Note: Descriptions are shown in the official language in which they were submitted.
CA 02239318 1998-OS-29
IMPROVED HYDROCARBON GELLING COMPOSITIONS USEFUL IN
FRACTURING FORMATIONS
FIELD OF THE INVENTION
The present invention is directed to the improved gellation of hydrocarbons
liquids for a
variety of applications. The present invention is specifically directed to an
enhancer for
improving the gelling of hydrocarbon liquids when treated with phosphate
esters and crosslinking
agents.
BACKGROUND OF THE INVENTION
In order to maximize the amount of oil derived from an oil well a process
known as
hydraulic pressure stimulation or, more commonly, formation fracturing is
often employed. In
formation fracturing, fluid is pumped under high pressure down the wellbore
through a steel pipe
having small perforations in order to create or perpetuate cracks in the
adjacent subterranean rock
formation. The fluid employed must be able to withstand exceptionally high
shear forces. Gelled
liquids, and particularly gelled hydrocarbons, are well-suited for this
application. The fracturing
fluid has entrained therein a particulate material called a proppant (e.g.,
sand or other particulate
matter). The proppant particles become wedged in the cracks of the formation
to keep the cracks
open once the external pressure is released, thereby enabling continued
production stimulation of
the well. It is ideal from the vantage points of time economy and cost-savings
to have the
gelling of the hydrocarbon take place more or less continuously on-site or "on
the fly" as the
I
CA 02239318 1998-OS-29
components are brought together as they are pumped down the well bore.
Accordingly, it is both
desirable and adavatageous that gellation occur as quickly as possible.
The viscosity of the hydrocarbon gel is important for proppant transport. Poor
gel
viscosity can lead to a phenomenon known as "screening out", whereby the gel
is not sufficiently
capable of suspending the proppant. Large quantities of proppant material,
upwards of 3 to 15
pounds of sand per gallon of pumping fluid, can settle out inside the well
bore, as well as in the
fracture. If the proppant has dropped, or screened out, part of the created
fracture is effectively
closed when the external pressure is released. When screening out occurs, the
fracturing process
must be interupted and the well bore cleaned out, costing both significant
time and expense.
Rapid gellation of hydrocarbon liquids is also beneficial when tanks or
vessels carrying
such liquids are damaged during transport and cause highly hazardous and
environmentally
damaging spillage. A fast gelling additive composition that can be added to
the leaking volume
of hydrocarbon liquid would serve to prevent or, at least, reduce or contain
the spillage and the
resultant damage. A variety of other applications exist which require the
rapid gellation of
hydrocarbon 1 iquids, and to which the present invention would apply.
Several means for gelling hydrocarbon liquids are disclosed in the prior art.
U.S. Patent
No. 5,417,287 to Smith et al. is directed to a method for fracturing a
subterranean formation
which involves adding to a hydrocarbon liquid (a) an organic phosphate of the
formula HP04RR'
2
CA 02239318 1998-OS-29
where R is an alkyl or alkaryl group having from 6 to 18 carbon atoms and R'
is hydrogen or an
aryl, alkaryl or alkyl group having from 1 to 18 carbon atoms; and (b) a
ferric salt.
Smith et al 5,614,010 teaches gelling agents suitable for use in methods of
fracturing
formations, comprising ferric salts, certain phosphate esters, a low molecular
weight amine such
as triethanolamine or triethylamine, and an optional surfactant. Smith '010,
however, does not
achieve, e.g., the impressive hydrocarbon viscosities achievable by the
present methods and
compositions, and moreover Smith uses twice as much phosphate ester and ferric
ion as required
herein.
Smith et al US 5,647,900 discloses gelling agents for hydrocarbon gels
comprising
combinations of certain orthophosphate esters and a composition comprising a
source of fernc
ions, a C2 - C12 amine, and a polycarboxylic acid or salt thereof. However,
the gels formed in
the Smith et al inventions demonstrate lower (Marsh funnel) viscosities than
those achieved by
the gels of the present invention. Moreover, the Smith et al gels are formed
using twice as much
phosphate ester and ferric ion ( 1 °Io of each relative to the volume
of liquid hydrocarbon to be
gelled) as compared to the invention as demonstrated, e.g., in the Examples of
the invention.
European Patent Application No. 551021A1 to McCabe et al. is directed to
gelling a
hydrocarbon liquid by adding thereto an at least partially neutralized alkyl
orthophosphate acid
ester, a C8-C18 surface active amine and C2 - C4 monohydric alcohol. The
surface active amine
employed includes alkyl and alkanol amines having from about 8 - 18 carbon
atoms,
3
CA 02239318 1998-OS-29
N-heterocyclic amines, alkyl substituted derivatives of such heterocyclics and
mixtures thereof.
Amines having more than one nitrogen group are preferred and imidazoline, such
as that
prepared from the reaction of a tall of 1 fatty acid with diethylenetriamine,
is most preferred.
U.S. Patent No. 4,316,810 to Burnham is directed to a fracturing composition
which is an
aluminum salt of an oxaalkyl phosphate in an oil base liquid. Surface active
agents are not
disclosed.
U.S. Patent No. 4,153,649 to Griffin is directed to the reaction product of a
hydroxy ether
and a pentavalent phosphorus compound and an alcohol. The hydroxy ether has
the formula
RORIOH wherein R is a C, to C6 alkyl group, Rl Is a C2 or C3 alkylene group
and the total carbon
atoms of Rl and R range from 3 to about 8. The disclosed reaction product may
be employed in
the gelling of hydrocarbon liquids when used with a compound containing a
multivalent metal
cation.
U. S. Patent No. 5,271,464 to McCabe is directed to a method of plugging or
sealing a
subterranean formation by introducing a rapidly gelling hydrocarbon thereto.
To the hydrocarbon
is added a first component which is an at least partially neutralized alkyl
orthophosphate ester
and a second component which is the reaction product of an aqueous source of
aluminum or
ferric ions and a C8 - C18 surface active amine in the presence of a water
miscible organic
solvent. The surface active amine is as defined above for European Patent
Application No.
4
CA 02239318 1998-OS-29
551021A1, also to McCabe. The water miscible organic solvent is generally a
monohydric
alcohol.
U.S. Patent No. 3,494,949 to Monroe et al. is directed to an additive for
improving the
viscosity of motor oils which is generally an aluminum salt of an alkyl
orthophosphate.
U.S. Patent No. 2,983,678 to Pellegrini et al. is directed to an additive for
lubricating oils
which is generally a rare earth metal salt of a diester phosphate.
US Patent Nos. 4,877,894, 5,057,233, 5,110,485, and 5,202,035 to Huddleston
are related
to phosphate esters as hydrocarbon gelling agents. The gelling agent is
generally formed by first
reacting phosphorus pentoxide with triethyl phosphate, followed by reaction
with a mixed
alcohol that may have a substantial hexanol component. The gelling agent may
also be in the
form of an aluminum salt, by reaction of the phosphate ester with aluminum
sulfate in the
presence of solvent. None of the gelling agents or systems of the Huddleston
patents appreciate
the benefit of adding an amine, e.g., oxyalkylated amine, or an amine blend
enhancer in the
gelling of liquid hydrocarbons. The Huddleston teachings are also. devoid of
appreciation of the
benefits obtained by using a ferric salt.
US Patent No. 5,190,675 and EP 225,661 to Gross (Dowell Schlumberger) employ
metal
phosphate diesters in the gelling of liquid hydrocarbons. The metal phosphate
diester is prepared
by reacting a phosphorus pentoxide with a triethyl phosphate , followed by
reaction with an
CA 02239318 1998-OS-29
alcohol to form the diester. The metal salt is formed in the presence of the
hydrocarbon to be
gelled by the addition of a non-aqueous source of aluminum, e.g., aluminum
isopropoxide. The
gelling agents of Gross are devoid of the presence of an amine enhancer and a
crosslinking ferric
salt, and accordingly, Gross' methods do not achieve the level of beneficial
gelling properties
achievable by the present invention.
While a variety of systems are available for gelling hydrocarbon liquids for
the
application discussed above, there exists a clear need in the art for a means
of improving the
known systems to achieve decreased gelling times and improved viscosity.
SUMMARY OF THE INVENTION
Therefore, it is one object of the present invention to provide such a means
for improving
known gellation systems.
It is a further object of the present invention to provide a novel gellation
system
exhibiting decreased gelling times and improved viscosity.
It is yet another object of the present invention to provide a composition for
decreasing
gelling time and improving viscosity for use in conventional methods of
gelling hydrocarbon
liquids.
6
CA 02239318 1998-OS-29
These as well as other objects are achieved by providing a composition for
improving the
gelling of hydrocarbon liquids, which composition comprises an enhancer chosen
from a
specific class of amines, a certain class of phosphate esters, and a
crosslinking agent.
Such objects are also achieved by providing a method of gelling hydrocarbon
liquids
which involves adding to a hydrocarbon liquid the enhancer, the phosphate
ester, and the
crosslinking agent. -
A further object of the invention is to provide synergistic combinations of
enhancers, as
well as synergistic phosphate ester combinations, useful in improving the
gelling of hydrocarbon
liquids.
More particularly, the objects of the invention are achieved by providing a
method of
gelling hydrocarbon liquids which involves adding to a hydrocarbon liquid (a)
a phosphate ester
or a mixture of phosphate esters; (b) a crosslinking agent; and (c) an amine
enhancer which is a
CZ - C22 amine, a C2 - C22 oxyalkylated amine, or mixtures thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is drawn, in part, to an enhancer for use in the gelling
of
hydrocarbon liquids when such a liquid is treated with a phosphate ester and a
crosslinking agent.
The invention is also directed to novel compositions comprising the enhancer,
a phosphate ester
(chosen from a specified class and to be described more fully below), and the
crosslinking agent.
7
CA 02239318 2002-09-04
The invention relates further still to gel compositions which results from
adding to a hydrocarbon
liquid the enhancer, the phosphate ester, and the crosslinking agent.
Hydrocarbon liquids which are appropriate for use in accordance with the
present
invention include kerosene, diesel oil and crude oil, gasoline and other
aliphatic and aromatic
hydrocarbons such as octane, heptane, paraffinic oils and lubricating oils.
The choice of the
liquid for use in accordance with the. present invention will depend o:n the
particular industrial or
chemical application. In industrial applications, diesel oil is typically
gelled, however other
liquid hydrocarbons are also well-suited for use in the present invention.
Other factors, such as
accessibility and economics(cost) of liquid hydrocarbons at a particular site,
dictate to a degree
the choice of hydrocarbon to be gelled.
The crosslinking agent or activator employed in the practice of the invention
is a salt of a
multivalent cation, and is preferably the salt of a multivalent metal cation.
Although a wide
variety of metal salts, such as aluminum salts and rare earth metal salts, are
within the scope of
the present invention, ferric salts are generally preferred. Preferred ferric
salts include ferric
nitrate and ferric sulfate.
The phosphate ester component of the present invention can be the reaction
product of a
pentavalent phosphorus compound and an alcohol, and their preparation is
according to well-
known synthesis procedures (see, for example, Crawford et al UPS 3,757,864,
Poklacki US
4,007,128, and Burnham et al US 4,200,539
More preferably, the phosphate esters useful herein are the reaction product
of 1) pentavalent
8
CA 02239318 2002-09-04
phosphorus (e.g., P205) reacted with a trialkylphosphate, and 2) at least one
alcohol. The
synthesis of these phosphate esters takes place according to well-known
procedure, for example,
as set forth in Huddleston US 5,202,035,, Alternatively, the
phosphate esters useful in the present invention can be prepared by
transesterification of
orthophosphate ester with triethyl phosphate, for example, Jones et al US
5,649,596.
More preferably, the phosphate ester is formed from P205 and a tri-loweralkyl
phosphate
when reacted with a mixture of alcohols and /or oxyalkylated al.cohols
yielding phosphate
monoesters, symmetric diesters, asymmetric diesters, symmetric triesters,
asymmetric triesters,
and mixtures of any of these. "Tri-loweralkyl phosphate" in the present
context is to be
understood as meaning tri -CI - C6 alkylphosphate. The alcohols suitable for
reaction with the
phosphate intermediate include alkyl alcohols, aralkyl alcohols, ether-
containing alkyl alcohols,
and aralkyl ether alcohols (or oxyalkylated aralkyl alcohols), and mixtures
thereof. It is to be
understood that the term "alkyl" as it applies to the present phosphate esters
includes straight and
branched alkyl groups. "Aryl" includes C6 to C12 aryl. Therefore, when ether
alcohols are
employed one or more oxyalkene groups such as oxyethylene, oxypropylene or
oxybutylene is
present in the "R" group of the alcohol designated as ROH. Accordingly, the
phosphate ester
that is formed is an ether phosphate ester. Thus, the term "phosphate esters"
as used herein
includes ether phosphate esters. The phosphate esters of the present invention
will thus be
mixtures of esters conforming to the following structures:
9
CA 02239318 1998-OS-29
RO- P -OH RO- P -ORi RO- P -ORS
OH ~ OH ~ ~d OR2
wherein R, RI , and R2 are independently CI- CI8 alkyl, C6 aryl, C1 - CI8
alkyl or di C1 - CI8
alkyl C6 aryl, C1 - CI8 alkyl ether, C6 aryl ether, or CI - CI8 alkyl or di CI
- CI8 alkyl C6 aryl ether,
and where any ether linkage has the following structure: -
-O(CH2-CHR')-
wherein R' is hydrogen, methyl or ethyl.
More preferably, the phosphate ester according to the invention is a mixture
of mixed
esters such as asymmetric phosphate diesters (i.e., where R ~ RI). The ability
to obtain
particularly useful phosphate ester mixtures within the scope of the invention
hinges upon the
specific alkyl, alkaryl, alkyl ether,alkaryl ether, aralkyl, and/or aralkyl
ether moieties in the
alcohol reactants. For example, a phosphate ester mixture that contains a
distribution of C2, C8,
CIO, and oxyalkylated C6 aryl groups is particularly useful herein.
The phosphate ester of the present invention is preferably non-neutralized.
However,
depending on the particular enhancer employed, it is also within the scope of
the invention to at
least partially neutralize the phosphate ester.
CA 02239318 2003-04-O1
The enhancer of the present invention is an amine, a mixture of amines, or an
amine and
another non-amine compound that iunetions as an enhancer. 'I"he following
amine structures are
within the scope of the enhancer of the present invention:
R~
R- N -R2
~,vhere R, R,, and RZ are independently hydrogen, C , - C,H alkyl, CS - C'f;
cycloalkyl, aryl,
C i - C, ~ substituted aryl., or
-(CH R' -CH20)"
wherein R' is hydrogen, methyl or ethyl. n is an integer from 1 to 10(h and
wherein the O atom
of the terminal or "n'h" -(CH R' -CH~O)" group is bound to a hydrogen atom,
R,~ /
N- R3 -N
R, R2
where R is hydrogen, C, - Cy~ alkyl, or a group of the structure
-(CH R' -CH20)" -
CA 02239318 2003-04-O1
wherein R' is hydrogen, methyl or ethyl, n is an integer fiom 1 to 100, and
wherein the O atom
of the terminal or ''n'h" -(CH R' -CH~O)" group is hound to a hydrogen atom;
R, is hydrogen, C~
alkyl or a group of the structure
.(CH R' -CH20)" -
wherein R' is hydrogen, methyl or ethyl, n is an integer from 1 to 100. and
wherein the O atom
of the terminal or "n'~'" -(CH R' -CHZO)" group is hound to a hydrogen atom;
R2 is hydrogen or
..(CH R' -CH20)" -
wherein R' is hydrogen, methyl or ethyl, n is an integer from I to 100. and
wherein the O atom
of the terminal or ''n'h" -(CH R' -Cl l~Ua" group is bound to a hydrogen atom;
and Ri is a C~ or
C ,; alkyl; or
R~,O -R2__- N
Rr
where R is C'~, - C,~ alkyl, R, is hydrogen or a group of the structure
-(Cl-1 R'-CHZO)"-
wherein R' and n are as defined above with respeca to the diamine; and R~ is a
C3 alkyl. With
regard to amine structures shown al7ove, the substi.tuent group "alkyl" or
"aralkyl" has the
meaning of both straight and branched alkyl groups.
More preferably, the amine enhancer an oxyalkylated amine. Thus, preferred
oxyalkylated
amines include oxyalkylated alkyl amines such as ethoxylated alkyl amines
having from 1 to
about 100 moles of ethylene oxide per mole of amine and ethoxylated alkyl
amines having from
about 1 to about 18 carbon atoms in the alkyl group; pulyoxypropylene alkyl
amine having from
12
CA 02239318 1998-OS-29
1 to about 100 moles of propylene oxide per mole of amine; and polyoxybutylene
alkyl amine
having 1 to about 100 moles of butylene oxide per mole of amine. The term
"oxyalkylated alkyl
amines" also encompasses oxyalkylated dialkyl amines, such as ethoxylated di
C2 - C8 alkyl
amines having from 1 to about 100 moles of ethylene oxide per mole of amine;
polyoxypropylene dialkyl amine having from about 1 to about 100 moles of
propylene oxide per
mole of amine; and polyoxybutylene dialkyl amine having from about 1 to about
100 moles of
butylene oxide per mole of amine. More preferably, the term "oxyalkylated
amines" means
oxyalkylated diamines and oxyalkylated C6 aryl amines. A particularly
preferred oxyalkylated
amine is N,N-di n-butyl ethanol amine, having the following structure
~aHs
C4H9 N -CH2CH20H
The amount of enhancer to be employed in the present compositions and methods
is an
amount effective to increase the rate of gel formation and to increase the
viscosity thereof,
relative to known gelling systems that do not incorporate an enhancer of the
present invention.
In general, an effective amount of amine enhancer is from 0.01 % to 5.0%
relative to the volume
of liquid hydrocarbon to be gelled. More preferably, 0.1 % to 0.5% of amine
enhancer is
employed.
- Enhancer blends or mixtures are also appropriate for use in the present
invention.
Preferred blends include at least one oxyalkylated amine as set forth above
with another enhancer
13
CA 02239318 1998-OS-29
component which is either an amine, a non-nitrogen containing compound, a
quaternary nitrogen
compound or an amide. It should be noted that blends containing more than two
components are
also within the scope of the present invention.
When a second enhancer component is another amine, this second amine may be
chosen
from oxyalkylated amines, such as those set forth above, or alkyl amines such
as C2 - C22 alkyl
amines, C2 - C22 dialkyl amines, C2 - C22 alkyl diamines, C2 - C22 dialkyl
diamines, C2 - C22
dialkyl amino C2 - C22 alkylamines, and analogs of these compounds having one
or more carbon-
carbon double bonds in the alkyl moiety. "Alkyl" within the context of , e.g.,
alkylamine, is to
be understood as meaning straight and branched alkyl groups. The term "C2 -
C22 dialkyl" is
intended to mean that each alkyl group can be from C2 - C22 . A preferred
class of alkyl
amines to be used in conjunction with an oxyalkylated amine are fatty amines,
and particularly
unsaturated fatty amines, such as mono- and di-oleyl amines.
Non-nitrogen containing components which are appropriate in the enhancer blend
include oxyalkylated glycerides, oxyalkylated mono- and di-esters and
oxyalkylated alcohols and
phenols, as well as non-oxyalkylated alcohols and phenols, a fatty acid, or a
mixture of a fatty
acid and a glyceride.
The specific proportion or ratio of enhancer components varies depending on
the nature
of the individual enhancer components, as well as on the particular
application requiring the
gelling of liquid hydrocarbon. However, in general, when the enhancer is a
blend comprising at
14
CA 02239318 1998-OS-29
least one oxyalkylated amine and another enhancer component, the components
may be mixed at
a ratio from about 9 : 1 to 1 : 9 oxyalkylated amine to other enhancer
component. When it is
advantageous that the enhancer be a mixture or blend of at least one
oxyalkylated amine (A) and
two other enhancer components (e.g., a second amine enhancer compound (B) and
a non-
nitrogen-containing enhancer compound (C)), the mixing ratio is from about 1 :
1 : 1 to 6 : 3 : 1
of A : B : C. Further, depending on the particular industrial application, it
is within the scope of
the invention to employ enhancer blends having, for example, four, five, or
more enhancer
components. When this is the case, the ratios of the individual components can
be determined by
the skilled practitioner without resort to undue experimentation.
The invention is further directed to a gel-forming hydrocarbon composition for
fracturing
formations comprising: 1 ) a hydrocarbon liquid capable of gellation, 2) 0.01
to 10.0% by weight of
a phosphate ester which is a reaction product comprising either A) phosphorus
pentoxide reacted
with a tri-loweralkyl phosphate and subsequently reacted with either an
alcohol, an oxyalkylated
alcohol or mixtures thereof or B) phosphorous pentoxide reacted with either an
alcohol, an
oxyalkylated alcohol or mixtures thereof to form a phosphate ester or mixed
phosphate ester which
is subsequently reacted with a tri-loweralkyl phosphate, 3) a crosslinking
agent in an amount
effective to gel said hydrocarbon liquid, 4) from about 0.085 molar equivalent
to about 0.31 molar
equivalent of the phosphate ester of an enhancer comprising an amine selected
from the group
consisting of alkyl amines, oxyalkylated amines, and mixtures thereof, and 5)
optionally a
surfactant.
CA 02239318 1998-OS-29
As demonstrated by several of the examples that follow, the invention includes
novel
synergistic combinations of enhancer components, as well as synergistic
phosphate ester
combinations. More specifically, the viscosities obtained(as indicated in
centipoises and Marsh
Funnel time (minutes)) for the present hydrocarbon gel systems using mixtures
of enhancer
components or mixtures of phosphate esters are greater than the viscosities of
the individual
components when used at comprable volumes. For example, in Table II below it
will be seen
that all of the enhancer mixtures have a synergistic effect on production of
gels of very high
viscosity (in centipoises), relative to the same volume of each of the
enhancer components
individually.
Particularly preferred synergistic enhancer combinations include, but are not
limited to,
an ethoxylated di-C4 alkyl amine having one mole of oxyethylene per mole of
amine in
combination with any of the following oxyalkylated amines: an ethoxylated C16 -
C18 alkyl amine
having two moles of oxyethylene per mole of amine; an ethoxylated Cg-C16 alkyl
amine having
two moles of oxyethylene per mole of amine; an ethoxylated C18 alkenyl amine
having two
moles of oxyethylene per mole of amine; an ethoxylated C16-C18 alkenyl amine
having two moles
of oxyethylene per mole of amine. Synergistic combinations of any of the
following enhancer
amines are also preferred: an ethoxylated C16 - C18 alkyl amine having two
moles of oxyethylene
per mole of amine; an ethoxylated di-C1 alkyl amine having one mole of
oxyethylene per mole of
amine; an ethoxylated di-C2 alkyl amine having one mole of oxyethylene per
mole of amine;
triethanolamine; and an ethoxylated Cg-C16 alkyl amine having two moles of
oxyethylene per
mole of amine.
16
CA 02239318 1998-OS-29
Mixtures of phosphate esters in accordance with the invention also have a
synergistic effect on gel viscosity. This feature of the invention is
exemplified in Table llI
below. Various combinations of the following phosphate esters are effective in
this particular
aspect of the invention: a C2, C8, CIO alkyl phosphate, having 30.3% C2, 32.1%
C8, and 37.6%
CIO; a C2-CIg alkyl, CI-CI8 alkyl ether phosphate having 30.2% C2, 30.3% C8,
35.6% CIO, and
3.9% CI alkyl ether oxyalkylated with 1 mole of oxypropylene; a C2-CI8 alkyl,
CI-CI8 alkyl ether
phosphate having 29.7% C2, 26.3% C8, 30.8% CIO, and 13.2% C6 alkyl ether
oxyalkylated with
1.5 mole ofoxyethylene; a C2-CI8 alkyl, CI-CI8 alkyl ether phosphate having
30.3%C2, 4.5% C4,
23.8% Cg, 27.9% CIO, and 13.5% C6 alkyl ether oxyalkylated with 1.5 moles of
oxyethylene; a
C2-CIg alkyl, CI-CI8 alkyl ether phosphate having 27.4%C2, 24.1% C8, 28.4%
CIO, and 20.1% C8
- CIO alkyl ether oxyalkylated with 3 moles of oxyethylene; a C2-CI8 alkyl, CI-
CI8 alkyl ether
phosphate having 25.7%C2, 22.7% C8, 26.7% CIO, and 24.9% C8 - CIO alkyl ether
oxyalkylated
with 5 moles of oxyethylene; a C2-CIg alkyl, CI-CIg alkyl ether phosphate
having 25.4%C2,
22.1% C8, 26.2% CIO, and 26.3% C16 - CIg alkyl ether oxyalkylated with 3 moles
of
oxyethylene; a C2-CIg alkyl, C6 aryl ether phosphate having 31 %C2, 25% C8,
30% CIO, and 14%
C6 aryl ether oxyalkylated with 1 mole of oxyethylene; a C2-CIg alkylr C6 aryl
ether phosphate
having 30.6%C2, 21.6% Cg, 25.4% CIO, and 22.4% C6 aryl ether oxyalkylated with
1 mole of
oxyethylene; a C2-CIg alkyl, C6 aryl ether phosphate having 25.9% C2, 22.8%
Cg, 26.8% CIO, and
24.5% C6 aryl ether oxyalkylated with 6 moles of oxyethylene; a C2-CI8 alkyl,
C6 aryl ether
phosphate having 23.8% C2, 21.0% C8, 24.6% CIO, and 30.6% C6 aryl ether
oxyalkylated with 9
moles of oxyethylene; a C2-CIg alkyl, C6 aryl ether phosphate having 26.2% C2,
25.5% C8, 29.9%
17
CA 02239318 1998-OS-29
Coo, and 18.5% aryl ether oxyalkylated with 10 moles of oxyethylene; a C2-C18
alkyl, C6 aryl
ether phosphate having 29.8% C2, 26.3% C8, 30.9% Clo, and 13.0% C6 aryl ether
oxyalkylated
with 1 mole of oxybutylene; a C2-Clg alkyl, Cl-C12 alkyl or dialkyl C6 aryl
ether phosphate having
25.2% C2, 22.3% C8, 26.1% Clo, and 26.4% C9 alkyl C6 aryl ether oxyalkylated
with 4 moles of
oxyethylene; and a C2-C1g alkyl, C1-Cl8 alkyl ether, C6 aryl ether phosphate
having 25.9% C2,
64.7% C8 - Clo alkyl ether oxyalkylated with 1 mole of oxyethylene, and 9.4%
C6 aryl ether
oxyalkylated with 1 mole of oxyethylene. Particularly preferred phosphates
ester combinations
are a C2, Cg, Clo alkyl phosphate, having 30.3% C2, 32.1% C8, and 37.6% Coo
with a C2-C~g
alkyl, C6 aryl ether phosphate having 30.6%C2, 21.6% C8, 25.4% Cio, and 22.4%
C6 aryl ether
oxyalkylated with 1 mole of oxyethylene; a C2-C1g alkyl, C6 aryl ether
phosphate having 31%C2,
25% C8, 30% Clo, and 14% C6 aryl ether oxyalkylated with 1 mole of oxyethylene
with a C2-C1g
alkyl, C6 aryl ether phosphate having 29.8% C2, 26.3% C8, 30.9% Clo, and 13.0%
C6 aryl ether
oxyalkylated with 1 mole of oxybutylene; a C2, C8, Clo alkyl phosphate, having
30.3% C2, 32.1 %
C8, and 37.6% Clo with a C2-C1g alkyl, C6 aryl ether phosphate having 31%C2,
25% C8, 30%
Clo, and 14% C6 aryl ether oxyalkylated with 1 mole of oxyethylene. Especially
preferred is the
combination of a C2, Cg, Clo alkyl phosphate, having 30.3% C2, 32.1% C8, and
37.6% CIO with
a C2-C18 alkyl, C6 aryl ether phosphate having 30.6%C2, 21.6% C8, 25.4% Clo,
and 22.4% C6
aryl ether oxyalkylated with 1 mole of oxyethylene.
EXAMPLES 1-103
The following examples set forth in Table I are representative of gelling
systems in
accordance with the present invention. For each of the examples below, 200
milliliters of
18
CA 02239318 1998-OS-29
kerosene was placed in a 500 ml Waring blender having a standard stirring
assembly. The
blender was plugged into a rheostat set at 30% output. The blender was
started. The type and
amount of activator and phosphate ester and system enhancer set forth below
were added to the
kerosene. Where a system enhancer was employed in accordance with the present
invention, 0.10
to 0.21 milliliters were added. The blender was stirred until the vortex
created from the agitator
closed. If the vortex had not closed after 120 seconds, the blender was
stopped at that point. The
kerosene gel was then poured into a Marsh funnel viscometer. The -time
required for 100
milliliters of the gelled kerosene to flow through the viscometer is set forth
for each example
below. Brookfield viscosity measurements (in centipoises) were also taken for
Examples 104 -
123d.
The specific components employed in each of the following examples are:
Enhancers:
Am-1: an ethoxylated C~6 - Clg alkyl amine having two moles of
oxyethylene per mole of amine;
Am-2: an ethoxylated Cg alkyl amine having two moles of
oxyethylene per mole of amine;
Am-3: an ethoxylated di-C4 alkyl amine having one mole of
oxyethylene per mole of amine;
Am-4: an ethoxylated C12 - C14 alkyloxy C3 alkyl amine having
three moles of oxyethylene per mole of amine;
Am-5: N, N-di-C1 alkyl C16 alkyl amine;
Am-6: N, N-di (C1) alkyl Clg alkyl amine;
Am-7: Ci6 - C18 imidazoline prepared from tall oil fatty acid and
diethylenetriamine;
19
CA 02239318 1998-OS-29
Am-8: an alkoxylated C16 - C18 alkyl amine having six moles of oxypropylene
per
mole of amine;
Am-9: an ethoxylated di-C4 alkyl amine having ten moles of oxyethylene per
mole
of amine;
Am-10: an alkoxylated C16 - C18 alkyl diamine having three moles of
oxypropylene
per mole of diamine;
Am-11: N, N-di-C4 alkyl amine;
Am-12: an alkoxylated C16 - C18 alkyl amine having two moles of oxybutylene
per
mole of amine;
Am-13: an alkoxylated di-C4 alkyl amine having one mole of oxybutylene per
mole of
amine;
Am-14: an alkoxylated di-C4 alkyl amine having one mole of oxypropylene per
mole of
amine;
Am-15: dimethylaminopropylamine;
Am-16: aminomethylpropanol;
Am-17: an ethoxylated aniline having two moles of oxyethylene per mole of
benzamine;
Am-18: a C16-Clg alkyl diamine;
Am-19: a C6 alkyl amine;
Am-20: a C8 alkyl amine;
Am-21: an alkoxylated C16-C1g alkyl amine having two moles of_oxypropylene per
mole
of amine;
Am-22: an ethoxylated di-C~ alkyl amine having one mole of oxyethylene per
mole of
amine;
Am-23: an ethoxylated di-C4 alkyl amine having four moles of oxyethylene per
mole of
amine;
Am-24: an ethoxylated di-C2 alkyl amine having one mole of oxyethylene per
mole of
amine;
CA 02239318 1998-OS-29
Am-25: an ethoxylated C16-C18 alkyl amine having five moles of oxyethylene per
mole
of amine;
Am-26: amino-bis (hydroxyethyl) C16-C1g alkyl etho-sulfate ( quaternized
product of
N, N' dihydroxyethyl C16-C18 alkyl amine with diethyl sulfate ) ;
Am-27: triethanolamine;
Am-28: an ethoxylated Cg-C16 alkyl amine having ten moles of oxyethylene per
mole of
amine;
Am-29: an ethoxylated C8-C16 alkyl amine having two moles of oxyethylene per
mole of
amine;
Am-30: an ethoxylated C16-Clg alkyl amine having twenty moles of oxyethylene
per
mole of amine;
Am-31: an ethoxylated C8-C16 alkyl amine having fifteen moles of oxyethylene
per mole
of amine;
Am-32: an ethoxylated C6 cyclo amine having two moles of oxyethylene per mole
of
amine;
Am-33: an ethoxylated C16-C1g alkyl amine having thirty two moles of
oxyethylene per
mole of amine;
Am-34: an ethoxylated tertiary C,~ alkyl amine having two moles of oxyethylene
per mole
of amine;
Am-35: an ethoxylated C8-C16 alkanol amide having three moles of oxyethylene
per
mole of amine;
Am-36: a C8-C16 alkyl amine;
Am-37: an ethoxylated C16-C18 alkyl amine having forty moles of oxyethylene
per mole
of amine;
Am-38: an ethoxylated C16-C18 alkyl amine having fifty moles of oxyethylene
per mole
of amine;
Am-39: a C16-C1g alkyl amine;
Am-40: dimethylaminopropylamine;
Am-41: C6 cyclohexylamine;
21
CA 02239318 1998-OS-29
Am-42: a C8-C16 alkyl akanol amide;
Am-43: an ethoxylated C16-C~8 alkyl amine having ten moles of oxyethylene per
mole of
amine;
Am-44: an ethoxylated C$-C16 alkyl amine having five moles of oxyethylene per
mole of
amine;
Am-45: tertiary C4 alkyl amine;
Am-46: a C12-C14 alkoxy propyl amine;
Am-47: an ethoxylated N-ethyl toluidine having one mole of oxyethylene per
mole of N-
ethyl toluidine ;
Am-48: an ethoxylated m-toluidine having two moles of oxyethylene per mole of
m-
toluidene;
Am-49: morpholine;
Am-50: an ethoxylated aniline having ten moles of oxyethylene per mole of
benzamine;
Am-51: m-toluidine;
Am-52: ethylenediamine;
Am-53: an ethoxylated m-toluidine having 100 moles of oxyethylene per mole of
m-
toluidine;
Am-54: tetraethylene pentamine;
Am-55: an ethoxylated Cl8 alkenyl amine having two moles of oxyethylene per
mole of
amine;
Am-56: an ethoxylated CI6-C1g alkenyl amine having two moles of oxyethylene
per mole
of amine;
Am-57: isobutanolamine;
Di-es-1: a polyethylene glycol (200) di-Cg-C16 ester;
Gl-1: an ethoxylated tri-CI8 alkyl glyceride having five moles of oxyethylene
per mole
of glyceride;
22
CA 02239318 1998-OS-29
G1-2: castor oil;
Et-1: an ethoxylated C12 - Cia alkyl ether having three moles of oxyethylene
per mole of
ether;
Et-2: an ethoxylated C16-C1$ alkenyl ether having two moles of oxyethylene per
mole of
ether;
Es-1: an ethoxylated unsaturated C16-C18 fatty acid having three moles of
oxyethylene per
mole of fatty acid;
Ph-l: phenol;
Ph-2: CS di-tertiary-alkyl phenol;
Ph-3: an alkoxylated C9 alkyl phenol having three moles of oxypropylene per
mole of
alkyl phenol;
Ph-4: an alkoxylated phenol having one mole of oxybutylene per mole of phenol;
Ph-5: a tertiary-C5, di-alkyl phenol ;
Ph-6: a C9 alkyl phenol;
Al-l: isodecyl alcohol;
Sol-1: methyl cellosolve;
Fa-1: coconut fatty acid;
B~-l: an alkoxylated bis-phenol-a, having one mole of oxypropylene per
equivalent of
phenolic; _
Phosphate Esters:
III(1a) (or PE-1): C2, Cg, Clo alkyl phosphate, having 30.3% C2, 32.1% Cg, and
37.6% Clo;
ITI(2a): C2-Ci8 alkyl, Cl-C18 alkyl ether phosphate (having 30.2% C2, 30.3%
Cg, 35.6%
Clo, and 3.9% CI alkyl ether oxyalkylated with 1 mole of
oxypropylene);
23
CA 02239318 1998-OS-29
>II(2b): C2-CI8 alkyl, CI-CI8 alkyl ether phosphate (having 29.7% C2, 26.3%
C8, 30.8%
CIO, and 13.2% C6 alkyl ether oxyalkylated with 1.5 mole of
oxyethylene);
)II(2c): C2-CIg alkyl, CI-CI8 alkyl ether phosphate (having 30.3%C2, 4.5% C4,
23.8% C8,
27.9% CIO, and 13.5% C6 alkyl ether oxyalkylated with 1.5 moles of
oxyethylene);
)II(2d): C2-CI8 alkyl, CI-CI8 alkyl ether phosphate (having 27.4%C2, 24.1 %
C8, 28.4%
CIO, and 20.1 % C8 - CIO alkyl ether oxyalkylated with 3 moles of
oxyethylene);
)II(2e): C2-CI8 alkyl, CI-CI8 alkyl ether phosphate (having 25.7%C2, 22.7% Cg,
26.7%
CIO, and 24.9% Cg - CIO alkyl ether oxyalkylated with 5 moles of oxyethylene);
)II(2f): C2-CI8 alkyl, CI-CI8 alkyl ether phosphate (having 25.4%C2, 22.1 %
C8, 26.2%
CIO, and 26.3% CI6 - CI8 alkyl ether oxyalkylated with 3 moles of
oxyethylene);
IZI(3a) (or EP-1): C2-CI8 alkyl, C6 aryl ether phosphate (having 31 %C2, 25%
C8, 30%
CIO, and 14% C6 aryl ether oxyalkylated with 1 mole of oxyethylene);
)II(3b): C2-CI8 alkyl, C6 aryl ether phosphate (having 30.6% C2, 21.6% C8,
25.4% CIO,
and 22.4% C6 aryl ether oxyalkylated with 1 mole of oxyethylene);
>II(3c): C2-CI8 alkyl, C6 aryl ether phosphate (having 25.9% C2, 22.8% C8,
26.8% CIO, and
24.5% C6 aryl ether oxyalkylated with 6 moles of oxyethylene);
)II(3d): C2-CI8 alkyl, C6 aryl ether phosphate (having 23.8% C2, 21.0% C8,
24.6% CIO,
and 30.6% C6 aryl ether oxyalkylated with 9 moles of oxyethylene);
III(3e): C2-CI8 alkyl, C6 aryl ether phosphate (having 26.2% C2, 25.5% C8,
29.9% CIO, and
18.5% C6 aryl ether oxyalkylated with 10 moles of oxyethylene);
11I(3f): C2-CI8 alkyl, C6 aryl ether phosphate (having 29.8% C2, 26.3% C8,
30.9% CIO, and
13.0% C6 aryl ether oxyalkylated with 1 mole of oxybutylene);
24
CA 02239318 1998-OS-29
)TI(4a): C2-C18 alkyl, C1-C12 alkyl or dialkyl C6 aryl ether phosphate (having
25.2% C2,
22.3% C8, 26.1% Clo, and 26.4% C9 alkyl C6 aryl ether oxyalkylated with 4
moles of oxyethylene);
)II(Sa): C2-C18 alkyl, Cl-C18 alkyl ether, C6 aryl ether phosphate (having
25.9% C2, 64.7%
C8 - Clo alkyl ether oxyalkylated with 1 mole of oxyethylene, and 9.4% C6 aryl
ether oxyalkylated with 1 mole of oxyethylene);
Crosslinking Agents:
Fe3+: a 60% solution of ferric sulfate;
A13+: a solution of an aluminum chloride tall oil imidazoline reaction
product, in
accordance with US Patent No. 5,271,464.
CA 02239318 1998-OS-29
TABLE I: EXAMPLES
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. secs. Mins.
)
1
ComparativeNone PE-1 Fe3+ > 120 0.6
(1 ml) (1 ml)
Am-l, Am-3 PE-1 Fe3+ 3 32.5
2 (29% / 79%)(1 ml) (0.79 ml)
(0.21 ml)
Am-1, Am-3 EP-1 Fe3+ 2 150
3 (29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
4 none EP-1 Fe3+ > 120 1.30
Com arative (1 ml) (1 ml)
5(*) none PE-1 A13+ 79 2.30
Com arative (0.77 ml) (1 ml)
6(*) Am-1, Am-3 PE-1 Fe3+ 45.7 39
(29% / 71 (0.77 ml) (0.77 ml)
%)
(0.21 ml)
7(*) none PE-1 Fe3+ > 120 8.5
Com arative (0.77 ml) (1 ml)
8 Am-2, Am-3 PE-1 Fe3+ 30 95
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
9 Am-5, Am-3 PE-1 Fe3+ 9 41.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
Am-3 PE-1 Fe3+ 45 14.5
(0.21 ml) (1 ml) (0.79 ml)
11 Am-3 EP-1 Fe3+ 19 >120
(0.21 ml) (1 ml) (0.79 ml
12 Am-3 III(Sa) Fe3+ >120 4.7
(0.21 ml) (1 ml) (0.79 ml)
13 Am-56, Am-3EP-1 Fe3+ 2.0 _ 140.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
14 Am-1, Am-3 III(2b) Fe3+ 5.8 105.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
Am-1, Am-3 III(2c) Fe3+ 5.5 87.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
16 Am-1, Am-3 III(2e) Fe3+ 7.5 33.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
17 Am-1, Am-3 III(2d) Fe3+ 6.6 64.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
26
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. secs. Mins.
18 Am-1, Am-3 III(3c) Fe3+ 21 30.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
19 Am-1, Am-3 III(3b) Fe3+ 11 60.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
20 Am-1, Am-3 III(4a) Fe3+ 4.7 141.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
21 Am-1, Am-3 III(5a) Fe3+ 2.6 20.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
22 Am-1, Am-3 III(2a) Fe3+ 9.7 18.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
23 Am-1, Am-3 III(2~ Fe3+ >120 2.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
24 Am-1, Am-9 EP-1 Fe3+ > 120 50.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
25 Am-8, Am-9 EP-1 Fe3+ > 120 5.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
26 Am-3, Am-10EP-1 Fe3+ > 120 15.5
(71% / 29%)(1 ml) (0.79 ml)
(0.21 ml)
27 Am-1, Am-18EP-1 Fe3+ > 120 15.0
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
28 Am-1, Am-19EP-1 Fe3+ 23 197.0
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
29 Am-l,Am-11 EP-1 Fe3+ 3.7 > 210
(25% / 75%)(1 ml) (0.79 ml) -
(0.21 ml)
30 Am-l,Am-20 EP-1 Fe3+ >120 112.0
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
31 Am-2l,Am-3 EP-1 Fe3+ 2.5 31.0
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
32 Am-12, Am-3EP-1 Fe3+ > 120 > 150
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
33 Am-1, Am-3 III(3c) Fe3+ 27 30.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
27
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. sets. Mins.
34 Am-1, Am-3 III(3d) Fe3+ >120 1.6
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
35 Di-es-1, EP-1 Fe3+ >120 61.0
Am-3
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. sees. Mins.
)
36 Gl-1, Am-3 EP-1 Fe3+ > 120 74
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
37 Et-1, Am-3 EP-1 Fe3+ 90 52
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
38 Et-2, Am-3 EP-1 Fe3+ >120 30.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
39 Am-21, Am- EP-1 Fe3+ 28 >120
22, Sol-1 (1 ml) (0.79 ml)
(33%:33%:33
%) (0.21
ml)
40 Am-1, Am-23EP-1 Fe3+ 4 262
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
41 Am-1, Am-13EP-1 Fe3+ 4 52
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
42 Am-1, Am-24EP-1 Fe3+ >120 170.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
43 Am-2, Am-3 EP-1 Fe3+ 9 420.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
44 Am-23 EP-1 Fe3+ >120 - 2.3
(0.21 ml) ( 1 ml) (0.79 ml)
45 Am-3, Am-23EP-1 Fe3+ >120 52.0
(25% / 75%)(1 ml) (0.79 ml)
(0.21 ml)
46 Am-21, Am-23EP-1 Fe3+ 3 45.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
47 Am-1, Am-14EP-1 Fe3+ 3 240.0
(29% / 71 (1 ml) (0.79 ml)
%)
(0.21 ml)
48 Am-1, Am-3 III(3f) Fe3+ 9 15.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
28
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. secs. Mins.
49 Am-2, Am-23EP-1 Fe3+ 36 300.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
50 Am-1, Am-3 III(3e) Fe3+ 17 67.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
51 Es-1, Am-3 EP-1 Fe3+ 90 88
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
52 Am-4, Am-3 EP-1 Fe3+ 4.8 360
(29% / 71%)(1 ml) (0.79 ml) -
(0.21 ml)
53 Am-5, Am-3 EP-1 Fe3+ 2 900
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
54 Ph-3, Am-3 EP-1 Fe3+ 90 85.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
55 Am-25, Am-3EP-1 Fe3+ >120 7.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
56 Am-26, Am-3EP-1 Fe3+ 3 133.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
57 Am-8, Am-27EP-1 Fe3+ >120 9.0
(50% / 50%)(1 ml) (0.79 ml)
(0.21 ml)
58 Am-1, Am-23EP-1 Fe3+ 4 262.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
59 Am-27, Am-3EP-1 Fe3+ 41 86.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
60 Am-1, Am-8,EP-1 Fe3+ >120 9.5
Am-27 (1 ml) (0.79 ml)
(33%:33%:33
%) (0.21
ml)
61 Am-21, Am-23EP-1 Fe3+ 3 45.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
62 Am-28, Am-3EP-1 Fe3+ >120 6.3
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
63 Am-29, Am-3EP-1 Fe3+ 2.3 300.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
64 Am-30, Am-3EP-1 Fe3+ >120 1.3
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
29
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. sets. Mins.
)
65 Am-31, Am-3EP-1 Fe3+ >120 8.2
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
66 Am-32, Am-3EP-1 Fe3+ 35 66.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
67 Am-33, Am-3EP-1 Fe3+ >120 2.5
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
68* Am-1, Am-34EP-1 Fe3+ 120 35.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
69 Ph-2, Am-3 EP-1 Fe3+ 90 38.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
70 Ph-4, Am-3 EP-1 Fe3+ 93 80.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
71 Ph-1, Am-3 EP-1 Fe3+ > 120 60
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml
72 Am-35, Am-3EP-1 Fe3+ 64 180.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
73 Al-l, Am-3 EP-1 Fe3+ 95 35
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
74 Fa-1, Am-3 EP-1 Fe3+ >120 45.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
75 Am-42, Am-3EP-1 Fe3+ 9 300.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
76 Am-36, Am-3EP-1 Fe3+ >120 75.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
77 Gl-2, Am-3 EP-1 Fe3+ 73 75.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
78 Am-37, Am-3EP-1 Fe3+ >120 7.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
79 Am-38, Am-3EP-1 Fe3+ >120 1.8
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
80 Am-39, Am-3EP-1 Fe3+ 14.4 345.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total secs. Mins.
vol. )
81 Am-1, Am-40EP-1 Fe3+ 90 300
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
82 Am-1, Am-41EP-1 Fe3+ >120 163.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml
83 Ph-5, Am-3EP-1 Fe3+ > 120 37.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
84 Ph-6, Am-3EP-1 Fe3+ 90 76.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
85 Bp-1, Am-3EP-1 Fe3+ 63 180.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
86* Am-1, Am-34EP-1 Fe3+ >120 53.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
87 Am-1, Am-32EP-1 Fe3+ 9.3 360.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml
88 Am-43, EP-1 Fe3+ >120 3.7
Am-3
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml
89 Am-44, EP-1 Fe3+ 7.5 25.0
Am-3
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
90 Am-1, Am-45EP-1 Fe3+ 12 78.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
91 Am-3, Am-6EP-1 Fe3+ 3 720
(71% / (1 ml) (0.79 ml)
29%)
(0.21 ml)
92 Am-46, EP-1 Fe3+ 15 720
Am-3
(25% / (1 ml) (0.90 ml) -
75%)
(0.10 ml)
93 Am-1, Am-47EP-1 Fe3+ 7.5 180.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
94 Am-1, Am-17EP-1 Fe3+ 10.7 240
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
95 Am-1, Am-48EP-1 Fe3+ 8.1 150.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
96 Am-1, Am-49EP-1 Fe3+ 90 120.0
(29% / (1 ml) (0.79 ml)
71%)
(0.21 ml)
31
CA 02239318 1998-OS-29
Ex. Enhancer Phosphate Salt Closure Viscosity
(total vol. secs. Mins.
)
97 Am-50, Am-3EP-1 Fe3+ 72 174.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
98 Am-1, Am-51EP-1 Fe3+ >120 150.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
99 Am-1, Am-57EP-1 Fe3+ 81 100.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
100 Am-1, Am-52EP-1 Fe3+ >120 46.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
101 Am-53, Am-3EP-1 Fe3+ >120 24.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
102 Am-1, Am-54EP-1 Fe3+ >120 7.0
(29% / 71%)(1 ml) (0.79 ml)
(0.21 ml)
103(*) Am-7 EP-1 Fe3+ > 120 0.12
Com arative (1 ml) (0.79 ml)
5(*): utilizes the aluminum system as described in US 5,271,464.
6(*) & 7(*): the phosphate esters of these examples are partially neutralized
with 0.23 ml of 45% KOH.
68(*): the enhancer was pre-blended with the ferric salt.
86(*): phosphate ester, enhancer, and ferric salt were each introduced
separately.
103(*): the surface active amine is as described in Halliburton, e.g., US
5,271,464 (@Col. 3, lines 1-3).
The gelling systems in accordance with the present invention demonstrate
increased
gelling speeds as compared to prior art systems. Of the comparative examples
set forth
hereinabove, only Comparative Example 5 has a gel closure time of less than
120 seconds. The
majority (63%) of the examples according to the invention required far less
than 120 seconds to
achieve gel closure. Some inventive examples are reported as having a closure
of >120 seconds.
It is important to clarify that a closure time of greater than 120 seconds is
not to be understood as
meaning that acceptable gel viscosity was not achieved in those examples.
Rather, a designation
of ">120 sec." means only that there was evidence of a vortex extant in the
gelled fluid after it
had stirred for 120 seconds. The significance of the rapid gel closure times
evidenced overall by
32
CA 02239318 1998-OS-29
the gel systems of the invention is that it is an indication to the skilled
field worker of the time
efficiency, or the rapidity of "on the fly" gelling of the system components.
The more dramatic difference between the examples of the present invention and
those of
the prior art can be seen in the viscosity of the gels. Increased gel
viscosity is necessary for
optimal proppant transport. Prior art example, Example 5, did not exceed a
viscosity of 10, as
measured in minutes required for 100 milliliters of gel to pass through a
Marsh funnel. Also,
comparative example 103, which utilized the surface active amine of
Halliburton '464 as the
enhancer component, gave a viscosity of 0.12 minutes. In the numerous examples
representative
of the invention, 54% of the inventive examples demonstrated a viscosity
requiring in excess of
50 minutes, and 34% of the inventive examples demonstrated a viscosity
requiring in excess of
100 minutes for 100 milliliters to pass through the funnel. Only 15%
demonstrated a viscosity
requiring less than 10 minutes for 100 milliliters of gel to pass through the
funnel.
Inventive examples 68 and 86 provide comparative results vis-a-vis each other.
Both
examples used the same components for gelling kerosene, the only difference
being the manner
by which they were introduced to the blender. In example 68, the enhancer was
pre-blended with
the ferric salt; the blend was introduced to the kerosene, as was the
phosphate ester. In example
86, the same enhancer, ferric salt, and phosphate ester were all introduced
separately to the
kerosene. The separate addition of components gave a gel of higher viscosity
(53 mins.) than
the method wherein the enhancer and the ferric salt were pre-blended (35
mins).
33
CA 02239318 1998-OS-29
For the following examples, the same experimental procedure as in Examples 1 -
103 was
used. Differences in volumes and ratios employed are specified in each of the
examples set forth
in Table II.
TABLE II. EXAMPLES 104 -119: DEMONSTRATING SYNERGISTIC
EFFECTS OF AMINE MIXTURES
Ex.Enhancer PhosphateSalt ClosureViscosityViscosity Calculated Viscosity
Based
(vol. Added)(vol. Secs. Mins. Centipoiseson Relative
& added) Contribution
of
mixing (Observed)Each Amine Component
ratio, -
where applicable in Centipoises
(Expected)
104Am-55 EP-1 Fe3+ >120 40.0 4400
(0.21 ml) (1 ml) (0.79m1)
105Am-3 EP-1 Fe3+ 19 215.0 10000
(0.21 ml) (1m1) (0.79m1)
106Am-1 EP-1 Fe3+ >120 23.0 4800
(0.21 ml) (1m1) (0.79m1)
107Am-56 EP-1 Fe3+ 4 23.0 5000
(0.21 ml) (1m1) (0.79m1)
108Am-22 EP-1 Fe3+ >120 5.0 7000
(0.21 ml) (1m1) (0.79m1)
109Am-24 EP-1 Fe3+ >120 1.5 4800
(0.21 ml) (1m1) (0.79m1)
110Am-27 EP-1 Fe3+ >120 1.5 150
(0.21 ml) (1m1) (0.79m1)
111Am-29 EP-1 Fe3+ >120 10.0 250
(0.21 ml) (1m1) (0.79m1)
112Am-55, EP-1 Fe3+ 2 150.0 10600 8376
Am-3
(29:71)(0.21(1m1) (0.79m1)
ml)
113Am-1, Am-3EP-1 Fe3+ 2 135.0 11000 8492
(29:71 (1 ml) (0.79m1) -
)(0.21
ml)
114Am-56, EP-1 Fe3+ 2 140.0 9600 8550
Am-3
(29:71 (1 ml) (0.79mi)
)(0.21
ml)
115Am-29, EP-1 Fe3+ 2 60.0 9200 7173
Am-3
(29:71)(0.21(1m1) (0.79m1)
ml)
116Am-1, Am-24EP-1 Fe3+ >120 120.0 7000 6816
(29:71 (1 ml) (0.79m1)
)(0.21
ml)
117Am-29, EP-1 Fe3+ 2 600.0 12200 3481
Am-24
(29:71 (1 ml) (0.79m1)
)(0.21
ml)
118Am-29, EP-1 Fe3+ 2 345.0 10400 5040
Am-22
(29:71 (1 ml) (0.79m1)
)(0.21
ml)
119Am-29, EP-1 Fe3+ 2 260.0 10000 180
Am-27
(29:71)(0.21(1m1) (0.79m1)
ml)
34
CA 02239318 1998-OS-29
The results in Table II exemplify the novel synergism, and its effect on
viscosity,
achieved in combining enhancer components of the invention. All of Examples
112 - 119
demonstrate surprising levels of viscosity which are unexpected based on the
viscosities of the
individual components on a same volume basis. In addition, the viscosities for
each of the
individual components separately have been calculated to take into account the
relative
contribution of each amine component in the mixture (see the column on the
extreme right). In
this way, a theoretical (or expected) value is obtained. The actual
viscosities obtained in all of
Examples 112 - 119 exceed the calculated viscosities.
For the following examples, the same experimental procedure as in Examples 1 -
103 was
used. Differences in volumes and ratios employed are specified in each of the
examples set forth
in Table III.
CA 02239318 1998-OS-29
TABLE III. EXAMPLES 120a -123d: EFFECT OF SYNERGISTIC PHOSPHATE
ESTER MIXTURES ON GEL VISCOSITY
Ex.Enhancer PhosphateSalt ClosureViscosity ViscosityCalculated
Mins.
(mixing Secs. CentipoisesViscosity
ratio Based on
& Relative
vol. Added)
Contribution
of
Each Amine
Component
- in
Centipoises
Ex acted
120aAm-56, PE-1 Fe3+ 2 1440+ 40000
Am-3
(29:71 (2m1) (1.58m1) (i.e.,
)(0.42) >24hrs)
120bAm-56, PE-1 Fe3+ 2 70.0 7000
Am-3
(29:71 (1 ml) (0.79m1)
)(0.21
)
120cAm-56, PE-1 Fe3+ 2 15.0 2800
Am-3
(29:71 (0.5m1) (0.40m1)
)(0.11
)
120dAm-56, PE-1 Fe3+ >120 0.8 600
Am-3
(29:71 (0.25m1)(0.20m1)
)(0.06)
121aAm-56, (III) Fe3+ 2 1440+ 31000
Am-3 (3b)
(29:71)(0.42)(2m1) (1.58m1)
121bAm56, Am-3(III) Fe3+ 2 20.0 5200
(3b)
(29:71 (1 ml) (0.79m1)
)(0.21
)
121cAm-56, (III) Fe3+ 3 12.0 2100
Am-3 (3b)
(29:71 0.5m1 (0.40m1)
)(0.11
)
121dAm-56, (III) Fe3+ 3 2.5 1200
Am-3 (3b)
(29:71 0.25 (0.20m1)
)(0.06) ml
122aAm-56, EP-1 Fe3+ 2 1260.0 45000
Am-3
(29:71)(0.42)(2m1) (1.58m1)
122bAm-56, EP-1 Fe3+ 2 150.0 10600
Am-3
(29:71 (1 ml) (0.79m1)
)(0.21
)
122cAm-56, EP-1 Fe3+ 2 10.0 3200
Am-3
(29:71 (0.5m1) (0.40m1)
)(0.11
)
122dAm-56, EP-1 Fe3+ >120 2.0 2000
Am-3
(29:71 (0.25m1)(0.20m1)
)(0.06)
123aAm-56, PE-1, Fe3+ 2.0 1440+ 76000 40000
Am-3 (III)
(3b)
(29:71 (50:50) (1.58m1)
)(0.42)
2m1
123bAm-56, PE-1, Fe3+ 2.0 340 15400 7600
Am-3 (III)
(3b)
(29:71 (50:50) (0.79m1)
)(0.21
)
1 ml
123cAm-56, PE-1, Fe3+ 3.0 30 4000 3300
Am-3 (III)
(3b)
(29:71 (50:50) (0.40mi)
)(0.11
)
0.5m1
123dAm-56, PE-1, Fe3+ >120 4.0 2400 800
Am-3 (III)
(3b)
(29:71 (50:50) (0.20m1)
)(0.06)
0.25m1
The results in Table )TI exemplify the novel synergism, and its effect on
viscosity,
achieved in combining phosphate esters according to the invention. All of
Examples 123a - 123d
demonstrate surprising levels of viscosity which are unexpected based on the
viscosities of the
36
CA 02239318 1998-OS-29
individual components on a same volume basis. In addition, the viscosities for
each of the
individual components separately have been calculated to take into account the
relative
contribution of each phosphate ester in the mixture (see the column on the
extreme right). In this
way, a theoretical (or expected) value is obtained. The actual viscosities
obtained in all of
Examples 123a - 123d are 190%, 202%, 121%, and 300%, respectively, of the
calculated values.
The foregoing description of preferred embodiments of the invention has been
presented
for purposes of illustration and description. It is not intended to be
exhaustive or to limit the
invention to the precise form disclosed, and modifications and variations are
possible in light of
the above teachings or may be acquired from practice of the invention. The
embodiments were
chosen and described in order to explain the principles of the invention and
its practical
application to enable one skilled in the art to utilize the invention in
various embodiments and
with various modifications as are suited to the particular use contemplated.
It is intended that the
scope of the invention be defined by the claims appended hereto, and their
equivalents.
37
