U.S. patent number 3,873,271 [Application Number 05/429,973] was granted by the patent office on 1975-03-25 for method and apparatus for detecting free water in hydrocarbon fuels.
This patent grant is currently assigned to Exxon Research and Engineering Company. Invention is credited to John F. Coburn, Jr., Alfred H. Miller, Dale A. Young.
United States Patent |
3,873,271 |
Young , et al. |
March 25, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Method and apparatus for detecting free water in hydrocarbon
fuels
Abstract
A method and apparatus for detecting the presence of free water
in hydrocarbons in which the water reacts with freshly ground
fuchsia dye and calcium carbonate having an average particle size
of less than 10 microns and a surface area of 5-8 square meters per
gram. The reagents are prepackaged in an evacuated glass vial. A
sample of the hydrocarbon is admitted to the interior of the
evacuated vial by a cannula mounted in a special receptacle adapted
to receive the vial. The sample is drawn into the vial by the
vacuum and reacts with the dye and carbonate to indicate the
presence or absence of free water in the hydrocarbon.
Inventors: |
Young; Dale A. (Basking Ridge,
NJ), Miller; Alfred H. (Somerset, NJ), Coburn, Jr.; John
F. (Cranford, NJ) |
Assignee: |
Exxon Research and Engineering
Company (Linden, NJ)
|
Family
ID: |
23705522 |
Appl.
No.: |
05/429,973 |
Filed: |
January 2, 1974 |
Current U.S.
Class: |
436/40; 436/165;
206/524.8 |
Current CPC
Class: |
G01N
31/222 (20130101); G01N 33/2847 (20130101) |
Current International
Class: |
G01N
31/22 (20060101); G01N 33/26 (20060101); G01N
33/28 (20060101); G01n 033/22 (); G01n 033/18 ();
G01n 021/06 () |
Field of
Search: |
;23/259,253,230 ;252/408
;206/47A |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Serwin; R. E.
Attorney, Agent or Firm: Wells; Harold N. Dimmick; Byron
O.
Claims
What is claimed is:
1. An apparatus for detecting the presence of free water in
hydrocarbons which comprises in combination:
a. an evacuated tube containing chemicals sensitive to the presence
of said free water, said tube being closed at one end and sealed at
the other end by a pierceable closure to maintain said vacuum;
b. a receptacle means for receiving said tube of (a);
c. a cannula having an inlet end and an outlet end mounted on said
receptacle and disposed to pierce said closure when said tube is
inserted into said receptacle, thereby providing a conduit into the
evacuated interior of said tube.
2. The apparatus of claim 1 further comprising a container for a
sample of said hydrocarbons adapted to receive said tube receptacle
means whereby said cannula is enabled to admit hydrocarbons from
said container into said tube as urged by the vacuum therein.
3. The apparatus of claim 1 wherein said receptacle means is a
cylidner open at both ends and having a transverse partition
intermediate said ends for mounting said cannula whereby said
cannula serves as a passageway through said partition.
4. The apparatus of claim 3 wherein one of said cylinder ends
extends beyond the inlet end of said cannula, thereby preventing
said cannula from touching the bottom of said container when said
receptacle is inserted therein.
5. The apparatus of claim 4 wherein the cylindrical wall adjacent
the inlet end of said cannula contains openings in the sides
thereof to admit said hydrocarbon sample when said receptacle is in
contact with the bottom of said container and thereby to prevent
sampling from the bottom of said container.
6. The apparatus of claim 1 wherein said chemicals for detecting
the pressure of free water comprise:
a. a finely-divided anhydrous solid having a surface area of
5-8m.sup.2 /gm selected from the group consisting of calcium
carbonate, barium carbonate, barium sulfate, magnesium carbonate,
and combinations thereof;
b. freshly ground fuchsia dye having a particle size between 44 and
74 microns.
7. The apparatus of claim 6 wherein the weight ratio of said solid
to fuchsia dye is within the range of 20:1 to 10,000:1.
8. A method for detecting free moisture in hydrocarbons
comprising:
a. obtaining a sample of said hydrocarbons in a container;
b. placing in said container a receptacle for receiving a means for
withdrawing a portion of said sample, said receptacle being adapted
to receive an evacuated sample vial containing moisture sensitive
chemical reagents, said sample vial being closed at one end and
sealed at the other end with a pierceable closure;
c. piercing said closure with a cannula mounted on said receptacle
and admitting a portion of said hydrocarbon through said cannula
into said vial as urged by the vacuum therein;
d. reacting said hydrocarbon portion drawn into said vial with said
moisture sensitive chemical reagents and thereby producing a color
proportional to the free water present in said hydrocarbon
portion;
e. comparing the color produced in said hydrocarbon portion drawn
into said vial with known standards and thereby determining the
amount of free water contained in said hydrocarbon portion.
9. The method of claim 8 wherein said moisture sensitive chemicals
comprise:
a. a finely-divided anhydrous solid having a surface area of
5-8m.sup.2 /gm and selected from the group consisting of calcium
carbonate, barium carbonate, barium sulfate, magnesium carbonate,
and combinations thereof;
b. freshly ground fuchsia dye having a particle size between 44 and
74 microns and in a weight ratio to said solid within the range of
1:20 and 1:10,000.
10. A packaged liquid useful for the detection of free water in a
liuqid hydrocarbon which comprises a mixture of:
a. a finely divided anhydrous solid having a surface area of from 5
to 8 square meters per gram, said solid being selected from the
group consisting of calcium carbonate, barium carbonate, barium
sulfate, magnesium carbonate, and mixtures thereof; and
b. freshly ground fuchsia dye having a particle size between 44 and
74 microns;
the weight ratio of said dye to said solid being within the range
of 1:20 to 1:10,000;
said mixture having been both prepared and sealed off from contact
with moisture and air at the time of grinding said dye.
11. Packaged composition as defined by claim 10 wherein said
mixture is maintained in a vacuum.
Description
BACKGROUND OF THE INVENTION
Detection of free (undissolved) water in hydrocarbon fuels is of
particular importance with regard to turbojet fuels for aircraft
which, operating at high altitudes, are subject to fuel system
plugging by ice crystals. To minimize this hazard, it is normal
practice to inspect all fuel for the presence of free water as it
is being loaded into aircraft. In general, less than about 10 parts
per million of free water is satisfactory, but 30 parts per million
is too high. Special filter separators are used for removing free
water from jet fuels, but testing of individual cargoes is
necessary to check their performance. U.S. Pat. No. 3,505,020
disclosed an improved composition for reacting with free water
present in jet fuels and producing a pink color which indicates the
presence of excessive free water. That composition comprised a
small amount of fuchsia dye (3
amino-7(dimethylamino-5-phenylphenazinium chloride) mixed with a
major portion of a finely divided anhydrous solid which was
selected from the group consisting of calcium carbonate, barium
carbonate, barium sulfate, magnesium carbonate, and combinations
thereof. The preferred anhydrous solid for the water detection
composition is calcium carbonate.
In the prior art, it was disclosed that the dye particles should
have a diameter less than 200 microns in order to be effective and,
in particular, a weight average particle size of 44 microns was
preferred. The particularly preferred composition would limit the
dye particle size to under 74 microns with about 40-60 wt. % of the
particles having a diameter of less than about 44 microns. The dye
is conventionally used in the textile industry and is commonly
referred to as Methylene Violet, Basic Violet Five, Color Index
50205, fuchsia and so forth. A further description of the dye may
be found in Color Index, the American Association of Textile
Chemists and Colorists, second edition (1956), at pages 1,635 and
3,414.
Also in the prior art, it was disclosed that the anhydrous solid
particles should be less than 10 microns in size and technical
grade crystalline powder.
In addition, the portions of anhydrous solid to dye would range
between 20 and 10,000 and preferably between 50 and 2,000 parts by
weight. One part by weight of dye to about 400 to 1,000 parts by
weight of anhydrous solid was particularly preferred.
The reagent mixture would be added to a fuel sample, about 0.05 to
2 grams of the mixture to 100 milliliters of hydrocarbon fuel. The
preferred range would be between 0.1 and 0.5 gram of mixture to
each 100 milliliters of hydrocarbon.
As indicated in the prior art patent, this mixture gives
satisfactory results. However, experience has shown that the method
is subject to some practical difficulties. It has been heretofore
typical to package the mixed dye and solids in closed containers of
a size suitable for testing of individual fuel cargoes. It has been
found that deterioration of the reagents occurs over a period of
time and shelf life is limited. Accordingly, results after an
extended period of storage may be erratic. In addition, it has been
found that the composition of the mixture had to be adjusted before
being placed into the closed containers in order to provide a
uniform response. The foregoing disadvantages have been overcome by
the method and apparatus of the present invention.
SUMMARY OF THE INVENTION
An improved composition for detection of free water in hydrocarbon
fuels is obtained by introducing product quality standards for both
the anhydrous carbonate and the fuchsia dye not heretofore known.
It has been found that the fuchsia dye is more sensitive if it is
finely ground immediately prior to being packaged rather than
simply being screened and then packaged from the material as
received from the supplier. As to the anhydrous carbonate, it has
been found that, not only particle size, but effective surface area
of the carbonate is important in obtaining a suitable sensitivity.
In particular, effective surface areas in the range of 5 to 8
square meters per gram have been found to be preferred for this
use. Surface areas greater than this range are generally not
sensitive enough and surface areas smaller than the recommended
range are too sensitive and neither will produce the desired
results.
In the present invention, both carbonate and dye are prepackaged in
an evacuated glass vial. The glass vial serves two functions:
first, to protect the quality of the chemical reagents used and
second, to provide a means for drawing a fuel sample into the vial
for reaction with the reagents without ever exposing them to
moisture in the air. In order to accomplish the introduction of
fuel into the evacuated vial, a special receptacle is provided,
mounting a small cannula which pierces a flexible closure at one
end of the vial and provides a passageway for the fuel.
In field use, a small sample of fuel is drawn from a fueling line
into a small container as an aircraft is being loaded, the
receptacle is placed inside the container so that the open end of
the cannula is suspended above the bottom of the fuel container,
and thereafter the glass vial is inserted into the receptacle. The
cannula punctures the flexible closure provided at one end of the
vial, thereby providing a passageway between the fuel in the
container and interior of the vial. The fuel is drawn in by the
vacuum present within the container where it reacts with the
reagents, producing a pink color should an excessive amount of free
water be present, or remaining clear if less than 10 ppm free water
is present.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded view of the apparatus of the invention prior
to its assembly.
FIG. 2 illustrates the apparatus of FIG. 1 in the assembled
condition immediately prior to admitting a fuel sample into the
glass vial.
FIG. 3 is a vial according to the invention after having received a
fuel sample in the manner indicated in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates the three main parts of the apparatus. A small
cylindrical container 10 is provided for receiving a small sample
of fuel from the loading line. The container 10 has no special
requirements except that it should contain sufficient sample to
fill the vial 12 which is to be discussed hereinafter. The
container 10 should preferably be made of a clear plastic material
in order to avoid breakage and to permit observation as to the
visual quality of the fuel drawn in, that is, whether it is clear
or cloudy and whether it contains any suspended solids. Either of
these conditions may indicate a failure of the fuel filter
separator which would be located upstream of the sampling
point.
The receptacle 14 consists of a cylindrical tube 16 with a flange
18 at one end for convenience in handling and open at either end.
Mounted within the tube 16 is a transverse disc 20 which supports a
cannula 21 mounted thereon. The cannula 21 provides a narrow
passageway and, being blunt at one end 21a where fuel is drawn in
and pointed at the opposite end 21b for piercing the flexible
closure of the glass vial 12. A slot (or other perforation) is
provided in the side of the receptacle 14 below disc 20 in order to
permit fuel to pass freely into the interior of the tube 16 and be
drawn into the blunt end 21a of the cannula. It is preferred that
the cannula 21 not touch the bottom of the container in order that
any extraneous materials which might be drawn in are not admitted
to the vial and, therefore, the blunt end 21a of the cannula 21 is
positioned approximately one-half inch above the bottom of the
receptacle 14.
The improved reagents are enclosed in an evacuated glass vial 12
which is sealed at one end by a flexible closure 22. This closure
22 serves at least two purposes: first, to prevent breaking of the
vacuum which was created in the tube at the time the reagents were
sealed inside it and second, to provide a means for ready access of
fuel to the reagents when the test is made without ever exposing
the reagent to the atmosphere. Use of an evacuated tube permits not
only protection of the quality of the reagents, but provides for
taking the required amount of fuel sample. In addition, an
indication of the quality of the reagents is obtained, for should
the vacuum be lost, no fuel sample would be drawn through the
cannula, indicating that the quality of the reagents was suspect
and should not be used.
In general, the particle size of the fuchsia dye is essentially the
same as that indicated in the prior art, but it has been found that
freshly ground dye is particularly sensitive and that the
sensitivity can be retained by packaging under vacuum. Table I
illustrates the significant improvement in sensitivity of the dye
when it is freshly ground as compared with the as-received
material.
TABLE I ______________________________________ Free Water Content
10 ppm (pass) 40 ppm (fail) Color Scale Rdg. Color Scale Rdg. Sieve
only 0 1/2 (white) (trace pink) Fresh ground 1/2 3 (trace pink)
(dark pink) ______________________________________
It will be noted that when as received dye is only sieved that only
a small color change can be found, whereas the same dye when
freshly ground has a much wider color change, which is easily seen
and permits some interpolation between 10 ppm and 40 ppm free
water. This greater sensitivity can be maintained if the dye is
kept sealed and away from moisture and air as in the evacuated vial
of the invention. Use of an inert gas in filling the vials will
further improve the stability of the dye sensitivity.
As has been mentioned heretofore, it was necessary to empirically
adjust the relative quantities of dye and anhydrous solid in order
to provide a uniformity of response. It has been found that this
irregularity in response of the as received materials was due, not
to the particle size which was heretofore thought to be important,
but rather to the effective surface area of the solid. It has been
found that a relatively low surface area in the range of 0.1 to 4.5
square meters per gram is too sensitive and should not be used.
Also, a relatively high surface area in the range of 8.5-10 square
meters per gram or more is insensitive and should also not be used.
While 5-8m.sup.2 /gm is the preferred range, small deviations
outside this range - ca. down to 4.5 or up to 8.5m.sup.2 /gm could
be used. However, added adjustments to the dye to carbonate ratios
may be necessary at these outer limits and the desired sensitivity
response is bordering on the too sensitive and/or the insensitive
areas.
It has been found that a preferred critical range of the order of
5-8 square meters per gram provides good sensitivity and permits
the accurate proportioning of dye to solid. The relative
sensitivity to surface area of the solid and the merits of
restricting the surface area of the solid used to the recommended
range will be evident from the data given in Table II below.
TABLE II ______________________________________ CaCO.sub.3 Free
Water Content Surface 10 ppm (pass) 40 ppm (fail) Area Color Scale
Color Scale Comment m.sup.2 /gm Rdg. Rdg.
______________________________________ 0.4 3 (dark pink) 3 too
sensitive 1.6 23/4 3 too sensitive 2.78 2 (pink) 23/4 too sensitive
6.5 1/2 (trace pink) 21/2 suitable sensitivity 8.53 1/2 21/2
suitable sensitivity 9.95 0 (white) 1 (light pink) insensitive
______________________________________
FIG. 2 shows the principal components of the invention in assembled
form. Fuel 23 has been placed inside the cylindrical container 10
in a quantity sufficient to more than fill the vial, but leaving
some residual amount in the container after the vial has been
filled. The receptacle 14 has been placed within the container 10
where it rests on the bottom and fuel is free to pass through the
slot 16a or other openings placed in the side of the receptacle 14.
The evacuated vial 12 containing the improved reagents 24 has been
placed within the receptacle 14 with the point of the cannula 21b
resting lightly against the flexible closure 22.
It will be apparent that once the indicated downward motion is
made, the cannula 21 will pierce the flexible closure 22 and admit
fuel, assuming vacuum within the glass vial, into the vial 12 for
reaction with the improved reagents 24. Once this downward motion
has taken place, fuel rushes through the cannula 21 into the glass
vial 12 which fills extremely rapidly owing to the presence of the
vacuum present inside and quickly mixing the desired amounts of
reagent and fuel.
In FIG. 3, a vial 12, after it has received a fuel sample, has been
withdrawn from the receptacle, the flexible closure 22 sealing
behind the cannula 21 as it is withdrawn, thereby retaining the
fuel sample therein. The vial 12 may be shaken lightly to mix the
reagents and fuel although this is essentially completed by the
rapid inrush of fuel as it displaces the vacuum. After a short
period, approximately 2 minutes, the color of the dye has developed
if the fuel contains free water in excess of 10 parts per million.
In general, the quantities of reagent and the sensitivity of the
reagents are adjusted so that no color change develops when the
free water content is 10 parts per million or below but a pink
color develops above that level which may be compared with a known
standard. If an excessively dark pink color has developed during
the 2-minute period, indicating that more than 30 ppm is present,
the fuel must be rejected and reprocessed in order to remove free
water present therein. Such standards were used in the results
shown in Tables I and II.
The foregoing test is primarily used in the field as a go/no-go
test in aircraft fueling. It is within the scope of the invention,
however, to package quantities of dye in measured quantities so as
to permit a series of such tests to make a more accurate
determination of the precise level of water contained. This may be
necessary to satisfy both military and commercial standards and to
closely measure the quantity of water when a go/no-go test is
insufficient.
The foregoing description of the preferred embodiments is for
illustration of the invention only and should not be deemed to
limit the scope thereof which is defined by the claims which
follow.
* * * * *