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A Reprint from

New process effectively


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

new process uses chemi-

A cally assisted, thermal


flashing to break diffi-
cult emulsions and recover EMULSION-TREATING PROCESS
Fig. 1

oil for reprocessing. The Condenser Vent


process is best suited for
refinery waste management
and slop oil systems, where
Condensate
Heater Flash
Flash drum

stabilizer
it can process streams with control Liquid light-ends recovery
high oil content to recover Emulsion
high-quality oil. feed
Three-phase
Recent testing of a full- centrifuge
scale, commercial prototype
Chemical
unit on slop oil emulsions at injection Cooler
a major Gulf Coast refinery
resulted in:
Solids recovery
97.9% recovery of oil
with 99.3-99.6% purity Oil recovery
99.5% recovery of
water with 99+% purity Water
A centrifuge cake con-
taining 49-60% solids, 23- Water
30% oil, and 17-22% water.
OGJ

Background centrifugal forces and retain crude tank sludges, and The feed emulsions are
The ``Ohsol process is unacceptably high levels of spent lubricating oils. mixed in a static mixer with
an emulsion-breaking and occluded hydrocarbons. an effective amount of sur-
separation technology that UniPure Corp. developed Process description factant, which acts as a
provides a continuous, low- the process, which can A simplified flow dia- demulsifier. At a system
cost means of completely recover clean, dry oil, and gram of the Ohsol process is pressure of 150 psi, water is
and permanently separating reduce the volume of solids shown in Fig. 1. added to the mixture, which
stable emulsions generated that must be disposed of. The process breaks strong is then heated to more than
by refinery process opera- And if a refiner wants to emulsions using a two-fold 300 F. Heating can be either
tions. process the recovered solids attack: direct, by steam injection, or
Specifically, the process is in coker, the unit can pro- 1. The addition, under indirect, by heat exchange,
designed to break the persis- duce a suitable slurry from pressure, of heat (and water, says Ohsol.
tent affinity of solids for oil, the centrifuge cake. if none exists) to the system After high-temperature,
and keep the solids from The process is applicable to raise the temperature and high-pressure blending, a
sticking together and form- to a wide range of refinery pressure of the system to at flocculating agent is added
ing small ``cages around waste materials, including least 100 C. and 150 psig. using static mixers. The use
the oil droplets, says process slop oils, desalter ``rag 2. A quick pressure drop, of a flocculant is particularly
inventer Dr. Ernest Ohsol. layer, dissolved air flotation which flashes off part of the desirable for emulsions con-
These cages resist strong float, API separator sludge, aqueous phase. taining inorganic solids.

Reprinted from the August 15, 1994 edition of OIL & GAS JOURNAL
Copyright 1994 by PennWell Corporation
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.
TECHNOLOGY
for downstream processing, Corp. provided contract The successful trials led tested the tank contents
such as in conventional emul- coordination. to modifications that give the intermittently and verified
sion treating, filter presses, In the projects initial process greater ability to that the oil and water did not
belt presses, centrifuges, and phase, ``paper studies of handle varying stream quali- emulsify again.
thermal dryers. The Ohsol the performance and eco- ty and flow rates.
unit is a modular, skid- nomics of eight treating tech- Costs
mounted process that can be nologies were conducted. A Second field trial Remediation Technolo-
transported easily (Fig.2). generic, 100,000 b/d refinery In the second quarter of gies Inc., Mandeville, La.,
This design reduces the cost was used as the basis, as this year, the modified unit performed a study of the
of installing the process. were average desalter was demonstrated on slop economics of the Ohsol
stream properties, as deter- oil and desalter rag-layer process. A 100,000 b/d refin-
PERF study mined by a survey of the emulsions at another major ery that does not send solid
The Petroleum Environ- PERF participants. Gulf Coast refinery. The feed streams to a coker is project-
mental Research Forum In late 1992, a committee streams ranged from 5% ed to save about $2.3 mil-
(PERF) is a group of oil com- comprising a representative bs&w to 60% bs&w, with the lion/year using the process.
panies that conducts cooper- from each participating com- solids content varying from A refinery of the same size
ative research under the aus- pany selected three comple- 2.5 to 17% (Table 2). that sends 100% of its solid
pices of the 1986 National mentary technologies on Typical results from this streams to its coker would
Cooperative Research Act. which to conduct field and test were: save about $780,000/year.
Ten oil companies joined for laboratory trials. UniPures Oil <1% bs&w (oil These cost savings stem
PERF Project 91-14 to evalu- Ohsol process was one of the purity as high as 99.62%) from three major factors:
ate technologies to minimize technologies tested. Water1.3% oil and 1. Enhanced recovery of
the environmental impact of In the third quarter of grease (no emulsion), with higher-valued oil
crude oil desalter operations. 1993, UniPure conducted <10 ppm benzene 2. Volume reduction of
Treatment options for the field trials on desalter emul- Solids65-71% dry solids for disposal
brine discharge and desalter sion and slop oil at one par- solids, with 14-18% water. 3. Breaking of intractable
mud wash were evaluated. ticipants refinerya major The recovered oil, light emulsions, thus avoiding
BP Oil Co.s environmental Gulf Coast facility. A sum- ends, and water discharged prolonged storage, disposal,
technology division was mary of the results of the from the unit were remixed or both.
selected as the prime con- PERF tests is shown in Table in a common header system The process has been
tract researcher, and Mobil 1. The purity of the recovered and pumped to a recovered- patented in the U.S. and
Research & Development oil was greater than 99%. products tank. The refiner Europe.

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