Supercritical water oxidation for the destruction of toxic organic wastewaters: A review

Journal of Environmental Sciences 19(2007) 513–522

Supercritical water oxidation for the destruction of toxic organicwastewaters: 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

AbstractThe 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 publicresentment; on the other hand, SCWO has proved to be a very promising method for the treatment of many different wastewaterswith extremely efficient organic waste destruction 99.99% with none of the emissions associated with incineration. In this review, theconcepts 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 toxicwastes today. Every year the amount of those wastes gen-erated by industrial and domestic sources increase rapidly.The treatment of organic and toxic waste is becoming moredifficult and costly because of more stringent treatmentstandards and discharge limitations. Public health concernsare the driving force for the continued legislation aimed atproviding a cleaner and safer environment. Furthermore,EPA (Environmental Protection Agency) goals suggestdestruction levels up to 99.9999% of some compounds anduse of totally enclosed treatment facilities. The increasedenvironmental constrains and unfavorable public opinionhave challenged the continuing application of conventionalwaste management techniques (Li et al., 1991).

Conventional technologies currently used to treat alltypes of organic and toxic wastes include adsorption,biological oxidation, chemical oxidation, land-based, andincineration. Each of these treatment methods has short-comings and therefore may not be the best option fortreating organic and toxic wastes. Supercritical water oxi-dation (SCWO) has been proposed as a technology capableof destroying a very wide range of organic hazardouswaste. It has been drawing much attention due to effec-tively destroy a large variety of high-risk wastes resultingfrom munitions demilitarization and complex industrialchemical.

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 dis-posal does not address the ultimate destruction of toxiccomponents of the waste and can result in the possiblecontamination of surrounding soil and groundwater. Deep-well injection systems are subject to plugging or foulingif organic concentration of 1% or higher are allowed.Landfills and lagoons can contribute to contaminationof the air by volatile organics. The increasing of publicconcern and regulatory action will restrict or prohibit land-based disposal of many organic wastes in the future.

Destruction methods based on oxidation of organic con-tent for aqueous wastes include activated carbon treatment,biological treatment, incineration, wet air oxidation, andsupercritical oxidation. For very dilute aqueous wastewhose organic contents are less than 1%, activated carbontreatment or biological treatment is often an effective de-struction method. In activated carbon treatment, organicsare first adsorbed onto carbon and then oxidized duringregeneration of carbon. Partially oxidized materials areperfectly destroyed by after-burner treatment. Main costis proportional to the organic content. So this method isnot economically useful for waste containing more than1% organic. Biological treatment systems often becomepoisoned and cannot be sustained for many wastes withorganic concentrations of 1% or more.

Incineration, on the other hand, is restricted for eco-nomic reasons to waste streams relatively high organicconcentrations. To attain high destruction efficiency forhazardous and toxic wastes, incineration must be operatedat very high temperature as 900–1100°C and often withexcess air of 100%–200%. With aqueous wastes, the

514 VERIANSYAH Bambang et al. Vol. 19

energy required to bring the water component of the wasteto this temperature is substantial. For the aqueous wasteswith organic content more than 25%, the heat requiredfor high temperature can be generated from wastes. Withdecreasing organic content, the supplemental fuel requiredto satisfy the energy balance becomes a major cost. Thus,controlled incineration of aqueous waste with less than20% organics is the only consideration in extenuatingcircumstances (Thomason and Modell, 1984). Incinerationis also being regulated to restrict stack gas emissionsto the atmosphere. Extensive equipment must now beused downstream of the reaction system to remove NOx,acid gasses, and particulates from the stack gases beforedischarge. The cost of this equipment often exceeds that ofthe incinerator itself.

In the range of concentration of 1% to 20% organic, wetair oxidation or SCWO is far less costly than incinerationor active carbon treatment. Wet air oxidation (WAO) hasbeen offered as a method to treat wastewater, industrialwastes, and sludge. From a public perception standpoint,WAO is more favorable than incineration, land application,deep well injection, and ocean dumping because the wasteproducts can be completely converted to inert materialsand the process can be conducted as a closed system whichdoes not produce any hazardous byproducts. Capital costsare often higher than incineration; however, operating costsare lower. It is possible to recover energy and inorganicin WAO. Wet air oxidation, commonly associated withsludge conditioning and some organic destruction, is a low-temperature process (Boock, 1996).

The Zimpro-Passavant’s WAO process is typically oper-ated in a temperature range of 150°C to 350°C and pressurerange of 2–20 MPa. The operating pressure is maintainedwell above the saturation pressure corresponding to theoperating temperature so that the reaction is carried outin the liquid phase. Residence times may range from 15–120 min, and the chemical oxygen demand (COD) removalmay typically be approximately 75%–90%. Volatile acidsconstitute a substantial portion of remaining COD. Theformation of volatile acids, particularly acetic acid, isa limitation for WAO. Furthermore, the effluent fromincomplete (partial) wet oxidation of some wastewaters

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 aque-ous wastes. However, a number of compounds, includingm-xylene and acetic acid are refractory towards oxida-tion at these conditions. Additionally, WAO often cannotachieve the 99.9% destruction efficiencies that many newerregulations require. This motivated a look at oxidationunder more severe conditions, such as higher temperaturesand pressures, which bring the reaction mixture above itscritical point. Thus, the supercritical oxidation process wasborn. Supercritical water oxidation, on the other hand, isknown to attain nearly complete destruction of variousorganics such as PCBs, and dioxins in very short time(Boock, 1996).

1 Supercritical water oxidation

Supercritical water oxidation defined as oxidation pro-cess which occurs in water above its critical point(Tc=374°C and Pc=22.1 MPa). It uses supercritical wateras a reaction medium and exploits the unique solvat-ing properties to provide enhanced solubility of organicreactants and permanent gases (like oxygen and carbondioxide), a single-phase environment free of inter-phasemass transfer limitations, faster reaction kinetics, andan increased selectivity to complete oxidation products(Tester et al., 1993; Savage et al., 1995; Schimeider andAbeln, 1999).

SCWO provides a potential alternative for process-ing hazardous military wastes without the concomitantproduction of noxious byproducts as might be experi-enced with combustion-based technologies (Downey etal., 1995). The process usually operates in a temperaturerange of 450–600°C and pressure range of 24–28 MPa.It consists of the general steps shown in the block flowdiagram in Fig.1. The aqueous waste stream containing theorganic is pressurized and preheated to reactor conditions.The oxidant stream, which can be an aqueous solutionof hydrogen peroxide, pure oxygen, or air, is pressurizedand mixed with the organic stream. The one-phase mixtureof water, organic and oxidant enters the reaction zone,

Fig. 1 Block flow diagram of typical SCWO process.

No. 5 Supercritical water oxidation for the destruction of toxic organic wastewaters: A review 515

where both organic compounds and oxygen are completelysoluble, and the temperature is high enough that freeradical oxidation reactions proceed rapidly. The organicoxidizes rapidly and completely (destruction efficiency>99.99% with residence times less than one minute) toCO2 and H2O (Tester et al., 1993; Savage et al., 1995;Schmieder and Abeln, 1999; Modell, 1989).

If any nitrogen is present, either introduced with thewaste or if air is used as the source of O2, the resultingproduct is N2 or N2O (Killilea and Swallow, 1992). NOx

and SOx gases, typical undesired by-products of combus-tion processes, are not formed because the temperatureis too low for these oxidation pathways to be favored.Any N2O found can be catalytically converted to N2.Heteroatoms (e.g., chlorine, phosphorous, sulfur) react toform their corresponding mineral acids. With the additionof a suitable base, acids are neutralized and form theircorresponding salts which precipitate out of the reactingmixture allowing for their removal. It has already beenproved that SCWO is an environment friendly wastetreatment 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 andDinjus, 2001; Kronholm et al., 2003; Lee et al., 2004; Riceand Steeper, 1998; Sullivan and Tester, 2004; Veriansyah etal., 2005a, 2005b, 2005c).

2 Toxic organic wastes treated with supercrit-ical water oxidation

The SCWO process as a hazardous waste treatmenttechnology has been proven to be a viable and effectivetechnique by both academia and industrial researchers.These researchers showed that SCWO indiscriminatelyand rapidly destroys a broad spectrum of organic wastes.SCWO has been shown effective in the treatment of toxicchlorinated chemicals such as polychlorinated biphenyls(PCBs) (Anitescu and Tavlarides, 2000, 2002, 2005; An-itescu et al., 2004, 2005; Fang et al., 2004, 2005; Hatakedaet al., 1997a, 1997b, 1999; Kubatova et al., 2003; O’Brienet al., 2005; Rahuman et al., 2000; Sako et al., 1999;Staszak et al., 1987; Weber et al., 2002) and the pesticideDDT (Modell, 1990), bacteria and dioxins (Thomason etal., 1990), chlorophenol and chlorobenzene (Lin et al.,1998, 1999; Lin and Wang, 1999a, 1999b, 2000a, 2000b,2001; Muthukumaran and Gupta, 2000; Namasivayam andKavitha, 2003; Svishchev and Plugatyr, 2006) processwaste 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 etal., 2002). Compounds which are problematic to recycleor dispose due to the formation of hazardous by-productsand residues such as the polymer polyvinylchloride(PVC), the flame retardant tetrabromobisphenol A, and thechlorocarbon γ-hexachlorocyclohexane and hexachloro-cyclohexane, are completely oxidized without hazardousby-product formation (Hirth et al., 1998). SCWO has

also been shown effective in the treatment of a highlycontaminated 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 paperindustry (Modell, 1990; Modell et al., 1992, 1995), de-inking sludge from the recycle paper industry (Gidner andStenmark, 2002), and a combination of sludge from a pri-mary clarifier mixed with effluent from a bleach plant and adecant of pond sludge (Cooper et al., 1997). Additionally,wastes which are typically treated by a bioremediationprocess, such as urea (Timberlake et al., 1982), humanwastes (Hong et al., 1987, 1988), and waste from mannedspace missions (Takahashi et al., 1988) are all destroyedby SCWO.

SCWO process has been identified as a promisingalternative technology to incineration for the destructionof the chemical weapons stockpile (NRC, 1993). In theUS, approximately 25000 t of chemical weapons areslated for destruction by 2006. Originally in 1982, theseweapons were to be incinerated at each of the eight storagesites in the continental USA (Umatilla Depot Activity,Oregon; Tooele Army Depot, Utah; Pueblo Depot Activity,Colorado; Pine Bluff Arsenal, Arkansas; Newport ArmyAmmunition Plant, Indiana; Lexington Blue Grass DepotActivity, Kentucky; Anniston Army Depot, Alabama; andAberdeen Proving Ground, Maryland) and on Johnston Is-land in the Pacific (Harigel, 2000; Hogendoorn, 1997). Dueto operational problems at the Johnston Island incinerator,the increasingly poor public perception of incineration andthe unanticipated local public opposition to building newincinerators at the remaining storage locations, the Armywas forced to consider alternative methods for destroyingthese weapons in the early 1990’s (U.S. Congress, 1992).In that report, SCWO was selected as one of four possiblealternative technologies.

SCWO has been shown effective for destroying thestockpiled chemical warfare agents (Bianchetta et al.,1999; Downey et al., 1995; Lachance et al., 1999; Snowet al., 1996; Sullivan and Tester, 2004; Veriansyah et al.,2005a, 2005c, 2006), propellants and energetics (Buelow,1990, 1992; Harradine et al., 1993), and military smokesand dyes (Robinson, 1992; Rice et al., 1994). Because ofthe ability of SCWO to destroy broad classes of organicwastes and its ability to destroy chemical warfare agents,the three branches of USA military are building SCWOunits for their purposes. The USA Navy is developing com-pact SCWO units for the on-board treatment of hazardouswastes (Kirts, 1995; Cohen et al., 1998). The USA Armycommissioned Foster Wheeler Development Corporationin conjunction with Sandia National Laboratories andGencorp Aerojet to build a SCWO facility at the PineBluff Arsenal in Arkansas for destroying smokes, dyes,and pyrotechnics (Haroldsen et al., 1996a, 1996b). TheArmy is also undergoing testing the SCWO facility built byGeneral Atomics in Toole, Utah for treating VX and GB.The USA Air Force awarded a contract to General Atomicsto design a plant for destroying solid rocket propellant


(Hurley, 1996).

3 Supercritical water oxidation reactor sys-tem

3.1 Batch system

Various batch reactors suitable for conducting SCWOof organic waste are described in the literature (Calvo andVallejo, 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 twotemperature zones, the upper part, to keep the reactor abovecritical temperature, and the lower part, to dissolve the saltprecipitant at subcritical temperature (Kupferer, 2002).

3.2 Continuous-flow system

Organic waste treated by SCWO mostly conduct incontinuous-flow system. This is due to its flexibility forexpansion to plant or industrial scale. The type of reactor isdeveloped from basic tubular type to the current transpiringwall 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 andan inner porous vessel (Daman, 1996; Kritzer and Dinjus,2001). Through the porous wall, supercritical water willget through to form a thin, protecting water film. Throughthis complex perspiration system, the porous liner is saidto protect the reactor against corrosion and salt deposition.Fig.2 shows a simple schematic diagram of TWR. Somegroup have developed a hydrothermal flame as internalheat source in TWR (Wellig et al., 2005) and another grouphave studied its application on halogenated hydrocarbons(2,4-dichlorophenol) with 98.7% conversion at residencetime of 32 s., temperature of 713 K and pressure of 25MPa (Lee et al., 2005). Current study and review related tothis type of reactor is described in literature (Fauvel et al.,2003, 2005; Marrone et al., 2004, 2005).

Fig. 2 Transpiring wall reactor (Daman, 1996).

3.2.2 Floating type reactor (SUWOX)SUWOX was designed to prevent corrosion problem,

which was solved by dividing the construction into twovessels, the pressure-resistant vessel and the inner vessel(Casal and Schmidt, 1998). Fig.3 shows the design of thereactor. The SCWO reaction occurs in the inner nonporousvessel. Between those two vessels, there is a gap for smallstream of water.

Fig. 3 SUWOX reactor (Baur et al., 2005).

Extensive study for this type of reactor was conductedin Germany (Baur et al., 2005). They explore four typesof SUWOX-base reactor for biocides treatment in SCWO.The destruction of organic with conversion 99.9% could beachieved, even at low oxygen supply and the shortest resi-dence time (1.37 min). Salt content in the effluent remaineddissolve, with concentration >200 g/L (NaCl). Anothergroup, successfully decomposed 2,4-dichlorophenol with99.9% conversion at residence time of 34 s, temperatureof 693 K and pressure of 25 MPa (Lee et al., 2005). Thisresult was higher, compare to when they employed TWRat the similar conditions.

4 Industrial status

Several reviews have summarized the current generalstate of SCWO technology, as well as pilot work re-cently performed or in progress in support of a numberof applications (Kritzer and Dinjus, 2001; NRC, 1998;Schmieder and Abeln, 1999; Shaw and Dahmen, 2000;Tester and Cline, 1999; Yoo et al., 2004). The promotionof SCWO for treating industrial wastes has also metwith limited success. The main drawbacks are the highoperating pressure, possible of the reactor plugging dueto salt formation, corrosive behavior under certain T-P-


xi conditions, and pre-commercial higher processing costs.With active research underway to understand and resolvethe problems of plugging from salts and corrosion, thedevelopment of novel reactor designs to alleviate theseproblems and the disappearance of landfills, SCWO mayyet become a viable waste treatment option for industrialwastes and find a nice market (Hodes et al., 2004; Kritzeret al., 1999; Kritzer and Dinjus, 2001; Kritzer, 2004).An even more serious problem facing SCWO havingnothing to do with the process itself is the unwillingness ofindustries to invest in novel, and potentially superior, wastetreatment technologies. This barrier will likely prove moredifficult than the technical problem facing SCWO. Regula-tory pressure does not suffer from these constraints, andchanges in industrial effluent discharge regulations maybe needed. The success of SCWO in treating the militarywaste will be important for its industrial acceptance.

Table 1 contains a list of full-scale facilities and li-censees of the SCWO processes developed by severalcompanies, along with recent feed material that have beenprocessed. MODAR, Inc., the first company to attempt toexploit the technology commercially, performed extensivestudies of destruction efficiencies for organic compoundin the 1980’s and early 1990’s in an attempt to validatethe SCWO process and develop large-scale reactor systemfor treating industrial wastes. MODAR, Inc., was acquiredby General Atomics (GA) in 1996, but GA is currentlyonly 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 OrganoCo. by Japan in 1998 (Oe et al., 1998). In addition tohaving a licence to the MODAR process, organo is a li-censee of the MODEC process (designed a SCWO reactorsystem capable of avoiding the salt plugging problemsand eliminating corrosion issues for many wastes). Twoother Japanese companies, Hitachi Plant Engineering andConstruction Co. and NGK Insulator Ltd., and a Canadianfirm, NORAM Engineering and Constructors, Ltd., are

also MODEC licensee. Hitachi and NGK are interested indeveloping the MODEC process further for sewage sludgetreatment (Japan Chemical Week, 1998).

Both GA and Foster Wheeler have been very active inrecent years with several projects being conducted for threebranches of the U.S. Armed Forces. GA has demonstratedsuccessful treatment of chemical agent (HD, GB and VX)hydrolysate and energetics hydrolysate/secondary wastesfor the U.S. Army’s Assembled Chemical Weapons As-sessment (ACWA) program (U.S. DOD ACWA, 1999),SCWO is part of GA’s Total Solution proposed to ACWAfor demilitarization of the complete munition (projectiles,mortars, rockets) and associated storage and process-ing materials. The energetics hydrolysate/secondary wastefeeds consisted of slurry of hydrolyzed energetics (tetry-tol, Composition B, and/or M28 propellant) along withshredded wood, plastics, and activated carbon. GA recentlycompleted further pilot testing for ACWA in support of afull-scale design for demilitarization of chemical weaponsstored in Pueblo, CO, and Lexington, KY (U.S. DODACWA, 2002). GA also designed and tested a compactSCWO system for the U.S. Navy in 1999 for destructionof shipboard wastes (Elliott et al., 2000). GA conductedhydrolysis and SCWO testing of rocket motor propellantfor the USA Air Force in 1995 using a 1 gpm (3.8 L/min)pilot-scale system (Defense, 1995). The Japanese compa-nies Komatsu, Ltd., and Kurita Water Industries, Ltd., havea licensing agreement with GA in commercializing SCWOtechnology in Asia (Schmieder and Abeln, 1999).

Foster Wheeler constructed a full-scale SCWO systembased on their transpiring wall reactor design for the U.S.Army’s Pine Bluff Arsenal in Arkansas in 1998 (Crookeret al., 2000). The system was designed to treat obsoletesmoke and dye munitions at a rate of 80 lb/h (36 kg/h)of munitions. It is being operated by Sandia NationalLaboratories and has been undergoing extensive system-ization with surrogate feed materials since constructioncompletion. Foster Wheeler has also conducted pilot-scale

Table 1 Commercially designed SCWO facilities currently in existence

Company Licenses Large-scale plants Application

MODAR Organo Nittetsu Semiconductor, Semiconductor manufacture wastesJapan (constructed by Organo)

MODEC Organo, Hitachi, None Pharmaceutical wastes, pulp, and paper mill wastes,NGK sewage sludge

General Atomics Komatsu, Kurita U.S. Army Newport Chemical Bulk VX nerve agent hydrolysate; other feed processedWaste Industries Depot, Newport, IN in smaller-scale system; chemical agent, explosives, and

dunnage (U.S. Army), shipboard wastes (U.S. Navy),rocket, propellant (U.S. Army Force)

Foster-Wheeler U.S. Army Pine Bluff Arsenal, Smokes and dyes; other feeds processed in smaller-Pine Bluff, AR (operate by scale systems: chemical agent and explosivesSandia National Laboratory) (U.S. Army), shipboard wastes (U.S. Navy)

EcoWaste Chematur Huntsman Chemical, Austin, TX Oxygenated and nitrogen-containing hydrocarbonTechnologies (EWT) (e.g., alcohols, glycols, amines)Chematur Shinko Pantec Johnson Matthey, Brimsdown, UK Spent catalyst (recover platinum group metals and

destroy organic contaminants)Japan (constructed by Shinko Pantec) Municipal sludge

SRI International Mitsubishi Heavy Japan PCBs, chlorinated wastesIndustries

Hydro-Processing Harlingen Wastewater Treatment Mixed municipal and industrial wastewater sludgePlant No.2, Harlingen, TX

Hanwha Chemical Namhae Chemical Corp, Korea Wastewater from DNT/MNT Plant and Melamine Plant


testing of a transpiring wall SCWO system for the USANavy and Army ACWA program similar to that describedfor GA. Testing for the Navy was performed in 1999with halogenated solvents and photographic solution feedsat 80–209 lbs/h (36–95 kg/h) (Crooker et al.,2000). Thesame system was used for ACWA testing in 2000, inwhich mixtures of agent (HD, GB, VX) and energetic(tetrytol, Composition B, M28 propellant) hydrolysateswere processed with minimal corrosion and salt buildupin the reactor (U.S. DOD ACWA, 2001). Foster Wheeler ispart of a team who’s proposed Total Solution to ACWA formunition demilitarization includes co-processing of agentand energetic hydrolysates via SCWO as demonstrated.The hydrolysate feed recipes were chosen to representcompositions expected from processing actual munitions.Foster Wheeler recently completed further pilot testingfor ACWA in 2002 in support of a full-scale design fordemilitarization of chemical weapons stored in Lexington,KY.

EcoWaste Technologies (EWT) designed and built thefirst operating commercial SCWO plant in the USA. Theplant was constructed for the Huntsman Co. (formerlyTexaco Chemical Co.) in Austin, TX, for destructionof non-halogenated organic wastes produced on-site attheir Austin Research Laboratories. The tubular reactorsystem began operation in 1994. The waste feed consistedprimarily of a blend of alcohols, glycols, and amines withan overall organic loading of 10 wt%, and was fed at a rateof 2425 lb/h (1100 kg/h) (McBrayer et al., 1996).

Chematur Engineering (1999) acquired a licensingagreement for the EWT SCWO process in Europe in 1995,and acquired the exclusive world-wide rights for EWTSCWO in 1999. SCWO is marketed by Chematur underthe trade name Aqua Critoxr. Chematur built a 550 lb/h(250 kg/h) pilot-scale SCWO system in 1998 that has sincebeen tested with several mostly nitrogen-containing wastes(amine production wastes, non-halogenated spent cuttingfluid, de-inking sludge, and sewage sludge) (Stenmark,2001; Gidner and Stenmark, 2002). Chematur has alsoconstructed its first full-scale SCWO facility for JohnsonMatthey in the UK (Chematur, 2001). Chematur has li-censed the EWT SCWO process to the Shinko PantecCo. of Japan. Under this license agreement, Shinko Pantechas constructed an 2425 lb/h(1100 kg/h) SCWO plant fortreating municipal sludge, which was commissioned in2000.

SRI International granted its first licensing agreement ofthe AHO process (i.e., carbonate-filled reactor for catalyticoxidation and salt product adsorption) to Mitsubishi HeavyIndustries (MHI) in 1999 (Waste Treatment TechnologyNews, 1999). MHI has been working with SRI on com-mercializing the AHO process since 1995, and plans touse it to destroy polychlorinated biphenyl (PCB) wastesat commercial facilities. Since 1998, MHI has conductedtests with PCBs in a pilot-scale system in Japan, demon-strating greater than 99.9999% destruction at 380°C and270 atm. MHI also owns a patent on the AHO processas applied to PCB decomposition (Tateishi et al., 2000).MHI is currently designing the first full-scale commercial

AHO system in Japan for PCB destruction, with plans tobuild several more plants for both government and privateclients.

HydroProcessing, LLC, has focused on the applicationof SCWO for treating municipal wastewater sludge. Theirpatented process (Griffith et al., 1999), referred to as theHydroSolidsr process, is intended to replace tradition-al sludge digestion and dewatering units in a standardwastewater treatment plant. They have operated a 0.4 gpm(1.5 L/min) tubular reactor pilot system with this feed since1996, and have built a full-scale system for the HarlingenWastewater Treatment Plant in Harlingen, TX. The systemis intended to process both municipal wastewater sludgeand industrial wastewater sludge from an adjacent factory(Wofford and Griffith, 2001). HydroProcessing states thatoperating costs are about 180 USD/t (dry) on (not includ-ing any projected benefits from energy or CO2 recovery),compared to a cost of 275 USD/t for sludge disposal bylandfill or land application (Parkinson, 2001). Because ofthe inherently greater amount of solids contained in thesludge feed (as compared to liquid wastes), the processincorporates a hydrocyclone after the reactor for solidsremoval, and a separate patented downstream system forhandling pressure letdown of the solids-containing effluentstream.

There are other companies trying to commercializeSCWO technology, as well. For example, Hanwha Chem-ical has constructed 2000 kg/h SCWO plant for treatingDNT/MNT Plant wastewater and 35000 kg/h SCWOplant for treating Melamine Plant wastewater, whichwere commissioned in 2000 (Hanwha Chemical, 2000).ProChemTech International, Inc. designed and built asmall tubular SCWO system of 0.1 gpm (0.4 L/min) capac-ity in 1993 for treating organic-laden wastewater from asemi-conductor manufacturer (ProChemTech, 2004). No-ram Engineering and Constructors, Ltd., has recently beenissued a patent (Boyd et al., 2001) on a process forutilizing SCWO for oxidation of redwater (a waste fromthe manufacture of nitroaromatic explosive compounds).Daimler Chrysler of Germany has also been interested inthe application of SCWO for the treatment of electronicscrap (e.g., circuit boards) and, in collaboration with theFraunhofer Institute ITC, has built a mobile plant (20L/h) containing a tubular reactor for treating this waste(Schmieder and Abeln, 1999).

5 Conclusions

SCWO provides a potential alternative for processinghazardous and toxic organic wastes without the con-comitant production of noxious byproduct, as might beexperienced with combustion based technologies. Theprimary challenges that are inhibiting the rapid commer-cialization of SCWO are the high operating pressure,possible plugging of the reactor due to salt formation,corrosive behavior, and pre-commercial higher processingcosts. With active research underway to understand andresolve the problems of plugging from salts and corrosion,the development of novel reactor designs to alleviate these


problems and the disappearance of landfills, SCWO mayyet become a viable waste treatment option for industrialwastes and find a nice market. Given the resolution of relia-bility and other engineering issues, SCWO technology hasthe potential to stake a claim in toxic waste managementindustry and to return a sufficient profit.

Acknowledgements

This work has been supported by the Korea Institute ofScience and Technology (KIST) program for supercriticalfluid research. The authors would like to thank to the KoreaInstitute of Science and Technology, Korea.

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Supercritical water oxidation for the destruction of toxic organic wastewaters: A review

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