Note: Descriptions are shown in the official language in which they were submitted.
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METHOD OF USING BIOLOGICALLY-DERIVED MONOESTERS AS DRILLING
FLUIDS
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Continuation-in-Part application of co-pending U.S.
Patent
Application No. 13/682,542, filed November 20, 2012.
FIELD OF THE INVENTION
This invention relates to monoester-based drilling fluid compositions, their
methods
of preparation and methods for use in a subterranean formation in oil and gas
recovery
operations, wherein they are made from at least one biologically-derived
precursor and/or
Fischer-Tropsch product(s).
BACKGROUND OF THE INVENTION
Drilling fluids employing synthetic fluids (i.e., monoester-based drilling
fluids) as the
base fluid are capable of achieving 96 hour LC50 Mysid shrimp (Mysidopsis
bahia) bioassay
test results greater than 100,000 ppm. However, even with these bioassay test
results their
commercial use has been severely restricted.
Accordingly, there is a need for a drilling fluid which employs an
inexpensive, non-
toxic synthetic fluid as the base fluid. The present invention satisfies this
need by providing a
drilling fluid comprising: (a) at least one drilling fluid additive (e.g., an
emulsifier, a
viscosifier, a weighting agent, and an oil-wetting agent) and (b) an
inexpensive, non-toxic
base fluid composed of monoester(s).
Previously, it has been reported that secondary esters can be used with invert
drilling
muds, wherein the esters comprised of C1-05 carboxylic acids and one or more
C3-C22 olefins
(see U.S. Patent No's. 6,100,223 and 6,191,076). Furthermore, the related U.S.
Patent
Application No. 13/682,542 (Monoester-Based Lubricants and Methods of Making
Same),
filed November 20, 2012, and incorporated in its entirety herein, provides a
simpler, more
efficient method of preparing monoesters.
As such, it would be extremely useful and desirable to employ methods of
drilling a
borehole in a subterranean formation with a biodegradable and non-toxic
monoester-based
drilling fluid, particularly when such methods utilize renewable raw materials
in combination
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with converting low value Fischer-Tropsch (FT) olefins and alcohols to high
value
monoester-based drilling fluids.
In this aspect, it has been found that the monoesters prepared from C6-C41
carboxylic
acids and C8-C84 olefins of the subject invention provide excellent properties
for use in
drilling fluids. In particular, the monoesters of this invention have a lower
viscosity and
excellent gel strength at high temperature and pressure than the current
commercially
available esters on the market today.
SUMMARY OF THE INVENTION
In one embodiment, the present invention is directed to a method for drilling
a
borehole in a subterranean formation comprising the steps of: a) rotating a
drill bit at the
bottom of the borehole; and b) introducing a drilling fluid into the borehole
to pick up drill
cuttings and to carry at least a portion of the drill cuttings out of the
borehole, wherein the
drilling fluid comprises: i) at least one additive selected from the group
consisting of
emulsifiers, wetting agents, viscosifiers, weighting agents, and fluid loss
control agents; and
ii) a quantity of at least one mono ester of Formula I:
0
>---R3
0
R1\ R2
wherein R1 and R2 and are independently selected from Ci to C8 and R3 is C5 to
C13.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a flow diagram illustrating a method of making monoesters for
incorporation in
monoester-based drilling fluid compositions.
Figure 2(a) illustrates a generic monoester, Figure 2(b) illustrates octyl
hexanoate monoesters
and Figure 2(c) illustrates decyl hexanoate monoesters.
DETAILED DESCRIPTION OF THE INVENTION
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation comprising the steps of: a) rotating a
drill bit at the
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bottom of the borehole; and b) introducing a drilling fluid into the borehole
to pick up drill
cuttings and to carry at least a portion of the drill cuttings out of the
borehole, wherein the
drilling fluid comprises: i) at least one additive selected from the group
consisting of
emulsifiers, wetting agents, viscosifiers, weighting agents, and fluid loss
control agents; and
ii) a quantity of at least one monoester of Formula I, wherein said steps are
performed
continually.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I is
biodegradable
and non-toxic.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I is
derived from an
isomerized olefin.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R1 and R2 are independently
selected from Ci
to C8 and R3 is C5 to C12.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R1 and R2 are independently
selected from Ci
to C5 and R3 is C5 to C8.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R1 and R2 are independently
selected from C1
to C3 and R3 is C5 to C6.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the kinematic viscosity of the
monoester of
Formula I at a temperature of 100 C is between about 0.5 cSt to 2 cSt, a
temperature of 40
C is between about 2 cSt to 4 cSt and a temperature of 0 C is between about 4
cSt to 12 cSt.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I has
an Oxidator
BN of greater than 30 hours.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I has
an Oxidator
BN of greater than 50 hours.
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In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I has
an Oxidator
BN of greater than 60 hours.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I has a
pour point
less than about -20 C.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I has a
pour point
less than about -60 C.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid has a pour
point less than
about 10 C and a viscosity at 40 C between about 1 cSt to about 10 cSt.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid has a 10
second gel strength
between about 2 lb/100 sq ft to about 15 lb/100 sq ft.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid has a 10
second gel strength
of about 2 lb/100 sq ft at about 93.3 C and about 1000 psig.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid has a 10
second gel strength
of about 1 lb/100 sq ft at about 121.1 C and about 15000 psig.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid produced a
rheological
property profile in the Fann 77 illustrated in Table 2A.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid produced a
rheological
property profile in the Fann 77 illustrated in Table 2B.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid has a 10
minute gel strength
between about 1 lb/100 sq ft to about 17 lb/100 sq ft.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R3 is C5.
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In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R3 is C5 and R1 and R2 are C2.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein R3 is C5 and R1 and R2 are C3.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the at least one monoester of
Formula I is an
octyl hexanoate, its isomers, and mixtures thereof
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the at least one monoester of
Formula I is
m decyl hexanoate, its isomers, and mixtures thereof
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the at least one monoester of
Formula I is a
mixture of an octyl hexanoate, its isomers, and a decyl hexanoate, its
isomers, and mixtures
thereof
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid of Step (b)
comprises
between about 20 wt% to 40 wt% of the monoester of Formula I.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid of Step (b)
further comprises:
a. between about 1.0 wt% to about 3.0 wt% of the emulsifier and wetting agent;
b. between about 0.1 wt% to about 1.5 wt% of an organophilic clay;
c. between about 5 wt% to about 12 wt% of water;
d. between about 1.0 wt% to about 4.0 wt% of a salt;
e. between about 0.1 wt% to about 1.0 wt% of the latex filtration control
agent;
f. between about 40 wt% to about 60 wt% of the weighting agent; and
g. between about 3.0 wt% to about 9.0 wt% of the simulated drill
solids.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid comprises a
monoester
selected from the group consisting of hexanyl hexanoate and isomers, hexanyl
octanoate and
isomers, hexanyl decanoate and isomers, hexanyl laureate and isomers, hexanyl
palmitate and
isomers, hexanyl hexadecanoate and isomers, hexanyl stearate and isomers,
octanyl
hexanoate and isomers, octanyl octanoate and isomers, octanyl decanoate and
isomers,
octanyl laureate and isomers, octanyl palmitate and isomers, octanyl
hexadecanoate and
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isomers, octanyl stearate and isomers, decanyl hexanoate and isomers, decanyl
octanoate and
isomers, decanyl decanoate and isomers, decanyl laureate and isomers, decanyl
palmitate and
isomers, decanyl hexadecanoate and isomers, decanyl stearate and isomers,
dodecanyl
hexanoate and isomers, dodecanyl octanoate and isomers, dodecanyl decanoate
and isomers,
dodecanyl laureate and isomers, dodecanyl palmitate and isomers, dodecanyl
hexadecanoate
and isomers, dodecanyl stearate and isomers, tetradecanyl hexanoate and
isomers,
tetradecanyl octanoate and isomers, tetradecanyl decanoate and isomers,
tetradecanyl laureate
and isomers, tetradecanyl palmitate and isomers, tetradecanyl hexadecanoate
and isomers,
tetradecanyl stearate and isomers, hexadecanyl hexanoate and isomers,
hexadecanyl
octanoate and isomers, hexadecanyl decanoate and isomers, hexadecanyl laureate
and
isomers, hexadecanyl palmitate and isomers, hexadecanyl hexadecanoate and
isomers,
hexadecanyl stearate and isomers, octadecanyl hexanoate and isomers,
octadecanyl octanoate
and isomers, octadecanyl decanoate and isomers, octadecanyl laureate and
isomers,
octadecanyl palmitate and isomers, octadecanyl hexadecanoate and isomers,
octadecanyl
stearate and isomers, icosanyl hexanoate and isomers, icosanyl octanoate and
isomers,
icosanyl decanoate and isomers, icosanyl laureate and isomers, icosanyl
palmitate and
isomers, icosanyl hexadecanoate and isomers, icosanyl stearate and isomers,
docosanyl
hexanoate and isomers, docosanyl octanoate and isomers, docosanyl decanoate
and isomers,
docosanyl laureate and isomers, docosanyl palmitate and isomers, docosanyl
hexadecanoate
and isomers and docosanyl stearate and isomers, and mixtures thereof
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the drilling fluid further
comprises the
components: (a) lime, (b) fluid loss control agent, (c) an aqueous solution
comprising water
and the shale inhibiting salt, (d) oil wetting agent, (e) non-sulfonated
polymer, (f) sulfonated
polymer and (g) non-organophilic clay.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the at least one monoester of
Formula I has a
molecular mass that is from at least about 144 a.m.u, to at most about 592
a.m.u.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I is
derived from an
internal olefin.
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In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I is
derived from a
secondary alcohol.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I is
secondary
monoester.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the ¨0(CO)R3 group of Formula I
is not bound
to the terminus of R1 or R2.
m In some
embodiments, the present invention is directed to a method for drilling a
borehole in a subterranean formation, wherein the monoester of Formula I does
not comprise
products derived from oligomerization.
In some embodiments, the present invention is directed to a method for
drilling a
borehole in a subterranean formation, wherein the monoester of Formula I does
not comprise
products derived from alpha olefins.
In one embodiment, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I:
0
>---R3
0
R1 \ R2
wherein R1 and R2 and are independently selected from Ci to Cs and R3 is C5 to
C13.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I is biodegradable and non-toxic.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I is derived from an isomerized olefin.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R1 and
R2 and are
independently selected from Ci to Cs and R3 is C5 to C12.
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In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R1 and
R2 are
independently selected from Ci to C5 and R3 is C5 to C8.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R1 and
R2 are
independently selected from Ci to C3 and R3 is C5 to C6.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
kinematic viscosity
of the monoester of Formula I at a temperature of 100 C is between about 0.5
cSt to 2 cSt, a
temperature of 40 C is between about 2 cSt to 4 cSt and a temperature of 0 C
is between
about 4 cSt to 12 cSt.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I has an Oxidator BN of greater than 30 hours.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I has an Oxidator BN of greater than 50 hours.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I has an Oxidator BN of greater than 60 hours.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I has a pour point less than about -20 C.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I has a pour point less than about -60 C.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid has a
pour point less than about 10 C and a viscosity at 40 C between about 1 cSt
to about 10 cSt.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid has a
10 second gel strength between about 2 lb/100 sq ft to about 15 lb/100 sq ft.
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In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid has a
second gel strength of about 2 lb/100 sq ft at about 93.3 C and about 1000
psig.
In some embodiments, the present invention is directed to a drilling fluid
composition
5 comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid has a
10 second gel strength of about 1 lb/100 sq ft at about 121.1 C and about
15000 psig.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid
produced a rheological property profile in the Fann 77 illustrated in Table
2A.
10 In some
embodiments, the present invention is directed to a drilling fluid composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid
produced a rheological property profile in the Fann 77 illustrated in Table
2B.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid has a
10 minute gel strength between about 1 lb/100 sq ft to about 17 lb/100 sq ft.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R3 is
C5.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R3 is C5
and R1 and R2
are C2.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein R3 is C5
and R1 and R2
are C3.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the at
least one
monoester of Formula I is an octyl hexanoate, its isomers, and mixtures
thereof
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the at
least one
monoester of Formula I is decyl hexanoate, its isomers, and mixtures thereof
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the at
least one
monoester of Formula I is a mixture of an octyl hexanoate, its isomers, and a
decyl
hexanoate, its isomers, and mixtures thereof
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In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid of
Step (b) comprises between about 20 wt% to 40 wt% of the monoester of Formula
I.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid
further comprises:
a. between about 1.0 wt% to about 3.0 wt% of the emulsifier and wetting
agent;
b. between about 0.1 wt% to about 1.5 wt% of an organophilic clay;
c. between about 5 wt% to about 12 wt% of water;
d. between about 1.0 wt% to about 4.0 wt% of a salt;
e. between about 0.1 wt% to about 1.0 wt% of the latex filtration control
agent;
f. between about 40 wt% to about 60 wt% of the weighting agent; and
g. between about 3.0 wt% to about 9.0 wt% of the simulated drill solids.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid
comprises a monoester selected from the group consisting of hexanyl hexanoate
and isomers,
hexanyl octanoate and isomers, hexanyl decanoate and isomers, hexanyl laureate
and
isomers, hexanyl palmitate and isomers, hexanyl hexadecanoate and isomers,
hexanyl
stearate and isomers, octanyl hexanoate and isomers, octanyl octanoate and
isomers, octanyl
decanoate and isomers, octanyl laureate and isomers, octanyl palmitate and
isomers, octanyl
hexadecanoate and isomers, octanyl stearate and isomers, decanyl hexanoate and
isomers,
decanyl octanoate and isomers, decanyl decanoate and isomers, decanyl laureate
and isomers,
decanyl palmitate and isomers, decanyl hexadecanoate and isomers, decanyl
stearate and
isomers, dodecanyl hexanoate and isomers, dodecanyl octanoate and isomers,
dodecanyl
decanoate and isomers, dodecanyl laureate and isomers, dodecanyl palmitate and
isomers,
dodecanyl hexadecanoate and isomers, dodecanyl stearate and isomers,
tetradecanyl
hexanoate and isomers, tetradecanyl octanoate and isomers, tetradecanyl
decanoate and
isomers, tetradecanyl laureate and isomers, tetradecanyl palmitate and
isomers, tetradecanyl
hexadecanoate and isomers, tetradecanyl stearate and isomers, hexadecanyl
hexanoate and
isomers, hexadecanyl octanoate and isomers, hexadecanyl decanoate and isomers,
hexadecanyl laureate and isomers, hexadecanyl palmitate and isomers,
hexadecanyl
hexadecanoate and isomers, hexadecanyl stearate and isomers, octadecanyl
hexanoate and
isomers, octadecanyl octanoate and isomers, octadecanyl decanoate and isomers,
octadecanyl
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laureate and isomers, octadecanyl palmitate and isomers, octadecanyl
hexadecanoate and
isomers, octadecanyl stearate and isomers, icosanyl hexanoate and isomers,
icosanyl
octanoate and isomers, icosanyl decanoate and isomers, icosanyl laureate and
isomers,
icosanyl palmitate and isomers, icosanyl hexadecanoate and isomers, icosanyl
stearate and
isomers, docosanyl hexanoate and isomers, docosanyl octanoate and isomers,
docosanyl
decanoate and isomers, docosanyl laureate and isomers, docosanyl palmitate and
isomers,
docosanyl hexadecanoate and isomers and docosanyl stearate and isomers, and
mixtures
thereof
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
drilling fluid
further comprises the components: (a) lime, (b) fluid loss control agent, (c)
an aqueous
solution comprising water and the shale inhibiting salt, (d) oil wetting
agent, (e) non-
sulfonated polymer, (f) sulfonated polymer and (g) non-organophilic clay.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the at
least one
monoester of Formula I has a molecular mass that is from at least about 144
a.m.u, to at most
about 592 a.m.u.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I is derived from an internal olefin.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I is derived from a secondary alcohol.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I is secondary monoester.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
¨0(CO)R3 group
of Formula I is not bound to the terminus of R1 or R2.
In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I does not comprise products derived from oligomerization.
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In some embodiments, the present invention is directed to a drilling fluid
composition
comprising a quantity of at least one monoester of Formula I, wherein the
monoester of
Formula I does not comprise products derived from alpha olefins.
I. Monoester-Based Drilling Fluid Compositions
The monoester-based drilling fluids of the present invention may comprise one
or
more of the following:
A quantity of at least one monoester of Formula I:
0
>---R3
0
R1\ R2
wherein R1 and R2 and are independently selected from C1 to C40 and R3 is C5
to C40.
Surfactants (e.g., emulsifiers, wetting agents), viscosifiers, weighting
agents, fluid
loss control agents, and shale inhibiting salts are also optionally used in
the drilling fluid of
the present invention. Because the drilling fluids of the present invention
are intended to be
non-toxic, these optional ingredients, like the monoester, are preferably also
non-toxic.
Exemplary emulsifiers include, but are not limited to, fatty acids, soaps of
fatty acids, and
fatty acid derivatives including amido-amines, polyamides, polyamines, esters
(such as
sorbitan monoleate polyethoxylate, sorbitan dioleate polyethoxylate),
imidaxolines, and
alcohols.
Typical wetting agents include, but are not limited to, lecithin, fatty acids,
crude tall
oil, oxidized crude tall oil, organic phosphate esters, modified imidazolines,
modified
amidoamines, alkyl aromatic sulfates, alkyl aromatic sulfonates, and organic
esters of
polyhydric alcohols.
Exemplary weighting agents include, but are not limited to barite, iron oxide,
gelana,
siderite, and calcium carbonate.
Common shale inhibiting salts are alkali metal and alkaline-earth metal salts.
Calcium
chloride and sodium chloride are the preferred shale inhibiting salts.
Exemplary viscosifiers include, but are not limited to, organophilic clays
(e.g.,
hectorite, bentonite, and attapulgite), non-organophilic clays (e.g.,
montmorillonite
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(bentonite), hectorite, saponite, attapulgite, and illite), oil soluble
polymers, polyamide resins,
and polycarboxylic acids and soaps.
Examples of fluid loss control agents include, but are not limited to,
asphaltics (e.g.,
asphaltenes and sulfonated asphaltenes), amine treated lignite, and gilsonite.
For drilling
fluids intended for use in high temperature environments (e.g., where the
bottom hole
temperature exceeds about 204.4 C (400 F)), the fluid loss control agent is
preferably a
polymeric fluid loss control agent. Exemplary polymeric fluid loss control
agents include, but
are not limited to, polystyrene, polybutadiene, polyethylene, polypropylene,
polybutylene,
polyisoprene, natural rubber, butyl rubber, polymers consisting of at least
two monomers
selected from the group consisting of styrene, butadiene, isoprene, and vinyl
carboxylic acid.
Individual or mixtures of polymeric fluid loss control agents can be used in
the drilling fluid
of this invention.
Optionally, one or more pour point depressants are employed in the synthetic
fluids
(i.e., monoester-based drilling fluids) of the present invention to lower
their pour point.
Typical pour point depressants include, but are not limited to, ethylene
copolymers,
isobutylane polymers, polyaklylnaphthalenes, wax-aromatic condensation
products (e.g.,
wax-naphthalene condensation products, phenol-wax condensation products),
polyalkylphenolesters, polyalkylmethacrylates, polymethacrylates,
polyalkylated condensed
aromatics, alkylaromatic polymers, iminodiimides, and polyalkylstyrene. (The
molecular
weights for polyaklylnaphthalenes, polyalkylphenolesters, and
polyalkylmethacrylates range
from about 2,000 to about 10,000) Because they are non-toxic, ethylene
copolymers and
isobutylene polymers are the preferred pour point depressants.
Up to about 1 weight percent pour point depressant is employed. (As used in
the
specification and claims, the weight percent of the pour point depressant is
based upon the
weight of the monoester, i.e., it is the weight of the pour point depressant
divided by the
weight of the monoester, the quotient being multiplied by 100%) Preferably,
the pour point
depressant is employed in a concentration of 0.005 to about 0.5, more
preferably about 0.01
to about 0.4, and most preferably about 0.02 to about 0.3, weight percent.
When employed,
the pour point depressant is preferably mixed with the monoester and the
resulting
composition is then combined with any additional additives as described
herein.
The properties (e.g., monoester to water ratio, density, etc.) of the drilling
fluids of the
invention can be adjusted to suit any drilling operation. For example, the
drilling fluid is
usually formulated to have a volumetric ratio of monoester to water of about
100:0 to about
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40:60 and a density of about 0.9 kg/1 (7.5 pounds per gallon (ppg)) to about
2.4 kg/1 (20 ppg).
More commonly, the density of the drilling fluid is about 1.1 kg/1 (9 ppg) to
about 2.3 kg/1
(19 ppg).
The drilling fluids are preferably prepared by mixing the constituent
ingredients in the
following order: (a) monoester, (b) emulsifier, (c) lime (when employed), (d)
fluid loss
control agent (when employed), (e) an aqueous solution comprising water and
the shale
inhibiting salt, (f) organophilic clay, (g) oil wetting agent, (h) weighting
agent, (i) non-
sulfonated polymer (when employed), (j) sulfonated polymer (when employed),
and (k) non-
organophilic clay (when employed).
II. Methods of Making Monoesters
As mentioned above, the present invention is additionally directed to methods
of
making the above-described lubricant compositions.
The olefins disclosed here may be alpha olefins produced by gas to liquid
processes
(GTL) refining processes, petrochemical processes, pyrolysis of waste plastics
and other
processes, are isomerized into internal olefins followed by conversion into
monoesters. The
alpha olefins are isomerized into internal olefins using double bond
isomerization catalyst
including molecular sieves such as SAPO-39 and medium pore zeolites such as
SSZ-32 and
ZSM-23.
Referring to the flow diagram shown in FIG. 1, in some embodiments, processes
for
making the above-mentioned monoester species, typically having lubricating
base oil
viscosity and pour point, comprise the following steps: (Step 101) epoxidizing
an internal
olefin (or quantity of olefins) having a carbon number of from C6-C84 to form
an epoxide or a
mixture of epoxides; (Step 102) opening the epoxide rings via reduction
methods to form the
corresponding mono secondary alcohol; and (Step 103) esterifying (i.e.,
subjecting to
esterification) the secondary alcohol with a C6-C41 carboxylic acid to form
internal
monoester species. Generally, lubricant compositions comprising such monoester
species
have a viscosity in the range from 0.5 centistokes to 2 centistokes at a
temperature of 100 C.
In some embodiments, where a quantity of such monoester species is formed, the
quantity of monoester species can be substantially homogeneous, or it can be a
mixture of
two or more different such monoester species.
In some such above-described method embodiments, the olefin used is a reaction
product of a Fischer-Tropsch process. In these or other embodiments, the
carboxylic acid can
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be derived from alcohols generated by a Fischer-Tropsch process and/or it can
be a bio-
derived fatty acid.
In some embodiments, the olefin is an a-olefin (i.e., an olefin having a
double bond at
a chain terminus). In such embodiments, it is usually necessary to isomerize
the olefin so as
to internalize the double bond. Such isomerization is typically carried out
catalytically using a
catalyst such as, but not limited to, crystalline aluminosilicate and like
materials and
aluminophosphates. (see, e.g., U.S. Patent No's. 2,537,283; 3,211,801;
3,270,085; 3,327,014;
3,304,343; 3,448,164; 4,593,146; 3,723,564 and 6,281,404); the last of which
claims a
crystalline aluminophosphate-based catalyst with 1-dimensional pores of size
between 3.8 A
and 5 A.
As an example of such above-described isomerizing and as indicated in Scheme 1
(FIG. 3), Fischer-Tropsch alpha olefins (a-olefins) can be isomerized to the
corresponding
internal olefins followed by epoxidation. The epoxides can then be transformed
to the
corresponding secondary mono alcohols via epoxide ring reduction followed by
esterifying
(i.e., di-esterification) with the appropriate carboxylic acids or their
acylating derivatives. It is
typically necessary to convert alpha olefins to internal olefins because
monoesters of alpha
olefins, especially short chain alpha olefins, tend to be solids or waxes.
"Internalizing" alpha
olefins followed by transformation to the monoester functionalities introduces
branching
along the chain in the produced esters and thus reduces the symmetry of the
molecules which
in turn reduces the pour point of the intended products. Internalizing the
ester may also
enhance the oxidative and hydrolytic stability. Internal esters show
surprising hydrolytic and
oxidative stabilities that are much superior to those of terminal esters.
Internalizing the ester
makes it sterically more hindered and that may contribute to the oxidative and
hydrolytic
stabilities.
The ester groups with their polar character would further enhance the
viscosity of the
final product. Branching, introduced by internalizing the ester groups, will
enhance the cold
temperature properties such as pour and cloud points. Viscosity can be
increased by
increasing the carbon number of the internal olefin or the acid used in the
esterification.
Regarding the step of epoxidizing (i.e., the epoxidation step), in some
embodiments,
the above-described olefin (preferably an internal olefin) can be reacted with
a peroxide (e.g.,
H202) or a peroxy acid (e.g., peroxyacetic acid) to generate an epoxide. (see,
e.g., D. Swern,
in Organic Peroxides Vol. II, Wiley-Interscience, New York, 1971, pp. 355-533;
and B.
Plesnicar, in Oxidation in Organic Chemistry, Part C, W. Trahanovsky (ed.),
Academic
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Press, New York 1978, pp. 221-253). Olefins can be efficiently transformed to
the
corresponding diols by highly selective reagent such as osmium tetra-oxide
(see M. Schroder,
Chem. Rev. vol. 80, p. 187, 1980) and potassium permanganate (see Sheldon and
Kochi, in
Metal-Catalyzed Oxidation of Organic Compounds, pp. 162-171 and 294-296,
Academic
Press, New York, 1981).
Regarding the step of epoxide ring opening to the corresponding secondary mono
alcohols, this step is done by epoxide ring reduction using metal hydrides
reduction
procedures or noble metal-catalyzed hydrogenations processes. Both procedures
are very
effective at making the needed secondary alcohols for internal epoxides.
Regarding the step of esterifying (esterification), an acid is typically used
to catalyze
the esterification reaction of alcohols and carboxylic acids. Suitable acids
for esterification
include, but are not limited to, sulfuric acid (see Munch-Peterson, Org.
Synth., V, p. 762,
1973), sulfonic acid (see Allen and Sprangler, Org Synth., III, p. 203, 1955),
hydrochloric
acid (see Eliel et al., Org Synth., IV, p. 169, 1963), and phosphoric acid
(among others). In
some embodiments, the carboxylic acid used in this step is first converted to
an acyl chloride
(e.g., thionyl chloride or PC13). Alternatively, an acyl chloride could be
employed directly.
Wherein an acyl chloride is used, an acid catalyst is not needed and a base
such as pyridine,
4-dimethylaminopyridine (DMAP) or triethylamine (TEA) is typically added to
react with an
HC1 produced. When pyridine or DMAP is used, it is believed that these amines
also act as a
catalyst by forming a more reactive acylating intermediate. (see, e.g., Fersh
et al., J. Am.
Chem. Soc., vol. 92, pp. 5432-5442, 1970; and Hofle et al., Angew. Chem. Int.
Ed. Engl., vol.
17, p. 569, 1978).
Regardless of the source of the olefin, in some embodiments, the carboxylic
acid used
in the above-described method is derived from biomass. In some such
embodiments, this
involves the extraction of some oil (e.g., triglyceride) component from the
biomass and
hydrolysis of the triglycerides of which the oil component is comprised so as
to form free
carboxylic acids.
Using a synthetic strategy in accordance with that outlined in Scheme 1,
Scheme 2,
and Scheme 3, a mixture of internal octenes was converted to the corresponding
mixture of
internal monoester derivatives, octyl hexanoates and octyl decanoates via
acylation of the
octyl alcohols intermediates with hexanoyl and decanoyl chlorides,
respectively. The
Examples below explain this process in more detail. Octyl and decyl hexanoates
are
particularly suitable for use in drilling fluid compositions.
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Definitions and Terms
The following terms will be used throughout the specification and will have
the
following meanings unless otherwise indicated.
The term "Drilling Fluid," refers to any of a number of liquid and gaseous
fluids and
mixtures of fluids and solids (as solid suspensions, mixtures and emulsions of
liquids, gases
and solids) used in operations to drill boreholes into the earth. Synonymous
with "drilling
mud" in general usage, although some prefer to reserve the term "drilling
fluid" for more
sophisticated and well-defined "muds."
The term "Rheology", refers to the study of deformation and flow of matter.
Rheological measurements of a drilling fluid include plastic viscosity (PV),
yield point (YP)
and gel strengths. The information from these measurements can be used to
determine hole
cleaning efficiency, system pressure losses, equivalent circulating density,
surge and swab
pressures and bit hydraulics.
The term "Fluid Loss Control Agent" includes, but are not limited to,
asphaltics (e.g.,
asphaltenes and sulfonated asphaltenes), amine treated lignite, and gilsonite.
For drilling
fluids intended for use in high temperature environments (e.g., where the
bottom hole
temperature exceeds about 204.4 C. (400 F.)), the fluid loss control agent
is preferably a
polymeric fluid loss control agent. Exemplary polymeric fluid loss control
agents include, but
are not limited to, polystyrene, polybutadiene, polyethylene, polypropylene,
polybutylene,
polyisoprene, natural rubber, butyl rubber, polymers consisting of at least
two monomers
selected from the group consisting of styrene, butadiene, isoprene, and vinyl
carboxylic acid.
Individual or mixtures of polymeric fluid loss control agents can be used in
the drilling fluid
of this invention.
The term "Organophilic Clay" or "Viscosifiers", refers to CARBO-GEL II (Baker-
Hughes), organophilic bentonite, hectorite, attapulgite and sepiolite.
Bentonite and hectorite
are platelet clays that will increase viscosity, yield point and build a thin
filter cake to aid in
reducing the fluid loss. A number of polymers are available for use in non-
aqueous fluids.
These polymers increase fluid carrying capacity and may also function as fluid
loss control
additives. They include: elastomeric viscosifiers, sulfonated polystyrene
polymers, styrene
acrylate, fatty acids and dimer-trimer acid combinations.
The term "Emulsifiers and Wetting Agents", refers to primary emulsifiers which
are
generally very powerful, fatty acid based surfactants. They usually require
lime to activate
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and build a stable emulsion. Secondary emulsifiers, often called wetting
agents, are typically
based on imidazolines or amides (e.g., OMNI-MUL , Baker-Hughes), and do not
require
lime to activate. They are designed to oil-wet solids and also emulsify oil.
To formulate
stable water in oil mixtures, the use of surfactants is required. Surfactants
lower surface
tension and emulsify the internal water phase and "oil wet" solids. In
practice, emulsifiers
are classified as either "primary" or "secondary", depending on the desired
application.
The term "Salt," refers to CaC12 used to make drilling fluids or brines with a
suitable
density. CaC12 can be blended with other brines, including NaC1, CaBr2 and
ZnBr2.
Emulsification of CaC12 brine as the internal phase of synthetic-based mud is
an important
use because the brine provides osmotic wellbore stability while drilling water-
sensitive shale
zones.
The term "Weighting Agents", refers to barite (barium sulfate) (e.g.
MICROMAXTm)
as used to increase the density of drilling fluids. Other weighting agents are
hematite (iron
oxide), managanese tetraoxide and calcium carbonate. These weighting materials
increase
the density of the external phase of the fluids.
The term "Latex Filtration Control Agent", refers to Pliolite (Goodyear)
polymers.
The term "Simulated Drill Solids", refers to powdered clay as used to simulate
drilled
formation particles.
The term "non-Organophilic Clay," refers to a clay which has not been amine-
treated
to convert the clay from water-yielding to oil-yielding.
The term "Mud Weight" or "Density", refers to a mud fluid property for
balancing
and controlling downhole formation pressures and promoting wellbore stability.
Mud
densities are usually reported in pounds per gallon (lb/gal). As most drilling
fluids contain at
least a little air/gas, the most accurate way to measure the density is with a
pressurized mud
balance.
The term "Lime," refers to quicklime (CaO), quicklime precursors, and hydrated
quicklime (e.g., slaked lime (Ca(OH)2).
The term "Surfactant," refers to substances that when present at low
concentration in
a system, has the property of adsorbing onto the surfaces or interfaces of the
system and of
altering to a marked degree the surface or interfacial free energies of those
surfaces (or
interfaces). As used in the foregoing definition of surfactant, the term
"interface" indicates a
boundary between any two immiscible phases and the term "surface" denotes an
interface
where one phase is a gas, usually air.
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The term "Lubricant," refers to substances (usually a fluid under operating
conditions)
introduced between two moving surfaces so to reduce the friction and wear
between them.
Base oils used as motor oils are generally classified by the American
Petroleum Institute as
being mineral oils (Group I, II, and III) or synthetic oils (Group IV and V).
See American
Petroleum Institute (API) Publication Number 1509.
The term "Pour point," refers to the lowest temperature at which a fluid will
pour or
flow. (see, e.g., ASTM International Standard Test Methods D 5950-96, D 6892-
03, and D
97). The results are reported in degrees Celsius. Many commercial base oils
have
specifications for pour point. When base oils have low pour points, the base
oils are also
likely to have other good low temperature properties, such as low cloud point,
low cold filter
plugging point, and low temperature cranking viscosity.
The term "Cloud Point," refers to the temperature at which a fluid begins to
phase
separate due to crystal formation. See, e.g., ASTM Standard Test Methods D
5773-95, D
2500, D 5551, and D 5771.
The term "Centistoke," abbreviated "cSt," is a unit for kinematic viscosity of
a fluid
(e.g., a lubricant), wherein 1 centistoke equals 1 millimeter squared per
second (1 cSt=1
mm2/s). See, e.g., ASTM Standard Guide and Test Methods D 2270-04, D 445-06, D
6074,
and D 2983.
With respect to describing molecules and/or molecular fragments herein, "Re,"
where
"n" is an index, refers to a hydrocarbon group, wherein the molecules and/or
molecular
fragments can be linear and/or branched.
The term "Cõ," where "n" is an integer, describes a hydrocarbon molecule or
fragment
(e.g., an alkyl group) wherein "n" denotes the number of carbon atoms in the
fragment or
molecule.
The prefix "Bio," refers to an association with a renewable resource of
biological
origin, such as resource generally being exclusive of fossil fuels.
The term "Internal Olefin," refers to an olefin (i.e., an alkene) having a non-
terminal
carbon-carbon double bond (C=C). This is in contrast to "a-olefins" which do
bear a terminal
carbon-carbon double bond.
The term "Group I Base Oil," refers to a base oil which contains less than 90
percent
saturates and/or greater than 0.03 percent sulfur and have a viscosity index
greater than or
equal to 80 and less than 120 using the ASTM methods specified in Table E-1 of
American
Petroleum Institute Publication 1509.
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The term "Group II Base Oil," refers to a base oil which contains greater than
or equal
to 90% saturates and less than or equal to 0.03% sulfur and has a viscosity
index greater than
or equal to 80 and less than 120 using the ASTM methods specified in Table E-1
of
American Petroleum Institute Publication 1509.
The term "Group II+ Base Oil," refers to a Group II base oil having a
viscosity index
greater than or equal to 110 and less than 120.
The term "Group III Base Oil," refers to a base oil which contains greater
than or
equal to 90% saturates and less than or equal to 0.03% sulfur and has a
viscosity index
greater than or equal to 120 using the ASTM methods specified in Table E-1 of
American
Petroleum Institute Publication 1509.
The term "Fischer-Tropsch Derived," refers to a product, fraction, or feed
that
originates from or is produced at some stage by a Fischer-Tropsch process.
The term "Petroleum Derived," refers to a product, fraction, or feed
originates from
the vapor overhead streams from distilling petroleum crude and the residual
fuels that are the
non-vaporizable remaining portion. A source of the petroleum derived product,
fraction, or
feed can be from a gas field condensate.
The term "Highly Paraffinic Wax," refers to a wax having a high content of n-
paraffins, generally greater than 40 wt %, but can be greater than 50 wt %, or
even greater
than 75 wt %, and less than 100 wt % or 99 wt %. Examples of highly paraffinic
waxes
include slack waxes, deoiled slack waxes, refined foots oils, waxy lubricant
raffinates, n-
paraffin waxes, NAO waxes, waxes produced in chemical plant processes, deoiled
petroleum
derived waxes, microcrystalline waxes, Fischer-Tropsch waxes, and mixtures
thereof
The phrase "Derived from Highly Paraffinic Wax," refers to a product,
fraction, or
feed originates from or is produced at some stage by from a highly paraffinic
wax.
The term "Aromatics," refers to any hydrocarbonaceous compounds that contain
at
least one group of atoms that share an uninterrupted cloud of delocalized
electrons, where the
number of delocalized electrons in the group of atoms corresponds to a
solution to the Huckel
rule of 4n + 2 (e.g., n = 1 for 6 electrons, etc.). Representative examples
include, but are not
limited to, benzene, biphenyl, naphthalene, and the like.
The phrase "Molecules with Cycloparaffinic Functionality," refers to any
molecule
that is, or contains as one or more substituents, a monocyclic or a fused
multicyclic saturated
hydrocarbon group. The cycloparaffinic group can be optionally substituted
with one or
more, such as one to three, substituents. Representative examples include, but
are not limited
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to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl,
decahydronaphthalene,
octahydropentalene, (pentadecan-6-yl)cyclohexane,
3,7,10-tricyc lohexylp entadecane,
decahydro-1-(pentadecan-6-yl)naphthalene, and the like.
The phrase "Molecules with Monocycloparaffinic Functionality," refers to any
molecule that is a monocyclic saturated hydrocarbon group of three to seven
ring carbons or
any molecule that is substituted with a single monocyclic saturated
hydrocarbon group of
three to seven ring carbons. The cycloparaffinic group can be optionally
substituted with one
or more, such as one to three, substituents. Representative examples include,
but are not
limited to, cyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, cycloheptyl,
(pentadecan-6-
yl)cyclohexane, and the like.
The phrase "Molecules with Multicycloparaffinic Functionality," refers to any
molecule that is a fused multicyclic saturated hydrocarbon ring group of two
or more fused
rings, any molecule that is substituted with one or more fused multicyclic
saturated
hydrocarbon ring groups of two or more fused rings, or any molecule that is
substituted with
more than one monocyclic saturated hydrocarbon group of three to seven ring
carbons. The
fused multicyclic saturated hydrocarbon ring group often is of two fused
rings. The
cycloparaffinic group can be optionally substituted with one or more, such as
one to three,
substituents. Representative examples include, but are not limited to,
decahydronaphthalene,
octahydropentalene, 3,7,10-tricyclohexylpentadecane, dec
ahydro-1-(pentadecan-6-
yl)naphthalene, and the like.
The term "Kinematic Viscosity," refers to a measurement of the resistance to
flow of
a fluid under gravity. Many base oils, lubricant compositions made from them,
and the
correct operation of equipment depends upon the appropriate viscosity of the
fluid being
used. Kinematic viscosity is determined by ASTM D445-06. The results are
reported in
mm2is .
The term "Viscosity Index" (VI), refers to an empirical, unitless number
indicating
the effect of temperature change on the kinematic viscosity of the oil.
Viscosity index is
determined by ASTM D2270-04.
The term "Oxidator BN," refers to a measurement of the response of a base oil
in a
simulated application. High values, or long times to adsorb one liter of
oxygen, indicate good
stability. Oxidator BN can be measured via a Domte-type oxygen absorption
apparatus (see
R. W. Dornte "Oxidation of White Oils," Industrial and Engineering Chemistry,
Vol. 28,
page 26, 1936), under 1 atmosphere of pure oxygen at 340 F. The time, in
hours, to absorb
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1000 ml of 02 by 100 grams of oil is reported. In the Oxidator BN test, 0.8 ml
of catalyst is
used per 100 grams of oil. The catalyst is a mixture of soluble metal-
naphthenates simulating
the average metal analysis of used crankcase oil. The additive package is 80
millimoles of
zinc bispolypropylenephenyldithiophosphate per 100 grams of oil.
Unless otherwise indicated herein, scientific and technical terms used in
connection
with the present invention shall have the meanings that are commonly
understood by those of
ordinary skill in the art. Further, unless otherwise required by context,
singular terms shall
include pluralities and plural terms shall include the singular. More
specifically, as used in
lo this specification and the appended claims, the singular forms "a",
"an" and "the" include
plural referents unless the context clearly dictates otherwise. Thus, for
example, reference to
"a fatty acid" includes a plurality of fatty acids, and the like. In addition,
ranges provided in
the specification and appended claims include both end points and all points
between the end
points. Therefore, a range of 2.0 to 3.0 includes 2.0, 3.0 and all points
between 2.0 and 3Ø
Furthermore, all numbers expressing quantities, percentages or proportions,
and other
numerical values used in the specification and claims, are to be understood as
being modified
in all instances by the term "about". As used herein, the term "include" and
its grammatical
variants are intended to be non-limiting, such that recitation of items in a
list is not to the
exclusion of other like items that can be substituted or added to the listed
items. As used
herein, the term "comprising" means including elements or steps that are
identified following
that term, but any such elements or steps are not exhaustive, and an
embodiment can include
other elements or steps.
EXAMPLES
The following examples are provided to demonstrate particular embodiments of
the
present invention. It should be appreciated by those of skill in the art that
the methods
disclosed in the examples which follow merely represent exemplary embodiments
of the
present invention. However, those of skill in the art should, in light of the
present disclosure,
appreciate that many changes can be made in the specific embodiments described
and still
obtain a like or similar result without departing from the spirit and scope of
the present
invention.
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Example 1
Epoxidation of Octenes into Epoxy Octanes
A mixture of 2-octene, 3-octene and 4-octene (1:1:1 mixture), purchased from
Aldrich
Chemical company, were epoxidized as follows using the general procedure
described below
(Scheme 1). To a stirred solution of 509 grams (2.95 mol) of 77% mCPBA (meta-
chloroperoxybenzoic acid) in 2000 mL n-hexane in an ice bath, 265 grams (2.36
mol) of 2-
octene, 3-octene and 4-octene (1:1:1) mixture were added drop-wise via an
addition funnel
over a period of 60 minutes. The resulting reaction mixture was stirred over 0
C for 2 hrs.
Then, the ice bath was removed and the reaction was allowed to stir overnight.
The resulting
milky solution was subsequently filtered to remove meta-chloro-benzoic acid
that formed
therein. The filtrate was then washed with a 10% aqueous solution of sodium
bicarbonate.
The organic layer was dried over anhydrous magnesium sulfate while stirring
for 1 hr. The
organic solvent (n-hexane) was removed by distillation at atmospheric pressure
and 67-71 C.
IR and NMR analysis and GCMS spectroscopy on the remaining solution confirmed
the
presence of the epoxide mixture with little residual n-hexane. This solution
was used as is for
next step (reduction of the epoxides to the corresponding secondary alcohols)
without any
further attempt to remove the remaining hexane. The epoxide is a little
volatile and care must
be taken to prevent any appreciable loss by distillation or condensation on a
rotary
evaporator. Epoxidation was also accomplished using formic acid/hydrogen
epoxide solution
of 1:1.5 parts.
Scheme 1
Octenes
1 [EPDXIDATION]
mCPBA
0 0 0
Epoxy Octanes
Example 2
Reduction of 2,3-Epoxy Octanes to Secondary Octanols
The epoxy octanes with little residual hexane produced according to example 1
were
reduced with lithium aluminum hydride in THF (Tetrahydrofuran) according to
the procedure
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described below. The products from example 1 were divided into two equal
portions and each
portion was reduced separately with lithium aluminum hydride in anhydrous THF.
Assuming
full conversion of the octenes to epoxides in example 1, each portion was
assumed to contain
1.18 moles (151.3 grams) of epoxy octanes. Accordingly, a suspension of 56
grams (1.48
mol.) of lithium aluminum hydride in 1000 mL anhydrous THF in 3-liter 3-neck
reaction
flask equipped with an overhead stirrer and reflux condenser, was cooled down
to 0 C in an
ice-bath. To this suspension and while stirring, one of the two portions of
the epoxy octanes
mixture (presuming 151.3 grams; 1.18 mol.) was added drop-wise via a sealed
dropping
funnel. Once the addition was complete, an additional 100 ml of THF was added
via the
dropping funnel to. The reaction mixture was left to stir at 0 C for 2 hrs.
The ice-bath was
then removed and the reaction left to stir overnight. The reaction was then
heated to reflux for
an hour or so to ensure reduction completion. The reaction progress was
monitored by NMR
and IR analysis on small aliquots work-up. Once completed, the heat source was
replaced
with an ice-bath and the reaction was worked up by first diluting with 500 ml
THF and then
adding 550 ml of 15% NaOH solution via a dropping funnel with vigorous
stirring and not
allowing the temperature of the reaction to rise above room temperature (very
slow addition).
The addition continued until all the grey solution transformed into a milky
solution which
was left to stir for addition 30 minutes. The stirring was stopped and the
solution nicely
separated into a clear liquid phase and a fine white precipitate. The mixture
was filtered and
the filtrate was dried over anhydrous MgSO4 and then concentrated on a rotary
evaporator to
remove the solvent THF and afford a mixture of 2-octanol, 3-octanol, and 4-
octanol as
colorless viscous oil that turned into a very soft waxy substance while
standing at room
temperature for few days. The reduction afforded 132 grams of the alcohols or
86% yield for
the two reactions described in examples 1 and 2. Reduction of the second
portion of the
epoxy octanes gave similar results with 84% overall yield. Reduction was also
accomplished
by mild hydrogenation over Pd/C catalyst on small scale.
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Scheme 2
o o o
Epoxy Octanes
[REDUCTION]
LiAIH4
OH OH OH
Octanols
Example 3
Esterification of Octanols with Hexanoyl Chloride: Synthesis of Octyl
Hexanoates
The mixture of 2-octanol, 3-octanol, and 4-octanol prepared in example 2 was
esterified according to the procedure below using hexanoyl chloride as the
esterification
agent as shown in Scheme 3. To a solution of 130.5 grams (1 mol.) of the
octanols mixture in
1000 ml cyclohexane in a 3-neck 3L round bottom reaction vessel equipped with
an overhead
stirrer and reflux condenser, 126.5 grams (1.25 mol.) of triethylamine and 6.5
grams (0.05
mol.) of 4-N,N-dimethylaminopyridine (DMAP). The mixture was cooled down by
means of
an ice-bath and left to stir at around 0 C for 15 minutes. To the stirring
cold solution, 148
grams (1.1 mol.) of hexanoyl chloride was added drop-wise via a dropping
funnel over 45
minutes. Once all hexanoyl chloride was added the reaction was left to stir
and warm slowly
to room temperature. The reaction, then, was refluxed and monitored by NMR and
IR
analysis. Once the reaction was completed, the resulting milky creamy solution
was worked
up by adding water until all the solids disappeared and a clear solution
formed (two phase
solution). The two phase solution was separated in a separatory funnel and the
organic phase
was washed with water and brine and saved. The aqueous phase was extracted
with ethyl
acetate. The ethyl acetate extract was washed with brine and was combined to
the organic
phase. The organic phase, containing the esters, was dried over anhydrous
Mg504, filtered
and concentrated on a rotary evaporator to give 218 grams (96% yields) of the
esters mixture
as slightly orange-colored oil. The product was passed through 15 cm x 5 cm
silica gel plug
and flushed with hexane. The hexane was removed on a rotary evaporator to give
the product
as colorless oil (214 gm were recovered).
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Scheme 3
OH OH OH
Octanols
0
triethylamine, DMAP
i
hexanoyl chlorideCi
0
/./.).
octan-2-y I hexanoate
0 0
0
octan-3-y1 hexanoate octan-4-y I hexanoate
Example 4
Esterification with Hexanoic Acid Using H3PO4 as Catalyst
The mixture of octanols was also esterified with hexanoic acid in toluene and
using
phosphoric acid as catalyst according to the procedure shown below. The
reaction apparatus
consisted of a 3-neck 1L reaction flask equipped with an overhead stirrer,
reflux condenser
with a Dean-Stark trap and a heating mantle. The reaction vessel was charged
with 50 gm
(0.38 mol.) of octanols mixture, 66 gm (0.57 mol.) hexanoic acid, 5 gm of 85%
phosphoric
acid, and 250 ml toluene. The mixture was heated at reflux (-110 C) for 6 hrs
and left to stir
at reflux overnight. One more gram of 85% H3PO4 was added and the reaction was
left to
continue stirring at reflux until no more water formation was observed (as
indicated by the
level of water collected in the Dean-Stark trap). In all, the reaction stirred
for approximately
36 hrs. The reaction was then cooled down and worked up by removing the
toluene on a
rotary evaporator followed by extraction in diethyl ether and extensive
washing with warm
water (4x500 ml) followed by rinsing with 300 ml of saturated sodium
bicarbonate solution
to remove any residual acids (organic and inorganic) and with brine solution
(300 m1). The
ether extract was dried over anhydrous Mg504, filtered and concentrated on a
rotary
evaporated to remove ether. The reaction afforded 76 gram of faint yellow oil.
The oil was
then passed through a 10 cm x 4cm silica gel plug to remove any residual
acids. After the
final purification step, 73 grams of the desired esters (octyl hexanoates) was
recovered as
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colorless oil with a sweet odor. Using identical synthesis procedures, decyl
hexanoates were
synthesized in similar yields.
Example 5
Lubrication properties of Octyl Hexanoates and Decyl Hexanoates
The table below shows the lubrication properties of octyl hexanoates and decyl
hexanoates.
Table 1
Esters Viscosity Viscosity Viscosity Pour Point BN
Oxidator
@100 C @40 C @0 C
Octyl Hexanoates 0.9 cSt. 2.2 cSt. 5.8 cSt. <-60
64 hrs
Decyl Hexanoates 1.2 cSt. 3.1 cSt. 10.8 cSt. <-60
N/A
N/A is defined as "not available".
Example 6
Oxidator BN Test
The octyl hexanoate mixture was evaluated for oxidation stability by measuring
how
much time it takes for a given amount of the ester to absorb 1 liter of Oxygen
using the
Oxidator BN test. Octyl hexanoates exhibited superior oxidation stability with
64 hrs (see
Table 1 above).
Example 7
Preparation of a Drilling Fluid From Example 4
An invert emulsion drilling fluid was prepared by (a) initially agitating
166.0 grams of
the ester from Example 4 (Octyl Hexanoates) for about one minute using a
blender and (b)
then sequentially adding the following ingredients (with continuous mixing for
about one
minute after the addition of each material): (i) 16.0 grams of an emulsifier
and wetting agent
(OMNI-MII LED, Baker-Hughes); and (ii) 3.0 grams of an organophilic clay
(CARBO-GELED
II, Baker-Hughes). Subsequently, 46.0 grams of water was added to the above
mixture and
mixed for about 10 minutes. Next, the following materials were added in
sequence, with
about 5 minutes of mixing after the addition of each of the materials: (i)
300.3 grams of
powdered barite (a non-toxic weighting agent); (ii) 17.2 grams of calcium
chloride dehydrate
(to provide salinity to the water phase without water wetting the barite);
(iii) 4.0 grams of a
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latex filtration control agent (Pliolite , Goodyear); and (iv) 40.0 grams of a
powdered clay to
simulate drilled formation particles. The final density of the drilling fluid
was 14 pounds per
gallon (about 1.7 kg/1).
Example 8
Preparation of a Drilling Fluid From Example 4
An invert emulsion drilling fluid was prepared by (a) initially agitating
168.076 grams
of the ester from Example 4 (Octyl Hexanoates) for about one minute using a
blender and (b)
then sequentially adding the following ingredients (with continuous mixing for
about one
minute after the addition of each material): (i) 12.0 grams of an emulsifier
and wetting agent
(OMNI-MU , Baker-Hughes); and (ii) 2.5 grams of an organophilic clay (CARBO-
GEL
II, Baker-Hughes). Subsequently, 48.3 grams of water was added to the above
mixture and
mixed for about 10 minutes. Next, the following materials were added in
sequence, with
about 5 minutes of mixing after the addition of each of the materials: (i)
300.3 grams of
powdered barite (a non-toxic weighting agent); (ii) 17.2 grams of calcium
chloride dehydrate
(to provide salinity to the water phase without water wetting the barite);
(iii) 2.0 grams of a
latex filtration control agent (Pliolite , Goodyear); and (iv) 40.0 grams of a
powdered clay to
simulate drilled formation particles. The final density of the drilling fluid
was 14 pounds per
gallon (about 1.7 kg/1).
Example 9
Rheology of a Drilling Fluid From Example 7
The rheology of the drilling fluid of Example 7 was evaluated in a Fann iX77
instrument (Fann Instrument Company, Houston, TX), according to procedures
described in
Recommended Practice-Standard Procedure for Field Testing Drilling Fluids, API
Recommended Practice 13B-2 (RP 13B-2), Second Edition, Dec.1, 1991, American
Petroleum Institute, Washington, D.C. The measured results are given in Table
2A. These
results show that the ester of Example 4 can be used to make an acceptable
drilling fluid, and
has exceptionally low gel strength at high temperature (200 F and higher).
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Table 2A
FANN
FANN 77
Test
Temperature, 120 80 150 200 250 300 80
F
Test Pressure, 0 0 5000 10000 15000 20000 0
psig
Dial Readings
*:
600 RPM 97 139 98 89 79 83 128
300 RPM 56 81 55 48 43 47 73
200 RPM 42 59 41 36 32 34 54
100 RPM 26 37 24 21 18 19 33
60 RPM N/A 27 18 14 12 14 24
30 RPM N/A 18 11 9 8 9 16
20 RPM N/A 15 9 7 6 7 13
10 RPM N/A 11 6 5 5 6 9
6 RPM 6 9 5 4 4 5 8
3 RPM 5 7 4 3 3 4 6
Plastic 41 59 43 41 36 36 55
Viscosity, cSt
Yield Point, 15 22 11 8 7 10 19
lb/100 sq ft
10 Second Gel, 7 6 3 2 1 2 5
lb/100 sq ft
10 Minute Gel, 9 7 4 2 1 7 6
lb/100 sq ft
Before Gels spin for 30 Seconds @ 600 RPM
10 Seconds @
N/A 139 98 85 79 86 127
600 RPM
10 Seconds @
N/A 79 56 48 43 49 73
300 RPM
10 Seconds @
N/A 135 96 85 79 87 126
600 RPM
End @ 600
N/A 136 96 88 82 91 126
RPM
N/A is defined as "not available".
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Example 10
Rheology of a Drilling Fluid From Example 8
The rheology of the drilling fluid of Example 8 was evaluated in a Fann iX77
instrument (Fann Instrument Company, Houston, TX), according to procedures
described in
Recommended Practice-Standard Procedure for Field Testing Drilling Fluids, API
Recommended Practice 13B-2 (RP 13B-2), Second Edition, Dec.1, 1991, American
Petroleum Institute, Washington, D.C. The measured results are given in Table
2B. These
results show that the ester of Example 4 can be used to make an acceptable
drilling fluid, and
has exceptionally low gel strength at high temperature (200 F and higher).
Table 2B
FANN
FANN 77
Test
Temperature, 120 80 50 67 104 190 80
F
Test Pressure, 0 0 6000 11000 16000 24000 0
psig
Dial Readings
*:
600 RPM 73 104 235 246 192 109 107
300 RPM 42 63 140 142 110 63 65
200 RPM 32 48 102 106 81 45 50
100 RPM 21 32 64 66 50 26 34
60 RPM N/A 24 47 49 36 18 26
30 RPM N/A 17 33 33 23 11 18
20 RPM N/A 15 27 27 19 9 16
10 RPM N/A 11 22 21 14 7 12
6 RPM 7 9 18 18 11 6 10
3 RPM 6 8 15 14 9 5 8
Plastic 31 42 95 104 81 46 42
Viscosity, cSt
Yield Point, 11 21 45 39 29 17 22
lb/100 sq ft
10 Second Gel, 7 8 14 12 7 3 7
lb/100 sq ft
10 Minute Gel, 10 9 16 15 9 4 8
lb/100 sq ft
Before Gels spin for 30 Seconds @ 600 RPM
10 Seconds @
N/A 104 247 244 191 116 103
600 RPM
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Seconds @
N/A 62 141 138 109 66 62
300 RPM
10 Seconds @
N/A 102 231 237 186 118 101
600 RPM
End @ 600
N/A 103 232 275 192 127 101
RPM
N/A is defined as "not available".
The monoester produced a rheological property profile in the Fann 77 test that
is
unique and different. The difference (and uniqueness) lies in the low gel
strengths at 200 F
5 and 250
F and high pressure. The formulation showed no indication of settling in the
instrument. In addition, the gel strengths are very flat and non-progressive.
The benefit itself
would be the reduced pump pressure required to initiate circulation after a
prolonged drilling
cessation.
10 All
patents, patent applications and publications are herein incorporated by
reference
to the same extent as if each individual patent, patent application or
publication was
specifically and individually indicated to be incorporated by reference.
The present invention if not to be limited in scope by the specific
embodiments
described herein, which are intended as single illustrations of individual
aspects of the
invention, and functionally equivalent methods and components are within the
scope of the
invention. Indeed, various modifications of the invention, in addition to
those shown and
described herein will become apparent to those skilled in the art from the
foregoing
description and accompanying drawings. Such modifications are intended to fall
within the
scope of the appended claims.
31
