U.S. patent number 3,923,643 [Application Number 05/479,343] was granted by the patent office on 1975-12-02 for removal of lead and other suspended solids from used hydrocarbon lubricating oil.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to Charles F. Goeking, Jr., Robert W. Lewis, Thomas A. Rodgers.
United States Patent |
3,923,643 |
Lewis , et al. |
December 2, 1975 |
Removal of lead and other suspended solids from used hydrocarbon
lubricating oil
Abstract
Lead and other dispersed solids present in used hydrocarbon
lubricating oil which also contains water and light hydrocarbon
impurities are removed by a process wherein agglomeration of the
suspended lead and other solids is induced by heat treatment of the
used oil at about 500 to 700.degree.F after flashing off the water
and light hydrocarbon material. The agglomerated solids are readily
separated from the heat treated oil by conventional physical
separation techniques such as centrifuging or gravity settling to
afford a used oil substantially free, i.e., at least 90% lead
removal, of lead and other solid contaminants.
Inventors: |
Lewis; Robert W. (Houston,
TX), Rodgers; Thomas A. (La Porte, TX), Goeking, Jr.;
Charles F. (Pasadena, TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
23903622 |
Appl.
No.: |
05/479,343 |
Filed: |
June 14, 1974 |
Current U.S.
Class: |
208/179; 208/184;
208/251R; 208/187; 423/92 |
Current CPC
Class: |
C10M
175/0025 (20130101) |
Current International
Class: |
C10M
175/00 (20060101); C10M 011/00 () |
Field of
Search: |
;208/179,182,184,186,187,251,184,179 ;423/92 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
670,725 |
|
Apr 1952 |
|
UK |
|
1,917,357 |
|
Apr 1968 |
|
DT |
|
Primary Examiner: Levine; Herbert
Assistant Examiner: Nelson; Juanita M.
Attorney, Agent or Firm: Vance; Dean F. Dinkler; Harold
L.
Claims
What is claimed is:
1. A process for removing suspended lead and other dispersed solids
from used hydrocarbon lubricating oil which comprises:
a. heating the used hydrocarbon lubricating oil under temperature
and pressure conditions at which substantially all the water and
volatile hydrocarbon materials boiling below about 500.degree.F at
atmospheric pressure will volatilize out of the used oil in a
devolatilization zone to afford a used hydrocarbon lubricating oil
substantially free of water and said volatile hydrocarbons, said
water and volatile hydrocarbons being removed as a gaseous
overhead,
b. subjecting the used hydrocarbon lubricating oil substantially
free of said water and volatile hydrocarbons to further heat
treatment at a temperature between about 500.degree. and
700.degree.F for about 1 to 12 hours in a heat treatment zone
thereby agglomerating the lead and other dispersed solids contained
in the used oil and
c. separating the agglomerated solids from the used hydrocarbon
lubricating oil.
2. The process according to claim 1 wherein the separation of
agglomerated solids from the used hydrocarbon lubricating oil is
effected in one or more gravity settling zones.
3. The process according to claim 1 wherein the heat treatment step
and the agglomerated solids separation step are carried out in a
single processing step in one or more gravity settling zones
wherein the lead and other dispersed solids are allowed to settle
as they agglomerate.
4. The process according to claim 1 wherein the volatilization of
water and volatile hydrocarbons contained in the used hydrocarbon
lubricating oil is effected continuously by recycling a portion of
the used hydrocarbon lubricating oil substantially free of water
and volatile hydrocarbons from the devolatilization zone through a
separate used oil heating zone and continuously introducing fresh
used hydrocarbon lubricating oil feedstock into this recycle line
at a point subsequent to the used oil heating zone but prior to
recycle of the used oil into the devolatilization zone.
5. The process according to claim 4 wherein the agglomeration of
the lead and other dispersed solids and at least partial separation
of said agglomerated solids are effected continuously by passing
the used oil substantially free of water and volatile hydrocarbons
into a heat treatment zone comprising at least two gravity
separation zones operated in parallel, one separation zone being
filled with said used oil while the other separation zone filled
with said used oil is utilized to effect the heat treatment for the
time required to substantially agglomerate and at least partially
separate the lead and other dispersed solids.
Description
BACKGROUND OF THE INVENTION
This invention relates to purification of used hydrocarbon
lubricating oil. More particularly, this invention is directed to a
process for renovating hydrocarbon oils used as lubricants in
internal combustion engines, i.e., crankcase oil, wherein
substantially all of the lead and other dispersed solids are
separated from the used oil.
The disposal of the approximately 500 million gallons of used
crankcase oil produced annually in the United States by
environmentally acceptable techniques is becoming an increasingly
significant challenge to both the private and public sectors of
modern day society. In the past much of this waste oil has been
disposed of by means such as pouring it onto the ground or into
sewers, oiling roads, burning it directly as fuel, etc. However,
primarily because of the accumulated solid impurities such as
combustion derived inorganic materials, particularly lead
compounds, which remain dispersed in this crankcase oil due to the
very effective dispersant characteristics of modern day lubricating
oil additives, many of the crankcase oil disposal techniques, such
as those mentioned above, are becoming unacceptable in today's
environmentally conscious society.
The insoluble, solid materials contained in a typical used
crankcase oil include sub-micron size carbon particles, inorganic
materials such as atmospheric dust, metal particles, lead and other
metal compounds originating from fuel combustion. Besides lead,
which is generally present at concentrations of 1.0 to 2.5%w,
appreciable amounts of zinc, barium, calcium, phosphorus and iron
are also present in the used crankcase oil. Examination of the used
oil under an optical microscope at 600 magnifications reveals the
very effective dispersant characteristics of modern day lube oils.
The particle size of the particulates is estimated from this
microscopic examination to be 0.1-1.0 microns with virtually no
occurrence of agglomerates in the oil.
Although this extremely effective dispersing action of today's
typical lube oil is advantageous when the hydrocarbon oil
composition is employed as a lubricating agent, it also provides a
distinct obstacle to the development of an environmentally
acceptable means of disposing of the used oil, in that it prevents
the separation of lead from the used oil by simple and relatively
inexpensive methods, a prerequisite to any viable disposal means.
For example, conventional physical separation techniques such as
gravity settling, centrifugation or filtration of the undiluted
waste oil which might be suitable from economic and ease of
operation standpoints are not effective in facilitating the desired
separation. Other separation methods have been previously proposed.
However, many of these methods require the addition of a
coagulating agent which is either not reuseable, e.g., see U.S.
Pat. No. 2,568,583, or recoverable only through the employment of a
supplemental recovery scheme with the associated costs of
auxilliary equipment and process control, e.g., see U.S. Pat. No.
3,763,036. Further, in crankcase oil purification methods such as
that described in U.S. Pat. No. 2,305,464 wherein no extraneous
coagulating agent is added (hydrolytic action of water apparently
relied on), it is an essential requirement that volatile materials
in the used oil (including water) be maintained in the used oil
phase during a heat treatment period to coalesce solid impurities.
This, of course, requires the use of expensive high pressure
resistant equipment as well as exposing operators of the process to
the hazards associated with such high pressure operation.
SUMMARY OF THE INVENTION
It has now been found that suspended lead and other dispersed
solids in used hydrocarbon lubricating oil can be readily
agglomerated and separated from the used oil by conventional
physical separation techniques if the used oil is subject to heat
treatment at a critically high temperature range, i.e., 500.degree.
to 700.degree.F, subsequent to removal by volatilization or
equivalent means of substantially all of the water and volatile
hydrocarbons contained in the used oil. Accordingly, the instant
invention provides a process for removing lead and other dispersed
solids from used hydrocarbon lubricating oil which comprises
a. heating the used hydrocarbon lubricating oil under temperature
and pressure conditions at which substantially all the water and
volatile hydrocarbon materials boiling below about 500.degree.F at
atmospheric pressure will volatilize out of the used oil to afford
a used hydrocarbon lubricating oil substantially free of water and
said volatile hydrocarbons, said water and volatile hydrocarbons
being removed as a gaseous overhead,
b. subjecting the used hydrocarbon lubricating oil substantially
free of said water and volatile hydrocarbons to further heat
treatment at a temperature between about 500.degree. and
700.degree.F for about 1 to 12 hours, thereby agglomerating the
lead and other dispersed solids contained in the used oil and
c. separating the agglomerated solids from the used hydrocarbon
lubricating oil.
In a preferred aspect of the invention the removal of lead and
other dispersed solids from the used hydrocarbon lubricating oil is
effected in continuous fashion by recycling a portion of hot used
oil with water and volatile hydrocarbons removed from the zone in
which volatilization occurs through a separate used oil heating
zone and introducing fresh used oil feedstock into this recycle
line at a point subsequent to the used oil heating zone but prior
to recycle of the hot used oil into the devolatilization zone. In
this continuous process the agglomeration and separation of
agglomerated solids (lead and other solid impurities) is preferably
effected by passing the devolatilized used oil into at least two
gravity separation zones (settlers) operated in parallel; one
settler being filled with hot used oil while the other settler
filled with hot oil is utilized to effect the heat treatment for
the time required to agglomerate and gravity separate the lead and
other dispersed solids. In this aspect all settlers operated in
parallel are maintained at a temperature in the 500.degree. to
700.degree.F range required to agglomerate the suspended
solids.
DETAILED DESCRIPTION OF THE INVENTION
In the first step of the process of the invention raw used
hydrocarbon lubricating oil which can contain up to 30%/w water and
up to 40%/w volatile hydrocarbons, i.e., gasoline and gasoline
boiling range fractions, in addition to the suspended lead and
other dispersed solids is subject to a flashing or devolatilization
treatment under temperature and pressure conditions at which
substantially all of the contained water and volatile hydrocarbons
are distilled away from the used oil. The specific temperature and
pressure conditions employed in this devolatilization operation may
vary within fairly wide limits dependent on factors such as the
specific concentration of water and volatile hydrocarbons in the
raw used oil, the rate of devolatilization desired, the heating and
vacuum facilities available, etc. For typical used lubricating oil
feedstocks, which contain 5-15%/w water and 15-35%/w gasoline range
volatile hydrocarbons, the flashing operation is suitably carried
out at pressures ranging from a mild vacuum, e.g., 2.5 psia up to
150 psia and at temperatures ranging from about 500.degree. up to
about 700.degree.F; the upper temperature limit being dictated by
the temperature at which thermal decomposition of the lubricating
oil becomes significant and/or loss of 500.degree.F+ boiling
material becomes excessive. In any case, the temperature, pressure
and flashing residence times should be selected such that the used
oil product of the flashing operation is substantially free of any
entrained water and volatile hydrocarbons boiling below
500.degree.F at atmospheric pressure. It is very advantageous to
recover the volatile hydrocarbon materials, which are distilled
overhead in this flashing operation, by means of conventional
condensing facilities for use in the flashing step, discussed
below, where they can supply all or part of the heat requirement of
this step.
After removal of substantially all of the contained water and
volatile hydrocarbons, the used lubricating oil is subject to heat
treatment at a temperature in the range of about 500.degree. to
about 700.degree.F for a time sufficient to cause agglomeration of
a substantial portion of the lead and other dispersed solids
contained in the used oil. While the basis for the occurrence of
this agglomeration phenomenon is not completely understood, it is
believed that heating of the used oil to this critically high
temperature range causes thermal decomposition of the peptizing
agents which hold the dispersed lead and other solids in collodial
suspension. With this heat treatment procedure it is possible to
agglomerate substantially all of the dispersed lead and other
solids contained in the used oil such that reductions in lead
content in excess of 90% can be readily obtained on subsequent
separation of the agglomerated solids by conventional physical
separation techniques. Since substantially all of the water and
volatile hydrocarbons have been previously removed from the used
lubricating oil, this heat treatment step can be very suitably
carried out at atmospheric pressure thereby avoiding the use of
high pressure equipment as required in the prior art procedures.
The specific residence time employed in this heat treatment step is
dependent, in part, on factors such as the solids content of the
lubricating oil, the quality of oil to be treated, etc., which vary
somewhat in any given practical application. However, in most
instances it has been found that heat treatment residence times
ranging from about 1 to about 12 hours will facilitate the high
degree of agglomeration contemplated by this invention.
The agglomerating heat treatment can be suitably carried out in a
reaction zone under an air or inert gas, e.g., nitrogen,
atmosphere. In this same connection it has been found that the
heat-induced agglomeration of the lead and other dispersed solids
can be enhanced by the addition of either H.sub.2 S or NH.sub.3.
Accordingly, in a preferred aspect of this invention, H.sub.2 S or
NH.sub.3 is admixed with the used oil after removal of water and
volatile hydrocarbons. In this instance it is adequate to operate
at atmospheric pressure since low concentrations of H.sub.2 S or
NH.sub.3 suffice.
In the final step of the process the heat treated lubricating oil
is subject to a physical separation procedure by which the
agglomerated solids are removed from the used lubricating oil.
Heat-induced agglomeration according to the process of the
invention affords agglomerated solid particles of a particle size
sufficient that any conventional physical separation technique may
be employed to effect this final separation. For example, suitable
separations are effected by centrifuging, filtration, gravity
settling and like techniques. For simplicity and economy of
operation, it is preferred that the separation be effected in one
or more gravity settling zones. With this technique the
agglomerated solids are collected in the bottom of the first
settling zone as a sludge-like material which can be drained away
from the purified oil and disposed of directly or passed into a
second gravity settling zone for further separation and recovery of
purified oil. Suitably the gravity settling is carried out at a
temperature which approximates that employed in the heat treatment
zone, i.e., 500.degree.-700.degree.F with a residence time of 1 to
12 hours. Most preferably the heat treatment step and the gravity
settling separation step are carried out in a single processing
step wherein the lead and other dispersed solids are allowed to
settle as they agglomerate. In this most preferred case the
combined residence time required for both agglomeration of
dispersed solids and settling of the agglomerated solids ranges
from 1 to 12 hours, depending upon the geometry of the vessel and
the degree of particulate removal which is desired.
The process of the invention may suitably be carried out in either
batch or continuous fashion. In batch operation the raw used
lubricating oil is passed into a suitable heating vessel having a
bottom discharge for product, e.g., a cone bottom tank equipped
with a bottom discharge valve, and a suitable means for heating the
raw used oil -- e.g., in tank stream coils, electrical heaters,
etc. After receiving the desired charge of raw used oil, the
heating vessel is heated to a temperature sufficient to distill off
the contained water and volatile hydrocarbons, e.g., 500.degree.F
at atmospheric pressure, which are collected in an overhead
condensing system. Optionally, during the water and light
hydrocarbon flashing operation a partial vacuum can be placed on
the heating vessel to reduce the heat and temperature requirements
of the flashing step. After removal of contained water and volatile
hydrocarbons, the used oil is subject to further residence time in
the heating vessel at a temperature in the range of 500.degree. to
700.degree.F to induce agglomeration of the dispersed lead and
other solids. In normal operation this heating vessel will also
function as a gravity settling vessel and as such will effect
separation of most of the agglomerated solids which collect as a
sludge in the bottom of the tank from the used oil. The total
residence time for agglomeration of dispersed solids and separation
of most of the agglomerated solids from the used oil suitably
ranges from 1 to 12 hours. At the end of the heating cycle the
sludge is drained from the bottom of the heating vessel into a
smaller vessel, e.g., cone bottom tank, where further settling and
separation takes place. In this manner considerably more than 90%
separation of dispersed lead and other solids from the used oil can
be effected.
Preferably, the process of the invention is carried out in a
continuous manner. To facilitate understanding of this preferred
mode of operating the process of the invention, reference will be
made to the Figure which shows, in schematic fashion, a suitable
apparatus for continuous operation of the process of the invention.
For the sake of simplicity, auxilliary equipment such as valves,
pumps, vacuum facilities and the like are not shown in this
figure.
Raw used lubricating oil feedstock is passed from storage tank 10
via line 11 through a feedstock preheater 12 in which it is heated
to a temperature in the range of 300.degree. to 500.degree.F. This
preheated oil is then introduced into the recycle loop 13 which
cycles hot used oil from the used oil flasher 15 through the
primary used oil heater or furnace 14 and back into the flasher. At
its point of introduction into the recycle loop 13, which
introduction is suitably accomplished by means of a mixing T
positioned on the recycle line 13 at a point subsequent to passage
of the recycled oil through the heater but prior to its
introduction back into the flasher, the raw used oil is admixed
with the hot recycled oil at a ratio selected to give the desired
temperature in the flasher, e.g., 600.degree.F, without overheating
the recycle oil. In the flasher 15, which may suitably be a cone
bottomed insulated vessel, the water and volatile hydrocarbon
components of the raw used lubricating oil are distilled overhead
via line 16 through a heat exchanger-condenser 17 into a water and
light hydrocarbons accumulator 18. This distillation or flashing
operation may be accomplished under partial vacuum conditions,
e.g., 300 mm Hg furnished by appropriate vacuum facilities (not
shown). In the accumulator 18 the water and volatile hydrocarbon
overhead are phase separated and passed via lines 19 and 20,
respectively, back into the primary used oil heater 14 where the
hydrocarbons supply at least a portion of the heat requirement of
that heater. Also, the water is incinerated in this heater for
disposal. Any non-condensed vapors, i.e., light hydrocarbons which
may also be present in the accumulator are also passed back into
the heater 14 via line 21 to furnish a portion of the thermal
requirement for that heater. The primary used oil heater 14 is
suitably constructed as a hydrocarbonaceous fuel furnace wherein
hydrocarbons are completely combusted in the presence of the waste
water. In this manner, the recycled oil is heated to maintain the
flasher at a temperature in the range of 500.degree. to
700.degree.F.
To affect agglomeration of the lead and other dispersed solids in
the used oil and concomitant separation of such agglomerated
solids, a stream of hot flasher bottoms is taken off the bottom of
flasher 15 and passed via lines 22 and 24 into two gravity settling
vessels operated in parallel. This stream of hot flasher bottoms is
substantially free of both water and volatile hydrocarbons.
Procedurally, the used oil is passed via line 22 into settler 23
until it is filled to the desired level afterwhich the used oil is
diverted by means of appropriate valving on line 22 into line 24
for passage into settler 25. In this manner the hot used oil is
given the desired agglomeration and settling residence time in one
of the settlers during the time period when the other settler is
filling with used oil. Gravity settlers 23 and 25 are of similar
size and construction, both suitably being cone bottomed insulated
tanks. During the solids agglomeration and settling residence time
in each of the settlers, the temperature of the used oil is
maintained at between 500.degree. and 700.degree.F. With the
combined agglomeration and settling residence times contemplated by
the instant invention, i.e., 1 to 12 hours, the desired temperature
range is suitably maintained by means of appropriate insulation on
the settlers since the hot flasher bottoms are already at
temperatures in this range. However, if desired, additional heat
may be supplied to the settlers by means of heating coils, e.g.,
high pressure steam or electrical, located in the walls of the
settlers. Upon completion of the desired agglomeration and settling
residence time in either of the settlers 23 or 25, the settler is
drained via a bottom outlet into lines 26 and 28, respectively,
wherein the first portion of the drained material, containing the
agglomerated solids and a minor portion of oil in the form of a
sludge, is diverted via appropriate valving into lines 27 and 29,
respectively. This sludge is passed by lines 27 and 29 into a
sludge pot 30 where additional settling could be achieved, if
desired. The used oil which remains after draining off of the
sludge is passed from the settler 23 and 25 via lines 26 and 28,
respectively into line 31 where the combined settler effluent, now
substantially free of lead and other dispersed solids, is cooled
via heat exchanger 34 and passed into a purified oil storage tank
36. The sludge present in the sludge pot 30 after being given the
desired settling time, e.g., 1 to 12 hours, at temperatures which
may be lower than those maintained in the settlers is drained from
the sludge pot via line 32 through a heat exchanger 33 where it is
cooled and passed into a concentrated solids storage tank (35). Any
additional purified oil which may separate in the sludge pot is
diverted on draining of the sludge pot from line 32 into line 29
which connects with the purified oil storage via line 28. Any
volatile materials, e.g., volatile hydrocarbons, which may
conceivably carry over into the settlers 23 and 25 and the sludge
pot 30 from the flashing operation are passed via overhead lines
37,38 and 39, respectively, into line 40 which joins line 16 at a
point prior to its introduction into the flasher overhead condenser
17.
Through operation of the process of the invention in the continuous
manner hereinbefore described, it is possible to remove in excess
of 90% of the lead and dispersed solids present in the used
hydrocarbon lubricating oil. The purified oil obtained by operation
of this continuous process may be suitably employed in many
industrial applications of such heavy oils, e.g., fuel oil, without
risk of environmental contamination such as lead emissions on
combustion which plagues the possible use of the unpurified used
lubricating oil. Further, the concentrated metal sludge obtained
from the process can be dispensed to suitable metal reclaimers for
recovery of the valuable metals contained therein or,
alternatively, can be utilized in amounts consistent with
acceptable environmental standards in asphalt manufacture.
* * * * *