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.

-------
  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.

-------
  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

-------
United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
Postage and
Fees Paid
Environmental
Protection
Agency
EPA 335
Official Business
Penalty for Private Use $300
       U S ENVJR  PROTECTION
       REGION ^ LibRMRY
       230 S  DtARBORN  iiTHEtT
       CHICAGO  IL

-------