I

* Ic

Demetallation and Recovery of Fuel Oil

from Hazardous Waste Oil
Nimish Dhuldhoya, A. R. Tarrer and Wen-Terng Wu
Department of Chemical Engineering, Auburn University

INTRODUCTION iron, lead, silicon and tin, while

In the United States, automotive and
other industrial sources generate
about 1 . 2 billion gallons of used oil
each year. The most pertinent
features of this oil with regard to
recycle and disposal problems are
flash point and water, sediments,
ash, nitrogen, and oxygen content.
Many of the impurities are dispersed
in the oil due to the very effective
dispersant characteristics of the
additives in a modern-day lubricant
system(1).
Waste o i l , although contaminated, has
a high energy value, and burning as a
fuel is a major outlet for used oil.
Unfortunately, used oil contains high
concentrations of metallic
contaminants, and its combustion can
cause adverse environmental effects.
Some of the metallic materials in
used motor oils are introduced during
use. Typically, the metals
introduced by means of wear or
corrosion are aluminum, copper,
sodium, barium, calcium, zinc and
magnesium usually come from
additives(2).
A number of re-refining processes
have been used in the past ( 3 - 5 ) .
The low yield, high operating cost
and generation of a large amount of
hazardous sludge make these processes
economically unattractive. In view
of today's problem it appears that an
economically viable re-refining
process is needed which can:
* eliminate or minimize potential
byproduct pollutants (spent acid,
spent caustic, spent clay, SO2 etc.)
* produce acceptable products, and
* remain flexible enough to adapt to
changing additives and/or
environmental considerations.
In principle, many methods could be
employed for the removal of the
contaminants, but economic

162
.9
considerations frequently dictate
using chemical treatment as a viable
alternative for the production of
fuel oils. Although demulsifiers,
flocculating aids, contaminant
oxidizer and conditioning reagents
(e.g. caustics) are available
commercially, chemical treatment of
waste oils has not yet been
demonstrated on a large scale.
However, low capital and operating
costs, high product yields, potential
wide application, low energy
treatments and especially low residue
production make chemical treatment an
attractive choice for waste oil
processing facilities involved
primarily in fuel oil production.
In this work, a chemical
demetallization agent was used to
convert entrained non-filterable
metals into a form which could be
effectively removed by filteration or
sedimentation. Waste oils were
demetallized by diammonium phosphate
(DAP). A detailed parametric study
was undertaken to map out the process
variables so as to identify the most
efficient demetallization conditions.
EXPERIMENTAL PROCEDURE
Materials. Used oil was collected
from the Auburn University waste oil
reprocessing pilot plant and from
different service stations in the
vicinity of Auburn.
EauiDment. A three-neck distillation
flask was used as a reactor. In a
typical run, the flask was charged
with waste oil and demetallizing
reagents. The content was agitated
and heated by a mechanical stirrer
and heating mantle respectively. The
reaction was carried out at
atmospheric pressure, and water vapor
and light ends were condensed and
collected during the process. Oil
was filtered immediately after the
reaction by means of a vacuum
filteration system, or allowed to
settle down at constant temperature
for a sedimentation study.
Analysis. Experimental results were
verified in accordance with an EPA
163
approved quality assurance project
plan. The properties of the
demetallized used oil were evaluated
to assess its potential as an EPA
specification-grade fuel oil by using
the following test methods: water
content, ASTM D4006-81 (water in
crude oil by distillation); ash
content, a modification of ASTM D482-
80 (ash from petroleum products); and
lead content by standard atomic
absorption analysis.
METAL REMOVAL MECHANISM
Lead and other metal contaminants are
present in waste oil in
organometallic form. The DAP
(NHq)2HP04) reacts with
organometallic compounds to form
insoluble and separable products.
The reaction of this type has been
discussed by Miller(6):
(RS03)aCab (OH), (co3)d + excess
(NHq)2HP04
+ C02 + H20
- Cag(P04)3(OH) + NH4RSO3
Based on the above reaction, the
calcium overbased sulfonate detergent
reacts with DAP to form a metallic
hydroxyl apatite (Cag(P04)30H), which
is insoluble in aqueous and oil
phase. This reaction mechanism is
general for Ca, Ba, Mg, and Zn
additives. Lead is present in a
physically different form than
additive compounds in the used oil.
The lead particles present in used
oil are too large in size to react
with DAP, except for surface
reactions.
The organometallic additives in waste
oil react with DAP in the interfacial
region as shown in figure 1. The
additives are oriented with the
metallic parts near the aqueous phase
and the organic parts toward the oil
phase. This what causes the outer
surface of the droplets to bear a
negative charge, which attracts the
positive dipole associate with the
organolead compounds. The ionic
attraction effect is enhanced when
water is removed from the
agglomerates. The lead particles are
entrained with the agglomerates of
metallic hydroxyl phosphates and then
settle down.
RESULTS AND DISCUSSIONS
The proposed DAP demetallization
mechanism suggest that water removal
during the reaction favors the
agglomeration of metallic hydroxyl
apatites, which would facilitate the
solid-liquid separation later on.
The presence of water during the
reaction was found to play an
important role as a carrier for the
DAP, aiding in its dispersion and
reducing the importance of mass
transfer. The DAP was dissolved in
the water (30 wt8 solution) prior to
the reaction. The optimum ratio of
DAP to ash content was found to be
between 2 to 4 wt%. A higher
percentage of DAP favors the ash and
lead reduction, but problems
associated with using a large amount
of DAP are: (i) the great deal of
sludge produced, which results in a
solid-waste disposal problem; (ii)
wear and tear of equipment: (iii) a
decrease in the filteration rate; and
(iv) the high cost of the reagent.
To investigate the effect of DAP on
ash and lead reduction, several
experiments were performed in which
waste oil was treated with different
amounts of DAP. The reaction was
carried out at 15OoC for an hour.
Oil was filtered after the reaction
by Whatman 3 filter paper. Table 1
shows the percentage reduction of ash
and lead with respect to DAP. It
should be noted that the amount of
DAP required to demetallized a waste
oil depends OR the ash content of the
waste oil. The higher ash content
requires a higher amount of DAP.
The reaction between additive metals
(Ca, Ba, Mg, etc.) and DAP goes to
completion and is less dependent of
reaction temperature and time. Lead
is present in motor oil in a form
that is physically and chemically
different from additive metals. The
additive metals are almost
exclusively group I and group I1
elements. Compounds of these
elements tend to be more reactive
than lead compounds and also are
more ionic in nature than their lead
counterparts. Since lead is not

x
x x METAL
HYDROXYL

x - PHOSPHATE
PARTICLES
FORM AT
INTERFACE

OIL PHASE >( OICPHASE x

% LEAD COMPOUND
%. PARTICULATES HEATING
EVAP0 R ATE S
AQUEOUS PHASE

AGGLOMERATION OF.
HYDROXYL PHOSPHATES
WITH ENTRAINED
LEAD PARTICULATES
(REMOVED BY FILTRATION).

Figure 1 Proposed Mechanisms f o r Additive Metal and Lead Removal(6)

164
 TABLE 1: EFFECT OF DAP ON ASH AND LEAD REDUCTION

% OF DAP % ASH % ASH LEAD % LEAD

w.r.t. OIL CONTENT REDUCTION CONTENT REDUCTION
(PPd
~ -
8 0.02 97 24 96

5 0.03 96 24 96

2 0.08 86 60 90

1 0.25 58 230 65

0 0.58 3 650 2

Reaction Temperature: 15OoC, Holding Time: 1 Hr

Ash and Lead-content of used o i l before reaction was 0 . 6 wt %, 660 ppm,

directly removed via chemical apparently combine with oxygen at the

reaction with DAP, its removal is not carbon atoms near the end of the
independent of the temperature or the chains, and the mechanism of
residence time. As seen in figure 2, oxidation has been suggested as:
increasing the residence time has a
great effect on the removal of lead (1) paraffinic hydrocarbons - - - -
from used oil. primary Alcohols - - - - aldehydes - - - -
acids.
Table 2 shows the effect of
temperature on the lead reduction.
There is hardly any lead reduction 100 I
when reaction temperature is less
than 100°C. Presence of water during
the reaction prevents agglomeration
of hydroxyl phosphates, which 75
facilitate the removal of lead
particles. As discussed earlier, the
removal of m t e r dwing ths rozctica
entrains the lead particles with the
agglomerates of metallic hydroxyl 50
phosphate.

SLUDGE REMOVAL

?
R
All hydrocarbon oils react with 25
oxygen upon exposure to air at
sufficiently elevated temperatures
for long periods of time. Over the
range of temperatures developed in
engine crankcase, the rate of oil 0 0 (Min)
25 Time 50
Holding
5
oxidation has been found to double
for every 20°F rise in temperature.
Although all lubricating oil
hydrocarbons are susceptible to
oxidation, of more importance to Fig. 2 Effect of Holding Time on
engine performance are the oxidation
products. Paraffinic hydrocarbons Reaction Temp.-
-
Lead Reduction (DAP 2 wt%,
150OC)

165
 TABLE 2: EFFECT OF REACTION TEMPERATURE ON LEAD REDUCTION
REACTION TEMP.
OC
200
150
120
80
Holding time: 1 Hr, DAP: 2% wt.
Ash and Lead content of used oil before reaction was 0.6 wt%
and 660 ppm.
( 2 ) paraffinic hydrocarbons - - - -
secondary alcohols - - - - ketones - - - -
ketonic acids.
Thus, oxidation of paraffins yields
alcohols, aldehydes, ketones and
acids. The acids formed are
vigorously corrosive to copper, lead
and cadmium engine bearings.
Naphtenic hydrocarbons yield products
similar to paraffins upon oxidation.
Aromatic hydrocarbons are the most
readily oxidized constituents of
lubricating oils. The end products
are very complex condensation and
polymerization products and tend to
be insoluble in oil. These products
constitute the sludges, resins and
varnishes which allegedly cause
piston ring sticking in the engine.
In particular, detergent additives
are used to disperse oxidative
products and other contaminants, and
to keep them in suspension. The
amount of additives and sludge
present roughly corresponds to 10% of
the used oil component. These
impurities clog the filter media and
slow down the filteration rate
considerably.
Removal of carbonaceous impurities
and sludge from lubricating and
industrial oils generally have been
achieved by acid-clay treatment.
During acid-clay treatment, a
substantial amount of the diaromatics
and polyaromatics-polarmaterials are
lost. The higher molecular weight
aromatics are generally associated
LEAD CONTENT % LEAD
(PPI REDUCTION
20 97
70 97
150 77
600 9
with natural lubricity
characteristics of the base oil, and
therefore selective removal of these
compounds by acid treatment would
affect this parameter of the
lubricant product. Acid treatment
produced a very large amount of acid
sludge which threatens to pose a
larger pollution problem than that
caused by the used lubricating oil.
Relatively l o w process yield (50-60%)
and almost intractable residue
problems lead to a firm
recommendation against its use in the
re-refining industry.
In order to remove the sludge from
the used oil, a large number of
chemical agents were tried as sludge
flocculants. Many of the reagents
were ineffective in removing the
sludge from the used oil. Of the
most effective materials,
triethanolamine (TEA) was found to be
a good sludge flocculant. TEA has
three hydroxyl groups and one amino
group. In general, it can be
considered that the hydroxyl group
serves to reduce the vapor pressure
and increase the water solubility,
while the amino group provides the
necessary alkalinity in water
solutions to cause the neutralization
of acids (8).
A detailed parametric study was done
in order to evaluate the
effectiveness of TEA and DAP on the
ash and lead reduction. Prior to
reaction TEA was dissolved in the DAP
solution (20 wt%) and was treated
with used oil for an hour. After the
reaction processed oil was allowed to
settle down for a day at 8OoC. The
amount of oil recovered is calculated
and analyzed for ash and lead
content.
Table 3 shows that ash and lead
content of oil is reduced
significantly at low temperature
(8OOC.). One possible explanation of
high lead reduction at low
temperature is that lead, being
heavier than additive metals,
separates with the sludge, while
reaction between additive compounds
and DAP is less dependent on the
temperature.
Tables 4 and 5 shows the effect of
different amounts of DAP and TEA on
ash and lead reduction. Significant
points emerging from the data of
tables 4 and 5 are: (1) without DAP,
-ool
1
0
Fig. 3 Effect of Settling
Temperature on Oil Recovery
(DAP = 1 wt%, TEA = 0.5
ut% Settling Time - 24 hrs)
167
only 25% ash reduction is obtained
compared to 87% with 1 wt% of DAP;
(2) ash reduction seems to increase
with increasing amount of DAP, and it
remains constant after further
increase in percentage of DAP; and
( 3 ) the low o i l recovery at high
concentration of TEA (table 5) is
due to separation of heavy .
hydrocarbons with the sludge. The
last colum2 of these tables (~01%
recovery) is based on the volume % of
recovered oil, whose ash and lead
content was below 0.15 wt% and 10
ppm, respectively. It can be seen
from these tables that 90% of oil is
recovered after the treatment, which
is very high considering the fact
that used motor oii contains roughly
8 to 10% of sludge and additives.
Figures 3 and 4 shows the effect of
settling temperature and time on oil
recovery. Higher temperature
facilitates the separation of sludge
from the oil.
25
I
O 0 10 20 30 L
40
Settling Time (hr)
-
Fig. 4 Effect of Settling Time on
Oil Recovery (DAP 1 wt%,
TEA = 0.5 wt%, Settling
-
Temperature 8OoC)
 TABLE 3: EFFECT OF REACTION TEMPERATURE ON ASH AND LEAD REDUCTION

TEMP ASH CONTENT RED. LEAD CONTENT RED.

oc. % % ( PPm) %
Before After Before After
Rea. Rea. Rea. Rea.

50 0.85 0.45 47 75 30 60

80 0.89 0.11 87 109 6 93

100 0.89 0.13 84 108 8 92
~~~ ~~

DAP: 1 w t %, TEA: 0.5 w t %, Holding T i m e : 1Hr.

TABLE 4: EFFECT OF DAP ON ASH AND LEAD REDUCTION

~

DAP ASH CONTENT RED. LEAD CONTENT RED. RECOVERY

% % % (P F d % vol%
Before Mter Before After
Rea. Rea. Rea. Rea.

0.0 0.86 0.65 25 114 50 56 0.0

0.5 0.89 0.47 47 91 25 73 0.0
1.0 0.89 0.11 87 109 6 93 89

1.5 0.80 0.10 86 89 4 95 92

2.0 0.82 0.11 86 69 2 97 92

TEA: 0.5 w t %, Reaction T e m p e r a t u r e : 8OoC.

TABLE 5: EFFECT OF TEA ON ASH AND LEAD REDUCTION

TEA ASH CONTENT RED. LEAD CONTENT RED RECOVERY

% % % (P P d % vol%
Before After Before After
Rea. Rea. Rea. Rea.

0.5 0.89 0.11 87 109 6 93 89

1.0 0.88 0.13 84 118 4 96 90

1.5 0.82 0.07 90 122 2 97 65

DAP: 1 w t %, R e a c t i o n T e m p e r a t u r e : 8OoC.

168
 FLOW SHEET FOR WASTE OIL RECOVERY PLANT
OIL FROM
VENDORS
I
.)-

STORAGE
TANK

D,000 GAL

I
BASKET
FILTER
F
TANK

2,500 f
RECIRCULATION LINE
r---------
EXHAUST
1
I
I
I

I VENT 1 DEMETALLATION
UNlT
- FEED POSITIVE
WInu2

PUMP DISPLACEMENT
PUMP
SETTLING
TANK

MSPLACEENT
PUMP

'RODUCT Ow
STORAGE
-------------
BY-PASS LINE
TANK

I
PLATE AND WATER
I FRAME FILTER !tTER CENTRIFUGE
EMULSION POSITIVE DISPLACEMENT
PUMP
TO TANKER
-SLUDGE FOR
DISPOSAL
Based on this work, the Chemical
Engineering Department of Auburn
University is developing a pilot
plant for waste oil recovery (see
flow diagram). The pilot plant will
have a capacity to treat 5
gallons\min of waste o i l . Further
research work is still being carried
out in this field.
CONCLUSIONS
and F. 0. Cotton, "Waste Lubricating
Oil Research: An Investigation of
Several Re-Refining Methods, I' Bumines
RI 7884 (1974).
(6) Miller, T. M. "An Investigation
of the Demetallization Chemistry
Associated with the Re-Refining of
Used Motor O i l , " M. S. thesis, North
Carolina State University, Raleigh,
N.C. (1983).

(1) The organometallic additives in (7) Comeford, J. J., "Test Procedures

waste oil react with DAP in the
interfacial region and form metal
hydroxyl phosphate.
(2) TEA was very effective in
removing sludge and lead from the
waste oil.
for Recycled Oil Program," NBS
special publication 556:133-137
(1979).
(8) Arthur Kohl, Fred Riesenfeld, Gas
Purification; Gulf Publishing Company
(1985).

(3) Reaction conditions of this

process were very mild compared to
other waste oil recovery processes.

(4) Oil recovery depends on settling

time and temperature and is greater
at higher temperature.

(5) More than 85% ash and lead

reduction is obtained by treating
waste oil with 1 wt% DAP and 0.5 wt%
TEA for an hour at 8OoC under
atmospheric pressure.

(1) Vaughn S. Kimball, Waste Oil

Recovery and Disposal; New Jersey:
Noyes Data Corporation (1975).

(2) T. D. Coyle and A. R. Siedle,

"Metals in Oil Occurrence and
Significance for Reuse of Spent
Automotive Lubrication Oil." NBS
special publication 556-559 (1979).

(3) Cotton, F. O., "Waste Lubricating

Oil. An Annotated Review," BETC /. IC-
79 / 4 (1979).
(4) Stubbs, Overbeck and Associates,
"Engineering Design of a Solvent
Treatment / Distillation Used
Lubrication O i l Re-Refinery, DOE /
BC / 1009-9 (1980).

(5) M. L. Whisman, J. W. Geotzinger,

170