Journal of Environmental Sciences 19(2007) 513–522
Supercritical water oxidation for the destruction of toxic organic
wastewaters: A review
VERIANSYAH Bambang, KIM Jae-Duck ∗
Supercritical Fluid Research Laboratory, Korea Institute of Science and Technology (KIST)–Department of Green Process and System Engineering,
University of Science and Technology (UST), 39-1 Hawolgok-dong, Seoungbuk-gu, Seoul 136-791, Korea. E-mail: [email protected]
Received 16 June 2006; revised 28 September 2006; accepted 11 October 2006
Abstract
The destruction of toxic organic wastewaters from munitions demilitarization and complex industrial chemical clearly becomes an
overwhelming problem if left to conventional treatment processes. Two options, incineration and supercritical water oxidation (SCWO),
exist for the complete destruction of toxic organic wastewaters. Incinerator has associated problems such as very high cost and public
resentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaters
with extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, the
concepts of SCWO, result and present perspectives of application, and industrial status of SCWO are critically examined and discussed.
Key words: supercritical water oxidation; toxic wastewater treatment; SCWO industrial status
Introduction
The world is facing a waste crisis from organic and toxic
wastes today. Every year the amount of those wastes generated by industrial and domestic sources increase rapidly.
The treatment of organic and toxic waste is becoming more
difficult and costly because of more stringent treatment
standards and discharge limitations. Public health concerns
are the driving force for the continued legislation aimed at
providing a cleaner and safer environment. Furthermore,
EPA (Environmental Protection Agency) goals suggest
destruction levels up to 99.9999% of some compounds and
use of totally enclosed treatment facilities. The increased
environmental constrains and unfavorable public opinion
have challenged the continuing application of conventional
waste management techniques (Li et al., 1991).
Conventional technologies currently used to treat all
types of organic and toxic wastes include adsorption,
biological oxidation, chemical oxidation, land-based, and
incineration. Each of these treatment methods has shortcomings and therefore may not be the best option for
treating organic and toxic wastes. Supercritical water oxidation (SCWO) has been proposed as a technology capable
of destroying a very wide range of organic hazardous
waste. It has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting
from munitions demilitarization and complex industrial
chemical.
The primary advantage of the SCWO process over such
Project supported by the Korea Institute of Science and Technology
(KIST). *Corresponding author. E-mail: [email protected].
land-based alternatives as land filling, deep-well injection,
and lagooning is the destruction method. Land-based disposal does not address the ultimate destruction of toxic
components of the waste and can result in the possible
contamination of surrounding soil and groundwater. Deepwell injection systems are subject to plugging or fouling
if organic concentration of 1% or higher are allowed.
Landfills and lagoons can contribute to contamination
of the air by volatile organics. The increasing of public
concern and regulatory action will restrict or prohibit landbased disposal of many organic wastes in the future.
Destruction methods based on oxidation of organic content for aqueous wastes include activated carbon treatment,
biological treatment, incineration, wet air oxidation, and
supercritical oxidation. For very dilute aqueous waste
whose organic contents are less than 1%, activated carbon
treatment or biological treatment is often an effective destruction method. In activated carbon treatment, organics
are first adsorbed onto carbon and then oxidized during
regeneration of carbon. Partially oxidized materials are
perfectly destroyed by after-burner treatment. Main cost
is proportional to the organic content. So this method is
not economically useful for waste containing more than
1% organic. Biological treatment systems often become
poisoned and cannot be sustained for many wastes with
organic concentrations of 1% or more.
Incineration, on the other hand, is restricted for economic reasons to waste streams relatively high organic
concentrations. To attain high destruction efficiency for
hazardous and toxic wastes, incineration must be operated
at very high temperature as 900–1100°C and often with
excess air of 100%–200%. With aqueous wastes, the
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VERIANSYAH Bambang et al.
energy required to bring the water component of the waste
to this temperature is substantial. For the aqueous wastes
with organic content more than 25%, the heat required
for high temperature can be generated from wastes. With
decreasing organic content, the supplemental fuel required
to satisfy the energy balance becomes a major cost. Thus,
controlled incineration of aqueous waste with less than
20% organics is the only consideration in extenuating
circumstances (Thomason and Modell, 1984). Incineration
is also being regulated to restrict stack gas emissions
to the atmosphere. Extensive equipment must now be
used downstream of the reaction system to remove NO x ,
acid gasses, and particulates from the stack gases before
discharge. The cost of this equipment often exceeds that of
the incinerator itself.
In the range of concentration of 1% to 20% organic, wet
air oxidation or SCWO is far less costly than incineration
or active carbon treatment. Wet air oxidation (WAO) has
been offered as a method to treat wastewater, industrial
wastes, and sludge. From a public perception standpoint,
WAO is more favorable than incineration, land application,
deep well injection, and ocean dumping because the waste
products can be completely converted to inert materials
and the process can be conducted as a closed system which
does not produce any hazardous byproducts. Capital costs
are often higher than incineration; however, operating costs
are lower. It is possible to recover energy and inorganic
in WAO. Wet air oxidation, commonly associated with
sludge conditioning and some organic destruction, is a lowtemperature process (Boock, 1996).
The Zimpro-Passavant’s WAO process is typically operated in a temperature range of 150°C to 350°C and pressure
range of 2–20 MPa. The operating pressure is maintained
well above the saturation pressure corresponding to the
operating temperature so that the reaction is carried out
in the liquid phase. Residence times may range from 15–
120 min, and the chemical oxygen demand (COD) removal
may typically be approximately 75%–90%. Volatile acids
constitute a substantial portion of remaining COD. The
formation of volatile acids, particularly acetic acid, is
a limitation for WAO. Furthermore, the effluent from
incomplete (partial) wet oxidation of some wastewaters
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may be intensely colored and toxic (Li et al., 1991).
The above examples illustrate the utility of WAO as an
alternative to incineration for the treatment of dilute aqueous wastes. However, a number of compounds, including
m-xylene and acetic acid are refractory towards oxidation at these conditions. Additionally, WAO often cannot
achieve the 99.9% destruction efficiencies that many newer
regulations require. This motivated a look at oxidation
under more severe conditions, such as higher temperatures
and pressures, which bring the reaction mixture above its
critical point. Thus, the supercritical oxidation process was
born. Supercritical water oxidation, on the other hand, is
known to attain nearly complete destruction of various
organics such as PCBs, and dioxins in very short time
(Boock, 1996).
1 Supercritical water oxidation
Supercritical water oxidation defined as oxidation process which occurs in water above its critical point
(T c =374°C and Pc =22.1 MPa). It uses supercritical water
as a reaction medium and exploits the unique solvating properties to provide enhanced solubility of organic
reactants and permanent gases (like oxygen and carbon
dioxide), a single-phase environment free of inter-phase
mass transfer limitations, faster reaction kinetics, and
an increased selectivity to complete oxidation products
(Tester et al., 1993; Savage et al., 1995; Schimeider and
Abeln, 1999).
SCWO provides a potential alternative for processing hazardous military wastes without the concomitant
production of noxious byproducts as might be experienced with combustion-based technologies (Downey et
al., 1995). The process usually operates in a temperature
range of 450–600°C and pressure range of 24–28 MPa.
It consists of the general steps shown in the block flow
diagram in Fig.1. The aqueous waste stream containing the
organic is pressurized and preheated to reactor conditions.
The oxidant stream, which can be an aqueous solution
of hydrogen peroxide, pure oxygen, or air, is pressurized
and mixed with the organic stream. The one-phase mixture
of water, organic and oxidant enters the reaction zone,
Fig. 1 Block flow diagram of typical SCWO process.
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Supercritical water oxidation for the destruction of toxic organic wastewaters: A review
where both organic compounds and oxygen are completely
soluble, and the temperature is high enough that free
radical oxidation reactions proceed rapidly. The organic
oxidizes rapidly and completely (destruction efficiency
>99.99% with residence times less than one minute) to
CO2 and H2 O (Tester et al., 1993; Savage et al., 1995;
Schmieder and Abeln, 1999; Modell, 1989).
If any nitrogen is present, either introduced with the
waste or if air is used as the source of O2 , the resulting
product is N2 or N2 O (Killilea and Swallow, 1992). NO x
and SO x gases, typical undesired by-products of combustion processes, are not formed because the temperature
is too low for these oxidation pathways to be favored.
Any N2 O found can be catalytically converted to N2 .
Heteroatoms (e.g., chlorine, phosphorous, sulfur) react to
form their corresponding mineral acids. With the addition
of a suitable base, acids are neutralized and form their
corresponding salts which precipitate out of the reacting
mixture allowing for their removal. It has already been
proved that SCWO is an environment friendly waste
treatment technology that produces disposable clean liquid
(pure water), clean solid (metal oxides) and clean gases
(CO2 and N2 ) (Bianchetta et al., 1999; Brunner, 1994;
Fang et al., 2000, 2005; Goto et al., 1999; Kritzer and
Dinjus, 2001; Kronholm et al., 2003; Lee et al., 2004; Rice
and Steeper, 1998; Sullivan and Tester, 2004; Veriansyah et
al., 2005a, 2005b, 2005c).
2 Toxic organic wastes treated with supercritical water oxidation
The SCWO process as a hazardous waste treatment
technology has been proven to be a viable and effective
technique by both academia and industrial researchers.
These researchers showed that SCWO indiscriminately
and rapidly destroys a broad spectrum of organic wastes.
SCWO has been shown effective in the treatment of toxic
chlorinated chemicals such as polychlorinated biphenyls
(PCBs) (Anitescu and Tavlarides, 2000, 2002, 2005; Anitescu et al., 2004, 2005; Fang et al., 2004, 2005; Hatakeda
et al., 1997a, 1997b, 1999; Kubatova et al., 2003; O’Brien
et al., 2005; Rahuman et al., 2000; Sako et al., 1999;
Staszak et al., 1987; Weber et al., 2002) and the pesticide
DDT (Modell, 1990), bacteria and dioxins (Thomason et
al., 1990), chlorophenol and chlorobenzene (Lin et al.,
1998, 1999; Lin and Wang, 1999a, 1999b, 2000a, 2000b,
2001; Muthukumaran and Gupta, 2000; Namasivayam and
Kavitha, 2003; Svishchev and Plugatyr, 2006) process
waste waters (Li et al., 1993; Sawicki and Casas, 1993;
Park et al., 2003; Portela et al., 2001a; Veriansyah et al.,
2005b), and pharmaceutical and biopharmaceutical waste
(Aki and Abraham, 1999; Johnston et al., 1988; Qi et
al., 2002). Compounds which are problematic to recycle
or dispose due to the formation of hazardous by-products
and residues such as the polymer polyvinylchloride
(PVC), the flame retardant tetrabromobisphenol A, and the
chlorocarbon γ-hexachlorocyclohexane and hexachlorocyclohexane, are completely oxidized without hazardous
by-product formation (Hirth et al., 1998). SCWO has
515
also been shown effective in the treatment of a highly
contaminated activated sludge (Patterson et al., 2001;
Griffith and Raymond, 2002; Stendahl and Jafverstrom,
2003), municipal sludges (Shanableh and Gloyna, 1991;
Tongdharmachart and Gloyna, 1991; Goto et al., 1997;
Mizuno et al., 2000), sludges from the pulp and paper
industry (Modell, 1990; Modell et al., 1992, 1995), deinking sludge from the recycle paper industry (Gidner and
Stenmark, 2002), and a combination of sludge from a primary clarifier mixed with effluent from a bleach plant and a
decant of pond sludge (Cooper et al., 1997). Additionally,
wastes which are typically treated by a bioremediation
process, such as urea (Timberlake et al., 1982), human
wastes (Hong et al., 1987, 1988), and waste from manned
space missions (Takahashi et al., 1988) are all destroyed
by SCWO.
SCWO process has been identified as a promising
alternative technology to incineration for the destruction
of the chemical weapons stockpile (NRC, 1993). In the
US, approximately 25000 t of chemical weapons are
slated for destruction by 2006. Originally in 1982, these
weapons were to be incinerated at each of the eight storage
sites in the continental USA (Umatilla Depot Activity,
Oregon; Tooele Army Depot, Utah; Pueblo Depot Activity,
Colorado; Pine Bluff Arsenal, Arkansas; Newport Army
Ammunition Plant, Indiana; Lexington Blue Grass Depot
Activity, Kentucky; Anniston Army Depot, Alabama; and
Aberdeen Proving Ground, Maryland) and on Johnston Island in the Pacific (Harigel, 2000; Hogendoorn, 1997). Due
to operational problems at the Johnston Island incinerator,
the increasingly poor public perception of incineration and
the unanticipated local public opposition to building new
incinerators at the remaining storage locations, the Army
was forced to consider alternative methods for destroying
these weapons in the early 1990’s (U.S. Congress, 1992).
In that report, SCWO was selected as one of four possible
alternative technologies.
SCWO has been shown effective for destroying the
stockpiled chemical warfare agents (Bianchetta et al.,
1999; Downey et al., 1995; Lachance et al., 1999; Snow
et al., 1996; Sullivan and Tester, 2004; Veriansyah et al.,
2005a, 2005c, 2006), propellants and energetics (Buelow,
1990, 1992; Harradine et al., 1993), and military smokes
and dyes (Robinson, 1992; Rice et al., 1994). Because of
the ability of SCWO to destroy broad classes of organic
wastes and its ability to destroy chemical warfare agents,
the three branches of USA military are building SCWO
units for their purposes. The USA Navy is developing compact SCWO units for the on-board treatment of hazardous
wastes (Kirts, 1995; Cohen et al., 1998). The USA Army
commissioned Foster Wheeler Development Corporation
in conjunction with Sandia National Laboratories and
Gencorp Aerojet to build a SCWO facility at the Pine
Bluff Arsenal in Arkansas for destroying smokes, dyes,
and pyrotechnics (Haroldsen et al., 1996a, 1996b). The
Army is also undergoing testing the SCWO facility built by
General Atomics in Toole, Utah for treating VX and GB.
The USA Air Force awarded a contract to General Atomics
to design a plant for destroying solid rocket propellant
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VERIANSYAH Bambang et al.
(Hurley, 1996).
3 Supercritical water oxidation reactor system
3.1 Batch system
Various batch reactors suitable for conducting SCWO
of organic waste are described in the literature (Calvo and
Vallejo, 2002; Goto et al., 1999; Mizuno et al., 2000;
Portela et al., 2001b; Jin et al., 2001; Lachance et al., 1999;
Thornton and Savage, 1992). This reactor usually has two
temperature zones, the upper part, to keep the reactor above
critical temperature, and the lower part, to dissolve the salt
precipitant at subcritical temperature (Kupferer, 2002).
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3.2.2 Floating type reactor (SUWOX)
SUWOX was designed to prevent corrosion problem,
which was solved by dividing the construction into two
vessels, the pressure-resistant vessel and the inner vessel
(Casal and Schmidt, 1998). Fig.3 shows the design of the
reactor. The SCWO reaction occurs in the inner nonporous
vessel. Between those two vessels, there is a gap for small
stream of water.
3.2 Continuous-flow system
Organic waste treated by SCWO mostly conduct in
continuous-flow system. This is due to its flexibility for
expansion to plant or industrial scale. The type of reactor is
developed from basic tubular type to the current transpiring
wall reactor (Crooker et al., 2000; Fauvel et al.,2003, 2005;
Lee et al.,2005; Marrone et al., 2004, 2005; Wellig et al.,
2005).
3.2.1 Transpiring wall reactor (TWR)
The concept behind the TWR design includes a dual
shell consisting of an outer pressure-resistant vessel and
an inner porous vessel (Daman, 1996; Kritzer and Dinjus,
2001). Through the porous wall, supercritical water will
get through to form a thin, protecting water film. Through
this complex perspiration system, the porous liner is said
to protect the reactor against corrosion and salt deposition.
Fig.2 shows a simple schematic diagram of TWR. Some
group have developed a hydrothermal flame as internal
heat source in TWR (Wellig et al., 2005) and another group
have studied its application on halogenated hydrocarbons
(2,4-dichlorophenol) with 98.7% conversion at residence
time of 32 s., temperature of 713 K and pressure of 25
MPa (Lee et al., 2005). Current study and review related to
this type of reactor is described in literature (Fauvel et al.,
2003, 2005; Marrone et al., 2004, 2005).
Fig. 3 SUWOX reactor (Baur et al., 2005).
Extensive study for this type of reactor was conducted
in Germany (Baur et al., 2005). They explore four types
of SUWOX-base reactor for biocides treatment in SCWO.
The destruction of organic with conversion 99.9% could be
achieved, even at low oxygen supply and the shortest residence time (1.37 min). Salt content in the effluent remained
dissolve, with concentration >200 g/L (NaCl). Another
group, successfully decomposed 2,4-dichlorophenol with
99.9% conversion at residence time of 34 s, temperature
of 693 K and pressure of 25 MPa (Lee et al., 2005). This
result was higher, compare to when they employed TWR
at the similar conditions.
4 Industrial status
Fig. 2 Transpiring wall reactor (Daman, 1996).
Several reviews have summarized the current general
state of SCWO technology, as well as pilot work recently performed or in progress in support of a number
of applications (Kritzer and Dinjus, 2001; NRC, 1998;
Schmieder and Abeln, 1999; Shaw and Dahmen, 2000;
Tester and Cline, 1999; Yoo et al., 2004). The promotion
of SCWO for treating industrial wastes has also met
with limited success. The main drawbacks are the high
operating pressure, possible of the reactor plugging due
to salt formation, corrosive behavior under certain T-P-
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Supercritical water oxidation for the destruction of toxic organic wastewaters: A review
xi conditions, and pre-commercial higher processing costs.
With active research underway to understand and resolve
the problems of plugging from salts and corrosion, the
development of novel reactor designs to alleviate these
problems and the disappearance of landfills, SCWO may
yet become a viable waste treatment option for industrial
wastes and find a nice market (Hodes et al., 2004; Kritzer
et al., 1999; Kritzer and Dinjus, 2001; Kritzer, 2004).
An even more serious problem facing SCWO having
nothing to do with the process itself is the unwillingness of
industries to invest in novel, and potentially superior, waste
treatment technologies. This barrier will likely prove more
difficult than the technical problem facing SCWO. Regulatory pressure does not suffer from these constraints, and
changes in industrial effluent discharge regulations may
be needed. The success of SCWO in treating the military
waste will be important for its industrial acceptance.
Table 1 contains a list of full-scale facilities and licensees of the SCWO processes developed by several
companies, along with recent feed material that have been
processed. MODAR, Inc., the first company to attempt to
exploit the technology commercially, performed extensive
studies of destruction efficiencies for organic compound
in the 1980’s and early 1990’s in an attempt to validate
the SCWO process and develop large-scale reactor system
for treating industrial wastes. MODAR, Inc., was acquired
by General Atomics (GA) in 1996, but GA is currently
only using the technology for treating military wastes.
A full-scale SCWO facility based on MODAR process
(i.e., reverse flow, tank reactor) was constructed by Organo
Co. by Japan in 1998 (Oe et al., 1998). In addition to
having a licence to the MODAR process, organo is a licensee of the MODEC process (designed a SCWO reactor
system capable of avoiding the salt plugging problems
and eliminating corrosion issues for many wastes). Two
other Japanese companies, Hitachi Plant Engineering and
Construction Co. and NGK Insulator Ltd., and a Canadian
firm, NORAM Engineering and Constructors, Ltd., are
517
also MODEC licensee. Hitachi and NGK are interested in
developing the MODEC process further for sewage sludge
treatment (Japan Chemical Week, 1998).
Both GA and Foster Wheeler have been very active in
recent years with several projects being conducted for three
branches of the U.S. Armed Forces. GA has demonstrated
successful treatment of chemical agent (HD, GB and VX)
hydrolysate and energetics hydrolysate/secondary wastes
for the U.S. Army’s Assembled Chemical Weapons Assessment (ACWA) program (U.S. DOD ACWA, 1999),
SCWO is part of GA’s Total Solution proposed to ACWA
for demilitarization of the complete munition (projectiles,
mortars, rockets) and associated storage and processing materials. The energetics hydrolysate/secondary waste
feeds consisted of slurry of hydrolyzed energetics (tetrytol, Composition B, and/or M28 propellant) along with
shredded wood, plastics, and activated carbon. GA recently
completed further pilot testing for ACWA in support of a
full-scale design for demilitarization of chemical weapons
stored in Pueblo, CO, and Lexington, KY (U.S. DOD
ACWA, 2002). GA also designed and tested a compact
SCWO system for the U.S. Navy in 1999 for destruction
of shipboard wastes (Elliott et al., 2000). GA conducted
hydrolysis and SCWO testing of rocket motor propellant
for the USA Air Force in 1995 using a 1 gpm (3.8 L/min)
pilot-scale system (Defense, 1995). The Japanese companies Komatsu, Ltd., and Kurita Water Industries, Ltd., have
a licensing agreement with GA in commercializing SCWO
technology in Asia (Schmieder and Abeln, 1999).
Foster Wheeler constructed a full-scale SCWO system
based on their transpiring wall reactor design for the U.S.
Army’s Pine Bluff Arsenal in Arkansas in 1998 (Crooker
et al., 2000). The system was designed to treat obsolete
smoke and dye munitions at a rate of 80 lb/h (36 kg/h)
of munitions. It is being operated by Sandia National
Laboratories and has been undergoing extensive systemization with surrogate feed materials since construction
completion. Foster Wheeler has also conducted pilot-scale
Table 1 Commercially designed SCWO facilities currently in existence
Company
Licenses
Large-scale plants
Application
MODAR
Organo
Semiconductor manufacture wastes
MODEC
Organo, Hitachi,
NGK
Komatsu, Kurita
Waste Industries
Nittetsu Semiconductor,
Japan (constructed by Organo)
None
General Atomics
Foster-Wheeler
U.S. Army Newport Chemical
Depot, Newport, IN
EcoWaste
Technologies (EWT)
Chematur
Chematur
U.S. Army Pine Bluff Arsenal,
Pine Bluff, AR (operate by
Sandia National Laboratory)
Huntsman Chemical, Austin, TX
Shinko Pantec
Johnson Matthey, Brimsdown, UK
SRI International
Mitsubishi Heavy
Industries
Hydro-Processing
Hanwha Chemical
Japan (constructed by Shinko Pantec)
Japan
Harlingen Wastewater Treatment
Plant No.2, Harlingen, TX
Namhae Chemical Corp, Korea
Pharmaceutical wastes, pulp, and paper mill wastes,
sewage sludge
Bulk VX nerve agent hydrolysate; other feed processed
in smaller-scale system; chemical agent, explosives, and
dunnage (U.S. Army), shipboard wastes (U.S. Navy),
rocket, propellant (U.S. Army Force)
Smokes and dyes; other feeds processed in smallerscale systems: chemical agent and explosives
(U.S. Army), shipboard wastes (U.S. Navy)
Oxygenated and nitrogen-containing hydrocarbon
(e.g., alcohols, glycols, amines)
Spent catalyst (recover platinum group metals and
destroy organic contaminants)
Municipal sludge
PCBs, chlorinated wastes
Mixed municipal and industrial wastewater sludge
Wastewater from DNT/MNT Plant and Melamine Plant
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VERIANSYAH Bambang et al.
testing of a transpiring wall SCWO system for the USA
Navy and Army ACWA program similar to that described
for GA. Testing for the Navy was performed in 1999
with halogenated solvents and photographic solution feeds
at 80–209 lbs/h (36–95 kg/h) (Crooker et al.,2000). The
same system was used for ACWA testing in 2000, in
which mixtures of agent (HD, GB, VX) and energetic
(tetrytol, Composition B, M28 propellant) hydrolysates
were processed with minimal corrosion and salt buildup
in the reactor (U.S. DOD ACWA, 2001). Foster Wheeler is
part of a team who’s proposed Total Solution to ACWA for
munition demilitarization includes co-processing of agent
and energetic hydrolysates via SCWO as demonstrated.
The hydrolysate feed recipes were chosen to represent
compositions expected from processing actual munitions.
Foster Wheeler recently completed further pilot testing
for ACWA in 2002 in support of a full-scale design for
demilitarization of chemical weapons stored in Lexington,
KY.
EcoWaste Technologies (EWT) designed and built the
first operating commercial SCWO plant in the USA. The
plant was constructed for the Huntsman Co. (formerly
Texaco Chemical Co.) in Austin, TX, for destruction
of non-halogenated organic wastes produced on-site at
their Austin Research Laboratories. The tubular reactor
system began operation in 1994. The waste feed consisted
primarily of a blend of alcohols, glycols, and amines with
an overall organic loading of 10 wt%, and was fed at a rate
of 2425 lb/h (1100 kg/h) (McBrayer et al., 1996).
Chematur Engineering (1999) acquired a licensing
agreement for the EWT SCWO process in Europe in 1995,
and acquired the exclusive world-wide rights for EWT
SCWO in 1999. SCWO is marketed by Chematur under
the trade name Aqua Critoxr . Chematur built a 550 lb/h
(250 kg/h) pilot-scale SCWO system in 1998 that has since
been tested with several mostly nitrogen-containing wastes
(amine production wastes, non-halogenated spent cutting
fluid, de-inking sludge, and sewage sludge) (Stenmark,
2001; Gidner and Stenmark, 2002). Chematur has also
constructed its first full-scale SCWO facility for Johnson
Matthey in the UK (Chematur, 2001). Chematur has licensed the EWT SCWO process to the Shinko Pantec
Co. of Japan. Under this license agreement, Shinko Pantec
has constructed an 2425 lb/h(1100 kg/h) SCWO plant for
treating municipal sludge, which was commissioned in
2000.
SRI International granted its first licensing agreement of
the AHO process (i.e., carbonate-filled reactor for catalytic
oxidation and salt product adsorption) to Mitsubishi Heavy
Industries (MHI) in 1999 (Waste Treatment Technology
News, 1999). MHI has been working with SRI on commercializing the AHO process since 1995, and plans to
use it to destroy polychlorinated biphenyl (PCB) wastes
at commercial facilities. Since 1998, MHI has conducted
tests with PCBs in a pilot-scale system in Japan, demonstrating greater than 99.9999% destruction at 380°C and
270 atm. MHI also owns a patent on the AHO process
as applied to PCB decomposition (Tateishi et al., 2000).
MHI is currently designing the first full-scale commercial
Vol. 19
AHO system in Japan for PCB destruction, with plans to
build several more plants for both government and private
clients.
HydroProcessing, LLC, has focused on the application
of SCWO for treating municipal wastewater sludge. Their
patented process (Griffith et al., 1999), referred to as the
HydroSolidsr process, is intended to replace traditional sludge digestion and dewatering units in a standard
wastewater treatment plant. They have operated a 0.4 gpm
(1.5 L/min) tubular reactor pilot system with this feed since
1996, and have built a full-scale system for the Harlingen
Wastewater Treatment Plant in Harlingen, TX. The system
is intended to process both municipal wastewater sludge
and industrial wastewater sludge from an adjacent factory
(Wofford and Griffith, 2001). HydroProcessing states that
operating costs are about 180 USD/t (dry) on (not including any projected benefits from energy or CO2 recovery),
compared to a cost of 275 USD/t for sludge disposal by
landfill or land application (Parkinson, 2001). Because of
the inherently greater amount of solids contained in the
sludge feed (as compared to liquid wastes), the process
incorporates a hydrocyclone after the reactor for solids
removal, and a separate patented downstream system for
handling pressure letdown of the solids-containing effluent
stream.
There are other companies trying to commercialize
SCWO technology, as well. For example, Hanwha Chemical has constructed 2000 kg/h SCWO plant for treating
DNT/MNT Plant wastewater and 35000 kg/h SCWO
plant for treating Melamine Plant wastewater, which
were commissioned in 2000 (Hanwha Chemical, 2000).
ProChemTech International, Inc. designed and built a
small tubular SCWO system of 0.1 gpm (0.4 L/min) capacity in 1993 for treating organic-laden wastewater from a
semi-conductor manufacturer (ProChemTech, 2004). Noram Engineering and Constructors, Ltd., has recently been
issued a patent (Boyd et al., 2001) on a process for
utilizing SCWO for oxidation of redwater (a waste from
the manufacture of nitroaromatic explosive compounds).
Daimler Chrysler of Germany has also been interested in
the application of SCWO for the treatment of electronic
scrap (e.g., circuit boards) and, in collaboration with the
Fraunhofer Institute ITC, has built a mobile plant (20
L/h) containing a tubular reactor for treating this waste
(Schmieder and Abeln, 1999).
5 Conclusions
SCWO provides a potential alternative for processing
hazardous and toxic organic wastes without the concomitant production of noxious byproduct, as might be
experienced with combustion based technologies. The
primary challenges that are inhibiting the rapid commercialization of SCWO are the high operating pressure,
possible plugging of the reactor due to salt formation,
corrosive behavior, and pre-commercial higher processing
costs. With active research underway to understand and
resolve the problems of plugging from salts and corrosion,
the development of novel reactor designs to alleviate these
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Supercritical water oxidation for the destruction of toxic organic wastewaters: A review
problems and the disappearance of landfills, SCWO may
yet become a viable waste treatment option for industrial
wastes and find a nice market. Given the resolution of reliability and other engineering issues, SCWO technology has
the potential to stake a claim in toxic waste management
industry and to return a sufficient profit.
Acknowledgements
This work has been supported by the Korea Institute of
Science and Technology (KIST) program for supercritical
fluid research. The authors would like to thank to the Korea
Institute of Science and Technology, Korea.
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