See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/299584220

OTC-26384-MS Development and Application of Ultra-High Temperature

Drilling Fluids in Offshore Oilfield Around Bohai Sea Bay Basin, China

Conference Paper · March 2016

DOI: 10.4043/26384-MS

CITATIONS READS

6 2,931

3 authors, including:

Hui Mao
China University of Petroleum - Beijing
10 PUBLICATIONS   193 CITATIONS   

SEE PROFILE

All content following this page was uploaded by Hui Mao on 03 April 2016.

The user has requested enhancement of the downloaded file.

OTC-26384-MS

Development and Application of Ultra-High Temperature Drilling Fluids in

Offshore Oilfield Around Bohai Sea Bay Basin, China
Hui Mao and Zhengsong Qiu, China University of Petroleum Binqiang Xie, Yangtze University Zaiming Wang,
Jidong Oilfield of PetroChinaZhonghou Shen and Weichao Hou, China University of Petroleum

Copyright 2016, Offshore Technology Conference

This paper was prepared for presentation at the Offshore Technology Conference Asia held in Kuala Lumpur, Malaysia, 22–25 March 2016.

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
any position of the Offshore Technology Conference, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the
written consent of the Offshore Technology Conference is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words;
illustrations may not be copied. The abstract must contain conspicuous acknowledgment of OTC copyright.

Abstract
It is known that ultra-high temperature drilling fluids are still quite a challenge to drilling engineering. When
bottomhole temperatures exceed 200°C, the design and formulation of drilling fluids can present a host of
problems. Drilling fluids destabilize under such extreme conditions, possibly causing wellbore instability, well
control problems, and ultimately loss of the well. Drilling buried hill hydrocarbon reservoir in offshore oilfield
around Bohai Sea Bay Basin in China has often resulted in failure to reach desired objectives. Bottomhole
temperatures up to 220°C, however, the pressures requiring drilling fluid weights just to 1.04 to 1.10 g/cm3
equivalent place severe limitations on the performance of drilling fluids and often contribute in failure to reach
the desired drilling objectives. Polymers as viscosifying agent that control rheological properties and fluid loss
create major challenges for drilling fluid performance and stability when temperatures over 200°C are reached.
Additionally, the gelation of drilling fluids containing low solids content and high fluid loss can become
difficult to control under ultra-high temperature conditions. Both of these issues are compounded when the
ultra-high temperature is coupled with a requirement for low drilling fluids density. The wildcat well NP3-81
and NP3-82 were drilled in this offshore oilfield around Bohai Sea Bay Basin on January 2014. TD of 6066
meters and 6037 meters were attained, respectively. Both of the bottomhole static temperatures were exceed
220°C and the pore pressure was 1.04 to 1.10 g/cm3 equivalent. Logs were run to bottom without incident and
drilling fluids related problems and the primary drilling objectives achieved. The success is attributed to the
new technology, fit-for-purpose drilling fluids and rigorous pre-well planning. The paper describes the
laboratory development and field application of a new technology of environmentally acceptable and seawater
discharged drilling fluids designed for ultra-high temperature environments, highlighting the viscosifying agent
which has excellent ultra-high temperature resistance and salt resistance viscosifying property, thermal stability
and thermo sensitive characteristics. The apparent viscosity retention rate of novel viscosifier after aging at
220°C after 16 h were 90.81% and 95.95% respectively and the EC50 value was 15.529⫻104 mg/L in both
fresh water based drilling fluid and salt-water based drilling fluid. Field application data shows that this new
polymer viscosifying agent could play a critical role even though at harsh conditions such as ultra-high
temperature and low density drilling fluids system which decreasing daily performance maintenance problems
at the expense of the large consumption of fluid additive including conventional sulfonate copolymer.
2 OTC-26384-MS

Introduction
Although a number of High Pressure and High Temperature (HTHP) wells have been drilled in offshore
oilfield or onshore oilfield in China during the last two decade, it is still quite a challenge to drill. With
the development and the global oil & gas exploration accessing to the deep layer continuously, the
technology of the high temperature, high density drilling fluids have become a key to the drilling of deep
wells. The rheological properties controlling, high temperature stability and sedimentation stability are the
core challenges to the high temperature and high density drilling fluids. In recent years, The majority of
the buried hill hydrocarbon reservoir which were buried in shallow, large-scale and easy to be found in
offshore oilfield around Bohai Sea Bay Basin in China have been drilled. Finding the larger scale of
reservoir is more and more difficult, but the remaining oil and gas resources of deep buried reservoirs are
still relatively abundant in Offshore Oilfield around Bohai Sea Bay Basin. For example, the well ND-1
which recorded a prolific oil flow of 5.2 tons and the gas flow of 563 thousands m3/d, discovered a buried
hill field in the Jizhong Sub-basin, Bohai Sea Bay Basin (Zhao X.Z, et al.). However, the reservoir of this
field was the deepest and its temperature was highest in Offshore Oilfield around Bohai Sea Bay Basin
and even in East China. The estimation of oil resources are (9.14 to 10.3)⫻108 t and natural gas resources
are 1237.66⫻108 m3 in deep reservoir (Zhao X.Z, et al.). So it is the key regions for exploration and
development of the buried hill reservoir in Jidong Oilfield of PetroChina in recent years. But drilling
buried hill hydrocarbon reservoir in this oilfield has often resulted in failure to reach desires objectives.
The geothermal gradient is big made the bottom hole temperatures up to 220°C and the well depth is over
6000 meters, however, the formation pressure coefficient is small made the pressures requiring drilling
fluid weights just to 1.04-1.10 g/cm3 equivalent which place severe limitations on the performance of
drilling fluids and often contribute in failure to reach the desired drilling objectives. Because of the high
formation temperature, there were mainly using oil-in-water based drilling fluids and low bentonite based
polymeric drilling fluids, and so on. But the field application found that it was not environmentally
friendly, prone to lost circulation and it can’t be emitted to sea for oil-in-water drilling fluids due to the
environment protection, and polymers as viscosifying agent for low bentonite based polymeric drilling
fluids that control rheological properties and fluid loss create major challenges for drilling fluid perfor-
mance and stability when temperatures over 200°C are reached. Additionally, the gelation of drilling
fluids containing low solids content and high fluid loss can become more difficult to control under
ultra-high temperature conditions.

Classifications of HT&HP drilling fluids

Various industry groups have set limits for the classifications of HTHP drilling fluids, but they lack
industrywide acceptance and vary widely. With reference to extreme environments that are broadly
referred to as HT/HP, they would like to socialize Schlumberger’s classifications (Ahmad, et al.), which
are based on the industry’s most commonly used technologies. The oil and gas industry has contended
with elevated temperatures and pressures for years; however, there are no industry-wide standards that
define HTHP conditions and the associated interrelationship between temperature and pressure. In an
effort to clarify those definitions, Schlumberger uses guidelines that organize HTHP wells into three
categories, selected according to commonly encountered technology thresholds (Belani, et al.). Generally
speaking, the temperature and pressure ratings should be considered together when defining thresholds.
Common wells
When the well depth is less than 4500 meters, we have defined the common drilling fluids which the
temperature resistance is generally less than 150°C and the density of drilling fluids is less than 1.56
g/cm3. For common drilling fluids, the technical problems can be effectively resolved currently. In
addition, without considering the case of abnormal geothermal gradient and taking into account the current
application situation of the drilling fluid technology and drilling technology, the definition of HTHP
OTC-26384-MS 3

drilling fluid has been made which is shown in Figure 1 and the classification boundaries represent
stability limits of common well-service-tool components-elastomeric seals and electronic devices.

Figure 1—HTHP classification system

HTHP
The rationale for declaring 69 MPa as the pressure threshold is related to the behavior of standard
elastomeric seals at 150°C. For the deep well which the depth is between 4500 meters to 6000 meters, we
have defined the high temperature and high pressure (HTHP) drilling fluids which the temperature
resistance is generally between 150°C to 205°C and the density of drilling fluids is generally between 1.56
g/cm3 to 2.35 g/cm3. The downhole equipment to temperatures in this range finds it prudent to replace
O-rings on makeup joints before running the tools to those temperatures again.
Ultra-HTHP
For the ultra-deep well which the depth is between 6000 meters to 9000 meters, we have defined the
ultra-high temperature and ultra-high pressure (Ultra-HTHP) drilling fluids which the temperature
resistance is generally between 205°C to 260°C and the density of drilling fluids is generally between 2.35
g/cm3 to 2.73 g/cm3. The rationale behind defining the upper boundaries of this market is the practical
operating limit of existing electronics technology. Operating electronics beyond this level will require
considerable technical development (Belani, et al.).
Extreme High Temperature & High Temperature (Ext-HTHP)
For the extreme deep well which the depth is more than 9000 meters, we have defined the extreme high
temperature and extreme high pressure (Ext-HTHP) drilling fluids which the temperature resistance is
generally more than 260°C and the density of drilling fluids is generally more than 2.73 g/cm3. In the past
years, the petroleum scientists and engineers thought it stands for an environmental operating condition
unlikely to be surpassed in the foreseeable future in the oil and gas industry and it should be noted that
in the low-to-moderate pressure thermal recovery markets, bottom hole production temperatures have
been projected as high as 650°F (Belani, et al.). However, the well Songke-2 which is drilling at present
in Songliao Basin in China since April 13, 2014 are the Chinese Continental Scientific Drilling program
project (CCSD), TD of 6400 meters are attained and the prediction bottom hole static temperature is up
to 242.2°C to 266.63°C, but the pore pressure is only 1.10 g/cm3 to 1.15 g/cm3 equivalent. In other
industries, such as those using geothermal heat sources for energy are already there. Some attempts have
been made over the years to adapt oil industry logging tools for use in geothermal wells with varied
success. Perhaps the research and innovation we need to reach our goals will provide as yet unrealized
capabilities that will enable commercial applications of oilfield technology in this market (Belani, et al.).
4 OTC-26384-MS

Properties of water at HT&HP environment

In the past years, drilling fluid researchers mainly focused on developing a variety of drilling fluid
additives to improve the properties of its temperature resistance to solve the HTHP drilling fluid problems,
and rarely focused on the properties of water under HTHP environment. However, through our research
we found that the interaction between drilling fluid additives, additives and hot water, additives and clay,
clay and clay had a big change due to the changes of physical and chemical properties of water under the
HTHP environment. The biggest changes of water were the polarity, force of hydrogen bonds, surface
tension and water inozation constant. Water is a good solvent because the molecules are polar and capable
of forming hydrogen bonds. The basic physical and chemical models of water are as shown in Figure 2,
and Figure 3 shows the water cluster which is discrete hydrogen bonded assembly or cluster of molecules
of water (Ben-Naim, et al.). Figure 4 shows the phase diagram of water, and Figure 5 shows the saturation
water vapor pressure with the temperature increases.

Figure 2—The basic physical and chemical models of water

(a) A water model. (b) The partial charges on the atoms in a water molecule. (c) Ball-and-stick model of water. (d) A separation of charge
in a water molecule is present with negative charge (red), and positive charge at the ends (blue). (e) Model of hydrogen bonds (1)
between molecules of water.

Figure 3—Water Clusters (two water molecules to seventeen molecules)

OTC-26384-MS 5

Figure 4 —Phase diagram of water

Figure 5—The saturation water vapor pressure with the temperature increases

Considering an ion dissolved in water, ion attracts water molecules, and as the result a number of
attracted waters are situated around the ion, and then form a ⬙shell⬙ around ion as shown in Figure 6. One
can see the asymmetry in cation and anion hydration that near cation water is rotated with the oxygen
towards ion, near anion water is oriented with hydrogens towards ion. Rest water molecules are also
attracted to ion and to the water molecules in the first ⬙shell⬙. But no more waters can come close to ion
because there is no space left. So, they are situated next to the waters in the first shell. They form the
second shell molecules around ion, and so on, until waters at certain distance do not feel the influence of
ion and behave as just bulk water molecules. All the water molecules that we decide are distinct from the
bulk water form the hydration shell around ion, which can be split to first, second, etc, hydration shells
according to its distance from the ion (Frolov A, 2011). The most frequently used criteria are to use
ion-water radial distribution function as shown in Figure 7 that indicates the relative density of water at
a certain distance from ion comparing to bulk density of water. Usually for condensed systems it has an
oscillatory view.
6 OTC-26384-MS

Figure 6 —The first solvation shell of a sodium ion dissolved in water

Figure 7—Definition of hydration shells (HS) based on ion-water radial distribution function

Moreover, one of the most important hydro-chemical properties is water ionization. Figure 8 shows the
balance equation of water ionization, and Figure 9, Figure 10 show the temperature dependence of water
inozation constant Kw (pKw equals –lg(Kw)) along the saturation line and and pressure dependence of water
inozation constant at 25°C, respectively (Bandura, et al.). From Figure 9 and Figure 10, we can see that the
water inozation constant becomes bigger with the increase of temperature and pressure, and the temperature
influences the Kw obviously. Figure 11 and Figure 12 show the thermal conductivity and the electrical
conductivity of water at saturation pressure, respectively (Fernández Prini, et al.). We can see that water may
become a buffered solvent to affect the pH of drilling fluid system under ultra-high temperature and ultra-high
pressure, so there may be existing a bottleneck technology about the water based drilling fluids at approxi-
mately 250°C.

Figure 8 —The balance equation of water ionization

OTC-26384-MS 7

Figure 9 —Values of water inozation constant along the saturation line with the increase of temperature

Figure 10 —Values of the water ionization constant at 25°C with different pressure

Figure 11—Values of thermal conductivity of water along the saturation line

8 OTC-26384-MS

Figure 12—Electrical conductivity of highly purified water at saturation pressure

The dielectric constant of a solvent is a relative measure of its chemical polarity. For example, water
is very polar, and has a dielectric constant of 80.10 at 20°C while n-hexane is non-polar, and has a
dielectric constant of 1.89 at 20°C. This information is important when designing separation, sample
preparation and chromatography techniques in analytical chemistry (Lide D R, et al.). According to the
dielectric constant can determine the strength of the polar of the polymer materials, which is as shown in
Table 1.

Table 1—The classification of molecular polarity according to

the dielectric constant
dielectric constant (F/m) strength of the polar

⬎3.6 strong polar

2.8 - 3.6 weak polar
⬍2.8 Non polar

For solubility, however, dichloromethane has a value of dielectric constant of 9.08 (20°C) and is rather
poorly soluble in water (13 g/L at 20°C); at the same time, tetrahydrofuran has its dielectric constant
equals 7.52 at 22°C, but it is completely miscible with water. In the case tetrahydrofuran, the oxygen atom
can act as a hydrogen bond acceptor; where as dichloromethane cannot form hydrogen bonds with water.
This is because for non-ionic solutes, the general rule is: like dissolves like. Polar solutes dissolve in polar
solvents, forming polar bonds or hydrogen bonds. On the other hand, non-polar solutes dissolve better in
non-polar solvents. Examples are hydrocarbons such as oil and grease that easily mix with each other,
while being incompatible with water. In chemistry, the dielectric constant is an important property of the
solvents. It can characterize the ability of solvent separated ion and solvation of solute molecules. The
larger the dielectric constant of the solvent makes the stronger ability of solvation. Some the dielectric
constants of the common solvents are as shown in Table 2 (Jin Hongyun), and the relative static dielectric
constant of water at 10MPa is as shown in Figure 13, and the average number of H-bonds per water
molecule (⬍n⬎HB) at various temperatureis as shown in Figure 14 (Suresh, et al.).
OTC-26384-MS 9

Table 2—The dielectric constant of water and some organic

solvents
dielectric constant (F/m)
Solvent (Tⴝ20°C, Pⴝ0.1MPa)

Water 80
n-Hexane 1.89
Cyclohexane 2.02
Benzene 2.27
Dichloromethane 8.93
Methyl ethyl ketone 18.51
Acetone 20.7
Ethanol 24
Methanol 33
Acetonitrile 37.5
Subcritical water 27
(T⫽250°C, P⫽5MPa)
Supercritical Water 5-15
(T⬎374°C
P⬎22.1MPa)

Figure 13—Relative static dielectric constant of water at 10MPa

Figure 14 —Average number of H-bonds per water molecule (<n>HB) at various temperature (K) (Suresh, 2000)
10 OTC-26384-MS

One of the most important chemistry properties of water is the change of surface tension which affected
by temperature and pressure (Cooper, et al.). Figure 15 and Figure 16 show the temperature dependence
surface tension of water at saturation pressure and pressure dependence surface tension of water at 65°C.
We can see that the surface tension of water is affected by temperature and pressure significantly, and the
surface tension is about 26 mN/m at 250°C and approximately 40 mN/m at 65°C with 20MPa,
respectively. We know that the surface tension influence the wettability between liquid and solid directly
as shown in Figure 17, and we believe that the lower surface tension led by the temperature and pressure
influence the hydration swelling and the dispersing properities of clay minerals and the dispersing
properities of weighting agent significantly, which means the filtration and sedimentation stability
properties of the drilling fluids are rather difficult to regulate and control under ultra-high temperature and
ultra-high pressure.

Figure 15—Surface tension of water with the increase of temperature at saturation pressure

Figure 16 —Pressure dependence surface tension of water at 65°C

OTC-26384-MS 11

Figure 17—Surface tension and wettability

Figure 18 shows the temperature dependence density of water. We know that the actual value of density
of HTHP drilling fluids mostly lower than the calculated value of density and most of the drilling
researchers thought it was led by the drilling circulating pressure loss. But from Figure 18 we can see that
the changes of density of water at high temperature maybe one of the reasons that lead the lower density
of HTHP drilling fluids except the circulating pressure loss. Moreover, another reasons for lower density
of HTHP drilling fluid drilling in deep well or ultra-deep well are that extrusion expansion function and
the changes of acceleration of gravity at different place on earth according to our recently research results.

Figure 18 —Density of water with the increase of temperature

Figure 19 and Figure 20 show the values of viscosity of water along the saturation line and values of
viscosity of water at different pressure (Fernández Prini, et al). This is because the movement and collision
of water molecules becomes severely with the increase of the temperature, as well as the the interaction
forces between the water molecules and the hydrogen bonds are weakened at high temperature environ-
ment. The changes of viscosity values of water influence the rheological parameters of drilling fluids let
us know that regulation of rheological properties of drilling fluids at ultra-high temperature and ultra-high
pressure should take full account of the properties of the continuous phase in future studies which
including water for water based drilling fluid and oil for oil based drilling fluid.
12 OTC-26384-MS

Figure 19 —Values of viscosity of water along the saturation line

Figure 20 —Values of viscosity of water at different pressure

Meanwhile, the phase behavior of polymer solutions is an important property involved in the
development and design of most polymer-related processes. Partially miscible polymer solutions often
exhibit two solubility boundaries, the upper critical solution temperature (UCST) and the lower critical
solution temperature (LCST), which both depend on the molar mass and the pressure. At temperatures
below LCST, the system is completely miscible in all proportions, whereas above LCST partial liquid
miscibility occurs (Charlet G, Delmas G, et al.) which is as shown in Figure 21. Some polymer solutions
have an LCST at temperatures higher than the UCST. As shown in Figure 21, this means that there is a
temperature interval of complete miscibility, with partial miscibility at both higher and lower temperatures
(Cowie, et al). In the case of polymer solutions, the LCST also depends on polymer degree of
polymerization, polydispersity and branching (Rimmer S, et al.) as well as on the polymer’s composition
and architecture (Ward M A, et al.).
OTC-26384-MS 13

Figure 21—The UCST and LCST of water

In summary, the changes of the polarity of water, weaken of hydrogen bonds, decrease of surface
tension, the increase of water inozation constant and phase changes, etc make the ⬙hot water⬙ be different
with the water we commonly known and influence the properities of drilling fluids significantly. For
example, When the temperature is at 250°C, the dielectric constant of water is 27 which is between the
dielectric constant of ethanol (24) and the dielectric constant of methanol (33), as well as the biggest water
inozation constant, indicating that the synthetic polymer may not be dissolved in water at 250°C and may
emerge a phenomenon of thermally induced phase separation (TIPS) and the discussion of the capacity
of anti-temperature for synthetic polymer has not really meaningful at this point, and it can be said that
the water based drilling fluid has already been in a fundamental bottleneck problem at this environment.
Moreover, most of the water-loluble drilling fluid additives will not be dissolved perfectly in water at such
high temperature. This is because most of the polar molecules dissolved in drilling fluid are gradually
extracted by water with the increase of temperature according to the principle of like dissolves like. In
addition, the clay minerals in drilling fluids are dispersion firstly and then flocculation with the increase
of the temperature, which is due to the changes of polarity of water, the weak interaction of hydrogen
bonds of hot water and as well as lower surface tension of hot water. At normal temperature environment,
water is very polar and the polar organic compounds can be well dissolved, and the clay minerals can also
be good hydration and dispersed in water, but the solvent power of water is very small for middle polar
and non-polar organic compounds, such as polycyclic aromatic compounds. However, the subcritical
water is more similar to an organic solvent which can dissolve middle polar and non-polar organic
compounds better, so the clay minerals is more prone to not be dispersed in the subcritical water. What’s
more, if the solute molecules and solvent molecules can form hydrogen bonds each other in a polar
solvent, the solubility of the solute will increase. Due to the hydrogen bonds interactions of water becomes
weake with the increase of temperature, resulting in the solubility of solute (such as drilling fluid
additives) decrease in a polar solvent (such as water). At last, a lot of researchers considered that the most
of phenomenon of thermally induced phase separation is an irreversible process at present.
Technical requirements
The wildcat well NP3-81 is the first and the deepest ultra-deep well in Jidong Oilfield in Offshore Oilfield
around Bohai Sea Bay Basin, China, which was to identify the gas and oil distribution in Shahejie
14 OTC-26384-MS

Formation and buried-hill of NP-3 structure. The ultra-high temperature drilling fluid was used to solve
the instability of large segment of hard brittle shale and ultra-high temperature at the bottom hole for the
fifth spud of Well NP3-81. TD of 6066 meters was attained and the bottomhole static temperatures
exceeded 220°C and the pore pressure was 1.04 to 1.08 g/cm3 equivalent. Solution fractures, fracture-
cavernous and solution pore are the main reservoir spaces of well NP3-81. Sandstone, shale and limestone
are the main reservoir types. Therefore, the stability of low density drilling fluids with low bentonite under
ultra-high temperature and ultra-deep well, viscosifying, lost circulation and the rheological properties of
drilling fluids become key problems, and the focus is on the design and formulation of drilling fluids. In
order to protect the reservoir effectively and to discover hydrocarbon shows timely, the drilling design
requires using underbalanced drilling technology in well NP3-81, and in order to solve the technical
problems of drilling fluids, a polymeric viscosifying agent (code as SDKP-1) with ultra-high temperature
resistant ability was synthetized by the method of micelle free radical emulsion polymerization. Recently,
the well Songke-2 which is drilling at present in Songliao Basin in China since April 13, 2014 is the
Chinese Continental Scientific Drilling program project (CCSD), TD of 6400 meters are attained and the
prediction bottom hole static temperature is up to 242.2°C to 266.63°C and the pore pressure is only 1.10
g/cm3 to 1.15 g/cm3 equivalent. Figure 22 shows the classification of drilling difficulty levels and
representative drilled well in China under high temperature and high pressure accrording to our recent
research results, as well as high the temperature and the low pore pressure in recent years.

Figure 22—The classification of drilling difficulty levels and representative drilled well in China

Molecular structure design of novel viscosifying agent

The viscosifying properties of polymeric aqueous solution is come from the friction between the polymer
molecules in aqueous solution, the strength of the internal network structure of polymer, and molecular
structure of polymer. The rigidity of the polymeric chains and the association structures between the
molecular chains are the key to influence the temperature resistance properties of polymeric solution.
Based on the research and analysis of characteristic relationship between polymer molecular structures
and its temperature resistance and viscosifying properties, the molecular structure of the copolymer was
designed based on the following principles mainly to improved temperature resistance properties and
viscositying properties in low density water based drilling fluids.
OTC-26384-MS 15

a. Optimization design of polymeric chain structure

The backbone of the copolymer must be composed of carbon-carbon bonds for high temperature
stability as a result of the strong bond energy of 347.3 kJ/mol. Molecular groups of the side chains
connecting to the backbone must have hydration and adsorption functional groups containing
carbon— carbon, carbon—sulfur and carbon—nitrogen bonds to withstand high temperature
(Huang W.A, et al.). We selected the sodium styrene sulfonate (SSS) as one of the anti-temperature
monomer.
b. Optimization design of aggregation structure of polymer
In early 1990s there was a special class of macromolecule, called thermo-associating polymers
pioneered by Hourdet and co-workers, which was an alternative strategy to improve the heat-
tolerant performance of water-soluble polymers. These polymers could be prepared via grafting or
specifically synthesized with monomers containing hydrophobic units which presented a loss of
water solubility above a critical temperature (Lower Critical Solution Temperature, LCST). At low
temperatures, water molecules initially reduced the entropy by forming ice-like structures around
the hydrophobic units of the polymer chains. However, as the temperature increased, the hydro-
phobic interactions between the hydrophobic units were enhanced due to a decrease in the
structuring of water. And when the temperature was up to a critical associative temperature (Tass)
which could be governed by the LCST of the hydrophobic units, these units could self-aggregate
into hydrophobic micro-domains giving rise to a viscosity enhancement macroscopically (Xie B.Q,
et al.). In this article, we were mainly to develop a new thermoassociating polymer which was
tolerant to ultra-high temperature in drilling fluid under ultra-deep well. And we selected the
N-Vinyl-epsilon-caprolactam (NVCL) as one of the anti-temperature monomer.
c. Optimization design of molecular configuration of polymer
In order to improve the ultra-high temperature resistant ability and viscosifying properties of
synthetic polymer, cross-linked polymer was synthesized by the method of micellar free radical
emulsion polymerization which using N-Vinyl-epsilon-caprolactam as temperature sensitive mono-
mer, sodium styrene sulfonate as hydrophilic monomer and N, N-methylene bis acrylamide as
crosslinking agent.
Property of thermoassociating interaction
The relationship of apparent viscosity of SDKP-1 aqueous solution on different temperature was
characterized by the digital viscometer (Brookfield DV-II⫹Pro, USA), and the result was as shown in
Figure 23.

Figure 23—The relationship of apparent viscosity of SDKP-1 aqueous solution on different temperature
16 OTC-26384-MS

As can be seen the results from Figure 23, the critical temperature (LCST) of the new thermoassoci-
ating polymer SDKP-1 aqueous solution was about 30°C. The apparent viscosity of new thermoassoci-
ating polymer (SDKP-1) aqueous solution decreased with the increase of temperature when the temper-
ature is less than 30 °C, and showed typical characteristics of polyelectrolyte. This is because the
hydrophilic interaction of the hydrophilic groups, such as sulfonic acid group in polymer chains is stronger
than the hydrophobic interaction of hydrophobic group, such as phenyl in polymer chains, and increased
temperature is not conducive to the hydration of hydrophilic group in polyelectrolyte. So its water solution
apparent viscosity decreased. However, the hydrophobic association interaction of the hydrophilic groups
in molecular chain of thermoassociating polymer gradually increased which led the hydrodynamic radius
of polymer molecular became larger and the solution apparent viscosity increased slowly when the
temperature exceeds 30°C.
Property of viscosifying ability
The indoor comparative evaluation of viscosifying abilities of SDKP-1 were tested in 4% fresh water
based drilling fluid and in 5% NaCl salt water based drilling fluid before and after aging at 220°C for 16
hours respectively, and the results were as shown in Figure 24.

Figure 24 —The temperature resistant viscosifying performance results of SDKP-1

It can be seen from Figure 24 that the apparent viscosity decreased just a little and the rate of apparent
viscosity retention was higher after the aging test under ultra-high temperature both in fresh water based
drilling fluid and in salt water based drilling fluid. The apparent viscosity after the aging test was smaller
than that before the aging test, meaning that the elevated temperature could raise API filtrate volume and
spoil a part of the mud gel structure. The retention rates of apparent viscosity of novel viscosifier after
aging at 220°C after 16 h were 90.81% and 95.95% respectively. This indicates the newly developed
viscosifying agent of drilling fluid has a better performance of high temperature resistance and better
viscosifying property of a certain extent of salt resistance. Firstly, the excellent properties of drilling fluid
were due to the unique molecular design of SDKP-1 which the thermoassociating polymer matrix with
high degree branching structure had big steric hindrance, such as the rigid side chains of phenyl group and
micro-cross-linked structure, and the thermoassociating polymer of the copolymer was composed of
carbon-carbon bonds for high temperature stability. Secondly, although the ionic charge of high molecular
polymer was shielded by the ion charge of external electrolyte under the influence of the external ion
which resulting in polymer molecular chain convergence curl and polymer hydrodynamic radius reduced,
the hydrophobic associated interaction and thermo associated interaction emerged in drilling fluid because
OTC-26384-MS 17

of the side chain of phenyl group and caprolactam in SDKP-1, and increased temperature is advantageous
for hydrophobic associated interaction and thermo associated interaction between the molecules of
SDKP-1 which can make the apparent viscosity increase further more in aqueous solution. The rate of
apparent viscosity retention was higher after the aging test under ultra-high temperature than that of other
polymer additives in drilling fluid. This is because the novel synthetic thermo associated and hydrophobic
associated polymers not only introduced temperature sensitive monomers and anionic sulfonate groups
extremely insensitive to salt, but also introduced a little bit of phenyl group in hydrophilic macro chain.
Due to the high charge density of sulfonic acid groups in SSS and strong hydration, it is conducive to
improve the water solubility behavior of the copolymer. Meanwhile, the two ␲ bond and three strongly
electronegative O atoms in molecule shared a negative charge which made the sulfonic acid group stable,
so it is insensitive to the cation in the drilling fluid system (Mao Hui, et al.). On the other hand, with the
increase of inorganic ions concentration, the ion shielding effect of on apparent viscosity declined, but the
solvent polarity enhanced with the increase of content of inorganic salt ions. Thus it is more conducive
to the association of hydrophobic associating polymer hydrophobic chain. The hydrodynamic radius of
polymer molecular became larger and the solution apparent viscosity increased slowly when the ion
shielding effect ended.
Development of Ultra-high Temperature Drilling Fluids
An ultra-high temperature and low density water-based drilling fluid formulation with environmentally
acceptable and sea water discharged properties had been designed by preferring the field commonly used
anti-high-temperature drilling fluid additives in laboratory for ultra-high temperature down hole environ-
ments and environmental protection requirements in Offshore Oilfield around Bohai Sea Bay Basin in
China, highlighting the viscosifying agent which has excellent ultra-high temperature resistance and salt
resistance viscosifying property, thermal stability and thermo sensitive characteristics. The basic formu-
lation is: bentonite slurry (1-3 %) ⫹ SDKP-1 (0.3-0.7 %) ⫹ sulfonated phenolic resin (2-4 %) ⫹
sulfonated lignite (2-5 %) ⫹ polymeric filtrate loss reducers (0.5-1.5%) ⫹ sulfonated gilsonite (3-4 %) ⫹
liquid lubricant (1.5-3 %) ⫹ high temperature stabilizer (0.3-0.8 %) and using the limestone to adjust the
drilling fluid density to 1.04-1.08 g/cm3 (code as CGW). The indoor comprehensive evaluation of the
novel sea water discharged drilling fluids were tested before and after aging at 220°C for 16 hours, and
the results were as shown in Table 3. From Table 3 one can see that the apparent viscosity and the plastic
viscosity of novel sea water discharged drilling fluids decreased slightly, and the API filtration volume
and HTHP filtration volume of this drilling fluid increased slightly too, and the yield point unchanged
after aging at 220°C for 16 hours, indicating that the newly developed viscosifying agent with thermoas-
sociating property had an good viscosifying performance at ultra-high temperature environment and could
meet the basic requirements for drilling engineering.

Table 3—The basic performance of novel sea water discharged drilling fluids before and after aging at 220°C for 16 hours
Formulation Aging condition AV mPa·s PV mPa·s YP /Pa Gel Pa/Pa FLAPI mL FLHTHP mL

CGW Before aging at 220°C/16h 28 16 12 2.5/7 3.8 19

After aging at 220°C/16h 24 12 12 1.5/3 4.6 23
Note: The density of drilling fluid was 1.10 g/cm3. The HTHP filtrate loss was tested under 180°C.

After the field application of well NP3-81 and well NP3-82 using the formulation CGW in Jidong oilfield
around Bohai Sea Bay Basin in China, we developed a novel ultra-high temperature drilling fluids with density
of 1.10 to 1.15 g/cm3 (formulation UCGW-1 and UCGW-2) which can resistant the temperature up to 248°C
based on the novel polymer viscosifying agent (code as SDT10), flow pattern regulator (code as SDT12) and
18 OTC-26384-MS

filtrate reducer (code as SDT11 and SDT13) according to the optimization design of molecular structure of
polymer, and the basic performance of ultra-high temperature drilling fluids before and after aging at 220°C,
240°C and 248°C respectively for 16 hours were as shown in Table 4. Figure 25 and Figure 26 show the mud
cake photos of API and HTHP filtration of ultra-high temperature drilling fluids (formulation UCGW-1 and
UCGW-2) after aging at 248°C for 16 hours, respectively. From Table 4 we can see that the formulation
UCGW-1 and UCGW-2 have good rheological properties, ultra high temperature resistance ability and the API
filtrate loss is controlled less than 5mL and HTHP filtrate loss is controlled less than 20mL. From Figure 25
and Figure 26, we can see that the mud cakes were very thin and very dense.

Table 4 —The basic performance of ultra-high temperature drilling fluids before and after aging at 248°C for 16 hours
Formulations Aging condition AV mPa·s PV mPa·s YP /Pa Gel Pa/Pa FLAPI mL FLHTHP mL

UCGW-1 Before aging at 240°C/16h 30 26 4 1/5.5 1.6 12

After aging at 240°C/16h 34 20 14 5/9 3.6 13
Before aging at 245°C/16h 32.5 30 2.5 1/6 1.6 12
After aging at 245°C/16h 46 25 21 6/18 5.0 18.6
Before aging at 248°C/16h 35.5 30 5.5 1/6 4.0 14
After aging at 248°C/16h 39 16 23 6.5/19 4.2 19
UCGW-2 Before aging at 240°C/16h 35 30 5 2/7 2.0 13
After aging at 240°C/16h 38 24 14 5/11 4.0 15.6
Before aging at 245°C/16h 37.5 30 7.5 2/8 2.2 13
After aging at 245°C/16h 30 19 11 3/10 4.0 19
Before aging at 248°C/16h 36 30 6 1/6 3.8 14
After aging at 248°C/16h 39 28 11 5/14.5 4.6 18

Note: The density of drilling fluid was 1.10 g/cm3. The HTHP filtrate loss was tested under 180°C.

Figure 25—The mud cake photos of API filtrate loss after aging at 248°C for 16 hours (Left) formulation UCGW-1 and (Right) formulation
UCGW-2

Figure 26 —The mud cake photos of HTHP filtrate loss after aging at 248°C for 16 hours (Left) formulation UCGW-1 and (Right)
formulation UCGW-2
OTC-26384-MS 19

In addition, we also developed a novel ultra-high temperature and ultra-high density drilling fluid with
density of 2.54 g/cm3 (code as UGWM) which can resistant the temperature up to 240°C. Table 5 shows
the basic performance of ultra-high temperature and ultra-high density drilling fluids before and after
aging at 240°C for 16 hours. From Table 5 we can see that the API filtrate loss is controlled less than 5mL
too, and HTHP filtrate loss is controlled less than 20mL.

Table 5—The basic performance of ultra-high temperature and ultra-high density drilling fluids before and after aging at 240°C for
16 hours
AV PV YP Gel FLAPI FLHTHP
Formulation Aging condition mPa·s mPa·s /Pa Pa/Pa mL mL

UGWM Before aging at 240°C/16h 88 80 8 2.5/8.5 3.0 12

After aging at 240°C/16h 107.5 58 49.5 22/36 4.4 18

Note: The density of drilling fluid was 2.54 g/cm3. The HTHP filtrate loss was tested under 180°C.

Marine Environment Protection

In recent years, the marine environment protection has been become a focus all around the world
gradually, so the environmental issues of the offshore drilling fluids are becoming more and more
important. Local and national governments around the world have enacted strict laws and regulations for
waste emissions, especially drilling fluids which come from the drilling engineering in offshore oilfield.
Therefore, the petroleum industry is looking for multi-functional, biologically degradable, thermally
stable, environmentally friendly, novel polymers or natural products for designing discharged sea water
based drilling fluids to use virtually in offshore oilfield of petroleum exploration and exploitation. The
discharged sea water based drilling fluids are that mainly use non-toxic and environmentally friendly
drilling fluid additives, can meet the high temperature stability, environment-friendly, reservoir protection
at the same time, and can save the cost of transportation fee between onshore bases and offshore platforms,
and recycling processing costs of wastes significantly. Based on the study of the viscosifying mechanism
of SDKP-1, high-temperature resistant discharged sea water based drilling fluid with low density suitable
for Bohai Bay Basin in China was built in order to meet the needs of offshore drilling project. In this
article, we used the EC50 value to characterize the biological toxicity of SDKP-1 and SDKP-1 based
drilling fluids (Formulation CGW), and the EC50 value was greater, the biological toxicity of SDKP-1 was
smaller. The biological toxicity test results of SDKP-1 and SDKP-1 based drilling fluids are as shown in
Table 4a. The grading reference standard of drilling wastes in offshore oilfield in China is as shown in
Table 5a.

Table 4a—The biological toxicity test results of SDKP-1 and SDKP-1 based drilling fluids
Results

EC50 Fitted value of EC50

Samples (104 mg/L) (104 mg/L) Levels of toxicity

SDKP-1 ⬎3 15.5 non-toxic and meet the recommended emission standard

SDKP-1 based drilling fluids ⬎3 13.3 non-toxic and meet the recommended emission standard
20 OTC-26384-MS

Table 5a—The toxicity grading reference standard

EC50 (mg/L) Levels of toxicity

⬍1 Extremely-toxicity
1-100 high-toxicity
100-1000 median-toxicity
1000-10000 micro-toxicity
⬎10000 non-toxic
⬎30000 recommended emission standard

It can be seen from Table 4a and Table 5a that EC50 value of SDKP-1 and SDKP-1 based drilling fluids
are 15.529⫻104 mg/L and 13.3⫻104 mg/L respectively, indicating that SDKP-1 and SDKP-1 based
drilling fluids are non-toxic. According the provision of national standard GB/T 18420.1-2009 named
⬙Biological toxicity for pollutants from marine petroleum exploration and exploitation-Part 1: Grading,⬙
which was released by China Oceanic Administration, the lowest achievable emission biological toxicity
value of water-based drilling fluids in China primary and secondary sea area were 3⫻104 mg/L and 2⫻104
mg/L respectively, indicating that SDKP-1 based drilling fluids meet the recommended emission standard.

Field application
Wildcat well NP3-81 and NP3-82 are high-risk exploration wells, facing the drilling fluid technologic
problems of stability of low density drilling fluids with low bentonite under ultra-high temperature and
ultra-deep well, viscosifying, lost circulation and the rheological properties of drilling fluids. So the
drilling engineer’s strategies are the design of drilling fluids with ultra-high temperature resistance and
formulation development of drilling fluids with ultra-high temperature resistance. The newly developed
drilling fluid with ultra-high temperature resistance and sea water emission (Formulation CGW) were
used in well NP3-81 at well depth of 5939m to 6066m and well NP3-82 at well depth of 5694m to 6037m,
respectively. The temperature of drilling fluid was 85°C to 90°C both in well NP3-81 and well NP3-82
when the drilling fluid was circulated to the vibrosieve from bottom hole. The properties of drilling fluid
at field application are as shown in Table 6. One cycle week was about 160 minutes when the drilling fluid
circulated from the entrance of mud pump to the exit of vibrosieve and the changes of funnel viscosity
at each cycle are as shown in Figure 27 and Figure 28.

Table 6 —The properties of drilling fluid at field application

Name Value Unit

Apparent Viscosity 25 mPa•s

Plastic Viscosity 14 mPa•s
Yield Point 7 Pa
Funnel Viscosity 57 s
FLAPI 3.6 mL
FLHTHP 22 mL
pH 9 -
Density 1.04 g/cm3
OTC-26384-MS 21

Figure 27—The funnel viscosity changes of entrance and exit on each cycle in well NP3-81

Figure 28 —The funnel viscosity changes of entrance and exit on each week in well NP3-82

From Figure 27 and Figure 28, we can see that the funnel viscosity remained basically unchanged
during the drilling fluid circulating from the entrance of mud pump to the exit of vibrosieve. Logs were
run to bottom without incident with no drilling fluids related problems and the primary drilling objectives
achieved which indicating that the viscosifying agent SDKP-1 had good property of excellent ultra-high
temperature resistance, viscosifying and thermal stability at circumstance of ultra-high temperature. And
field application data shows that this new polymer viscosifying agent could play a critical role even though
at harsh conditions such as ultra-high temperature and low density drilling fluids system which decreasing
daily performance maintenance problems at the expense of the large consumption of drilling fluid
additives including the conventional sulfonate copolymer.
Conclusion
The newly developed thermoassociating and cross-linked polymer as viscosifying agent had excellent
properties of ultra-high temperature resistance and salt tolerance, and the novel development sea water
discharged drilling fluid had significant performance of thermal stability while temperatures over 220°C.
EC50 value of SDKP-1 and SDKP-1 based drilling fluids are 15.529⫻104 mg/L and 13.3⫻104 mg/L
respectively, indicating that SDKP-1 and SDKP-1 based drilling fluids are non-toxic and meet the
recommended emission standard. The success is attributed to the new technology, fit-for-purpose drilling
fluids and rigorous pre-well planning and the unique molecular structure of the polymer with thermoas-
sociating interaction and its micro crosslinking form in solution could keep the viscosity of drilling fluid
effectively at ultra-high temperature and low solid content so that it could play a role in reducing the
amount of fluid loss. Field application indicate that this new technology of sea water discharged drilling
fluids could decrease daily performance maintenance problems at the expense of the large consumption
of fluid additive including conventional sulfonate copolymer and save cost for the drilling company.
 22 OTC-26384-MS

Acknowledgments
This work is supported by Natural Science Foundation of China (No.U1562101), Science and Technology
Major Project of CNPC (No.2014E38-2), Fundamental Research Funds for the Central Universities
(No.15CX06019A) and Postgraduate Innovative Project of China University of Petroleum, East China
(No.YCX2015019).

References
1. Zhao X.Z, Jin F.M, Wang Q, et al. Niudong 1 ultra-deep and ultra-high temperature subtle buried hill field in Bohai
Bay Basin: Discovery and significance [J]. ACTA PETROLEI SINICA, 32 (6): 915–927, 2011.
2. Zhao X.Z, Wang Q, Jin F.M, et al. Main controlling factors and exploration practice of subtle buried hill hydrocarbon
reservoir in Jizhong depression [J]. ACTA PETROLEI SINICA, 33 (1): 71–79, 2012.
3. Ahmad, Izhar, et al. Drilling Operations in HP/HT Environment. Offshore Technology Conference-Asia. Offshore
Technology Conference, OTC-24829-MS, 2014.
4. Belani, Ashkok, Steve Orr. A systematic approach to hostile environments [J]. Journal of Petroleum Technology 60
(07): 34 –39, 2008.
5. Ben Naim, Arieh. Molecular Theory of Water and Aqueous Solutions. World Scientific, 2011.
6. Frolov A. Ion Interactions with Carbon Nanomaterial Surfaces in Aqueous and Non-aqueous Solutions [D].
Universität Duisburg-Essen, Fakultät für Chemie, 2011.
7. Bandura, Andrei V, Serguei N. Lvov. The ionization constant of water over wide ranges of temperature and density
[J]. Journal of physical and chemical reference data 35 (1): 15–30, 2006.
8. Fernández Prini, Roberto, R. B. Dooley. The International Association for the Properties of Water and Steam. 1998.
9. Lide D R, Frederikse H P R. Handbook of chemistry and physics 78th [J]. 1997.
10. Jin Hongyun. Application and Research Development of Subcritical Water [J]. Hydrometallurgy of China, 24(2):
66 –68, 2005.
11. Suresh, S.J, and V. M. Naik. Hydrogen bond thermodynamic properties of water from dielectric constant data [J]. The
Journal of Chemical Physics 113 (21): 9727–9732, 2000.
12. Cooper, J. R., and R. B. Dooley. IAPWS release on surface tension of ordinary water substance. International
Association for the Properties of Water and Steam (IAPWS), Charlotte, NC,1994.
13. Charlet G, Delmas G. Thermodynamic properties of polyolefin solutions at high temperature [J]. Polymer, 22(9):
1181–1189, 1981.
14. Charlet G, Ducasse R, Delmas G. Thermodynamic properties of polyolefin solutions at high temperature [J]. Polymer,
22(9): 1190 –1198, 1981
15. Cowie, John Mackenzie Grant, and Valeria Arrighi. Polymers: chemistry and physics of modern materials. CRC press,
2007.
16. Rimmer S, Carter S, Rutkaite R, et al. Highly branched poly-(N-isopropylacrylamide) s with arginine– glycine–
aspartic acid (RGD)-or COOH-chain ends that form sub-micron stimulus-responsive particles above the critical
solution temperature [J]. Soft Matter, 3(8): 971–973, 2007.
17. Ward M A, Georgiou T K. Thermoresponsive terpolymers based on methacrylate monomers: Effect of architecture
and composition [J]. Journal of Polymer Science Part A: Polymer Chemistry, 48(4): 775–783, 2010.
18. Huang W, Zhao C, Qiu Z, et al. Synthesis, characterization and evaluation of a quadripolymer with low molecular
weight as a water based drilling fluid viscosity reducer at high temperature (245°C) [J]. Polymer International, 2015.
19. Xie B, Qiu Z, Huang W, et al. Characterization and Aqueous Solution Behavior of Novel Thermo-associating
Polymers [J]. Journal of Macromolecular Science, Part A, 50(2): 230 –237, 2013.
20. Mao H, et al. Hydrophobic associated polymer based silica nanoparticles composite with core–shell structure as a
filtrate reducer for drilling fluid at utra-high temperature [J]. Journal of Petroleum Science and Engineering 129: 1–14,
2015.

View publication stats