United States
                                  Environmental Protection
                                  Agency
                                  Industrial Env ronmental Research
                                  Laboratory
                                  Research Triable Park NC 27711
SEPA
                                  Research and Development
                                  EPA-600/S2-81-052 Sept. 1981
Project  Summary
                                  Two-Stage  Biological
                                  Treatment of Coke  Plant
                                  Wastewater

                                  R. Osantowski, A. Geinopolos, James Meverden, and Joseph Milanowski
                                   The report documents a pilot-plant
                                  study of the use of advanced waste
                                  treatment methods in upgrading metal-
                                  lurgical  cokemaking wastewaters to
                                  Best Available Technology (BAT) levels.
                                  Mobile treatment units, operable at a
                                  flow rate of 19 l/min, were  used.
                                  Methods used included two-stage acti-
                                  vated sludge treatment for removal of
                                  organic carbon compounds and ammo-
                                  nia; filtration and activated carbon were
                                  also studied as polishing steps. For each
                                  treatment studied, samples (including
                                  toxic pollutants) and operational data
                                  were obtained for later use in assessing
                                  and  comparing  treatment adequacy.
                                  The  study showed that high levels of
                                  organic pollutant  removal  were
                                  achieved in the first stage of biological
                                  oxidation. Abnormal  operating condi-
                                  tions in the coke plant wastewater pre-
                                  treatment system during the testing
                                  resulted in ammonia levels as high as
                                  2000 mg/l, making it necessary to
                                  dilute the second stage feed before nitri-
                                  fication could be achieved. Ammonia
                                  reductions of > 97% were achieved in
                                  the second stage. Activated carbon and
                                  filtration effectively removed suspend-
                                  ed solids, total organic carbon,  color,
                                  and thiocyanate.

                                   This  Project  Summary  was
                                  developed by  EPA's  Industrial
                                  Environmental Research Laboratory,
                                  Research  Triangle  Park,  NC,  to
                                  announce hey 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
                                    In 1972, the Federal Water Pollution
                                  Control Act (PL92-500) was enacted by
                                  the U.S. Congress. The Act directed the
                                  U S. Environmental Protection Agency
                                  (U S EPA) to develop effluent limitation
                                  guidelines   for all  major  industrial
                                  groups, among them the steel industry.
                                  EPA was also mandated to recommend
                                  appropriate levels of treatment and esti-
                                  mate costs to meet the proposed limita-
                                  tions. As part of its overall mission, the
                                  EPA's  Industrial  Environmental  Re-
                                  search Laboratory (Research Triangle
                                  Park, NC) funded this study to determine
                                  the  feasibility  of treating steel plant
                                  wastewater to Best Available Technol-
                                  ogy  (BAT)  Economically Achievable
                                  levels.  This particular project was con-
                                  cerned with the'biological treatment of
                                  coke plant wastewater.
                                    The  primary purpose of this project
                                  was to investigate the technical and
                                  economical  feasibility of  biological
                                  treatment  of by-product cokemaking
                                  wastewater to  Best Available Technol-
                                  ogy (BAT) levels.* Principal wastewater
                                  sources produced from the by-product
                                  recovery process  at the plant investi-
                                  gated included excess ammonia liquor
                                  and  benzol plant wastes. Wastewater
                                  treatment at this plant  consisted of
                                  stripping the waste ammonia liquor via
                                  steam  and caustic solutions, followed

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by  blending  with' the  benzol  plant
wastes and biological treatment with a
single-stage activated sludge system.
The wastewater for the pilot study was
obtained after an equalization basin and
prior to the existing  biological system.
The  combined wastewater contained
pollutants such as suspended solids, oil
and  grease, ammonia, phenolic com-
pounds, cyanide, sulfide, thiocyanates,
and toxic materials.

  The study was performed  using the
mobile bio-oxidation system of the EPA.
This pilot plant is contained in a semi-
trailer  van  (van  No.  3)  as shown in
'Figure 1. Near the end of the investiga-
tion, a second EPA semi-trailer van (van
No. 2) containing the activated carbon
pilot  plant  system  (Figure  2) was
brought to  the test site. The purpose of
this system wastoevaluatetheefficien-
cy of activated carbon for removing toxic
pollutants  present  in the coke plant
wastewater. A  small pilot-size dual-
media  filter was also set up  in the
second   trailer.   Dual-media  filtration
was investigated as a method of polish-
ing the biological oxidation effluent.

'Because  the  development of final  Effluent
Limitation Guidelines was under way during the
time  of this  study, the  reference BPT (Best
Practicable  Technology)   and   BAT   pollutant
parameters used throughout this report are those
listed m the "Development Document for Proposed
Effluent Limitations  Guidelines and Standards for
the Iron and  Steel  Manufacturing Point Source
Category  -  Vol   II, By-Product  Cokemaking
Subcategory," October 1979

  The wastewater treatment trains that
were  investigated  on  a pilot scale
included:
   1. AS(C) +AS(N)
   2. AS(C) + AS(Nj + AC
   3. AS(C) + AS(N) + DMF

         Key
AS(C):  activated sludge
        (carbonaceous removal)
AS(N):  activated sludge
        (nitrification)
AC:     activated carbon
DMF:   dual-media filtration

   In the first treatment  train, plant
wastewater from downstream  of  the
coke  pla.nt cooling tower was  passed
through a mixing tank, through the first-
stage activated sludge system (carbon-
aceous removal), and then through the
second-stage activated sludge  system
(nitrogen removal).  The second treat-
ment train consisted of the first treat-
ment train (bio-oxidation) followed by
                    45' L
                                                        Trailer
                                                       8'W x 13'-6"H
                Aeration
                  Tank
  Sample
Refrigerator
Clarifier
                                                                     Blower
                      Temperature
                     Control System
                     Biological Treatment
                         System No. 2
Biological Treatment
    System No. 1
Figure 1.   Steel plant mobile bio-oxidation treatment system—trailer No.  3.
           Trailer
    45'L x 8'W x 13'-6"H
         Sample
       Refrigerator
 Carbon
Columns
  Ozone
 Generator
                                           Reverse Osmosis
                                                System
  Ozone Contact
      Tanks
 Figure 2.   Steel plant mobile treatment system—trailer No. 2.
 activated carbon adsorption. The third
 treatment tram included the compon-
 ents of the first treatmenttramfollowed
 by dual-media filtration. The detailed
 treatment  train   arrangements   are
 shown graphically in Figure 3.
   The small sump tank shown in Figure
 3 was used for pH adjustment, dilution,
             and chemical dispersal. As the waste
             water  flowed through  the first-stag*
             activated sludge system, carbonaceoui
             material (BOD,  phenol,  etc.) was re
             moved. Effluent from  the first-stage
             clarifier  was  pumped  through  th<
             second-stage activated sludge systen
             where ammonia nitrogen was oxidize<

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(1)  Activated Sludge, Nitrification

Waste water—.
Tap water—,  |       Air Polymer
Chemicals
                           Air-
                                 Powdered
                                 Activated
                                  Carbon  Polymer
                                                                     Effluent
                                  WAS

(2)  Activated Sludge. Nitrification, Activated Carbon
                                                              WAS
                                                                     Effluent
                           WAS               WAS

(3)  Activated Sludge, Nitrification, Dual-Media Filtration
                                                                     Effluent
                           WAS
                                  WAS
 Figure  3.
Process trains investigated  for treatment of by-product coke plant
wastewater.
by the nitrification process. The use of
powdered activated carbon was investi-
gated for removal of toxics and to im-
prove settling. Final  effluent from the
second-stage activated sludge system
was  passed  through  the  activated
carbon/dual-media  filtration  system
late in the test program to complete the
second   and  third  treatment   tram
arrangements, respectively
  During the pilot study, samples were
collected for both conventional and toxic
pollutants. Operational data were also
recorded on a daily basis to evaluate the
effectiveness of the respective treat-
ment trains. The pilot study results were
evaluated using three primary criteria-

  1. Process and/or treatment  train
     performance.
  2  Capital and operating costs.
  3. Space requirements.

Conclusions
  The   two-stage  activated   sludge
treatment  train  was successful  in
reducing  influent concentrations  of
coke plant pollutants. Because of upsets
in the coke  plant pretreatment system
during the pilot study period, high  dilu-
                            tion of the waste stream was necessary.
                            Significant reductions in pollutant con-
                            centrations were still achieved,  how-
                            ever.
                              The treatment  tram consisted of. (1)
                            diluting the raw coke plant wastewater
                            in a ratio of 1 part  service water to 3
                            parts coke plant wastewater; (2) blend-
                            ing the mixture for pH control and phos-
                            phorus addition;  (3) removing carbon-
                            aceous   material in  the  first-stage
                            activated sludge system,  followed by
                            clarification  of  the  wastewater  with
                            polymer  addition; (4) further  waste-
                            water dilution in a  ratio of 3 5  parts
                            service water to  1 part first-stage acti-
                            vated  sludge effluent;  (5) addition of
                            sodium carbonate, powdered activated
                            carbon, and pH control chemicals to the
                            second-stage mixed  liquor; and (6) oxi-
                            dation of ammonia in the second-stage
                            activated sludge unitto nitrate, followed
                            by clarification with polymer addition.
                            Late  in   the  study,  filtration  of the
                            second-stage activated sludge effluent
                            was investigated.

                              1  The  first-stage  activated  sludge
                                unit was capable of removing  95
                                percent of the  influent BOD and
                                90-100 percent of the incoming
   phenol.  Thiocyanate  and  TOC
   reductions  were  also  achieved.
   An  estimated  capital  cost   of
   $2,654,000 and annualizedcostof
   $4 51/3,785 I  ($4.51 /1,000 gal )
   would be  realized  for  a  1,892
   m3/day   (0.5   mgd)  treatment
   facility, assuming current waste-
   water pollutant concentrations If
   ammonia still (fixed and free) effi-
   ciency could be improved, capital
   costs could be  reduced to $2,427,
   000  and   annualized  costs   to
   $4 21/3,785 I  ($4.21 /1,000 gal.),
   assuming a similar design flow

2.  Influent  ammonia to the second
   •(nitrification)-stage activated
   sludge system  was quite variable,
   ranging  from 230 mg/l  to 2,090
   mg/l  It was necessary  to dilute
   the  first-stage activated sludge
   effluent  to  maintain a consistent
   feed  ammonia  strength before
   nitrification  could be  achieved
   After  a  sufficient population  of
   nitrifiers were  in the system, am-
   monia reductions of > 97 percent
   were consistently achieved. Due to
   the large quantity of dilution water
   required, it was not possible  to
   determine the  effect of other con-
   taminants   on  the  nitrification
   process  Suspended solids, oil and
   grease,  thiocyanate,  and phenol
   were also reduced to low levels. To
   treat a  1,892  mVday (05 mgd)
   wastewater  stream as  received
   during the pilot study would  re-
   quire an estimated capital invest-
   ment of $3,209,000 The expected
   annualized cost would be $14.17/
   3,785 I  ($14 17/1,000 gal) For
   comparison, if thefeedwater were
   from  an   efficiently   operating
   ammonia still, a similar size design
   would have a capital cost of about
   $1,238,000  and  an  annualized
   cost of only $4.12/3,785 I ($4.12/
   1,000 gal.).).

3.  Activated carbon, when used as a
   polishing  step for  the nitrified
   effluent, was capable of removing
   53 percent of the influent TOC, 60
   percent of  the color, 40 percent of
   the  BOD,  and  79 percent  of the
   remaining  thiocyanate.

4.  Dual-media filtration was found to
   remove  about  50 percent of the
   suspended  solids present  in the
   second-stage   activated  sludge
   nitrified  effluent.  The  expected

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        capital cost for a 1,892 mVday
        (0.5 mgd) design is $237,000 The
        corresponding annualized cost  is
        $0.27/3,785 I ($0.27/1,000 gal.).

      5. Priority pollutant analyses  were
        performed  on 13 samples taken
        from  various points  in the treat-
        ment system All priority pollutant
        metals were reduced to less than
        100 yug/l  except  selenium  and
        zinc. The biological treatment train
        was efficient in removing all vola-
        tile  organics,  base/neutral ex-
        tractable   organics,   and   acid-
        extractable   organics   to   non-
        detectable  levels.
    References
      1.  Development  Document  for
        Proposed   Effluent   Limitations
        Guidelines and Standards for the
        Iron  and  Steel  Manufacturing
        Point  Source  Category-Vol.  II,
        By-Product Cokemaking Subcate-
        gory, October 1979, EPA-440/1-
        79/02400.
          R. Osantowski, A. Geinopolos, and J. Meverden are with Rexnord, Inc., 5103
             West Beloit Road, Milwaukee,  Wl 53201
          Robert V. Hendriks is the EPA Project Officer (see below).
          The complete report, entitled "Two-Stage Biological Treatment of Coke Plant
             Wastewater," (Order No PB81 -240 798. Cost: $18.5O, subject to change) will
             be available only from:
                  National Technical Information Service
                  5285 Port Royal Road
                  Spring field, VA 22161
                  Telephone: 703-487-4650
          The EPA Project Officer can be contacted at:
                  Industrial Environmental Research  Laboratory
                  U.S Environmental Protection Agency
                  Research Triangle Park,  NC 27711
                                                                             U S GOVERNMENT PRINTING OFFICE, 1981 — 757-012/7332
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