H/
United States
Environmental Protection
Agency
Robert S. Kerr Environmental
Research Laboratory
Ada OK 74820
Research and Development
EPA-600/S2-83-010 Apr. 1983
Project Summary
Environmental Assessment
Data Base for Petroleum
Refining Wastewaters
and Residuals
Francis S. Manning and Eric H. Snider
The objectives of this study were to
develop a comprehensive environment-
al data base for the characterization and
control treatment of petroleum refinery
wastewaters and residual sludges and
the recommendation of areas where
further research is needed to improve
the data base.
The project was conducted in three
phases. Phase one was the establish-
ment of a Peer-Group Review
Committee to provide direction to the
project and to ensure that a diversity of
viewpoints was considered. Six
eminent experts in the field of waste
treatment were chosen to serve on the
committee.
Phase two involved the preparation of
four state-of-the-art reviews, by
outside consultants, to provide a
comprehensive environmental data
base on refinery wastewaters and
residual sludges as well as identifying
the control technologies used in the
refining industry.
Phase three included a critical
examination of the four individual state-
of-the-art reviews and selection of
specific areas where further research
was needed to improve the data base.
Each of the specific research areas
selected as needing improvement is
discussed in some detail so as to
explain why further research might be
fruitful and to highlight the benefits that
might be expected of such research.
The study also includes a summary of
conclusions regarding future trends in
refinery processing technology, future
trends in wastewater reuse within
refineries, and the performance
capabilities of current wastewater
treatment technology.
This Project Summary was developed
by EPA's Robert S. Kerr Environmental
Research Laboratory, Ada, OK, to
announce key findings of the research
project that is fully documented in a
separate report of the same title (see
Project Report ordering information at
back).
Introduction
This study developed a comprehensive
environmental assessment data base for
the characterization of petroleum refin-
ery wastewaters and residuals, and for
the performance capabilities of refinery
wastewater treatment technology. As a
result of the study, areas were selected
where further research was needed to
improve the data base. The work was
accomplished by establishing a Peer-
Group Review Committee; developing
four state-of-the-art reviews by outside
consultants; critical examination of those
reviews and selection of specific areas
where further research was needed.
A Peer-Group Review Committee of six
eminent experts in the field of refinery
wastewater treatment, most of whom
had actual experience in refinery
wastewater management, were chosen
to serve on the committee which provided
oversight direction to the project. The
committee members chosen represented
a broad spectrum of diverse viewpoints
from industry, universities, and the
consulting field.
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To develop the environmental assess-
ment data base, state-of-the-art reviews
were prepared by outside consultants on
four topics:
1. Characterization of the petroleum
refining industry and refinery
wastewaters. The parameters
affecting the generation of waste-
water pollutants are discussed,
including crude oil compositions,
refinery technologies and classifi-
cations, wastewater sources and
wastewater pollutants.
2. A pollutant discussion and
rationale for characterizing the
wastewaters from petroleum
refineries and their toxicity effects
upon aquatic organisms. This
rationale includes a review of the
analytical procedures used to
measure, define, and assess the
effects of the various pollutants.
The pollutants considered include
the current permit parameters
(COD, BOD, etc.) as well as the
priority pollutants.
3. A comprehensive discussion and
evaluation of existing and
emerging wastewater treatment
and control technology. Data on the
performance capabilities of the
various technologies are included.
4. A compilation of data on the
discharge levels of refinery waste-
water pollutants including their
avenues of discharge. The data
include estimates of accuracy,
precision, variances and causes of
variance.
Research Needs
The amount and composition of waste-
waters and sludges generated by
petroleum refineries are highly variable
and are dependent upon a complete
matrix of factors. There is a large existing
data base on the characteristics and
variability of refinery wastewaters. There
is also a large body of literature, data, and
case histories concerning the existing
control technologies for treating refinery
wastewaters and sludges. The four
state-of-the-art reviews included in the
complete study report present the details
of the existing data base in a comprehen-
sive manner. Based upon a critical
examination of the individual state-of-
the-art reviews, key areas within the
existing data base were selected as
needing further research in order to
provide:
• More valid and better correlated
data on the variability in the char-
acteristics of refinery waste-
waters and sludges.
• More information related to the
long-term toxicity effects of
refinery wastewaters upon fish.
• Better demonstrated data on the
design parameters, economics, and
performance capabilities of specific
control technologies for the
treatment of refinery wastewaters
and sludges.
• More and better guidance as to the
technological and economic
feasibility of methods proposed for
the ultimate disposal and/or reuse
of treated wastewaters, concen-
trated pollutant brines and residual
sludges.
Based upon the above criteria, eight
specific areas are identified in the study
report as being in need of further
research in order to improve the existing
data base. Each specific area is discussed
in detail to explain why further research
is needed and what benefits might be
expected from such research. Two of the
areas selected involve gathering and
correlating actual plant data from existing
control technologies: activated sludge
biotreatment and chemical oxidation
treatment. Two other areas selected
involve laboratory research to: identify
specific refinery pollutants which exhibit
long-term, lethal or sublethal fish toxicity;
develop techniques for the more rapid
determination of long-term fish toxicity;
and develop new pollutant analysis
methods which are more reliable and
would therefore reduce the effect of
unreliable analytical methods upon
effluent quality variability. Three of the
selected research areas involve pilot-
scale and demonstration-scale testing
and development work: the development
of a method for regenerating spent
powdered activation carbon (PAC) used to
enhance biotreatment; large-scale
demonstration of the granular activated
carbon process (GAC), and pilot testing of
landfarming to define odor and air
emission problems and their mitigation.
The final research area selected
involves a comprehensive feasibility and
guidance study regarding the methods of
producing a concentrated residual
pollutant brine (reverse osmosis and
evaporation), and the ultimate disposal of
residual wastewater pollutants in
subsurface injection wells, evaporation-
percolation ponds or remote disposal
dumps.
Conclusions and
Recommendations
Existing refinery technology is very
complex, and the development of new
technology is an on-going process.
Within the period 1940 to 1960, a
number of technological "breakthroughs"
occurred which included the develop-
ment of fluid catalytic cracking and
processes involving catalysis in a
hydrogen atmosphere. With the current
body of knowledge on catalytic processes,
the future development of new refinery
technology is expected to be more evolu-
tionary in nature. Another period of rapid
technological breakthroughs is not
expected.
Many refineries already practice the in-
plant reuse of treated wastewaters to
some extent, and air cooling has replaced
much water cooling. For those reasons,
there is little likelihood that more
intensive emphasis on wastewater reuse
will dramatically reduce wastewater
volumes.
The current technology for refinery
wastewater treating includes the in-plant
reduction of wastewater generation,
primary removal of oil and suspended
solids, and secondary treatment via
biological oxidation. In general, that
current technology can satisfy the regula-
tory criteria for control of the convention-
al pollutants such as oil, suspended solids,
BOD, COD, phenols, sulfides, ammonia,
etc. There is also much evidence that the
current technology essentially removes
or degrades those pollutants which cause
lethal short-term (96-hour) toxicity to fish.
Eight areas are identified in which
further research is needed to improve the
environmental data base for character-
izing and treating petroleum refinery
wastewaters and residual sludges. Those
areas of research needs are briefly listed
below:
Actual Plant Data and
Correlation
1. Correlation of the key design factors
in activated sludge biotreatment,
such as mixing horsepower and
reaction retention time, with pollut-
ant removal efficiency.
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2. Correlation of actual case history
data on the use and effectiveness
of chemical oxidants (hydrogen
peroxide, chlorine and ozone) in
treating refinery wastewaters.
Laboratory-Scale
Research and Development
3. Identifying the specific refinery
wastewater pollutants which ex-
hibit long-term fish toxicity. Devel-
opment of techniques for the rapid
determination of long-term fish
toxicity effects.
4. Determination of which analytical
test methods are the least reliable
and quantifying their contribution
to overall effluent quality variability.
Development of more reliable test
methods, if possible.
Pilot and
Demonstration-Scale Research
5. Development of an economic
method for recovering and
regenerating the spent powdered
activated carbon (PAC) used to
enhance the performance of
activated sludge biotreaters.
6. Funding the demonstration and
operation of the granular activated
carbon process (for the secondary
or tertiary treatment of refinery
wastewaters) at a scale capable of
the treatment of 200-400 gpm of
refinery wastewater.
7. For the landfarming of oily sludges,
determination of the relationship
between sludge vapor pressure
and problems of odor control and
air emissions. Development of
methods for mitigating such
problems; and investigation of
methods of resolving problems
with landfarming vis-a-vis RCRA
regulations if such problems exist.
Feasibility and Guidance Study
8. Development of a comprehensive
feasibility and guidance study
regarding the methods of
producing a concentrated pollutant
brine (by reverse osmosis and
evaporation) and the ultimate
disposal of residual wastewater
pollutants in evaporation-percola-
tion ponds, subsurface injection
wells and remote disposal dumps.
The study should include: realistic
assessment of capital costs and
energy usages, realistic
assessment of the benefits to be
gained in terms of the magnitude of
improvement in the quality of the
nation's waters, and determination
of the cost-benefit ratio of the
EPA's current NSPS "no
discharge" requirement for
refineries relative to control of
other pollutant sources such as
non-point sources.
Francis S. Manning and Eric H. Snider are with fulsa University, Tulsa, OK
74104.
Fred M. Pfoffer is the EPA Project Officer (see below).
The complete report, entitled "Environmental Assessment Data Base for
Petroleum Refining Wastewaters and Residuals," (Order No. PB 83-164 749:
Cost: $20.50, subject to change) will be available only from:
National Technical Information Service
5285 Port Royal Road
Springfield, VA 22161
Telephone: 703-487-4650
The EPA Project Officer can be contacted at:
Robert S. Kerr Environmental Research Laboratory
U.S. Environmental Protection Agency
P.O. Box 1198
Ada, OK 74820
fcU.S. Government Printing Office: 1983-659-017/7027
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Environmental Protection
Agency
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