Utilization of Revex™ Technology for Benzene

Reduction in Desalter Water Effluent

from Refinery Operations

Revex Technologies operated a pilot scale unit at La Gloria Oil and Gas Company’s Tyler, Texas
refinery. The purpose of the pilot test was to prove the effectiveness of Revex™ technology in
removing benzene and fractions of all other volatile organic compounds (VOC) from the water
effluent of the crude oil desalting process.

Background
The first step in the crude oil refining process mixes the crude oil with water to extract salt from
the crude. In addition, the process causes solids to precipitate as bottom sediments. The three
phases are then separated to prevent downstream corrosion from the salt and fouling from bottom
sediments. Although most hydrocarbons are minimally soluble in water, certain light hydrocarbon
compounds exhibit dilute solubilities. Benzene, toluene, xylene, and lower molecular weight ali-
phatics, such as hexane, exhibit solubilities as high as 100 ppm depending on the solution temper-
ature. Benzene emissions are currently controlled under the Clean Air Regulations by the
National Emission Standards for Hazardous Air Pollutants (NESHAP) regulations. Under certain
conditions these regulations require point source control of potential benzene emissions from
waste water.
Historically, benzene removal from the waste water stream from refinery desalter units has pre-
sented considerable operating difficulties due to potential process complications including:
1. Difficulty in breaking emulsions created by the process,
2. Solids or bottom sediments accumulated in the process,
3. Upsets in the process due to the necessity of “mud washing” to remove accumulated solids
from the desalter vessel, and
4. Temperature and pressure variations during “mud washing” operations.

REVEX TECHNOLOGIES, INC. • P.O. Box 940129 • Houston, Texas 77094-7129 • 281-493-9221 • Fax 281-721-0506
REVEX TECHNOLOGIES

Pilot Test Equipment and Fluids

The equipment used to perform the pilot test at the La Gloria refinery is represented on the draw-
ing on page 4 of this report. The primary fluid streams for the test, which are depicted in the draw-
ing, are described in some detail in the following two subsections.

Liquid Stream
The Revex™ unit was supplied with desalter effluent at the available system pressure of the
desalter, which varied between 50 and 100 psig. The driving pressure and piping system together
flowed 45 to 75 gpm to the Revex™ unit with no additional flow control or throttle valve. How-
ever, an auxiliary pump may be required for larger systems.
Variations of the Total Petroleum Hydrocarbon (TPH) concentration and the solids content of the
liquid stream, primarily due to mud washing, do not affect the operation of the Revex™ unit. Oils
and solids flow through the liquid side of the unit without plugging and without significantly
affecting the final benzene concentration of the treated stream.
Desalter temperature does affect the solubility of benzene in the stream and thus the incoming
concentration. High concentrations in the liquid phase generally occur at lower operating temper-
atures.

Gas Stream
The gas utilized in the Revex™ unit to strip VOCs from the desalter effluent was the fuel gas pro-
duced by the refinery reformers. This fuel gas primarily contains hydrogen and methane, but it
also contains many other hydrocarbons, including benzene. There are two reformers of varying
capacities at La Gloria, and the off-gas from the higher volume reformer is generally processed
through a cryogenic unit to recover propane and heavier hydrocarbons. The discharge from the
cryogenic unit is subsequently mixed with the discharge gas from the smaller reformer to produce
the refinery fuel gas. This gas is used as an energy source for the production of steam and for fuel-
ing fired equipment involved in the processing of crude oil.
During the test, a portion of the fuel gas was piped to the Revex™ unit where it was used to con-
tact and strip volatile components from the desalter water effluent. The discharge gas from the
Revex™ treatment unit was piped back to a fuel gas burner where it was burned to heat crude oil.
The fuel gas simply made a detour through the Revex™ unit to remove benzene and other volatile
hydrocarbons from the water, without altering its original purpose or utility.
The pressure differential between the main fuel gas header and the downstream heater provided
adequate driving pressure to flow the necessary volume of gas through the Revex™ unit. This
available pressure drop was approximately 20 psig. The unit operated with the pressure drop
available without additional flow control of the gas. Larger processing units may require a pres-
sure increase on the order of 10 to 15 psig.
The amount of “blowby” or entrainment of liquid carried over into the gas phase and thus to the
knockout pot was approximately 0.2%.

Page 2 of 6
REVEX TECHNOLOGIES

Due to complications involved in operating the reformers and to the cryogenic recovery of higher
hydrocarbons, spot gas analyses of the fuel gas stream indicated that the benzene content of the
influent fuel gas varied from approximately 0.03 to 0.1 mole percent. The benzene concentration
of the fuel gas limits the ultimate equilibrium concentration of benzene in water treated with this
gas. With the Henry’s constant value of benzene estimated at 2000 atmosphere/mole fraction at
230° Fahrenheit, the lower equilibrium limit of Revex™ treatment of the liquid can be estimated.
The resulting calculations show the lower limit of benzene concentration in the Revex™ dis-
charge water was about 2 ppm when the cryogenic unit was not in operation and about 0.7 ppm
when it was in operation. Although the above limits were calculated on spot analyses of the gas
stream, these limits yield a more in-depth understanding of the results achieved by the Revex™
treatment unit.

Test Performance Data

The analytical performance data which were gathered during the pilot test of the Revex™ system
in the desalter unit operation are shown on the chart on page 5 and in the table on page 6.

Summary
The test performance data show that the overall benzene removal rate varied significantly, depend-
ing on the operating conditions of the refinery. However, the net result of the treatment was gener-
ally within the theoretical limits established by the gas phase equilibrium calculations for volatile
hydrocarbons. The objective, to reduce the overall stream to less than 10 ppm VOC, was achieved
with one exception (see data for March 26). The Revex™ unit will perform on a consistent basis
with no degradation in VOC reduction efficiency due to fouling by the oil or solids content of the
treated water.
For more information or for continuing updates on the status of the expanding set of Revex™ unit
applications, please contact:

Revex Technologies, Inc.

P.O. Box 940129
Houston, Texas 77094-7129

Phone: 281-493-9221
Fax: 281-721-0506
Email: sales@RevexTechnologies.com

Page 3 of 6
 LA GLORIA BENZENE REDUCTION PILOT TEST
DESALTER WATER EFFLUENT TO REVEX UNIT

40 220
ppm
35 spike

30
BENZENE, PPM

25

20 96.0%

68.6% 90.6%
15
80.6% 84.8% 87.0%
10
84.4%
86.6% 84.0% 62.8%
90.0%
5 79.6%
84.0%
0
3-25 3-25 3-26 3-27 3-28 3-29 3-30 3-31 4-1 4-8 4-9 4-10 4-11
FUEL GAS CRYOGENIC UNIT OUT OF SERVICE
DURING MOST OF TESTING
TEST DATES
Revex Technologies, Inc.
REVEX TECHNOLOGIES, INC.
LA GLORIA PILOT TEST FOR BENZENE REDUCTION - ANALYTICAL RESULTS

DAY MON MON TUE WED THUR FRI SAT SUN MON MON TUE WED THUR
DATE 3-25 3-25 3-26 3-27 3-28 3-29 3-30 3-31 4-1 4-8 4-9 4-10 4-11
TIME 1115 1415 715 1315 1300 500 600 600 700 1400 1200 1200 1400

BENZENE 86.6 80.6 68.6 90.0 84.4 84.0 84.8 90.6 96.0 84.0 62.8 79.6 87.0
% REDUCTION

INITIAL BENZENE 29 16 35 26 25 15 25 32 220 5.8 9.4 9.3 20

PPM

FINAL BENZENE 3.9 3.1 11 2.6 3.9 2.4 3.8 3 8.7 0.93 3.5 1.9 2.6
PPM

TOTAL PETROLEUM ************ ********** ********** 1500 16 1900 41 18 550000 6.9 110 15000 **********
HYDROCARBONS
PPM

DESALTER WATER 212 216 170 220 218 215 200 200 200 238 240 240 170
TEMPERATURE

LIQUID FLOW 53 53 44 50 50 64 65 71 54 69 69 60 59
RATE GPM

GAS DELTA P 14 17 18 20 20 19 23.5 22 20 17 16 20 20

GAS FLOW 114 126 129 136 136 133 148 143 136 126 122 136 136
RATE SCFM

NOTES: CYROGENIC UNIT OUT OF SERVICE FOR ALL TEST DATES AND TIMES EXCEPT 4-8-96 AND 4-10-96 DATA.

FUEL GAS STREAM IS COMPOSED OF GAS FROM THE PLATFORMER (75%) AND THE REFORMER (25%).

ALL THE PLATFORMER GAS IS PROCESSED THROUGH THE CYROGENIC UNIT WHEN OPERATIONAL BUT
REFORMER GAS IS NOT PROCESSED THROUGH THE CRYOGENIC UNIT.

GAS ANALYSIS (3-29) SHOWS BENZENE CONCENTRATION IN THE FUEL GAS STREAM AT 2000 PPM.

NOTE ELEVATED DESALTER WATER TEMPERATURE ON TEST DATES 4-8,4-9,4-10 AND NOTE THE
CORRESPONDING DECREASE IN INCOMING BENZENE CONCENTRATION.

ON 4-8, DECREASED DESALTER WATER RATIO FROM 8% TO 7.4%.