SPE 71541
The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen
Sulphide Scavengers
J.G.R. Eylander, SPE, H.A. Holtman, Nederlandse Aardolie Maatschappij, T. Salma, SPE, M. Yuan, SPE, M. Callaway,
and J.R. Johnstone, SPE, Baker Petrolite
Copyright 2001, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2001 SPE Annual Technical Conference and
Exhibition held in New Orleans, Louisiana, 30 September–3 October 2001.
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Abstract
The toxicity of hydrogen sulphide in hydrocarbon
streams is well known in the industry and considerable
expense and efforts are expended annually to remove
hydrogen sulphide to a safe level. In large production
facilities, it is generally economical to install a regenerative
system for treating sour gas streams. However, during the
development stages of relatively small low-sour gas fields at
remote and normally unmanned locations where regenerative
systems are not practical nor economical, it is necessary to
treat the sour gas production with non-regenerable scavenging
processes. In the development of its low-sour Zechstein gas
reserves in the Coevorden field in the North-East The
Netherlands, the Nederlandse Aardolie Maatschappij (a Shell
operating unit, hereafter referred to as NAM) decided to adopt
continuous direct-injection of liquid scavenging agents as the
lowest overall cost process having the least environmental
impact and the highest energy efficiency. At the inception of
the project, the operating parameters controlling the
scavenging efficiency using direct injection of liquid
scavengers in this system were largely unknown.
Consequently, numerous field trials using different chemistries
and different injection mechanics had to be carried out.
In this paper we present the results of these field
trials, which ultimately led to a very successful and profitable
field development strategy. A variety of very challenging
operational problems were encountered, and solved. Reference
is made to injection nozzle blockages, fouling of glycol gas
dehydration systems, severe scaling problems in production
and downstream water treatment/injection facilities,
inadequate hydrogen sulphide removal efficiencies and HS&E
related issues. A better understanding of the fundamental
relationships between operating parameters governing direct-
injection processes and associated chemical development and
application methods has been gained. Communication and
integration of experience and knowledge between the
operating unit and its chemical supplier were key success
factors in this achievement, as was the endurance and
continuing support of field operations staff in facilitating the
resolution of difficult problems.
Introduction
NAM’s Ten Arlo system (Fig. 1) produces gas from
32 satellite locations and four gas treatment / compression
plants. The majority of the fields in the system produce sweet
gas from the Limburg reservoir. However, the system’s
heavily compartmentalized Coevorden field also contains gas
accumulations in the Zechstein reservoir with H2S
concentrations up to 300 ppm(v). Developing these
accumulations would require extensive modifications to
existing (sweet) gas production / treatment facilities to ensure
safe operations and the prevention of H2S emissions. The
producible reserves were small yet economically attractive.
However, due to their geographical scatter, a pipeline grid
connecting these low-sour accumulations to an existing nearby
plant utilizing a regenerative solvent process for gas
sweetening was found to be economically unfeasible. In-field
desulpherisation with, for example, a solid-bed adsorption
process, was found to be technically feasible, but the required
capital investment and perceived life-cycle costs could not be
justified. In order to allow production of the low-sour gas
without violating the Ten Arlo sales gas specification for
maximum allowable H2S concentration (5 mg H2S/Nm3 or 3
ppm(v)), in-field desulpherisation utilizing a commercially
attractive alternative technology was looked for.
Direct-Injection H2S Scavenging
The injection of chemicals into produced gas streams
to remove H2S is a fairly old industry practice. Formaldehyde
2 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone
has been one of the most frequently used materials, but its use
is strongly discouraged owing to the reported carcinogenic
properties. Chemistries such as sodium chlorite, caustic soda,
glyoxal and others have been tested as well. These chemistries
often have severe disadvantages associated with them, ranging
from handling and operational problems as a result of high
reactivity to slow reaction rates. The development of a non-
regenerable class of chemistry commonly referred to as
triazines was disclosed in 1990. The term ‘triazines’ is used
for a group of compounds, which in reality are substituted
hexa-hydro triazines. In this paper, the terms ‘triazine’ and
‘hexa-hydrotriazine’ will be used interchangeably. A general
representation of a substituted hexa-hydro triazine is given in
Fig. 2, in which R1 to R6 may be arbitrary hydrocarbon
groups. Two well-known triazine forms are disclosed in
patents1,2, in which R1, R2 and R3 are ethanol or methyl
groups, respectively, and R4, R5 and R6 are hydrogen. The
products are produced on a technical scale by reacting either
monoethanolamine (MEA) or a trimethylamine (TMA) with
formaldehyde.
The actual reaction mechanisms of triazine
compounds with H2S are not well understood. The reaction is
complex and produces multiple reaction products. However,
repeated laboratory analysis of spent MEA triazine using
NMR C13 spectroscopy has established that H2S reacts
irreversibly with MEA triazine with the S-atom being built
into the ring structure forming primarily two sulfur containing
products – thiazine and dithiazine. In the reaction of MEA
triazine with H2S, the sulfur atoms are in the S2- oxidation
state so that solid elemental sulfur does not form and the
reaction products are liquid. Depending upon treatment rates,
the reaction also releases either one or two molecules of
water-soluble alkanolamine molecules: R-NH2. Because at
least one R group is retained in each product, the primary
products of the reaction of MEA triazine with H2S are low
volatility liquids that are soluble in water (see Fig. 2).
First field experiences
A first field trial was carried out in 1995 at the
Coevorden-24 location utilizing a 1,3,5-trimethyl-hexahydro-
1,3,5 triazine (product A from supplier A), with injection
upstream of the glycol dehydration unit (Fig. 3). During the
trial gas production originated primarily from two wells, with
the gas containing 24 and 45 ppm(v) H2S respectively.
Injection took place without the use of an atomizer and at a
dosage rate of approximately 6 L/kg H2S. As a result of the
injection, the H2S concentration in the location’s export gas
decreased to well below the 5 mg/Nm3 limit. However, it was
found that 40% by weight of the chemical did not react and
ended up in the produced water phase. Not only did this result
in a potential water disposal problem (owing to prevailing
legislation), also an unusual accumulation of solids was
encountered in the glycol system. The subsequently required
change-out of the wet glycol filters resulted in unacceptable
amine-type emissions spreading well beyond the location.
Furthermore, the functioning of the in-line H2S analyzer (of
the type utilizing a lead acetate tape) was disrupted.
SPE 71541
Given the disappointing product yield (i.e. percent
reduction in H2S) and the encountered operational problems,
the decision was taken to repeat the trial with a more
concentrated version of the same triazine. Initially this product
was injected downstream of the glycol dehydration unit
directly into the location’s export gas flowline with the aid of
an atomization nozzle at a dosage rate of approximately 4
L/kg H2S. Repeated blockages of the nozzle quickly resulted
in its removal and the trial was continued without it. Emphasis
was placed on determining the product yield and
substantiation of the manufacturer’s claim that reaction
products would preferentially dissolve in the co-produced
condensate. It was found that injection of the more
concentrated product in the pipeline-wet export gas stream
rapidly reduced the H2S level to well below the contractual
limit, with an H2S reduction of approximately 97%. This
represented a major improvement with respect to the first trial.
As illustrated in Table 1, both unreacted and reaction products
were preferentially soluble in the produced water phase. The
presence of unspent and reacted scavenger in the water
necessitated permit application for the installation and use of
permanent injection facilities on the location, which were
installed in 1996. The chemical cost associated with the
subsequent continuous H2S scavenging treatment of the export
gas stream amounted to approximately US$ 30 per kg H2S.
Field development progression
Several problem areas developed over time with the
chemical scavenging application as described above. Ten
Arlo’s central gas treatment plant was confronted with
increasing pH levels in the glycol dehydration system and
amine emissions from vessels and drain pits, phenomena
which were traced to the scavenger application on the
Coevorden-24 location. Development of low sour gas
accumulations at certain satellite locations lacking gas drying
facilities was not feasible with this scavenger application, not
only because transport lines did not meet the NACE
specification for sour service but also chemical costs would
quickly become prohibitive. By 1997, the requirement for
H2S scavenging at the wellhead, driven by economics of the
operation combined with increasing operator complaints about
amine emissions, triggered field testing of an alternative H2S
scavenger consisting of 1,3,5-tri(2-hydroxyethyl)-hexahydro-
1,3,5-triazine (product B from supplier B). To distinguish
between the tests, three principal injection regimes were tested
as depicted in Fig. 4, without the use of atomization nozzles.
Results are given in Table 2.
Test A: wet gas injection regime, moderate residence time
Scavenging of H2S from 40 ppm(v) to the required
<3 ppm(v) required a scavenger dosage of approximately 10
L/kg H2S. In order to establish whether the H2S is indeed
removed via the produced water phase, a sulfur balance was
made on the water, condensate and gas phases. During the test
period the sulphide concentration in the produced water phase
is seen to increase and the sulfur balance (gas to liquid) climbs
from an initial 44% to an 85% fit at the end of the test. The
SPE 71541 The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen Sulphide Scavengers
slow establishment of equilibrium is explained by the inability
to fully drain produced water from the test separator prior to
test execution.
During the test, the pH of the produced water
increased from an initial 5.6 to 7.4 as the scavenger dosage
increased. Massive overdosing of the scavenger raised the pH
to 7.6. Throughout the test period and even for a prolonged
period thereafter, no solids or scale formation was observed in
the sampled fluids. However, produced water samples
developed a yellowish color over time.
Test B: wet gas injection regime, short residence time
Decreasing the contact time between the scavenger
and gas had a negative impact on the consumption of the
product. Given the short duration of the test, no other
conclusion from this observation was drawn other than that it
could possibly support an observation from other work3 that
the chemical injection rate has an effect on the mass transfer
of the chemical.
Test C: dry gas injection regime, long residence time
In this regime, we expected the scavenger to
scavenge H2S from the dry gas, albeit inefficiently, with the
reaction products falling out as solids in the absence of water.
In this test, injection of the scavenger in the dry gas stream
downstream of the glycol dehydration system had no
noticeable effect on the H2S concentration in the gas. This
confirmed the earlier observation that the scavenging reaction
takes places in the produced water phase. The product’s
manufacturer claimed that a minimum required water content
of 2 L/million Nm3 of gas was needed.
One of the objectives of the above tests was to prove
that neither the chemical nor its reaction products would cause
any adverse effects on water-condensate separation/quality
and on the performance of the glycol dehydration system. No
such effects were observed, but the relatively short test period
could not provide conclusive evidence. From the test results it
was concluded that the scavenger was very effective at
removing small quantities of H2S from wet/saturated gas
streams. If sufficient contact time was provided for, the
required dosage of 10L/kg H2S, while a factor 2.5 higher than
that required for the export gas scavenger, still provided a
reduction in chemical costs to approximately US$ 10 per kg
H2S. Given the positive trial outcome, permanent injection
facilities for product C were installed on the location’s main
header while retaining the scavenger (product B) injection into
the export gas stream as back-up facility. In order to gain
confidence that product C could also be used on satellite
locations by direct-injection at the wellhead, a more rigorous
field trial was designed that was also aimed at optimizing the
treatment to achieve further cost reductions.
3
Extended field testing
Well Coevorden-26 on the Coevorden-24 location
was selected for this field trial. This well is completed on both
the (sweet gas producing) Limburg reservoir and the (low sour
gas producing) Zechstein reservoir. The pressure balance
quickly favors (fractured carbonate) Zechstein production
after the well is opened up to the extent that steady state gas
production with an H2S concentration increasing to
approximately 130 ppm(v) can be maintained for a period of
about 10 days (see Fig. 5). After this time, the on-set of liquid
loading necessitates well shut-in for several weeks to achieve
pressure build-up.
Early 1998 the well was connected to the test header
(see Fig. 4), with the injection point (without atomization
nozzle) as per Test A of the previous field trial. Injection of
product C commenced simultaneously with gas production,
with the scavenger injection rate set at the maximum expected
H2S level at the recommended dosage of 10 L/kg H2S. The
implied over-injection of the chemical was intended. During
the trial period, the H2S scavenging performance matched that
of the first trial, yielding H2S reduction in excess of 99%.
However, a gradual increase in the pressure drop across the
flowline connecting the well to the test header from an initial
(normal) 2 bar to 8 bar was also observed. Subsequent internal
inspection of the flowline revealed that massive calcium
carbonate scaling had occurred at and several meters
downstream of the injection point. Following flowline clean-
up through acidization, a repeat trial was carried out, this time
utilizing an atomization nozzle and preventing over-injection
by tailoring the scavenger injection rate to the actually
produced H2S concentration. Although this reduced scale
deposition to a certain extent, the net results were far from
satisfactory.
Given the potential threat to the Coevorden field
development plans, a major effort was undertaken in
conjunction with the chemical supplier to solve the scaling
problem. An experimental scavenger was developed (product
D from supplier B), in which product C was blended with a
phosphonate-type scale dispersant. Late 1998 through 1999, a
prolonged period of often-problematic field-testing followed
utilizing this experimental product. Without going into details,
the following observations were made during this period:
‰ The experimental product appeared to be effective in
mitigating the deposition of calcium carbonate scale.
However, the chemistry employed in formulating the
product resulted in excessive formation of a very viscous
foam, disrupting flow and liquid level control systems and
carrying the risk of spillover into the glycol dehydration
facilities.
‰ To counteract foam formation, a silicone polymer
emulsion was mixed into the scavenger/scale dispersant
blend. The resulting mixture appeared to be inherently
unstable, requiring continuous mixing on site to avoid
phase separation. Notwithstanding, it proved to be
impossible to achieve a homogeneous mixture and foam
suppression was only partially achieved. In addition, a
4 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone
50% reduction in the product performance in terms of
liters of product required per unit mass of hydrogen
sulphide removed was experienced.
‰ Sludge formation occurred in the flowline (see Fig. 6), in
the test separator and in downstream water/condensate
storage facilities to the extent that it became unacceptable.
Irrespective of the encountered problems, it was observed that
the scavenger injection rate had an effect on the product yield,
but contrary to published results from earlier work3, no clear
pattern could be established. Factors complicating result
interpretation are that (a) lowering of the flowing tubing head
pressure results in higher linear gas velocities in the flowline
and (b) the concomitant increase in the hydrostatic head in the
well results in higher water-gas ratio’s. The dilution resulting
from the latter could alter the stoichiometry of the reaction
between the triazine and H2S such that the triazine could
possibly react with more H2S (on a molar basis) than in the
(relative) absence of dilution effects. During the various trials,
in going from higher to lower linear gas velocities the net
reduction in H2S was seen to decrease at first, but after passing
through a minimum a higher reduction in H2S was observed
again. This would seem to indicate higher scavenger injection
rate requirements at lower linear gas velocities, when there is
less water production. The significance of these observations
could only be ascertained after a solution was found for the
encountered problems. It was conceded at the time by the
incumbent chemical supplier that such a solution could not be
made available in the time remaining for the required firming
up of field development plans.
Further product developments
The field testing of hydrogen sulphide scavengers
carried out thus far had generated a number of very clear
technical performance criteria for wet gas application.
Claiming the successful development of a combined
scavenger/scale inhibitor formulation, which could meet these
criteria, supplier C was invited to participate in field testing of
this product (product E). The claim was founded as follows:-
Product E was developed specifically to minimize
calcium carbonate scale formation that would normally arise
from using a highly alkaline triazine scavenger in calcium and
/ or high bicarbonate produced water. Based on extensive
laboratory evaluation of various scale inhibitors, a proprietary
phosphonate scale inhibitor was identified as the most
effective at combating calcium carbonate scaling resulting
from injection of triazine into a produced brine. The
laboratory experiments indicated that, (a) addition of the
chosen scale inhibitor significantly reduced calcium carbonate
scaling tendency, (b) it had no adverse effect on H2S
scavenging efficiency of the triazine, and (c) it did not cause
fluid foaming. The result was the development of product E
that contained an optimum percentage of the chosen scale
inhibitor.
The scale inhibitor is completely soluble in high pH
brines and it exhibits a high efficiency at inhibiting high pH
induced scale precipitation. It is known that this is a nucleation
SPE 71541
inhibitor, that is, it inhibits the nucleation of calcium carbonate
scale crystals, thus keeping the scaling ions in solution.
Next generation field-testing
Following flowline clean up through acidization,
field testing of product E was initiated on well Coevorden-26
in the same manner as the preceding field test, i.e. injection at
the wellhead through an atomization nozzle. Results are
shown in Fig. 7. Injection at a dosage of 10 L/kg H2S (slightly
higher than the supplier recommendation of 8 L/kg H2S)
yielded an average H2S reduction of 70%. By increasing the
dosage to approximately 15 L/kg H2S, the reduction in H2S
rose to approximately 93% (against a stipulated performance
criterion of >99%). Reducing this dosage to lower levels was
immediately coupled with increasing residual H2S levels.
The influence of the linear gas velocity on the
product yield is shown in Fig. 8, whereby the observed data
have been fitted to a calculated trend utilizing Holt’s two-
parameter linear exponential smoothing method4. The trend
appears to indicate the existence of a threshold limiting value
above which the product yield is independent of the linear gas
velocity; the injection rate seems to have little influence.
During the test no increase in the pressure drop
across the flowline was observed. However, a camera-run
revealed the presence of a thick layer of calcium carbonate
scale blocking the top half of the flowline (Fig. 9). From this
observation was concluded that the flowline acidization
preceding the test had only been partially effective. It was
therefore decided to repeat the test after cleaning the flowline
through sequential high-pressure water jetting and acidization,
followed by a camera-run to confirm that the required clean-
up had been achieved. With the scavenger injection rate set at
the maximum expected H2S level (and hence an initial
massive overdosing), the results shown in Fig. 10 were
obtained. Throughout the test, as the amount of overdosing
decreased with increasing H2S level in the produced gas, an
average H2S reduction (product yield) of 97% was achieved at
the expense of an overall average dosage of 20 L/kg H2S.
Again, no increase in pressure drop across the flowline was
observed, but a camera-run revealed the presence of thick
sludge layer on the bottom of the flowline and randomly
deposited cauliflower-like deposits (Fig. 11). Clearly,
overdosing to achieve the targeted H2S reduction was not the
way forward. The disappointing product yield at higher than
expected dosage requirements seen in the first test also
indicated that an alternative approach was required to reach
our objectives.
Challenge of chemical delivery method
Following a period of consultation with the chemical
supplier, the suitability of the hitherto used chemical delivery
method was challenged. In the preceding field tests, use had
been made of an atomization nozzle specifically designed to
avoid the blockage problems experienced with the
conventionally designed nozzles some years earlier. Design
review raised the suspicion that an inefficient atomization
process might be the key contributing factor to the problems
SPE 71541 The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen Sulphide Scavengers
experienced. It was proposed to utilize Bete® PJ series direct-
pressure atomization nozzles, adapted to allow the use of high-
pressure gas to boost the velocity in the atomizer nozzle. Both
laboratory and field evaluation of such gas-assisted (2-phase)
atomization nozzles had shown approximately 30% efficiency
improvement over the normal single phase atomization.
Again, utilizing sequential high-pressure water jetting
and acidization, the flowline was cleaned (confirmed through
camera-run) and a 2-phase atomization nozzle installed, the
high-pressure gas being delivered via nitrogen batteries.
Injection was subsequently initiated, initially at the supplier
recommended product dosage and gas-assist pressure of 20 –
25 bars above the flowing tubing head pressure. Results of this
next test are provided in Fig. 12. The percentage H2S removal
initially obtained with the 2-phase atomizer was disappointing.
However, scavenging performance could be improved upon
by changing product injection rates and nozzle sizes.
Ultimately, the desired reduction in H2S was achieved, but
only at a high product dosage of some 20 L/kg H2S. By
reducing the gas-assist pressure to only 2 – 3 bar above the
flowing tubing head pressure, an H2S reduction (product yield)
>99% could be consistently achieved at a product dosage of
approximately 15 L/kg H2S. This result was maintained at the
tail end of the test, when the gas-assist needed to be shut-in
due to depletion of the nitrogen batteries. A subsequent
camera-run through the flowline showed the complete absence
of any scale deposits or sludge.
Mitigation of scale build-up in the flowline was only
one of the two objectives that were successfully met by the use
of the gas-assisted atomizer. The other objective was to obtain
higher scavenging efficiencies as was observed in previous
laboratory and field trials using the gas-assisted atomizer.
However, further evaluation indicated that such increased
scavenging efficiencies were primarily observed in low-
pressure systems with operating pressures less than 5 to 10
barg. In the Coevorden field, the operating pressures were
significantly higher, ranging from 35 to 75 barg. This is
thought to be the key contributing factor in not achieving
further improvement in scavenging efficiency using gas-
assisted atomization. The matter was not further pursued,
principally because very few of the locations targeted for
development had gas available at sufficiently high pressure to
achieve 2-phase atomization (implying a compression
requirement) and commercially available nitrogen gas
generators could also not deliver the required pressures. Given
the observation at the tail end of the last test that product yield
could be maintained without gas-assist, the decision was made
to carry out an additional trial.
Prior to discussing this additional trial, it is of interest
to revisit the trial discussed above. The influence of the linear
gas velocity on the product yield is shown in Fig. 13, whereby
as before the observed data have been fitted to a calculated
trend utilizing Holt’s two-parameter linear exponential
smoothing method4. Comparing with previously obtained
results, recalling that then also different atomization nozzles
are compared, it is again seen that the product dosage (and
hence injection rate) seems to have little influence. In this test,
5
the linear gas velocity did not enter the region lower than 4
m/s where the earlier test showed evidence of the existence of
a threshold limiting velocity value. A more rigorous
examination of the data obtained from the current test revealed
that they could be fitted to the equation:
Product yield (%) = m * linear velocity (ms-1) + b (r2 = 0.71)
through linear regression analysis with the same mean
absolute percentage error as the fit obtained with Holt’s
method.
Dual injection
In gas systems where short contact times and high
H2S loading are specifically challenging towards efficient
reduction in H2S, injection of chemical at multiple injection
points has often been used to improve the scavenging
efficiency. After the 2-phase atomizer trial, a dual injection
approach was utilized in the Coevorden system by injecting
the chemical both at the wellhead and at the test header.
Use of dual injection resulted in >99% removal of
H2S and thus yielded the desired results in scavenging
efficiency. Improved scavenging efficiency in a multiple
injection system (in this case two-point injection) can be
explained as follows. Firstly, the volume of scavenger injected
at the first injection point (wellhead) is typically less than the
stoichiometric amount needed to react with the total H2S in the
gas. Presence of scavenger in limiting quantities allows for
optimum utilization of the scavenger. Therefore, scavenger
injection at the first point removed the bulk of the H2S (75 –
85% reductions in H2S). Secondly, injection of the scavenger
at the second point (test header) provides a polishing or
finishing effect. The neat high strength scavenger contacts the
lean gas (low in H2S) to react with the residual H2S molecules
that were not removed after the first scavenger injection. The
limiting reactant at the second point is the H2S and can be
removed by the high concentration of the scavenger. The dual
injection system using product E, applied through single phase
Bete® nozzles, yielded removal efficiencies in the range of
99%, reduced scavenger consumption to, on average 9 L/kg
H2S and provided effective control of calcium carbonate
scaling.
Current development status
Prior to the high gas nomination period of the Winter
2000/2001, two satellite locations of the Coevorden-17 gas
treatment plant were converted to facilitate the production of
low-sour gas wells with H2S levels of up to 220 ppm(v)
through dual injection of product E. An extended optimization
program, through which overall product dosages of as low as 7
L/kg H2S could be achieved as well as consistent product
yields of >99%, is coupled with further investigation of the
operating parameters affecting the scavenging reaction.
Scientifically intriguing but operationally of little consequence
are the following observations. Well Coevorden-31 produces
gas at an initial rate of 420,000 Nm3/day, gradually declining
to 310,000 Nm3/day at a constant flowing tubing head
6 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone SPE 71541

pressure of approximately 90 bar and with a constant H2S
concentration of approximately 220 ppm(v). The linear gas
velocity is in the range 9 – 12 m/s. Injection of product E at
the wellhead alone does not result in the desired H2S reduction
(product yield), and it needs to be augmented with a second
point injection at the main production header. At another
satellite location, well Coevorden 36 produces gas at a fairly
constant rate of 400,000 Nm3/day at a flowing tubing head
pressure of 70 bar and with a constant H2S concentration of
220 ppm(v). The linear gas velocity is approximately 6 m/s.
Injection of product E at the wellhead alone yields the desired
H2S reduction, and at this location no second point injection is
required. As other wells are being brought on stream, more
data can be gathered to hopefully unravel the apparently
complex role of interlinked process parameters on the physical
chemistry of direct-injection hydrogen sulphide scavenging.
No evidence of scale formation has been encountered
to date at any of the locations where product E is being
applied. Chemical costs are approximately US$ 11 per kg H2S
(slightly lower or slightly higher in individual cases). Back-up
facilities utilizing product B (in pipeline-dry export gas
treament) are required during well start-up, but only when fast
production ramp-ups are employed. The benefits5 of
automation of the hydrogen sulphide chemical scavenger
injection systems, combining currently available technology
into a multi-faceted cost saving and reliable tool, are
recognized and its economic implementation is being pursued.
support and dedication in the face of adversity. We have
exceptional pride in their and our refusal to yield.
References
1. Dillon, E.T., Composition and method for sweetening
hydrocarbons. U.S. Patent no. 4,987,512, December 1990.
2. Bhatia, K., Thomas, A.R. & Sullivan, D.S., Method of
treating sour gas and liquid hydrocarbon streams.
European Patent Application 94305225.8, February 1995.
3. Fisher, K., Initial results from GRI’s 30 MMscf/day
direct-injection H2S scavenging test facility. Paper
presented at the Eight Gas Research Institute Sulfur
Recovery Conference, Austin, Texas, October 1997.
4. Kvanli, A.H. et al, Introduction to Business Statistics.
West Publishing Co., 1992, p. 745 f(f).
5. Roth, D. et al, Automated chemical control of H2S content
of natural gas. Paper SPE 67247, presented at the SPE
Production and Operations Symposium, Oklahoma City,
Oklahoma, 24-27 March 2001.

Conclusions
1. Selection and application of direct-injection liquid
hydrogen sulphide scavengers requires an understanding
of the fundamental relationships between operating
parameters and scavenging (physico-)dynamics.
2. More fundamental research, preferably executed ‘in the
field’ is required to unequivocally identify these
relationships and to allow ‘best in class’ design of
treatment applications.
3. In applying direct-injection liquid hydrogen sulphide
scavenging technology, a systematic as well as a systemic
approach, with continuing challenge of chemical supplier
claims, is required to achieve the desired results.
4. Mutually beneficial solutions to problems can be found
between operating companies and their preferred
chemical suppliers by not concentrating on internally
focused commercial ambitions but by concentrating on:
we shall solve this problem together, regardless. And
reaping the benefits of such solutions.

Acknowledgements

We thank NAM and Baker Petrolite Corporation for

their permission to publish this paper. In particular, very
special thanks goes out to NAM’s operations staff, not only
for providing gas treatment plants and field personnel to
support this project while maintaining active production
operations, but more importantly also for their continuing
 Table 1: Fate of unreacted triazine (product A) and reaction products

Stream Concentration Concentration

unreacted triazine reaction products
(mg/kg) (mg/kg)

Produced water ± 200 ± 250

Condensate None detected <1

Table 2: Test results with product B

Qgas Pgas Tgas Contact Linear Qinj.pump H2S H2S Scavenger S2- in Sulfur Produced
Time gas removed Dosage water balance water
velocity pH
(E3 m3) (bar) (oC) (s) (m/s) (L/d) (ppm(v)) (%) (L/kg) (mg/kg) (%)

Test A 145 61 36 - 5.4 0 40 0 0 4 - 5.6

145 61 36 19.3 5.4 41 21 48 9.9 2100 43.9 7.0

245 45 45 8.2 12.7 123 4 90 9.6 6800 75.1 7.4

245 45 45 8.2 12.7 159 0.4 99 10.9 8500 85.3 7.4

245 45 45 8.2 12.7 327 0 100 - 7.6

Test B 234 41 49 - 13.6 0 29 0 0 - - -

234 41 49 1.8 13.6 95 10 65 14.2 - - -

234 41 49 1.8 13.6 136 3 90 14.7 - - -

234 41 49 1.8 13.6 218 1.2 96 22.1 - - -

8 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone SPE 71541

Figure 1: the Ten Arlo gas gathering system

Ten Arlo
gathering station

Wannerperveen De Wijk
satellites satellites

Coevorden-24 gathering Coevorden-17 gathering

station station

Coevorden-33 satellite Coevorden-31 satellite

Coevorden-20 satellite Coevorden-5 satellite

Coevorden-21 satellite Coevorden-10 satellite

Den Velde satellite Hardenberg-2 satellite

Hoogenweg satellite Hardenberg-4 satellite

Fig. 2. Reaction pathway of triazine and H2S

H2S(g) H2S absorbs into the aqueous triazine solution where, because of the latter's
alkaline pH, it can be expected to fully dissociate into the HS- ion. It is this
species which subsequently reacts with the triazine molecule. The rate of
the chemical reaction is dependent on the mass transfer rate, which in turn
is dependent both on physical (diffusion) and chemical processes in the
aqueous phase.

R1 R1 R1

N N N

H2C CH2 H2S H+ + HS- H2C CH2 H2C CH2

N N
R3 R2 N S S S
C R3 C C
H2 H2 H2

1,3,5-hexahydro-triazine thiazine dithiazine

SPE 71541 The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen Sulphide Scavengers 9

Fig. 3. Simplified set-up field trial with product A

Injection point with product A

Gas from satellites

Main header
COV-2

Glycol
COV-21 contactor
tower Injection point with product B

COV-33
Export gas to Ten Arlo

Fig. 4. Simplified set-up field trial with product B

Gas samples
Injection point Test B

Gas to slugcatcher

Injection point Test A

Testheader

Testseparator
(approx. 100m, 4" line)

Liquid samples
COV-24 well, 40 ppm(v) H2S (approx. 25 m, 4" line)

Water/condensate to tank

Gas from satellites

Main header
COV-2

Glycol
COV-21 contactor
tower Injection point Test C

COV-33
Export gas to Ten Arlo

(approx. 70m, 10" line)

Gas samples
10 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone SPE 71541

Fig. 5. H2S production profile of well Coevorden-26 at Q = 100,000 Nm3/day

ppm(v) kg/day

1000

100
H2S concentration

10

1
0.00
4.00
14.33
33.50
50.50
61.00
74.00
86.00
96.67
114.50
117.58
120.00
122.00
127.67
141.17
145.50
156.27
218.27
236.52
0
Time (hours)

Fig. 6. Sludge formation in flowline

Sludge layer
SPE 71541 The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen Sulphide Scavengers 11

Fig. 7. Results 1st field trial with product E

H2S at wellhead H2S at manifold Scavenger injection

20.00 18.0

18.00
16.0

16.00
14.0

14.00
12.0

12.00

10.0
kg H2S/day

L/kg H2S
10.00

8.0

8.00

6.0
6.00

4.0
4.00

2.0
2.00

0.00 0.0
00

00

00

00

0
50

50

58

50

00

00

00

42

84

17

50

50

42

27

77

27

52

52
.3

.0

.5

.2

.5

.0

.0

.0

.0

.0

.0

.5

.6

.0
0.

1.

4.

9.

4.

5.

7.

8.

0.

1.

2.

3.

9.

1.

2.

5.

6.

6.

2.

8.

4.

6.
14

29

33

45

50

55

61

68

74

80

86

91

96

98
11

11

11

11

12

12

12

12

13

14

14

14

14

15

21

21

23

23
Normalized time (hours)

Fig. 8. Influence of linear gas velocity

Measured Calculated Inj. rate

100.0 500
Scavenger ing. rate (L/d)

80.0 400
Product yeild (%)

60.0 300

40.0 200

20.0 100

0.0 0
3.83 3.87 3.91 3.95 3.99 4.03 4.04 4.21 4.29 4.33 4.35 4.38 5.31 5.40
Linear gas velocity (m /s)
12 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone SPE 71541

Fig. 9. Calcium carbonate scale in flowline

Top of line

CaCO3 scale deposit

top of flowline Picture Orientation

Bottom of line
SPE 71541 The Development of Low-Sour Gas Reserves Utilizing Direct-Injection Liquid Hydrogen Sulphide Scavengers 13

Fig. 10. Results 2nd field trial with product E (overdosing conditions)

H2S wellhead H2S manifold Scavenger inj.

25.00 40.0
35.0
20.00
kg H2S/day

30.0

L/kg H2S
15.00 25.0
20.0
10.00 15.0
5.00 10.0
5.0
0.00 0.0
0
0
0

11 5
14 0
14 0
16 3
18 3
25 3
83
00
75
.0
.5
.0
.7

5
0
8
8
3
9.
2.
8.
2.
6.
4.
0.
4.
26
29
48
75

Normalized time (hours)

Fig. 11. Sludge layer and cauliflower-like deposits

14 J.G.R. Eylander, H.A. Holtman, T. Salma, M. Yuan. M. Callaway, J.R. Johnstone SPE 71541

Fig. 12. Results of 2-phase atomization trial with product E

H2S wellhead H2S manifold Scavenger inj.

25.00 30.0

20.00 25.0
kg H2S/day

20.0

L/kg H2S
15.00
15.0
10.00
10.0
5.00 5.0
0.00 0.0

133.25
162.25
168.25
189.92
210.00
225.25
22.75
40.25
43.25
46.25
64.75
93.25
0.00
7.08

Normalised time (hrs)

Fig. 13. Influence of linear gas velocity

Measured Calculated Dosage

120.00 30
Product dosage (L/kg H 2S)
100.00 25
Product yield (%)

80.00 20

60.00 15

40.00 10

20.00 5

0.00 0
15

46

68

02

14

27

53

94

63

70

86

02

02
4.

4.

4.

5.

5.

5.

5.

5.

6.

6.

6.

7.

7.

Linear velocity (m /s)