A Reprint from

New process effectively

recovers oil
from refinery waste streams
Anne Rhodes, Refining/Petrochemical Editor

EMULSION-TREATING PROCESS
Vent

Condenser

Heater Flash
control
Emulsion
feed

Chemical
injection

Condensate
stabilizer

Fig. 1

Flash drum

new process uses chemically assisted, thermal

flashing to break difficult 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 fullscale, 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 containing 49-60% solids, 2330% oil, and 17-22% water.

Liquid light-ends recovery

Three-phase
centrifuge

Cooler
Solids recovery
Oil recovery
Water
Water
OGJ

Background
The ``Ohsol process is
an emulsion-breaking and
separation technology that
provides a continuous, lowcost means of completely
and permanently separating
stable emulsions generated
by refinery process operations.
Specifically, the process is
designed to break the persistent affinity of solids for oil,
and keep the solids from
sticking together and forming small ``cages around
the oil droplets, says process
inventer Dr. Ernest Ohsol.
These cages resist strong

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 produce 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,

crude tank sludges, and

spent lubricating oils.

Process description
A simplified flow diagram 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.

The feed emulsions are

mixed in a static mixer with
an effective amount of surfactant, 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 containing inorganic solids.

Reprinted from the August 15, 1994 edition of OIL & GAS JOURNAL
Copyright 1994 by PennWell Corporation

TECHNOLOGY

In demonstration trials earlier this year, UniPure Corp.s skid-mounted, emulsion-treating

unit recovered 97.9% of the oil contained in the waste streams of a U.S. Gulf Coast refinery
(Fig. 2).
Table 1

PERF TEST SUMMERY

Oil recovery
Water recovery
Steam consumption
Total output of centrifuge

84.7% in centrifuge product + 13.2% in overhead = 97.9%*

99.5%
94.5 lb/bbl feed
192 lb/min or 24 gpm

Composition:

Solids, wt %

Oil, wt %

Water, wt %

1.07-1.20
0.56-0.7
0.5-0.9
49-60

29.05-32.40
99+
1,200 mg/l. TPH
23-30

69.8-65.8
0.0-0.1
99+
17-22

Feed
Recovered oil
Recovered water
Centrifuge cake

*For this test, the waste water containing a small amount of nonemulsified oil (1-2%) was discharged to the process sewer. Oil recovery can be enhanced by discharging the waste water to a tank to skim off the oil before treatment.
Slop oil emulsion.
Analyticals: solids by acetone/methylene chloride solvent extraction, oil by difference, water by ASTM D-95 (water by distillation),
TPH by EPA Method 418.1
Total petroleum hydrocarbons.

Table 2

RESULTS OF SECOND DEMONSTRATION TRIAL*

Feed, recovered oil:
Feed 1
Feed 2
Recovered oil

Oil, wt %
97.04
40.00
99.62

Water, wt %
2.24
53.000
0.30

Solids, wt %
2.72
7.00
0.08

Solids, wt %
71.14
67.71

Inorganic solids, wt %
40.28
30.77

Water, wt %
18.60
14.69

Benzene, ppm
2.7

Oil & grease wt %

1.36

Recovered solids:
Solids 1
Solids 2
Recovered water:
Recovered water
*Modified unit
Slop oil emulsions

The pressure is released

suddenly by passing the
fluid through a Venturi nozzle, which flashes it and
cools the mixture. This
process of pressurized heat-

ing, followed by flashing,

ruptures the small cages that
stabilize the emulsion and
produces an atomized mist
of tiny, evenly divided oil
and water droplets.

The temperature drop

caused by the flashing also
interrupts degradation of
the polyamide, or other surfactant, added to enhance
solids removal.

This mist is an ideal environment for phase transition. The surfactants promote separation of the phases, and the polymers coat the
solids before they can recombine 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, Tricanter-type centrifuge. The
flashed vapors are condensed, 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 sudden expansion in the
desalter vessel, requiring
rejection with the brine to
avoid carry-over to the heat
exchangers, crude charge
heater, and fractionater.
Rejection with the brine protects these facilities, but
transfers the problem to the
process sewer system and
API separators, where emulsion formation is exacerbated.
As an added benefit, benzene and other volatiles are
flashed from the incoming
feed stream and condensed
for recovery. The oily waste
stream discharged from the
process therefore contains
only low concentrations of
benzene. The small amount
of condensed water may
contain regulated contaminants, but this stream can be
stripped of these compounds
easily, or sent to complying
sewer lines.
Because volatile organic
compounds such as benzene
are removed in the flash step
and recovered, the cost of
complying with the benzene
waste operations requirements (national emissions
standards for hazardous air
pollutants, or Neshaps) and
future hazardous organic
Nashaps regulations, is built
into the process.
The high flow capability
of the process (150 gpm)
enables it to handle all of a
refinerys slop oil and oil
sludge streams economically. This eliminates the need

TECHNOLOGY
for downstream processing,
such as in conventional emulsion treating, filter presses,
belt presses, centrifuges, and
thermal dryers. The Ohsol
unit is a modular, skidmounted process that can be
transported easily (Fig.2).
This design reduces the cost
of installing the process.

PERF study
The Petroleum Environmental Research Forum
(PERF) is a group of oil companies that conducts cooperative research under the auspices of the 1986 National
Cooperative Research Act.
Ten oil companies joined for
PERF Project 91-14 to evaluate 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 contract researcher, and Mobil
Research & Development

Corp. provided contract

coordination.
In the projects initial
phase, ``paper studies of
the performance and economics of eight treating technologies were conducted. A
generic, 100,000 b/d refinery
was used as the basis, as
were
average
desalter
stream properties, as determined by a survey of the
PERF participants.
In late 1992, a committee
comprising a representative
from each participating company selected three complementary 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 emulsion and slop oil at one participants refinerya major
Gulf Coast facility. A summary of the results of the
PERF tests is shown in Table
1. The purity of the recovered
oil was greater than 99%.

The successful trials led

to modifications that give the
process greater ability to
handle varying stream quality and flow rates.

tested the tank contents

intermittently and verified
that the oil and water did not
emulsify again.

Second field trial

Remediation Technologies Inc., Mandeville, La.,

performed a study of the
economics of the Ohsol
process. A 100,000 b/d refinery that does not send solid
streams to a coker is projected to save about $2.3 million/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.

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 recoveredproducts tank. The refiner

Costs

UniPure Corporation
12 Greenway Plaza
Suite 1380
Houston, Texas 77046
Phone: (713) 850-0010
Facsimile: (713) 850-7776