v/EPA
                                    United States
                                    Environmental Protection
                                    Agency
                                   Industrial Environmental Research
                                   Laboratory
                                   Cincinnati OH 45268
                                    Research and Development
                                  EPA-600/S2-82-011    Oct. 1982
Project Summary
                                    Emerging Technologies for the
                                    Control  of  Hazardous Wastes
                                    Barbara H. Edwards, John N. Paullin, and Kathleen Coghlan-Jordan
:. Environmental Protection  Agency
'; C:c--;;.-. DC, .rijorn Street
'cago,  iinnois  60604.
                          .-.;>
                                     Investigations were conducted of
                                    new and emerging technologies for
                                    the disposal of hazardous wastes.
                                    These methods involve new techno-
                                    logies or a recent variation on an
                                    established one. In addition, a survey
                                    was made of potential users of haz-
                                    ardous waste information. The  need
                                    for a data base for emerging hazardous
                                    waste technologies and/or a news-
                                    letter was evaluated. Information on
                                    the emerging technologies was ac-
                                    quired by computerized search, library
                                    searching, and personal contacts. The
                                    emerging technologies discussed
                                    include molten salt combustion,
                                    f luidized bed incineration, high energy
                                    electron  treatment  of trace organic
                                    compounds in aqueous solution, the
                                    catalyzed wet oxidation of toxic
                                    chemicals, dehalogenation of com-
                                    pounds by treatment with ultraviolet
                                    (UV) light and hydrogen, UV/ chlo-
                                    rinolysis of organics in aqueous
                                    solution, the catalytic hydrogenation-
                                    dechlorination of polychlorinated bi-
                                    phenyls (PCBs), and ultraviolet/ozone
                                    destruction. Theory, specific wastes
                                    treated, and economics are discussed.
                                     The major technologies investigated
                                    in detail were molten salt combustion,
                                    fluidized bed incineration, and ultra-
                                    violet/ozone destruction.
                                     Among the wastes treated by emerg-
                                    ing technologies are  PCBs, various
                                    Dioxins, pesticides and herbicides,
                                    chemical  warfare agents, explosives
                                    and propellents, nitrobenzene, and
                                    hydrazine plus its derivatives.
                                     This document encompasses a
                                    target audience ranging from laymen
                                    to natural scientists. The information
                                   presented here was derived solely for
                                   application to hazardous wastes.
                                   Readers requiring more specific in-
                                   formation about theory and the eco-
                                   nomics of start-up plus operating and
                                   maintenance costs for technologies
                                   that may by applied to a specific haz-
                                   ardous waste not discussed in this re-
                                   port are referred to the literature cited
                                   in this report and to documents about
                                   state-of-the-art situations for a parti-
                                   cular technology.
                                    This Project Summary was devel-
                                   oped by EPA's Industrial Environ-
                                   mental Research Laboratory. Cincin-
                                   nati, OH. 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
                                    The material for the identification and
                                   evaluation of these technologies  has
                                   been gathered through an intensive
                                   literature survey conducted over  the
                                   course of  a year. Although extensive
                                   use has been made of manual and
                                   computerized data bases, it was also
                                   necessary to monitor the recent liter-
                                   ature and forthcoming conferences and
                                   symposia abstracts access material not
                                   yet in the literature. Personal commun-
                                   ications were alsp used in the survey.
                                    Major hazardous waste generators in
                                   the  United  States were surveyed for
                                   their hazardous waste information
                                   needs. Fifty-three of the 72 companies
                                   surveyed were identified by a Waste
                                   Disposal Site Survey Report from  the
                                   House of Representatives  Committee
                                   on Interstate and Foreign  Commerce

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(Subcommittee  on Oversight  and In-
vestigations) as the  largest domestic
generators of hazardous waste.
Conclusions
Molten salt combustion
  Molten salt technology has existed
for many years, but it has not been used
for  the  disposal of hazardous wastes
until recently In the process, hazardous
material is combusted at temperatures
below its normal  ignition point, either
beneath or  on the surface of a pool of
molten salt  Individual alkali carbonate
salts such  as sodium  carbonate, or
mixtures of these salts, are usually used
as  the  melt, but  other  salts can  be
employed based on the characteristics
of the waste. Containers for the molten
salts are made of ceramics,  alumina,
stainless steel,  or iron.  Ideally, during
the molten  salt process, organic  sub-
stances are totally oxidized to carbon
dioxide and  water. Generally,  the salt
bath is stable, nonvolatile, nontoxic, and
may be recycled for further use  until the
bath is no longer viable. The technology
has progressed from bench-scale through
the pilot plant stage to the construction
of a demonstration-sized coal gasifi-
cation unit. Portable units mounted on
trucks have been tested.
  Some of the advantagesof molten salt
combustion are  as follows:
    • Combustion is nearly complete.
    • Non-polluting off-gases are gen-
      erally emitted.
    * Operating temperatures are lower
      than  in  normal incineration;
      thus, they are fuel efficient.
    • The system is amenable to  recy-
      cling generated heat.
    • A wide variety of wastes can be
      combusted.
    • Bulky wastes can be combusted
      after recycling.
    • Many wastes can be combusted
      in compliance with EPA regula-
      tions.
        Some of the problems of mol-
      ten salt combustion are as follows:
    • Particulate emissions from some
      wastes are  high.
    • The  technology  is not readily
      adaptable to aqueous wastes.
    • Eventually  waste  salt and ash
      must be disposed of or the fluidity
      of the melt  will be destroyed.
    • A hazardous waste with greater
      than  20% ash cannot be  com-
      busted.
    • Detailed  economic information
      for a demonstration-sized system
      is not currently  available for
      many wastes (1980).
                                  2
Fluid/zed bed incineration
  Fluidized bed systems have had many
industrial  uses since the technology
was proposed by C.E. Robinson about a
century ago, yet fluidized bed inciner-
ation of hazardous wastes is a relatively
new technique. A hot fluidized bed is
ideal  for  combustion.  Air  passage
through the bed produces strong
agitation of  the bed particles, which
promotes rapid and relatively uniform
mixing of carbonaceous materials The
bed mass is large  in relation to the
injected waste,  and bed temperatures,
which usually range from 750°-1000°C,
are usually uniform Bed materials have
included sand, sand mixtures, dolomite,
and alumina.
  Some advantages of  fluidized bed
incineration  are as follows:
    • The combustor design  is simple
      and does not require moving
      parts after the initial feeding of
      fuel and waste.
    • Fluidized  bed  incineration has a
      high combustion efficiency.
    • Designs are more compact due to
      high volumetric rates.
    •  Comparatively  low gas temper-
      atures and excess air require-
      ments minimize the formation of
      nitric oxide.
    • In some  cases, the bed itself
      neutralizes some of the hazardous
      products of combustion.
    • A vertical induced draft inciner-
      ator was converted into a fluidized
      bed.
    • The bed  mass provides a large
      surface area for reaction.
    • Temperatures throughout the
      bed are relatively uniform
    • Fluidized beds are able to process
      aqueous waste slurries
    • If the  waste contains  sufficient
      calorific value, the use of auxiliary
      fuel is unnecessary; moreover,
      the excess heat'may be recycled
      in some cases.
    • The bed can function as a heat
      sink;  start-up after weekends
      may require little or no pre-heat
      time.

Disadvantages of fluidized bed com-
bustion are as follows:

    • Bed diameters and height are
      limited by design technology.
    • Ash removal presents a potential
      problem.
    • Systems requiring low tempera-
      tures  may have carbon build-up
      in the bed  due  to increased
      residence time.
    • Certain  organic wastes w
      cause the bed to agglomerate.
    • Paniculate  emissions  can be
      major problem.


UV/ozone destruction

  Ozone treatment  is  an  estabhshe
technology for the treatment of som
hazardous wastes; the  combination c
UV light and ozonation recently ha
been  found to be  a  more  effectiv
process for destroying hazardous wast
than the use of ozonation alone. Th
addition of UV  light to the ozonatio
process has greatly expanded th
number of compounds that can  b
destroyed. PCBs are among  the halo
genated compounds destroyed  Com
pounds with shielded multi-bondei
carbon atoms, sulfur compounds, ani
phosphorous compounds  are les
susceptible to UV/ozonation. Dioxms
nitrobenzene,  and hydrazines hav<
been destroyed  by UV/ozonation
  Some advantages of UV/ozonatior
are as follows:

    •  Aqueous or  gaseous waste
      streams can be treated.
    •  Capitol and operating  costs are
      not excessive.
    •  Chemical carcinogens  and mut
      agens can be treated.
    •  The system is readily adaptable
      to on-site treatment of the haz-
      ardous waste.
    •  It can be used as a final treatment
      to supplement partial treatment
      systems.
    •  It can be used as a  preliminary
      treatment for certain hazardous
      wastes.
    •  It can be used to meet effluent
      discharge standards.
    •  Modern  systems are usually
      automated, thereby reducing
      labor requirements.
Some disadvantages of UV/ozonation
are as follows:

    •  Ozone is a non-selective oxidant;
      therefore,  the  waste stream
      should contain  primarily the
      waste of interest.
    •  UV/ozone systems are generally
      restricted to 1 % or lower levels of
      hazardous compounds.  Frequent-
      ly, hazardous substances  are
      treated at ppm levels
    •  Ozone  decreases rapidly with
      increasing temperature; therefore
      excess heat must  be rapidly
      removed.

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Results of hazardous waste
information survey.

  Fifty-three major hazardous waste
generators  were surveyed for their
hazardous  waste information needs.
Major information needs are
    • new  technologies for hazardous
      waste disposal,
    • state-of-the-art methods  for
      hazardous waste disposal,
    • best  technologies available  for
      destruction of specific wastes
      plus costs,
    • updated federal and state regu-
      lations for waste generation,
      transportation, storage, and  de-
      struction of landfills,
    • techniques to  identify  mixed
      waste streams,
    • toxicity data on specific hazardous
      wastes,
    • location of approved hazardous
      waste disposal  sites and tech-
      nology available at the site;
      identity of  hauling contractors,
    • waste exchange and recycling
      information.


Recommendations
  The emerging technologies evaluated
in this study can be considered  as
alternatives to  landfill disposal of
hazardous waste. It is presumed that
the emerging technologies will destroy
the waste or at  least attenuate it to
acceptable levels. The advantages and
disadvantages of each emerging tech-
nology presented must be carefully
considered when  selecting the technol-
ogy most suitable for the control of
specific hazardous wastes is selected.
  The  information  needs for major
hazardous waste generators could best
be met by the use of a hazardous waste
data base supplemented by newsletters
and telephone "hotlines "

Hazardous wastes destroyed
by emerging technologies


A.  Molten salt combustion:
    Miscellaneous
      PCB's
    Chloroform
    Perchloroethylene distillation bottoms
    Trichloroethane
    Tributyl Phosphate
    Nitroethane
    Monoethanolamine
    Diphenylamine  HCI
    Rubber tire buffings
    Para-Arsanilic Acid
    Contaminated ion  exchange  resins
      (Dowex and Powdex)
    High-Sulfur Waste Refinery Sludge
    Acrylics Residue
    Tannery wastes
    Aluminum Chlorohydrate

Pesticides and herbicides
   Chlordane
   Weed B Gone
   DDT powder
   Malathion
   Sevm
   DDT powder with Malathion
   2, 4-D Herbicide-Tar Mixed waste


Real and simulated pesticide
containers
   plastic, rubber, and  a blend of these
Feasible pesticides and nitrite
herbicides
Pesticides          Nitrile Herbicides
                          trifluralin
               2, 4, 5-T dichlorobinil
                            MCPA
 dieldrin
 heptachlor
 aldrin
 toluidme
B.  Fluidized bed incineration:
    Miscellaneous
      HCI  spent pickling liquor
    Organotin in spent steel slag blasting
      abrasive
    Organic dye slurries
       red dye slurry (1 -methylaminoan-
       thraquinone and starch gum)
       yellow dye slurry (dibenzpyrene-
       quinone and benzanthrone)
Chlorinated hydrocarbons
   PVC waste from a chemical plant
   PVC mixed with coal
   PVC insulation over copper wire
   Chlorinated hydrocarbon waste with
   90% chlorine
Munitions (slurry)
   TNT
   RDX(cyclotrimethylenetrinitramme)
   Composition B
C.  UV/ozonation technology:
    Miscellaneous
      PCB's
    TCDD  (2,  3, 7, 8-tetrachlorodi-
    benzo-p-dioxin)
    OCDD  (octachlorodibenzo-p-dioxin)
    Chlorodioxins (other  dioxins  are
    feasible)
    Hydrazine
    Monomethyl hydrazine
    Dimethyl hydrazine (asymmetrical)
    Copper process waste stream
    Nitrobenzene
                                         Barbara H. Edwards, John N. Paullin, and Kathleen Coghlan-Jordan are with
                                           Ebon Research Systems, Washington, DC 20011
                                         T. L. Baugh is the EPA Project Officer (see below).
                                         The complete report,  entitled  "Emerging Technologies for the Control of
                                           Hazardous  Wastes," (Order No. PB 82-236 993; Cost: $15.00, subject to
                                           change) will be available only from:
                                                 National Technical Information Service
                                                 5285 Port Royal Road
                                                 Springfield, VA22161
                                                 Telephone: 703-487-4650
                                         The EPA Project Officer can be contacted at:
                                                 Industrial Environmental Research Laboratory
                                                 U.S. Environmental Protection Agency
                                                 Cincinnati, OH 45268
                                                                                  ĞU.8.GOVERNMENTHtlNTWa OFFICE: 1M2-559-017/0839

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Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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