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Prospect of Production Optimization Challenges of Gas Wells with Liquid

Loading Problem Using New Surfactant and Nanotechnology

Conference Paper · May 2015

DOI: 10.4043/25745-MS

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OTC-25745-MS

Prospect of Production Optimization Challenges of Gas Wells with Liquid

Loading Problem Using New Surfactant and Nanotechnology
Junwen Wu, Qun Lei,Chunming Xiong, Jianjun Zhang, Jun Li, and Guangqiang Cao, Research Institute of
Petroleum Exploration & Development; Dong Liao, Geological Exploration and Development Research Institute,
Chuanqing Drilling Engineering Co. Ltd; Yun Wang, Min Jia, Nan Li,Yan Liu, and Chunyan He, Research
Institute of Petroleum Exploration & Development

Copyright 2015, Offshore Technology Conference

This paper was prepared for presentation at the Offshore Technology Conference held in Houston, Texas, USA, 4 –7 May 2015.

This paper was selected for presentation by an OTC program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Offshore Technology Conference and are subject to correction by the author(s). The material does not necessarily reflect
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Abstract
Decrease of gas production is an indicator that liquid column is probably building up in the well and an
additional energy is required to lift the liquid out should be applied to control this situation.
Foaming agents provide a means to reduce the density of the liquid so that it can be removed from the
well with the gas flow, unloading the accumulated liquid in gas and gas condensate wells. The main
constituents of foaming agents are surface active agents. Foam stabilizers are added to increase foam
stability. Foaming agent should be selected to form a stable foam under given condition, which means in
the presence of salt or sweet water, hydrocarbon phase, at given temperature and pressure.
Currently, there are lots of different types of foaming agents. Previous studies mainly focused on the
complex between anionic surfactant and anionic surfactant, anionic surfactant and amphoteric ion
surfactant, however, the stability of the foam formed by such foaming agents is poor. Therefore, it is
necessary to develop a robust foaming agent to cope with the harsh conditions. Traditional research
neglect the study of complex between anionic surfactant and cationic surfactant, nevertheless the
synergies between them through appropriate method can greatly improve the foam stability compared to
one-component system. The strong electrostatic interaction between the opposite charge ionic head groups
and the hydrophobic interaction between the hydrocarbon groups made the solution exhibit a complex
phase behavior and microstructure which has a high surface activity and foam stability. Gemini surfactant
contains a spacer and thus made the packing of molecules tighter and increased the cohesion of surfactant
within the monolayer and enhanced the foam stability. Single molecule film formed by surfactant has
certain dynamic characteristics, the gas can easily diffuse through the liquid film, so that the bubble burst.
However, particles can be adsorbed in the gas/water interface to form a solid film which will reduce the
drainage speed of the bubble to enhance the foam stability.
In summary, we proposed to develop a robust foaming agent using anionic-nonionic surfactant mixed
with gemini cationic surfactant, stabilized by nanoparticles with certain hydrophilicity and size.
2 OTC-25745-MS

Introduction
Natural gas plays a very important role in the world’s energy demand. However, the liquid accumulation
inside the production string is a common problem that usually reduces the gas well’s performances. In
these low volume gas wells, there is insufficient energy to continuously lift produced water and
condensate to the surface. Liquid loading in the wellbore eventually causes the well to “log off” or cease
production until sufficient pressure is built up and the liquid can be lifted to the surface.
Most gas wells will have liquid loading occur at some point during the productive life of the well.
When this occurs, a common course of action to move accumulated liquids to the surface includes1-3:
1. Flow the well at a high velocity to stay in mist flow by use of smaller tubing or by creating a lower
wellhead pressure.
2. Pump or gas lift the liquids out of the well (many variations).
3. Foam the liquids, enabling the gas to lift liquids from the well.
4. Inject water into an underlying disposal zone.
5. Prevent liquid formation or production into the well (e.g., seal off a water zone or use insulation
or heat to prevent condensation).
Compared to other artificial lift methods, using of foam is one of the not just least costly but also
effective applications for unloading gas wells. Foam reduces the density and surface tension of the fluid
column, which reduces the critical gas velocity needed to lift fluids to surface and aids liquid removal
from the well. Foams are dispersions of gas bubbles in a continuous liquid phase, and are thermodynam-
ically unstable systems. Absolutely pure liquids do not foam. For foaming to occur, the presence of
surface-active materials is required. They are present at the interfaces and are responsible for both the
tendency of a liquid to foam and the persistence of the resulting dispersion of bubbles.
All foams are thermodynamically unstable, due to their high interfacial free energy. Their stability is
therefore inherently difficult to model. The destabilisation of foams is governed by three principal
mechanisms: drainage, coarsening and coalescence4-5. Drainage is the gravity driven and surface tension
gradient driven removal of the liquid between bubbles, facilitating not only gas diffusion from smaller to
bigger bubbles (coarsening) but also the rupture of thin films separating neighbouring bubbles (coales-
cence). Drainage can be slowed down by increasing bulk and surface viscosity, surface stiffness and the
elastic moduli of the gas-liquid interfaces6-7. In conclusion, characterization of foams is important in many
applications, and this makes investigation of foaming agents an active field of research.
Different types of foaming agents are necessary for different wells based on the water/condensate
content and the salt concentration in the water produced. This kind of agent is mainly surfactant, including
anionic surfactant, nonionic surfactant, anionic-nonionic surfactant, amphoteric ion surfactant and cationic
surfactant8-9. Previous studies mainly focused on the complex between anionic surfactant and anionic
surfactant, anionic surfactant and amphoteric ion surfactant, however, the stability of the foam formed by
such foaming agents is poor. Therefore, it is necessary to develop a robust foaming agent to cope with the
harsh conditions. Traditional research neglect the study of complex between anionic surfactant and
cationic surfactant, nevertheless the synergies between them through appropriate method can greatly
improve the foam stability compared to one-component system10. The strong electrostatic interaction
between the opposite charge ionic head groups and the hydrophobic interaction between the hydrocarbon
groups made the solution exhibit a complex phase behavior and microstructure which has a high surface
activity and foam stability11-12.
In this investigation, we introduced gemini cationic surfactant in the complex system between anionic
surfactant and cationic surfactant and screened the foaming properties (foaming power and foam stability)
by using the Ross–Miles foaming device to identify which surfactants have high foaming ability for
application. Gemini surfactant is a kind of amphiphilic molecular compound by connecting the head group
OTC-25745-MS 3

of two monomers. The gemini-structure of amphiphile was found to be very suitable to the construction
of the adsorption film with tightly packing of molecules and thus increased the cohesion of surfactant
within the monolayer and enhanced the foam stability. The spacers of geminis could play the role of
promoting molecules packing tightly. This role could be further enhanced by increasing the length of alkyl
tails.
However, single molecule film formed by surfactant is still a liquid film which has certain dynamic
characteristics, the gas can easily diffuse through the liquid film, so that the bubble burst. Therefore,
developing high efficiency foam stabilizers is in great demand.
It is well known that nanotechnologies have already contributed significantly to technological advances
in a number of industries, including the electronics, biomedical, pharmaceutical, materials and manufac-
turing, aerospace, photography, and more recently the energy industries13. Nanotechnologies have the
potential to introduce revolutionary changes in several areas of the oil and gas industry, such as
exploration, drilling, production, enhanced oil recovery, refining and distribution14-15.
In the present work, we introduced suitable nanoparticles in foams to increase bubble lifetime. In a
collection of bubbles, gas transfer from smaller to larger bubbles due to differences in Laplace pressure
leading to a compression of the interfaces of the shrinking bubbles. The affinity of the colloidal particles
to the gas-liquid interface can prevent (or, at least, slow down) both coalescence and coarsening or
Ostwald ripening of bubbles16. Particle shape, size, concentration and hydrophobicity have been identified
as the main factors responsible for the foam stabilization. This affinity depends on the wetting behaviour
of the particles which is given by the balance between the solid-liquid, liquid-gas, and gas-solid interfacial
tensions, and which is quantied by the contact angle ␪. As a result, when ␪ is around 90° and when the
particle is not too small, the energy of desorption largely exceeds the thermal energy kBT (kB represents
the Boltzmann constant, T is the absolute temperature, and the adsorption becomes irreversible17-18. Since
many particle types are inherently hydrophilic, attaching weakly to fluid interfaces, we use silica particles
which were modified by chemical reaction with a silane coupling agent to increase their hydrophobicity.
Totally, in this work, we study the synergistic effect between anionic-nonionic surfactant and gemini
cationic surfactant to establish a robust foaming agent which can form a tightly packing of surfactant
molecules at the gas-liquid interfaces and thus increased the cohesion within the monolayer and enhanced
the foam stability. The comb structured gemini amphiphile which can promote molecules packing tightly
was found to be very suitable to the construction of the compact bubble film. Moreover, we introduced
nanoparticles with certain hydrophilicity and size as solid foam stabilizers to adsorb to the gas-liquid
interface and prevent both coalescence and coarsening or Ostwald ripening of bubbles. Combinations of
such technologies seem to achieve the goal quite successfully.
Experimental section
Materials
Gemini surfactants with different spacer and alkyl tails length, the chemical structures of which are shown
in Scheme 1, were synthesized in our laboratory according to the method reported by Zana et al. The
products were confirmed by H NMR and elemental analysis. Sodium alcohol ether sulphate (AES) was
purchased from Chengdu kehongda chemical company. Tetraethylorthosilicate (TEOS), silane coupling
agent, ammonium hydroxide (NH4OH), ethanol, Sodium Bicarbonate (NaHCO3), Magnesium chloride
(MgCl2), Calcium chloride (CaCl2), Sodium chloride (NaCl), Potassium chloride (KCl), Sodium sulfate
(Na2SO4) were purchased from the Beijing chemical plant, they were of analytical grade and were not
purified further before use. Ultra pure water (18M⍀.cm) was used throughout the experiments. All
glassware was cleaned by scouring powder and then rinsed with ultra pure water prior to the experiments.
Simulated accumulated liquid with different concentration (50000 ppm, 100000 ppm, 150000 ppm,
200000 ppm, 250000 ppm) were prepared according to the analysis of accumulated liquid of different gas
well in china.
4 OTC-25745-MS

Synthesis of modified silica colloidal spheres

Firstly, silica nanospheres were synthesized by the Stöber method. The obtained silica nanospheres were
centrifuged and washed with ethanol several times, and then dried at 40 °C for 3 h. Secondly, these silica
nanospheres were functionalized with silane coupling agent. Typically, 500 mg of silica nanospheres was
dispersed in 3 mL of ethanol, subsequently, 100 ␮L of silane coupling agent and 50 ␮L of ammonium
hydroxide were added to the silica dispersion. The resulting mixture was stirred for 8 h at 30 °C. The
modified silica nanospheres were centrifuged and washed with ethanol several times to remove excess
reagents, then dried at 100 °C for 1 h.

Ross-Miles Test
Ross-Miles Test was applied to determine foam properties including foaming and stable properties. The
experiment stages are as follows:
1. The cylindrical glass container (50 mm internal diameter, 1100 mm height), was put in a water
bath with a constant temperature of (80.0⫾0.1) °C.
2. Wash the Ross–Miles foaming device with ultra pure water and then wash it 2~3 times with fluid
to be tested.
3. Put 50 ml solution to be tested into the Ross–Miles foaming device to be heated to (80.0⫾0.1) °C.
4. Inject 200 ml preheated solution into the dropping funnel.
5. Put dropping funnel onto the pipe rack, make it vertical to the cylindrical glass container.
6. Open the dropping funnel piston, keep the solution flows into the center of the calibration tube.
When the dropping funnel flow out of solution, start the stopwatch immediately, record the initial
foam volume, marked as Vo which is used to to evaluate the foaming property, and the time when
the foam height reduce to half of the original height, which is called half life period. The half life
period, marked as t1/2, is used to evaluate the stable property.
7. The experiments were repeated at least three times, and the average value was adopted.

Optical microscopy
Some of the studied solutions were inspected by light microscopy in transmitted light in order to observe
the morphology of bubbles stabilized by different foaming agents. Microscope Axioplan (Zeiss, Germany)
with objective ⫻20 and ⫻50 was used for all optical observations.

Zeta potential characterization

Zeta potential characterization of the surface charge of our particles were carried out at 25 °C and a
scattering angle of 173° by ZetaSizer Nano Series, Nano ZS, Malvern Instruments, equipped with a
thermostated chamber, employing a 4 mW He–Ne laser (␭⫽632.8 nm). The zeta potential was investi-
gated using 100 ␮L of sample in the standard cuvette provided by Malvern.

Result and discussion

Investigation of the effect of enhancing foam stability by geminis with different spacers and
alkyl tails lengths
Scheme1 shows the chemical structure of gemini surfactants with different spacer and alkyl tails length.
We named gemini1, gemini2, gemini3 for the gemini surfactant with spacer length from small to large and
gemini4, gemini5 for the gemini surfactant with alkyl tails length from small to large.
OTC-25745-MS 5

Scheme 1—Chemical structure of gemini surfactants with different spacer and alkyl tails length named gemini1, gemini2, gemini3,
gemini4, gemini5 separately.

We added different amount of gemini surfactant to the 1 % AES solution and measured their foam
properties. Figure1 illustrates that the initial foam volume Vo and the time t1/2 needed for the collapse of
foam to half its initial height both reduce as a result of increasing of the spacer length of gemini surfactant.
This phenomenon verified our inference that the gemini surfactant with a short spacer could stabilize the
foams more efficiently. Significantly, the gemini surfactant with the shortest spacer produces the
maximum t1/2 as high as 815 s. This value is 3-folds that of traditional cationic surfactant which is
generally considered as the corresponding monomer of geminis19, which testified gemini surfactant can
increase the cohesion of surfactant within the monolayer and better to stabilize foam.

Figure 1—Initial foam volume Vo (a) and half life period t1/2 (a) of foams produced by different concentration of gemini1, gemini2,
gemini3 with spacer length from small to large mixed with 1 % AES solution.

We expanded the study to gemini4 and gemini5 with different alkyl tails length, for comparison,
gemini1 with medium alkyl tails length was also examined. Figure2 shows that the gemini surfactant with
6 OTC-25745-MS

medium alkyl tails length have larger initial foam volume Vo and the half life period t1/2 than gemini
surfactant with smaller or larger alkyl tails. We explain this result as follows: the liquid film formed by
gemini surfactant with smaller alkyl tails is thinner and the gas in the bubbles can diffuse through the
liquid film easily which causes bubbles coarsening and coalescence. For the gemini surfactant with larger
alkyl tails, the liquid film stiffness is too large while the its elastic moduli is too small, this makes the
liquid film rupture easily and lower the foam stability. However, the gemini surfactant with medium alkyl
tails length can form liquid film with moderate stiffness and elastic moduli, which lowers the coarsening
and coalescence of bubbles and make the foam more stable. It can be inferred from Figure1 and Figure2
that all curves have the same regular that there are optimum concentrations for all the gemini surfactant
to achieve the best effect to stabilize the bubbles (bigger foam volume and longer half life period), larger
or smaller concentrations can’t play the best synergistic effect with anionic-nonionic surfactant. This
means that a highly stable foam system is found.

Figure 2—Initial foam volume Vo (a) and half life period t1/2 (a) of foams produced by different concentration of gemini1, gemini4,
gemini5 with alkyl tails length from small to large mixed with 1 % AES solution.

We chose the compositions named foaming agent A, foaming agent B, foaming agent C, foaming agent
D and foaming agent E which are composed of 0.03 % gemini1, gemini2, gemini3, gemini4 and gemini5
mixed with 0.1 % AES solution for the further investigation. Figure3 represents that when we changed the
temperature from 80 °C to 130 °C, the initial foam volume Vo and half life period t1/2 all decrease to a
lower value. The reason for the phenomenon may be concluded as follows: When the temperature
increase, both the bulk and surface viscosity slow down and thus increase the drainage of liquid film.
Besides, the increase of temperature can also lead to the gas expansion which makes the liquid film
become thinner and increase the bubbles coarsening and bubbles coalescence. The initial foam volume Vo
and half life period t1/2 of foaming agent A at 130 °C are higher than others, so we chose this one for the
further study.
OTC-25745-MS 7

Figure 3—Contrast of initial foam volume Vo (a) and half life period t1/2 (a) of foams produced by foaming agent A, foaming agent B,
foaming agent C, foaming agent D and foaming agent E which are composed of 0.03 % gemini1, gemini2, gemini3, gemini4 and gemini5
mixed with 0.1 % AES solution at 80 °C and 130 °C.

Investigation of the effect of enhancing foam stability by silica nanospheres

In order to increase the foaming agent property at high temperature, we introduce partly hydrophobic
fumed silica nanospheres which were modified by chemical reaction with a silane coupling agent in the
foaming agent A. Figure4 shows that when the concentration is below 20 ppm, both the initial foam
volume Vo and half life period t1/2 increase with the increase of foaming agent concentration, which
illustrate the fact that nanospheress can be able to stabilize aqueous foams, however, when the concen-
tration is higher than 20 ppm, the stabilization effect declines as the initial foam volume Vo and half life
period t1/2 begin to fall. This result illustrates the fact that 20 ppm partly hydrophobic fumed silica
nanospheres have the best foams stabilization ability.

Figure 4 —Foaming properties (initial foam volume Vo and half life period t1/2) of foaming agent A stabilized by silica nanospheres
modified by silane coupling agent as a function of concentration.

Optical microscope images of foams stabilized by foaming agent A alone and foaming agent A mixed
with silica nanospheres were also taken to study the structural of the foam bubbles, and the result are
shown in Figure5. For both the systems, the bubbles are polydisperse (with diameters of 50-500 ␮m).
However, the average size of bubbles stabilized by foaming agent A mixed with silica nanospheres is
8 OTC-25745-MS

smaller than bubbles stabilized by foaming agent A alone. The relation between half life period t 1/2 and
diameter of bubbles are as follows:

Figure 5—Optical microscope images of foams stabilized by foaming agent A alone and foaming agent A mixed with silica nano-
spheres. The foaming agent concentration is fixed at 1 % and the nanosphere concentration is fixed at 20 ppm. The scale bars in both
a and b are 100 ␮m.

where d represents diameter of bubbles, ␮L represents the velocity of liquid, h represents the initial
foam height, ␳ represents the density of liquid, VLf represents the liquid proportion, g represents
gravitational acceleration. From the formula we can conclude that lower diameter bubbles have larger half
life period t1/2 and thus make the bubbles more stable. This can explain the reason for Figure4 that bubbles
stabilized by nanospheres have larger half life period t1/2. Figure5b also shows there is a solid shell of
particles attached to air bubbles. The adsorption of particles at the interface plays a crucial in the high
foam stability. They can not only increase the velocity of liquid but also can prevent (or, at least, slow
down) both coalescence and coarsening or Ostwald ripening of bubbles.
In order to better understand the mechanism of foams stabilization effect by nanospheres, the variations
of the zeta potentials of different concentrations of silane coupling agent modified silica nanospherers in
foaming agent solution was studied, the results are shown in Figure6. It clearly shows that the nanospheres
have an initial low negative potential (close to—58 mV). The zeta potential first increases with
increasingly naoparticles concentration and then reached about—30 mV, indicating a monolayer of
surfactant is adsorbed on the particle surface. The particles with a monolayer of surfactant can adsorb onto
the air-water interface. When the concentration is higher than 20 ppm, the zeta potential reduces which
results from the very few adsorption of surfactant on nanospheres, however, nanospheres in this state can
adsorb onto the bubble surface and can play the best foams stabilization effect20.
OTC-25745-MS 9

Figure 6 —Zeta potentials of silane coupling agent modified silica nanospherers in foaming agent solution as a function of
concentration.

Conclusions
1. Other than traditional research, we study the complex between anionic surfactant and cationic
surfactant by introduce a new surfactant named gemini surfactant which contains a spacer and thus
made the packing of molecules tighter while increased the cohesion of surfactant within the
monolayer and enhanced the foam stability. The result shows that the gemini surfactant with
shorter spacer length and medium alkyl tails length can play the best enhancing effect to stabilize
foams, and this enhancing effect is 3-folds that of traditional cationic surfactant which is generally
considered as the corresponding monomer. Through system experiment, we acquired the best
foaming agent named foaming agent A which contains 0.03 % gemini1 and 1 % AES.
2. Single molecule film formed by surfactant has certain dynamic characteristics, the gas can easily
diffuse through the liquid film, so that the bubble burst. However, we introduced silica nano-
spheres with certain hydrophilicity and size as solid foam stabilizers to adsorb to the gas-liquid
interface and prevent both coalescence and coarsening or Ostwald ripening of bubbles, thus reduce
the drainage speed of the bubble to enhance the foam stability. Optical microscope and zeta
potential were also taken to investigate this phenomenon. Besides, we find 20 ppm of this kind of
nanospheres has the best stabilization effect.
3. The obtained results have direct implications for the understanding the foaming and defoaming
mechanisms in production optimization challenges of gas wells with liquid loading problem.

Acknowledgement
This work was supported by financial support from PetroChina Company Limited (projrct 2014E-32-07).

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