A Reprint from
New process effectively
recovers oil
from refinery waste streams
new process uses chemi-
A cally assisted, thermal
flashing to break diffi-
cult emulsions and recover
oil for reprocessing. The
process is best suited for
refinery waste management
and slop oil systems, where
it can process streams with
high oil content to recover
high-quality oil.
Recent testing of a full-
scale, commercial prototype
unit on slop oil emulsions at
a major Gulf Coast refinery
resulted in:
97.9% recovery of oil
with 99.3-99.6% purity
99.5% recovery of
water with 99+% purity
A centrifuge cake con-
taining 49-60% solids, 23-
30% oil, and 17-22% water.
Background
The ``Ohsol process is
an emulsion-breaking and
separation technology that
provides a continuous, low-
cost means of completely
and permanently separating
stable emulsions generated
by refinery process opera-
tions.
Specifically, the process is
designed to break the persis-
tent affinity of solids for oil,
and keep the solids from
sticking together and form-
ing small ``cages around
the oil droplets, says process
inventer Dr. Ernest Ohsol.
These cages resist strong
Reprinted from the August 15, 1994 edition of OIL & GAS JOURNAL
Anne Rhodes, Refining/Petrochemical Editor
EMULSION-TREATING PROCESS
Condenser
Heater Flash
control
Emulsion
feed
Chemical
injection
centrifugal forces and retain
unacceptably high levels of
occluded hydrocarbons.
UniPure Corp. developed
the process, which can
recover clean, dry oil, and
reduce the volume of solids
that must be disposed of.
And if a refiner wants to
process the recovered solids
in coker, the unit can pro-
duce a suitable slurry from
the centrifuge cake.
The process is applicable
to a wide range of refinery
waste materials, including
slop oils, desalter ``rag
layer, dissolved air flotation
float, API separator sludge,
Copyright 1994 by PennWell Corporation
Vent
Condensate
Flash drum
stabilizer
Three-phase
centrifuge
Cooler
crude tank sludges, and
spent lubricating oils.
Process description
A simplified flow dia-
gram of the Ohsol process is
shown in Fig. 1.
The process breaks strong
emulsions using a two-fold
attack:
1. The addition, under
pressure, of heat (and water,
if none exists) to the system
to raise the temperature and
pressure of the system to at
least 100 C. and 150 psig.
2. A quick pressure drop,
which flashes off part of the
aqueous phase.
Fig. 1
Liquid light-ends recovery
Solids recovery
Oil recovery
Water
Water
OGJ
The feed emulsions are
mixed in a static mixer with
an effective amount of sur-
factant, which acts as a
demulsifier. At a system
pressure of 150 psi, water is
added to the mixture, which
is then heated to more than
300 F. Heating can be either
direct, by steam injection, or
indirect, by heat exchange,
says Ohsol.
After high-temperature,
high-pressure blending, a
flocculating agent is added
using static mixers. The use
of a flocculant is particularly
desirable for emulsions con-
taining inorganic solids.
 TECHNOLOGY
This mist is an ideal envi-
ronment for phase transi-
tion. The surfactants pro-
mote separation of the phas-
es, and the polymers coat the
solids before they can recom-
bine with the oil. Once the
emulsion mixture has been
flashed, the oil, water, and
solids are separated easily
using conventional means,
such as a three-phase, Tri-
canter-type centrifuge. The
flashed vapors are con-
densed, and they separate
spontaneously into water
and light naphtha.
The process eliminates
the need to send slop oils
back to the desalter.
Small, stabilized, slop-oil
rag layers are prone to sud-
den expansion in the
desalter vessel, requiring
rejection with the brine to
In demonstration trials earlier this year, UniPure Corp.s skid-mounted, emulsion-treating avoid carry-over to the heat
unit recovered 97.9% of the oil contained in the waste streams of a U.S. Gulf Coast refinery exchangers, crude charge
(Fig. 2). heater, and fractionater.
Rejection with the brine pro-
Table 1 tects these facilities, but
transfers the problem to the
PERF TEST SUMMERY process sewer system and
API separators, where emul-
Oil recovery 84.7% in centrifuge product + 13.2% in overhead = 97.9%*
Water recovery 99.5% sion formation is exacerbat-
Steam consumption 94.5 lb/bbl feed ed.
Total output of centrifuge 192 lb/min or 24 gpm
As an added benefit, ben-
Composition: Solids, wt % Oil, wt % Water, wt % zene and other volatiles are
Feed 1.07-1.20 29.05-32.40 69.8-65.8 flashed from the incoming
Recovered oil 0.56-0.7 99+ 0.0-0.1 feed stream and condensed
Recovered water 0.5-0.9 1,200 mg/l. TPH 99+ for recovery. The oily waste
Centrifuge cake 49-60 23-30 17-22
stream discharged from the
*For this test, the waste water containing a small amount of nonemulsified oil (1-2%) was discharged to the process sewer. Oil recov- process therefore contains
ery can be enhanced by discharging the waste water to a tank to skim off the oil before treatment.
Slop oil emulsion. only low concentrations of
Analyticals: solids by acetone/methylene chloride solvent extraction, oil by difference, water by ASTM D-95 (water by distillation), benzene. The small amount
TPH by EPA Method 418.1
Total petroleum hydrocarbons. of condensed water may
contain regulated contami-
Table 2 nants, but this stream can be
stripped of these compounds
RESULTS OF SECOND DEMONSTRATION TRIAL* easily, or sent to complying
Feed, recovered oil:
sewer lines.
Oil, wt % Water, wt % Solids, wt % Because volatile organic
Feed 1 97.04 2.24 2.72 compounds such as benzene
Feed 2 40.00 53.000 7.00
Recovered oil 99.62 0.30 0.08 are removed in the flash step
and recovered, the cost of
Recovered solids:
Solids, wt % Inorganic solids, wt % Water, wt % complying with the benzene
Solids 1 71.14 40.28 18.60 waste operations require-
Solids 2 67.71 30.77 14.69 ments (national emissions
Recovered water: standards for hazardous air
Benzene, ppm Oil & grease wt % pollutants, or Neshaps) and
Recovered water 2.7 1.36
future hazardous organic
*Modified unit
Slop oil emulsions
Nashaps regulations, is built
into the process.
The high flow capability
The pressure is released ing, followed by flashing, The temperature drop of the process (150 gpm)
suddenly by passing the ruptures the small cages that caused by the flashing also enables it to handle all of a
fluid through a Venturi noz- stabilize the emulsion and interrupts degradation of refinerys slop oil and oil
zle, which flashes it and produces an atomized mist the polyamide, or other sur- sludge streams economical-
cools the mixture. This of tiny, evenly divided oil factant, added to enhance ly. This eliminates the need
process of pressurized heat- and water droplets. solids removal.

for downstream processing,
such as in conventional emul-
sion treating, filter presses,
belt presses, centrifuges, and
thermal dryers. The Ohsol
unit is a modular, skid-
mounted process that can be
transported easily (Fig.2).
This design reduces the cost
of installing the process.
PERF study
The Petroleum Environ-
mental Research Forum
(PERF) is a group of oil com-
panies that conducts cooper-
ative research under the aus-
pices of the 1986 National
Cooperative Research Act.
Ten oil companies joined for
PERF Project 91-14 to evalu-
ate technologies to minimize
the environmental impact of
crude oil desalter operations.
Treatment options for the
brine discharge and desalter
mud wash were evaluated.
BP Oil Co.s environmental
technology division was
selected as the prime con-
tract researcher, and Mobil
Research & Development
Phone: (713) 850-0010
TECHNOLOGY
Corp. provided contract
coordination.
In the projects initial
phase, ``paper studies of
the performance and eco-
nomics of eight treating tech-
nologies were conducted. A
generic, 100,000 b/d refinery
was used as the basis, as
were average desalter
stream properties, as deter-
mined by a survey of the
PERF participants.
In late 1992, a committee
comprising a representative
from each participating com-
pany selected three comple-
mentary technologies on
which to conduct field and
laboratory trials. UniPures
Ohsol process was one of the
technologies tested.
In the third quarter of
1993, UniPure conducted
field trials on desalter emul-
sion and slop oil at one par-
ticipants refinerya major
Gulf Coast facility. A sum-
mary of the results of the
PERF tests is shown in Table
1. The purity of the recovered
oil was greater than 99%.
UniPure Corporation
12 Greenway Plaza
Suite 1380
Houston, Texas 77046
Facsimile: (713) 850-7776
The successful trials led
to modifications that give the
process greater ability to
handle varying stream quali-
ty and flow rates.
Second field trial
In the second quarter of
this year, the modified unit
was demonstrated on slop
oil and desalter rag-layer
emulsions at another major
Gulf Coast refinery. The feed
streams ranged from 5%
bs&w to 60% bs&w, with the
solids content varying from
2.5 to 17% (Table 2).
Typical results from this
test were:
Oil <1% bs&w (oil
purity as high as 99.62%)
Water1.3% oil and
grease (no emulsion), with
<10 ppm benzene
Solids65-71% dry
solids, with 14-18% water.
The recovered oil, light
ends, and water discharged
from the unit were remixed
in a common header system
and pumped to a recovered-
products tank. The refiner
tested the tank contents
intermittently and verified
that the oil and water did not
emulsify again.
Costs
Remediation Technolo-
gies Inc., Mandeville, La.,
performed a study of the
economics of the Ohsol
process. A 100,000 b/d refin-
ery that does not send solid
streams to a coker is project-
ed to save about $2.3 mil-
lion/year using the process.
A refinery of the same size
that sends 100% of its solid
streams to its coker would
save about $780,000/year.
These cost savings stem
from three major factors:
1. Enhanced recovery of
higher-valued oil
2. Volume reduction of
solids for disposal
3. Breaking of intractable
emulsions, thus avoiding
prolonged storage, disposal,
or both.
The process has been
patented in the U.S. and
Europe.