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Low-Level Hydrogen Sulphide Detection using Wireline Formation Testers

Mohamed Hashem and Hani Elshahaw, Shell; Ryan Parasram, Peter Weinheber, and Michael OKeefe,
Schlumberger;
and Craig Borman, and Scott Jacobs, Schlumberger OilphaseDBR
Copyright 2007, International Petroleum Technology Conference This paper was prepared for presentation at the International Petroleum Technology
Conference held in Dubai, U.A.E., 46 December 2007. This paper was selected for presentation by an IPTC Programme Committee following review
of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the International Petroleum Technology
Conference and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the International Petroleum Technology
Conference, its officers, or members. Papers presented at IPTC are subject to publication review by Sponsor Society Committees of IPTC. Electronic reproduction, distribution,
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by whom the paper was presented. Write Librarian, IPTC, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Abstract
Many development projects will rely on producing through existing production facilities, which may not have been
Designed for sour hydrogen sulphide (H2S) service. This problem is compounded if production is routed to an NGL
or GTL facility because even a tiny amount of H2S may dictate a prohibitively expensive upgrade.Detecting the
presence of H2S early in the life of a discovery can help to accurately assess the feasibility of a project, and
determining if an offset discovery can be produced without a facility upgrade can economically make or break a
project. Traditionally, operators have relied on well tests to determine H2S levels. In addition to the expenses
associated with a well test, there is the ever-present issue of H2S scavenging. Many days of flow may be required in
order to sufficiently passivate the metals so that an accurate H2S concentration can be determined.
Wireline formation testers have historically been regarded as a non-viable alternative. In this paper we are
challenging this historical concept. By using carefully designed laboratory experiments; we have studied the H2S
scavenging effects of different metals. The tests were conducted for different concentrations of H2S at a pre-defined
flowrate and in the presence of water in order to quantify H2S scavenging effects.
We have also identified all the components in the formation tester string, which could lead to scavenging. These
parts were then redesigned and manufactured with the upgraded metals. This enhancement to wireline formation
testers helps the technology to encompass a wider spectrum of functionalities. In this paper, we will review the
choice of materials, the verification test procedures and the laboratory test results. In addition we will discuss
options for the design of the downhole tool in order to optimize sample recovery. We feel that this is a new level of
refined utility for wireline formation testers in approaching well test functionalities.
Introduction
H2S is an extremely hazardous, toxic compound that occurs in a number of natural and industrial environments.
Naturally, it can be found in coal pits, sulfur springs, gas wells, and as a product of decaying sulfur-containing
organic matter, particularly under low oxygen conditions. Industrial sources of H 2S include petroleum and natural
gas extraction and refining, pulp and paper manufacturing, rayon textile production,leather tanning, chemical
manufacturing and waste disposal.The Hydrogen Sulfide (H2S) content of subsurface hydrocarbon reservoirs has a
profound impact on completion design and on project economics in general. The need for accurate determination of
H2S concentration in the reservoir fluids to be produced is crucial. It may mean higher processing fees or a lower
price for the oil or gas. It may also determine if it will be possible to access existing producing facilities or not and
thus the feasibility of a project. The accurate measurement of H2S concentration in the reservoir fluid can often be
critical to completion, surface production,and process design and is important for many reasons including the
following:
- Determine which (if any) HSE measures must be implemented for dealing with H2S at the various stages of
exploration, appraisal, development, production, and abandonment of a given prospect.
- Indicate the need for special metallurgical or process design to deal with certain levels of H2S in the presence of
various other mitigating or accentuating factors.
- - Detect the onset and evolution of reservoir souring upon the implementation of water injection or other enhanced
recovery techniques.
- Determine the price of a unit hydrocarbon produced and its conditional reception at pre-existing pipelines or
facilities.
Conventionally, the measurement of H2S concentration in fluid samples was limited to production tests. Wireline
Formation Testers (WFT) were considered unusable for this purpose due to the relatively small pumped volumes as
well as the partial-to-total loss of the gas by reaction with the metal components of the tools used in sampling.
Analysis of the fluid samples will therefore generally underestimate the H2S content. Many practical challenges
must be overcome to accurately determine H2S levels in formation tester samples.

These include metallurgical design considerations, sampling environment and system selection as well as the timing
and type of H2S analyses required. In the past, service companies could only promise a tool that would resist sulfide
stress cracking due to H2S impregnation (i.e. that were NACE-compliant). However, as noted, the system itself was
scavenging the H2S, thus previous attempts to determine the concentration levels were not successful, especially in
the case of low concentrations. With carefully designed laboratory tests, we studied the scavenging effects of
Different metals at different H2S partial pressures and succeeded in overcoming that problem. We identified all the
Components in the formation tester flow stream that could cause scavenging. These parts were then redesigned and
manufactured with the upgraded metals. Several modules in the string were upgraded, and we implemented
laboratory tests at pressure and temperature for different concentrations of H2S at a defined flow rate in order to
quantify H2S scavenging effects.
Equally important is the detection methodology (both timing and type of tests). We describe the on-site and lab
analysis measurements required to maximize accuracy and minimize scavenging effects. Finally, it is important to
minimize the contamination level of the acquired sample. Our experience shows that the H2S may partition into or
even react with any drilling liquid left over in the sampling bottles. This is particularly important for muds that are
designed with scavenging additives. Few droplets of such mud can completely bias the results of the H2S analysis
carried out on the gas.
Source of H2S in the subsurface
The abundance of H2S in subsurface hydrocarbon reservoirs results primarily from interactions between the
ubiquitous sulfate reducing bacteria and exogenous sulfate under anaerobic conditions. Altogether there are three
main mechanisms responsible for H2S generation in petroleum reservoirs (Hland et al., 1999).
1. Bacterial Sulfate Reduction
This reaction is mainly anaerobic and tends to occur at low temperatures (lower than 80oC) and is often triggered by
injection of seawater, which tends to be rich in sulfates. The H2S concentrations generated are usually less than 5%,
and the chemical reaction takes the following form: Sulfates + Organics + Nitrogen H2S
2. Theromochemical sulfate reduction (TSR)
TSR occurs primarily in carbonate reservoirs that are deficient in iron and at temperatures above 100oC. The H2S
concentrations generated are usually greater than 10%, and the chemical reactions take one of the following forms:
Gas + Anhydrite H2S + Carbonate
Calcium Sulfate + Organics H2S + CaCO3
3). Thermal cracking
In these reactions, the H2S is generated by the thermal alteration of the sulfur in the kerogen and occurs at
temperatures higher than 140oC. The concentration of thermally sourced H2S tends to increase with temperature, and
the H2S concentrations generated are usually less than 5%.The most common reaction products of BSR and TSR are
identical and include carbonate material, sulfides (usually as base, or transitional metals, sulfur, H 2S, and sulfurized
or oxidized hydrocarbons).
Importance of Measuring H2S Concentrations
The presence of H2S in produced fluids can give rise to critical safety problems. The exposure limit recommended
by the US National Institute for Occupational Health (Ref 8, NIOSH website) is 10 ppm per 10 minutes of exposure,
and most countries have legal limits in force that govern the maximum allowable levels of exposure to hydrogen
sulfide in the working environment. The only reliable way to determine exposure levels is to measure the amount in
the air. The human nose can detect concentrations as low as 0.02 ppm with maximum sensitivity at around 5 ppm
and becomes increasingly unable to detect H2S at concentrations of 150-200 ppm. The effect of H2S on health
depends on both concentration and exposure time with concentration affecting the human body as follows:
- 0.15ppm: Smell of rotten eggs
- 10-20 ppm: Irritation of nose, eyes, and throat
- 20-100 ppm: Loss of sense of smell, headache, cough, and nausea.
- 200-300 ppm: Irritation of lungs and difficulty breathing
- 300-600 ppm: Central Nervous System effects: numbness of limbs, tremors, weakness, convulsions, and
unconsciousness.
- 600-1000 ppm: Rapid (One breath to several minutes) unconsciousness resulting in death if first aid is not
promptly administered.
- 1000+ ppm Instant death
Wherever possible, exposure should be minimized by employing adequate engineering controls and safe working
practices. Where these cannot adequately control levels of exposure, it may be necessary to supplement them with
the use of suitable personal protective equipment (PPE) such as supplied-air respirators (JPT Forum, 1971).

Overall, it has been estimated that H2S alone is responsible forabout 20% of metal corrosion losses in the petroleum
industry.
Sulfide stress cracking (SSC) is a form of hydrogen embrittlement that occurs when a susceptible material is
exposed to a corrosive environment containing water and H2S at a critical level of applied or residual tensile stress.
SSC is commonly observed in high strength or high hardness steels in which the hydrogen is generated by the
sulfide corrosion process on the metal surface making the steel less resistant to breakage and generally much weaker
in tensile strength (Kane et al., 1998). On a molecular level, hydrogen ions work their way between the grain
boundaries of the steel, where hydrogen ions recombine into molecular hydrogen, taking up more space and
weakening the bonds between the grains. The formation of molecular hydrogen can cause sudden metal
failure due to cracking when the metal is subjected to tensile stress (Wilhelm et al., 1986).
To address the problem of hydrogen embrittlement, emphasis is placed on controlling the amount of residual
hydrogen in steel, controlling the amount of hydrogen pickup in processing, developing alloys with improved
resistance to hydrogen embrittlement, developing plating or coating processes, and restricting the amount of in-situ
hydrogen introduced during the service life of a part. H2S reacts with Fe from tubulars, valves, etc. to form iron
sulfide or "black water". It is important to note that in the last decade, there has been a move away from chemical
inhibition due toenvironmental & engineering limitations (Williams, 2003).
The National Association of Corrosion Engineers (NACE) has established guidelines for dealing with H 2S in
industrial applications. The NACE Material Requirement standard MR0175 defines the lower limit for sour
service conditions in which sulfide SSC could occur as 0.0003 MPa or 0.05 psia partial pressure (Figure1). Partial
pressure is defined as the product of absolute pressure and concentration.
For example, 10 ppm of H2S at 16,000 psi is equal to a partial pressure of 0.16 psi = (10/1,000,000)x16,000
There are actually quite a number of factors, other than H2S partial pressure, that affect the susceptibility of a
material to sulfide stress cracking. Corrosion rates depend on H2S and CO2 PP, pH, sand and water production,
tubular metallurgy, heat treatment, corrosion-inhibitor treatments, temperature, fluid velocity, flow regime, etc
(NACE 2003).
NACE MR0175 paragraph 1.3 lists the following factors:
- Chemical composition, strength, heat treatment and microstructure of the material. Certain compositional
elements (for example, nickel in steels) have been identified as SSC promoters. In general, for a particular
alloy, as strength and hardness increase, the susceptibility to sulfide stress cracking increases.
- Hydrogen ion concentration (pH) of the process environment (Fig. 2).
- Total tensile stress (accounting for both applied and residual stresses).
- Process temperature.
- Exposure time.
Accurate measurement of H2S concentration in sampled fluid is critical to completion, surface production, and
process design. The impact on the cost structure is potentially huge. Typical completion costs can increase by at least
one order of magnitude as we move from carbon steel through 13-chrome to high Ni alloys (Kermani, 1995)
H2S Analysis Methods
The accurate determination of the H2S content in a hydrocarbon sample is a challenging task given the reactivity
of that compound. Selecting the type and timing of any H2S analysis to be carried out will also have a significant
impact on the accuracy of the results obtained. There is a clear benefit for immediate onsite analysis with subsequent
lab analysis to support the onsite result. A precise measurement in the PVT laboratory does not take into
consideration what has been lost during transportation by adsorption, a reversible phenomenon, and absorption, an
irreversible chemical reaction. (Bethea et al., 1973) It is therefore recommended that measurement of H2S contents
of gases and oils be carried out onsite as soon as possible after sampling. Measurements carried out in the
laboratory, after sampling onsite, should only be used to provide approximate lower bounds on the H2S
concentration.
It is best to combine several methods and operate according to a referenced standard. This allows an estimation of
the uncertainty inherent in the results. Several analytical methods exist for measurement of H2S. These include the
following:
1. Multigas Monitors rely on electrochemical sensor, and provide quick, easy to read digital output, limited to a max
concentration of 1000 ppm (Williams et al., 2003).
2. Gas detection (length of stain) tubes use ASTM D4810-88 standard (re-approved 1994) Method for Hydrogen
Sulfide in Natural Gas Using Length of Stain Detectors. Various manufacturers including Dragger, Kitagawa,
GasTec, Sensydine etc. produce gas detection tubes that can be used in the range of 0.5 ppm by volume to 40% by
volume with reasonable accuracy with appropriate range selection, use, storage, and ambient corrections although
the majority of these applications will be on the lower end of this range (<120 ppm) (Volkan et al., 1998).

Gas detection tubes are quick, easy to use, and inexpensive and reliable for low concentrations of H2S (<10ppm)
and CO2. Inert Teflon plastic bags are usually used to collect the sample prior to passing through the tube. Each
sample point must have its own bag, correctly labeled. The gas must be immediately passed through the tube after
filling the bag.
Below are our recommendations for H2S length of stain tubes.
- For the 0.2-6 ppm range, use HgCl2 tubes.
- For the 0.5-15 ppm range, use starch Iodine tubes.
- For the 2-60 ppm range, use Lead Acetate tubes.
- For the 1-200 ppm range, use Copper Chloride tubes.
3. Potentiometric titration uses the following standards:
UOP 163-89-H2S and Mercaptans in Hydrocarbon Liquid, IP 272/71 and UOP 212/77-H2S, Mercaptans and
Carbonyl Sulfide in Hydrocarbon Gases. The potentiometric titration method is used to determine hydrogen sulfide,
mercaptan sulfur and carbonyl sulfur in hydrocarbon gas and liquid in the 0.1 to 1 ppm level and the 1 ppm or higher
level. UOP 212/77 can be used for H2S in both the gas and liquid phase, and UOP 212/77/IP342 can be used to
check the liquid phase for any H2S left behind and non-volatile mercaptans. This method is recommended to H2S
concentrations that are above 0.3 to several thousand wt-ppm, and is also used for H2S and mercaptans in liquid
above 1.0 ppm (Bethea, 1973). Samples may be analyzed directly if viscosity permits injection by
syringe. Samples having a high content of sulfur may be analyzed after dilution with a suitable solvent. Halides in
excess of 10 times the sulfur level, nitrogen content greater than 10% and heavy metals interfere with the analysis.
Gas or liquid used for this titration will be collected from a purge from a coated sampling bottle or a sub-sample
from an inert bag filled from a coated bottle's transfer. The UOP 212/77 titration is a time consuming process that
may take up to 6+ hours to complete at the wellsite.
4. Iodimetric titration (ASTM D2385) uses the following
standards: ASTM D2385-81 standard (re-approved in 1990,
discontinued in 1995), IP 103/70 (re-approved proved 1978,
no later version currently available), GPA STD 2265-ASTM
D 2385-IP103. The technique uses cadmium sulfate
adsorption followed by iodimetry. This method is very
accurate but is rather time consuming with each titration
taking 4-6 hours. The Cadmium sulfate method is applicable,
according to the ASTM D2385, in the range of 0-5 grains of
H2S per 100cu-ft, corresponding to a range of 0-115 mg/mcu
or 80 ppm by volume (Bethea, 1973).
5. The Tutwiler method uses the UOP 9-59 standard. UOP 959 is adapted to H2S concentrations that are above 5
grains/100 cu-ft, which corresponds to 80 ppm by volume. It
is a wet chemistry method that takes over from the Iodimetric
titration method for concentrations above the limit of 80 ppmv
(Elshahawi et al., 2005).
6. Gas Chromatography uses the ASTM D 1945-91, GPA
2261-90 standard. The gas chromatography technique (ASTM
D 1945-91) is used to determine H2S content in gas. This
method is recommended for H2S concentrations above 20 ppm
up to 40% by mol. Recent developments is micro-GC
technology appear promising in being able to extend the
applicability of GC methods to lower concentrations
(Elshahawi at al., 2005). To avoid any contamination with air,
it is recommended to purge for at least 10 minutes until the
trap system becomes saturated with produced gas before
running a GC. It is also recommended to run at least 4
injections and record immediately the results of H2S, CH4 and
N2. The latter two are to compare with produced gas and

check if there is any dilution with air.


Upon retrieving the tools to surface, it is recommended to
proceed immediately with heated and pressurized transfers of
any H2S samples. Upon commencement of a pressurized
wellsite transfer, a portion of any bottle designated for H2S
should be purged across the top of the bottle through a
passivated valve and fitting assembly to the top of the coated
transfer receptacle. Continue the purge across the top of the
coated transfer receptacle and capture in one or more inert
Teflon bag(s). For low H2S concentrations in the low tens of
ppm range, it is recommended that gas chromatography and a
wet chemistry method should be used addition to length of
stain tubes. As best practice, some ordinary (non-coated)
bottles also be analyzed to ensure that the measurement that is
made is indeed indicative of true H2S concentrations and are
not simply a measurement artifact. For low tens of ppm of
H2S, one should expect to find no trace of H2S in the uncoated
bottles. (Elshahawi et al., 2005). Some of the Teflon bags may
be saved and shipped to a full laboratory for an eventual H2S
concentration determination via a gas chromatograph outfitted
with a chemiluminescence detector. After the result of micro
GC, it is recommended to run a dragger test to compare H2S
results.
H2S Sampling Options
There are essentially three methods available for sampling
H2S:
1) Surface well testing: Surface separator PVT sampling is
another option for H2S analysis. However, with this method
there is a large potential for H2S in the produced fluids to react
with the metallic surfaces of the completion/DST string,
surface testing flow lines and/or test separator. Scavenging by
the mud or completion fluids and partitioning of the H2S into
the various phases is also likely. All this can lead to a large
undetermined loss of H2S by the time the produced reservoir
fluids reach the sample bottle. During extended well tests,
where large quantities of fluid are flowed, stability in H2S
levels may be achieved although cannot be guaranteed,
especially for low H2S concentrations. Onsite analysis during
an extended well test has the advantage of repeated
measurements with large volumes of liquid and gas to analyze.
2) Cased hole sampling: Capturing down-hole samples in a
cased-hole environment has advantages over the previously
mentioned methods. Down-hole samplers can be positioned
very close to the reservoirs perforated intervals so scavenging
of H2S through contact with completions and sub-surface
equipment is virtually eliminated. Downhole samplers can be
fired when the well is fully conditioned. This means highly
representative or fresh reservoir fluids can be captured for
analysis. The use of single-phase samplers avoids partitioning
of trace components between phases and allows controlled
flashing of the sample to obtain accurate measurements of H2S
in the gas, oil and water phases.
3) Open-hole sampling: Taking samples in openhole
environments using formation testers has been carried out for
years. High quality PVT samples are achievable with singlephase
samplers in Low-shock mode, and sample bottles have

been successfully coated with inert materials for sometime. In


theory, the H2S content of reservoir fluids can be determined
from samples collected by wireline fluid sampling tools. Fluid
samples are usually collected in metal containers, which can
be maintained at Pressure-Volume-Temperature (PVT)
conditions that can be directly compared to those at which the
samples were collected. However, the problem associated with
sampling fluids containing H2S is the partial-to-total loss of
the gas by reaction with components, particularly those made
from iron-based metals. The H2S gas readily forms nonvolatile
and insoluble metal sulfides by reaction with many
metals and metal oxides, and analysis of the fluid samples can
IPTC 11582 5

therefore underestimate the true H2S content. Because of these


and several other potential sources of H2S loss to the tool, the
pump, sample transfer connections, and drilling fluids, openhole
sampling for the determination of low-level H2S
concentrations has been considered largely unachievable.
A combination of lab testing, material improvements, and
procedural changes has enabled us to transform openhole
sampling into the method of choice for H2S sampling. Part of
the improvement has come from switching to a novel
sampling technique termed reverse-low shock sampling
which avoids passing the fluids through the pump altogether.
Another part of the improvement is the successful testing of
the practical limits of the tools with better coating and
preparation for H2S sampling. This will be discussed in some
detail later.
H2S Coupons
Despite the many downhole fluid analysis advances made in
recent years, there does not yet exist a robust downhole
measurement technique for H2S, with the exception of H2S
coupons. All other existing methods rely on acquiring a
sample and measuring the H2S content on surface.
Certain metal alloys discolor, as a result of corrosion, only due
to the presence of H2S. As mentioned earlier, the H2S
corrosion phenomenon is largely a function of partial pressure,
not concentration, and weakly dependent on temperature and
exposure time. This is true for both gas phase and liquid
phase. H2S coupons are made of certain metal alloys that
corrode or discolor when exposed to the fluid entering from
the formation (oil, water or gas), indicating the presence of
low levels of H2S. These coupons are deployed in the probe
module of the formation tester, close to the probe itself, with
the intent of seeing fluids with the lowest possible amounts of
scavenging. Different sensitivity coupons are typically
employed on any given job. As shown in Fig.3, The coupons
turn brown, gray, or black with the discoloration thresholds
levels coinciding with the QHSE and materials thresholds
discussed earlier. Upon withdrawal of the tool from the well,
the coupons can be removed and inspected. It should be
possible to tell if the coupons have been exposed to:
a) No H2S
b) A trace level of H2S. The most sensitive CDA-706
coupon will turn black when exposed to H2S levels with
less than 0.005 psi partial pressure. This is 10 times less

than the NACE corrosion limit, but is high enough for


human safety problems.
c) A low level of H2S. The medium-sensitivity Hastelloy B
coupon will turn more of a brown color when exposed to
H2S levels in the 0.018-0.025 psi partial pressure range.
This is just below the level at which significant sulfide
stress cracking (a form of corrosion) will occur, but a
level at which there is a lethal health risk.
d) Higher levels of H2S. The least sensitive Alloy 600
coupon will turn a brown color upon exposure to H2S
levels in the 0.05-0.10 psi partial pressure range. This is
enough H2S to require special chrome alloy materials to
prevent sulfide stress cracking which then leads to
material failure.
H2S coupons can be quite useful in exploration and appraisal
work, but they have two significant weaknesses. Firstly, it
was found that other materials present in the wellbore were
capable of causing a tarnish to appear on the coupons, which
can complicate the interpretation. Secondly, the nominal
implementation of the coupons requires that they be inserted
in the resistivity cell of the Formation Tester Single Probe
module. This meant that the coupons would be very close to
the probe where the fluids would be least affected by
scavenging but it also meant that they would be exposed to all
fluids encountered in the well, including all fluids seen during
the pretests as well as all zones sampled on a given descent.
Accordingly, this will represent the maximum detected levels
of H2S in all the samples or fluids that went through the probe
and past the coupons. This made it impossible to differentiate
H2S content from zone to zone. Note that a partial mitigation
does exist for the second point. The coupons can be placed
within the sample bottles. However with the coupons in the
bottle the fluid sensed by the coupons will have passed
through the entire sampling string and will have been
scavenged.
Clearly, the more reliable method to evaluate the H2S content
of individual zones would be to acquire formation fluid
samples with minimum contamination, minimum scavenging
in the Formation Tester and during transfer, and to perform a
laboratory analysis of the fluids on surface. This involves
designing a tool string with the following three criteria:
1) Minimize the length of the flow line path from the
sandface to the sample bottle.
2) Use materials along the tool flow path that will not
scavenge H2S.
3) Where scavenging materials must be used, coat with an
inert, non-scavenging material.
Henceforth, we will address each of these points individually.
Minimizing the length of the flow path
Most modern formation testers are modular; they offer a
considerable degree of flexibility in tool string design. A
pump may be placed below a probe, a fluid analyzer maybe
placed before or after a pump, etc. For most standard
sampling operations a mode known variously as low shock or
zero shock or positive overbalance sampling is employed. In
this configuration the backside of the piston in the sample

chamber is exposed to the hydrostatic pressure of the mud


column, and the sample chambers are positioned downstream
of the pump. This method ensures that large pressure
differentials are not imposed on the formation or the fluid
when the sample bottle is opened for fluid collection, but it
requires a pump to push the fluid into the bottle against mud
pressure and also that the pump be placed in the flow path
between the single probe module and the sample bottle. This is
inconsistent with our desire to maintain as short a sample path
as possible. Additionally, the unmodified pump itself is
6 IPTC 11582

particularly troublesome as it can be the single biggest


scavenging module in the tool string. (Figure 4)
To remedy this we need a toolstring configuration that
removes the pump module from the flow path but still gives us
the advantages of low shock sampling. This is available using
a technique known as reverse low shock sampling as shown
in Figure 5. In conventional low shock sampling, left side, we
begin with valve A opened and valve B closed. Fluid from the
probe enters the pump and is pumped through valve A and out
the exit port. This continues until the fluid is judged to be
sufficiently clean to sample. At this time valve B is opened
and valve A is closed. The fluid is pumped into the bottle and
additionally; the bottle is over-pressured before closing valve
B and capturing the sample.
In reverse low shock sampling (right side of Figure 5), the
backside of the piston is not open to hydrostatic but instead is
filled with water. We begin with fluid entering the tool at the
probe and being drawn down and away by the pump situated
below the sample chamber. When the fluid is judged to be
sufficiently clean for sampling Valve B is opened and Valve C
is closed. Now the pump will draw the water from the
backside of the piston. This will pull the piston down and
draw in the fluid from the probe. This fluid entering the
sample chamber has not passed through the pump module.
One important difference is noted: with the reverse low shock
method the sample is not overpressured as a result of filling.
If an overpressure on the sample is required then two options
exist. Firstly, prior to closing valve B, we can open valve C
and close valve A. Then the pump unit is reversed and then
we can pump up to overpressure the sample. For the second
option a single-phase sample chamber can be run that imparts
a high-pressure nitrogen cushion on the backside of the piston
automatically when the bottle fills.
A reverse low shock sampling string may be configured as
shown on the right side of Figure 6. Note the placement of the
sample chambers and pump below the probe module. The
probe itself is close to the bottom of the single probe module
so situating the collection chamber on the bottom will give us
the shortest possible flow path. Figure 6 shows the difference
in flowline length between a conventional low shock string
and a reverse low shock string with the sample chamber
placed below the single probe module. In the typical low
shock case there is 35 ft between probe and sample bottle. In
the reverse low shock case there is less than 2 ft.
Material Selection

As for any complex mechanical engineering project, material


selection is based on many criteria which may include, among
others, cost, weight, strength, corrosion resistance, workability
and compatibility with other materials. Common materials
used in formation testers are Inconel, Titanium and Monel.
However, all of these materials will exhibit different
scavenging properties in the presence of H2S. (Shammai et
al., 2004)
Figure 7 shows the scavenging that occurs in a length of
Monel tube with 50 ppm H2S inlet gas. Plotted on the vertical
axis is the concentration of H2S in the outlet gas versus time
on the horizontal axis. Note that after several hundred minutes
of flow, only ~10 ppm had been retained with the Monel
scavenging 40 ppm of the 50 ppm inlet. Given the H2S
concentrations we are trying to measure, this is clearly
unacceptable.
Several materials were selected to provide an alternative to
Monel: Titanium, Inconel, and Hastelloy. These materials
were tested according to the procedures outlined in Appendix
B and using the C.I. Analytics 2010L Dry Colorimetric
Detector (DCD) described in Appendix A. The results of the
most demanding test, 10 ppm H2S inlet gas, are shown in
Figure 8. Additional tests were performed using 55 ppm and
500 ppm H2S inlet gas and showed similar results.
In Figure 8, the inlet gas to the tube under test has an H2S
concentration of 10 ppm. This is verified by the control curve
in red. (Samples taken off the control point are through a
Teflon tube that should see no scavenging whatsoever.) Note
at time one minute the sample taken from the Titanium tube
(blue curve) reads ~8 ppm meaning that there is 2 ppm of
scavenging. The Hastelloy (green) and Inconel (black) are
both reading about 10 ppm meaning there is essentially no
scavenging. All materials exhibit zero scavenging within 10
minutes. Note that the vertical bars on the test points are the
accuracy/repeatability limits of the Dry Colorimetric Detector
(DCD)
Toolstring Design and Testing
Earlier we stated that the three criteria for designing a
Formation Tester tool string to optimize the recovery of low
concentrations of H2S were tool string configuration, material
selection and inert coatings. We have demonstrated that
reverse low shock sampling both eliminates the pump from
and greatly shortens the flow path. We have shown that
materials such as Titanium and Inconel will have minimal
scavenging, and finally we have shown that a multi-layer
silica coating such as Resteks Sulfinert can reduce
scavenging to minimal levels. It remains now to implement
these findings and test them.
All testing of tool strings was performed according to the
analysis techniques described in Appendix A. All the tests
reported in this paper used Nitrogen as a carrier gas, but we
have tested Methane and Nitrogen as a carrier gas and did not
detect an appreciable difference between the two (Table 1).
For a variety of reasons, not every component along the flow
path can be converted to a non-scavenging material.
Additionally, the fluids will be stored in the sample bottle

itself for some period of time before they are brought to


surface and their contents analyzed. Therefore, the use of a
non-reactive, inert coating is essential. Testing was performed
on sample bottles coated with single layer and multi-layer
silica coatings to determine their propensity to protect low
levels of H2S over time. The results are plotted in Figure 9
IPTC 11582 7

and are derived from tests performed with either 50 or 55 ppm


H2S test gas. A full description of the test procedure and
configuration is in Appendix C.
Figure 9 shows that the multi-layer silica coating essentially
retains all the H2S out to 24 hours. But note that additional
time in the sample bottle does result in loss of H2S
concentrations. This emphasizes the importance of testing
acquired samples as early as possible after they are retrieved.
Best practices for this will be discussed later. The multi-layer
silica coating is available commercially from RESTEK under
the name Sulfinert.
Additional testing was performed separately on formation
tester flow tubes that had been coated with the Sulfinert
coating in a 10-ppm H2S environment. This testing was
performed using the apparatus described in Appendix A and
B. The results of this testing, shown in Figure 10, indicate that
the Sulfinert-coated tube (blue) exhibits zero scavenging even
in very early time. Our recommendation is that all sampling
and transfer equipment including the sample bottles along
with the transfer bottles and the various valve assemblies and
liners that may come into contact with hydrocarbon, from the
probe to the sample chamber, must be newly anodized with
the Sulfinert coating before the job.
Testing of Probe and Multisample Modules
A typical formation testing and sampling toolstring normally
includes at least one probe/snorkel section, one downhole
pump, one sample chamber or multi-sample chamber section,
and a fluid identification section. In the following, we will
look at the testing of each one of these sections. The first
toolstring to be tested consists of a Focused Probe module
(Quicksilver Probe) and a six bottle Multisample module. The
toolstring tested and the testing configuration is shown in
Figure 11. The Quicksilver Probe module was chosen for two
reasons. Firstly, the internals are somewhat more complex
than a regular single probe so this should represent a worst
case for scavenging. Secondly, the presence of either WBM
or OBM filtrate has been shown to adversely affect H2S
measurements and the Quicksilver Probe has been proven to
significantly reduce the levels of filtrate contamination.
(Weinheber et al 2006). Real world applications where
detection of low levels of H2S is critical will probably use the
Quicksilver Probe.
Note that we have configured the tool string with the sample
module on top of the Focused Probe module. This will be the
longest flow path for a reverse low shock sampling string and
again represents a worse case scenario. The inlet test gas
stream is supplied at 1.25 liter/min (21 cc/s) at the probe. A
sample stream of 0.5 liter/min (8.3 cc/s) is pulled off the top of
the probe module and 0.25 liter/min (4.2 cc/s) streams are

taken off the lower bottle bank, upper bottle bank and module
top. Tests were performed with the tool at 212oF (100oC) and
at 1000 psi. The results of the 11 ppm test are shown in
Figure 12.
Note that the data are plotted as ppm of H2S scavenging versus
time. This means that the 11 ppm H2S concentration of the
source gas has been subtracted. Also note that although
sample streams were taken at both sample bottle banks of the
multisample module, for clarity we present only the results of
the stream at the top of the Quicksilver Probe module and for
the top of the Multisample module.
Table 2 summarizes the results plotted in Figure 12. The
results indicate that in very early time we were losing 2 ppm
of H2S through the Focused Probe module and a further 5 ppm
of H2S through the Multisample module. A total of ~7 ppm
(versus the 11 ppm inlet) was being scavenged. However, by
100 minutes of pumping the internals of the tool had become
partially passivated and we were losing less than 0.5 ppm
through the Focused Probe module and 2.0 ppm through the
Multisample. By 6.7 hrs total H2S scavenging was down to
less than 1.0 ppm.
One important difference between this laboratory testing and
the real world must be noted. As seen in Figure 11 there are
three flow streams being taken off the tool string before the
top of the sample module. This has the obvious effect of
reducing the flow rate through the sample module and
therefore increasing the time required to passivate the
internals. Actual field performance, with the full flow stream
passing through the sample module can be expected to yield
much faster passivation
The results from the Multisample have particular utility.
When sampling multiple zones it is common to stack several
Multisample modules on top of each other. Using the results
from this test total scavenging along the flow path can be
accumulated and scavenging in a string with 2, 3 or more
modules can be estimated.
Testing of the Fluid Analyzer Module
A Live Fluid Analyzer (LFA) was modified with an Inconel
flowline. The results of the 11 ppm test are in Figure 13. The
actual H2S output and the scavenged difference from the
control inlet gas is plotted. Note that even after 24 hrs of flow
the Fluid Analyzer is still showing almost 2 ppm of
scavenging. This is thought to be due to the types of seals in
the tool that are used to couple the optics to the flowline.
Fortunately, the reverse low shock technique allows the Fluid
Analyzer to be taken out of the sample flow stream. If,
however, circumstances require the Fluid Analyzer to be
before the sample chamber then the scavenging can be
estimated.
Testing of the Pump Out Module
The reverse low shock technique described earlier eliminates
the need for placing the Pump Out (MRPO) in the sample flow
stream. However there may be situations where this would be
desirable or necessary, especially when pressurizing a sample
is essential. Acknowledging this, we investigated the
construction of the Pump Out module with a view to

converting or coating scavenging parts.


8 IPTC 11582

As expected, even after material modifications and coating


there is considerable scavenging in the Pump Out module.
Figure 14 shows the results with 10-ppm inlet gas. Even after
400 minutes (4h40min) fully 8 ppm of the 10 ppm inlet gas is
lost. Figure 15 shows results with 50 ppm of inlet gas. After
400 minutes scavenging is down to a few ppm. Figure 16
shows results with a 500 ppm inlet gas. The last data point at
400 minutes shows 36 ppm of scavenging about 7% of the
500 ppm inlet gas. Finally, a single test was performed using
the high-pressure displacement unit in the Pump Out. This
displacement unit allows pumping at lower flow rates against
higher-pressure differentials. It has a smaller internal surface
area and a higher internal sealing pressure. These two facts
were thought to improve the scavenging characteristics. Data
from the high pressure DU is shown in Figure 17.
Conclusions
We have demonstrated that different levels H2S
concentrations, from the very low to the very high, can be
accurately measured in downhole fluid samples. We feel
confident enough to report these numbers for reservoir fluids
assessment or for system design, and not depend on the well
test to measure them. But we believe that this task can only be
accomplished with careful planning. It is imperative to
understand the factors that affect the measurement and in
using a comprehensive process/workflow.
Depending on the H2S levels we are interested in measuring,
the process may include a number of modifications and
replacements to several parts of the formation tester tool and
to the sample chambers themselves to ensure that the bulk of
the H2S does not get absorbed by the time the tool arrives to
the surface. The process may also include rearrangement of
sampling modules to eliminate H2S absorption in the
downhole pump, which is generally the major culprit for H2S
absorption. On surface, a number of techniques can be used to
measure H2S concentration in the sample bottles, but this must
be done as soon as possible after the formation tester tool is
brought to the surface. In addition, downhole measurements
made close to the fluid entry into the sampling tool are used to
cross check and verify the surface measurements. By using a
systematic approach to H2S sampling and analysis, we are
now able to capture and analyze subsurface fluid samples that
accurately represent the concentrations in the native reservoir
fluid.
References
1. Bethea, R.M., Comparison of Hydrogen Sulfide Analysis
Techniques, Journal of Air Pollution Control Assoc.,
23, 710-713 (1973).
2. Hland, K., H.P. Barrufet, H.P. Rnningsen, and K. K.
Meisingset, An Empirical Correlation Between
Reservoir Temperature and the Concentration of
Hydrogen Sulfide, 1999 SPE International Symposium
on Oilfield Chemistry, Houston, Texas, Feb. 1999, SPE
50763.
3. Elshahawi H. and M. Hashem: Accurate Measurement of

the Hydrogen Sulfide Content in Formation Fluid


Samples-Case Studies, Paper SPE 94707 presented at
the 2005 SPE Annual Technical Conference and
Exhibition held in Dallas, Texas, U.S.A., 9 12 October
2005.
4. JPT Forum, H2S A Toxic Gas That Can Kill, Journal
of Petroleum Technology, March 1971, Paper SPE
3202.
5. Kane, R.D. and G.B. Greer, Sulfide Stress Cracking of
High Strength Steels in Laboratory and Oilfield
Environments, Journal of Petroleum Technology, Nov
1977, SPE 6144.
6. Kermani, M.B. and D. Harrop, The Impact of Corrosion
on the Oil and Gas Industry, 1995 Middle East Oil
Show & Conference, Bahrain, SPE 29784.
7. NACE (2003), NACE Standard TM0177-96, Laboratory
Testing of Metals for Resistance to Specific Forms of
Environmental H2S Environments, (Houston, TX;
NACE International).
8. National Institute for Occupational Safety and Health
Website accessed 5-April-07
http://www.cdc.gov/niosh/npg/npgd0337.html
9. Shammai, M. and M. Hashem, Optimum sampling
techniques for fluid samples containing H2S,
presentation at the SPWLA Spring Topical Conference,
Taos, New Mexico, March 28 April 1st, 2004.
10. Volkan, M, T. Eroglu, A.E. Eroglu, O.Y. Ataman and
H.B. Mark, A Novel Sorbent Tube for Ambient
Hydrogen Sulfide Determination, Talanta, 47, 585-593
(1998).
11. Weinheber, P. and R. Vasques, New Formation Tester
Probe Design for Low-Contamination Sampling
SPWLA 47th Annual Logging Symposium Veracruz,
Mexico, June 4-7, 2006
12. Wilhelm, S.M. and R.D. Kane, Selection of Materials for
Sour Service in Petroleum Production, Journal of
Petroleum Technology, October 1986, PP 1051.
13. Williams, J.M., Getting Reliable On-site H2S and CO2
Concentrations for Anti-corrosion Measures in Gas
Wells, SPE 13th Middle East Oil Show & Conference,
Bahrain June 9-12, 2003, SPE 81495.
IPTC 11582 9
Table 1. Summary of Test Characteristics
Test H2S
Concentration
(ppm)
Pressure
(psi)
H2S
Partial
Pressure
(psi)
Carrier
Gas

1 11 1000 0.011 Methane


2 11 1000 0.011 Nitrogen
3 55 1000 0.055 Nitrogen
4 510 1000 0.510 Nitrogen
Table 2. Summary of H2S scavenging results

Time
(min)
MRPQ
ppm H2S
MRMS
Ppm H2S
Total
Ppm H2S
1 2.0 4.8 6.9
5 2.1 5.7 7.8
10 1.6 5.8 7.5
20 0.5 4.8 5.3
50 0.6 2.1 2.7
100 0.4 2.1 2.5
400 (6.6 hr) -0.2 0.8 0.6
1440 (24 hr) 0.0 0.4 0.4
Figure 1 Sulfide Stress Cracking and Partial Pressure from NACE
MR0175-2000 standard.
Figure 2 NACE MR0175-2000 - note that this standard applies
between 0.05 and 10.0 psi partial pressure H2S.
Figure 3 H2S Coupons from least (left) to most sensitive (right).
10 IPTC 11582
Figure 4 Scavenging in unmodified pump m showing 100%
scavenging after less than 100 minutes.
Figure 5 Schematic of low shock and reverse low shock sampling
procedures.
Figure 6 Low shock and reverse low shock Tool strings.
Figure 7 H2S Absorption in a Monel Tube.

10ppm H2S @ 300F


0
4
8
12
0.1 1 Time1 0(min) 100 1000
H2S (ppm)
Control
Titanium
Inconel
Hastelloy

Figure 8 Results of absorption tests using a 10-ppm inlet gas H2S


concentration.
Figure 9 The multi-layer silica coating retains most of the H2S
past 24 hours.
IPTC 11582 11

10ppm H2S @ 300F


0
4
8
12
0.1 1 10 100 1000
Time (min)
H2S (ppm)

Control
Sulfinert
Figure 10 Results of 10-ppm H2S test on a Sulfinert-coated tube.
Figure 11 Multisample - Focused Probe Tool String Test
Configuration.
Methane 11 ppm H2S
MRMS + MRPQ
0
3
6
9
12
0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
MRPQ Scavenging
MRMS Scavenging
Control

Figure 12 Scavenging results from 11 ppm test on Multisample


and Quicksilver Probe Modules
11ppm H2S @ 212F
0
2
4
6
8
10
12
14
0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
End of MRFA
Control
MRFA Scavenging

Figure 13 Results of 11 ppm test in Fluid Analyzer.

MRPO at 10 ppm H2S


0
2
4
6
8
10
12
0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
Control
End of MRPO
MRPO Scavenging

Figure 14 Results of 10 ppm test in Pump Out with Standard


Displacement Unit
12 IPTC 11582

MRPO at 50 ppm H2S


0
10
20
30
40
50
60
0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
Control
Top of MRPO
MRPO Scavenging

Figure 15 Results of 50 ppm test in Pump Out with Standard


Displacement Unit

MRPO at 500 ppm H2S


0
100
200
300
400
500
600
0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
Control
Top of MRPO
MRPO Scavenging

Figure 16 Results of 500 ppm test in Pump Out with Standard


Displacement Unit.
MRPO at 500 ppm
with High Pressure DU
0
100
200
300
400
500
600

0.1 1 10 100 1000 10000

Time (min)
H2S (ppm)
Control
Top of MRPO
MRPO Scavenging

Figure 17 Results of 500 ppm test in Pump Out with High

Pressure Displacement Unit


IPTC 11582 13

APPENDIX A
H2S DETECTOR FOR LABORATORY TESTING
Classical Colorimetery utilizes an impinger to collect gas in a
liquid medium. Chemical reagents are then added to the
medium for a color change that is in proportion to the gas
concentration present. The resulting color change is measured
by a laboratory spectrophometer and compared to known
standards.
Ultra-sensitive tape detectors are also colorimetric based,
but these are dry reaction substrates that serve as gas
collecting and analyzing media. Individually formulated for a
specific gas or family of gases, each detection tape is a nontoxic,
proprietary chemical reagent system. When exposed to
a target gas, the tape will change color in proportion to the
amount of gas. The higher the target gas concentration, the
darker the stain will become.
The change in color, or stain, on the tape is read by a photooptical
system in the analysis instrument, and the intensity of
this stain is then compared to a standard response curve
preprogrammed into the instruments data system.
The materials and tool testing described in this paper was
performed with a C.I. Analytics 2010L Dry Colorimetric
Detector (DCD). Nominal specifications are as follows:
H2S Detection Range: 150ppb 2000ppm
Accuracy: +/- 5% of reading
Repeatability: +/- 5% of reading > 1ppm
Calibration
The DCD is calibrated using certified traceable H2S test gases
prepared by Air Liquide. A three-point calibration curve is
generated using the response (number of counts) vs. the
known H2S concentration of the calibration standards. This
calibration curve is then used to determine the concentration
of H2S in the unknown samples. The instrument is calibrated
before each run.
Analysis
During operation, the detection tape is incremented through a
sampling window where it is exposed to a metered sample
stream. If the target gas is present, a stain proportional to the
concentration develops. Simultaneously, a beam of light is
reflected off the exposed portion of the tape and the intensity
of this light is measured continually. As the amount of
reflected light decreases due to stain development, the
reduction is sensed as an analog signal by a photocell detector.
The signal is amplified by the electronics that are part of the
miniature PCB mounted inside the Optics Block. This signal is
converted to a digital format, matched to the gas response
curve stored in the analyzers permanent memory, and
displayed/documented as the actual concentration value. All
of these functions are microprocessor controlled.
The use of this dry spectrophotometeric technique, in
combination with microprocessor control, provides excellent
accuracy, repeatability, and detect-ability of low ppb (partsperbillion) concentrations.
14 IPTC 11582

APPENDIX B
MATERIAL TESTING
86in2 of material surface area was exposed to the test
conditions. The following materials were selected:
- Titanium 0.206ID x 11
- Inconel 0.152ID x 15
- Hastelloy 0.120ID x 19
- Sulfinert coated stainless steel
All connection tubing, regulators and valves were coated with
Resteks Sulfinert.
Tests were conducted using laboratory standard source gases
of 10, 55 and 500 ppm H2S concentrations.
Additionally, the gas was humidified with Acetic Acid prior to
being introduced to the material under test. The temperature
in the oven was kept at 300 degF and the flow line pressure
was kept at 1000 psi.
For the sampling procedure the gas was flowed through the
system, through the sight glass and onto the scrubber. At the
desired test times samples were taken into inert Kevlar bags
from the sampling points. The contents of the Kevlar bags
was then tested using the DCD described in Appendix A
IPTC 11582 15

Appendix C
Testing apparatus and procedure for Silica Coated Bottles
(RESTEK Sulfinert)
All testing was conducted at 300 psig and 158 degF over a 14day period. H2S detection was carried out using a Varian
3800 gas chromatographic system with a sulfur specified
Pulsed Flame Photometric Detector.
A schematic of the experimental apparatus use to purge and
charge the sample bottles is shown in Fig C-1.
This procedure was carried out by first displacing the sample
bottle floating piston down to the bottom of the bottle using
Oxygen-free Nitrogen while allowing glycol to freely drain.
The cylinders were then purged by repeated pressurization and
release cycles with the Oxygen-free Nitrogen, before finally
using the liquid displacement pump to lift the floating piston
back to the top of the sample chamber. The remaining dead
space volume was then thoroughly flushed with Oxygen-free
Nitrogen followed by the nominal 500 ppmv H2S / CH4
mixture.
Charging of the sample bottles was carried out by using the
pressure within the supply cylinder to displace the floating
piston back to the bottom of the bottle while again allowing
glycol to drain freely. The test bottles were then heated to 158
degF using a heating rope and an insulating blanket. The final
3000 psig test pressure was achieved by using the liquid
displacement pump to raise the floating piston after sealing
and properly thermosetting the bottles at 158 degF.
Following achievement of the full test conditions (3000 psig
and 158 degF), time zero was noted and the apparatus was
disengaged from the feed cylinders. Samples of both the feed
gas and test cylinders were then analyzed immediately after
charging and additional analyses were performed roughly
every day for the first 3 to 4 days and then every other day
after this period.

The sampling procedure consisted of using a double block and


bleed system that was intentionally kept to a minimum
practical size. This system was comprised of the bottle valve
itself at one end attached to a short piece of high pressure
tubing and valve, and was purged twice before sending the gas
to the injection loop of the gas chromatograph. Generally
three consecutive analyses were obtained with a full depletion
and recharging of the sample system between each analysis.