Note: Descriptions are shown in the official language in which they were submitted.
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POLYESTER DEMULSIFIER
BACKGROUND
[0001] Oil
extraction is the removal of oil from an oil reservoir. Oil is often recovered
from a reservoir as a water-in-oil emulsion. Crude oil typically contains
appreciable quantities
of water as part of a crude oil emulsion. Demulsifiers are chemical compounds
used to separate
water-in-oil and/or oil-in-water emulsions into separate water and oil phases,
and are
commonly used to remove water from crude oil. It is desirable to remove water
from crude oil
shortly after extraction, as oil extractors prefer to store and/or ship "dry"
oil (i.e. oil with low
concentrations of water). Storing water with the oil takes up space on
oilfield installations, and
shipping crude oil containing a significant amount of water to an oil refinery
is both expensive
and inefficient. Thus, oil extractors aim to demulsify crude oil emulsions at
the earliest after
extraction and in particular at offshore platforms where space is typically
limited.
[0002] Most
state of the art demulsifier compositions are environmentally unfriendly.
However, many environmentally friendly demulsifier compositions have
performance
limitations, and they typically do not work as well as those that are less-
friendly. Currently
used demulsifiers that are environmentally unfriendly may be banned from
future use. Thus,
a need exists for environmentally friendly demulsifier compositions that
possess similar or
superior properties to standard (less-friendly) demulsifiers. This disclosure
describes such
demulsifier compositions.
SUMMARY
[0003] A
demulsifier comprises the reaction product of a) a combination of a
monoglyceride and polyethylene glycol (PEG), b) an acid having at least two
carboxyl groups,
a full or partial ester thereof, an anhydride thereof and combinations
thereof, and c) optionally,
a fatty acid, a fatty alcohol, and combinations thereof.
[0004] A method
of demulsifying an emulsion, wherein the emulsion is a water-in-oil
emulsion or an oil-in-water emulsion is also provided. The method comprises
the steps of
adding the demulsifier to the emulsion, the water component of the emulsion,
and/or the oil
component of the emulsion, and separating the emulsion into an oil phase and a
water phase.
[0005] A method
of making a demulsifier composition is also provided. The method
comprises the step of reacting a) a combination of a monoglyceride and PEG
with b) an acid
having at least two carboxyl groups, a full or partial ester thereof, an
anhydride thereof and
combinations thereof and, optionally, a fatty acid, a fatty alcohol, and
combinations thereof.
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DETAILED DESCRIPTION
[0006] A
demulsifier according to this disclosure includes the reaction product of a)
(i)
an alkoxylated monoglyceride, (ii) a combination of an alkoxylated polyol and
a fatty acid, and
(iii) a combination of a monoglyceride and PEG, with b) an acid having at
least two carboxyl
groups, full or partial esters thereof, an anhydride thereof and combinations
thereof. In another
embodiment, the demulsifier includes the reaction product of a) (i) an
alkoxylated
monoglyceride, (ii) a combination of an alkoxylated polyol and a fatty acid
and (iii) a
combination of a monoglyceride and PEG; b) an acid having at least two
carboxyl groups, full
or partial esters thereof, an anhydride thereof and combinations thereof, and
c) a fatty acid, a
fatty alcohol and combinations thereof. In still another embodiment, the
demulsifier includes
the reaction product of a) a combination of a monoglyceride and PEG, b) an
acid having at
least two carboxyl groups, full or partial esters thereof, an anhydride
thereof and combinations
thereof, and c) optionally, a fatty acid, a fatty alcohol and combinations
thereof. The disclosed
demulsifier separates oil-in-water and/or water-in-oil emulsions. The water-in-
oil emulsions
are typically observed in crude oil.
[0007] Polyol
alkoxylate derivatives. An alkoxylated monoglyceride, a combination
of an alkoxylated polyol and a fatty acid, and a combination of a
monoglyceride and PEG, once
reacted according to the present disclosure, may all be considered polyol
alkoxylate
derivatives. Depending on the selection, the location of the alkoxylate moiety
in the final
demulsifier may be different. Each of these "derivatives" will be described in
further detail
below.
[0008]
Monoglycerides are compounds having a glycerol moiety linked to a fatty acid
via an ester bond. The fatty acid may be linked to either a primary alcohol or
the secondary
alcohol of the glycerol moiety. The following structure (1) illustrates one
embodiment of a
monoglyceride:
HO
OH
0
1/C¨R
0 (1)
where R is the alk(en)y1 component of the fatty acid. In some embodiments, the
R group is an
alkenyl group having from 7 carbon atoms to 21 carbon atoms. Commercially
available
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monoglycerides are typically not "pure" but instead contain a mixture of
monoglycerides,
diglycerides and triglycerides. As used herein, the term "monoglyceride"
refers to products in
which the monoglyceride moiety is the most prevalent.
[0009] PEG.
Polyethylene glycol or PEG is a polyether having the general formula
H¨(0¨CH2¨CH2).¨OH. The number n may vary and determines whether a particular
PEG
has a low molecular weight or a high molecular weight. In some embodiments,
the PEG used
in the demulsifier described herein has a number n between about 4 and about
200. Suitable
PEGs include PEG 200, PEG 400, PEG 600, PEG 1000, PEG 1450, PEG 2000 and PEG
8000
where the number following "PEG" is the approximate ( 5%) average molar mass
(g/mol) of
the PEG. For example, PEG 400 has an average molar mass between about 380
g/mol and
about 420 g/mol. PEGs having other molecular weights may also be used.
[00010]
Alkoxylated monoglyceride. Alkoxylation is a reaction that involves the
addition of an epoxide (a cyclic ether) to a compound. Suitable epoxides for
alkoxylation of
monoglycerides include ethylene oxide (C2H40), propylene oxide (CH3CHCH20) and
epoxy
butanes. Once alkoxylated, it is expected that the hydroxyl and ester groups
of the
monoglyceride will be linked to alkoxy groups (e.g., ethyleneoxy, propoxy,
etc.). In an
embodiment, the alkoxylated monoglyceride is ethoxylated monoglyceride. One
example of
an ethoxylated monoglyceride is shown in the diagram (2) below:
0
HOOH H¨(-0
in 0 0
EO
0 n II
0 (2)
[00011] The
extent of alkoxylation of alkoxylated monoglycerides may vary. Different
alkoxylation sites, each hydroxyl group and the ester linkage, may contain
different numbers
of alkoxy groups. In some embodiments, each mole of alkoxylated monoglyceride
contains,
on average, between 5 alkoxy units and 40 alkoxy units (i.e., from 5 to 40
moles of alkoxy
units per mole of monoglyceride). In some embodiments, the 5 alkoxy units to
40 alkoxy units
are ethyleneoxy units. In other embodiments, each mole of alkoxylated
monoglyceride
contains, on average, less than 8 propyleneoxy units.
[00012]
Alkoxylated polyol. Alkoxylated polyols or polyol alkoxylates, such as
alkoxylated glycerol, are commercially available. Like alkoxylated
monoglycerides, polyol
alkoxylates contain linkages to alkoxy groups at hydroxyl sites. For example,
the following
structure (3) illustrates an ethoxylated glycerol:
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n 0'0
0)¨H
(3)
In some embodiments, the polyol (in its unalkoxylated form) contains from 3 to
6 carbon atoms.
In some embodiments, the polyol contains 3 or 4 hydroxyl groups. In some
embodiments, the
ratio of primary alcohols to secondary alcohols on the polyol (unalkoxylated)
is from 2:1 to
4:0, or 2:1, or 3:0, or 4:0. Suitable alkoxylated polyols include glycerol
alkoxylates,
pentaerythritol alkoxylates, and trimethylolpropane alkoxylates.
[00013] Fatty
acid. Fatty acids have the general formula R-COOH where R is an
alk(en)y1 or an aryl group. An alk(en)y1 R group may be saturated or
unsaturated, linear or
branched and cycloalkyl or aryl. In some embodiments, the R group contains
between 7 carbon
atoms and 21 carbon atoms. In these embodiments, the fatty acid has between 8
and 22 carbon
atoms in total. A mixture of fatty acids may be present. Suitable fatty acids
include tallow
fatty acids, tall oil fatty acids, coconut fatty acids, palmitic acid, stearic
acid, myristic acid,
oleic acid, palmitoleic acid, linoleic acid, linolenic acid, lauric acid,
decanoic acid, caprylic
acid and combinations thereof. In some embodiments, a majority of the fatty
acid contains
chains having between 12 and 18 carbon atoms.
[00014]
Carboxylic acid. The acid having at least two carboxyl groups may have two,
three or four carboxyl (¨COOH) groups. The acid having at least two carboxyl
groups may be
linear or branched and saturated or unsaturated. When two carboxyl groups are
present and
the acid is linear, the acid is a dicarboxylic acid and has the general
formula
HOOC(CH2).COOH. In some embodiments, n has a value between about 2 and about
34. In
these embodiments, the acid has between 4 and 36 carbon atoms in total. The
value of n may
be the same for branched acids. Suitable acids include succinic acid, adipic
acid, glutaric acid,
sebacic acid, and combinations thereof. When three carboxyl groups are
present, the acid is a
triacid. Suitable triacids include citric acid (C6H807). When four carboxyl
groups are present,
the acid is a tetracid. Suitable examples of branched acids include itaconic
acid and citraconic
acid. In an embodiment, the acid having at least two carboxyl groups comprises
an acid
selected from succinic acid, adipic acid, glutaric acid, citric acid, and
combinations thereof.
[00015] Ester. A
full or partial ester of the acids described above may be used in place
of the above acid. For example, in the case of a linear dicarboxylic acid, a
full ester (diester)
has the general formula R100C(CH2)õCOOR2 where Rl and R2 are alkyl or aryl
groups. In
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some embodiments, n has a value between about 2 and about 34. IV and R2 may be
different
alkyl or aryl groups or the same. In a partial ester, less than all the
carboxylic acid groups are
replaced with an ester group. In some embodiments, both an acid having at
least two carboxyl
groups and a full or partial ester are used to produce the demulsifier.
[00016]
Anhydride. An organic acid anhydride may be used in place of the above
carboxylic acid. An anhydride of a linear dicarboxylic acid has the general
formula Ri(C0)-
0-(CO)R2 where Rl and R2 are alkyl or aryl groups. Rl and R2 may be different
alkyl or aryl
groups or the same. Suitable organic acid anhydrides include succinic
anhydride, maleic
anhydride, alkenyl succinic anhydride, itaconic anhydride, citraconic
anhydride and
combinations thereof. In some embodiments, both an acid having at least two
carboxyl groups
and an organic acid anhydride are used to produce the demulsifier.
[00017] In some
embodiments, the demulsifier is the reaction product of (i) an
alkoxylated monoglyceride and (ii) a combination of a monoglyceride and
polyethylene glycol
(PEG); an acid having at least two carboxyl groups, a full or partial ester
thereof, an anhydride
thereof and combinations thereof (as described above); and a fatty acid, a
fatty alcohol and
combinations thereof.
[00018] Fatty
acid. When used in the embodiment described in the preceding paragraph,
the fatty acid has the same properties as the fatty acid previously described,
the fatty acid has
the general formula R-COOH where R is an alkyl or an aryl group. An alkyl R
group may be
saturated or unsaturated, linear or branched, and cycloalkyl or aryl. In some
embodiments, the
R group contains between 7 carbon atoms and 21 carbon atoms. In these
embodiments, the
fatty acid has between 8 and 22 carbon atoms in total. A mixture of fatty
acids may be present.
Suitable fatty acids include tallow fatty acids, tall oil fatty acids, coconut
fatty acids, palmitic
acid, stearic acid, myristic acid, oleic acid, dibasic acid, palmitoleic acid,
linoleic acid, linolenic
acid, lauric acid, decanoic acid, caprylic acid and combinations thereof. In
an embodiment, the
fatty acid comprises an acid selected from tallow fatty acids, tall oil fatty
acids, palmitic acid,
stearic acid, myristic acid, oleic acid, dibasic acid, palmitoleic acid,
linoleic acid, linolenic acid,
and combinations thereof. In some embodiments, a majority of the fatty acid
contains chains
having between 12 and 18 carbon atoms.
[00019] Fatty
alcohol. When used, the fatty alcohol has the general formula R-OH
where R is an alkyl group. The R group may be saturated or unsaturated and
linear or branched.
In some embodiments, the R group contains between 6 carbon atoms and 22 carbon
atoms. A
mixture of fatty alcohols may be present. Suitable fatty alcohols include
decyl alcohol, lauryl
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alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol and
combinations
thereof. In some embodiments, a majority of the fatty alcohols contain chains
having between
12 and 18 carbon atoms. In some embodiments, both a fatty acid and a fatty
alcohol are used
to produce the demulsifier.
[00020] The
molar ratio of the polyol alkoxylate derivatives to the acid having at least
two carboxyl groups, full or partial ester thereof, the anhydride thereof and
combinations
thereof is between about 1:3 and about 5:1, or between about 1:2 and about
2:1. The molar
ratio of polyol alkoxylate derivatives to the fatty acid, the fatty alcohol
and combinations
thereof, when used, is between about 1:3 and about 5:1, or between about 1:2
and about 2:1.
[00021] In some
embodiments, the combination of both a glycerol ethoxylate and a
monoglyceride as reactants is avoided.
[00022] The
reaction product is prepared by reacting the selected polyol alkoxylate
"derivative"; the acid having at least two carboxyl groups, full or partial
ester thereof, the
anhydride thereof and combinations thereof; and, optionally, the fatty acid,
the fatty alcohol
and combinations thereof described herein. The reaction may occur without
using any catalyst
or in the presence of a basic or acidic catalyst. Suitable base catalysts
include sodium
hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
Suitable acid
catalysts include phosphorous acid, hypophosphorous acid, hypophosphoric acid,
and para-
toluenesulfonic acid monohydrate. The reaction may proceed at temperatures up
to about 200
C in a nitrogen environment and/or under vacuum conditions (e.g., from about 7
to about 20
kPa).
[00023] The
reaction product yielded by the above reaction conditions is a polyester
suitable for use as a demulsifier. When the polyol alkoxylate derivative is a
combination of
monoglyceride and PEG, it is believed that a compound having the following
structure (4) is
predominantly produced:
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HO
+ HOOC ¨X ¨COOH + HO'h.µ"=- r-H + R1¨COOH
OH
DIACID PEG FATTY ACID
(or Anhydride) (or FATTY
ALCOHOL)
0
(Optional)
,C ¨R
MONOGLYCERIDES
0 0
n R2
- -
0
C ¨R R2= H or -CO-R1
MONOGLYCERIDE PEG POLYESTERS (4).
The presence of the optional fatty acid or fatty alcohol affects the end caps
of the demulsifier
with R2 being hydrogen, ¨(CO)Ri (a fatty acid), or a fatty alcohol residue. In
some
embodiments, m is a number between 1 and 50, or between 2 and 10. In some
embodiments,
n is a number between 4 and 200.
[00024] In an embodiment, the monoglyceride is glycerol monooleate.
[00025] When the
polyol alkoxylate derivative is an alkoxylated monoglyceride, it is
believed that the general reaction pathway shown below is followed, with a
compound having
the following structure (5) being predominantly produced:
0
HOOH R¨COOH
OH SOY FATTY ACID OR EO
GLYCEROL 11
nII
0 0
SOY MONOGLYCERIDE ETHOXYLATED SOYMONOGLYCERIDE
(idealized structure)
0 0
HOOC¨X¨COOH R2 ( ) 1 R2
DIACID
OYC R OYC R
R1¨COOH n II n II
0 0
FATTY ACID
(or FATTY ALCOHOL) R2 = H or -CO-R1 (when fatty
acid is used)
(Optional) ETHOXYLATED SOYMONOGLYCERIDE POLYESTER (5)
This reaction pathway uses ethoxylated soy monoglyceride as the alkoxylated
monoglyceride.
Propoxylated monoglycerides and monoglycerides having different fatty acid
chains are
expected to behave similarly. The presence of the optional fatty acid or fatty
alcohol affects
the end caps of the demulsifier with R2 being ¨(CO)Ri (fatty acid) or a fatty
alcohol residue.
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In some embodiments, m is a number between 1 and 50, or between 2 and 10. In
some
embodiments, the total of n per alkoxylated monoglyceride residue is a number
between 5 and
40.
[00026] When the
polyol alkoxylate derivative is a combination of an alkoxylated polyol
and a fatty acid, it is believed that the general reaction pathway shown below
is followed, with
a compound having the following structure (6) being predominantly produced:
+ R¨COOH + HOOC¨X¨COOH
0)¨H FATTY ACID DIACID
ETHOXYLATED GLYCEROL
0 0
R2 ( 0 (:)0)¨riC X C¨(-00 ) R2
n
0)¨C¨R
n n II
0 0
R2 = H or -CO-R
ETHOXYLATED GLYCEROL POLYESTER (6).
This reaction pathway uses ethoxylated glycerol as the alkoxylated polyol.
Propoxylated
glycerols and other alkoxylated polyols are expected to behave similarly.
Alkoxylated polyols
may also contain a mixture of alkoxylates (e.g., some ethyleneoxy units and
some
propyleneoxy units). In some embodiments, m is a number between 1 and 50, or
between 2
and 10. In some embodiments, the total of n per alkoxylated polyol residue is
a number
between 5 and 40.
[00027] The
reaction product may also include water. In some embodiments, water is
removed from the reaction product so that the total water concentration is
below about 5 percent
by weight, or less than about 3 percent by weight, or less than about 2
percent by weight, or
less than about 1 percent by weight. Alternatively, the water may remain in
mixture with the
reaction product until after demulsification of the target emulsion.
[00028]
Alternatively, the reaction product may be thought of as containing
monoglyceride residues, PEG-type residues, diacid-type residues and,
optionally, fatty acid
residues. The PEG-type residues refer to the alkoxylate or PEG groups
described herein. The
diacid-type residues include the diacid, triacid and tetracid described herein
(or the full or
partial ester thereof and/or the anhydride thereof). When present,
approximately two fatty acid
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residues, excluding the fatty group present on the monoglyceride residue, are
present for each
monoglyceride residue, PEG-type residue, and diacid-type residue.
[00029] A method
according to this disclosure includes a method of making a polyester
demulsifier by reacting a) (i) an alkoxylated monoglyceride, (ii) a
combination of an
alkoxylated polyol and a fatty acid, and (iii) a combination of a
monoglyceride and
polyethylene glycol (PEG) with b) an acid having at least two carboxyl groups,
a full or partial
ester thereof, an anhydride thereof and combinations thereof. Alternatively, a
method of
making a polyester demulsifier includes reacting a) (i) an alkoxylated
monoglyceride, (ii) a
combination of an alkoxylated polyol and a fatty acid, and (iii) a combination
of a
monoglyceride and polyethylene glycol (PEG), with b) an acid having at least
two carboxyl
groups, a full or partial ester thereof, an anhydride thereof and combinations
thereof, and c) a
fatty acid, a fatty alcohol and combinations thereof. In another embodiment, a
method of
making a demulsifier includes the step of reacting a) a combination of a
monoglyceride and
polyethylene glycol (PEG) with b) an acid having at least two carboxyl groups,
a full or partial
ester thereof, an anhydride thereof and combinations thereof and, optionally,
a fatty acid, a
fatty alcohol and combinations thereof. Generally, the reaction takes place at
temperatures up
to about 200 C in a nitrogen environment and/or under vacuum conditions
(e.g., from about 7
to about 20 kPa) for a period of time sufficient to form the polyester
demulsifier.
[00030] Another
method according to this disclosure includes a method of demulsifying
an oil-in-water emulsion or a water-in-oil emulsion. The method includes
adding an effective
amount of the demulsifier prepared by reacting a) a combination of a
monoglyceride and
polyethylene glycol (PEG) with b) an acid having at least two carboxyl groups,
a full or partial
ester thereof, an anhydride thereof and combinations thereof and, optionally,
a fatty acid, a
fatty alcohol and combinations thereof, described herein, to the emulsion, the
water component
of the emulsion, and/or the oil component of the emulsion. In some
embodiments, the emulsion
is a water-in-oil emulsion, such as a crude oil emulsion containing salt
water, sea water and/or
ocean water. Alternatively, the demulsifier may be added to an oil (e.g.,
crude oil) before an
emulsion is formed with the oil. For instance, the demulsifier may be added to
a crude oil
upstream of a separator at an oilfield installation. The demulsifier may also
be used to prevent
emulsification as a nonemulsifier. The method further includes the step of
separating the
emulsion into an oil phase and a water phase.
[00031] The
demulsifier described herein may be used alone as a demulsifier or
combined with other demulsifiers to separate the phases of oil-in-water and/or
water-in-oil
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emulsions. The exact composition of a demulsifier formulation (the demulsifier
described
herein alone or used in combination with other demulsifiers, droppers and/or
dryers) may vary
depending on the properties of the targeted emulsion. Crude oils obtained from
the same well
may change over time and changing environmental conditions (e.g., temperature,
pressure)
may require changes to the demulsification formulation in order to maintain
effectiveness.
[00032] The
demulsifier formulation may be used at a concentration between about 1
part per million (ppm) and about 1000 ppm. In some embodiments, the
demulsifier formulation
is used at a concentration between about 5 ppm and about 500 ppm. In some
other
embodiments, the demulsifier formulation is used at a concentration between
about 10 ppm
and about 400 ppm. In still other embodiments, the demulsifier formulation is
used at a
concentration between about 20 ppm and about 200 ppm.
EXAMPLES
[00033] For
illustrative purposes, the following examples are disclosed. All percentages
used are by weight unless otherwise stated.
Example 1. Preparation of ethoxylated soy monoglyceride (10 EO) polyester
[00034] 318
grams of ethoxylated soy monoglyceride (sourced from Nouryon), 47
grams of adipic acid (Alfa Aesar), and 1.7 grams of phosphorous acid catalyst
(Acros Organics)
were added to a 500-mL flask. On average, the ethoxylated soy monoglyceride
contained 10
moles of ethyleneoxy units for each mole of ethoxylated soy monoglyceride. The
flask was
flushed with nitrogen gas. While the flask contents were mixed the flask was
heated in an oil
bath at an oil bath temperature of 200 C. After about two hours of mixing, a
vacuum was
applied to the flask. After about eight hours of mixing, the acid value
reached a constant value
and the reaction product was cooled to about 80 C and then collected.
Approximately 3.5
grams of water was removed from the flask before the vacuum was applied.
Example 2. Preparation of ethoxylated glycerol/TOFA (12 EO) polyester
[00035] 850
grams of ethoxylated glycerol, 161 grams of adipic acid (Alfa Aesar), 384
grams of tall oil fatty acid (Nouryon) and 4.6 grams of para-toluenesulfonic
acid were added
to a 2-L flask. On average, the ethoxylated glycerol contained 12 moles of
ethyleneoxy units
for each mole of ethoxylated glycerol. The flask was flushed with nitrogen
gas. The pressure
in the reactor was reduced to 20 kPa and the reactor was heated to a
temperature of 180 C.
Once the temperature reached 180 C, full vacuum (7-8 kPa) was applied and the
temperature
was increased to 200 C. After about eight hours of mixing, the reaction
product was cooled
to 60 C and then collected.
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Examples 3. Preparation of Monoglyceride/PEG Polyester
[00036] 35.6
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 20 grams of polyethylene
glycol (PEG-
200, available from Acros), 21.9 grams of adipic acid (Alfa Aesar), and 0.4
grams of NaOH
catalyst (used as a 50 wt% solution in water) were added to a 100 mL 3-neck
flask immersed
in an oil bath and set up with downward distillation, magnetic stirrer,
thermometer, and an N2
inlet. No fatty acid was added. The flask was flushed with N2 gas and heated
to 220 C under
stirring until the acid value stabilized. The reaction product was cooled to
around 60 C and
then collected.
Example 4. Preparation of Monoglyceride/PEG Polyester
[00037] 24.92
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 42 grams of polyethylene
glycol (PEG-
600, available from Acros), 15.33 grams of adipic acid (Alfa Aesar), and 0.28
grams of NaOH
catalyst (used as a 50 wt% solution in water) were added to a 100 mL 3-neck
flask immersed
in an oil bath and set up with downward distillation, magnetic stirrer,
thermometer, and an N2
inlet. No fatty acid was added. The flask was flushed with N2 gas and heated
to 220 C under
stirring until the acid value stabilized. The reaction product was cooled to
around 60 C and
then collected.
Example 5. Preparation of Monoglyceride/PEG Polyester
[00038] 21.36
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 36 grams of polyethylene
glycol (PEG-
600, available from Acros), 13.14 grams of adipic acid (Alfa Aesar), 8.34
grams of oleic acid
(Voleic 0A00 available from Vantage), and 0.24 grams of NaOH catalyst (used as
a 50 wt%
solution in water) were added to a 100 mL 3-neck flask immersed in an oil bath
and set up with
downward distillation, magnetic stirrer, thermometer, and an N2 inlet. The
flask was flushed
with N2 gas and heated to 220 C under stirring until the acid value
stabilized. The reaction
product was cooled to around 60 C and then collected.
Example 6. Preparation of Monoglyceride/PEG Polyester
[00039] 21.36
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 36 grams of polyethylene
glycol (PEG-
200, available from Acros), 26.28 grams of adipic acid (Alfa Aesar), and 0.24
grams of NaOH
catalyst (used as a 50 wt% solution in water) were added to a 100 mL 3-neck
flask immersed
in an oil bath and set up with downward distillation, magnetic stirrer,
thermometer, and an N2
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inlet. No fatty acid was added. The flask was flushed with N2 gas and heated
to 220 C under
stirring until the acid value stabilized. The reaction product was cooled to
around 60 C and
then collected.
Example 7. Preparation of Monoglyceride/PEG Polyester
[00040] 42.72
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 24 grams of polyethylene
glycol (PEG-
200, available from Acros), 23.76 grams of dibasic acid (dibasic acid flakes
available from
Invista), and 0.46 grams of p-toluene sulfonic acid catalyst (used as a 50 wt%
solution in water)
were added to a 100 mL 3-neck flask immersed in an oil bath and set up with
downward
distillation, magnetic stirrer, thermometer, and an N2 inlet. No fatty acid
was added. The flask
was flushed with N2 gas and heated to 220 C under stirring until the acid
value stabilized. The
reaction product was cooled to around 60 C and then collected.
Example 8. Preparation of Monoglyceride/PEG Polyester
[00041] 17.80
grams of glycerol monooleate (GMO, 1-01eoyl-Rac-Glycerol, technical
grade of about 40%, available from Millipore Sigma), 30 grams of polyethylene
glycol (PEG-
200, available from Acros), 19.80 grams of dibasic acid (dibasic acid flakes
available from
Invista), 13.9 grams of oleic acid (Voleic 0A00 available from Vantage), and
0.19 grams of p-
toluene sulfonic acid catalyst (used as a 50 wt% solution in water) were added
to a 100 mL 3-
neck flask immersed in an oil bath and set up with downward distillation,
magnetic stirrer,
thermometer, and an N2 inlet. The flask was flushed with N2 gas and heated to
220 C under
stirring until the acid value stabilized. The reaction product was cooled to
around 60 C and
then collected.
[00042] The
ethoxylated soy monoglyceride polyester prepared in Example 1 was
screened for toxicity and for biodegradability in seawater. Toxicity was
assessed using
Daphnia magna and algae. Biodegradability in seawater was performed according
to the
OECD Guideline for Testing of Chemicals, Section 3; Degradation and
Accumulation, No.
306: Biodegradability in Seawater, Closed Bottle Test. Table 1 illustrates
toxicity and
biodegradability test results for the Example 1 ethoxylated soy monoglyceride
polyester.
Table 1. Toxicity and Biodegradation Results
Toxicity (mg/L) Biodegradation (%)
Sample 7 14 21 28 42 56 84 112
Daphnia Algae
days days days days days days days days
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Example
>100 >100 23 30 36 43 50 53 53 53
1
[00043] As is
stated in the Introduction to Section 3 of the OECD Test Guidelines¨
Biodegradation and Bioaccumulation (2005), a biodegradation result greater
than 20% after
28 days is indicative of potential for (inherent) primary biodegradation in
the marine
environment.
[00044] The
toxicity and biodegradation test results in Table 1 demonstrate that the
Example 1 ethoxylated soy monoglyceride polyester shows favourable results. It
is expected
that the Example 2 ethoxylated glycerol/TOFA polyester will provide comparable
results to
that of Example 1.
[00045] The
performance of the Example 1 and Example 2 demulsifiers was evaluated
by carrying out tests on emulsions of crude oil from the North Sea and
synthetic North Sea
water. The speed of separation and the clarity (transmission) of the water
phase were assessed
using a TurbiscanTm Lab Expert instrument (Formulaction SA, France). The
TurbiscanTm
instrument is an automated, vertical scan analyzer that may be used for
studying the stability
of concentrated emulsions. It is equipped with a near-infrared light source
and detection
systems for transmission as well as light scattering (backscattering). The
demulsifiers were
diluted with/dissolved in butyl diglycol (BDG) to facilitate dosage of small
concentrations in
the tests.
[00046] Table 2
illustrates TurbiscanTm data for Example 1 and Example 2 polyesters in
addition to a demulsifier that does not meet the OSPAR regulatory requirements
for a "green"
demulsifier (Witbreak DGE 169, available from Nouryon). The ppm column
indicates the
concentration of the demulsifier used in the test. "Avg Transmission" (of the
water layer) is
the average transmission reading between the 0 distance and the position of
the crude oil-water
boundary at 40 minutes. "StartTime" is the first non-zero signal of
transmission, which is later
developed into the water layer at the bottom of the testing vial. "HalfTime"
is the time when
the crude oil-water boundary reaches the midway height of a completely
demulsified mixture
(e.g., 8 mm when a completely demulsified mixture has a height of 16 mm in the
test vial).
"End distance" is the position of the crude oil-water boundary at the end of
the experiment (40
minutes). "WaterOut" is the (End distance - height of completely demulsified
mixture)/height
of completely demulsified mixture x 100.
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Table 2. TurbiscanTm Results
Avg
StartTime HalfTime WaterOut End
Demulsifier ppm Transmission
(minutes) (minutes) (%) distance
(%)
Witbreak
50 63.8 0 1 103 16.5
DGE 169
Example 1 50 73.9 6 20.8 82 13.1
Example 2 50 78.3 3 18 74 11.9
Example 3 50 86.7 11 38 54 8.6
Example 4 50 83.4 11 38 55 8.8
Example 5 50 81.6 5 29 63 10.1
Example 6 50 73.1 0 0 102 16.3
Example 7 50 85.4 9 30 64 10.2
Example 8 50 80.0 8 23 74 11.9
[00047] The
TurbiscanTm results demonstrate that the Example 1 and Example 2
ethoxylated glyceride polyesters provide an adequate level of demulsification.
The
TurbiscanTm results also demonstate that the Examples 3-8 monoglyceride/PEG
polyesters also
provide an adequate level of demulsification.
[00048] While
the present disclosure has been described with reference to exemplary
embodiments, it will be understood by those skilled in the art that various
changes may be
made and equivalents may be substituted for elements thereof without departing
from the scope
of the present disclosure. In addition, many modifications may be made to
adapt a particular
situation or material to the teachings of the present disclosure without
departing from the
essential scope thereof. Therefore, it is intended that the present disclosure
not be limited to
the particular embodiments disclosed, but that the present disclosure will
include all
embodiments falling within the scope of the appended claims.
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