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Investigation of Interactions between Gas Hydrates
and Several Other Flow Assurance Elements
Shuqiang Gao
Energy Fuels, 2008, 22 (5), 3150-3153 • DOI: 10.1021/ef800189k • Publication Date (Web): 12 July 2008
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3150 Energy & Fuels 2008, 22, 3150–3153

Investigation of Interactions between Gas Hydrates and Several

Other Flow Assurance Elements
Shuqiang Gao*
Champion Technologies, Fresno, Texas 77545

ReceiVed March 17, 2008. ReVised Manuscript ReceiVed May 15, 2008

Flow assurance is a critical task during oil/gas production, especially in deep-water or cold weather conditions.
It involves effectively handling many solid deposits, such as, hydrates, asphaltene, wax, scale, and naphthenates.
Because these deposition elements can coexist, evaluating and addressing each problem in isolation may be
inefficient and risky. Instead, a comprehensive approach needs to be sought to take into account the impact of
one element on the others. In this work, experiments were conducted to systematically investigate how gas
hydrates are related to other flow assurance factors and how these interactions could affect the performance of
antiagglomerate hydrate inhibitors (AAHI). It was demonstrated that one type of solid precipitate can promote
and exacerbate others. It was also shown that the elimination of one issue can alleviate other associated risks.

Introduction Wax5 is composed of high molecular weight, highly saturated

As hydrocarbon production moves into more hostile environ-
ments, like deeper water1 and arctic regions,2 flow assurance
increasingly becomes more difficult. Assuring the profitable flow
of fluids from the well to the point of sale involves properly
handling organic and inorganic deposits, such as gas hydrates,
asphaltene, paraffin, scale, and napthenates.
Gas hydrates3 are non-stoichiometric crystalline compounds
composed of nanoscale water clathrate cages that enclose guest
molecules that have appropriate diameters. The light alkanes
(methane, ethane, propane, etc.) commonly encountered during
oil/gas exploration can form gas hydrates with the produced
water under appropriate temperature and pressure conditions,
such as 40 °F and 500 psi. The hydrate particles can agglomerate
into hydrate plugs that restrict or completely block the flow of
produced fluids in flowlines, resulting in lost production and
posing potential safety hazards for operational personnel. Gas
hydrates are a chief flow assurance concern for deep water
production because of the low temperatures (40 °F) and high
pressures (>1000 psi) that exist in such environments.
Asphaltenes4 are a collection of heavy polar components in
crude oils that are soluble in aromatic solvents like toluene but
insoluble in alkanes such as heptane. The solubility of asphalt-
enes in crude oils depends on fluid composition, pressure, and
temperature. Disturbance to these parameters during oil produc-
tion can change the asphaltene solubility and cause asphaltene
precipitation. This is a flow assurance issue because they can
deposit in production tubing and flowlines, thus decreasing the
production capacity.
Phone: 281-710-9598. Fax: 281-431-3615. E-mail: shawn.gao@champ-
tech.com.
(1) Mehta, A.; Walsha, J.; Lorimerb, S. Ann. N.Y. Acad. Sci. 2000, 912,
366–373.
(2) Peyton, H. R. J. Petrol. Technol. 1970, 22 (9), 1076–1082.
(3) Sloan, D. Hydrate Engineering; Society of Petroleum Engineers:
Richardson, TX, 2000.
(4) Branco, V. A. M.; Mansoori, G. A.; Xavier, L.G.D.A.; Park, S. J.;
Manafi, H. J. Petrol. Sci. Eng. 2001, 32, 217–230.
hydrocarbons that only contain hydrogen and carbon. Its
solubility in crude oil is strongly dependent on temperature and
slightly influenced by pressure. Wax is stable under reservoir
conditions where the temperature is above the wax appearance
temperature (WAT) of the crude. WAT can vary wildly from
crude to crude, ranging from below 10 °C to higher than 50
°C. When the crude oil flows into the flowlines, the temperature
may fall below the WAT, where solid wax starts to precipitate
out of the oil phase. The wax crystals can deposit inside the
flowlines and restrict the production stream. Therefore, wax is
a serious flow assurance threat for offshore and cold weather
productions.
Scale6 is defined as inorganic mineral constituents of water
that precipitate from solution to form hard adherent deposits.
Scale can form whenever the amounts of dissolved minerals
exceed their solubilities in water, which can be induced by
changes in pressure, temperature, or water chemistry. The most
common scales encountered in the oilfield are calcium carbonate
(CaCO3), calcium sulfate (CaSO4), barium sulfate (BaSO4), and
strontium sulfate (SrSO4). A build-up of these scales in the
flowlines can significantly restrain the flow of produced fluids.
More and more fields produce crude oils with high concentra-
tions of naphthenic acids, a term that refers to all the carboxylic
acid components. The known challenge that naphthenic acids
pose for flow assurance is that they can form naphthenates,7
which can stabilize emulsions or create deposits.7
When selecting treatments such as anti-agglomerate hydrate
inhibitors (AAHI), the effect of each potential deposition issue
on the AAHI performance needs to be considered. However,
the interactions among the various flow assurance issues have
not been systematically studied and are not well understood.
These interactions may impact the effectiveness of the flow
assurance program and jeopardize production. In this work,
(5) Misra, S.; Baruah, S.; Singh, K. SPE Prod. Facil. 1995, 10 (1), 50–
54.
(6) Dyer, S. J.; Graham, G. M. J. Petrol. Sci. Eng. 2002, 35 (1-2),
95–107.
(7) Goldszal, A.; Hurtevent, C.; Rousseau, G. Presented at SPE Oilfield
Scale Symposium, Aberdeen, United Kingdom, 2002.

10.1021/ef800189k CCC: $40.75  2008 American Chemical Society

Published on Web 07/12/2008
Gas Hydrate and Flow Assurance Element Interaction Energy & Fuels, Vol. 22, No. 5, 2008 3151

Table 1. Summary of the Hydrate/Asphaltene Interaction Tests

with Oil-A and Brine-A
test # water cut, % AAHI-1, % AI-1, ppm P, psi results
1 30 0 0 2000 fail
2 30 2 200 2000 pass
3 30 2 0 2000 fail
4 0 a 0 2000 pass
a The oil sample was dosed with AAHI so that it had the same AAHI

concentration as the oil phase in the tests with the water phase.

Table 2. Summary of the Hydrate/Wax Interaction Tests with

Oil-B and Brine-B
test # water cut, % AAHI-2, % PI-1, ppm P, psi results
5 60 0 0 2000 fail
6 60 2 0 2000 fail
7 60 2 200 2000 pass
8 60 2 0 ambient pass

Table 3. Summary of the Hydrate/Scale Interaction Tests with

Figure 1. Champion Technologies Hydrate Rocking Cell apparatus. Oil-C and Brine-C and Brine-D

interactions between several flow assurance risk factors were
investigated. It was demonstrated that failure to address one
particular flow assurance problem can spawn other new produc-
tion hazards. Results also showed that failure to consider these
interactions can result in misleading laboratory performance data
that can in turn lead to costly design decisions.
Experimental Details
The experiments were performed on state of the art Champion
Technologies Hydrate Rocking Cell (CTHRC) apparatus.8 It
contains pressure cells made of sapphire tubes, each of which
contains a stainless steel ball inside. For each hydrate test, the cells
are charged with appropriate sample liquids prior to being placed
on a rack. The rack is then immersed in a water bath, whose function
is to control the cell temperature. Once the cells are immersed in
the temperature bath they can be charged with a test gas to the
desired pressures. The rack is then rocked up and down so that the
ball in the cell moves back and forth to induce mixing between
different fluid phases. Figure 1 shows a schematic of the Rocking
Cell device.
Unlike most of other rocking cells, CTHRC utilizes sensors to
monitor the ball movements within the cells, with one sensor placed
near each end of the cell, a top sensor and a bottom sensor. The
times for the ball to travel from one end of the tube to the top
sensor and the bottom sensor are automatically recorded to a
terminal computer. Other recorded parameters are bath temperature
and individual cell pressures. A certain period of time is allowed
for the ball to travel under gravity from one end to the other. If the
sensor at the receiving end does not detect the ball during this period
because of either very high fluid viscosity or the formation of solid
agglomerates, it is considered a “failure”, indicating a potential flow
assurance issue. Besides the ball travel time, another criterion for
judging a test as “Pass” or “Fail” is by visually inspecting whether
solid agglomerates are present since the entire internal cell volume
allows visual observation. This double confirmation drastically
reduces the possibility of misinterpreting the results.
The following interactions were investigated in this work:
hydrate/asphaltene, hydrate/wax, hydrate/scale, and hydrate/naph-
thenic acids. The detailed experimental parameters and procedure
for each interaction study are described below. All of the hydrate
inhibitor dosages in this paper were based on the volume of water
unless specified otherwise. Each test was run in at least duplicates
for confirmation.
Hydrate/Asphaltene Interaction. The goal of this experiment
was to evaluate whether asphaltene precipitation could compromise
the hydrate blockage prevention program. The fluid and chemical
(8) Gao, S.; Chapman, W. G.; House, W. Ind. Eng. Chem. Res. 2005,
44, 7373–7379.
test # water cut, % AAHI-3, % brine P, psi results
9 30 3.0 Brine-C 3200 fail
10 30 3.0 Brine-D 3200 pass
11 30 3.0 Brine-C ambient pass
samples used for the tests were crude sample Oil-A (6.3%
asphaltenes), synthetic brine Brine-A (3.5 wt % salinity), antiag-
glomerant hydrate inhibitor AAHI-1, and asphaltene inhibitor AI-
1. The test matrix is presented in Table 1.
The Rocking Cell test procedure (Procedure #1) was as follows:
1. Rock at 2000 psi (Green Canyon gas8) and 75 °F for 2 h to
allow the system to equilibrate.
2. Cool from 75 °F to 40 °F in 3 h while rocking.
3. Continue rocking at 40 °F for 7 h.
4. Stop rocking and shut in for 12 h at 40 °F.
5. Resume rocking for another 3-5 h to simulate cold start-up.
Hydrate/Wax Interaction. The goal of this experiment was to
evaluate whether the potential interaction between wax deposition
and hydrate formation could put the flow assurance program at risk.
The tested fluid and chemical samples were crude sample Oil-B
(11.2 wt % C 16+ paraffin, WAT 70 °F), synthetic brine Brine-B
(3.25 wt % salinity), an antiagglomerant hydrate inhibitor AAHI-
2, and a paraffin inhibitor PI-1. The coldfinger paraffin deposition
test was first conducted to find the minimum effective dosage
(MED) of PI-1 on Oil-B. Hydrate tests conducted on the Rocking
Cell were summarized in Table 2.
The Rocking Cell test procedure (Procedure #2) was as follows:
1. Rock at 2000 psi (Green Canyon gas) and 80 °F for 2 h to
allow the system to equilibrate.
2. Cool from 80 °F to 40 °F in 4 h while rocking.
3. Continue rocking at 40 °F for 12 h.
4. Stop rocking and shut in for 24 h at 40 °F.
5. Resume rocking for another 2-4 h to simulate cold start-up.
Hydrate/Scale Interaction. Rocking Cell testing for hydrate/
scale interaction was conducted with a scaling Brine-C (3.9 wt %
salinity), a crude sample Oil-C, and an antiagglomerant hydrate
inhibitor AAHI-3. Hydrate Procedure #1 was followed with the
same test gas, except that the system was pressurized to 3200 psi
instead of 2000 psi. Another brine sample, Brine-D, was prepared
with the scaling anions replaced with certain amount of chloride
so that the total ionic strength stayed the same and the hydrate
phase diagram remained unchanged. Brine D was used to perform
the same test under the same conditions to evaluate the effect of
scale formation on hydrate plugging. All the tests are summarized
in Table 3.
Hydrate/Naphthenic Acid Interaction. Naphthenic acids are
known to interact with the calcium in the produced water to form
calcium naphthenates, which can cause emulsion and deposition
problems. The goal of this study was to investigate the interaction
of naphthenic acids with the AAHI hydrate management program,
since both of them have certain surface active features.
3152 Energy & Fuels, Vol. 22, No. 5, 2008 Gao

Table 4. Summary of the Hydrate/Naphthenic Acids Interaction

Tests with Oil-D and Brine E
test # water cut, % AAHI AAHI, % naph acids, %a P, psi results
12 30 AAHI-4 1 0 1200 pass
13 30 AAHI-4 1 1 1200 pass
14 30 AAHI-4 1 2 1200 pass
15 30 AAHI-4 1 3 1200 fail
16 30 AAHI-5 2 0 1200 pass
17 30 AAHI-5 2 3 1200 fail
a Based on the volume of oil phase.

In this study, the MED of AAHI-4 on a condensate Oil-D and

a synthetic brine Brine-E (<1.0 wt % salinity) was first screened
on the Rocking Cell. The test procedure was similar to Procedure
#1 with the same gas phase, but it used an initial pressure of 1200
psi instead of 2000 psi. This condensate had negligible amounts of Figure 2. Waxy deposits on the inner cell wall with the presence of
wax and asphaltene. Various dosages of naphthenic acids were then gas hydrates.
added into samples of the condensate treated with the MED of
AAHI-4 to examine how naphthenic acids affect the performance
of the AAHI-4. Such interaction was also evaluated with AAHI-5.
The tests are summarized in Table 4.

Results and Discussion

Hydrate/Asphaltene Interaction Results. Hydrate testing
on the untreated Oil-A/Brine-A at 30% water cut was first
conducted to evaluate the hydrate formation potential for this
system. The ball in the cell was completely blocked by chunks
of hydrates in Test #1. Since the Oil-A was known to have an
asphaltene problem, the asphaltene inhibitor AI-1 was tested
on Turbiscan MA20009 to find the MED for this crude oil. The
MED was found to be 200 ppm of AI-1. A sample of Oil-A
was dosed with 200 ppm AI-1. This sample was subsequently Figure 3. Wax deposition on cold fingers from Oil-B: blank vs treated.
used for hydrate Rocking Cell testing to find the MED for
AAHI-1, which turned out to be 2.0% (Test #2).
To evaluate the effect of asphaltene precipitation on hydrate
formation, a sample of Oil-A without AI-1 was used to conduct
the same hydrate testing. Test #3 demonstrated that 2.0%
AAHI-1 could not effectively prevent hydrate blockage if the
asphaltene problem was not addressed. Large solid particles were
observed and the liquid phase turned very viscous. Test #4 was
conducted with Oil-A only and no water phase to make sure
the failure in Test #3 was not caused by asphaltene deposition
only. The Test #4 result showed that the ball was able to move
freely in this case.
The hydrate/asphaltene interaction results indicated that the
effectiveness of the hydrate management program with AAHI
could be jeopardized if the asphaltene treatment program is not Figure 4. No waxy deposition on the cell wall when hydrates are not
sufficient to prevent asphaltene flocculation. If taken out of present.
context, Test #3 can easily lead to the false belief that the hydrate Cold finger tests10 were utilized to find the best paraffin
inhibitor at this dosage was not sufficient to prevent hydrate inhibitor for Oil-B. Cold finger results demonstrated that PI-1
blockage. In turn, this can unnecessarily augment design costs worked the best for Oil-B and its MED was 200 ppm. As shown
during field development phase. in Figure 3, PI-1 at 200 ppm significantly decreased the wax
Hydrate/Wax Interaction Results. Hydrate testing was first deposition on the cold fingers. A sample of Oil-B was then dosed
conducted on the untreated Oil-B/Brine-B at 60% water cut to with 200 ppm PI-1 and subsequently used for hydrate testing.
evaluate the hydrate formation potential for this system. Chunks Test #7 demonstrated that 2.0% AAHI-2 effectively prevented
of hydrates were visually observed in Test #5. Dosage screening blockages with the help of 200 ppm PI-1. An ambient pressure
for AAHI-2 on the Rocking Cell turned out to be difficult. Waxy Rocking Cell test was conducted on Oil-B and Brine-B at a
gel-like deposits on the cell wall kept the ball from moving 60% water cut to evaluate whether wax still came out when
freely (Figure 2). As shown in Test #6, the sample treated with gas hydrate was absent. As shown in Figure 4, the cell wall in
2.0% AAHI-2 was still a failure. Test #8 was free of any waxy deposits.
The hydrate/wax interaction experiments suggested that
hydrate particle formation could assist wax to precipitate out
(9) ASTM D7061-04: Standard test method for n-Heptane induced phase
separation of asphaltene containing heavy fuel oils as separability number (10) Thomas, D. C. Presented at International Meeting on Petroleum
by an optical scanning device. Engineering, Tianjin, China, 1988.
Gas Hydrate and Flow Assurance Element Interaction
of the solution and result in deposition. A plausible explanation
was that hydrate particles provided large solid surface areas and
consequently created nucleation sites for wax crystals to deposit
on. As such, the resulting deposits on the cell wall were probably
a mixture of wax and hydrate particles. (Additional laboratory
testing is needed for verification.) Therefore, if hydrate and wax
risks coexist in the field, both hydrate and wax treatment
programs must be concurrently effective at all times.
Hydrate/Scale Interaction Results. Hydrate inhibitor AA-
HI-3 dosage screening was conducted on the Rocking Cell with
Oil-C and a scaling brine Brine-C at a 30% water cut under
3200 psi and 40 °F conditions. Hydrate blockages still formed
at unusually high AAHI dose rates. As an example, 3.0%
AAHI-3 still did not prevent hydrate blockage formation in the
cell in Test #9. These results prompted suspicion that scale
formation from Brine-C probably had a detrimental effect on
the hydrate blockage prevention. Another brine Brine-D was
then formulated to have the same ionic strength but with the
scaling anion components replaced with chloride.
Another hydrate Rocking Cell test (Test #10) was then
performed with the nonscaling Brine-D as the water phase, and
the system was dosed with 3.0% AAHI-3. This led to a clear
passing result. The hydrate slurry was finely dispersed, and there
were no visible size hydrate particles in the cell. It was necessary
to determine if scale formation obstructed the ball and resulted
in a nonhydrate related failure in Test #9. Therefore, an ambient
pressure Rocking Cell test (Test #11) was carried out to
investigate the scale deposition potential without the presence
of hydrate particles. Very fine scale particles were observed in
the cell, but they were too small to hinder the ball movement.
The results from the hydrate/scale interaction studies dem-
onstrated that scale particle formation from the produced water
might not cause blockages by themselves, but they could
function as nucleation sites for gas hydrates and result in hydrate
failures.
Hydrate/Naphthenic Acids Interaction. Crude oil with a
high naphthenic acid content was difficult to treat with AAHI.
This led to a controlled study to gauge the effect of naphthenic
acids on the AAHI’s ability to prevent hydrate blockages (Table
4). Hydrate Rocking Cell tests were first conducted on Oil-D
and Brine-E at 30% water cut to find the MED for AAHI-4.
Oil-D did not have any naphthenic acid components. After the
MED for AAHI-4 was found out to be 1.0% (Test #12),
increasing dosages of naphthenic acids were added into the oil
phase for hydrate testing (Test #13-15). As the dosage of
naphthenic acids was increased, the effectiveness of AAHI-4
decreased. As shown in Test #15, a hydrate blockage was finally
formed when the naphthenic acids concentration was increased
to 3% (based on the oil volume). Another commercial AAHI
product (AAHI-5) was tested with and without the presence of
naphthenic acids. The same negative effect from naphthenic
acids was observed (Test #16-17).
This was different from the previous cases in that there was
no deposition of naphthenates physically interacting with hydrate
particles. Instead, the surface activity of the naphthenic acid
was probably interfering with the performance of the AAHI.
Work is ongoing to develop products to minimize the effects
of the naphthenic acids. The realization that naphthenic acids
could create extra hurdles for selecting an effective AAHI
Energy & Fuels, Vol. 22, No. 5, 2008 3153
program will help the producers to plan early and avoid potential
flow assurance problems. It may be necessary for the producers
to explore other options for hydrate control in this case.
Conclusions
Systematic experimental studies were carried out to investi-
gate the hydrate/asphaltene interaction, hydrate/wax interaction,
hydrate/scale interaction, and hydrate/naphthenic acids interac-
tion. Results demonstrated that those pairs were closely related
and could negatively impact each other. The following conclu-
sions were drawn from these studies.
(i) Asphaltene precipitation in the presence of gas hydrates
can cause catastrophic agglomeration and result in blockages.
Therefore, if both asphaltene and hydrate risks exist in a
production system, the failure of an asphaltene treatment
program can potentially jeopardize the hydrate prevention
strategy.
(ii) Gas hydrate particles can facilitate wax crystals to come
out of solution. Wax deposition in return can potentially cause
hydrate particles to agglomerate. The resulted hydrate/wax
composite will decrease the fluid mobility and could ultimately
result in blockage. It is therefore recommended that both hydrate
and wax risks are adequately addressed in order to ensure
uninterrupted production.
(iii) Scale crystals can provide nucleation sites for gas
hydrates to grow into large size particles. This creates the danger
of uncontrolled agglomeration and hydrate blockage. Therefore,
it is important to maintain the integrity of the scale prevention
program so that the risk of hydrate blockage can be minimized.
(iv) The presence of naphthenic acids can compromise the
effectiveness of a hydrate inhibition program. Therefore, if the
crude oil from a production is known to contain naphthenic
acids, besides the risks associated with naphthenate, special
cautions are required when designing the hydrate prevention
strategy to avoid potential flow assurance problems.
In summary, a successful flow assurance program needs to
start with a holistic perspective that does not only effectively
address each potential risk but also takes into consideration the
interactions between different factors. Failure to do so during
the field development phase will result in misleading laboratory
data and lead to costly design decisions. Neglect of these
associations during the production phase can potentially lead
to catastrophic flow assurance failures. The interactions inves-
tigated in this work are not exclusive and were not meant to be
so. The author’s intention was to bring awareness to the
existence and the importance of interplays between various flow
assurance factors.
Acknowledgment. The author thanks the support and help from
the following highly capable colleagues at Champion Technologies:
Ann Davis, Brad Smith, Sharon Simkins, Anthony Rodriguez, Tom
Williams, Alvin Webb, Ying Jiang, James Outlaw, and Virgil Seale.
Supporting Information Available: Two graphs demonstrating
what “Fail” and “Pass” typically look like based on ball falling
time. This material is available free of charge via the Internet at
http://pubs.acs.org.
EF800189K