U.S. patent application number 10/772217 was filed with the patent office on 2007-03-15 for apparatus and methods for drilling a wellbore using casing.
This patent application is currently assigned to Weatherford/Lamb, Inc.. Invention is credited to Samir Alkhatib, William M. Beasley, David J. Brunnert, Gregory G. Galloway, Richard L. Giroux, Raymond H. Jackson, Tuong Thanh Le, Brent J. Lirette, Dave McKay, Gregory R. Nazzal, Albert C. Odell, James C. Swarr, Jim Terry, Mike Wardley.
Application Number | 20070056774 10/772217 |
Document ID | / |
Family ID | 46300777 |
Filed Date | 2007-03-15 |
United States Patent
Application |
20070056774 |
Kind Code |
A9 |
Giroux; Richard L. ; et
al. |
March 15, 2007 |
APPARATUS AND METHODS FOR DRILLING A WELLBORE USING CASING
Abstract
The present invention relates to emulsion compositions for
starting a reformer of a fuel cell system. In particular, the
invention includes oil-in-water-in-oil (O/W/O) emulsion
compositions comprising hydrocarbon fuel, water, alkoxylated alkyl
alcohol, alkoxylated alkyl ester and alkyl polyglycerol surfactants
for starting a reformer of a fuel cell system.
Inventors: |
Giroux; Richard L.;
(Cypress, TX) ; Galloway; Gregory G.; (Conroe,
TX) ; Le; Tuong Thanh; (Katy, TX) ; Jackson;
Raymond H.; (Spring, TX) ; Nazzal; Gregory R.;
(Kingwood, TX) ; Swarr; James C.; (The Woodlands,
TX) ; Brunnert; David J.; (Cypress, TX) ;
Beasley; William M.; (Waller, TX) ; Lirette; Brent
J.; (Houston, TX) ; Odell; Albert C.;
(Kingwood, TX) ; Terry; Jim; (Houston, TX)
; McKay; Dave; (Stonehaven, GB) ; Alkhatib;
Samir; (Aberdeen, GB) ; Wardley; Mike;
(Aberdeen, GB) |
Correspondence
Address: |
William B. Patterson;MOSER, PATTERSON & SHERIDAN, L.L.P.
3040 Post Oak Blvd. Suite 1500
Houston
TX
77056
US
|
Assignee: |
Weatherford/Lamb, Inc.
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20040245020 A1 |
December 9, 2004 |
|
|
Family ID: |
46300777 |
Appl. No.: |
10/772217 |
Filed: |
February 2, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10257662 |
Mar 5, 2003 |
6848517 |
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PCT/GB01/01506 |
Apr 2, 2001 |
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10772217 |
Feb 2, 2004 |
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10331964 |
Dec 30, 2002 |
6857487 |
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10772217 |
Feb 2, 2004 |
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60444088 |
Jan 31, 2003 |
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60452202 |
Mar 5, 2003 |
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60452186 |
Mar 5, 2003 |
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60452317 |
Mar 5, 2003 |
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Current U.S.
Class: |
175/61 ;
175/171 |
Current CPC
Class: |
B05B 1/002 20180801;
E21B 21/103 20130101; E21B 2200/04 20200501; E21B 43/105 20130101;
E21B 41/0078 20130101; E21B 7/208 20130101; E21B 7/18 20130101;
E21B 7/065 20130101; E21B 47/01 20130101; E21B 7/06 20130101; E21B
33/14 20130101; E21B 17/14 20130101; E21B 10/61 20130101 |
Class at
Publication: |
175/061 ;
175/171 |
International
Class: |
E21B 7/04 20060101
E21B007/04 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 13, 2000 |
GB |
0008988.8 |
Claims
1. In a fuel cell system comprising a reformer to produce hydrogen
containing gas for use in a fuel cell stack, the improvement
comprising: feeding to the reformer, at start-up, an emulsion
composition comprising, at least 40 wt % of hydrocarbon, from 30 to
60 wt % of water, and from 0.01 to 5 wt % of a surfactant mixture
comprising at least one surfactant from each of two types of
surfactants, one type of surfactant comprising surfactants selected
from the group consisting of alkoxylated alkyl alcohols,
alkoxylated alkyl monoesters and alkoxylated alkyl diesters and the
other type of surfactant comprising surfactants selected from the
group consisting of alkyl polyglycerol monoesters and alkyl
polyglycerol diesters, said alkoxylated alkyl alcohols represented
by the formula, R--(CH.sub.2).sub.n--O-(M-O).sub.m--H; said
alkoxylated alkyl monoesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--H said alkoxylated alkyl
diesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--CO--(CH.sub.2).sub.n--R
where R is a methyl group, n is an integer from about 5 to 17, m is
an integer from about 2 to 50, M is CH.sub.2--CH.sub.2,
CH.sub.2--CH.sub.2--CH.sub.2, CH.sub.2--CH--CH.sub.3,
CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH--(CH.sub.3)--CH.sub.2 or mixtures thereof, said alkyl
polyglycerol monoesters represented by the general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2OH and, said alkyl polyglycerol diesters represented by the
general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2--O--CO--R' where R' is an alkyl group of 2 to 26 carbon
atoms and p is an integer from about 0 to 15.
2. The improvement of claim 1 wherein the emulsion further
comprises up to 20 wt % alcohol based on the total weight of the
said emulsion wherein said alcohol is selected form the group
consisting of methanol, ethanol, n-propanol, iso-propanol,
n-butanol, sec-butyl alcohol, tertiary butyl alcohol, n-pentanol,
ethylene gylcol, propylene glycol, butyleneglycol and mixtures
thereof.
3. The improvement of claim 1 wherein said hydrocarbon is in the
boiling range of -1.degree. C. to 260.degree. C.
4. The improvement of claim 1 wherein said water is substantially
free of salts of halides, sulfates and carbonates of Group I and
Group II elements of the long from of The Periodic Table of
Elements.
5. The improvement of claim 1 wherein the emulsion is a complex
oil-in-water-in-oil emulsion.
6. The improvement of claim 1 wherein said alkoxylated alkyl
alcohols, alkoxylated alkyl monoesters, alkoxylated alkyl diesters,
alkyl polyglycerol monoesters and alkyl polyglycerol diesters
thermally decompose at temperatures in the range of about
250.degree. C. to about 700.degree. C.
7. The improvement of claim 1 wherein in said alkoxylated alkyl
alcohols, alkoxylated alkyl monoesters, alkoxylated alkyl diesters
the alkoxylated group is an ethoxylated group.
8. A method to prepare a complex oil-in-water-in-oil emulsion
comprising mixing at mixing energy in the range of
0.15.times.10.sup.-5 to 0.15.times.10.sup.-3 kW/liter of fluid, at
least 40 wt % of hydrocarbon, from 30 to 60 wt % of water, and from
0.01 to 5 wt % of a surfactant mixture comprising at least one
surfactant from each of two types of surfactants, one type of
surfactant comprising surfactants selected from the group
consisting of alkoxylated alkyl alcohols, alkoxylated alkyl
monoesters and alkoxylated alkyl diesters and the other type of
surfactant comprising surfactants selected from the group
consisting of alkyl polyglycerol monoesters and alkyl polyglycerol
diesters, said alkoxylated alkyl alcohols represented by the
formula, R--(CH.sub.2).sub.n--O-(M-O).sub.m--H; said alkoxylated
alkyl monoesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--H said alkoxylated alkyl
diesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--CO--(CH.sub.2).sub.n--R
where R is a methyl group, n is an integer from about 5 to 17, m is
an integer from about 2 to 50, M is CH.sub.2--CH.sub.2,
CH.sub.2--CH.sub.2--CH.sub.2, CH.sub.2--CH--CH.sub.3,
CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH--(CH.sub.3)--CH.sub.2 or mixtures thereof, said alkyl
polyglycerol monoesters represented by the general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2OH and, said alkyl polyglycerol diesters represented by the
general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2--O--CO--R' where R' is an alkyl group of 2 to 26 carbon
atoms and p is an integer from about 0 to 15.
9. The method of claim 8 wherein mixing is conducted by an in-line
mixer, static paddle mixer, sonicator or combinations thereof.
10. The method of claim 8 wherein said mixing is conducted for a
time period in the range of 1 second to about 15 minutes.
11. A complex oil-in-water-in-oil emulsion comprising: at least 40
wt % of hydrocarbon, from 30 to 60 wt % of water, and from 0.01 to
5 wt % of a surfactant mixture comprising at least one surfactant
from each of two types of surfactants, one type of surfactant
comprising surfactants selected from the group consisting of
alkoxylated alkyl alcohols, alkoxylated alkyl monoesters and
alkoxylated alkyl diesters and the other type of surfactant
comprising surfactants selected from the group consisting of alkyl
polyglycerol monoesters and alkyl polyglycerol diesters, said
alkoxylated alkyl alcohols represented by the formula,
R--(CH.sub.2).sub.n--O-(M-O).sub.m--H; said alkoxylated alkyl
monoesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--H said alkoxylated alkyl
diesters represented by the formula,
R--(CH.sub.2).sub.n--CO--O-(M-O).sub.m--CO--(CH.sub.2).sub.n--R
where R is a methyl group, n is an integer from about 5 to 17, m is
an integer from about 2 to 50, M is CH.sub.2--CH.sub.2,
CH.sub.2--CH.sub.2--CH.sub.2, CH.sub.2--CH--CH.sub.3,
CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH--(CH.sub.3)--CH.sub.2 or mixtures thereof, said alkyl
polyglycerol monoesters represented by the general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2OH and, said alkyl polyglycerol diesters represented by the
general formula,
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2--O--CO--R' where R' is an alkyl group of 2 to 26 carbon
atoms and p is an integer from about 0 to 15.
12. The complex oil-in-water-in-oil emulsion of claim 11 further
comprising up to 20 wt % alcohol based on the total weight of the
said emulsion wherein said alcohol is selected from the group
consisting of methanol, ethanol, n-propanol, iso-proponal,
n-butanol, sec-butyl alcohol, tertiary butyl alcohol, n-pentanol,
ethylene gylcol, propylene glycol, butyleneglycol and mixtures
thereof.
13. The composition of claim 11 wherein in said alkoxylated alkyl
alcohols, alkoxylated alkyl monoesters and alkoxylated alkyl
diesters the alkoxylated group is an ethoxylated group.
14. The complex oil-in-water-in-oil emulsion of claim 11 wherein
said emulsion has conductivity in the range of 3 to 15 mhos at
25.degree. C.
15. The complex oil-in-water-in-oil emulsion of claim 11 wherein
said emulsion is stable to freeze thaw cycles in the temperature
range of -54.degree. C. to +50.degree. C.
Description
[0001] This application claims the benefit of U.S. Provisional
application No. 60/435,044 filed Dec. 20, 2002.
[0002] The present invention relates to compositions for use at
start-up a reformer of a fuel cell system. In particular, this
invention includes emulsion compositions comprising hydrocarbon
fuel, water and surfactant for use at start-up of a reformer of a
fuel cell system.
[0003] Fuel cell systems employing a partial oxidation, steam
reformer or autothermal reformer or combinations thereof to
generate hydrogen from a hydrocarbon need to have water present at
all times to serve as a reactant for reforming, water-gas shift,
and fuel cell stack humidification. Since water is one product of a
fuel cell stack, during normal warmed-up operation, water generated
from the fuel cell stack may be recycled to the reformer. For
start-up of the reformer it is preferable that liquid water be well
mixed with the hydrocarbon fuel and fed to the reformer as an
emulsion. The current invention provides complex
oil-in-water-in-oil emulsion compositions suitable for use at
start-up of a reformer of a fuel cell system.
SUMMARY OF THE INVENTION
[0004] One embodiment of the invention provides emulsion
compositions suitable for use at start-up of a reformer of a fuel
cell system comprising hydrocarbon, water and at least one
surfactant from each of two types of surfactants. One type of
surfactant (Type-A) is selected from the group consisting of
alkoxylated alkyl alcohols, alkoxylated alkyl monoesters and
alkoxylated alkyl diesters. The other type of surfactant (Type-B)
is selected from the group consisting of alkyl polyglycerol
monoesters and alkyl polyglycerol diesters.
[0005] In a preferred embodiment, the emulsion composition is a
complex oil-in-water-in-oil emulsion.
[0006] In another embodiment of the invention is provided a method
to prepare a complex oil-in-water-in-oil emulsion comprising mixing
hydrocarbon, water and Type-A and Type-B surfactants at low
shear.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 shows a schematic diagram of a typical prior art
conventional fuel cell system.
[0008] FIG. 2 shows a schematic diagram of an improved fuel cell
system wherein a start-up system is operably connected to a
reformer
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0009] The emulsion compositions of the present invention can be
used for start-up of a reformer of a fuel cell system. In a
preferred embodiment the emulsion compositions can be used for
start-up of a reformer of an improved fuel cell system described
hereinafter. The improved fuel cell system comprises a convention
fuel cell system to which a start-up system is operably connected.
A conventional fuel cell system and the improved fuel cell system
are described below.
[0010] A conventional fuel cell system comprises a source of fuel,
a source of water, a source of air, a reformer, a water gas shift
reactor, reactors for converting CO to CO.sub.2 and a fuel cell
stack. A plurality of fuel cells operably connected to each other
is referred to as a fuel cell stack. FIG. 1 shows a schematic of
one embodiment of a prior art hydrogen generator based on a
hydrocarbon liquid fuel and using partial oxidation/steam reforming
to convert the fuel into a syngas mixture. This system design is
similar to that being developed by A. D. Little, except for the
allowance of feeding water to the reformer to practice autothermal
reforming (Ref.: J. Bentley, B. M. Barnett and S. Hynke, 1992 Fuel
Cell Seminar--Ext. Abs., 456, 1992). The process in FIG. 1 is
comprised as follows: Fuel is stored in a fuel tank (1). Fuel is
fed as needed through a preheater (2) prior to entering the
reformer (3). Air is fed to the reformer (3) after it is preheated
by the air preheater (5). Water is stored in a reservoir tank (6).
A heat exchanger (7) is integral with a portion of tank (6) and can
be used to melt portions of the water if it should freeze at low
operation temperatures. Some water from tank (6) is fed via stream
(9) to preheater (8) prior to entering the reformer (3). The
reformed syngas product is combined with additional water from tank
(6) via stream (10). This humidified syngas mixture is then fed to
reactors (11) which perform water gas shift (reaction of CO and
water to produce H.sub.2) and CO cleanup. The H.sub.2 rich-fuel
stream then enters the fuel cell (12) where it reacts
electronically with air (not shown) to produce electricity, waste
heat and an exhaust stream containing vaporized water. A
hydrogen-oxygen fuel cell as used herein includes fuel cells in
which the hydrogen-rich fuel is hydrogen or hydrogen containing
gases and the oxygen may be obtained from air. This stream is
passed through a condenser (13) to recover a portion of the water
vapor, which is recycled to the water reservoir (6) via stream
(14). The partially dried exhaust stream (15) is released to the
atmosphere. Components 3 (reformer) and 11 (water gas shift
reactor) comprise a generalized fuel processor.
[0011] FIG. 2 shows a schematic of one configuration for the fuel
cell start-up system for connection to the conventional fuel cell
system. The system in
[0012] FIG. 2 is comprised as follows: fuel is stored in a fuel
container (1), water in a water container (2), antifreeze in an
antifreeze container (3), surfactant in a surfactant container (4),
and emulsion is made in an emulsion container (5). The fuel and
surfactant containers (1) and (4) are connected to the emulsion
container (5) via separate transfer lines (6) and (7) respectively.
The water container (2) is connected to the emulsion container (5)
via a transfer line (8) to dispense water or water-alcohol mixture
to the emulsion container. The water container is further connected
to an antifreeze container (3) via a transfer line (9). The
emulsion container is fitted with a mixer. An outlet line (10) from
the emulsion container (5) is connected to the fuel cell reformer
of a conventional system such as a reformer (3) shown in FIG.-1;
(reformer (3) of FIG.-1 is equivalent to reformer (11) shown in
FIG.-2). The fuel, water and surfactant containers are all
individually connected to a start-up microprocessor (12) whose
signal initiates the dispensing of the fuel, water and surfactant
into the emulsion container. The water container is connected to a
temperature sensor (13), which senses the temperature of the water
in the water container. The temperature sensor is connected to a
battery (not shown) and the antifreeze container. The temperature
sensor triggers the heating of the water container or dispensing of
the antifreeze as desired. The configuration for the fuel cell
start-up described above is one non-limiting example of a start-up
system. Other configurations can also be employed.
[0013] In an alternate embodiment of the start-up system the water
container is the water storage chamber of the conventional fuel
cell system. In another embodiment of the start-up system the
emulsion container is eliminated. Fuel, water and surfactant are
dispensed directly into the transfer line (10) shown in FIG.-2. In
this embodiment the transfer line (10) is fitted with in-line
mixers. A typical in-line mixer is comprised of a tubular container
fitted with in-line mixing devices known in the art. One
non-limiting example of an in-line mixing device is a series of
fins attached perpendicular to the fluid flow. Another example is a
series of restricted orifices through which fluid is propagated.
In-line mixers are known to those skilled in the art of mixing
fluids. The placement of the number and angle of the fins to the
circumference of the tube is known to those skilled in the art of
in-line mixer design. A sonicator can also be used as an in-line
mixing device. The sonicator device for in-line mixing comprises a
single sonicator horn or a plurality of sonicator horns placed
along the transfer line (10).
[0014] A mixture comprising fuel and surfactant can be
simultaneously injected with water into the front portion of the
in-line mixer. Alternately, a mixture comprising water and
surfactant can be simultaneously injected with fuel into the front
portion of the in-line mixer. The fuel, water and surfactant are
mixed as they flow through the in-line mixer to form an emulsion.
The end portion of the in-line mixer delivers the emulsion to the
reformer through an injection nozzle.
[0015] One function of the improved fuel cell system is that at
start-up, the fuel and water are delivered as an emulsion to the
reformer. One advantage to using an emulsion at start-up is that a
well-mixed water/fuel injection is achieved. This can improve the
efficiency of start-up of the reformer. Another advantage of using
an emulsion is that the fuel-water mixture can be sprayed into the
reformer as opposed to introducing vapors of the individual
components into the reformer. Delivery of the fuel and water as an
emulsion spray has reformer performance advantages over delivery of
the fuel and water in a vaporized state. Further, spraying the
emulsion has mechanical advantages over vaporizing the components
and delivering the vapors to the reformer. Among the desirable
features of emulsions suitable for use in the improved fuel cell
start-up system described herein are: a) the ability to form
emulsions are low shear; (b) the ability of the surfactants to
decompose at temperatures below 700.degree. C.; (c) the viscosity
of the emulsions being such that they are easily pumpable, and, (d)
the emulsion is stable at low temperature. The emulsions of the
instant invention possess these and other desirable attributes.
[0016] The fluid dispensed from the emulsion container or the
in-line mixer into the reformer is the emulsion composition of the
instant invention suitable for start-up of a reformer of a fuel
cell system. Once the reformer is started with the emulsion
composition it can continue to be used for a time period until a
switch is made to a hydrocarbon and steam composition. Typically a
start-up time period can range from 0.5 minutes to 30 minutes
depending upon the device the fuel cell system is the power source
of. The emulsion composition of the instant invention comprises
hydrocarbon, water and surfactant. In a preferred embodiment the
emulsion further comprises low molecular weight alcohols. Another
preferred embodiment of the emulsion composition is a complex
oil-in-water-in-oil (O/W/O) emulsion.
[0017] An oil-in-water emulsion is one where oil droplets are
dispersed in water. A water-in-oil emulsion is one where water
droplets are dispersed in oil. An oil-in-water emulsion has water
as the continuous phase. A water-in-oil emulsion has oil as the
continuous phase. These are simple emulsions. In contrast, when
water is dispersed in oil and the said dispersed water has further
oil dispersed in it such an emulsion is a complex emulsion and
called an oil-in-water-in-oil (O/W/O) emulsion. The types of
surfactants required to form complex oil-in-water-in-oil emulsions
are unique to the oil and water phases comprising the emulsion. A
complex oil-in-water-in-oil emulsion has oil as the continuous
phase.
[0018] In the instant invention the preferred oil is a hydrocarbon.
The hydrocarbon component of the emulsion composition of the
instant invention is any hydrocarbon boiling in the range of
30.degree. F. (-1.1.degree. C.) to 500.degree. F. (260.degree. C.),
preferably 50.degree. F. (10.degree. C.) to 380.degree. F.
(193.degree. C.) with a sulfur content less than about 120 ppm and
more preferably with a sulfur content less than 20 ppm and most
preferably with a no sulfur. Hydrocarbons suitable for the emulsion
can be obtained from crude oil refining processes known to the
skilled artisan. Low sulfur gasoline, naphtha, diesel fuel, jet
fuel, kerosene are non-limiting examples of hydrocarbons that can
be utilized to prepare the emulsion of the instant invention. A
Fisher-Tropsch derived paraffin fuel boiling in the range between
30.degree. F. (-1.1.degree. C.) and 700.degree. F. (371.degree. C.)
and, more preferably, a naphtha comprising C5-C10 hydrocarbons can
also be used.
[0019] The water component of the emulsion composition of the
instant invention comprises water that is substantially free of
salts of halides sulfates and carbonates of Group I and Group II
elements of the long form of The Periodic Table of Elements.
Distilled and deionoized water is suitable. Water generated from
the operation of the fuel cell system is preferred. Water-alcohol
mixtures can also be used. Low molecular weight alcohols selected
from the group consisting of methanol, ethanol, normal and
iso-propanol, normal, iso and secondary-butanol, ethylene glycol,
propylene glycol, butylene glycol and mixtures thereof are
preferred. The ratio of water:alcohol can vary from about 99.1:0.1
to about 20:80, preferably 90:10 to 70:30.
[0020] An essential component of the emulsion composition of the
instant invention is a surfactant mixture comprising at least one
surfactant from each of two types of surfactants. One type of
surfactant (Type-A) is selected from the group consisting of
alkoxylated alkyl alcohols, alkoxylated alkyl monoesters and
alkoxylated alkyl diesters. The other type of surfactant (Type-B)
is selected from the group consisting of alkyl polyglycerol
monoesters and alkyl polyglycerol diesters.
[0021] Type-A surfactants comprise alkoxylated alkyl alcohols,
alkoxylated alkyl monoesters and alkoxylated alkyl diesters having
respective general chemical structures 1a), 1b) and 1c) shown
below: [0022] Structure--1a):
R--(CH.sub.2).sub.n--O-(M-O).sub.m--H; [0023] Structure--1b)
R--(CH.sub.2).sub.n--CO--O--(M-O).sub.n--H and [0024]
Structure--1c)
R--(CH.sub.2).sub.n--CO--O--(M-O).sub.m--CO--(CH.sub.2).sub.n--R
[0025] where R is a methyl group, n is an integer from about 5 to
17, m is an integer from about 2 to 50, [0026] M is
CH.sub.2--CH.sub.2, CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH--CH.sub.3, CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH--(CH.sub.3)--CH.sub.2 or mixtures thereof. Preferably
in the Type-A surfactants, alkoxylated alkyl alcohols, alkoxylated
alkyl monoesters and alkoxylated alkyl diesters the alkoxylated
group is an ethoxylated group. That is, the preferred M is
CH.sub.2--CH.sub.2 in structures 1a), 1b) and 1c).
[0027] Type-B surfactants comprise alkyl polyglycerol monoesters
and alkyl polyglycerol diesters having respective general chemical
structures 2a) and 2b) shown below: [0028] Structure 2a): [0029]
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2OH and [0030] Structure 2b): [0031]
R'--CO--O--CH.sub.2--CHOH--CHOH--(CHOH--CHOH--CHOH).sub.p--CHOH--CHOH--CH-
.sub.2--O--CO--R' [0032] where R' is an alkyl group of 2 to 26
carbon atoms and p is an integer from about 0 to 15 and mixtures
thereof.
[0033] The term "alkyl" in the alkoxylated alkyl alcohols,
alkoxylated alkyl monoesters, alkoxylated alkyl diesters, alkyl
polyglycerol monoesters and alkyl polyglycerol diesters is meant to
represent saturated alkyl hydrocarbons, unsaturated alkyl
hydrocarbons or mixtures thereof.
[0034] Preferably the Type-A and type-B surfactants decompose in
the temperature range of 250.degree. C. to 700.degree. C.
Preferably at about 700.degree. C. substantially all of the
surfactant is decomposed. The total concentration of Type A plus
Type-B surfactants in the emulsion composition is in the range of
0.01 to 5-wt %. The preferred total concentration of Type A plus
Type-B surfactants is in the range of 0.05 to 1 wt %. The ratio of
Type-A to Type-B can be in the range of 1:1 to 1:4 i.e., equal
amounts of Type-A and Type-B surfactants to four times more Type-B
surfactant than Type-A surfactant. The preferred ratio of Type-A to
Type-B surfactant is 1:1 to 1:2 and more preferred is 1:1 of Type-A
to Type-B surfactants.
[0035] The ratio of hydrocarbon: water in the emulsion can vary
from 40:60 to 60:40 based on the weight of the hydrocarbon and
water. In terms of the ratio of water molecule: carbon atom in the
emulsion, the ratio can be 0.25 to 3.0. A ratio of water molecule:
carbon atom of 0.9 to 1.5 is preferred.
[0036] It is preferred to store the surfactant mixture comprising
Type-A and Type-B surfactants as a concentrated surfactant solution
in the start-up system of the fuel cell reformer. The concentrated
surfactant solution can comprise the said surfactant mixture and
hydrocarbon. Alternately, the concentrated surfactant solution can
comprise the said surfactant mixtures and water. The amount of
surfactant in the concentrated surfactant solution can vary in the
range of about 80% surfactant to about 30-wt %, based on the weight
of the hydrocarbon or water. Optionally, the concentrated
surfactant solution can comprise the said surfactant mixture in a
water-alcohol solvent. The amount of surfactants can vary in the
range of about 80 wt % to about 30 wt %, based on the weight of the
water-alcohol solvent. The ratio of water:alcohol in the
water-alcohol solvent can vary from about 99:1 to about 1:99. The
hydrocarbon, water and alcohol used for storage of the concentrated
surfactant solution are preferably those that comprise the emulsion
and described in the preceding paragraphs.
[0037] Oil-in-water-in-oil emulsions can be prepared by mixing oil,
water and a mixture of Type-A and Type-B surfactants.
Oil-in-water-in-oil emulsions generally referred to as O/W/O
emulsions are more complex than and different from simple
oil-in-water or water-in-oil emulsions hence, oil-in-water-in-oil
emulsions are normally referred to as complex oil-in-water-in-oil
emulsions. One preferred method to form the complex
oil-in-water-in-oil emulsion is to first mix required amounts of
oil and water with Type-B surfactant to from oil-in-water emulsion
and excess oil. To the oil-in-water emulsion and excess oil is then
added Type-A surfactant and the mixture mixed to from the complex
oil-in-water-in-oil emulsion. A more preferred method is to add the
concentrated surfactant solution comprising Type-A and Type-B
surfactants dissolved in hydrocarbon, water or water-alcohol
solvent to the mixture of oil and water and thereafter mixing at
low shear. Low shear mixing can be mixing in the shear rate range
of 1 to 50 sec.sup.-1, or expressed in terms of mixing energy, in
the mixing energy range of 0.15.times.10.sup.-5 to
0.15.times.10.sup.-3 kW/liter of fluid. Mixing energy can be
calculated by one skilled in the art of mixing fluids. The power of
the mixing source, the volume of fluid to be mixed and the time of
mixing are some of the parameters used in the calculation of mixing
energy. In-line mixers, low shear static mixers, low energy
sonicators are some non-limiting examples for means to provide low
shear mixing.
[0038] When Type-A and Type-B surfactants of the instant invention
are added to a hydrocarbon, preferably naphtha and distilled water
and subject to low shear mixing complex oil-in-water-in-oil
emulsions are formed. Substitution of water with water/methanol
mixture in the ratio of 80/20 to 60/40 does not alter the
emulsifying performance of the surfactants or the nature of complex
oil-in-water-in-oil emulsion that is formed.
[0039] In a preferred embodiment, the reformer of the fuel cell
system is started with a complex oil-in-water-in-oil emulsion. In
the operation of the fuel cell it is expected that the complex
oil-in-water-in-oil emulsion composition will be utilized at
start-up of the reformer and extending for a time period when a
switch to hydrocarbon and steam is made. One embodiment of the
invention is the feeding to the reformer of a fuel cell system,
first a composition comprising the emulsion composition of the
instant invention, followed by a hydrocarbon/steam composition. The
complex oil-in-water-in-oil emulsion composition allows a smooth
transition to the hydrocarbon/steam composition.
[0040] The following non-limiting examples and experiments
illustrate the invention.
EXAMPLE-1
[0041] The effectiveness of the surfactants to form emulsions is
expressed quantitatively by the reduction in interfacial tension
between the hydrocarbon and water phases. In our experiments
naphtha (a hydrocarbon mixture distilling in the boiling range of
50.degree. F.-400.degree. F.) was used as the hydrocarbon and
double distilled deionized water as the aqueous phase. Table-1
provides interfacial tension data. Interfacial tensions were
determined by the pendant drop method known in the art. Greater
than 96% reduction in interfacial tension was observed indicative
of spontaneous emulsification of the water and hydrocarbon phases
by the Type-A and Type-B surfactants. TABLE-US-00001 TABLE 1
Interfacial tension Solution (dynes/cm) Naphtha/Water 53.02
Naphtha/Water + 1 wt % 1.51 alkoxylated alkyl alcohol (structure
1a), n = 17; m = 2, M is CH.sub.2--CH.sub.2) added to naphtha
Naphtha/Water + 1 wt % 0.86 alkoxylated alkyl esters (structure
1b), n = 10; m = 6, M is CH.sub.2--CH.sub.2) added to water
Naphtha/Water 7.0 1 wt % alkyl polyglycerol mono ester (structure
2a), R' = C.sub.17H.sub.35; p = 1) added to naphtha
EXAMPLE-2
[0042] Thermogravimetry experiments on the representative Type-A
and Type-B surfactants shown in Table-1 revealed decomposition or
thermal degradation in the range of 250.degree. C. to 700.degree.
C. At about 700.degree. C. substantially all of the surfactant is
decomposed.
EXAMPLE-3
[0043] Emulsions can be characterized by their droplet sizes as
macro and micro type emulsions. A macro emulsion has dispersed
droplets that are greater than 1 micron in diameter. A micro
emulsion has droplet sizes that are less than 1 micron in diameter.
The complex O/W/O emulsions disclosed herein are preferably macro
emulsions of water-in-oil with 1 micron and less size oil droplets
dispersed in the water. Thus, we describe the preferred
oil-in-water in-oil emulsion as a micro-macro O/W/O emulsion. A
more preferred O/W/O emulsion is a micro-micro O/W/O emulsion. By
using dyes to color the hydrocarbon and water, optical microscopy
enables determination of the type of emulsions by direct
observation. An O/W/O emulsion will exhibit oil droplets dispersed
in water and said oil-in-water droplets dispersed in oil. The sizes
of the dispersed droplets of oil and water can be determined by
microscopy using a calibration scale.
EXAMPLE-4
[0044] An oil-in-water emulsion has water as the continuous phase
whereas; a water-in-oil has oil as the continuous phase. The
preferred oil is a hydrocarbon. An O/W/O emulsion is oil
continuous. Conductivity measurements are ideally suited to
determine the phase continuity of the emulsion. A water continuous
emulsion will have conductivity typical of the water phase. A
hydrocarbon continuous emulsion will have negligible conductivity.
An O/W/O emulsion with oil continuity will have conductivity
corresponding to the oil or hydrocarbon.
EXAMPLE-5
[0045] 0.5 g of alkyl polyglycerol Type-B surfactant (Structure
2a), R'=C17; p=1) (sold by Abietic Corporation as Caprol 3GO) was
added 61 g isooctane (dyed orange) and 39 g water (dyed blue) and
mixed using a Fisher Hemetology/Chemistry Mixer Model 346. Mixing
was conducted for 5 minutes at 25.degree. C. The mixture was
allowed to stand for 30 minutes. An oil-in water emulsion with
excess oil splitting out was observed. To this mixture was added
0.6 g of polyethylene glycol 600 monolaurate (sold by Henkel
Corporation as Emerest 2661 (structure 1b), n=10; m=6) and 0.4 g of
polyethylene glycol 200 dilaurate (sold by Henkel Corporation as
Emerest 2622 (structure 1c), n=10; m=2) and the mixture mixed again
as described above. A milky white emulsion was observed with no
phase separation even after 6 hours of standing. Using a Leitz
optical microscope the emulsion was characterized as an O/W/O
emulsion. Additionally it was characterized as a macro-macro O/W/O
emulsion as described in Example-3. The conductivity of water was
recorded as 47 micro mho, naphtha as 0.1 micro mho and the emulsion
8 micro mho confirming the oil continuity as described in
Example-4.
EXAMPLE-6
[0046] The emulsion of example-5 was stable for at least 6 hours at
25.degree. C. in the absence of shear or mixing. In comparison, in
a control experiment wherein the stabilizing Type-A and Type-B
surfactants were omitted and only the hydrocarbon and water were
mixed, the resulting emulsion phase separated within 5 seconds upon
ceasing of mixing. Yet another unexpected feature of the emulsions
of the instant invention is that when the emulsions were frozen or
cooled to -54.degree. C. they solidified and when thawed or heated
to +50.degree. C. the emulsions liquefied and retained their
stability and complex oil-in-water-in-oil nature. This freeze-thaw
stability property is unique and in sharp contrast to simple O/W or
W/O emulsions that phase separate upon freezing and thawing.
[0047] Using stable complex oil-in-water-in-oil emulsions comprised
of hydrocarbon, water and mixtures of Type-A and Type-B surfactants
of the instant invention has reformer performance advantages and
enhancements compared to using unstable emulsions of hydrocarbon
and water in the absence of stabilizing surfactants as disclosed in
U.S. Pat. No. 5,827,496. The stability, complex oil-in-water-in-oil
characteristic and the observed unique freeze-thaw stability
property are at least three distinguishing features of the emulsion
composition of the instant invention that can result in unexpected
enhancement in reformer performance compared to conventional simple
emulsions.
* * * * *