U.S. patent number 3,763,036 [Application Number 05/224,222] was granted by the patent office on 1973-10-02 for a method of reducing the lead content of a used hydrocarbon lubricating oil by adding methylethyl ketone to separate the resulting mixture into a coagulated insoluble phase.
This patent grant is currently assigned to Texaco Inc.. Invention is credited to Terence B. Jordan, Joseph W. McDonald.
United States Patent |
3,763,036 |
Jordan , et al. |
October 2, 1973 |
A METHOD OF REDUCING THE LEAD CONTENT OF A USED HYDROCARBON
LUBRICATING OIL BY ADDING METHYLETHYL KETONE TO SEPARATE THE
RESULTING MIXTURE INTO A COAGULATED INSOLUBLE PHASE
Abstract
A method of reducing the lead content of a used hydrocarbon
lubricating oil comprising mixing a used hydrocarbon lubricating
oil having a lead content of at least about 0.5 wt. percent with
methylethylketone, separating the resulting mixture into coagulated
insoluble layer and a clarified hydrocarbon lubricating
oil-methylethylketone layer, said mixing and said separating
conducted under anhydrous conditions at a temperature between about
65.degree. and 95.degree.F.
Inventors: |
Jordan; Terence B. (Fishkill,
NY), McDonald; Joseph W. (Wappingers Falls, NY) |
Assignee: |
Texaco Inc. (New York,
NY)
|
Family
ID: |
22839759 |
Appl.
No.: |
05/224,222 |
Filed: |
February 7, 1972 |
Current U.S.
Class: |
208/180;
208/179 |
Current CPC
Class: |
C10M
175/005 (20130101) |
Current International
Class: |
C10M
175/00 (20060101); C10g 027/00 () |
Field of
Search: |
;208/180,251,179 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gantz; Delbert E.
Assistant Examiner: Nelson; Juanita M.
Claims
We claim:
1. A method of reducing dispersed lead impurities in a used
hydrocarbon lubricating oil composition having dispersed lead
content of at least about 0.5 wt. percent consisting essentially of
mixing under anhydrous conditions said composition with
methylethylketone utilizing a methylethylketone to used oil
composition volume ratio of at least about 2:1, forming a
methylethylketone-clarified oil upper layer and a lead containing
insoluble lower layer, separating the resultant
methylethylketone-oil upper layer from said lead containing
insoluble lower layer, and recovering from said
methylethylketone-clarified oil upper layer, a lubricating oil
composition of reduced lead content, said mixing, said forming, and
said separating conducted at a temperature of between about
65.degree. and 95.degree.F.
2. A method in accordance with claim 1 wherein said forming
comprises passing the used oil-methylethylketone mixture to a
settling tank and maintaining said mixture in said tank until said
methylethylketone-clarified oil layer is formed as an upper layer
and said lead containing insoluble layer is formed as a lower
layer, said separating comprising subsequently decanting from said
tank said methylethylketone-clarified oil upper layer, and said
recovering comprising passing the decanted
methylethylketone-clarified oil upper layer to a distillation zone,
recovering methylethylketone as distillation overhead, recovering a
lubricating oil composition of reduced lead content as a
distillation residue, and recycling the recovered methylethylketone
to said mixing step.
3. A method in accordance with claim 1 wherein said forming
comprises centrifuging the used oil-methylethylketone mixture to
separate methylethylketone-clarified oil solution as an upper layer
and lead containing coagulated insolubles as a lower layer,
decanting said methylethylketone-clarified oil upper layer from the
centrifuge, said recovering comprising passing the decanted
methylethylketone-clarified oil upper layer to a distillation zone,
recovering methylethylketone as distillation overhead, recovering a
lubricating oil composition of reduced lead content as
dis-tillation residue, and recycling the recovered
methylethylketone to said mixing step.
4. A method in accordance with claim 1 wherein said mixing
comprises in-line blending the methylethylketone and used oil
composition, said forming and said separating comprising passing
the resultant mixture into a series of settling vessels so that at
least one of said vessels is continuously filling with said mixture
while simultaneously continually removing from another vessel
formed methylethylketone-clarified oil upper layer, and said
recovering comprising passing to a distillation zone the removed
methylethylketone-clarified oil upper layer, recovering
methylethylketone as distillation overhead, recovering lubricating
oil composition of reduced lead content as distillation residue,
and recycling the recovered methylethylketone to said mixing step.
Description
BACKGROUND OF INVENTION
Hydrocarbon lubricating oil compositions used as lubricants in
internal combustion engines contain additives which serve as
dispersants so that accumulated impurities such as metallic salts
particularly lead salts remain dispersed in the oil rather than
settling as a sludge in the crankcase. Although the function of the
dispersants is a distinct advantage when the hydrocarbon oil
composition is employed as a lubricating agent, it becomes a
distinct hindrance in the disposal of the used oil composition or
the reclaiming thereof, in that it prevents the ready separation of
lead from the used oil.
Used oil such as that accumulated from the automobile service
stations is sometimes disposed of by burning. The removal of lead
prior to disposal is desirable for ecological reasons, for during
burning, lead if not removed, is volatilized into the atmosphere in
substantial quantities, the remainder entering the soil, both
outlets being undesirable. In addition, if the oil is to be reused
via a reclaiming process, lead must be removed therefrom in order
to render it commercially saleable.
In the past, various materials have been employed to remove lead
impurities such as reacting the impurities with N-phenyl alkylol
amines as disclosed in U. S. Pat. No. 2,568,583. However, these
materials are of relatively high cost, normally require the
employment of elevated temperatures during separation, and are not
reuseable.
SUMMARY OF INVENTION
We have discovered and this constitutes our invention a low cost
method of readily separating lead from hydrocarbon lubricating oil
compositions used in internal combustion engines which is conducted
at moderate temperatures, preferably room temperature, utilizing a
particular agent which is readily recoverable for reuse.
DETAILED DESCRIPTION OF THE INVENTION
Specifically, the invention comprises contacting a hydrocarbon
lubricating oil having a dispersed lead content of at least about
0.5 wt. percent, normally between about 0.5 and 1.5 wt. percent
with methylethylketone (MEK) under anhydrous and mixing conditions
at a temperature between about 65.degree. and 95.degree.F.
utilizing a volume ratio of methylethylketone to hydrocarbon oil of
at least about 2:1, preferably between about 2:1 and 3:1,
separating the resultant mixture into an upper layer of clarified
lubricating oil and methylethylketone and a bottom coagulated,
insoluble layer containing the bulk of the lead impurities under
said anhydrous and temperature conditions. Separation can be
effected, for example, by either gravity separation which is
normally conducted for a period of between about 4 and 10 hours or
centrifuging, either means followed by decanting or filtering to
spatially separate the layers. The methylethylketone is readily
recovered from the separated oil-methylethylketone layer by
standard means such as distillation, leaving essentially a lead
free (less than about 0.1 wt. percent) clarified dark oil. The
recovered methylethylketone is either forwarded to storage for
eventual reuse or recycled directly to the mixing stage for
immediate reuse. Another means of separating the clarified
oil-methylethylketone layer from the coagulated insoluble would be
employing a high speed centrifuge and then upon the completion of
centrifuging spatially separating the layers, and recycling the
recovered methylethylketone for reuse or storage.
The separated lead containing sludge is normally deoiled by
extraction with solvent, for example, additional methylethylketone,
pentane or heptane to yield a dry powder of relatively high lead
content, e.g., 20-40 wt. percent. The thus recovered lead can be
containerized and the resultant lead filled container can be
employed as land fill or the lead can be accumulated and
reprocessed for industrial use.
Hereinbefore and hereinafter the term "anhydrous" denotes water
content less than about 0.5 wt. percent.
In regard to mixing of the methylethylketone and used oil, this can
be accomplished by standard means such as "in line" blending,
paddle mixing, etc., and is normally conducted for only that period
of time which is required to insure thorough contact of the oil and
ketone, e.g., 0.5-10 minutes.
The process of the invention may be conducted on a batch or
continuous basis. An example of a continuous operation would be to
employ initial "in line" blending using adjustable proportioning
pumps to provide the proper used oil-methylethylketone mix and
introducing the mixture into a series of settling vessels. At least
two separation vessels are employed in the continuous procedure
with the flow of the mix, for example, being alternated between
settling vessels, e.g., one being filled while recovering the
separated layer from the other. Another approach would be to
connect a number of settling vessels in series, introducing the mix
into the first of the series and withdrawing the clarified
oil-ketone layer from the last of the series. Still another
approach would be to feed the used oil-methylethylketone mix
directly into a number of high speed centrifuges and alternating
such feed between the centrifuges.
In the method of the invention it is theorized the
methylethylketone functions to solubilize a yet unidentified resin,
said resin believed to provide a chemical bond between the lead
impurity and lube oil dispersants, the latter maintaining the lead
impurity in the dispersed state. Once this bond is broken via
solubilization the lead and other metallic materials become
desolubilized, coagulate and separate from the
oil-methylethylketone layer.
In regard to the material and unexpected features of the invention,
the ability of methylethylketone to function in desolubilizing lead
impurities is surprising since many materials utilized in the
solvent refining of virgin lubricating oils such as pentane,
heptane, benzene and N-methyl-pyrrolidone were not effective in
facilitating the removal of lead impurity from the used lubricating
oil. Further, even closely related acetone is substantially
unsatisfactory in lead impurity removal.
Another surprising material feature of the invention is that
normally in purifying processes elevated temperatures of the order
of 100.degree. to 300.degree.F., preferably above 150.degree.F.,
are employed. In contrast, our procedure preferably employs ambient
temperatures, that is, of the order of 65.degree. to 95.degree.F.,
and therefore, affords a substantial saving in process costs since
normally heat does not have to be supplied to the desolubilizing
reaction. Temperatures above about 95.degree.F. in our procedure
result in somewhat reduced lead removal.
Another feature of the invention is that a volume ratio of
methylethylketone to used oil of at least about 2:1 is
advantageous. Volume ratios substantially below 2:1 such as 1:1,
except when high speed centrifuge separation is employed, result in
a treated oil have an unsatisfactory high lead content, that is,
above about 0.1 wt. percent.
Still another material feature is the requirement that the
desolubilization be conducted under anhydrous conditions, i.e., the
initial oil-ketone mixture have a water content below about 0.5 wt.
percent. Higher water contents prevent separation of the lead
impurity layer. If the oil to be treated has a water content which
would bring the oil-ketone mixture above the aforementioned maximum
value, it is subjected to a dehydration pretreatment. Such
dehydration can be accomplished by standard means such as by
passing used oil over a hot surface to flash off the water, by
blowing with hot air or with steam above about 250.degree.F. or by
vacuum treatment at ambient or elevated temperatures, preferably at
about 150.degree.F.
Hereinbefore and hereinafter by the term "used hydrocarbon
lubricating oil" it is intended to mean oils removed from the
crankcases after extended use in operating internal combustion
engines, wherein the lead therein has been "solubilized" by
dispersant additive(s) in said oil and the initial lead content
therein is at least about 0.5 wt. percent.
The used hydrocarbon lubricating oil compositions contemplated
herein are derived from the hydrocarbon lubricating compositions,
normally lead free, comprising between about 85 and 99 wt. percent
hydrocarbon lubricating oil and between about 1 and 15 wt. percent
additives. These additives in addition to the aforementioned
dispersants normally comprise one or more of the following: pour
depressors, anti thickening agents, antioxidants, corrosion
inhibitors, VI improvers, and oiliness agents.
Examples of lube oil dispersants are overbased calcium
alkylsulfonates, overbased sulfurized calcium alkyl-phenolates and
polyisobutylene (e.g. 50 to 200 carbons) succinimide of
tetraethylenepentamine.
The base oils employed in formulating the initial lubricating oil
compositions from which the used oils are derived include a wide
variety of hydrocarbon lubricating oils such as naphthenic base,
paraffinic base and mixed base mineral oils or other hydrocarbon
lubricating oils such as derived from coal products, synthetic
oils, e.g., alkylene polymers such as polypropylene,
polyisobutylene, of a molecular weight between 250 and 2500.
Advantageously, the lubricating base oils employed have an SUS
viscosity at 100.degree.F. between about 50 and 2000.
The following examples further illustrate the method of the
invention but are not to be construed as limitations thereof.
EXAMPLE I
This example illustrates the method of the invention as practiced
as a batch process.
The used crankcase lubricating oil employed in the following
procedure was obtained from the waste oil disposal tank at a
service station catering to automobiles. It was derived from motor
oils which initially contained no lead. The used oil was introduced
into a mixing kettle where it was stirred at ambient temperature to
assure uniform distribution of materials therein and then stored in
1-gallon cans. Before use, the gallon cans were vigorously shaken
on a mechanical shaker to redisperse any separated material and
thereby assure uniform samples. The thus mixed and shaken used
motor oil was subjected to analysis and the following was typically
found:
Used crankcase oil results Lead as Pb, wt. % 1.25 Sulfated ash, wt.
% 2.95 Viscosity at 100.degree.F., SUS 319 Viscosity at
210.degree.F., SUS 61.6 Viscosity Index 158 Pour, .degree.F. -35
Chlorine, wt. % 0.95 Bromine, wt. % 0.30 Water, wt. % 0.4 Fuel
Dilution 0.8
The overall procedure employed was as follows:
To a cylinderical tank there was sequentially charged the used
crankcase oil and methylethylketone. The resultant mixture was
mixed to assure uniform contact between the used oil and ketone.
The mixing was then ceased and the mixture was left undisturbed
until coagulated insolubles settled to the bottom of the vessel
leaving a clarified used oil MEK upper solution. The separated
insolubles represented about 10 percent of the total volume and the
used oil MEK solution about 90 percent. Coagulation was relatively
rapid. It took no longer than six hours under laboratory
conditions. This translated into commercial operating conditions
would be expected to be about 24 hours. The clarified
methylethylketone-oil solution was transferred to a distillation
unit and methylethylketone was distilled off and returned to
storage for reuse. The clarified oil residue was forwarded to
storage for subsequent disposal. As an alternative, centrifuging
was also employed.
Following Table I represents the procedure of the invention
utilizing gravity separation and demonstrates in Run E the gravity
separation of 1:1 volume ratio is ineffective. Table II represents
the method of the invention utilizing centrifugal separation and
gravity separation. Table II further demonstrates in comparative
Run F the ineffectiveness of comparative known lube oil solvent
materials. Table III shows the property difference between the
untreated used oil and the clarified oil resulting from treatment
of the used oil via the method of the invention.
TABLE I
METHYLETHYLKETONE TREATMENT OF USED CRANKCASE OIL
Run A B C D E Ingredients Methyl- ethyl- ketone, 45 40 34 1400 25
mls. Used Oil, mls. 5 10 17 600 25 (1.25 wt. % Pb) MEK/Waste Oil,
wt. 9:1 4:1 2:1 2.3:1 1:1 ratio Treating Tempera- 70-80 70-80 70-80
70-80 70-80 ture, .degree.F. Sludge Separation yes yes yes yes no
Tests on Clarified Oil Lead as Pb, wt. % 0.01 0.01 0.01 0.02 --
Sulfated Ash, wt. % -- -- -- 0.64 --
TABLE II
METHYLETHYLKETONE CLEAN-UP OF USED CRANKCASE OIL
Reference Run Used Oil F G H I Ingredients Methyl- ethyl- ketone,
mls. -- -- 600 2800 800 Benzene, mls. -- 600 -- -- -- Used Oil,
mls. -- 600 300 1400 800 Solvent:Oil, -- 1:1 2:1 2:1 1:1 wt. ratio
Treating Temp., .degree.F. -- 70-80 70-80 70-80 70-80 Sludge
Separation -- partial yes yes yes Method Sludge Sepa- -- gravity
gravity gravity centri- ration fuge Tests on Recovered Oil Lead as
Pb, wt. % 1.25 0.88 0.10 0.03 0.06 Sulfated Ash, wt. % 2.95 2.55 --
-- 0.81
TABLE III
EFFECT OF MEK TREATMENT (RUN D) ON OIL PROPERTIES
MEK treated Used Oil 2:1 MEK:used oil SUS Viscosity, 100.degree.F.
319 283 SUS Viscosity, 210.degree.F. 61.6 55.4 Viscosity Index 155
133 Pour, .degree.F. -35 -40 Sulfated Ash, wt. % 2.95 0.64 Lead as
Pb, wt. % 1.25 0.02 Chlorine, wt. % 0.19 0.07 Bromine, wt. % 0.30
0.05
EXAMPLE II
This example illustrates the method of invention as practiced as a
continuous process.
From two one-gallon storage vessels there was respectively drawn
used crankcase oil and methylethylketone via proportioning pumps
for inline blending of the materials at the desired ratio. The
proportioning pumps were adjusted to provide the desired volume
ratio of used oil to methylethylketone and also the desired flow
rate. The mixture was then passed through 5 to 6 receiving vessels
connected in series. The coagulation of the insoluble was
accelerated by the inline blending and was completed in the
receiving vessels. Rapid settling occurred providing a clear, dark
brown used oil methylethylketone affluent equivalent to that
obtained in the batch operation. The clearest fluid from the last
vessel was continuously directed to a rotary evaporating
distillation unit where the methylethylketone was distilled off
leaving the treated used oil. The methylethylketone was returned to
the methylethylketone storage vessel for reuse. The recovered oil
was transferred to oil storage for subsequent disposal.
The test data and results are reported below in Table IV. The data
further demonstrates the importance of maintaining a MEK:Used Oil
volume ratio of at least about 2:1 under gravity separation
conditions as can be seen from the high lead content in No. 5 and
No. 6 Receivers of Run L.
TABLE IV
METHYLETHYLKETONE TREATMENT -- CONTINUOUS OPERATION
Run J K L MEK:Used Oil Ratio 2.2:1 2:1 1.1:1 liters/hr. (MEK+ 2.05
5.75 2.05 Used Oil) Total hours 4.25 6.0 8.5 Processed Volume, 13
34.5 16.3 liters Type Separation Gravity gravity gravity
Temperature, .degree.F. 80-90 80-90 80-90 Lead as Pb., wt. %
Original Used Oil 1.25 1.25 1.25 Receivers as Filled No. 1
(4liters) 0.039 0.040 0.043 No. 2 (2 liters) 0.069 0.040 0.068 No.
3 (2 liters) 0.065 0.040 0.094 No. 4 (2 liters) 0.057 0.035 0.093
No. 5 (2 liters) 0.043 0.035 0.163 No. 6 (2 liters) -- -- 0.200
EXAMPLE III
This example illustrates the ineffectiveness of closely related
materials to methylethylketone in separating lead from used
crankcase oil.
The procedure of Example I (gravity separation) was repeated
utilizing pentane, heptane, N-methyl-1-pyrrolidone,
N-methyl-2-pyrrolidone and acetone. These materials were
substantially ineffective in coagulating and settling out the
dispersed lead and other suspended materials.in the used crankcase
oil.
EXAMPLE IV
This example illustrates the importance of conducting the reaction
under essentially anhydrous conditions. The procedure of Example I
was employed utilizing a 10 volume percent water content in a 1:2
volume ratio of used oil to methylethylketone. An emulsion was
formed which was stable for several days with no significant sludge
coagulation being evidenced.
* * * * *