J.

of Supercritical Fluids 29 (2004) 289–312

Salt precipitation and scale control in supercritical water

oxidation—part B: commercial/full-scale applications
Philip A. Marrone a , Marc Hodes b , Kenneth A. Smith c , Jefferson W. Tester d,∗
a Geo-Centers, Inc., 7 Wells Avenue, Newton, MA 02459, USA
b Bell Laboratories, Lucent Technologies, 700 Mountain Avenue, Room 1A-323, Murray Hill, NJ 07974, USA
c Department of Chemical Engineering, Massachusetts Institute of Technology,

77 Mass. Avenue, Room 66-540, Cambridge, MA 02139, USA

d Department of Chemical Engineering, Massachusetts Institute of Technology,

77 Mass. Avenue, Room 66-454, Cambridge, MA 02139, USA

Received 28 May 2002; received in revised form 14 March 2003; accepted 16 May 2003

Abstract

Despite the potential of supercritical water oxidation (SCWO) as a viable technology for organic waste destruction, its
commercial development has been hindered by the problems of corrosion and salt precipitation/solids buildup. The extremely
low solubility of polar inorganic salts in the supercritical water environment causes salts present in the feed, or formed during
reaction, to precipitate inside the reactor. If left unchecked, these salts can rapidly accumulate on reactor walls or process surfaces
and form plugs, causing expensive and frequent downtime of the SCWO system. Other solids such as oxides exhibit low solubility
in water over the range from ambient to supercritical conditions and, although they have much less tendency to adhere to process
surfaces, may still hinder operations if not accommodated. Many wastes will have a combination of salt-type and oxide-type solids,
and may have an intermediate tendency to stick to process surfaces. Many of the companies that have attempted to commercialize
the SCWO technology over the past two decades have developed innovative approaches to dealing with the corrosion and salt
precipitation/solids buildup problems. These are often the distinguishing features of each company’s SCWO process. This
paper objectively reviews several commercial approaches that have been developed and/or used to control salt precipitation and
solids buildup in SCWO systems. The approaches reviewed consist of specific reactor designs and operating techniques, and
include the following: reverse flow tank reactor with brine pool, transpiring wall reactor, adsorption/reaction on a fluidized solid
phase, reverse flow tubular reactor, centrifuge reactor, high velocity flow, mechanical brushing, rotating scraper, reactor flushing,
additives, low turbulence/homogeneous precipitation, crossflow filtration, density separation, and extreme pressure operation.
Recent commercial SCWO applications utilizing these approaches are also discussed. A companion paper by Hodes et al. (J.
Supercrit. Fluid., see this volume) reviews fundamental principles and research pertinent to scale control in SCWO processes.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Supercritical water oxidation; SCWO; Hydrothermal oxidation; Salt precipitation; Scale

∗ Corresponding author. Tel.: +1-617-253-7090; fax: +1-617-258-5042.

E-mail addresses: pmarrone@geo-centers.com (P.A. Marrone), hodes@lucent.com (M. Hodes), kas@mit.edu (K.A. Smith),
testerel@mit.edu (J.W. Tester).

0896-8446/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0896-8446(03)00092-5
290 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
1. Introduction
Supercritical water oxidation (SCWO) is an effec-
tive technology which can be used to destroy a wide
variety of organic wastes, particularly those already
in aqueous solution. Above the thermodynamic criti-
cal point of water (374◦ C, 221 bar), nonpolar organic
compounds and oxygen are generally highly soluble
and often completely miscible in water, while polar in-
organic compounds such as salts are insoluble. In the
presence of an oxidant such as O2 , the dense, high tem-
perature environment characteristic of the SCWO pro-
cess results in rapid and complete oxidation of organic
species to CO2 , H2 O, and N2 without toxic and/or
undesirable byproducts such as NOx . Typical operat-
ing conditions for commercial systems (550–650◦ C,
250 bar) often result in reactor residence times of 1
min or less for complete organic destruction (Tester
et al. [1]). Dealing with the insoluble salts, however,
can represent a challenge for many potential SCWO
process applications.
Salts may be present in feeds processed by com-
mercially designed SCWO systems for any of several
different reasons. One is simply that they are part of
the waste stream to be treated and cannot be easily
separated or removed. For organic feeds which con-
tain heteroatoms such as chlorine, sulfur, or phospho-
rus, pre-neutralization of the feed with a base such
as caustic leads to another source of salt. This tech-
nique is sometimes used for the reduction of corrosion
associated with acid formation in the reactor during
oxidation of these feeds. The subsequent neutraliza-
tion reaction between the resulting mineral acid and
the added base produces the corresponding salt, which
precipitates immediately within the reactor (or possi-
bly the feed line if heated). The result is to reduce the
corrosion problem in favor of a salt precipitation prob-
lem. Finally, salts can enter a SCWO feed by delib-
erate addition of a particularly chosen salt in order to
create a salt mixture with transport properties that are
more favorable than those of the original salt mixture.
The purpose is to achieve better overall management
of the precipitation and transport of salt through the
reactor than could be attained with the original salt
composition (see Section 2.2.5).
The need to understand what controls salt precipi-
tation and buildup in commercially designed SCWO
operations and why it is an issue of concern is driven
by the considerably reduced solubility of salts (and
all ionic substances) in supercritical water (see the
companion paper by Hodes et al. [2] for more details
on this behavior). Such low solubility results in rapid
precipitation of the salts as soon as they enter or are
formed in the high temperature supercritical environ-
ment within the SCWO reactor. Any solid particles
present in the fluid phase will tend to contact sur-
faces within the reactor and can remain on the surface
if the attractive forces (van der Waals and/or electro-
static) exceed the hydrodynamic shear stress that will
tend to remove them. This surface is often the reac-
tor wall, but it can be any surface extending into the
reactor chamber (e.g., thermocouples). Solid salt may
also nucleate directly on the process surfaces. In any
case, the resulting deposit, if left unchecked, can lead
to increased pressure drop and degraded heat transfer,
and can eventually form a plug. The same effect may
also occur in the feed line leading to the reactor if it
is heated. Depending on the particular salts involved,
salt plugs can form in as little as a few hours in an ini-
tially clean reactor with a diameter of several inches.
The obvious problem with this occurrence is that the
SCWO system must be shut down and the reactor (and
any other affected piping or components) cleaned of
salt deposits. If performed frequently enough, the col-
lective downtime associated with system shutdown,
cleaning, reassembly, pressure testing, and restarting
can be sufficient to make the use of the SCWO tech-
nology uneconomical or otherwise unfavorable for the
particular application. Therefore, a key feature of ef-
fective scale control methods is that they minimize
system shutdown and/or disassembly (i.e., they work
online as feed is oxidized without interruption).
It is important to note that many potential SCWO
applications involve some solids that exhibit low solu-
bility over the entire range of conditions present in the
SCWO process, from ambient conditions to reactor
temperatures and pressures. The most common solids
in this category are silica, alumina, and other metal ox-
ides and silicates. These are frequently encountered in
the form of sand, clay, and rust. These types of solids
are much less prone to adhere to process surfaces than
are nascent salt particles and of themselves are of little
concern for scaling or plugging. However, such solids
may be present in combination with the more adherent
or ‘sticky’ salt-type solids and thus be incorporated
into deposits that form. Conversely, a high proportion
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
of ‘nonsticky’ oxide-type solids to ‘sticky’ salt-type
solids can prevent or minimize problems of salt depo-
sition in a SCWO system.
Despite the many advantages of the SCWO process
with respect to oxidation of organic compounds (i.e.,
single dense phase, rapid reaction, and benign reac-
tion products), salt plugging and corrosion have been
important factors which have challenged the commer-
cial development of SCWO. This situation has ex-
isted since the inception of SCWO technology and
the first attempts to commercialize the process more
than two decades ago. Consequently, much research
in academia and government laboratories has been de-
voted to understanding the fundamental principles be-
hind these two phenomena as they relate to SCWO
operation. In addition, many companies that have at-
tempted to commercialize SCWO technology over the
years have also devoted considerable effort to these
issues because of the critical importance of these is-
sues in achieving a viable SCWO process. As a re-
sult, it is often the specific design or method used to
control/eliminate solids plugging and corrosion which
distinguishes a particular SCWO process developed
by one company from that of another.
The purpose of the present paper is to review and
summarize the various approaches to controlling salt
precipitation and solids buildup that have been devel-
oped, patented, and/or used in applications of SCWO
technology. A companion paper by Hodes et al. [2] re-
views basic principles and fundamental research per-
tinent to salt precipitation and buildup under SCWO
conditions, primarily in the areas of phase behavior,
heat transfer, and salt deposition rates.
2. Engineering approaches to salt precipitation
and scale control
Table 1 lists several companies that have been ac-
tively involved in commercializing SCWO technology
on a large-scale. MODAR, which began operations
in 1980, was the first commercial SCWO company
and a pioneer in exploring and developing the ba-
sic concepts associated with SCWO operation. Early
work at MODAR resulted in the compilation of a sub-
stantial database of organic destruction efficiencies
and material compatibility. Six years later, MODEC
and Oxidyne entered the commercial scene. The
291
Table 1
Past and present companies involved in commercializing SCWO
technologya
Company Year of Establishment
or First Involvement
MODAR, Inc.b 1980
MODEC (Modell Environmental Corp.) 1986
Oxidyne Corp.c 1986
EcoWaste Technologies, Inc.d 1990
Abitibi-Price, Inc.e 1991
General Atomics 1991
Foster Wheeler Development Corp. 1993
SRI International 1993
KemShredder, Ltdf 1993
Chematur Engineering AB 1995
HydroProcessing, L.L.C. 1996
a See Table 5 for active Japanese firms who are licensees of
processes of several companies listed here.
b Acquired by General Atomics in 1996 (Waste Treatment Tech-
nology News [3]).
c Ceased operations in 1991 (Gloyna and Li [4]).
d Acquired by Chematur Engineering in 1999 (Process Engi-
neering [5]).
e Sold its SCWO technology to Connor Pacific Environmental
Technologies in 1997 (Mergers & Acquisitions in Canada [6]).
f Acquired by HydroProcessing in 1996 (Gloyna and Li [4]).
Oxidyne SCWO process was unique in that the reac-
tor was a cased deep well, as opposed to a standard
skid-mounted vessel. Several additional companies
became involved with SCWO during the 1990s, as
the potential advantages and difficulties associated
with this technology became clear. Most of the salt
precipitation and scale control designs or techniques
described in this review article have been developed,
patented, and utilized (in some cases) by one or
more of the companies listed in Table 1. In addition
to the companies listed, a number of US National
Laboratories (e.g., Los Alamos National Laboratory,
Idaho National Engineering and Environmental Lab-
oratory (INEEL), Sandia National Laboratories) and
other companies (e.g., ProChem Tech International,
NORAM Engineering and Contractors) have also
played a role in developing specific designs and/or
small-scale commercial applications of SCWO.
Although each company has its own specific de-
signs and expertise, all SCWO processes consist of
the general steps shown in the block flow diagram in
Fig. 1. The waste feed mixture is first prepared, pres-
surized, and preheated (if necessary) before entering
292 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312

Fig. 1. Basic SCWO process.

the reactor. The oxidation reaction takes place under
supercritical conditions in the reactor. The effluent
leaving the reactor is then usually cooled and depres-
surized prior to separation of gaseous, liquid, and
solid products (although in some cases, solids may be
removed while still at high temperature and pressure).
In general, salts will precipitate in the reactor and
redissolve once the effluent temperature is reduced
to a subcritical value. Hence, most of the designs or
techniques developed to manage salt precipitation and
solids buildup are associated with the unit operations
upstream of the effluent cooldown.
Table 2 summarizes the commercially designed ap-
proaches that have been developed, mostly within the
last decade, for salt precipitation/solids control. They
are arbitrarily divided into two categories: those that
involve unique system or component designs (usu-
ally of the reactor), and those that employ specific

Table 2
Commercially developed approaches to SCWO salt precipitation and solids deposition control
Approach Method Companies holding patent(s) and/or using method

Reactor designs Reverse flow, tank reactor with brine pool MODAR
Transpiring wall reactor Foster Wheeler
Adsorption/reaction on fluidized solid phase SRI International
Reversible flow, tubular reactor Abitibi-Price
Centrifuge reactor Nonea

Specific techniques High velocity flow MODEC, Chematur, Organo, Shinko Pantec
Mechanical brushing MODEC
Rotating scraper MODAR, General Atomics
Reactor flushing General Atomics, Abitibi-Price, Chematur
Additives EcoWaste Technologies, General Atomics
Low turbulence, homogeneous precipitation HydroProcessing
Crossflow filtration University of Texas, Austin
Density separation Oxidyne, General Atomics, HydroProcessing
Extreme pressure operation Los Alamos National Laboratory, Eco Waste Technologiesb
a Patent owned by inventors (see Section 2.1.5).
b Owns patents for several reactors designed for use at very high pressures.
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312 293

Table 3
Classification of salt precipitation and scale control methods according to function
Avoids salt precipitation
Extreme pressure operation
Allows salts to precipitate but prevents wall surface Removes salts after accumulating
contact and/or accumulation on surfaces
Reverse flow, tank reactor with brine pool Reversible flow, tubular reactor
Transpiring wall reactor Mechanical brushing
Adsorption/reaction on fluidized solid phase Rotating scraper
Centrifuge reactor Reactor flushing
High velocity flow Additives (those which alter properties
of salt mixture)
Additives (those which provide surface for nucleation)
Low turbulence, homogeneous precipitation
Crossflow filtration
Density separation

operating techniques. For each case, companies which temperature (e.g., 300◦ C). The supercritical reaction
hold the patens to the design or technique cited and/or zone of the vessel functions as a continuous stirred
have utilized the design or technique in its process are tank reactor (CSTR), with the agitation provided by
listed. Existence of a patent to a particular design or the feed entering the vessel through a nozzle jet which
technique, however, does not necessarily imply that extends into the vessel from the top (Oh et al. [9]).
the technology is in current practice. Table 3 further Salts which precipitate in the supercritical zone are
categorizes these approaches according to where in
the salt precipitation/scale formation process they are
intended to function. As one can see, the majority of
these approaches do not eliminate precipitation—they
either prevent precipitated salts or solids from con-
tacting surfaces or periodically remove deposits from
surfaces.
Each of the designs and techniques for salt
precipitation and solids control is described and dis-
cussed in more detail below. While some of the de-
signs/techniques cited here also apply to minimizing
corrosion, the focus in this review is on those aspects
relevant to salt precipitation/plugging control. Meth-
ods developed exclusively for corrosion control are
not treated in this review. Table 4 provides a summary
of patents associated with the salt precipitation/solids
control methods discussed.

2.1. Reactor designs

2.1.1. Reverse flow, tank reactor with brine pool

The reverse flow tank reactor (Fig. 2) was originally
developed by MODAR (Hong et al. [7]). It consists
of a vertical pressure vessel with two distinct thermal
zones (Barner et al. [8]). The upper part of the ves-
sel is kept at a supercritical temperature (e.g., 600◦ C)
and is the region where organic species are oxidized. Fig. 2. Reverse flow tank reactor with brine pool (adapted from
The lower part of the vessel is kept at a subcritical Hong et al. [7]).
294 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312

Table 4
Summary of patents pertaining to SCWO salt precipitation/solids deposition control
Control method Patent no. Inventors Assignee Date issued Description

Reverse flow, tank 4822497 Hong et al. MODAR 4/18/89 Tank reactor with upper
reactor with brine pool supercritical and lower subcritical
temperature zones; effluent exits out
top while salts are transported to
the bottom and redissolve

Transpiring wall reactor 5387398 Mueggenburg Aerojet-General 2/7/95 Transpiring wall reactor platelet
et al. Corp. liner design
5571423 Daman Foster Wheeler 11/5/96 SCWO process utilizing transpiring
wall reactor
5571424 Ahluwalia Foster Wheeler 11/5/96 SCWO process utilizing transpiring
wall reactor with concentric platelet
liners (reaction zone is the annular
space between the two liners)
5670040 Ahluwalia Foster Wheeler 9/23/97 SCWO apparatus utilizing
transpiring wall reactor with
concentric platelet liners (reaction
zone is the annular space between
the two liners)
5723045 Daman Foster Wheeler 3/3/98 SCWO apparatus utilizing
transpiring wall reactor

Transpiring wall reactor 5384051 McGuinness None 1/24/95 Reactor with porous liner for
related designs introducing supercritical water and
oxidant
5437798 LaRoche et al. Sulzer Chemtech 8/1/95 Solid wall reactor with subcritical
AG water film

Adsorption/reaction on 5409617 Ross et al. SRI International 4/25/95 Hydrothermal decomposition in the
fluidized solid phase presence of salt catalysts (silicates,
borates, phosphates)
5709800 Ross and SRI International 1/20/98 Hydrothermal decomposition in the
Jayaweera presence of salt catalysts (silicates,
borates, phosphates, and nitrites)
5746926 Ross et al. SRI International 5/5/98 AHO process for halogenated
compounds with sodium carbonate
as solid phase
5837149 Ross et al. SRI International 11/17/98 AHO process with sodium
carbonate as solid phase
6010632 Ross et al. SRI International 1/4/00 Revised AHO process to prevent
sodium carbonate from caking
within reactor
6162958 Tateishi et al. Mitsubishi Heavy 12/19/00 AHO process for PCB destruction
Industries

Reversible flow, tubular 5560823 Whiting Abitibi-Price 10/1/96 Tubular reactor with alternating heat
reactor exchange and reaction zones, which
can be operated with flow in either
direction
5667698 Whiting Abitibi-Price 9/16/97 SCWO process utilizing the
reversible flow tubular reactor
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312 295

Table 4 (Continued )
Control method Patent no. Inventors Assignee Date issued Description
Centrifuge reactor 5425883 Reid and Halff None 6/20/95 Rotating device which functions as
a combined reactor and centrifuge
5252224 Modell et al. MODEC 10/12/93 Use of process flow velocity
sufficient to avoid solids settling;
use of process fluid propelled metal
brushes for on-line removal of
solids from the reactor wall
High velocity flow; 6264844 Modell et al. MODEC 7/24/01 Apparatus to accommodate use of
mechanical brushing high velocity and mechanical
brushing for scale control in SCWO
process
Mechanical brushing 5890531 Gairns and NORAM 4/6/99 Use of a process fluid propelled
Joustra Engineering and cleaning device and recycle conduit
Constructors for on-line removal of solids from a
tube without requiring manual
launching or removal of the device

Rotating scraper 5100560 Huang ABB Lummus 3/31/92 Device consisting of rotating
Crest blade(s) for dislodging solids from
reactor wall (designed for reverse
flow tank reactor)
5461648 Nauflett et al. US Navy 10/24/95 Helical rotating shaft for solids
movement through horizontal,
diamond-lined reactor
6054057 Hazlebeck General Atomics 4/25/00 Design for vertical, tubular SCWO
et al. reactor; cites optional cylindrical
rotating scraper device for
dislodging solids from reactor wall

Reactor flushing 5200093 Barner et al. ABB Lummus 4/6/93 Addition of quench flow
Crest downstream of the reactor to
redissolve residual salts in the
effluent; designed for use with the
MODAR reverse flow tank reactor
5501799 Bond et al. Abitibi-Price and 3/26/96 Method using two or more parallel
General Atomics reactors, where cooled effluent from
an on-line reactor is sent to flush
one or more off-line reactors
5560822 Bond et al. None 10/1/96 Apparatus for using two or more
parallel reactors, where cooled
effluent from an on-line reactor is
sent to flush one or more off-line
reactors
6054057 Hazlebeck General Atomics 4/25/00 Design for vertical, tubular SCWO
et al. reactor; describes quench section
downstream of the reactor to cool
effluent and redissolve salts
6056883 Bond et al. Abitibi 5/2/00 Use of two reactors where
Consolidated alternately one is oxidizing feed
while the other is being flushed

Additives 5543057 Whiting and Abitibi-Price 8/6/96 Addition of solid particles forming
Mehta a mobile phase to which salts may
adhere in the reactor
296 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312

Table 4 (Continued )
Control method Patent no. Inventors Assignee Date issued Description

5620606 McBrayer RPC Waste 4/15/97 Addition of inert solid particles to a

et al. Management feed stream or system to inhibit
Servicesa reactor plugging
5755974 McBrayer RPC Waste 5/26/98 Controlled addition of one or more
et al. Management salts to a feed stream containing or
Servicesa generating a different salt to form a
eutectic blend within the reactor
6238568 Hazlebeck General Atomics 5/29/01 Use of phosphate compounds as
additives to allow precipitating salts
to transport through the reactor
without plugging
Low turbulence, 6475396 Wofford et al. HydroProcessing 11/5/02 Control of operating conditions
homogeneous (e.g., feed component velocities,
precipitation temperatures) to restrict salt
precipitation to bulk process fluid
flow before contacting reactor walls
or solid surfaces
Crossflow filtration 5421998 Li and Gloyna Board of Regents, 6/6/95 Use of metal crossflow filtration
University of element to remove salts formed
Texas System after reaction within the reactor
Density separation 4594164 Titmas None 6/10/86 Design for deep well SCWO
system; describes use of a baffle to
rotate process fluid at the end of the
reaction zone for separation of
solids by centrifugal forces

Extreme pressure 5427764 Barber RPC Waste 6/27/95 Vortex reactor; reactants are
operationb Management injected to form axial vortex at the
Servicesa reactor center, keeping hot reaction
away from vessel walls
5552039 McBrayer RPC Waste 9/3/96 Reactor with cylindrical reaction
et al. Management chamber isolated from pressure
Servicesa shell; turbulent feed injection
through single tube from bottom
5591415 Dassel et al. RPC Waste 1/7/97 Tubular reactor with lined reaction
Management chamber isolated from pressure
Servicesa shell; feed introduced from top;
cool water film injected near bottom
a Parent company of EcoWaste Technologies.
b The patents cited are for reactors designed to operate at very high pressures to maintain salt solubility.

directed to the bottom of the vessel by gravity, inertia,
and forced convection, and redissolve in the subcrit-
ical zone, forming a dense brine. The main process
effluent flow is withdrawn from the top of the vessel
(hence the reversal of flow) and this produces a recir-
culation flow pattern in the supercritical zone. As a
result, most of the salts are effectively removed from
the process flow without impeding the oxidation reac-
tion or any downstream processes (e.g., cooling and
pressure letdown).
Any residual salts entrained in the effluent can be
handled downstream of the reactor if necessary by sev-
eral different supplemental techniques. One approach
is the optional addition of quench water to redissolve
the salts (see Section 2.2.4). Another is the use of a
zirconium oxide filter, which has been employed for
residual salt removal when high purity effluent is re-
quired (Hong [10]). The materials of construction of
the filter enable it to be placed just downstream of the
reactor, allowing removal of any entrained salts from
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
the supercritical stream before reaching the cooldown
heat exchanger. Although used in the past by MODAR
for specific applications, neither the quench water nor
the filter are considered part of the standard design for
the reverse flow tank reactor.
2.1.2. Transpiring wall reactor
The general concept behind the transpiring wall
reactor is to introduce a flow of solute-free water
through a porous reactor liner in order to keep salt
particles and corrosive species away from the reactor
wall. The most prominent example of this reactor
design is the one developed by Foster Wheeler Devel-
opment Corp. (Daman [11,12]) in collaboration with
Aerojet-General Corp. and Sandia National Laborato-
ries. The liner was designed by Aerojet-General Corp.
using technology originally developed for cooling of
high pressure rocket engines (Schoenman et al. [13]).
The cylindrical liner, which fits within a tubular pres-
sure housing, consists of many thin metal layers or
platelets bonded together (Mueggenburg et al. [14]).
Each platelet is etched with a specific pattern of in-
dentations such that a three-dimensional network of
channels is formed when the platelets are combined
to form the liner. The channels are designed to meter
and distribute clean water through the liner to its inner
surface, which forms the outer boundary of the reac-
tion chamber (Fig. 3). The water exits the liner inner
surface through pores and forms a thin, protective film
Fig. 3. Transpiring wall reactor (adapted from Daman [11]).
297
on the metal surface. The temperature of the transpi-
ration water can be either subcritical or supercritical,
but is usually less than the temperature achieved in
the center of the reactor where oxidation takes place.
In principle, the continuous film of water prevents
any precipitated salts from depositing on to the sur-
face by entraining the solid salt particles in the flow
and/or by redissolving the salts (if the transpiration
water temperature is subcritical). The continuous flow
of clean water through the porous wall also prevents
or minimizes corrosive species from reaching the
metal surface of the liner. An alternate design devel-
oped by Foster Wheeler utilizes a compound reactor
consisting of concentric platelet liners such that the
reaction zone is the annular region between the two
liners (Ahluwalia [15,16]). A more simple transpiring
wall reactor design utilizing a porous tube within a
pressure shell has also been developed by researchers
at Forschungszentrum Karlsruhe (FZK) in Germany.
There are several variations of the transpiring wall
reactor concept that have been patented. One design
uses a tubular reactor with a permeable liner, through
which a mixture of water and oxidant is passed uni-
formly over the entire length (McGuinness [17]). The
mixture is forced inward toward the center of the re-
actor, where the oxidizer reacts with feed entering
from the top of the reactor. This flow through the
liner prevents salts from depositing on the surface.
Another design under development by researchers in
Prof. Rudolph von Rohr’s group at the Swiss Federal
Institute of Technology (ETH Zurich) utilizes a solid
wall tubular reactor with water film cooling (LaRoche
et al. [18,19]). A subcritical ‘by-pass’ water flow is
injected coaxially with the oxidant and organic feeds
at the top of the reactor. The by-pass water flow en-
velops the supercritical reaction zone in the center of
the reactor and keeps salts from sticking to the reactor
walls. ETH Zurich is also currently pursuing modeling
and testing of a porous liner transpiring wall reactor.
2.1.3. Adsorption/reaction on fluidized solid phase
Ross and co-workers at SRI International have de-
veloped a variant of the SCWO process which em-
ploys a bed of fluidized solids functioning as both a
reactant and adsorptive surface for salt control. The
process is referred to as Assisted Hydrothermal Oxi-
dation (AHO). Early descriptions of the process (Ross
et al. [20]; Ross and Jayaweera [21]) suggested a
298 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
wide variety of possible solid phases, including sili-
cates, borates, phosphates, and nitrites. More recent
descriptions have focused on the use of sodium car-
bonate as the solid phase (Ross et al. [22]). Com-
pared to conventional SCWO systems, AHO operates
at milder temperatures (typically 380–420◦ C) which
are just high enough to ensure that the sodium car-
bonate remains insoluble. In the AHO process, a feed
stream of organic material, supercritical water, and ox-
idant is fed to a reactor containing a fluidized bed of
sodium carbonate (Ross et al. [23,24]). According to
the inventors, the organic species adsorb to the car-
bonate and react with oxygen from both the carbonate
and oxidant. Because the carbonate provides a much
greater surface area than the reactor walls, product
salts (e.g., NaCl) are more likely to adhere to the car-
bonate. Immobilization of product salts within the flu-
idized bed is therefore the means of salt control in
this design. Use of subcritical pressures and agitation
have been found to minimize caking of the carbon-
ate salt, thereby maintaining its high surface area over
time and leading to improved performance (Ross et al.
[25]).
2.1.4. Reversible flow tubular reactor
The reversible flow tubular reactor (patented by
Abitibi-Price) is a single tube segregated into two dif-
ferent thermal zones, through which process fluid can
be fed in either direction (Whiting [26,27]). Heat ex-
changers are placed at each end and in between the
Fig. 4. Reversible flow tubular reactor (adapted from Whiting [26]).
two reaction zones to supply or remove heat from the
process, depending on which way process fluid is trav-
eling through the system. The heat transfer fluid and
the process fluid always flow countercurrent to each
other, but the direction of each is periodically reversed.
Only one reaction zone is kept at a supercritical tem-
perature at any one time, whereas the other is kept at
a subcritical temperature. In the proposed method of
operation, pressurized feed is alternately fed through
either end ‘A’ or end ‘B’ in Fig. 4. We arbitrarily start
with the case of feed from end ‘A’ (i.e., with Cycle 1
of the figure). In this case, the heat transfer fluid first
passes through Heat Exchanger II in order to cool the
hot effluent from reaction zone #1, and then passes to
Heat Exchanger I in order to preheat the feed to reac-
tion zone #1. Oxidation of the feed constituents occurs
in the supercritical reaction zone #1 and precipitated
salts are allowed to accumulate on the reactor wall
in this zone. The cold process effluent from Heat Ex-
changer II is then used as a purge for salts that had pre-
viously been deposited in reaction zone #2. When salt
buildup in reaction zone #1 becomes significant, Cycle
3 needs to be initiated to reverse the process. However,
it is necessary to first pre-heat reaction zone #2 and
this is accomplished via Cycle 2. Likewise, when it is
desired to revert to Cycle 1, it is necessary to pre-heat
reaction zone #1 and this is accomplished via Cycle 4.
The duration of Cycles 2 and 4 is short. This method
of alternating flow direction and reaction zones (i.e.,
one supercritical reaction/salt accumulation, the other
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
subcritical flushing) has the effect of allowing salts to
be removed without interrupting operation.
2.1.5. Centrifuge reactor
Most attempts to deal with salt handling in SCWO
reactor designs involve modifying a reactor vessel to
accommodate salt removal. An interesting alternative
is to approach the problem from the opposite per-
spective, namely, modifying a solids removal device
to function as a reactor. Such an approach has been
proposed by Reid and Halff [28] with a centrifuge re-
actor. In their design, an aqueous waste feed and any
other necessary chemicals (e.g., caustic) are injected
into a high speed centrifuge. The rotation of the cen-
trifuge generates a pressure above the critical pressure
of water. It appears that their intent is to operate in a
batch, rather than continuous, mode. After achieving
the required supercritical pressure, the centrifuge is
heated to bring the contents up to the required super-
critical temperature. Oxidant is then injected into the
centrifuge, initiating reaction. The normal operation of
the centrifuge separates salts as they form during reac-
tion as well as any solids that may have already been
in the feed. Reid and Halff [28] claim that the waste
feed is kept at supercritical conditions until an appro-
priate level of organic destruction and separation of
solids has been achieved. The reactor has two effluent
streams: a main, aqueous stream that may be passed
to a turbine and heat exchanger for energy recovery,
and a solids-laden stream. Removal of the solids in the
latter stream is performed downstream by an unspec-
ified means. Temperature is maintained in the reactor
by the heat of reaction, and if needed, can be aug-
mented by auxiliary fuel added to the feed, recovered
effluent heat, and/or an external heat source.
One operating concern with this design is that the
inherent nature of a batch-operated centrifuge is to
separate components, which runs counter to the need
for intimate mixing of reactants for a rapid and effec-
tive SCWO reaction. This is particularly true if the
reactants (i.e., waste, oxidant, water, fuel) are not fully
preheated and/or are fed separately to the reactor. In
this case, slugs of one or more of the incoming feed
components may not get a chance to achieve homo-
geneous mixing in the spinning centrifuge, resulting
in the possibility of pockets of higher concentrations,
which would inhibit a uniform reaction. Thus, it
may be more difficult to achieve a sufficient level of
299
oxidation in this particular reactor design than in a
more conventional SCWO reactor. The significance
of this concern and whether the reactor performs
as claimed is unclear, as we are not aware of any
commercial operation of this centrifuge design.
2.2. Specific operating techniques
2.2.1. High velocity flow
One way to minimize buildup in a solid wall SCWO
reactor is to ensure that the particles are well sus-
pended in a high speed flow. The particles must remain
suspended until they redissolve once the effluent is
cooled (in the case of salts), or until they can be other-
wise removed. This approach has been utilized in the
SCWO process developed and patented by MODEC
(Modell et al. [29]; Modell et al. [30], Modell [31]),
and is primarily applicable to feeds with a relatively
high proportion of nonsticky to sticky solids.
The particular velocity necessary to avoid perma-
nent deposition of solid particles depends on a number
of variables specific to the application, such as the
reactor diameter and orientation, fluid phase physical
properties, particle size, particle density, and particle
concentration. Thus, necessary velocities will vary for
different types of feed. For a horizontal reactor with
an inner diameter of 6.7 mm, a nominal solid particle
diameter of 20 ␮m, particle density of 2.7 g/cm3 , and
particle concentration of 1 wt.%, Modell et al. [29])
have estimated minimum fluid velocities of about
1–5 m/s for suspension flow of solids under supercrit-
ical conditions. This translates to a feed flow rate of
several liters/minute. As an example of the effective-
ness of this approach, MODEC utilized an inlet (i.e.,
ambient temperature) velocity of 0.5 m/s or flow rate
of 1.1 l/min for a pharmaceutical sludge feed in a 6.8
mm ID pilot-scale tubular reactor (Modell et al. [32]).
It is important to note that velocities and volumet-
ric flow rates in the reactor under typical operating
conditions are approximately an order of magnitude
higher than under ambient conditions due to the de-
creased density. At these higher velocities, settling of
solids and scale deposition in the reactor was reduced
to between 10 and 15% of the total solids.
The downside to this approach for solids control
is that the reactor length must be correspondingly in-
creased in order to maintain constant residence time.
The MODEC pilot plant reactor is 144 m in length in
300 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
a horizontal orientation, which is almost 50 times that
of a typical, vertically oriented, large diameter SCWO
reactor not employing high feed velocities. Chematur
Engineering AB has also utilized this approach of high
velocity (subject to the constraint of also minimizing
erosion) to avoid fouling and plugging in their SCWO
process design (Stenmark [33]).
2.2.2. Mechanical brushing
This technique involves sending a mechanical de-
vice down the reactor (usually tubular) to physically
remove and sweep downstream solid particles that
have either settled or adhered to the wall. Brushing
(also known as pigging) is performed at regular in-
tervals, with its frequency depending on the rate of
solids deposition expected for a particular feed. For
solids that include various insoluble inorganic com-
pounds and char, Modell et al. [29] cite a preferred
brushing frequency ranging from 15 min to 20 h. The
type of brush used also depends on the type of the salt
or solids that is generated and the hardness of the scale
deposits formed. Examples of acceptable devices for
brushing that have been used or proposed include wire
or bristle brushes, metal or rubber balls, and metal or
foam cylinders.
There are several ways in which this brushing ap-
proach can be implemented. In the horizontal reactor
cited by Modell et al. [29], each end of the reactor is
flanged to an additional section of tubing which has
an end cap that may be opened for addition or removal
of the brushing device. With the brush installed in the
initially isolated upstream section, process flow is di-
verted by a series of valve operations so that the feed
enters the reactor through the upstream section con-
taining the brush. The brush is thus propelled down the
reactor by the force of the process flow, scouring the
reactor wall to remove solids along the way. It stops at
the end of the opposite additional section downstream
of the reactor. By another series of valve actions, this
end section is isolated from the process flow, allow-
ing removal of the brush. In a variation (not restricted
to a SCWO process) proposed by Gairns and Joustra
[34], a passageway of tubing connects one end of the
reactor to the other end, thereby allowing the brush-
ing device to cycle back to the start without the need
for manual loading and removal of the brush.
The MODEC SCWO process utilizes a combination
of mechanical brushing and high fluid velocity as its
complete approach to controlling solids deposition. In
the same series of tests in the MODEC pilot-scale
system cited earlier, settling of solids and scale in the
reactor was reduced to 1.2% of the total solids when
brushing was used in addition to high velocities (i.e.,
1 m/s at the ambient inlet temperature) (Modell et al.
[32]).
2.2.3. Rotating scraper
The rotating scraper is similar to mechanical brush-
ing in that it provides a mechanical means of salt re-
moval after salts have been allowed to deposit on the
reactor walls. The scraper generally consists of one or
more metal blades connected to a drive shaft, which is
located on the axis of a cylindrically shaped reactor.
As they rotate, the blades dislodge and/or push the pre-
cipitated salts down the reactor, allowing a maximum
scale buildup which is dependent on the tolerance be-
tween the blade tip and reactor wall. The continuous
rotation of the scraper prevents scale from accumulat-
ing to the point at which process flow is impeded. The
frequency of rotation depends on the nature and rate
of buildup of the particular salts formed/processed.
Huang [35] describes a scraper specifically designed
for the MODAR reverse flow tank reactor. The scraper
blades are axially oriented and extend from the upper
supercritical region of the reactor vessel into the lower
subcritical brine region. Dislodged salt deposits from
the vessel wall in the supercritical region fall by grav-
ity into the subcritical brine, where they redissolve.
The blades are connected to a drive shaft at either
the top or bottom of the reactor. Huang recommends
a rotation speed of 1–10 revolutions per hour. This
scraper design was never actually used in operation of
the MODAR reactor. A similar design for a rotating
scraper in a vertical tubular reactor is proposed by Ha-
zlebeck et al. [36] as one possible means of salt con-
trol in a patent for the General Atomics (GA) SCWO
reactor and process. In addition to a rotating cylin-
drical scraper, they also suggest several other scraper
geometries, including axially moving, oscillating, and
auger type scrapers. A rotating scraper has been used
and demonstrated by GA during testing of a SCWO
reactor system built for the US Navy for processing
of shipboard wastes (Elliott et al. [37]). Another vari-
ation of a scraper device for a SCWO reactor is pro-
posed by Nauflett et al. [38]. Their patent describes a
horizontal, lined reactor with a rotating central shaft.
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
Baffles mounted to the shaft in a helical pattern allow
the shaft to function in a manner similar to a screw
conveyor, which helps move settling salts through the
reactor.
2.2.4. Reactor flushing
The reactor flushing technique involves simply rins-
ing the SCWO reactor periodically during operation
with a fluid that will dissolve accumulated salts and
scale. This technique is a more general version of
the idea employed in the reverse flow tubular reac-
tor design, but usable with any type of reactor or re-
actor combination. The most common flushing fluid
is cool (i.e., subcritical temperature) pressurized wa-
ter, although alternatives such as acid solutions have
also been used. As with other control methods that
function after salts are allowed to accumulate, the fre-
quency of flushing depends on the type of feed and
the nature and rate of buildup of the particular salts
formed/processed. The interval between flushes must
be short enough to allow removal of salt buildup be-
fore the thickness of the deposit begins to impede the
process flow and reduce the effectiveness of the oxi-
dation reaction.
While the most straightforward way to apply this
flushing control technique is to take the reactor
off-line before switching to the wash fluid, this ap-
proach can result in undesirable downtime. To avoid
such downtime, Bond et al. [39–41] have developed
an alternative flushing sequence in a series of patents
assigned jointly to GA and Abitibi-Price. Their ap-
proach involves the use of two (or more) parallel
reactors. While one reactor is on-line processing feed
at supercritical conditions, the other is off-line be-
ing flushed to remove salt deposits. When the salt
buildup in the on-line reactor is sufficient to require
removal (or at a prescribed time before this situation
is reached), the feed is diverted to the other clean
reactor and flushing fluid is sent to the scaled reactor.
The time necessary to dissolve the scale will depend
not only on the type and thickness of salt, but also
on its solubility in the flushing fluid and the flow rate
of the fluid. Once clean, the reactor is ready to come
back on-line when the scale thickness in the second
reactor becomes unacceptable. Thus this operating
scheme allows continuous processing of feed (since
one reactor is always active) while also allowing for
the necessary periodic removal of salt buildup. If
301
the salt dissolution time is much greater than the
accumulation time, more than two reactors may be
needed to ensure that one reactor is always avail-
able for processing feed. In the earlier patents, Bond
et al. [39,40] specify that the flushing fluid should be
cooled effluent from the on-line reactor. In the later
patent (Bond et al. [41]), they relax their definition
of the flushing fluid to include fluid from any source
and of any temperature (but generally subcritical and
aqueous) in which the accumulated salt is soluble.
A related technique to flushing is quenching. As de-
scribed by Barner et al. [42] and Hazlebeck et al. [36],
quenching involves directing a spray of cooled fluid
(usually subcritical water) into the main process flow
at the exit of the reactor. The purpose is to dissolve any
salt particles that reach the end of the reactor (where
the oxidation reaction is complete) to prevent plugging
of the exit port. While similar in concept to flushing,
quenching occurs continuously in an on-line reactor
as part of normal operations, and has been employed
in conjunction with several different reactor designs.
The quench design cited by Barner et al. [42], for ex-
ample, is for use with the MODAR reverse flow tank
reactor. Because quenching is used only to dissolve
salts at the reactor exit, it is not a complete solution to
salt precipitation control. It therefore must be used in
conjunction with another technique or reactor design
that will either control salt deposition in the super-
critical region of the reactor or transport salts to the
quench zone of the reactor.
2.2.5. Additives
Additives are substances that are mixed with the
feed upstream of the reactor or at its entrance in or-
der to control salt buildup. Additives generally control
scale in one of two ways: either by providing a sur-
face on which nucleation can occur (with no chemical
interaction) or by changing the chemical properties of
the solids mixture. An example of the former is de-
scribed by Whiting and Mehta [43], where nonsticky
solid particles are injected into the waste feed stream.
The solid particles are inert (e.g., sand, silica, ceramic)
or may be catalytic with respect to the oxidation re-
action (e.g., zeolites, metal oxides, noble metals). In
either case, the purpose of the particles with respect to
salt formation is to provide a mobile, large surface area
(e.g., more than 1000 times greater than that of the re-
actor walls) so that salts will be more likely to adhere
302 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
to the particles rather than the reactor walls or other
components. The adhered salts are then transported
with the particles and process fluid out of the reactor.
The particles also scour the reactor walls, thereby re-
moving any salt which may have managed to reach the
walls. The particles can be injected directly into the
feed stream in a co-current way as described above, or
can be added separately to the reactor so that they flow
counter-current to the process flow. In a proposed ex-
ample of the latter case, the particles would be injected
at the top of a vertically oriented reactor while the pro-
cess flow would enter from the bottom of the reactor
and flow upward (opposite to that of the falling parti-
cles), in a manner resembling operation of a stripping
column. One concern with the use of solid particles is
that they can cause severe valve stem erosion in a con-
ventional pressure let-down system and may require
an alternate design for reducing system pressure.
McBrayer et al. [44,45] provide an example of the
second type of additive. In this case, the added solid
is another salt. It may seem counterintuitive to add
more salt to a system for which salts are problem-
atic. However, the goal is to choose the type and
amount of added salt such that, when it mixes with
the existing or reaction-generated salt in the reactor,
the resulting mixture forms a eutectic with a melt-
ing point less than the operating temperature at the
system pressure. The resulting molten salt blend will
thus flow more easily through the reactor, particularly
in one which is vertically oriented (due to gravity),
avoiding excessive buildup that can lead to the for-
mation of salt plugs. The choice of what salt to add
depends on the nature of the feed. For instance, when
the feed contains sulfur or chlorine, McBrayer et al.
[45] cite NaNO3 , NaOH, KNO3 , and/or KOH as pos-
sible choices for the added salt. Regardless of which
particular salt is chosen, this approach to salt control
provides an excellent example of the importance and
benefits of research in developing practical applica-
tions; in this case, for quantifying the phase behavior
of salt–water systems at supercritical conditions (see
Tester and Cline [46] and Hodes et al. [2] for more
examples). Accurate multi-component phase diagrams
allow one to choose the correct type and concentration
of salt to add to a given feed and avoid choices of salt
species and/or quantities which would have a detri-
mental effect. GA has employed its own proprietary
additives for reliable salt transport in testing performed
on chemical agent and energetic hydrolysates for the
US Army (US DOD ACWA [47]). A recently issued
patent to GA (Hazlebeck [48]) describes the use of
phosphate compounds to aid salt transport through the
reactor.
2.2.6. Low turbulence, homogeneous precipitation
The basic concept behind this technique is to control
operating conditions such that salts precipitate only in
the bulk fluid. Such a technique has been patented and
employed by HydroProcessing, LLC, in their SCWO
process (Wofford et al. [49]). The reason for requiring
salt precipitation in the bulk fluid (i.e., homogeneous
nucleation) is the claim that salts which have already
precipitated tend not to adhere to surfaces, whereas
salts that are formed via heterogeneous nucleation do
tend to adhere to surfaces.
To achieve the desired conditions, separately pres-
surized and preheated feed, water, and oxidant streams
are fed coaxially into a ‘contactor vessel’ (which es-
sentially functions as the inlet portion of a tubular re-
actor). In order to ensure that salts do not nucleate at
the walls or on the feed injection surface, it is asserted
that turbulence must be minimized. Thus, it is sug-
gested that feed and water velocities be low enough
to maintain laminar or low turbulence flow condi-
tions (contrary to the highly turbulent initial mixing of
feed components encouraged in most SCWO operat-
ing schemes). With this approach, the feed is initially
contained in the center of the vessel by a surrounding
annular flow of supercritical water. The oxidant, in the
outer-most annulus, must diffuse through the water
to reach the organic feed. This is aided by the favor-
able mass transport properties of the supercritical wa-
ter. Nonetheless, reaction initiation occurs somewhat
downstream of the injector device as a result.
Reaction and subsequent salt formation and precip-
itation begin at the zone where oxidant and organic
meet (defined as the ‘initial contact zone’). By control-
ling feed component velocities and temperatures, it is
claimed that the location of the initial contact zone can
be positioned away from the walls. Eventually, pro-
cess flow from the center will reach the vessel walls
far enough downstream. However, the goal is to have
most of the salt precipitated before this occurs so that
adherence of these salt particles to the walls will be
minimized or avoided. In its patent, HydroProcessing
specifically cites an application of this technique for
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
sewage sludge, which typically has a relatively low
salt content.
2.2.7. Crossflow filtration
While popular and straightforward for many solids
removal applications, conventional filtration is difficult
to utilize within a SCWO reactor for several reasons.
Examples include the likelihood of frequent plugging
of the filter element, potential interference with feed
component mixing if placed too close to the reac-
tor entrance, and the lack of filtering materials which
can withstand the combined high temperatures and
pressures and chemical environments encountered in
SCWO processes. In one application which required
high purity effluent, a dual filter bank of zirconium
oxide filters was utilized by MODAR in the hot, pres-
surized effluent line of the reverse flow tank reactor
system (Hong [10]). This filter design, which required
periodic backflushing when tested, is effective only as
a secondary means of solids removal. The primary re-
moval step in this case was the specific reactor design
(i.e., dissolution of salts in the subcritical section of
the reverse flow tank reactor used).
Li and Gloyna [50] have proposed an alternate
design to avoid the difficulties of conventional filtra-
tion by using in situ crossflow filtration. The patent
claims that crossflow filtration is effective under
SCWO conditions because of the low densities of
the supercritical process fluid. In the simplest em-
bodiment of the stated design, reaction occurs within
the annular section formed between two tubes. The
tubes are vertically oriented and the reactant flow is
down. At some point near the reactor bottom, the
impermeable inner tube becomes a crossflow fil-
tration element. Typically, this element would be a
sintered metal tube. Because the main flow is parallel
to the filter element (unlike in conventional filtra-
tion), some process fluid (i.e., the filtrate) may pass
through the element without creating a substantial
buildup of solids on the surface. With a small pore
size (0.05–5 ␮m diameter preferred), larger solid
particles will not plug the pores and will instead
be rinsed away by the force of the fluid flow and
gravity toward the bottom of the reactor. These
solids are removed from the reactor bottom through
a separate line. The filtrate flows up the central
tube, which helps to preheat the incoming reac-
tants via heat exchange across the impermeable
303
tube wall. The claimed net effect is that solid par-
ticles are separated from the process flow without
clogging the filter. By installing more concentric
tubes, several stages of filtration could be achieved if
desired.
2.2.8. Density separation
Density separation is a standard industrial tech-
nique which separates solid particles from a fluid
stream by centrifugal forces. In terms of classification,
this technique is analogous to that of the centrifuge
reactor design discussed in Section 2.1.5. In engi-
neering practice, this kind of separation is commonly
implemented by using a cyclone or hydrocyclone.
By causing a solids-containing fluid to rotate within
the cyclone chamber, the solid particles are forced
outward toward the chamber walls by negative buoy-
ancy. The clean fluid usually exits through the center
top of the cyclone, thereby achieving separation. In
SCWO systems, a hydrocyclone can be placed either
before or after an effluent cooldown heat exchanger,
but usually before the pressure let-down device. In
this location, however, an additional control technol-
ogy may be required in order to ensure that solids are
first transported through the reactor successfully so
that they can reach the downstream hydrocyclone.
Several studies have been performed regarding the
effectiveness of hydrocyclones in removing solids
from SCWO effluent. In pilot-scale experiments per-
formed at supercritical pressures (276 bar) and ambi-
ent to near critical temperatures (25–340◦ C), Laspidou
et al. [51] demonstrated greatly improved separation
of ␣-alumina particles in a hydrocyclone with in-
creasing temperature. In an early bench-scale tubular
SCWO system, MODAR utilized a hydrocyclone for
downstream solids removal at supercritical conditions
in tests for which the feed to the reactor was dilute hu-
man waste (Killilea et al. [52]). However, significant
salt accumulation occurred in the hydrocyclone during
these tests. Apparently, the tendency for salts to stick
to the reactor walls in a supercritical environment
also causes these salts to adhere to the hydrocyclone
walls upon impact rather than sink to the bottom.
This eventually leads to plugging of the hydrocy-
clone. As a result, hydrocyclones are better suited for
non-salt solids removal in SCWO systems. Several
companies, such as HydroProcessing and GA, have
employed hydrocyclones in their SCWO processes
304 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
before or after effluent cooldown for removal of
suspended particles and grit to protect downstream
pressure letdown components from erosion.
Another variation of the density separation tech-
nique is to impart rotational spin to the process fluid
without the use of a specific unit operation such as a
cyclone to achieve the same effect of separating solids
from a fluid. An example of this approach is pro-
vided by Titmas [53]. This patent generally describes a
SCWO process using a deep well or hydraulic column
as the reactor, thereby taking advantage of the hydro-
static increase in pressure with depth as the means of
achieving supercritical conditions at the bottom (this
concept forms the basis of the SCWO process devel-
oped by Oxidyne). Feed streams are transported to
the bottom of the well (≈3400 m (11 000 ft) deep)
and effluent streams are withdrawn back to the top
through several concentric pipes. A spiral rib or baf-
fle in the furthest downstream section of the reaction
zone is used to impart spin to the process fluid, thereby
forcing solids and particulates toward the pipe wall.
This action segregates the fluid into a particle-rich and
particle-depleted flow, which eventually is separated
into two different annular sections of piping for sep-
arate downstream processing. No specific control is
described to avoid accumulation of sticky salts on the
walls of the pipe, however. This may be the reason
behind the stated need for the system to be flushed
occasionally with a nitric acid wash to remove ‘ag-
gressively adhesive precipitates’.
2.2.9. Extreme pressure operation
As has already been discussed, most salts exhibit
very low aqueous solubilities at typical SCWO op-
erating conditions (e.g., 550–650◦ C, 221–262 bar
(3200–3800 psi)). However, the solubility of many
salts increases again as pressure approaches very
high values. This is because density increases enough
to recover some hydrogen bonding and polar inter-
actions. At pressures on the order of 690–1379 bar
(10 000–20 000 psi), many salts are at least partially
soluble. Thus the salt precipitation problem may be
substantially avoided while maintaining supercritical
conditions if these very high pressures are utilized.
This approach has been used by Los Alamos Na-
tional Laboratory (see for example Foy et al. [54,55]),
most recently for treatment of hydrolyzed energetics
in a SCWO system installed at the Pantex Department
of Energy facility in Amarillo, TX (Stone & Webster
[56]; Shaw and Dahmen [57]). Caustic hydrolysis of
the energetics results in a high salt concentration in the
SCWO feed. The operating conditions are 1034 bar
(15 000 psi) and 450◦ C. The relatively low (but still
supercritical) temperature was chosen to further im-
prove salt solubility in the reactor. To ensure enough
residence time (i.e., several minutes) for organic de-
struction at this temperature, the vertical coil tubular
reactor is 152 m (500 ft) long (with an inner diameter
of 0.953 cm (0.375 in)). The Los Alamos group has
also operated a smaller SCWO system for treatment
of radioactive contaminated wastes at the less extreme
conditions of 462 bar (6700 psi) and 540◦ C.
Another practical example has been demonstrated
by the Forschungszentrum Karlsruhe in Germany with
their version of SCWO, which is usually referred to
by its German acronym, SUWOX. At operating con-
ditions of 500 bar (7250 psi) and 426◦ C for process-
ing a feed of leachate water from an industrial dump
site containing halogenated organics, 91% of the
salt load was determined to pass through the system
(Schmidt et al. [58]). To compensate for this low tem-
perature, a relatively long residence time of 8.5 min
was used, resulting in an organic destruction level of
greater than 99.2%. Most of the salt not recovered
(e.g., CaSO4 ) was insoluble under these conditions
and accumulated as a thin scale in the heating zone
of the reactor. This problem was addressed through
further manipulation of temperature and pressure in
the organic feed line to ‘pre-precipitate’ these salts
before reaching the reactor.
None of the above mentioned examples for extreme
pressure operation have indicated that the waste feed
or oxygen solubility was inhibited at the high pressures
utilized. In principle, however, conditions which lead
to higher salt solubility can also result in diminished
solubility of oxygen and organic compounds. Thus,
the operating pressure to be used when following this
approach must be carefully chosen in order to maintain
good oxidation while achieving a sufficient level of
salt solubility.
A particular problem with the use of these high
pressures to avoid salt precipitation is the require-
ment that the reactor withstand the combination of
extreme pressure and high temperature. As a result,
the main design concern shifts from salt management
to mechanical integrity. Several patents have been
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
issued for SCWO reactors designed specifically for
operation at ultra-high pressures to avoid salt precip-
itation. Many involve designs that isolate a hot, but
pressure-balanced, reaction chamber from an outer,
cooler containment shell. Thus, the reaction chamber
and pressure shell need to withstand only one extreme
(pressure or temperature) instead of two, which allows
a wider choice of acceptable materials for each one.
Such is the case in the SUWOX reactor, for which a
floating alumina liner (which contains the reaction) is
held within a steel pressure-containment housing, with
a flow of water filling the annular gap between the two
(Casal and Schmidt [59]). Other examples are the tur-
bulent flow cold wall reactor proposed by McBrayer
et al. [60] and the lined vessel proposed by Dassel et al.
[61]. Both utilize a pressurized inert fluid in the annu-
lar region between the outer wall of the reaction cham-
ber and the pressure shell, and both use a form of solid
insulation. The former patent specifies a porous solid
insulator in the annular region (e.g., beads or powder),
while the latter patent calls for a non-porous solid
insulator or shield (e.g., ceramic). The lined vessel of
Dassel et al. is reported to function at pressures of 690
bar (10 000 psi) and temperatures from 815 to 1100◦ C.
As an alternative to the pressure-balanced liner ap-
proach, one can use a single walled reaction chamber
if the walls are kept sufficiently cool. A high pressure
reactor design by Barber [62] has a tangential (with
respect to the reactor walls) feed injection system and
effluent is withdrawn from the center of the reactor.
This causes the flow within the reactor to rotate in a
vortex-like fashion. The resulting centrifugal force is
expected to protect the reactor walls because, with the
normally higher density of cooler fluids as compared
to warmer fluids, the outer regions of the circulating
mass will always be cooler than the inner regions. The
Barber design is reported to withstand pressures of 690
bar (10 000 psi) and temperatures from 700 to 850◦ C.
3. Recent commercial/full-scale applications
Several reviews have summarized the current gen-
eral state of SCWO technology, as well as pilot work
recently performed or in progress in support of a num-
ber of applications (Stone & Webster [56]; Schmieder
and Abeln [63]; Shaw and Dahmen [57]; Tester and
Cline [46]; National Research Council [64]; Kritzer
305
and Dinjus [65]). Our purpose here is to briefly sum-
marize the current or pending full-scale applications of
several of the companies attempting to commercialize
SCWO, highlighting the particular design or approach
employed for control of salt precipitation and deposi-
tion of solids. Table 5 contains a list of full-scale facil-
ities and licensees of the SCWO processes developed
by several companies, along with recent feed materi-
als that have been processed.
The original SCWO companies, MODAR, MODEC,
and Oxidyne are no longer active on their own. The
MODAR technology was acquired by GA in 1996.
However, a full-scale SCWO facility based on the
MODAR process (i.e., reverse flow, tank reactor)
was constructed by Organo Corp. of Japan in 1998
(Oe et al. [66]). Organo, which is a licensee of the
MODAR process, had previously built a 2 ton/day
pilot plant in 1995 which they had tested on a variety
of wastes. The 138 lb/h (63 kg/h) full-scale facility
was built for the Nittetsu Semiconductor factory for
destruction of semiconductor manufacturing wastes
(tetramethylammonium hydroxide, ammonia, and iso-
propanol) (Stone & Webster [56]). Despite using the
MODAR vessel design, the reactor does not operate
with a brine pool because this feed produces a mini-
mal amount of effluent salts. In addition to having a
license to the MODAR process, Organo is a licensee
of the MODEC process (i.e., horizontal reactor with
high velocity and brushing). Two other Japanese com-
panies, Hitachi Plant Engineering & Construction
Co. and NGK Insulators Ltd, and a Canadian firm,
NORAM Engineering and Constructors, Ltd, are also
MODEC licensees. For a few years up until 1996,
MODEC operated a 2000 l/day pilot plant in Ger-
many funded by several pharmaceutical companies
which was used to process pharmaceutical industry
waste, pulp and paper mill waste, and sewage sludge
(Modell et al. [32]; Svensson [67]). Hitachi and NGK
are interested in developing the MODEC process
further for sewage sludge treatment (Japan Chemical
Week [68]).
Both GA and Foster Wheeler have been very active
in recent years with several projects being conducted
for three branches of the US Armed Forces. As part of
a team with the Ralph M. Parsons Co., GA was con-
tracted by the US Army in 1999 to provide a full-scale
SCWO system design for destruction of hydrolyzed
VX nerve agent at the Newport Chemical Depot in In-
306 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312

Table 5
Commercially designed SCWO facilities currently in existence
Company Licensees Large-scale plants Applications

MODAR Organo Nittetsu Semiconductor, Japan Semiconductor manufacture wastes

(constructed by Organo)
MODEC Organo, Hitachi, None Pharmaceutical wastes, pulp and
NGK paper mill waste, sewage sludge
General Atomics Komatsu, Kurita US Army Newport Chemical Depot, Bulk VX nerve agent hydrolysate;
Water Industries Newport, IN (design completed) Other feeds processed in
smaller-scale systems: chemical
agent, explosives, and dunnage (US
Army), shipboard wastes (US Navy),
rocket propellant (US Air Force)
Foster-Wheeler US Army Pine Bluff Arsenal, Pine Smokes and dyes; Other feeds
Bluff, ARa processed in smaller-scale systems:
chemical agent and explosives (US
Army), shipboard wastes (US Navy)
EcoWaste Technologies Chematurb Huntsman Chemical, Austin, TX Oxygenated and nitrogen-containing
(EWT) hydrocarbons (e.g., alcohols,
glycols, amines)
Chematur Shinko Pantec Johnson Matthey, Brimsdown, UK Spent catalyst (recover platinum
(under construction) group metals and destroy organic
contaminants)

Japan (constructed by Shinko Municipal sludge

Pantec)
SRI International Mitsubishi Japan (under construction) PCBs, chlorinated wastes
Heavy
Industriesc
Hydro-Processing Harlingen Wastewater Treatment Mixed municipal and industrial
Plant No. 2, Harlingen, TX wastewater sludge
a Operated by Sandia National Laboratories.
b Chematur acquired rights to the EWT SCWO technology for Europe in 1995; acquired world-wide rights in 1999.
c Has license rights in Asia.

diana (Waste Treatment Technology News [69]). The
design calls for a hydrolysate feed rate of 2092 lb/h
(949 kg/h), and a platinum-lined reactor for corrosion
control with periodic flushing for scale control. GA
performed testing in support of the Newport design
on a 1/10 scale pilot system during 2000–2001. GA
has also demonstrated successful treatment of chemi-
cal agent (HD, GB, and VX) hydrolysate and energet-
ics hydrolysate/secondary wastes for the US Army’s
Assembled Chemical Weapons Assessment (ACWA)
program (US DOD ACWA [47]). SCWO is part of
GA’s Total Solution proposed to ACWA for demilita-
rization of the complete munition (projectiles, mortars,
rockets) and associated storage and processing materi-
als. The energetics hydrolysate/secondary waste feeds
consisted of a slurry of hydrolyzed energetics (tetry-
tol, Composition B, and/or M28 propellant) along with
shredded wood, plastics, and activated carbon. GA re-
cently completed further pilot testing for ACWA in
support of a full-scale design for demilitarization of
chemical weapons stored in Pueblo, CO, and Lexing-
ton, KY (US DOD ACWA [70]). This testing utilized a
titanium or Hastelloy-lined reactor for corrosion con-
trol, with scale control based on the additives concept
and periodic flushing with subcritical water.
GA also designed and tested a compact SCWO
system for the US Navy in 1999 for destruction of
shipboard wastes (Elliott et al. [37]). The system was
designed for processing 100 lb/h (45 kg/h) of waste
for 10 h/day, and was tested with several different
representative feed materials including lube oil, halo-
genated solvents, hydraulic fluid, antifreeze, paints,
photographic solution, and black and gray water. GA
utilized a titanium-lined reactor with a rotating scraper
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
for these tests. GA conducted hydrolysis and SCWO
testing of rocket motor propellant for the US Air Force
in 1995 using a 1 gpm (3.8 l/min) pilot-scale system
(Spritzer et al. [71]; Defense Daily [72]). The Japanese
companies Komatsu, Ltd, and Kurita Water Industries,
Ltd, have a licensing agreement with GA in commer-
cializing SCWO technology in Asia (General Atomics
[73]; Schmieder and Abeln [63]).
Foster Wheeler constructed a full-scale SCWO
system based on their transpiring wall reactor design
for the US Army’s Pine Bluff Arsenal in Arkansas in
1998 (New Technology Week [74]; Rice et al. [75];
Crooker et al. [76]). The system was designed to treat
obsolete smoke and dye munitions at a rate of 80 lbs/h
(36 kg/h) of munitions. It is being operated by San-
dia National Laboratories and has been undergoing
extensive systemization with surrogate feed materials
since construction completion. Foster Wheeler has
also conducted pilot-scale testing of a transpiring wall
SCWO system for the US Navy and Army ACWA
program similar to that described for GA. Testing for
the Navy was performed in 1999 with halogenated sol-
vents and photographic solution feeds at 80–209 lbs/h
(36–95 kg/h) (Crooker et al. [76,77]). The same sys-
tem was used for ACWA testing in 2000, in which
mixtures of agent (HD, GB, VX) and energetic (tetry-
tol, Composition B, M28 propellant) hydrolysates
were processed with minimal corrosion and salt
buildup in the reactor (US DOD ACWA [78]). Foster
Wheeler is part of a team whose proposed Total Solu-
tion 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 demili-
tarization of chemical weapons stored in Lexington,
KY.
Based on the extensive testing conducted for the
ACWA program and reviews by the National Research
Council [79,80], the US Deputy Secretary of De-
fense signed a memorandum on 11/20/02 identifying
‘neutralization’ (i.e., hydrolysis) followed by SCWO
as the preferred approach for the destruction of as-
sembled chemical weapons stored at the Blue Grass
Army Depot in Lexington, KY. Once the Record of
Decision (ROD) is signed, a Request for Proposals
307
(RFP) will be released to solicit bids (including
SCWO designs) from potential contractors.
EcoWaste Technologies (EWT) designed and built
the first operating commercial SCWO plant in the US.
The plant was constructed for the Huntsman Corp.
(formerly Texaco Chemical Co.) in Austin, TX, for de-
struction of non-halogenated organic wastes produced
on-site at their Austin Research Laboratories (Svens-
son [67]). The tubular reactor system began opera-
tion in 1994. The waste feed consisted primarily of a
blend of alcohols, glycols, and amines with an over-
all organic loading of 10 wt.%, and was fed at a rate
of 1100 kg/h (2425 lb/h) (McBrayer et al. [81]). Be-
cause the feed contains no heteroatoms, salt formation
is minimal and no specific technique has been cited
to control salt buildup. As of February 2003, the plant
was not in operation.
Chematur Engineering AB 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 (Gidner et al. [82]). SCWO
is marketed by Chematur under the trade name
Aqua Critox® . 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).
These wastes would not be expected to generate high
salt quantities. In past testing, however, Chematur
has utilized both periodic reactor flushing with nitric
acid and/or high velocities for removal/avoidance of
scale (Stenmark [33], Gidner and Stenmark [83]).
Recently, Chematur announced plans to construct its
first full-scale SCWO facility for Johnson Matthey
in the UK (Chematur [84]). The plant, which will
have a capacity of 3 m3 /h (13.2 gpm), will be used
to recover platinum group metals from spent cat-
alysts. Carbonaceous and organic contaminants on
the catalyst will be destroyed in the SCWO process,
while the metal will be recovered in its oxide form.
No details have been provided as to how the oxide
solids will be collected. This application appears to
be one of the first in which the precipitation and
recovery of a solid in a SCWO process is the main
focus of the process instead of being an undesirable
side effect. At the time of announcement, Chematur
expected to commission the new plant in mid-2002.
Chematur also has plans to build a larger SCWO
308 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
plant for processing electronic scrap (Schmieder and
Abeln [63]), and is pursuing opportunities for con-
struction of additional commercial SCWO plants in
Europe. Chematur has licensed the EWT SCWO pro-
cess to the Shinko Pantec Co. of Japan. Under this
license agreement, Shinko Pantec has constructed
an 1100 kg/h (2425 lb/h) SCWO plant for treating
municipal sludge, which was commissioned in 2000.
SRI International granted its first licensing agree-
ment of the AHO process (i.e., carbonate-filled
reactor for catalytic oxidation and salt product adsorp-
tion) to Mitsubishi Heavy Industries (MHI) in 1999
(Waste Treatment Technology News [85]). 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, demonstrat-
ing greater than 99.9999% destruction at 380◦ C and
270 atm. MHI also owns a patent on the AHO pro-
cess as applied to PCB decomposition (Tateishi et. al.
[86]). MHI is currently designing the first full-scale
commercial AHO system in Japan for PCB destruc-
tion, with plans to build several more plants for both
government and private clients. The first plant is ex-
pected to be operational before 2005 (Jayaweera [87]).
HydroProcessing, LLC, has focused on the appli-
cation of SCWO for treating municipal wastewater
sludge (Griffith [88]). Their patented process (Griffith
et al. [89]), referred to as the HydroSolids® 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
recently built a full-scale system for the Harlingen
Wastewater Treatment Plant in Harlingen, TX (Grif-
fith and Raymond [90]). The system consists of two
HydroSolids® trains, each with a capacity of 12.5 gpm
(47 l/min) of thickened sludge feed. The system is
intended to process both municipal wastewater sludge
and industrial wastewater sludge from an adjacent fac-
tory. Operation of the first train began in April, 2001.
At last report, the HydroProcessing plant was still in a
startup mode (Wofford and Griffith [91]). HydroPro-
cessing states that operating costs are about $180/dry
ton (not including any projected benefits from energy
or CO2 recovery), compared to a cost of $275/ton
for sludge disposal by landfill or land application
(Parkinson [92]). 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. Regarding salt handling, HydroProcessing
has recently been issued a patent (Wofford et al.
[49]) which describes specific control of operating
conditions and feed injection points to keep precip-
itating salts away from the walls until reaching the
hydrocyclone.
There are other companies trying to commer-
cialize SCWO technology, as well. For example,
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
[93]). No pre-neutralization of the feed (which con-
tained halogenated solvents) was performed, resulting
in acidic effluent but minimal salt formation. Noram
Engineering and Constructors, Ltd, has recently been
issued a patent (Boyd et al. [94]) on a process for
utilizing SCWO for oxidation of redwater (a waste
from the manufacture of nitroaromatic explosive com-
pounds). Daimler Chrysler of Germany has also been
interested in the application of SCWO for the treat-
ment 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
[63]). Their design uses high fluid velocities to keep
solid particles suspended in flow under the conditions
of operation (Pilz [95]).
4. Summary
SCWO is a maturing waste treatment technology
which has been hindered in its development by salt
precipitation, solids deposition, and plugging prob-
lems. Nonetheless, a number of creative and effective
engineering solutions have been implemented to ad-
dress the challenges of solids management. These
include a variety of commercially developed reactor
designs and operating techniques to eliminate deposi-
tion or minimize its effects or impacts. Presently, no
one design or method has proven itself to be clearly
 P.A. Marrone et al. / J. of Supercritical Fluids 29 (2004) 289–312
superior to the others, although some are better suited
for certain types of wastes than others. For example,
the reactor flushing and quenching technique works
better on feeds with high concentrations of salts that
have a high solubility in subcritical water. Tubular
reactors operated at high velocities are being used by
several companies for treating sewage sludges, which
have a relatively high proportion of non-salt solids.
Also, some approaches (e.g., additives, extreme pres-
sure operation) require more detailed information
regarding the composition of the feed and/or salts
that will form than other approaches in order to be
effective. Continued fundamental research on salt
precipitation and deposition dynamics and on phase
behavior of multi-component systems is important for
further advancement of effective approaches for salt
management in some potential applications. Selection
of chemical additives and determination of optimal
concentrations to maintain adequate salt transport in
a reactor, for example, require further research to
establish comprehensive phase diagrams for many
different salt species and mixtures commonly encoun-
tered. Results of recent on-going pilot-scale testing
with aggressive feeds, and the current or anticipated
operation of several new full-scale SCWO facilities
by a number of companies, will also provide neces-
sary data for further development and refinement of
salt precipitation control methods.
Acknowledgements
The authors would like to thank Dr. Glenn Hong
and Dr. Michael Modell for providing historical infor-
mation and valuable insights on various aspects of salt
precipitation and scale control in SCWO. We would
also like to thank Dr. Robert Shaw of the US Army
Research Office and Dr. Azar Nazeri of the Office of
Naval Research for their support of SCWO technol-
ogy. Finally, we thank all of our SCWO colleagues for
sharing data, experiences, and results.
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