAND - Maximum of fpur screening values at the valve gland.

NON-METH LK RATE - Measured or estimated nonmethane leak rate (Ib/hr).
% REDUC - Percent reduction due to maintenance.

      °i DT7TMT/-   i AA   /Lk rate before maintenance - Ik rate after maintenance\
      /o KhJJUL = IUU x i	I
                      \              Lk rate before maintenance               /

                                                       Continued
-------
                      TABLE  B6-1.   Continued


Stream
AAAX
AABX
AACX
AADX
AAEX
AAFX
ABAA
ABAB
ABBA
ABBB
ABCX
ABDA
ABDB
ABDC
ABDD
ABDE
ABEX
• Process Stream Classifications ,
Gas/Vapor Streams
Stream Description""
Ci - C2 Hydrocarbons
C} - Ci, Hydrocarbons
C5 - C9 Hydrocarbons
CIQ+ Hydrocarbons
Mixed Molecular Weight Hydrocarbons
Aromatic Hydrocarbons
Streams Containing 10 - 50% Hydrogen
Streams Containing >50?0 Hydrogen
Streams Containing 5 - 50% H2S
Streams Containing >50% H2S
Streams Containing >50% H20
Hydrofluoric Acid
Methyl Ethyl Ketone
Sulf olane
Monoethanolamine
Sulfuric Acid
Miscellaneous Gas Streams
-The most  volatile  stream component  present  at  a concentration of 2070
 or more determines  the  stream classification.

                                                Continued
-------
                       TABLE B6-1.   Continued
Stream
 BCAX
 BCBX
 BCCX
 BCDX
 BCEX
 BCFX
 BCGX
 BCHX
 BCIX
 BCJA
 BCJB
 BDAX
 BDBX

 BDCA
 BDCB
 BDCC
 BDCD
 BDCE
 CAAX

 CBAB
Process Stream Classifications
        Liquid Streams
                    Stream Description
         Ct - C2 Hydrocarbons
         C3 - C.« Hydrocarbons
         C5 - C6 Hydrocarbons
         C7 - C9 Hydrocarbons
         Naphtha
         Kerosene/Diesel/Heating Oil
         Gas Oil
         Atmospheric Bottoms/Vacuum Gas Oil
         Vacuum Residual/Asphalt
         Low Molecular Weight Aromatics
         Polynuclear Aromatics
         Streams Containing >50% H20
         Streams Made up of Mixed Molecular Weight
           Components
         Hydrochloric Acid
         Methyl Ethyl Ketone
         Sulfolane
        ., Monoethanolamine
         Sulfuric Acid
         Two-Phase Stream containing methane gas  and
           light liquid hydrocarbons
         Two-Phase Stream Containing >50% Hydrogen
-------
TABLE  B6-1.  Continued
II.
b
L
HKbl

DAI t
S
/\
M
Mb AIM
SILM
JltgG INf-UKMATlUM
(^ax MLAI'J MAX
SILM bLANU GLAND
LK KA-|L KLUUt
MAINTENANCE
PERFORMED
Undirected Maintenance
2 1 V A 1 '>
21VA 1M
21V/> 12
21VA 1?
21VA 13
21VA 13
13VA 11
13VA U
13VA 1]
13VA 11
13VA It
13VA l>
13VA 6
13VA f,
13VA 6
13VA f.
13VA 3
13VA 3
13VA 3
13VA 3P
13VA 3U
13VA "«9
13VA "«9
13VA 1
13VA 1
i;
b
H
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b
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b
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b
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b
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AAAX
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AAAX
AAAX
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bV-UX
HLtfX
bUJX
btUX
bUIX
HV-bX
bLBX
Ht-BX
Bt-HX
BLbX
AABX
A«UX
A«BX
ULBX
bLIJX
bLHX
HLBX
AAKX
A/»t)X
2h
2b
120
120
220
220
100000
luuuuu
luouuu
luuuuu
1000UO
luouou
100000
100000
1UQUUU
1UOOOO
luuuuu
luooou
lUOuuu
IbUO
IbOU
400
400
10000
lOuoo
102670
11U670
1U26/0
110670
102fc7b
110670
12 12 7 1)
12 m 7O
1217 70
1 2 1 (1 7 O
121970
121278
1211 70
1215/0
121870
121978
11227U
1201 /O
120i» /B
110678
HUf 70
110670
11U670
1122'H
121)170
US
Ml
bS
Ml
bS
Ml
bS
Ml
LS
LS
LS
bS
Ml
LS
LS
LS
bS
Ml
LS
US
Ml
BS
HI
OS
Ml
49730
U
66?bO
13
1 03PO
b<5
82^00
1*30
St.3
1*08
778
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2198
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65000
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14M6
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7U5
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1UIIUUU
0
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30
24000
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100000
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1000
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3700
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280
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8400
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3300
270
280U
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900
21000
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0800
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20UU
14UUU
2900
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0.04if>7
O.OOOQ2 99.^5
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O.OObQ7 96.37
0.01752
0.021flb
0.0070"
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0.023ll 96.48
0.04801
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>i turn top nut; Vs turn
bottom nut.
Vs turn top nut; 1 turn
bottom nut.
Vi turn top nut; >j turn
bottom nut.

1>5 turn each, top and
bottom nuts .



l»i turn each, top and
bottom nuts.



l
-------
TABLE  B6-1.  Continued
II'

I:
L
I'KSl

l\
M
UATt H
SL'KttNlNti 1MFOHMAI1OM
MLAIM MAX MLAM MAX MON-MtTM *
Sltf SHI*1 (iLAI.'U GLAill) LK HAit HLUUC
MAINTENANCE
PERFORMED

Undirected Maintenance (Continued)
13VA
13VA
1 3 V A
A S V A
X ^ V A
15V,\
15V A
21V/V
21VA
21VA
21VA
13V A
13V A
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12197B tS
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1 torn on both nuts .
1% turn west nut;
turn east nut.
1 torn each, west
east nuts.

2 turns each, top
bottom nuts.



J/a turn top nut;
bottom nut (could
tighten further).


.%
and

and




Vs turn
not



                       Continued
-------
TABLE  B6-1.  Continued
II.'

L

A
M
UATL H
SCKLLN1NG INFOKMAItOM
MC'^N MAX MtA|j MAX
K!L" SHf1 bLAlJU GL'Uin
LK KAfL KtlJUt
MAINTENANCE
PERTORMED
Undirected Maintenance (Continued)
ISVft
IbVft.
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13V/,
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bottom nut.


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Tightened packing.

2 turns on both nuts.


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thread on packing nuts).

l'/3 turn south nut; Vj
turn north ni/t.
                         Continued
-------
                                     TABLE B6-1.  Continued
00


Ill



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bottom nuts.



1% turn on right nut;
1 turn on left nut.

% turn each, north and
south nuts.



1\» turns on top nut; 1H
turns on bottom nut.

1 turn on both nuts.


Continued
-------
TABLE  B6-1.   Continued
II-
1,
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11 v
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A
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ME AM MAX MLAN MAX NON-MLy" % MAINTENANCE
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                      Continued
-------
TABLE  B6-1.  Continued


11.

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-------
TABLE  B6-1.  Continued
11
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SCHLtNING INF
CLnN MAX
Slf M SI*-"
UHMM 111
bLANU
IN
MAX I
NUM-«LIM * MAINTENANCE
LK HATL KLUUC PERFORMED
Undirected Maintenance (Continued)
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.00174 99. *3 'A turn north nut; 1H
.uuifoO turn south nut.
.09*3* 3 turns on west nut; 3
,
-------
TABLE  B6-1.  Continued


IP
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0^750 1 turn each, west and
umn7 ^H.'jy east nuts.
                        Continued
-------
TABLE  B6-1.   Continued


in
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LK
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Maintenance (Continued)
AAf.X
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4U 790
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37ip4 east nuts.
                        Continued
-------
TABLE  B6-1.  Continued


I.



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Maintenance (Continued)
AALX
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U ^ 1 td tJ f\ A
0 0 0 ^ t V
U.uu3i4b -28. b "» turn east nut; 1 turn
u.uui>2i west nut.
O.OU1J2
O.UU122
0.ool5^
u.uu2i)i -ba.4 Vn turn east nuts.
u.uuu^J
U . DUlIf**
u.uuupa
u.uuupi
O.UUlQb
O.UU26? -i'*9 1 turn each, west and
O.uUb^i east nuts.
O.UUbo1*
O.UU4g3
O.UUbyU
U.UUUjl
                        Continued
-------
TABLE  B6-1.  Continued
Ill

b
L
I'KS1
1LV
UATL
S
n
H
H
SCKLLN1NG INUJKMAIIUH
MLAN MAX MEAN MAX
STIW STLM bLANU CL«HU
NUN-MLTH * MAINTENANCE
LK KATL HLUUL PERFORMED
Undirected Maintenance (Continued)
13VA
1 5V A
«:?««
2? V.I
13VA
UVA
13VA
13V/V
•MM
15V*
15VA
13VA
13VA
13VA
15VA
15VA
15V/<
15V<\
15Vfl
15VA
15VA
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90
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210
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0.00013
O.OOOQ3 -bbo 1 torn on each not.
O.OOlQ*
O.lb731* -e7*«b 3 torns on both nots.
O.M07gO
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1.04320
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o.oonji
                        Continued
-------
TABLE B6-1.  Continued


IP



1
1
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DATL
s
A SC>(C-LN
ll ML OH
f S 1 f i'1
IIO(, IMF UKMA 1 1UIJ
NAX MLrtu MAX DON-MI yn * MAINTENANCE
Sit" C.LAIIU GLAIIU LK KAjt. HLUUC PERFORMED
Maintenance (Continued)
I.V 1 X.
|ii.l X
AAAX
A'lAX
AAAX
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AMAX
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JMU
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LS Ihi
UL 2U
LS 41
LS 2U
LS ^0
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1 JU At 1 / U .UUl 1 /
100 mj su o.oui^b
-------
TABLE  B6-1.  Continued
If

Directed
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5>s turns east nut; 5^
turns west nut.


% turn top nut; 4 turn
bottom nut.



1 turn north nut; 1 turn
south nut.




3 turns top nut ; 3'j turns
bottom nut.



                       Continued
-------
                                        TABLE B6-1.   Continued
CO
in
L>
L
K
I'KJjl FLV
UATL
S
A
M
H
STLM
JiNO INF UKMA 1 1UN
MflX MLflN MAX
SiL" GLAND GLAMU
NOM-MLTH * MAINTENANCE
LK KAyt- KtuuL PERFORMED
Directed Maintenance (Continued)
1 5V<\
J3VA
13V,.
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ISVft
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13VA
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13VA
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,Uii3
-------
                                        TABLE  B6-1.  Continued
vD
i:
Di rected
2 7 V A ') I"1
2 7 V /, bl1
2 7 V A ^ f
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MAX MLA(J MAX
SlLfi bLAUU f,LAI>|L)
MOM-MLTH * MAINTENANCE
L«. KArL KLU"L PERFORMED
Maintenance (Continued)
i)
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li
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A«AX 100000
AAAX 100000
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ni-nx
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000?3
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oooj1^ 7i. 10 40 pomps of grease; 1
ouo7o turn each nut.
00030
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00133
00172
OUU;>3
ooiqf 3 turns north nut; 3
Ooi(]b 45. ^7 turns sooth nut.
                                                                Continued
-------
                                          TABLE  B6-1.   Continued
oo
o
L
in K,
rusl
TLV
UAFf
S
It
M
SCKLIN1NG INfl
PLAN MAX
STtM STLN
JKMA F 1C
MLAM
M
MAX
GL«NU
NOM-MLT" > MAINTENANCE
LK KAfL HI DUC PERTORMEO
Directed Maintenance (Continued)
1 3 V A 2 ( b
27VA :>;•• c
27Vn '>3 |:
2 7 V A ' > .' H
27Vrt '.).' h
27vM '.'< H
2 7Vf M b
d 7 V A -1 1 b
27>'A "i] l<
2 7 V A lj 1 IS
27V/. si f
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1.3V A ': H
1 3 V ft 'i t'
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1 3 W A 11 1 •
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A A AX
LAAX
LA AX
L AAA
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L A A X
L t\ A X
LA AX
LA AX
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.1«2PV
. u 2 1, n o
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, UU5}3
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.U4uni south nut.
, U2 Vj V
.oiv7u
.UUUpB
. UUU^b
. UUl7
-------
                                         TABLE  B6-1.   Continued
oo


I'
Directed
1 3 V A 11
13VA  ;
1 3 v ft «' ;.
13Vft <•?
13VA 2 (•
13V ft "-"i.
13V 7i '/I.
1 3 V ft ? (
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50000
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029J9
U7b7»
lH2n^»
01B7U
MU7qt)
MU7gB
M U 7 Q «
MU7g«
U U 9 ", 1
UUO()0 loo 1 turn east nut; 1 turn
00357 west nut.
UUbq3
0«.U7«
                                                                 Continued
-------
                                          TABLE  B6-1.  Continued
00
N>
in
Directed
1 3 V A
1 5VA
1 3 v A :
L WA 1
HVA -
t'7V^ 'lb
i; 7 v A 4 r>
^7VA '^
't^\l^ n ;.
i?7VA 4b
1 5 V /\ 'I J
15VA 'U
15VA 41
l"5Vrt 4 i
15VA 'M
15VA 4]
15VA 4 ]
1'jV.-. 1 ".
I'iV-. If
IbVA U
1'JVA !;•
15VA If
13V A V
13V A >
livr. ''
13VA '•
13VA ;
M
L
K
rt-MX 92UOO
trU-LlX 92°UO
11LHX 9?UUO
Ht-flX 9?UOO
l)Ct-.X 92UUO
UCHX 3UUO
IjLlIX 3UUO
M«-HX 3UUU
KLHX 3UUII
ht-UX 3UUO
b>-HX 1400
tjcnx 14 u n
LS«-HX 14UU
U«-h(X 14IJO
tJ>-l'.X 14DU
111/9
12279
129 /9
130/9
1M/9
111/9
11779
119/9
122/9
123/9
112/9
112/9
119/9
12? 79
123/9
124/9
129/9
112/9
119/9
122/9
12379
124 /9
111/9
117/9
119/9
122/9
123/9
US
cs
Ml
LS
ES
HS
Ml
LS
LS
LS
US
LS
LS
LS
ES
LS
Ml
OS
Ml
LS
ES
LS
OS
Ml
LS
LS
ts
40/5
53*5
46
23
iy
3'«UOO
370
200
593
47SUU
.
52500
47
H5
52*5
1?00
*
2fc75
;?u
23
i»U
21
1//5
245
?6t>
160
4i4
eouu
6300
90
30
40
73000
bun
i>40
1UUO
1UUUUO
,
5BOOO
49
92
58UO
14UO
•
peon
<:n
AC
in
*4
20UII
4UQ
330
33U
12UO
13SU
232b
y.2.0
34b
3*3
2U
.
.
.
•
.
i!1750
30
3S
50U
30b
•
73H
20
20
31H
?u
bl
!-»
150
20
29
1BUU
4500
310
b40
b40
?u
.
.
•
'
.
320UU
3*
4U
6>UO
370
•
lucu
20
20
1000
?0
10U
3U
200
20
4i!
0
0
0
0
0
u
0
0
0
0
0
0
u
0
0
0
0
0
0
0
0
u
0
0
0
0
0
.01013
.0357 '
,oooi>o 97.01 2>s turns north nut; 2'5
.00470 turns south nut.
. UUl<1 1
.OOf-,3
.uoojj 95.00 VB turn west nut.
.00201
. 007(18
.407ga
.01/3'«
. 2b25b
,00050
.OOUfl /
,U332fe
,0095«!
.00096 94. 4f, i!, turns each nut.
.0126*
.001)1 91. *2 8 turns north nut; 8
.00032 turns south nut.
. U07flM
.0002 '
.00249
.00029 UP. 40 3>j turns north nut; 3>s
.uui-fU turns south nut.
.O02ni
.UUtMl
                                                                  Continued
-------
                                         TABLE  B6-1.   Continued
co


If



Directed
UWrt
13VA
13 v.i
1 JVf,
I 3V«
l3V/>
13V «
13V/<
13V1
13V/V
15VA
I'lV /\
15v/\
15V-*
1-jVrt
13VA
1 3W
J 3VA
13V <\
13V A
^7VA
;'7V,\
«>7V(\
«r 7 V 1
,-7V/>
«!7tf;,
<>7VA
1 1-
) «•
1 (
1 i.
1'-
!••-
] '.
i :
I s
i ^
)U GLAliU


MOM-Mti" » MAINTENANCE
LK
NftTL Hf-UUL PERFORMED
Maintenance (Continued)
L
L
L
L
L
L
L
L
C
L
L
L
L
L
L
C
L
L
L
L
L
L
L
L
I
L
L
AAAX lUUUUU
AAAX lUUUUU
"A AX lUUUUU
/WVAX lUUUUU
AAAX 1UCUUU
/i»/\X p.uut)
«AAX (1UUU
AAAX 6UUI)
/uiflx auwu
A /(AX dUUU
L>*-r_ x iiuu
I:LI.X 1.1 uo
i-IM X 1 iUU
'J L L X 1 1 U IJ
t-"-LX llt.'U
AAAX ?i?UO
A/VAX 2*!UU
/I « A X ? «! U U
A« AX 2«^un
A A A X 2 ^ U U
ULUX ltll'0
HL;)> 16IM)
ULtJX ItJUU
b>-UX 10UU
liLDX 10UU
A/U5X iff.UUU
A/.LIX hUUU
11?7-J
1197*
1^^ 1?
1 ? 37*
12U7V
1127*
1197*
122 /*
1^3 /*
1?'.7*
1127V
122 7*
1?* /*
130 7*
131 ;*
n?/9
lib?*
11 7 /*
1 IB /*
1197*
ii5?y
IK, 7V
11 77V
119/*
l->^/*
1 1 17U
1117*
MS
Ml
LS
LS
LS
bS
Ml
LS
ES
LS
US
LS
Ml
LS
LS
uc
LS
LS
LS
LS
LS
riL
LS
LS
LS
UC
LS
9bou pouuu 335u bbuu
2b50 26UII IbUU i!lUU
1 It* 2UU 1.J9U iUIIU
130U 1MUO lf>UU .J1UU
2bbH 3^011 13UU «ibUU
HbU 12UU . .
MMb biu . •
"«i?b 7UU , .
1 4UU 22UU . •
10fi3 13UO . .
700 i uoo 30 ta
if>i!b i /on 3ib iau
l?25 l^UO ^23 12U
1U50 11UU b^b 1UUU
7^0 11IUO f, ; 7-2
bb3 UUO . .
13*b 37UU . .
2M5U b2UU . •
IflbU 2UUO
l"2b UUO
f>^3 dUO M3 5*
iVb 3UU U U
7h3 a^U 4b Hu
'*UU bUO 7b» ^2UU
T33 300 71 IUU
, . .
2UbO 3UUO u*uu Mi?OU
u.
U.
U .
U .
u.
u.
u.
u.
Ui
u.
0.
u .
u.
u.
u.
0.
u.
u.
p .
0,
u.
0 .
u.
u .
"•
n.
u.
UU21-*
uuuu* 77.1* 4 turn east nut; '5 turn
uiBf,*? west nut.
u 2 u 70
U19/U
U U U 5 U
UUU?f "»b./l l"a turn on nut.
UUbj /
uini /
uu«9a
UUl 5*
0 1 Ip*
uu3u<> -119 Z'a turns west nut; 2*j
uu77" turns east nut.
UU I(]O
ouinb
U*i?3*
OJUpl
0130^
uu2-»
UUSljl
uu2n^
UUbi3
(iit\t
uu^,,u
OU'J,-,1*
U-»bi*
                                                                 Continued
-------
                                      TABLE B6-1.   Continued
s
I' A SCKLLN1NG IMI-UKMAllUN

It-


Directed
c!7Vft
H7Vf
?7v/i
s.TM r
•4 7
'< 7
>4 /
•. 7
L
h l-«^l
Maintenance
C A A U X
L UUU 1147^
oUUU I'SZf'J
M KQAN M/\x
P 5ILM STL"

E.S 350 ^30
LS 33UU 3bUO
Lb b3U 7"U
tb ibu <;<:o
MLAM MAX
(JLAIMU GLAND

eob luou
31b3 OBUU
Tbtt 
U.U1M] /
O.U^2.^
CO
-p-
-------
                                                   LLL>LNL):  A = 1 UbSt H = 1 OUSi LlL,
CO
Ul
              l.uUll <
                   t
                   t
                   4
                                           A
                                         A   A
                                           A
                                                            AA
                                                            AA
A        A
   A
                                       u.nui
                                                                                    Leak rate before =
                                                                                    — Leak rate after
                                                                                      maintenance
                                                          u.uiu

                                                 LtAK KAIL ULt-Uht MAIN!., LB/HR
                                                                                                l.QUO
                       Figure B6-1.   Directed maintenance - leak after  maintenance
                                       versus leak  before  maintenance.
-------
                                                   Ltt>ENU:  A =' 1  UDSi H = * ObS. t. ft .
-P-
00





L
L
A
K

l(
A
r
E

A
F
1
t
rl

M
A
I
N
1
•

L
B
/
H
t
1.000 *
1
1
1
1
1
1
.U.I 00 ^
1
4.
4
i
*
i
^
u.ul.t +
/
/
/
/
/
/
t
U . U 0 1 ^
^
4
1
1
f
1
/
              . j 0 U
                  II. 'MIL
                                                                      Leak rate before =
                                                                       Leak rate after
                                                                       maintenance
                                                                A  A
                                      U.Ulil
    U.U1U                U. }QU


HAFL ULUWL .lAlNT., (LB/HR)
                                                                                                1 .QUO
                     Figure  B6-2.   Undirected maintenance - leak after  maintenance
                                     versus  Leak before maintenance.
-------
          Figure B6-3 summarizes the percent reduction data
with histograms comparing directed and undirected maintenance.
The effectiveness of directed versus undirected maintenance is
obvious when comparing the distributions of percent reduction.

          The effects of the valve maintenance studies are
summarized in Table B6-2.  The results are shown for both the
directed and the undirected maintenance programs,  and are
grouped according to the level of emission rates.   Two results
are noteworthy.  It is evident that the percentage leak reduc-
tion for those valves that were subjected to directed mainte-
nance is considerably greater than that of the valves that had
undirected maintenance.   It is also apparent that the level of
the initial leak rate has a marked effect on the percentage
reduction in emission rate for both directed and undirected
maintenance.   The percentage reduction achieved by maintenance
is lower for the initially small leak rates.  In the very low
initial leak range, £ 0.001 pounds per hour, the average and
weight percent reduction was actually negative.

          It should be noted that as the magnitude of the leak
rate becomes smaller, both the mean percent reduction and weight
percent reduction decrease rapidly.  Both of these parameters
are dependent on the magnitude of the leak rate and are highly
influenced by extremes within the leak rate range.  The median
percent reduction,  however, is a more robust measure of central
tendency and cannot be affected by the very large negative values
of percent reduction encountered at low leak rates with undirected
maintenance.
                             487
-------
lo-
g-
s'
7-
x 6-
U
c
1 5"
*-
3-
2-
Undirected Maintenance

—




1 1

_• i 1 i I I 1 1
I
VI



\







^




P75



1
1
^




\
I



1







£T


i
1
%
\
f
^
\

!
i




O 23 O O


Percent Reduction
IS-
9.
«
3-
7-
x5-
^
Is-
OJ
L.
4-
3-
2-
i
1-


Dlrected Maintenance


P
i * M
x ^ ^tyy^/
^oo d^^-o o d 	 '6 6eA36^^^g


^
|
1

o


1
I
!
i
i
o







           1)11
                    Percent deduction
Figure B6-3.   Histograms for percent  reduction in
               leak rate directed vs.  undirected
               maintenance.
                        488
-------
            TABLE B6.-2.   SUMMARY OF  MAINTENANCE REDUCTION BY LEAK RATE LEVEL
Original Leak Kate
Level Range (Ib/lir)
1 £0.001 n
P"
pw
pm
2 0.001 - 0.01 n
pw
pm
3 0.01 - 0.1 n
P
pm
4 >0.1 n
P"
pw
pm
n = Number of valves maintained
77 — Axr^» T n o£» np>T^*3nt" -roHn^ f- n rm — VP • /n
Directed Maintenance
4
30.7
35.2
52.6
12
48.7
56.9
86.2
10
93.8
93.0
93.8
1
98.0
98.0
98.0

_ _ (leakage before - leakage
Undirected Maintenani
6
-105.5
-26.3
5.6
16
-530.0
-276.4
30.4
22
31.7
45.1
60.9
15
73.4
83.5
85.4

after maintenance)
                                                            -= - -. - :— H - ^ - : -- — =- x 100
                                                            leakage before maintenance
pw =
     ,, .  . ,_           ...     Eleakage before maintenance - Zileakagc after maintenance
     Weight percent reduction =	fi	=-	;-	,—	r-—	•	
                                              )lc*'-*Lrr*rrf*i'\airr\-vt~* m ^ i nf"/inon«-»ri




pm = Median percent reduction
L\_  1I1C-1 _!_*.! l_V~lLCLl.lt_*_   L-i ±.\— Cl L*-dfZj*~- Cl -I- I


 Zleakage  before maintenance
                                                                                             _n
                                                                                         x 100
-------
          The median percent reduction does show the same
patterns as the average and weight percent reductions.   The
comparison between the median percent reductions for the two
types of maintenance indicates that directed maintenance yields
a higher reduction in leak rate.   Undirected maintenance appears
to be less reliable at low leak rate levels ( 0.001 Ib/hr)  with
the potential for causing more increases in leakage.

          The individual percent reduction from the two mainte-
nance methods was plotted against the original screening value
in Figures B6-4 and B6-5.  It appears on these graphs that  the
positive percent reductions for directed maintenance are generally
higher than for undirected maintenance.   Also, a greater per-
centage of the undirected maintenance valves appears to have
increased in leak rate after being maintained than for the
directed maintenance.  Table B6-3 bears out these observations.
The median percent reduction for directed maintenance (91.2
percent) is significantly higher than that for undirected mainte-
nance (53.8 percent).

          In Table B6-3 the valves are grouped according to the
categories of the three variables used in the experimental design
for selecting valves.  One of these variables was valve function
(block or control).  Control valves which had directed maintenance
had a slightly higher median percent reduction in leak rate than
block vlaves which had the same type of maintenance.  However,
the opposite is true for valves which underwent undirected mainte-
nance.  Again, even within the block/control groupings, directed
maintenance appears to yield a higher percent reduction in leak
rate than undirected maintenance.

          The screening value range was also used in selecting
valves for the study.  For directed maintenance, the median percent
reduction stays approximately constant across the screening value
                              490
-------
                          Lt(.L»ni: « -  i OU.-J, I- r S III-.';* LT(.

-p-
vO
I-1
i
t
I ii U f i\ A « A A A AC
I1 ' A A « « A A ,|
L ; A U /\
K ' ' />
t '.)U . A i\
L /
fM ,
f
K
t
1 J /
U -'jd 1
t / ;,
1 ,
1
U - 1 jU <
                juil                lui'u                 luuuP               luuniju

                            MAX SCREENING VALUE, PPMV
Figure B6-4.   Directed maintenance -  percent  reduction
              .  versus screening  values.
-------
 loll
                                           i:  A  = 1 OKbt  U : ? UUSi L1L.
 100  f       ,\
     /
  •j(l
                           A  A
                         C    A
                                                                    A A
                                                                    AA
-lull
- 1 L) 0  t
                                               A A
           (-550)
           --A---
 (-8745)
----A-	*		
       icon

 MAX SCREENING VALUE, PPMV
  (-377)
.--A---
 1 U IH> 0
                          luu
Note:  3 values were out of range
         Figure  B6-5.   Undirected maintenance  - percent  reduction
                          versus  screening  value.
-------
                      TABLE B6-3.    STATISTICAL  SUMMARY  OF  MAINTENANCE  DATA  -  PERCENT  REDUCTION
LO
                  Screening
                                      Block Valves
                                                                       Directed Halnte_nancc
                                                                                Control Valves
Range
(ppojv)

<5K


5K-50K


>50K

C/V
Stream
2 58.8
56.5
58.8
2 76.1
90.7
76.1
3 93.8
97.8
98.0
LL
Stream
5 6:) . 1
90.5
93.1
4 89.8
89.0
90.1
2 -?.b. '<
56. 7
-26. 'i
HI.
Stream
0


0


0





Total*
Block
7 61.8
86.5
87.3
6 85.2
89.1
88.7
5 65.7
92.3
91.7







G/V
Stream
0
1


1


18 64.2 (12.96)
91.0 (82,99)
86.2 (75,97)
45.7
45.7
45.7
77.2
77.2
77.2
1,1.
S t ream
4 39.5
84.9
89.8
1 95.0
95.0
95.0
2 97.2
96.4
97.2
HL
Si ream
0


0


0





Total
Control
4 39.5
84.9
89.8
2 70.4
91.5
70.4
3 90.5
95.0
94.5







All
Valves
11 53. 74
85.6
88.4
8 81.5
89.2
88.7
8 62.5
92.6
93.1
9 66. 8 (12.100)
80.7 (79,99)
91.2 (9.3,98)



CJ.7,100)
(77,99)
(IB, 98)
(65,98)
(69,100)
(-55,96)
(-7.9,100)
(81,100)
(-31,99)







21 64.6 (38,91)
90.7 (83,98)
91.2 (79,9.'))
                  *Numbers in parentheses Indicate an approxlra.ite  95Z confidence  Interval for the average reduction for the three different  estimations.
                                                                                                                                     (ContInuod)
                    Code for
                    Kach Cell
                    In Table
1 = Number of valves maintained
                                                   100 x (leak before - leak after maintenance)
2 = Average of percent reduction where percent reduction -  	   "ITak before maTntenaW

                           £ leak rate before maintenance  Lleak rate aftrr maintenance
3 - Weielir_ percent  reduction D	-TT,	— •	 ,      .   ~ 	-	
      *  '                              }. l<>.ik int e hpfure ma inlcnance

/i a Median percent  reduction
-------
             TABLE B6-3.   Continued
Undirected Maintenance
Screening Block Valves Control Valvc6
Value
Range
(ppmv)










<5K


5K-50K

1
>50K


fi/V
Strcuu '•
6 54.0
52.2
65.2
4 69.8 ;
47.8
82.6
3 75.3
88.4
84.3

I.I.
Stream '
6 42.6
58.9
76.9
4 -64.9
- 9-°
28.2 ;
4 81.3
93.0
90.9

Hi.
Stream '•
4 -26.1
-43.4
7.37
0


o ;


MD
-P-






Total*
Block
16 29.7
48.5
33.1
8 2.4
20.2 '
50.1 '
7 78.7
91.1
85.4





'




(;/;v ;
Stream :
7 -1320
- 717
-58.4
2 54.2
53.8
54.2
8 29.4
81.3
19.3

LL
St ream
5 5.2
91.1
26.56
4 87.8
96.9
95,6
1 90.6
90.6
90.6

IIL :
Stream '•
0


1 ,8.2.1 :
82.1
82.1
.0


31 33.7 (-1.8.69)
68.7 (48,89)
61.1 .(31.85)
Total*
Total All
Coutrol Valves
12 - 769
-50.5
24.1
7 77.4
90.2
82.1
9 36.2
87.0
29.5









28 -312 C-950.100)
33.0 (-39,100)
28.9 (-0.5, 79)
15 37.4 (-28.100)
67.4 (34.100)
82.1 (42,88)
16 54.8 (31,78)
89.6 (81,98)
67.0 (21,92) :









28 298 (-940.100) 59 -124 (-410,100)
81.0 (64,98) /3.9 (69,88)
51.4 (13,85) 53.0 (29,82)

*Nur.ibcrs In parcnthcscc Indicate an approximate 95X confidence Interval for the average percent reduction fnr the three different estimations.
Cudc for 1 2 1 - Number of valves maintained
* 3 2 - Average of percent reduction where percent reductl
4
3 - Weight percent reduction =
100 x (leak before - leak after maintenance)
Leak before maintenance
£leak rate before maintenance - £leak rate after maintenance x ,QQ
l^leak rate before maintenance


4 a Median percent reduction
-------
range.  However, for the undirected maintenance group the median
percent reduction increases dramatically with increasing screen-
ing values.  Within the low screening value range the median
percent reduction is very low, only 28.9 percent.  This may
indicate that undirected maintenance at this screening level
is not effective at all.  For the middle screening value range,
the median percent leak reduction increases to 82.1 percent,
almost as high as the value for directed maintenance (88.7
percent).   However, the median percent leak reduction drops
again for the high screening value range (67.0 percent).  The
effectiveness of the maintenance program appears to be much
more consistent when the directed method is used rather than
the undirected method.

          The differences in percent reduction discussed above
should be considered as trends.  Confidence intervals were cal-
culated for the key values in Table B6-3.  Differences in per-
cent reduction cannot be considered statistically significant
if confidence limits for the estimates overlap.  The statistical
procedures used to calculate the confidence intervals are dis-
cussed in subsection 6.3.

          A graphic representation of the differences between
the effect of maintenance on block and control valves is shown
in the next several figures.  The leak rates before and after
maintenance are plotted for block and control valves in Figures
B6-6 and B6-7.  The percent reduction in leak rate for each
valve is plotted against the original screening value for block
and control valves in Figures B6-8 and B6-9.

          Finally,  Figures B6-10 and B6-11 are histograms of
percent reduction for block and control valves for directed
and undirected maintenance.   The differences described in Table
                              495
-------
   J.'il.n  •)
L
L

K  U.IOO

K
A
T
L
        /
        /
        /
   u.C id  «
        I
        t
        I
        I
        t
        1
        t
   U.uDl  «
        t
        I
        i
        t
        I
        I
        l
   u.udU  »
                U = Undirected
                I = Directed
                                                     II  II
                           U ,UU1
                                              u.Ulu

                                      l_t«(N KAIL ULI-UKL i^AiUl., LB/HR
                                                                                   • - - _ * -
                                                                                    1 . 01' 0
         i  i...is ilium ,i
   Figure B6-6.   Directed and undirected maintenance  .r, leak, after• maintenance'
                  versus leak  before  maintenance - block valves.
-------
L
L
ft
K

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L
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M
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  1 . 0 0 0 *
       t
       I
U. 1UU
U.OlU
   O.HOO
              U = Undirected
              • = Directed
                         II .IIUl
                                           U.U1U

                                   Ll Ar. HAIL ULl-UKL ilAINT.,' LB/HR
   Figure B6-7.   Directed and undirected maintenance - leak after  maintenance
                  versus leak before maintenance  -  control valves.
-------
CO
/ U = Undirected
lbu * 1 = Directed
luU » i. u u ft
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-------
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           I = Directed
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    '
  1) t
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                                                             II   •
                                                            •   •
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                                                                                 III
                                                                                   a
                        (-550)
                                      (-8745)
                        1UU
                                           1UUU

                                    MAX SCREENING VALUE, PPMV

                                     5 OBS hidden
                                                              10UOO
  Figure B6-9.   Directed and  undirected maintenance  - percent reduction
                  versus screening value - control valves.
-------
Undirected Maintenance Control Valves
1
o
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VI

oooooo o o
t t t t t t * t

i
o

I
o

1
o

1
i

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o o o o o
n
5-1
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Frequency
>— • r*o i*j ^> t.
1 I 1 I

Undirected Maintenance Block Valves
!
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~^ i i t t i
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Figure E6-10.
i
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00 O


Percent Reduction
Histograms for percent reduction in
leak rate - undirected maintenance.
              500
-------
    5-
    4-
  §• 3
                   airected Maintenance Control Valves

                    Percent Reduction
    5-
    4-
  3
  
-------
B6-2 can be seen on these histograms.   While no large differences
between valve function are obvious,  the differences between the
percent reduction in emissions for valves undergoing directed
and undirected maintenance can be seen.  The advantages of
directed maintenance are usually apparent.

          The data from this study can be used to assess the
short term effectiveness of maintenance in a leak reduction
program.  In extrapolating the data from the study to a general
population of valves,  it is important to review how the valves
x^ere selected for study.  The selection of valves was not random;
rather, a specific experimental design was attempted.  This
design called for at least four valves in each cell in Table B6-3
(directed versus undirected maintenance was not considered in the
original design).

          In extrapolating the percent reduction estimates from
this study to a general population of valves, the following
factors must be considered:

          •    Will directed or undirected maintenance be
               employed?

          •    For what screening values will maintenance be
               required?

          Note that the type of valve and the type of process
fluid need not be considered since no consistent differences were
found for these factors in this study.

          Suppose directed maintenance for all valves with
screening values greater than 5,000 ppmv is required.  Estimates
of the short term effectiveness of maintenance can be obtained
                            502
-------
by appropriately weighing the percent reduction statistics for
valves in the 5k to 50K and >50K screening ranges which under-
went maintenance.

          From Table B6-3, the appropriate statistics for directed
maintenance are as follows:
  ,,      .                    Percent Reduction in Emissions
  Screening
    range	             Average       Weight        Median

5,000 - 50,000              81.5         89.2          88.7
   > 50,000                 62.5         92.6          93.1

          All three of the percent reduction statistics are
potential estimates for the population percent reduction.  Perhaps
the most useful of these statistics, however, is the weight
percent reduction since it allows an estimation of the total mass
emissions reduction resulting from a valve maintenance program.
Continuing the above example, assume that for a random sample of
valves, 70 percent of all valves that will require maintenance
are in the 5K to 50K screening range and 30 percent of the valves
requiring maintenance are in the >50K screening range.  Using the
weight percent reduction statistics and the percentage of  valves
in each screening group, an estimate of the mass reduction for the
the population would be:

          Estimated effectiveness (total mass reductions)

               = (0.7 X 89.2%) + (0.3 X 92.6%)

               = 90.2%

An appropriate confidence interval for this estimate would
be (72%,  100%).
                             503
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6.2       LONG-TERM MAINTENANCE STUDIES

          The effect of maintenance procedures on the long-term
reduction of .emissions is currently being studied for a limited
number of valves.  The staffs of three refineries are monitor-
ing several of those valves that were sampled and maintained as
part of Radian's refinery field study.  Approximately 60 valves
are being screened with TLV Sniffers at intervals of one week to
one month for a total period of 6 months.  The program has not
been completed.  The results will be published in a separate
Technical Note when they are available.

6.3       CONFIDENCE INTERVALS FOR PERCENT REDUCTION

          Approximately 95 percent confidence intervals were
calculated for the three types of estimates of percent reduction
presented in Table B6-3.  The statistical procedures used to
develop these intervals are discussed below.

          The mean percent reduction in leak rate, being an
average of identically distributed random variables, was
assumed to be approximately normally distributed by the central
limit theorem.  Thus, the 95 percent confidence limits are:
          where x is the mean,
          s—  is the standard error of x, and
           A.
          t   is the critical t-value obtained from a table.
-------
           The  calculation of the confidence  limits  for  the
median percent reduction in leak rate did not require an  assump-
tion regarding the type of distribution.  The method, which is
valid for  all  continuous distributions, is described briefly as
follows.

           Suppose  the  data for which the median has been  calcu-
lated are  ordered  so  that
                     P,  £ P2  < P3 1  ....<. Pm

where P.  is  the  i    value of percent reduction, and m is the
number of values.   Then the  two points whose indices are
                         m+1 .  1.96/ln"
                                   2
are the desired  confidence limits.   Since these two indices  are
actually not  integers,  interpolation between values was per-
formed to achieve  slightly increased accuracy.

          Confidence  limits were also computed for the percent
total reduction  in leak rate,

                           100 CB~A)
                               B

where B is  the  total  leak rate before maintenance, and A  is  the
total leak  rate after maintenance.

          'I'll*- c- .» j I I c-::;:: i i ij 1  I ill  I tie- V.-tl i.;l!Ji t* I'll ;l I -1 I  I •'•  C-Ul'li  UG
I. l)f ,'tl«,VI-  | r; ||li|  1'UiiWII  >;»..-||-| 1%' hill  l/.-lfl l_if_i ;l [ i [i f < i :'.;j III ^ (' p> | MFJIIK  ?
second-order Taylor's series  expansion, as is discussed by
Mood, et al. -1
                             505
-------
          The type of distribution of this ratio is unknown.
                             ,\
It was felt, however, that ±2a confidence limits provide a
reasonable indication of the uncertainty.  If the ratio were
normally distributed, these would be 95 percent confidence
limits.

6.4       REFERENCES

1.  Mood, et al.  Introduction 'to the Theory of Statistics,
    Third Edition, 1974, p. 180-181.
                              506
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                          SECTION 7
                  GENERAL SURVEY INFORMATION
          There are many factors in a refinery which might
contribute directly to the fugitive emission load or indirectly
affect the overall emission level.  However, they do not lend
themselves to direct sampling.  Among these factors are mainte-
nance practices, laboratory techniques, unit shutdown proce-
dures, blind changing procedures and blending operations.  In
order to evaluate these items, a general survey form for each
of them was submitted to the refiner.  In this way, the informa-
tion necessary to compare these factors froni one refinery to the
next was obtained.

7.1       MAINTENANCE PRACTICES

          It is widely acknowledged that good preventive
maintenance is one of the best ways to minimize fugitive emis-
sions.  If the effectiveness of maintenance plans in reducing
fugitive emissions can be characterized, a valuable correlation
could be obtained.  This correlation could be used when applying
the results of this study to other refineries.

          Generally speaking,  the refineries used combinations
of in-house and contract maintenance personnel.  The in-house
maintenance people did much of the routine maintenance, and
supplemental contract labor, was used during turnarounds and
larger maintenance projects.
                             507
-------
          None of the refineries sampled during this study were
utilizing an extensive valve maintenance program during the period
when sampling was conducted.  That is,  routine screening of large
numbers of valves for the purpose of preventing or reducing hydro-
carbon emissions was not encountered.

          Some form of preventive maintenance program was in
force at five of the six refineries responding to this survey.
The extent of these programs varied, however, among refineries.
In one refinery an inspection of each unit is performed once a
year.  Piping, furnace tubes, etc., are replaced if it is felt
that they might fail during the following year.  Maintenance
records are not kept for extended periods of time; work orders
are held for one year.  These work orders cover pump repairs
and seal replacement.  Pumps, valves,  flanges, etc., are in-
spected and adjusted/replaced only when a problem is reported.

          At another refinery, however, a preventive maintenance
program is practiced on instrumentation, electric motors and
pumps.  This includes a prescribed maintenance schedule for each
piece of equipment.  The program is supplemented by an equipment
file.  These records are maintained of failures and service life
of various equipment items.  The packing and seals of pumps,
valves, etc. are routinely inspected by operating personnel.
Some minor adjustments may be made when the need is observed.
More extensive work, as well as minor work on critical pieces
of equipment, is done by maintenance personnel after they
receive requirest by the operator.

          In five of the six refineries, equipment files are
kept on pumps and compressors.  Seal failures and packing leaks
are recorded.  However, valve maintenance records were kept at
only one refinery.
                             508
-------
          Maintenance personnel were generally not assigned
permanently to a particular unit in the smaller refineries.
They could be assigned to specific refinery areas which might
include several process units.   Some maintenance people are
assigned to major process units in large refineries.

          Three of the six refineries reported that 17 percent,
18 percent and 20 percent of the operating budget is  devoted to
maintenance.  One reported that 44 percent of its manpower was
devoted to maintenance.  No information on the criteria used to
establish these numbers was available.

          Significant differences in emission rates were not
found amont the refineries.  This would indicate that the
variations in maintenance programs found do not affect the
emissions rates.

7.2       PROCESS UNIT TURNAROUND PROCEDURES

          Most normal maintenance in a refinery can be performed
while running, but some major items require that the  unit be
shut down and opened.  Since maintenance personnel must physi-
cally enter the vessels to work,  the entire unit must be purged
of all hydrocarbons and tested to insure that it is "gas free".
This large scale overhaul of a processing unit is called a
"turnaround".   A survey was made to determine the frequency of
turnarounds on various process units as well as the disposition
of the purged hydrocarbons.

          The following purging procedure is typical  of industry
practice.   The unit is shut down and process gases are vented to
a vapor recovery system,  if available,  or to the flare.   Then
steam is charged to the unit to strip out the remaining hydro-
carbons.  Most of this steam is vented to a closed blowdown
                              509
-------
system which will remove condensed water and route the gases  to
the flare.  A few "high-point" vents are opened to the atmos-
phere during the latter stages of steaming out, but it is  felt
that there is little significant hydrocarbon evolution by  that
time.  Then the steam flow is stopped and the unit is cooled,
thus condensing the steam.  The condensate is drained off.
Atmospheric vents must be open at this stage to prevent  the
formation of a destructive vacuum.  Then the vessel manways  are
opened and the interiors are gas tested.  This procedure is
thorough and effective, and its overall impact on fugitive
emissions is negligible, especially in light of the infrequent
nature of its occurrence.

          The frequency of shutdowns for various units at  one
refinery is pres.ented below.  These frequencies are typical  of
the refining industry.

               TABLE B7-1.  SHUTDOWN FREQUENCY
                         Times Down in          Scheduled Period
      Unit               Last 12 Months         Between Turnarounds
Crude Unit
Crude Unit
Catalytic Cracker
Fuel Reformer
Naphtha HDS
Alkylat iun
Aronatics Reformer
Aromatics Extraction
1
1
1
0
0
1
2
1
1 year
1 year
1 year
1 year
3 years
1 year
1 year
3 years
Only the Aromatics Reformer had  exceeded  its  scheduled down times
with one unscheduled shutdown  for  catalyst  regneration.
                              510
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7.3       BLIND CHANGING

          A blind changing survey was included in this study
largely because of the results of the Los Angeles County study.
It was initially believed that the. practice of routinely changing
pipeline blinds is unusual.  This belief has been substantiated
in Refineries "A" through "I".  Only when handling very expensive
and exotic materials, such as some lube oil stocks, would the use
of blinds be warranted as a means of controlling direction of
flow to prevent any cross-contamination.  The refineries reported
that they do not routinely change a significant number of blinds.
Most blind changing takes place during the start-up or shutdown
of a unit, and at these times, the unit has generally been purged
of hydrocarbons.  The refineries were unable to supply any detailed
information on the times, the hydrocarbon properties, or amounts
spilled during the limited amount of blind changing they did.

7.4       SAMPLING PROCEDURES

          Quality control sampling in a modern refinery can
potentially add significantly to the overall fugitive emissions.
It is very difficult to quantify the emissions from sampling
because of their irregular and transient nature.  General surveys
were made of sampling, flushing and sample waste disposal proce-
dures.  It was hoped that this information could be correlated
into a sampling emission factor.

          At one large refinery, laboratory personnel were observed
while drawing routine liquid samples in the field.  Line flushings
were routed to a covered oily water drain system with a maximum
of 18 inches free fall and minimum exposed retention time (i.e.,
less than 2 minutes).  Readings were taken with the J. W. Bacharach
"TLV Sniffer" at the drain entrance immediately before and after
sampling.  No significant difference in readings was discernible,
                             511
-------
and the absolute parts per million readings were below the
selected sampling limit of 200 ppm.  Thus, it was concluded that
the flushing of liquid samples did not significantly contribute
to the fugitive emission load at this refinery.

          A common control test for light hydrocarbon fraction-
ators, the reflux end-point, or "boil-away end-point", may cause
significant emissions.  In this test, 100 milliliters of column
reflux are collected in a graduated vessel with a conical
bottom.  Since the reflux of these "stabilizer" towers is
primarily butane and lighter hydrocarbons, the sample will begin
to evaporate at ambient conditions.  The vessel is then fitted
with a two-hole stopper, one side  of which held a thermometer.
The sample is allowed to boil away, and the temperature noted
when 5 milliliters remain.  This value is the reflux end-point,
or more precisely, the 95 percent  point on the distillation
curve.  At one refinery, it was observed that approximately
400 milliliters were flushed to the atmosphere in order to
obtain a sample representative of  current operations.  A survey
of the operating units revealed that this test was routinely run
33 times per day at one large refinery.  Therefore, 16.5 liters
of light hydrocarbon were lost to  the atmosphere per day.
Assuming that this material may be characterized as butane, this
would represent an emission of 0.87 pounds per hour or 21 pounds
per day.  The number of reflux end-point tests reported by the
refineries varied from 6 to 33 per day.  Thus, the losses from
this test varied from 4 to 21 pounds per day.

          The overall sample load at one large refinery was
approximately 200 samples per day.  Of these, about 40 percent
were gas samples for chromatographic analysis, about 24 percent
were volatile liquids (naphtha or  lighter), and about 36 percent
were nonvolatile liquids.   Sample wastes were emptied into one
-------
of two slop oil collection systems, one for naphtha and one for
heavier materials.

          The six refineries responding to the survey reported
sample loads of 50 to 200 samples per day.

7.5       BLENDING OPERATIONS

          Although blending operations were not considered for
sampling as a refinery process module, they do employ many of
the same pieces of equipment and are therefore subject to fugi-
tive emissions.   The only unique piece of equipment would be the
mechanical tank mixers.   This emission source consists of a low-
pressure seal on a rotating shaft.   The pump emission factors
should not be used as estimates of emissions from this source
for two reasons:  (1) only a few samples were obtained from these
sources and there are no data to suggest that the pump emission
factors would be appropriate, and (2) these seals are often
exposed to vapor rather than liquid, particularly when vertical
mixers are employed.   A portion of the survey included questions
to determine what facilities are allocated to blending at each
refinery.

          One large refinery uses only batch blending.  This is
done in two parallel systems, one for leaded gasolines and one
for unleaded.  These two share no common facilities.  Agitation
in the blending tanks is provided by side-entering mechanical
mixers.  Emissions control on the leaded system is by floating
roof,  while the unleaded system uses a vapor recovery system.
This is a conventional compression-absorption-stripping system
using light cycle gas oil from the catalytic cracker as the
absorption medium.  There are nine tanks involved in this
operation,  six in the leaded system and three in the unleaded.
                             513
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          Another large refinery blends all gasoline using in-
line blending.   Both pump-around loops and mechanical mixers are
used to agitate tanks.  There are eight tanks used in blending
service, and they are all equipped with floating roofs.   Two
independent, parallel blending systems are employed.

          A small refinery reported using batch blending.   They
employ only two tanks in blending service.  Both are equipped
with vapor recovery systems, and pump-around loops are used to
agitate these tanks.

          Another refiner employs six tanks in their single
train, batch blending system.  All six tanks are equipped with
floating roofs.
                             514
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7.6
CONVERSION FACTORS
          To Convert j'rom
          Btu
          bbl
          gal
          ton
          Ibs
          cm
          ft3
          psi
          g/gal
          Btu/bbl
          kWh/bbl
          Ib/bbl
          lb/106 Btu
          grain/ft3
          gal/MMcf
          gpm
          lb/1000 gal
To
kcal
a
a
kg
kg
in
m3
kg/cm2
g/*
kcal/£
kWh/£
kg/A
g/Mcal
g/m3
£/(hm)3
m3/hr
mg/£
Multiply By
0.252
159.0
3.785
907.2
0.454
0.394
0.0283
14.223
0.264
0.0016
0.0063
0.0285
18.0
2.2.9
133.7
0.227
119.8
                              515
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                                 TECHNICAL REPORT DATA
                             st: rcsd /niisiic lions or she reverse it/ore completi
  . RFPOST NO.
  EPA-600/2-80-075c
                                                      13. RECIPIENT'S AC
 4, T:7LE AND SUSTITLc
  Assessment of Atmospheric Emissions from
  Petroleum Refining: Volume 3. Appendix B
             5. REPORT DATE
            April 1980
 7. ALi
                                                      8. PERFORMING ORGANIZATION REPORT NO.
  E.G. Wetherold, L. P. Provost, and C.D. Smith
 •3. PERFORMING ORGANIZATION NAME AND ADDRESS
  Radian Corporation
  P.O. Box 9948
  Austin. Texas  78766
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office of Research and Development
 Industrial Environmental Research Laboratory
 Research Triangle Park, NC  27711
             5. PERFORMING ORGANIZATION CODE
             10. PROGRAM ELEMENT NO.
             1AB604      	
             iTcONTRACf/GHIANT NO.
             68-02-2147, Exhibit B
             13. TYPE OF REPOH~ AND PERIOD COVERED
             Final; 3/76-6/79	
             14. SPONSORING AGENCY CODE
              EPA/600/13
  . SUPPLEMENTARY NOTFS
 919/541-2547.
                    IERL-RTP project officer is Bruce A. Tichenor,  Mail Drop 62,
 16. ABSTRACT
          The report gives results.of-a 3-year program to assess the: environmental.
  impact of petroleum refining atmospheric emissions. This volume contains a de-
  tailed compilation of the data and a summary of the results obtained from measure-
  ments taken at 13 refineries throughout the U.S.  The sampled sources included
  valves, flanges, pump and compressor seals, relief valves,  drains, cooling towers,
  oil/water separators, dissolved air flotation units, and various process stacks.<^—~
  Nonmethane hydrocarbon emission factors for the various fugitive emission sources
  arc presented. Nomographs illustrating the  relationship between screening (monitor-
  ing) values  and emission rates are included.  Correlations of leak rates with various
  process and equipment parameters are graphically displayed.  The frequency and
  distribution of emission sources in refineries are estimated.  The effect of simple
  valve maintenance on  valve leak rates  is  described.  Many organic species present
  in liquid process streams and vapor emissions were identified and quantified.  These
  species and their concentrations in the various streams are listed.
17.
                             KEY WORDS AND DOCUMENT ANALYSIS
 Pollution           Maintenance
 Petroleum Refining Organic Compounds
 Assessments
 Sampling
I Analyzing
 Hydrocarbons
                                          b.lDENTIFIt.HS/UPEN cNU = D TF RMS
Pollution Control
Stationary Sources
Nonmethane Hydro-
 carbons
                        c.  COSATI FieUl/Group
                         13B
                         13H
                         14B
                        07C
15E
  D I S f H i " \j r I <_• \ STATEMENT
 Release to Public
i?A Form ZZ21-1 ('i•^^^
                                          19 SECURITY CLA5S (This Report)
                                          Unclassified
                                                                  21. NO. OF
20. SECURITY CLASS (Tins page)
Unclassified
                                                                  22. PRiCE
-------