U.S. patent number 3,635,677 [Application Number 05/033,537] was granted by the patent office on 1972-01-18 for glycol detection in oil.
This patent grant is currently assigned to Cities Service Oil Company. Invention is credited to Harry N. Drake, Jr., Leo A. Fabbro, Ronald E. Fanucci.
United States Patent |
3,635,677 |
Drake, Jr. , et al. |
January 18, 1972 |
GLYCOL DETECTION IN OIL
Abstract
A sample of engine oil is taken from a crankcase and introduced
into an aqueous oxidizing solution. The mixture is shaken and
allowed to separate into the oil and aqueous phases. A sample of
the aqueous phase is then introduced onto a chromogenic aldehyde
reagent adsorbed on a suitable supporting media. The sample and
reagent are contacted and the presence or absence of glycol in the
engine oil is observed by chromogenic determination. The method
allows the observation of as little as several parts per million of
glycol in oil.
Inventors: |
Drake, Jr.; Harry N.
(Yardville, NJ), Fabbro; Leo A. (Morrisville, PA),
Fanucci; Ronald E. (Yardville, NJ) |
Assignee: |
Cities Service Oil Company
(Tulsa, OK)
|
Family
ID: |
21870978 |
Appl.
No.: |
05/033,537 |
Filed: |
April 30, 1970 |
Current U.S.
Class: |
436/60; 436/131;
436/178 |
Current CPC
Class: |
G01N
33/2888 (20130101); G01N 31/22 (20130101); Y10T
436/255 (20150115); Y10T 436/203332 (20150115) |
Current International
Class: |
G01N
33/26 (20060101); G01N 33/28 (20060101); G01N
31/22 (20060101); G01n 033/26 (); G01n
021/06 () |
Field of
Search: |
;23/253TP ;252/408 |
Other References
sawicki et al., "The 3-Methyl-2-Benzothiazolone Hydrazone Test,"
Analytical Chemistry, Vol. 33, No. 1, January 1961 pp. 93-96. .
Hauser et al., "Increasing Sensitivity of
3-Methyl-2-Benzothiazolone Hydrazone Test for Analysis of Aliphatic
Aldehydes in Air," Analytical Chemistry, Vol. 36, No. 3, March
1964, pp. 679-681..
|
Primary Examiner: Wolk; Morris O.
Assistant Examiner: Serwin; R. E.
Claims
Therefore, we claim:
1. A method for the detection of glycol in oil comprising the steps
of:
a. introducing a sample of the oil to be tested into an aqueous
solution of an oxidizer which preferentially oxidizes glycol to an
aldehyde;
b. mixing the oil and aqueous solution containing the oxidizer;
c. separating the resulting aqueous and oil phases; and
d. contacting a sample of the resulting aqueous phase with a
chromogenic aldehyde reagent selected from the group consisting of
3-methyl-2-benzothiazolinone hydrazine hydrochloride monohydrate,
salicyhalhydrazone, p-nitrobenzalhydrazone,
2-hydrazinobenzothiazole, and
2-hydrazinobenzothiazole-4-nitrobenzenediazonium fluoborate, said
reagent being adsorbed on a support medium.
2. The method of claim 1 in which the oil is acidic.
3. The method of claim 2 in which the chromogenic aldehyde reagent
is 3-methyl-2-benzothiazolinone hydrazone hydrochloride
monohydrate.
4. The method of claim 3 in which
a. the oxidizer is selected from the group consisting of sodium
periodate, potassium periodate, hydrogen peroxide, sodium
perborate, ceric nitrate, ceric sulfate; and lead
tetra-acetate.
5. The method of claim 4 in which the aldehyde reagent support
media is selected from the group consisting of silica gel,
anhydrous alumina, diatomaceous earth, firebrick and polymeric
material.
6. The method of claim 4 in which:
a. the oxidizer is about a 0.01 to 1.0 molar aqueous solution of
sodium periodate;
b. the aldehyde reagent support media is particulate polyethylene;
and
c. the chromogenic aldehyde reagent is prepared by adsorbing
3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate on
polyethylene.
7. The process of claim 6 in which:
a. the oil sample and aqueous phase are mixed for about 1 to about
2 minutes;
b. the aqueous phase and chromogenic aldehyde reagent are mixed for
about 5 to about 10 seconds; and
c. the color is allowed to develop for 15 minutes.
8. The process of claim 7 in which the glycol is ethylene
glycol.
9. The process of claim 7 whereby the detection takes place in a
syringe which contains the chromogenic aldehyde reagent MBTH on
particulate polyethylene.
Description
BACKGROUND OF THE INVENTION
The present invention relates to the indication of ethylene glycol
antifreeze contamination in crankcase oil. More particularly, the
invention discloses a method for the detection of ethylene glycol
contaminates in small quantities in engine oils by a simple
oxidation and an aldehyde chromogenic test.
The presence of contaminants in engine oil may have derogatory
effects upon the performance of the engine and its internal parts.
The cleanliness of internal parts of an engine depends upon the
equilibrium between the oil-polluting substances and the remaining
effective oil-lubricating molecules. Various methods are available
for testing engine oils as to their effective lubrication and
cleansing properties upon engine parts. Both laboratory and field
tests have shown that ethylene glycol is one of the most hazardous
contaminants which may enter engine oil. The ethylene glycol is
derived from the antifreeze added to the engine's cooling system.
Through abusive wear of the engine and failure of sealing members
within the engine's parts, ethylene glycol may enter the crankcase
and lubricating system of the engine and cause pasty emulsions
which may plug oil filters, pump screens, oil feedlines and
passages within the engine. The ethylene glycol also presents a
problem in the engine combustion chamber where temperatures are
high enough to convert the glycol into a varnishlike substance
which causes valves to stay open, valve lifters to bend in their
guides, and piston rings to stick in their grooves. Consequences of
the above-mentioned malfunctions of the engine may result in
extreme engine abuse, engine lifetime diminishment and eventual
engine failure. The elimination of ethylene glycol in the crankcase
oil is a matter of extreme importance in maintenance of the engine
in that no engine oil additives are available on the market to
combat the engine seizure properties of glycol.
The most common method used to combat ethylene glycol contamination
in engine oil and subsequent varnishing of engine parts is to
change the engine oil periodically so that the concentration of
ethylene glycol never exceeds a minimal quantity which would damage
the engine's moving members. What is required is an ethylene glycol
testing method which will indicate the concentration of ethylene
glycol after certain periodic intervals of engine-hour usage such
that the engine may be serviced and the oil changed when ethylene
glycol reaches the maximum tolerable concentration. This ethylene
glycol test method must include a procedure by which servicing
personnel may periodically check engine oil for glycol
concentration without a rigorous analytical technique being
required. The test must, therefore, be simple enough for layman's
usage and also provide positive identification of the ethylene
glycol content. To date, no suitable ethylene glycol test method is
available for service station or industrial usage. Therefore, an
ethylene glycol detection method which may be taught to untrained
personnel, easily used, and which is not time consuming is
desirable.
It is an object of the present invention to provide a method by
which the ethylene glycol content in the crankcase oil of an
internal combustion engine may be determined.
It is still another object of the present invention to provide a
method by which the ethylene glycol content of the crankcase oil
may be determined by usage of a simplified testing procedure which
may be taught to untrained personnel.
It is still another object of the present invention to provide a
method for ethylene glycol detection which utilizes stabilized
chemical compounds which will have a long term usage and which will
not deteriorate.
With these and other objects in mind, the present invention is
hereinafter presented with particular reference to the following
description.
SUMMARY OF THE INVENTION
The objects of the present invention are achieved by a method for
the detection of ethylene glycol in oil. The method involves
introducing a sample of the oil to be tested into an aqueous
solution of water and an oxidizer which preferentially oxidizes
ethylene glycol to formaldehyde. The oil and aqueous solution
containing the oxidizer are thoroughly mixed and the mixed solution
is allowed to separate into the aqueous and oil phases. Some of the
aqueous phase is then mixed with a chromogenic formaldehyde reagent
adsorbed on a suitable supporting media to determine the presence
of formaldehyde and thereby indicate the presence of ethylene
glycol in the original oil. Suitable oxidizers include sodium
periodate, potassium periodate, hydrogen peroxide, sodium
perborate, ceric nitrate, lead tetra-acetate and ceric sulfate.
Suitable chromogenic formaldehyde reagents include
3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate,
salicylalhydrazone,
p-nitrobenzalhydrazone,2-hydrazinobenzothiazole,
2-hydrozinobenzothiazole-4-nitrobenzenediazonium fluoborate, etc.,
adsorbed on supporting media which may be any suitable material,
such as silica gel, anhydrous alumina, diatomaceous earth, or
firebrick or polymeric material. Suitable polymeric material
includes polyethyline, nylon, etc. and is preferably present in
particulate form such as chips or powder.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a method for the detection of ethylene
glycol trace contamination in engine oils. The method comprises an
analytical technique for chromogenically determining the presence
of ethylene glycol in the engine oil. The method consists of
sampling the engine oil and mixing the sample of engine oil with an
aqueous solution containing an ethylene glycol oxidizer. After the
mixing step, the aqueous and oil phases are allowed to separate
such that the aqueous phase may be sampled and introduced into a
chromogenic formaldehyde reagent absorbed on a supporting
media.
Most oxidizers which will transform glycols into aldehydes may be
used in the present invention, however, the oxidizer must have the
characteristic of not tainting the aqueous solution such that the
colormetric determination may not be used. Therefore, standard
oxidizers such as potassium permanganate and ferric sulfate would
not be suitable for the present invention as they would leave a
distinct color in the aqueous phase which would conceal the color
change of the colormetric formaldehyde indicator. Suitable
oxidizers for use in practicing the invention include sodium
periodate, potassium periodate, hydrogen peroxide, sodium
perborate, ceric nitrate, ceric sulfate and lead tetra-acetate. In
particular, the sodium and potassium periodates are preferred
oxidizers which selectively oxidize ethylene glycol to the
formaldehyde without the presence of byproduct reactions which form
other oxidized compounds. In most cases, the oxidizer, in
particular the periodate solution, will be about 0.01 to 1.0 molar
concentration. By this procedure, an economic quantity of the
oxidizer is utilized and strong oxidation does not take place. In
most instances, between about 1 and about 10 milliliters of
oxidizing solution per milliliter of oil sample will be sufficient
to fully oxidize the ethylene glycol contained in an oil sample
withdrawn from an engine crankcase.
In the field application of a preferred embodiment of the present
invention generally 5 to 10 milliliter oil samples are withdrawn
from the engine oil by use of a piece of tubing or by a
syringe-type instrument introduced into the crankcase through the
dip tube. The engine oil is withdrawn and dropped into the solution
of oxidizer held in a container. The container is then sealed and
vigorously shaken. After the mixing has occurred, the solution is
allowed to separate into a lower aqueous phase and an upper oil
phase. The aqueous phase contains the oxidized ethylene glycol or
the resultant formaldehyde which may be withdrawn to test the
amount of aldehyde present.
Many chromogenic formaldehyde reagents exist, but the reagent used
must be highly specific for formaldehyde or other aldehydes and not
be influenced by other substances which may be oxidized or may be
contained as additives or original components of the engine oil.
Many aldehyde reagents, which are specific to aldehyde indication,
may be utilized in accordance with the present invention such as
3-methyl-2-benzothiazolinone hydrazine hydrochloride monohydrate,
salicylalhydrazone, p-nitrobenzalhydrazone,
2-hydrazinobenzothiazole,
2-hydrazinobenzothiazole-4-nitrobenzenediazonium fluoborate, etc.
Oil samples tested in accordance with the present invention,
especially crankcase oils, are usually acidic by nature. The
aldehyde reagent used must therefore be able to respond to the
presence of formaldehyde in an acidic media when testing these
acidic oils. This criterion eliminates a number of excellent
aldehyde reagents as they will not perform under acidic conditions.
Indicators such as 2-hydrazinobenzothiazole and
2-hydrazinobenzothiazole-4 -nitrobenzenediazonium fluoborate are
excellent for the detection of aliphatic, aromatic, and
heterocyclic aldehydes; however, these indicators require an
alkaline media and are not suitable for practicing the preferred
embodiment of the invention wherein the oil sample tested in an
acidic crankcase oil.
Another criteria for preferred aldehyde indicators is the
stabilization of the coloring test after introduction of the
formaldehyde into the chromogenic formaldehyde reagent. The color
should remain stable for several minutes so that the operator may
observe the reagent color against predetermined charts or a blank
for a quantitative determination of the amount of ethylene glycol
present in the original sample. A study has been made by Sawicki,
et al. Analytical Chemistry, Vol. 33, No. 1, Jan. 1961, p. 93, and
has indicated that 3-methyl-2-benzo-thiazolinone hydrazine
hydrochloride monohydrate (MBTH) is an excellent reagent for the
determination of formaldehyde and this is a preferred reagent in
practicing the present invention. We have found in particular that
the application of the above-mentioned reagent adsorbed on silica
gel, polyethylene chips, or other chromatographic supports has
proven to be a stable reagent which may be kept for a long period
of time and ultimately used in the field. Silica gels of wide mesh
sizes may be used. In particular, the mesh size range of 28 to 200
mesh has proven favorable. Polyethylene in chipped or powered form
gives an excellent support. Other chromatographic supports which
may be used in the present invention may be selected from the group
consisting of silica gel, anhydrous alumina, diatomaceous earth,
and firebrick. Although it is preferred to use silica gel, or
polyethylene chips the other chromatographic supports have proven
satisfactory. As with the oxidizing agents, the chromatographic
supports used to adsorb the formaldehyde reagent thereto should be
translucent or opaque, such that any color imparted from the
support will not interfere with the chromogenic test. Therefore, it
is a necessary criterion of the chromogenic support that it not
have an interfering background color which would interfere with the
color test.
In the preparation of a chromogenic reagent, which would generally
be unstable on exposure to air and unsuitable for the determination
of aldehydes contained in samples, the chromogenic reagent
generally is dissolved in a solvent. In most applications, the
solvent used for the solution makeup would be deionized or
distilled water. After the solution is formed it is introduced onto
a suitable support medium which will adsorb the chromogenic
reagent. An inert atmosphere is maintained about the support medium
during the adsorption process so that no oxidation of the
chromogenic reagent will occur during its preparation. The
adsorbing step may be enhanced by simultaneously drying the
chromogenic reagent on the support medium to strip off the solvent.
This drying process may take from 5 minutes to an hour depending on
the amount of solution introduced onto the adsorbing medium. As
mentioned, a preferred reagent to be used is
3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate.
The MBTH solution in deionized water would generally be a 0.5 to 5
percent solution.
The inert atmosphere is maintained by introducing an inert gas such
as nitrogen into the column of support medium with the MBTH
adsorbed thereon and the solvent thereabout. The column may consist
of a graduated cylinder or buret. A nitrogen containing cylinder
may be connected to the column and nitrogen transferred
therethrough so that inert atmosphere is continuously in contact
with the MBTH and support medium. The drying procedure utilizes
temperatures below about 100.degree. C. so that no destructive
degradation of the MBTH takes place during the adhesion process.
The MBTH in effect forms a complex with the support material so
that after it is adsorbed on the active surfaces of the silica gel,
polyethylene chips, or other support medium used, it will remain
stable and will not be subject to attack by oxygen in the
atmosphere about it. It has been found that 0.01 to 10 grams of
chromogenic formaldehyde reagent adsorbed for each 10 grams of
support material such as silica gel, preferably 0.005 to 1 gram per
gram, provides sufficient reagent to give the results desired.
In a preferred embodiment of the present invention, chromogenic
reagent contained on the support is introduced into a container
such as a hypodermic syringe. It has been found that about 2
milliliters in a 5 milliliter syringe is an appropriate quantity. A
sample of the aqueous phase is withdrawn from the container holding
the oil and aqueous phases onto the chromogenic reagent in the
syringe by means of the syringe plunger. Generally, from about 0.5
to about 2.0 milliliters of aqueous phase are used per milliliter
of chromogenic reagent. The reagent will turn blue within 15
minutes if ethylene glycol is present in the oil.
In practicing the invention using sodium periodate oxidizer and
MBTH reagent, the reactions occurring may be summarized as follows.
Sodium periodate oxidizes the ethylene glycol to formaldehyde. The
aldehyde then contained in the aqueous phase is withdrawn and
placed on the MBTH chromogenic reagent. The aldehyde reacts with
the MBTH to form the azine. In addition, some MBTH is oxidized to a
reactive cation which combines with the azine to form a blue dye.
Therefore, a normally translucent chromogenic formaldehyde reagent
contained on a support will turn a dark blue if ethylene glycol is
present. A blank solution may be run by taking an uncontaminated
sample of the oil, mixing it with periodate solution, and then
introducing the aqueous phase, which is separated, onto the
chromogenic formaldehyde reagent. The reagent turns green when
absorbed on silica gel or red when absorbed on polyethylene to give
a blank test to indicate that no ethylene glycol is present. Shades
of color between the blank color and blue indicate increased
concentration of ethylene glycol. A color chart may be presented to
quantitatively show the relative amount of ethylene glycol in parts
per million which was contained in the engine oil. With this method
the operator knows at any time in the ethylene glycol contamination
process what the ethylene glycol concentration is and when the oil
must be changed. Each time the oil is checked the reading is
recorded until a maximum allowable concentration of ethylene glycol
in the engine oil is experienced. The oil is then changed and the
process repeated. The procedure is formulated below for the
reaction of formaldehyde with 3-methyl-2-benzothiazolinone
hydrazone , to form the azine, ; oxidation of to a reactive cation,
, and formation of the blue cation, . ##SPC1##
A preferred embodiment of the present invention is a method whereby
the oil sample for a given test is withdrawn in a ratio in
accordance with the stated quantities from the crankcase by means
of a plastic syringe, of about 10-milliliter capacity, equipped
with a suitable length of small bore plastic tubing. In this
method, about 7 milliliters of oil sample is discharged into the
container, for example a 1 -ounce vial, containing about 10
milliliters of a 0.1 molar aqueous sodium periodate solution. A
plastic closure tip is removed from the discharge end of the
syringe which contains a chromogenic formaldehyde reagent such as
MBTH on silica gel or particulate polyethylene. The tip of the
syringe is introduced into the aqueous phase of the periodate
solution after it has been shaken and the oil and water phases have
separated. About 2 to 5 milliliters of the aqueous solution are
withdrawn onto about 2 milliliter chromogenic formaldehyde reagent
adsorbed on silica gel or particulate polyethylene. As in the
previous preferred embodiment of the invention, the chromatographic
support is prepared by placing about 0.5 grams of MBTH on 100 grams
of 28 to 200 mesh silica gel or particulate polyethylene.
Therefore, as the aqueous solution is drawn up onto the silica gel
or particulate polyethylene to saturate them, the chromogenic check
will be made by observing whether green or dark blue or
intermediate color indication is given.
To further understand the application of the present invention the
following example and data are presented.
EXAMPLE
Five experiments were run with 30 SAE motor oil. Measured
quantities of ethylene glycol were added to each of the five motor
oil samples so that a precise indication of the effectiveness of
the chromogenic-ethylene glycol detection method could be
determined. Each 5-milliliter sample was placed in a 1-ounce vial
containing 10 milliliters of an aqueous 0.1 molar solution of
sodium periodate. The vial was sealed with a cap and shaken
vigorously for 2 minutes to ensure complete oxidation of the
ethylene glycol contained in the oil. The cap was then removed and
the vial set on a flat surface in an upright position for 3 minutes
so as to allow the oil and aqueous liquid phases to separate. A
second 1-ounce vial contained granular material which consisted of
0.5 grams of the chromogenic formaldehyde color reagent MBTH
adsorbed on 100 grams of 28 to 200 mesh silica gel. An eye dropper
was inserted into the lower aqueous phase of the 1-ounce vial
containing the aqueous and oil phases. A sample of the aqueous
phase was removed by squeezing and releasing the rubber bulb upon
insertion so that the clear liquid was raised into the dropper
until 10 milliliters of liquid had been withdrawn. The eye dropper
was wiped and the liquid added to the granular material in the
other 1-ounce vial. The vial was stoppered and shaken vigorously
for approximately 5 seconds. The vial was then placed on a flat
surface. Color indication for each test was noted as shown in the
following table. The color became apparent to be either a green,
dark blue, or an intermediate color within a 15 minute period. No
glycol was indicated by a negative response with a green color
formed and glycol presence was indicated by different shades of
blue color formation. As can be seen, the sensitivity to the silica
gel based MBTH test for ethylene glycol was effective and stable
down to 30 parts per million of ethylene glycol in the motor oil,
therefore giving a positive test for ethylene glycol content in
motor oil. More than about 50 p.p.m. glycol in motor oil is
generally considered to be excessive and requires an oil change.
---------------------------------------------------------------------------
TABLE
Sensitivity of Silica Gel Based MBTH Test for Glycol
Motor oil Blue color 30 SAE Formation
__________________________________________________________________________
1000 p.p.m. glycol Positive 100 Positive 60 Positive 30 Positive 0
Negative
__________________________________________________________________________
It can be seen by use of the present invention that the ethylene
glycol content in motor oils may be specifically determined by
testing the crankcase motor oil with the present invention. The
invention then enhances the ability of service attendants to remove
the hazards of ethylene glycol varnish deposits which cause valves
to stay open, valve lifters to bend in their guides, and piston
rings to stick in their grooves. The method provides the ability to
warn of ethylene glycol leakage into the engine crank case and
avoid severe damage therefrom.
While the present invention has been described above with respect
to certain embodiments thereof it will be understood by those
skilled in the art that various changes and modifications may be
made without departing from the spirit and scope of the invention
as set forth herein.
* * * * *