GPA TP-20 - Effect of Ammonia On LP-Gas Odorant

G P A TP-20 7b 3824679 0017873 T58
Technical Publication
TP-20
Effect of Ammonia on LP-Gas Odorant
J. W. Goetzinger
D. L. Ripley
National Institute for Petroleum Energy Research
Bartlesville, Oklahoma
May, 1996
6526 East 60th Street . Tulsa, Oklahoma 74145 . Phone: 918/493-3872 . Fax: 9181493-3875
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Copyright Gas Processors Association

Provided by IHS Markit under license with GPA Licensee=Ecopetrol/5915281001, User=Soto, Oscar
No reproduction or networking permitted without license from IHS Not for Resale, 02/18/2021 10:48:43 MST
G P A TP-20 7b m 3824b99 0017874 994 m
DISCLAIMER
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desiring to do so. Every effort has been made by GPA to assure accuracy and reliability of the
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covered.
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G P A TP-20 96 m 3 8 2 4 6 9 9 0037875 8 2 0 m
NIPERIBDM-O220
FINAL REPORT
EFFECT OF AMMONIA ON LP-GAS ODORANT
RESEARCH REPORT
BY
J.W. Goetzinger and D. L. Ripley
Work Performed Under Contract No.

DE-AC22-94PC91008
Prepared for
US. Department of Energy
Bartlesville Project Office
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DISCLAIMER
' h i s report was prepared an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of
their employees, makes any warranty, expressed or implied, or assumes any legal liability ar
responsibility for the accuracy, completeness, or usefuiness of any infomiation, apparatus,
product, or process disclosed, or represents that its use would not infringeprivately owned
rights. Reference herein to any specific commeraai product, process, or service by trade
name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its
endorsement, recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein do not necgsarily
state or reflect those of the United States Government or any agency thereof.
BDM-OKLAHOMA, INC.
PO Box 2565
Bartlesville, Oklahoma 74005

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G P A TP-20 96 3824679 00L787b 7b7
TABLE OF CONTENTS
SUmrnary .................................................................................................................................... 1
Background ................................................................................................................................ 1
Objective .................................................................................................................................... 1
Introduction................................................................................................................................ 2
Recul......................................................................................................................................... 2
Conclusions ................................................................................................................................ 3
Appendix ................................................................................................................................. 11
TABLES
Table 1 Ethyl Mercaptan Gas Chromatograph Peak Areas ................................................. 4

Table 2 Ethyl Mercaptan Concentrations. pprn ................................................................... 5
Table 3 Ammonia Concentrations in Propane. ppm ............................................................ 6
Table 4 Hydrocarbon composition of commercial propane ............................................... 15
Table 5 Initial determination of ethyl mercaptan in test tanks .......................................... 15
Table 6 Initial ammonia concentrations in propane blends ............................................... 17
FIGURES
Figure 1 Change in Ethyl Mercaptan Peak Area with Time;
Propane plus 4 ppm Ammonia in Tank 1-12.......................................................... 7
Propane plus 3 pprn Ammonia in Tank 1-3............................................................ 7
Propane plus 12 ppm Ammonia in Tank 1 4.......................................................... 8
Propane plus 50 ppm Ammonia in Tank 1-10........................................................ 9
Propane with no Ammonia, in Tank 1-11 ............................................................ 10 --``,,,````,`,,,,`````,,`,``,`,-`-`,,`,,`,`,,`---
..
11
GPA TP-20 96 3824679 0037877 bT3
FINAL REPORT
EFFECT OF AMMONIA ON LP-GAS ODORANT

by John W. Goetzinger and Dennis L. Ripley
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SUMMARY
This project was designed to examine the effect, if any, of ammonia contamination ai the ethyl
mercaptan odorant in commercial LP-Gas. Standard 20-pomd propane tanks were filled with
commercial odorized propane, and the ethyl mercaptan concentration in each was determined by gas
chromatography. After the ethyl mercaptan concentration trends had been established, ammonia was
added to the tanks in concentrations ranging from 3 - 78 ppm, comparable to the concentration of ethyl
mercaptan. Liquid propane from each of the tanks was analyzed periodically for both ethyl mercaptan
and ammonia for about 6 weeks, to detect any changes in the concentrations resulting from a reaction.
No change in ethyl mercaptan concentration attributable to the addition of ammonia could be detected.
Therefore, it was concluded that there was M reaction between ammonia and ethyl mercaptan, and
that contamination of propane with low concentrations of ammonia would have m effect on the
concentration of ethyl mercaptan odorant.,
BACKGROUND
Although ammonia is not a naturally occurring contaminant of LP-Gas, certain industry practices,
including dual use of transportation or storage equipment, may inadvertently result in contamination of
LP-Gas by ammonia. For example, tank trucks used for transporting LP-Gas in the winter are also
frequently used to transport liquid ammon,ia during the summer months. Regulations require that tanks
that have been used for storing or transporting ammonia must be adequately cleaned before they are
used for LP-Gas; however, there is a possibility that inadequate cleaning could leave traces of
ammonia in the tank, which would then contaminate the LP-Gas. Although such contamination is not
considered likely to happen, this project was directed to determining if ammonia will react with ethyl
mercaptan odorant in LP-Gas, reducing the odorant concentration.
OBJECTIVE
The objective of this project was to determine the effect of ammonia contamination ai the concentration
of ethyl mercaptan odorant in LP-Gas.
1
INTRODUCTION
Seven standard 20-pound propane tanks were filled with commercial odorized propane and allowed to
equilibrate. The initial concentration of ethyl mercaptan odorant in the liquid propane was
determined by gas chromatography shortly after the tanks were filled, and the odorant concentration
was then measured periodically over a period of 12 days to determine the stability or rate of decline of
the odorant concentration. After the decline rate of the ethyl mercaptan concentration had been
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established, a small quantity of ammonia was added to six of the tanks. The target concentrations of
ammonia to be added were 5/25, and 50 ppm, with duplicates of each concentration. These target
ammonia concentrations range from less than the normal concentration of ethyl mercaptan to greater
than the typical ethyl mercaptan concentration. Analysis of the propane with Gastec detector tubes
after addition of ammonia showed that the actual ammonia concentrations were about 3 to 4 pprn in two
tanks, 12 ppm in two tanks, 50 ppm in one tank, and 70 ppm in one tank. The seventh tank was left
without ammonia as a reference control.
Following the addition of ammonia, the concentrations of both ethyl mercaptan and ammonia in the
liquid propane in each tank were determined periodically over a period of about 6 weeks to detect any
change in the respective concentrations that would indicate a reaction between ethyl mercaptan and
ammonia. The ethyl mercaptan determinations were accomplished by gas chromatography, using a
packed Chromosil 330 column and an electrolytic conductivity detector. The ammonia concentrations
were determined with Sensidyne Gastec gas detector tubes. Details of the experimental procedures are
contained in Appendix 1.
RESULTS
After ammonia was added to the propane, the liquid propane in each tank was analyzed for both
ammonia and ethyl mercaptan at frequent intervals in order to determine any significant change in
their concentrations, which would signal a possible reaction between the ammonia and ethyl
mercaptan. The analyses were performed each day for the first 3 days, then every few days, and after
2 weeks about once a week, over a total time period of about 6 weeks after the ammonia was added, or
over 7 weeks after the tanks were first filled with propane.
A sample of liquid propane was taken from each of the seven tanks, allowed to evaporate, and
analyzed at each time period. Each sample of vaporized liquid propane, contained in a Tedlar bag,
was analyzed first for ammonia, using a single Gastec detector tube, then for ethyl mercaptan by gas
chromatography. Several GC determinations were made ai each sample and the individual results
averaged to give the ethyl mercaptan peak area for each sample. The ethyl mercaptan peak areas for
the propane samples from all seven tanks, both before and after addition of ammonia, are summarized
in Table 1.Table 2 shows the same results converted to pprn concentration of ethyl mercaptan. The ppm
values were computed from the sample peak areas compared to the average peak area of the 50 ppm
calibration blend.

2
The data are also shown graphically in Figures 1through 7, in which the ethyl mercaptan peak areas
are plotted against the time the propane was in each test tank.
The measured concentration of ethyl mercaptan in propane samples from each tank varied somewhat
from day to day, due to inherent variability of the GC procedure and response of the electrolytic
conductivity detector, but there was a small general downward trend in ethyl mercaptan concentration
in all the tanks. Although the decline rate was faster in some tanks than in others, in each tank i t
appeared to be the same both before and after ammonia was added. Tank 1-11,which did not have
any ammonia added, exhibited the greatest decline in ethyl mercaptan concentration.
In all the tanks, there appeared to be a drop in ethyl mercaptan concentration at the time the ammonia
was added, with the concentration subsequently increasing again. The magnitude of the concentration
drop did not appear to be related to the quantity of ammonia added, and it was also apparent in
propane from the tank to which m ammonia had bem added. Therefore, it was concluded that the
apparent drop in ethyl mercaptan concentration was simply an artifact of the analysis, caused by
variability in the gas chromatograph and detector. All tanks exhibited very similar levels of ethyl
mercaptan concentration throughout the entire test period, with m indication of any reaction of the
ethyl mercaptan with ammonia. In fact, as mentioned previously, the greatest change in the ethyl
mercaptan concentration occurred in the tank with no ammonia.
ïhe ammonia concentrations, as determined by Gastec detector tubes, are shown in Table 3. At the low
and intermediate concentrations, there appeared to be a slow decline in the ammonia concentration over
the course of the study, while in the two high ammonia concentration blends the ammonia concentration
remained constant within the reproducibility of the detector tubes.
CONCLUSIONS
Three different concentrations of ammonia were added to commercial odorized propane from a local
supplier to determine if there was any reaction between the ammonia and the ethyl mercaptan odorant
in the propane. The addition of ammonia to the propane had m detectable impact an the ethyl
mercaptan concentration, although the ethyl mercaptan concentration in all the test tanks decreased
slowly with time. The decrease in ethyl mercaptan concentration was actually greater in the tank
that contained no ammonia than in any of the tanks to which ammonia had been added.
Based on our experimental results, we concluded that there is m reaction between low concentrations of
ammonia, which might occur if a tank were contaminated with traces of ammonia, and the ethyl
mercaptan odorant in commercial propane. These experimental results indicate that ammonia does not
have any effect on the ethyl mercaptan odorant, and does not reduce the concentration of the odorant.
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3
Table 1 Ethyl Mercaptan Gas Chromatograph Peak Areas
Days Days
after after
Propane Ammonia
Date Fill Added Tank 1-12Tank 1-3 Tank 1-4 Tank 1-5 Tank 1-10Tank 2-2 Tank 1 - 1 1
Nov. 15 O 364,650 347,241 353,988 357,198
Nov. 16 1 337,133 373,925 352,422
Nov. 17 2 31 8,269 350,304 346,162 349,854 344,145 339,658 320,902
Nov. 20 5 31 3,477 342,586 331,330 334,985 325,419 336,018 303,512
Nov. 27 12 301,152 339,798 325,726 344,522 328,775 350,435 299,430
Nov. 28 13 AMMONIA ADDED, ppm NO

3.5 2.6 12 12 50 78 AMMONIA
Nov. 29 14 1 295,354 316,499 312,753 314,673 297,856 315,622 262,570
Nov. 30 15 2 279,466 302,660 31 8,073 298,469 283,991 321,031 274,789
Dec. 1 16 3 299,459 302,682 323,581 322,940 31 1,857 327,128 285,309
Dec. 4 19 6 290,924 306,870 296,530 31 1,248 296,544 329,084 266,554
Dec. 8 23 10 288,318 314,383 306,968 31 8,053 295,698 337,630 272,116
Dec. 13 28 15 264,734 302,085 291,129 306,049 '282,345 31 9,599 246,319
Dec. 20 35 22 267,981 292,772 297,636 278,575 286,800 320,855 234,199
Dec. 29 44 31 269,437 298,206 303,695 314,958 285,384 334,125 256,012
Jan. 5 51 38 276,751 304,845 308,834 31 5,749 287,833 332,517 249,396

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G P A TP-20 76 3824677 OOL788L 0 2 4 =
Table 2 Ethyl Mercaptan Concentrations, ppm
Days Days
after after
Propane Ammonia
Date Fill Added Tank 1-12 Tank 1-3 Tank 1-4 Tank 1-5 Tank 1-10 Tank 2-2 Tank 1-11
~
Nov. 15 O 51.6 49.1 50.1 50.5
Nov. 16 1 47.7 52.9 49.9
NOV. 17 2 45.0 49.6 49.0 49.5 48.7 48.1 45.4
Nov.20 5 44.4 48.5 46.9 47.4 46.1 47.6 43.0
Nov.27 12 42.6 48.1 46.1 48.8 46.5 49.6 42.4
Nov. 28 13 AMMONIA ADDED, ppm NO

3.5 2.6 12 12 50 7 8 AMMONIA
Nov.29 14 1 41 .8 44.8 44.3 44.5 42.1 44.7 37.2
Nov.30 15 2 39.5 42.8 45.0 42.2 40.2 45.4 38.9
Dec. 1 16 3 42.4 42.8 45.8 45.7 44.1 46.3 40.4
Dec. 4 19 6 41.2 43.4 42.0 44.0 42.0 46.6 37.7
Dec. 8 23 10 40.8 44.5 43.4 45.0 41.8 47.8 38.5
Dec. 13 28 15 37.5 42.7 41.2 43.3 40.0 45.2 34.9
Dec. 20 35 22 37.9 41.2 42.1 39.4 40.6 45.4 33.1
Dec. 29 44 31 38.1 42.2 43.0 44.6 40.4 47.3 36.2
Jan. 5 51 38 39.2 43.1 43.7 44.7 40.7 47.1 35.3
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5
Table 3 Ammonia Concentrations in Propane, ppm
Days after
Ammonia
Date Added Tank 1-12 Tank 1-3 Tank 1-4 Tank 1-5 Tank 1-10 Tank 2-2
Nov. 29 1 3.5 2.6 12 12 50 78
Nov. 30 2 2.8 2.8 10 10.5 45 68
Dec. 1 3 3 2.5 9 11 45 78
Dec. 4 6 2.5 1.8 10 10.5 50 80
Dec. 8 10 2.5 2.2 9 12.2 48 80
Dec. 13 15 1.3 4 9.7 10.5 45 80
Dec. 20 22 3 1.8 9 10.5 50 85
Dec. 29 31 2.4 2.4 8.5 9.5 50 80
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Jan. 5 38 2.2 1.8 8 10.5 48 85
6
G P A TP-20 96 m 3824b99 O O L 7 ô ô 3 9T7 m
400,000
350,000
300,000
(A
250,000
a "3Added
Y 200,000
n 150,000
100,000
50,000
O
O 10 20 30 40 50 60
Days after filling with propane
Figure 1 Change in Ethyl Mercaptan Peak Area with Time; Propane plus
4 ppm Ammonia in Tank 1-12
400,000
350,000
300,000 -- I
I
-
I I
(A
d
250,000 i
I
"3 Added
Y 200,000
n 150,000
100,000
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50,000
o 1 I I1 I I 1l I
O 10 20 30 40 50 60
7
= 3824699 0037884 8 3 3
~~~
G P A TP-20 9b
400,000
T
350,000
300,000 --
-I
-
I -
I I
CR
250,000 "3 Added
4
Y
200,000
I
n 150,000
100,000
50,000
I I I I
I
I
O 10 20 30 40 50 60
400,000T
250,000 --
a
Y
o
200,000
150,000
100,000
50,000
i
o ! , I I 1 ,l 1
I
O 10 20 30 40 50 60
Figure 4 Change in Ethyl Mercaptan Peak Area with Time;Propane plus

8
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~ ~ ~ ~
G P A TP-20 96 m 382467% 0017885 7 7 T m
(A
250,000 -- "3Added
a --
Y
200,000
QI 150,000--
o.
100,000--
50,000 --
o : I I 1 i 1 4
O 10 20 30 40 50 60
400,000
350,000 I
H
300,000
E 250,000 "3 Added
Y 200,000
nQI. 150,000
100,000
50,000
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9
~
G P A TP-20 96 m 3 8 2 4 6 7 9 0017886 bob m
(R I
2 250,000 --
a --
x 200,000
8 150,000 --
n
100,QOO --
50,000 --
Q I I I I I I i
O 10 20 30 40 50 60
Days after filling wlth propane
Figure 7 Change in Ethyl Mercaptan Peak with Time; Propane with no

Ammonia, in Tank 1-11
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10
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GPA TP-20 96 3824699 0037887 5 4 2
APPENDIX I
EXPERIMENTAL PROTOCOL
Gas Chromatograph Procedure for Propane Analysis
Ethyl mercaptan concentration in the propane was determined by gas chromatography, using
the same equipment and procedure as used previously for analyzing propane for ethyl mercaptan. (GPA
RR-143,1993). The equipment and chromatograph operating conditions are listed below:
Chromatograph: Hewlett-Packard Model 5880A, with electronic integrator.

Column: 1/8 inch diameter by 6 feet long Teflon tubing, packed with "Chromosil 330" (a
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specially treated silica gel), purchased from Supelco, Inc., Catalog No. 1-1496.
Sample Injection Valve: Valco &port gas injection valve.
Sample Loop: 1/8 inch Teflon tubing, with capacity of 0.5 mL.
Detector: Finnigan (formerly Tracor) Hall Model lo00 electrolytic conductivity
detector.
Chromatograph operating conditions:
Carrier gas: Helium, at flowrate of 30 mL/ minute
Column temp.: 50°C (Isothermal)
Detector operating conditions:
Reactor temperature 800°C
Air flow rate 10mL /minute
Solvent Methanol
Solvent flow rate 0.66 mL/ minute
Vent: Open first 1.2 minutes after injection
With the chromatograph operating conditions listed above, the retention time of ethyl
mercaptan was 2.2 minutes. Propane eluted in less than one minute, and by having the detector vent
open for the first 1.2 minutes after sample injection, most of the propane was vented before it reached
the detector cell.
Chromatograph Calibration
A calibration blend containing a known concentration of ethyl mercaptan in propane vapor

was prepared and used to determine the retention time and detector response of ethyl mercaptan.
Preparation of the calibration blend was a two step process. The first step was preparation of a high
concentration blend of ethyl mercaptan in propane. This concentrated blend was prepared in a 1-gallon,
Teflon-lined stainless steel sample cylinder with stainless steel valves. The cylinder had been
11
previously used to contain similar blends of ethyl mercaptan in propane. It was evacuated to remove
the previous blend, then a small quantity of liquid ethyl mercaptan was measured in a microliter
syringe and injected into the evacuated cylinder through a septum and ball valve. Immediately after
injection of ethyl mercaptan, the cylinder was filled with unodorized pure-grade propane vapor to a
pressure of 30 psig. The ethyl mercaptan concentration in the cylinder, calculated from the volume of
liquid injected and the final propane pressure, was 500 pprn (mole/mole).
A lower concentration calibration blend was prepared from the concentrated cylinder blend
by dilution of the concentrated blend with additional unodorized propane vapor. A Tedlar bag with
stainless steel fittings and stainless steel valve was evacuated, then a measured quantity of the
concentrated cylinder blend was injected into the evacuated bag with a syringe. The proper volume of
unodorized pure-grade propane vapor was added to the bag to dilute the concentrated blend by a factor
of 10, producing a working calibration blend with an ethyl mercaptan concentration of 50 ppm
(mole/mole).
A fresh 50 ppm calibration blend was prepared from the concentrated cylinder blend and
analyzed at the same time each set of samples were analyzed, following the same procedure as used for
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the samples. There was some day-to-day variation in the detector response to ethyl mercaptan;
however, the overall average ethyl mercaptan peak area of all determinations an the 50 ppm
calibration blend was 353,331 integrator units, with a relative standard deviation of 6.48 percent.
Propane Analysis Procedure
The experimental plan required determination of the ethyl mercaptan concentration in the
liquid phase propane, In order to analyze the liquid, a small quantity of the liquid propane was
transferred from the tank to a Tedlar plastic bag and allowed to vaporize, then the vapor was injected
into the chromatograph.
The plastic bags were constructed in-house from Tedlar film. A stainless steel fitting and
stainless steel toggle valve were installed QI each bag. The bags were flushed with nitrogen and
evacuated before use.
The following procedure was used to obtain liquid propane samples for analysis. The
propane tank was inverted and the valve was opened very briefly to flush the valve and adapter
fitting with liquid propane. The toggle valve on an evacuated Tedlar bag was connected to the adapter
fitting m the tank valve. The tank valve was opened completely, then the toggle valve an the bag
was rapidly opened and Closed to allow a small quantity of liquid propane to flow into the bag. The
tank valve was closed, and the bag was disconnected from the tank. The liquid propane in the bag was
allowed to vaporize, then analyzed as vapor.
Several samples of vapor phase propane were also taken from the tanks and analyzed. To
obtain vapor phase samples, the tank was left upright, an evacuated Tedlar Bag was connected to the
tank valve, and the tank valve and bag valve were opened briefly to allow the propane vapor to flow
into the bag.

12
G P A TP-20 96 = 3 8 2 4 b 9 9 0037889 315 m
For Gc analysis of the propane in the Tedlar bag, either vapor phase or vaporized liquid,
the bag was COM@^ directly to the inlet of the gas injection valve QI the chromatograph with a
suitable length of 1/8 inch OD Teflon tubing. With the injection valve in the "Load" position, the
propane vapor was pulled from the bag through the injection valve and sample loop by means of a
small vacuum pump COM^^ to the outlet fitting of the injection valve. Rotating the valve to the
"Inject" position then injected the vapor contained in the sample loop into the chromatograph column.
Occasional samples of the liquid propane were also analyzed for ethyl mercaptan with
Sensidyne Gastec detector tubes, Type 72, for comparison with the GC results. The detector tube was
attached via a short length of flexible tubing to the Tedlar bag containing the vaporized liquid
propane sample, and a known volume of the propane vapor was drawn through the tube with the
Censidyne Gastec pump. The length of yellow color stain in the tube indicated the ethyl mercaptan
concentration, with a claimed accuracy of k 25 percent. The Type 72 detector tubes performed quite well
when used with the calibration blend, which was composed of ethyl mercaptan in pure-grade propane.
Two separate Gastec detector tube determinations of ethyl mercaptan in the calibration blend, QI
different days, gave a value of about 40 ppm both times, which is within 25 percent of the calculated
value of 50 ppm.
However, Gastec Type 72 detector tube determinations of ethyl mercaptan in the commercial
propane used for the test blends were unsuccessful. in every case, when the commercial propane was
drawn through the detector tube, the indicating material throughout the entire length of the tube
changed from its original white color to a pale brown, with a slight yellow color at the inlet aid of the
tube but m sharp distinction between the yellow color and the remainder of the material. This was
probably due to interferences from ethylene and/or propylene with the Type 72 tubes used.
Late in the project, another type of detector tube for mercaptans, Gastec Type 75, was
obtained. Type 75 tubes use a different chemistry, which is not affected by the same interferences as
Type 72 tubes, and gave a very distinct color change for ethyl mercaptan in the commercial propane.
The ethyl mercaptan concentration range indicated by these tubes for the calibration blend and propane
samples from all the test tanks was 35 to 40 ppm, which was the same as indicated by gas
chromatography within the accuracy of the detector tubes.
Propane Tanks
The propane tanks used in this project were standard steel propane tanks with a capacity of
20 pounds of propane, which are commonly used on portable gas grills. They were the same tanks t h a t
had been used in a previous research project to investigate treatment with passivating agents as a
means of reducing odorant depletion in new steel containers. (GPA Research Report RR-143, December
1993.) The tanks had been purchased new at a local retail store prior to use in the passivation research
project. in that project, the tanks were first opened to the atmosphere for several months to create a
reactive surface. The tanks were then treated with potential passivating agents, with the goal of
finding an agent or agents that would passivate the interior surface of a new tank to prevent loss of
ethyl mercaptan from propane stored in the tank. After a tank had bem treated with a candidate
passivating agent, it was filled with commercial liquid propane containing ethyl mercaptan odorant.
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13
G P A TP-20 9b W 3824649 O037890 037
The liquid propane was then analyzed periodically over a period of time to determine the stability or
rate of decline of the ethyl mercaptan concentration. At the md of the project, the tanks were left
filled with odorized propane and stored outdoors at ambient conditions.
Seven tanks from the passivation project were selected for use in the current study of the
effect of ammonia on ethyl mercaptan odorant in propane. Six were the treated, passivated tanks that
had exhibited the smallest loss of ethyl mercaptan from stored propane. The ID numbers of these six
treated tanks were 1-3, 1-4, 1-5, 1-10, 1-11, and 1-12. The seventh tank, ID number 2-2, had not beai
opened to the atmosphere and had not been given any passivating treatment; it had simply beai used,
as purchased, to store propane. All seven tanks were still filled with o d o r i d propane, which had
been in the tanks for approximately 2 years.
Propane Supply
An aliquot of liquid propane that had been left in the tanks from the previous project was
withdrawn from each tank and analyzed for ethyl mercaptan by gas chromatography to determine the
existing odorant concentration. The experimental plan was that if the stored propane still contained an
adequate concentration of ethyl mercaptan, ammonia would simply be added to the propane that was
already in the tanks. However, the analysis showed that very little ethyl mercaptan remained in any
of the tanks. Consequently, the tanks were emptied of liquid propane, leaving a slight positive
pressure of propane vapor in each tank to prevent entry of air.
The seven test tanks were then refilled with fresh commercial odorized propane, which was
purchased from a local propane distributor. The fresh propane in each tank was analyzed for ethyl
mercaptan, either on the same day the tanks were filled or the next day, to establish the initial
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concentration of ethyl mercaptan in each tank. One sample of the fresh propane was also analyzed for
hydrocarbon composition to determine the purity of the propane.
Hydrocarbon Analysis of Propane
A sample of the fresh liquid propane was analyzed for hydrocarbon composition on a gas
chromatograph equipped with a flame ionization detector. The chromatograph column was a 60 meter
fused silica column containing a thin coating of methyl silicone stationary phase. The hydrocarbon
composition analysis for this commercial propane is shown in Table 4. According to the analysis, i t
contains 91.2 mole percent propane, with a significant concentration of ethane and smaller amounts of
other hydrocarbons. The specifications for commercial propane simply state it shall be composed
predominantly of propane.
14
G P A TP-20 9 6 W 382467s 0017841 T73
Table 4 Hydrocarbon Composition of Commercial Propane
Gnnponent Mole Fraction (Percent)

Methane 0.5
Ethane 5.4
Propylene 1.0
Propane 91.2
Unidentified 03
--``,,,````,`,,,,`````,,`,``,`,-`-`,,`,,`,`,,`---
Isobutane 13
Unidentified O2
n-Bu tane 0.1
Initial Ethyl Mercaptan Determination
The fresh liquid propane in each tank was analyzed for ethyl mercaptan by gas
chromatography to establish the initial concentrations of ethyl mercaptan, which are shown in Table
5. Several gas chromatograph determinations were made (3n each sample, and the individual values
were averaged to give the values listed in the table. The table shows both the area of the ethyl
mercaptan peak, as read from the electronic integrator, and the concentration in ppm. The concentration
in pprn was calculated by comparing the sample ethyl mercaptan peak area to the peak area of ethyl
mercaptan in the 50 ppm calibration blend.
Table 5 Initial Determination of Ethyl Mercaptan in Test Tanks

~
Tank Ethyl Mercaptan PPM

Identification GC Peak Area Ethyl Mercaptan
1-3 364,650 50.6
1-4 347,241 48.1
1-5 353,988 49.1
1-10 357,198 49.5
1-11 352,422 48.9
1-12 337,133 46.7
2-2 373,925 51.8
15
G P A TP-20 7 6 W 3824699 0017872 70T W
The calculated concentrations in Table 5 appear to be somewhat higher than the theoretical
value would be if the propane contained 1.5 p o d of ethyl mercaptan per 10,ûûû gallons of propane,
which would be equivalent to about 26 ppm (mole/mole) in the liquid phase. This suggests either that
the propane that was purchased contained more ethyl mercaptan than required, or that the actual
concentration of the calibration blend was lower than calculated. Since all conclusions of this study are
based m relative ethyl mercaptan concentrations, rather than absolute concentrations, an error in
converting to absolute concentrations would have no effect on the results.
Establishment of Ethyl Mercaptan Decline Rate
The liquid phase propane was analyzed periodically over a period of 12 days to determine
the rate at which the ethyl mercaptan concentration declined. At least three samples were analyzed
to obtain the average ethyl mercaptan concentration. Although there was some variation between
tanks, there was a slow decline in the ethyl mercaptan concentration in all seven tanks,
Addition of Ammonia
After the ethyl mercaptan decline rate in the test tanks had been established, ammonia was
added to six of the tanks, ID Numbers 1-3, 14, 1-5, 1-10, 1-12, and 2-2. The target concentrations of
ammonia were 5, 25, and 50 ppm, with duplicates of each concentration. One tank, No. 1-11, was left
without ammonia for use as a reference tank.
The ammonia was anhydrous grade liquid ammonia, purchased from Scott Specialty Gases.
A short length of stainless steel tubing, either 1/8 inch or 1/4 inch OD, with a stainless steel ball valve
at each end, was used to measure and contain the liquid ammonia. One aid of the measuring tube was
connected to the valve on the ammonia cylinder, the cylinder was inverted and the valves were o p e d
momentarily to flush the tubing and valves with ammonia and expel any air. The outlet end of the
measuring tube was then connected to the valve on the propane tank. With the ammonia cylinder still
inverted and the propane tank upright, operation of the valves in the proper q u e n c e filled the
measuring tube with liquid ammonia and then allowed the measured quantity of ammonia to flow into
the propane tank. The ammonia measuring tube was also heated gently to assist transfer of the
ammonia into the propane. The valves were then closed, the ammonia cylinder and measuring device
were disconnected from the propane tank, and the propane tank was shaken and agitated to insure good
mixing of the propane and ammonia. After addition of ammonia, the tanks were allowed to stand
overnight to achieve equilibrium before the propane in the tanks was analyzed for ammonia and ethyl
mercaptan.
Analysis for Ammonia
The concentration of ammonia in the propane was determined with Sensidyne Gastec
detector tubes. A small quantity of the liquid propane was released into an evacuated Tedlar bag, as
described above, and allowed to vaporize. A known volume of the vaporized propane was then drawn
through a Type 3L or 3LA Gastec detector tube with the Sensidyne Gastec hand pump. Ammonia
--``,,,````,`,,,,`````,,`,``,`,-`-`,,`,,`,`,,`--- 16
~~
~
G P A TP-20 76 H 3824677 0037873 ô 4 b m
produced a very pronounced and distinct color change in the detector tube. The concentration of
ammonia in the propane vapor was determined from the length of the color change in the tube. The
ammonia concentrations reported are for single determinations each day.
.
The lowest and highest ammonia concentration blends were reasonably close to the target
concentrations. The intermediate concentration blends were somewhat lower than the target
concentration; however, they were considered to be within the acceptable range. The initial ammonia
concentrations are shown in Table 6.
Table 6 Initial Ammonia Concentrations in Propane Blends
TankID Anunonia
-~
Conc.
1-12 3.5 PPm

1-3 2.6ppm
1-4 12 PPm
1-5 12 PPm
1-10 50 PPm
2-2 78 ppm
--``,,,````,`,,,,`````,,`,``,`,-`-`,,`,,`,`,,`---
17

GPA TP-20 - Effect of Ammonia On LP-Gas Odorant

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G P A TP-20 7b 3824679 0017873 T58

Effect of Ammonia on LP-Gas Odorant

Copyright Gas Processors Association

Copyright Gas Processors Association

EFFECT OF AMMONIA ON LP-GAS ODORANT

Work Performed Under Contract No.

Copyright Gas Processors Association

G P A TP-20 96 3824679 00L787b 7b7

Table 1 Ethyl Mercaptan Gas Chromatograph Peak Areas ................................................. 4

EFFECT OF AMMONIA ON LP-GAS ODORANT

Copyright Gas Processors Association

Copyright Gas Processors Association

Nov. 15 O 364,650 347,241 353,988 357,198

Nov. 16 1 337,133 373,925 352,422

Nov. 17 2 31 8,269 350,304 346,162 349,854 344,145 339,658 320,902

Nov. 20 5 31 3,477 342,586 331,330 334,985 325,419 336,018 303,512

Nov. 27 12 301,152 339,798 325,726 344,522 328,775 350,435 299,430

Nov. 28 13 AMMONIA ADDED, ppm NO

Nov. 29 14 1 295,354 316,499 312,753 314,673 297,856 315,622 262,570

Nov. 30 15 2 279,466 302,660 31 8,073 298,469 283,991 321,031 274,789

Dec. 1 16 3 299,459 302,682 323,581 322,940 31 1,857 327,128 285,309

Dec. 4 19 6 290,924 306,870 296,530 31 1,248 296,544 329,084 266,554

Dec. 8 23 10 288,318 314,383 306,968 31 8,053 295,698 337,630 272,116

Dec. 13 28 15 264,734 302,085 291,129 306,049 '282,345 31 9,599 246,319

Dec. 20 35 22 267,981 292,772 297,636 278,575 286,800 320,855 234,199

Dec. 29 44 31 269,437 298,206 303,695 314,958 285,384 334,125 256,012

Jan. 5 51 38 276,751 304,845 308,834 31 5,749 287,833 332,517 249,396

Copyright Gas Processors Association

Table 2 Ethyl Mercaptan Concentrations, ppm

Nov. 15 O 51.6 49.1 50.1 50.5

Nov. 16 1 47.7 52.9 49.9

NOV. 17 2 45.0 49.6 49.0 49.5 48.7 48.1 45.4

Nov.20 5 44.4 48.5 46.9 47.4 46.1 47.6 43.0

Nov.27 12 42.6 48.1 46.1 48.8 46.5 49.6 42.4

Nov. 28 13 AMMONIA ADDED, ppm NO

Nov.29 14 1 41 .8 44.8 44.3 44.5 42.1 44.7 37.2

Nov.30 15 2 39.5 42.8 45.0 42.2 40.2 45.4 38.9

Dec. 1 16 3 42.4 42.8 45.8 45.7 44.1 46.3 40.4

Dec. 4 19 6 41.2 43.4 42.0 44.0 42.0 46.6 37.7

Dec. 8 23 10 40.8 44.5 43.4 45.0 41.8 47.8 38.5

Dec. 13 28 15 37.5 42.7 41.2 43.3 40.0 45.2 34.9

Dec. 20 35 22 37.9 41.2 42.1 39.4 40.6 45.4 33.1

Dec. 29 44 31 38.1 42.2 43.0 44.6 40.4 47.3 36.2

Jan. 5 51 38 39.2 43.1 43.7 44.7 40.7 47.1 35.3

Nov. 29 1 3.5 2.6 12 12 50 78

Nov. 30 2 2.8 2.8 10 10.5 45 68

Dec. 4 6 2.5 1.8 10 10.5 50 80

Dec. 8 10 2.5 2.2 9 12.2 48 80

Dec. 13 15 1.3 4 9.7 10.5 45 80

Dec. 20 22 3 1.8 9 10.5 50 85

Dec. 29 31 2.4 2.4 8.5 9.5 50 80

Figure 4 Change in Ethyl Mercaptan Peak Area with Time;Propane plus

Copyright Gas Processors Association

G P A TP-20 96 m 382467% 0017885 7 7 T m

G P A TP-20 96 m 3 8 2 4 6 7 9 0017886 bob m

Figure 7 Change in Ethyl Mercaptan Peak with Time; Propane with no

GPA TP-20 96 3824699 0037887 5 4 2

Gas Chromatograph Procedure for Propane Analysis

Chromatograph: Hewlett-Packard Model 5880A, with electronic integrator.

A calibration blend containing a known concentration of ethyl mercaptan in propane vapor

Propane Analysis Procedure

Copyright Gas Processors Association

Hydrocarbon Analysis of Propane