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Measurement of

Hydrogen Sulfide
in Crude Oil

Author: Ian Mylrea


Date 10th March 2014
Issue 1.1

Stanhope Seta,
London Street,
Chertsey,
United Kingdom
KT16 8AP
Tel. +44 1932 564391
www.stanhope-seta.co.uk

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Ian Mylrea

Page 2 of 15

Executive Summary
Crude oil samples from Bakken, North Dakota were tested by two methods. This was a very
successful experiment. Repeatability for the proposed Crude Oil Appendix to ASTM D7621/IP 570
Procedure A (with Vapor Phase Processor) was similar to the precision studies done for distillate and
marine residual fuels and is estimated to be 9%. A strong correlation was found between the liquid
phase results from ASTM D7621/IP 570 and the vapor phase results for a modified ASTM D5705
method.
Hydrogen Sulfide in Crude Oil vapor versus liquid phase measurement

D7621 Crude Oil Appendix

140

y = 0.015x
R = 0.97

120
100
80
60
40
20
0
0

2000

4000

6000

8000

10000

D5705 Modified

There are practical advantages to doing the proposed test when compared to the modified ASTM
D5705: smaller test volume which maintains the bulk material volume and headspace; faster the
test can be completed in 25 minutes; the liquid phase result may allow a more precise stoichiometric
calculation of the amount of hydrogen sulfide scavenger to be estimated.
Caution: Storage container vapor phase hydrogen sulfide concentrations should not be used to
estimate liquid phase concentrations (and vice versa) as the vapor phase result depends on the
temperature, the headspace volume and container size and shape. The ASTM D7621/IP 570 liquid
phase results are independent of the container size, shape and the temperature.

Thanks and acknowledgements


We appreciate the contribution to this study by Intertek who allowed us to use their facilities,
provided the samples and carried out the measurements using their in house (modified) ASTM
D5705 procedure.

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Ian Mylrea

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Contents
Executive Summary............................................................................................................................. 2
Thanks and acknowledgements .......................................................................................................... 2
Introduction ........................................................................................................................................ 4
Background ......................................................................................................................................... 4
ASTM D7621/IP 570 Background ........................................................................................................ 5
Methods Modifications for Crude Oil Measurements ........................................................................ 7
Test Protocol ....................................................................................................................................... 7
Results ................................................................................................................................................. 9
Results Discussion ............................................................................................................................. 10
Appendix 1 ........................................................................................................................................ 12
ASTM D7621/ IP 570 Crude Oil Appendix Proposal .......................................................................... 13
References ........................................................................................................................................ 15

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Introduction
The purpose of this study was to show that IP 570/ASTM D7621 can be modified to extend the range
to measure the concentration of hydrogen sulfide in stabilised crude oil. At the ASTM D02 meeting
at Tampa in December 2013, a study was proposed to compare a modified version of ASTM D5705
(Measurement of Hydrogen Sulfide in the Vapor Phase Above Residual Fuel Oils) with the proposed
Crude Oil Appendix to ASTM D7621/IP 570 (Determination of hydrogen sulfide in fuel oils Rapid
liquid phase extraction method). The study would take place a suitable laboratory in the United
States of America which has access to typical samples of crude oil with applicable levels of hydrogen
sulfide.

Background
Hydrogen Sulfide can occur naturally in crude3. In addition to being toxic, hydrogen sulfide is highly
reactive and is responsible for corrosion of infrastructure such as pipelines and rail cars. The recent
increase in production of volatile crude oil in Wyoming, Colorado and North Dakota has lead to a
surge in demand for transportation by railcar as pipeline access was unavailable. In 2008
approximately 10,000 cars were transported by rail, compared to 400,000 in 20131. On May 5th,
2013 a tank in Berthold, North Dakota was found with a sample measuring over 1200 ppm which is
an extremely hazardous level2.
Hydrogen sulfide is a volatile gas at room temperature with a vapor pressure of 252 psig (1740 kPa),
and a boiling point of -60oC. As such, if it is present in a sample then it normally can be found in both
the liquid and vapor spaces within a closed container at normal ambient temperature. It is worth
noting that not all the hydrogen sulfide can transfer to the vapor phase at once. A vapor liquid
equilibrium is achieved which depends on the temperature, how full the vapor space is and what
other volatile components of the crude oil sample are present. Typically a sample containing 70
mg/kg hydrogen sulfide in the liquid phase can give rise to 7000 ppmv in the vapor space above it3.
The concentration in the vapor space is typically measured using a colorimetric gas detector tube to
identify its presence and whether the level is hazardous.
Hydrogen sulfide can be removed by treatment with scavengers. Some scavengers work by reacting
with hydrogen sulfide to form other less harmful compounds. The scavenger dosage required is a
function of how much hydrogen sulfide is present in the liquid phase.
Earlier work in 2011 funded by the CCQTA4 showed that measurement of the hydrogen sulfide
concentration in crude oil was difficult. Since no standardised method for the measurement of
hydrogen sulfide in crude oil had been developed a variety of modified test methods were
simultaneously trialled on a variety of crude oils and crude oil condensates. The report concluded
that results between methods did not agree. When examining the data in the report significant
differences and so far unexplained anomalies are present (GC results seemed to max out at around
70 to 80ppm; the titration method gave 0ppm when the other three methods showed hydrogen
sulfide was present; GC and titration gave 10s of ppm in liquid whilst the vapor method showed
almost no hydrogen sulfide was present, which was supported by the modified ASTM D7621/IP 570
method. However, of the four methods two methods results did make basic sense when compared.
Whilst the actual values differed significantly the following trends were apparent: high hydrogen
sulfide in vapor predicted by D5705 gave relatively high liquid phase hydrogen sulfide by modified

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ASTM D7621/ IP 570; low hydrogen sulfide in vapor predicted by D5705 gave relatively low liquid
phase hydrogen sulfide by modified ASTM D7621/ IP570.
Encouragement was provided in the executive summary to continue the workIt is recommended
that the IP-570 for crude method continue to be developed under the direction and efforts of
Stanhope-Seta, and that the H2S in Crude Measurement Project participants individually continue to
support those efforts by providing access to field experience/expertise and crude petroleum samples
as required.
Figure 1 Data provided by the Canadian Crude Quality Technical Association (CCQTA)
Result (ASTM
D5705)
>2000
0.00
>2000
2.00
268.0
0.75

Sample
1
2
3
4
5
6

Result (ASTM D7621/IP


570)
117
0.00
206
0.05
10.5
0.03

Hydrogen Sulfide in Crude Oil -

ASTM D7621 modified

measurement of vapor phase versus liquid phase

250.0
200.0
150.0
100.0
50.0
0.0
0

500

1000

1500

2000

2500

ASTM D5705

ASTM D7621/IP 570 Background


ASTM D7621/IP 570 was developed to measure hydrogen sulfide in marine fuels and blend streams
and was first standardised in 2009. The test method precision enabled specification writers to
include it in ISO 8217, the marine fuel specification, in 2010, with a maximum limit of 2.00 mg/kg
(liquid phase). A separate hydrogen sulfide in distillate grade marine fuels study was carried out in
2011 which was added to the test method scope. A study into potential interferences revealed that
mercaptans and sulphides could elevate the readings. Extensive research followed, which enabled
the vapor phase process to be developed and in 2012 IP 570 was standardised with a new
procedure, known as Procedure A (Vapor Phase Process). ASTM D7621 which is jointed with IP 570
had similar updates and is currently technically equivalent.

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The method uses a hydrogen sulfide specific detector in conjunction with a cold vapor phase process
to separate hydrogen sulfide from potential interferences. This places the detectors peak signal for
hydrogen sulfide in a specific time frame, similar to chromatography column techniques. Inspection
of the graph produced not only shows the magnitude but also the time which the peak occurred,
giving enormous confidence that the measurement is really hydrogen sulfide. See Figure 2 Relative
Elution for Hydrogen Sulfide and Methyl Mercaptan using VPP & Figure 3 Typical H2S Analyser
output for Hydrogen Sulfide

Figure 2 Relative Elution for Hydrogen Sulfide and Methyl Mercaptan using VPP

Figure 3 Typical H2S Analyser output for Hydrogen Sulfide

A recent innovation in 2013 enabled the test method to employ a liquid phase hydrogen sulfide
standard with a 3 month shelf life, which enabled the accuracy and precision to be confirmed. Test
results obtained from a proficiency testing scheme which uses the standard show very close
agreement between reference values and consensus values. A standard was tested during the tests
of which this paper is the subject, and is discussed later on.
Following recent experiences, three successful round robin (ILS) studies, all with good precision and
extensive research into interferences, coupled with the earlier positive signs in the CCQTA
programme and industry need with the development of an increase in production in the USA, it was

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decided to develop an appendix in the hydrogen sulfide test method to enable wider use for
measuring hydrogen sulfide in crude oil.

Methods Modifications for Crude Oil Measurements


ASTM D7621/ IP 570 Procedure A and ASTM D5705 were modified to cater for the high hydrogen
sulfide concentrations and high vapor pressures.

Figure 4 The test chamber for ASTM D7621/IP 570


ASTM D7621/IP 570 measurements were made with the sample at room temperature. Small sample
sizes such as 0.05 or 0.1mL were employed in order to extend the range of the detector. In addition
the 5 minute equilibrium time no longer applied.
ASTM D5705 measurements were carried out with the sample at 25oC (rather than 60oC) due to the
volatile nature of the samples. Colorimetric gas detector tubes in the range from 1000 to 10000 ppm
(up to 1%) were used.

Test Protocol
Measurements by ASTM D7621/ IP 570 and ASTM D5705 were carried out within approximately 30
minutes of each other.
A 1 litre sample of crude oil from
North Dakota, supplied over 95% full
was gently turned end over end.
Approximately 500ml was placed in
a 1 litre glass bottle and the screw
cap applied. A 4 oz (125mL) glass
bottle was also filled to the top
(95%+). The 1 litre bottle was placed
in a 25oC water bath for 30 minutes. Figure 5 ASTM D5705 Apparatus and a crude oil sample
During the 30 minutes one test was carried out on the H2S Analyser using the 4 oz bottle following
ASTM D7621/ IP 570. Attention to replacing the cap promptly after each test was given. After 30
minutes the modified ASTM D5705 procedure was used to determine the vapor space hydrogen
sulfide concentration of the 1 litre bottle. Another test on the H2S Analyser was carried out back to
back with the first from the 4 oz bottle. Effectively one test was done before and one after the ASTM

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D5705 test. Occasionally a 3rd test was done using the modified ASTM D7621/IP 570 to gather
additional data.
Once the results were available the sample was recombined into the original 1 litre bottle and
shaken to lower the hydrogen sulfide concentration. A second full test as described above was
carried out that is the sample was turned gently end over end and then split into the two
containers, placed in a water bath and tested.
This procedure (split, measure, combine, shake) was employed using two different crude oil samples
and various levels to build up a picture of the repeatability for ASTM D7621/IP 570 and for the
relationship between the vapor phase test and the liquid phase test.

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Results
The ASTM D7621/ IP 570 apparatus was verified as per the test method. Tests were then carried out
to determine whether the typical sample injection volumes were practical. Tests were conducted to
demonstrate repeatability for D7621 and also comparison with vapor phase numbers. It was not
always possible to do a D5705 test due to the volume of sample available. More detailed results can
be found in Appendix 1.
D5705 Modified
Vapor Phase H2S
(mg/kg)
9000
7000
6000
2500
2500
0

ASTM D7621/IP 570 Appendix


Standard
Liquid Phase H2S
Deviation
(mg/kg)
(mg/kg)
146
6.4
98
9.5
81
4.4
50
2.4
39
0.1
0
n/a

Hydrogen Sulfide in Crude Oil - vapor


measurement versus liquid phase
measurement
D7621 Crude Oil Appendix

140

y = 0.015x
R = 0.97

120
100
80
60
40
20
0
0

2000

4000

6000

D5705 Modified

8000

10000

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Results Discussion
The main comparison shows that the vapor and liquid results correlate well with R2 = 0.97. The vapor
liquid equilibrium is approximately 66, that is Liquid Phase H2S = 0.015 x Vapor Phase H2S. This is
typical when compared to previous estimates in the literature3, and is only applicable as a
relationship for this particular crude oil, the container proportions (headspace versus liquid space)
and temperature used.
Repeatability was only tested for ASTM D7621 since the sample volume available meant that two
ASTM D5705 tests could not be done at the same time. The average repeatability for ASTM D7621
was 9% (See Appendix 1).
During the initial tests with ASTM D7621/ IP 570 it was observed that the following were important
1. Due to the low sample volumes, getting an accurate weight for the sample was critical. This
was achieved in practice making sure the balance was a 4 place balance, mounted on a
granite block, vibration free, and away from draughts with the doors closed as far as was
practical. The best way to achieve this was to place the pipette in a beaker as shown.

During the main study sample weights from 0.04 and 0.08g were achieved with good
repeatability, equating to 50 and 100 L respectively.
2. The crude oil sample settled over time. This was observed with a sample which had been left
for 24 hours and as it was poured it gradually became less transparent and more opaque
towards the bottom of the container. As the samples were of low viscosity it was decided
during the tests that prior to the ASTM D7621 determination a sample should be gently
turned end over end two times before the sample was taken.
3. It was observed that when injecting the sample into the test chamber during the ASTM
D7621 tests that the pipette should not be released until it has been removed from the test
chamber to avoid drawing in hydrogen sulfide vapor into the pipette and reducing the
concentration in the test chamber.

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4. The following table describes the most appropriate volume of charge for the ASTM D7621/
IP 570 Crude Oil Appendix
Hydrogen Sulfide (mg/kg)
0 to 10 mg/kg
10 to 20 mg/kg
20 to 100
100 to 200
above 200

Sample volume
5mL
1 or 2mL
0.1mL
0.05mL
0.025mL

type of device
Syringe
Syringe
Positive Displacement Pipette
Positive Displacement Pipette
Positive Displacement Pipette5

5. The diluent oil used became very full of air during the 5 minutes equilibrium time mentioned
in ASTM D7621/IP 570 (11.3). The equilibrium time was not required as the test chamber
was at ambient and therefore this step was omitted during the testing.
Other observations were as follows
6. Good stability of the samples over time was observed. Even severe shaking of the sample
and leaving open for a few minutes only seemed to change the value by a small amount.
(See tests F and H). However any attempt to blend with either a neutral diluent or zero
hydrogen sulfide crude oil was unsuccessful with the hydrogen sulfide being immediately
lost.
7. Not all hydrogen sulfide is purged during the D5705 tests. Effectively the value obtained by
this method will be a function of temperature (controlled at 60 oC normally or 25 oC for these
tests), headspace and time allowed for the equilibrium to form (3 minutes).

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Appendix 1
Notes
Tests A, B, C, J and K were conducted following the test protocol i.e. in parallel by both methods.
Tests B final test (0.00 mg/kg) was an experiment to demonstrate that all the hydrogen sulfide is
measured during D7621. This is different to D5705 where the sample is in equilibrium with its vapor
and the liquid still contains high levels of H2S after the test. Tests D were carried out on the 1 litre
sample container prior to blending with a 0.00 mg/kg sample (to try to make 20 mg/kg). The tests
are useful to show potential repeatability. A D5705 test was not carried out. Test E was the
measurement of the subsequent blend. Unfortunately all the hydrogen sulfide had been removed. It
is quite likely that the sample containing 0.00 mg/kg had either a natural scavenger or applied
scavenger and reacted with the hydrogen sulfide on blending. Tests F and G were on previously
bottled samples which were approximately 60% full. It was not possible to carry out a D5705 as the
sample was too small, however the results are useful to estimate repeatability. Tests H was on one
of the same bottles as G and H after shaking to lower the levels. Again no D5705. Tests I were by a
different operator. No D5705. Test L was carried out to show the accuracy of the analyser when
measuring a hydrogen sulfide standard. The certified value was 3.04 mg/kg which compares very
well to the 3.21 mg/kg measured on the day.

Test

ASTM D7621
(Crude Oil
Appendix)

Repeat

(mg/kg)
A
A
B
B
B
B
C
C
D
D
D
D
E
F
F
G
G
H
H
I
I
J
J
K
K
L

141
150
109
92.8
92.2
0
83.8
77.6
55.6
46.3
46.3
41.2
0
74.3
75.6
82.6
81.6
63.9
54.9
52.8
58.6
48.4
51.8
39.4
39.2
3.21

repeatability
max

%
1
2
1
2
3
n/a
1
2
1
2
3
4
n/a
1
2
1
2
1
2
1
2
1
2
1
2
1
Average repeatability

6.2

17.1

7.7
18.3
11.7

1.7
1.2
15.2
10.4
6.8
0.5
8.8%

Sample
Mass

Sample
Volume

ASTM
D5705
modified

(g)

(L)

(ppmv)

0.038
0.038
0.037
0.038
0.041
0.041
0.04
0.037
0.041
0.037
0.079
0.082
1.625
0.076
0.081
0.079
0.08
0.08
0.078
0.074
0.071
0.076
0.074
0.078
0.079
4.644

50
50
50
50
50
50
50
50
50
50
100
100
2000
100
100
100
100
100
100
100
100
100
100
100
100
5000

9000
7000

6000

2500
2500
2500
2500
n/a

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ASTM D7621/ IP 570 Crude Oil Appendix Proposal


APPENDIX
(Nonmandatory Information)
X1. Alternative procedure for the measurement of hydrogen sulfide in crude oil at room temperature
X1.1 This alternative procedure may be used to extend the scope and range of the apparatus to estimate the
amount of hydrogen sulfide in crude oils. In this procedure the test vessel is located in a support bracket at room
temperature. The vapor phase processor (Procedure A) is required for this procedure as vapor present in the
crude oil can damage the detector and chemical interferences may be present (See A2.2).
X1.2 Apparatus
X1.2.1 Support bracket

X1.3 Procedure
X1.3.1 Prepare the apparatus as per Section 9 & 10 ASTM D7621/IP 570.
X1.3.2 Follow the steps in Section 11 for Procedure A with the following additions.
X1.3.2.1 Place the support bracket in the temperature controlled test vessel heating jacket.
X1.3.2.2 Insert the test vessel in the support bracket and fit the input/output tubing, so that the test vessel is at
room temperature.
X1.3.2.3 Carefully invert the sample end over end two times to mix the sample.
X1.3.2.4 The appropriate volume shall be determined by reference to Table X1.
NOTE 1 If it is suspected that the sample contains a large amount of volatile components such as butane then
use 0.1ml sample size to prevent pressurization of the test vessel.
NOTE 2A single mass can be entered rather than entering the mass before and after sample introduction if the
balance is tared.
NOTE 3This procedure is critically dependent on the weighing of the sample and injection of the sample into
the sample test chamber. During sample injection avoid drawing sample vapors into the pipette before removing
the pipette from the test chamber.

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Expected H2S
Concentration
0 to 10 mg/kg
10 to 20 mg/kg
20 to 100 mg/kg
100 to 200 mg/kg
Above 200 mg/kg

Required
Test Volume
5 mL
2 mL
0.1 mL
0.05mL
0.025mL

Page 14 of 15

Sample
Introduction
Disposable syringe
Disposable syringe
Pipette
Pipette
Pipette

TABLE X1 Appropriate Test Volume for Expected H2S Concentration

X1.4 Precision
A small repeatability study on samples with different hydrogen sulfide levels in the range 0 to 150
mg/kg was carried out which gave an average repeatability of 9%.

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References
1

th

New York Times, January 25 , 2014: Accidents surge as oil industry takes the train, by Clifford Krauss and Jad
Mauawad
2
th
Reuters News Agency, May 15 2013: Enbridge may shut Bakken oil rail terminal in sulfide gas dispute, by
Jeanine Prezioso
3
Crude Oils Their Sampling, Analysis and Evaluation, Harry N Giles & Clifford O. Mills
4
Canadian Crude Quality Technical Association Hydrogen Sulfide in Crude Measurement Report Bill Lywood
& Dave Murray, March 2012
5
The Gilson Microman positive displacement pipette was used during the study and found to be suitable