J.

of Supercritical Fluids 51 (2009) 83–103

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Review

Corrosion control methods in supercritical water oxidation and

gasification processes夽
Philip A. Marrone a,∗ , Glenn T. Hong b,1
a
Science Applications International Corporation (SAIC) – FOCIS Division, 60 Wells Avenue, Suite 103, Newton, MA 02459, United States
b
General Atomics, 3550 General Atomics Court, San Diego, CA 92121, United States

a r t i c l e i n f o a b s t r a c t

Article history: Use of supercritical water (SCW) as a medium for oxidation reactions, conversion of organic materials
Received 19 June 2009 to gaseous or liquid products, and for organic and inorganic synthesis processes, has been the subject
Received in revised form 5 August 2009 of extensive research, development, and some commercial activity for over 25 years. A key aspect of
Accepted 5 August 2009
the technology concerns the identification of materials, component designs, and operating techniques
suitable for handling the moderately high temperatures and pressures and aggressive environments
Keywords:
present in many SCW processes. Depending upon the particular application, or upon the particular loca-
Supercritical water
tion within a single process, the SCW process environment may be oxidizing, reducing, acidic, basic,
Supercritical water oxidation (SCWO)
Hydrothermal oxidation
nonionic, or highly ionic. Thus, it is difficult to find any one material or design that can withstand the
Corrosion effects of all feed types under all conditions. Nevertheless, several approaches have been developed to
Supercritical water gasification (SCWG) allow successful continuous processing with sufficient corrosion resistance for an acceptable period of
Hydrothermal gasification time. The present paper reviews the experience to date for methods of corrosion control in the two most
Supercritical water partial oxidation prevalent SCW processing applications: supercritical water oxidation (SCWO) and supercritical water
gasification (SCWG).
© 2009 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
2. Corrosion phenomena in SCW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3. Supercritical water oxidation (SCWO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.1. Process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.2. Key location areas for corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.3. Common types of corrosion encountered . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.4. Corrosion control approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.4.1. Use of high corrosion resistance materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.4.2. Liners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.4.3. Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.4.4. Transpiring wall/film-cooled wall reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.4.5. Adsorption/reaction on fluidized solid phase (Assisted Hydrothermal Oxidation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.4.6. Vortex/circulating flow reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.4.7. Pre-neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.4.8. Cold (ambient temperature) feed injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.4.9. Feed dilution with non-corrosive wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.4.10. Effluent dilution/cooling (quench water addition) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.4.11. Optimization of process operating conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

夽 Reproduced with permission from NACE International, Houston, TX. All rights reserved. Paper 08422 presented at CORROSION 2008 New Orleans,
LA. ©NACE International 2008.
∗ Corresponding author. Tel.: +1 617 618 4686; fax: +1 617 618 4697.
E-mail addresses: marronep@saic.com (P.A. Marrone), glennhong@aol.com (G.T. Hong).
1
Tel.: +1 858 455 4347; fax: +1 858 455 4470.

0896-8446/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2009.08.001
84 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103

3.4.12. Avoidance of corrosive feeds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95

3.4.13. Pretreatment to remove corrosive species . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4. Supercritical water gasification (SCWG) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.1. SCWG background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.2. SCWG process description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.3. Key location areas for corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.4. Common types of corrosion encountered or anticipated . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.5. Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.6. Corrosion protection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

1. Introduction Depending on the particular feeds and materials of construction

involved, corrosion rates in SCW processes such as SCWO can be
Supercritical water (SCW), or water that is above its thermo- as high as several mils/h (tens of ␮m/h) [6]. If not controlled, both
dynamic critical point (374 ◦ C, 22.1 MPa), is a unique medium that salt precipitation and corrosion phenomena associated with SCW
has been studied and utilized over the years for a variety of diverse can lead to rapid shutdown and/or failure of expensive process
applications. As with all supercritical fluids, SCW exists as a single, equipment. Because of the obvious impact of both problems on
noncondensable phase and has physical property values interme- commercial SCW applications, a number of methods have been
diate between that of its liquid and gaseous phases, with density developed over the years to manage salt and corrosion issues with-
typically being closer to that of a liquid and transport properties out impeding successful continuous system operation. Methods
being closer to that of a gas. However, water is different from other that have been developed to control salt precipitation and plugging
fluids in that it undergoes a dramatic change in its solvent nature in SCW systems have already been reviewed elsewhere [7,8]. In a
as it is heated from sub- to supercritical conditions. Due primarily similar manner, the purpose of the current paper is to review and
to a loss of hydrogen bonding that occurs with decreasing den- summarize the various approaches to handling corrosion that have
sity [1], SCW behaves more like a nonpolar solvent than the polar been developed, patented, and/or utilized in SCW processes, par-
substance familiar under ambient conditions. In addition to den- ticularly in SCWO and in supercritical water gasification (SCWG).
sity, two other key parameters that are indicators of the change in
water’s behavior from sub- to supercritical conditions are its dielec- 2. Corrosion phenomena in SCW
tric constant and ion product or dissociation constant. At 25 MPa,
the dielectric constant of water drops monotonically from a value Although much of the understanding of corrosion in SCW envi-
of 80 at ambient temperature down to about 10 at the critical tem- ronments comes from the context of SCWO, there are several
perature (similar in value to octanol at ambient conditions), and general observations that are relevant to all applications involving
then down to about 2 at 425 ◦ C (similar in value to cyclohexane SCW. This is because a good deal of the behavior associated with
at ambient conditions). From a value of 10−14 (mol/kg)2 at ambient corrosion is heavily influenced by the solvent characteristics of the
temperature and 25 MPa, the ion product of water initially rises to a water itself.
maximum of 10−11 (mol/kg)2 between 200 and 300 ◦ C before drop- All forms of electrochemical corrosion require the presence of
ping to less than 10−23 (mol/kg)2 above 550 ◦ C. As a result, most aggressive ionic species (as reactants, products, or both) to pro-
ionic substances such as inorganic salts that are soluble in ambi- ceed. This in turn requires the existence of an aqueous environment
ent water are insoluble or nearly so at typical conditions of interest capable of stabilizing these ionic species. Based on thermal effects
for applications involving SCW. Conversely, most nonpolar organic alone, the speed (and thus severity) of corrosion reactions would
compounds that are immiscible in ambient water such as alkanes be expected to increase with increasing temperature. The fact that
and aromatics are fully soluble in SCW. water at typical SCW operating conditions loses the ability to sol-
SCW in essentially pure form is used commercially as the work- vate charged (polar) species, however, leads to the counterintuitive
ing heat transfer fluid in conventional and nuclear power plants observation that corrosion is typically more severe in subcritical
because of its high thermal efficiency (due to its combined high water than supercritical water. In fact, there is often a maximum
temperature and pressure and its existence as a single phase) and point of corrosion exhibited in the region just below the critical
allowance for a simpler system design (due to elimination of equip- point — where temperature is high enough to promote fast kinet-
ment for handling multiple phases) [2,3]. In contrast, the focus of ics and concentrations of corrosion-causing species such as halide
the present paper is on chemical processing systems where SCW is ions (and their corresponding dissociation constants) are still suf-
present along with high levels of other substances. The combina- ficiently high for reaction to occur. From a practical perspective,
tion of good solubility of nonpolar organics and oxygen, inherently this means that components and/or piping used to preheat or cool-
high temperature, and dense single phase behavior of SCW has down fluids in a SCW system are more susceptible to corrosion than
led to the most common processing use of SCW as a medium for the reactor. A good example of this behavior is provided by Mitton
waste destruction. Supercritical water oxidation (SCWO) is the pri- et al. [9] in the analysis of several failed Alloy C-276 tubes. The tubes
mary example of this application. By exploiting the full range of were used to preheat a dilute, aqueous, salt-free solution of methy-
its solvent characteristics, SCW has more recently been studied lene chloride as the organic feed component for a lab-scale SCWO
and utilized as a medium for reforming/gasification and synthesis system. All tubes failed due to the formation of a through-wall inter-
reactions as well [4,5]. However, the high temperature and harsh granular crack at a point in the tubing where the fluid temperature
chemical environment inherent to many of these applications lead was calculated to be between 110–350 ◦ C and 24.6 MPa. Significant
to the two biggest problems that affect SCW processes: salt pre- intergranular corrosion and dealloying was also observed upstream
cipitation/accumulation and corrosion. Salt precipitation is a direct and downstream of the crack in a region where the fluid tem-
result of the poor solubility of most salts in SCW and can lead to perature was below 380 ◦ C. The corrosive agent was chloride ions
rapid plugging of the reactor or associated piping if not controlled. from HCl formed from hydrolysis of the methylene chloride in the
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103 85

heated tubing. The hydrolysis also caused hydrogen formation and the corrosive species present, and (2) for metals, the resistance of
hence reducing conditions. However, both ends of the preheater any oxide surface coating that may form (itself a product of a cor-
tube (one at ambient temperature and the other at a supercriti- rosion reaction via passivation) to further corrosive attack. A more
cal temperature between 450 and 600 ◦ C) showed no appreciable detailed discussion and review of corrosion mechanisms, factors
signs of corrosion. The lack of corrosion can be explained by too affecting corrosion, and material compatibility guidelines in SCW
slow a hydrolysis reaction at the ambient temperature end and too environments have been provided by Kritzer et al. [12,14].
low a dissociation constant for HCl at the supercritical end. Simi- Important though it is, however, a complete strategy for corro-
lar trends (but no cracking) were observed within the thicker-wall sion control in a SCW system is usually more than just choosing
cool-down heat exchanger of the SCWO system, where oxidizing a good material of construction. This is particularly true if the
conditions prevailed. “best” material is not good enough with respect to its corrosion
It is important to note that while potential for corrosion is rate to allow viable system operation. A complete corrosion con-
greatly reduced under supercritical conditions, there can still be trol strategy may also need to include active control or adjustment
significant corrosion that occurs in SCW depending on the particu- of operating conditions to favor low corrosion, minimization of
lar chemical environment. When salts are present or formed via exposure through innovative engineering design, periodic compo-
reaction, they will often stick to the walls of the vessel or tub- nent replacement, or combinations of some or all of these. More
ing where they first experience supercritical conditions. In this detailed descriptions of corrosion control strategies that have been
case, a layer of water or brine can be trapped between the solid developed for SCWO and supercritical water gasification (SCWG)
salt layer and the vessel or tubing wall, creating a microenvi- systems are discussed in the following sections.
ronment different in concentration and/or temperature than that
in the bulk fluid phase. In these cases, there may be consider- 3. Supercritical water oxidation (SCWO)
able corrosion of the vessel or tubing wall. In particular, corrosion
can occur under the salt layer if the salt is present as a molten 3.1. Process description
state. This has been seen, for example, in SCWO reactor tests with
The high solubility of most nonpolar organic compounds and
chemical agent hydrolysate feeds, where corrosion rates up to
oxygen in SCW, the inherently high temperature, and the relatively
2.5 mils/h (64 ␮m/h) were observed in a titanium-lined reactor ves-
dense, single phase environment all provide ideal conditions for
sel underneath a molten salt layer containing phosphate salts [6].
oxidation in SCW. In the typical SCWO process (Fig. 1), an organic
In addition, even though the SCW environment typically does not
feed (aqueous or pure), oxidant (e.g., oxygen, air, peroxide), water,
support the more traditional ionic-based corrosion mechanisms,
and auxiliary fuel (if necessary) are heated and pressurized up to a
there are other pathways by which corrosion can still occur. At
range of 550–650 ◦ C and 23–25 MPa. Under these conditions, the
high temperatures (>600 ◦ C), metal attack by undissociated gaseous
organic feed is rapidly oxidized to CO2 , and H2 O. Typically less
species through a direct contact, “noncoupled” mechanism can
than 1 min residence time is required for complete feed destruc-
occur, which proceeds at a single site without ionic current flow
tion. Despite the similarity in many ways to a combustion reaction,
[10]. Additionally, the high solubility of gases in SCW can result
the relatively lower temperature and higher density of SCWO com-
in highly corrosive environments by creating strongly oxidizing
pared to air incineration results in a cleaner reaction without the
(SCWO) or reducing (SCWG) conditions.
formation of undesirable byproducts such as CO, dioxins, NOx , and
A more accurate way of predicting the likelihood of corro-
SO2 . Nitrogen, if present, is oxidized mainly to N2 or N2 O. Other het-
sion is not simply noting whether the conditions are subcritical
eroatoms, such as halogens, sulfur, and phosphorus, are converted
or supercritical but rather by monitoring density. At supercritical
to their corresponding mineral acids (e.g., HCl, H2 SO4 , H3 PO4 ).
temperatures, most salts will remain soluble in dense ionic solution
These acids are a potential source of corrosion if not neutralized,
at sufficiently high pressures. For example, at a typical SCW oper-
particularly downstream of the reactor where conditions become
ating pressure of 25 MPa, sodium chloride forms dense brines at
subcritical.
temperatures up to 450 ◦ C, while sodium chloride–sodium sulfate
The most common application of SCWO is for the destruction of
mixtures form melts with low water content at temperatures above
hazardous organic wastes, particularly those that are dilute aque-
about 520 ◦ C. Above 40 MPa, solid sodium chloride will not precip-
ous solutions (i.e., 1–20 wt% organic). There has been considerable
itate out of an aqueous solution at any temperature. Regardless of
effort over the past three decades at both the research and commer-
the specific temperature and pressure, density values that are closer
cial levels in understanding and developing a viable SCWO process,
to that of liquid water (i.e., >0.2 g/ml) are more likely to promote an
particularly with respect to corrosion and salt precipitation con-
environment where charged species can exist and thus corrosion
trol. Currently there are several full-scale commercial SCWO plants
can occur. Conversely, density values that are low and closer to that
in operation around the world operating with a variety of feeds
of steam (i.e., <0.2 g/ml) are much less conducive to corrosion.
[15]. More detailed information about the SCWO process and tech-
In summary, while there are always exceptions, the worst corro-
nology are provided in several earlier review articles [15–21]. A
sion in a SCW system can be expected to occur in high density, high
more recent review by Brunner [22] discusses the current status of
temperature, and high aggressive ion concentration (e.g., acidic)
SCWO based on data published over the years in this journal. Sev-
environments. Although there has been much research over the
eral commercial firms, including General Atomics (GA), Chematur
years in search of a material that can withstand all three conditions,
AB,2 Organo, SRI International, Mitsubishi Heavy Industries, and
the collective results indicate that such a material is not likely to be
Hanwha Chemical have designed, built, and offer full-scale SCWO
found [11–13]. It is therefore necessary for one to understand the
facilities around the world.
physical operating conditions and chemical environment (includ-
ing feed stream composition) to which materials will be exposed in 3.2. Key location areas for corrosion
an application in order to choose the most appropriate material for
each set of conditions. This often means using different materials The heart of the SCWO process is the reactor, where organic
in different sections of the system (e.g., preheating section, reac- wastes are mineralized. Supercritical conditions (with respect to
tor, and heat exchanger) depending on the specific combination of
conditions and composition in any one zone. What determines the
corrosion resistance of a material to a particular environment is 2
The SCWO business unit of Chematur AB was acquired in 2007 by Super Critical
mainly (1) the degree of inherent resistance to chemical attack by Fluids International.
86 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
Fig. 1. Typical SCWO process flow diagram with approximate temperature and pressure values.
both temperature and pressure) are always achieved in this part
of the system during normal operation. Depending on the specific
design for feed introduction and effluent cool-down, parts of the
reactor near the beginning and end may be cooler or even subcrit-
ical, leading to a more complex design with respect to materials of
construction. As discussed earlier, electrochemical corrosion is of
less concern in this part of the system due to the limited dissocia-
tion in the SCW environment of ionic species that are responsible
for corrosion. Nevertheless, corrosion can occur in the reactor in
the presence of salts and oxygen (particularly under deposits of
precipitated salts), high densities, and high oxygen concentrations.
The unexpected formation of regions or pockets of fluid at sub-
critical temperatures such as in isolated lines or areas of stagnant
fluid flow may also lead to unexpected corrosion in the reactor [23].
Other forms of material degradation that are not electrochemical
in nature such as hydride formation/hydrogen embrittlement and
erosion can also occur in the SCWO reactor. Because the reactor is
often the most expensive piece of equipment and must withstand
both high temperature and pressure, some form of corrosion con-
trol is prudent if not essential, unless it is certain that the system
will process feeds containing only carbon, hydrogen, oxygen, and
nitrogen (CHON), with the exception of nitric acid.
The most vulnerable sections of the SCWO system are the hot
but subcritical regions, such as found in the heat-up and cool-down
sections. Upstream of the reactor, any tubing used to preheat the
feed is susceptible, especially if the feed has a low pH and/or can
begin to decompose into corrosive species upon heating (e.g., halo-
genated hydrocarbons). Many SCWO designs avoid preheating of
the feed in favor of cold feed injection (see Section 3.4.8) to elimi-
nate this concern. At some point, however, the feed must come up
to temperature before or upon entering the reactor, and this is a
location where corrosion can occur. Typically this would be near
the end of a feed nozzle or feed entrance ports to the top of the
reactor, depending on the specific design. The area of feed intro-
duction at the top or entrance to the reactor is often a complex
and turbulent zone subject to erosive as well as corrosive action,
particularly along protruding surfaces within the reactor such as
thermocouples. Crevices or restricted spaces formed from overlap
of components near the top or bottom of the reactor can also be
subject to excessive corrosion.
At the other end of the system, the heat exchanger is another
component (and unlike the preheater, unavoidable) highly suscep-
tible to corrosion as the hot effluent is brought down to ambient
temperature. Severe corrosion can often occur within the first few
feet of heat exchanger tubing, although the real correlating fac-
tor is wherever the effluent temperature is most often within the
150–350 ◦ C range. One approach to minimizing heat exchanger
corrosion is to invert the usual order of components so that the
pressure is reduced prior to rather than after the heat exchanger.
However, this approach can result in severe erosion of the pressure
let down valve and fouling of surfaces as any salts fall out of the
resulting steam after pressure let down. In some SCWO designs,
cooling (or quench) water is added at the exit of the reactor to
aid in re-dissolution of salts before entering the smaller diameter
heat exchanger. Addition of this quench water can create a sub-
critical temperature zone at the reactor exit that is particularly
susceptible to corrosion. Because of the considerable change in con-
ditions, materials or approaches used for corrosion control further
upstream in the supercritical region of the reactor often will not be
acceptable in the quench zone.
Components that typically are kept at ambient temperature and
pressure are not usually of concern with respect to corrosion and no
special materials of construction are required. There can be excep-
tions, however, depending on the unique nature of the feed or
effluent produced.
3.3. Common types of corrosion encountered
The most common materials of construction for SCWO systems
are nickel-based alloys and austenitic stainless steels. Stainless
steel alloys are acceptable only for relatively benign feeds (i.e., con-
taining no heteroatoms) or in cooler sections of the process. For
higher temperature sections of the process, nickel-based alloys are
most often used due to their combination of reasonably good cor-
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
rosion resistance and high temperature strength under the widest
range of conditions. Materials such as titanium are more special-
ized; having much better corrosion resistance than nickel alloys
under some conditions (e.g., for chlorinated feeds) but not under
other conditions (e.g., in the presence of phosphates). Titanium
does not have good high temperature strength, so its use in hotter
sections of the process is generally restricted to liners or pressure-
balanced components.
Metals such as nickel-based alloys that have good corrosion
resistance under SCWO conditions are such usually because they
form a strong impermeable oxide surface coating when they
corrode (i.e., passivate), protecting the underlying material from
any further degradation. However, the high oxygen concentra-
tion typical for SCWO systems creates a very high electrochemical
(oxidative) potential, favoring corrosion via metal oxidation. A
common problem for SCWO systems is that the trivalent chromium
species responsible for the usual passivating layer in nickel-based
alloys and stainless steels is converted to soluble hexavalent
chromium species by the high electrochemical potential, resulting
in a phenomenon known as transpassive dissolution. Aside from
transpassive dissolution, anything that interferes with or breaches
the passivating oxide layer, such as the presence of chloride, will
result in material loss or corrosion. In addition, those substances
that form a more porous oxide (such as iron rust) or worse, have
their oxide converted to soluble species, also result in continuous
loss of material and corrosion that can ultimately lead to compo-
nent failure.
Most of the major types of corrosion have been seen in SCWO
systems under certain process conditions either in test coupon
studies or in actual process equipment. As stated earlier, corrosion
usually is much worse in the hot but subcritical heat-up and cool-
down zones of SCWO systems, but is not always insignificant under
supercritical conditions depending on the environment. More spe-
cific information on the common types of corrosion associated with
SCWO is as follows:
• General corrosion – characterized by a relatively uniform, pre-
dictable rate of surface material degradation. General corrosion
in SCWO systems is typically a result of the inability of any of
the alloy constituents to form or maintain a passivated layer.
All of the typical materials of construction for SCWO systems
can undergo general corrosion under the right conditions. While
predictable, the rates can be high enough such that the mate-
rial cannot be considered viable for economic operation with the
chosen feeds. Examples include stainless steels and nickel-based
alloys at transpassive conditions, and titanium at high phosphate
concentrations.
• Dealloying – can occur, for example, when a particular alloy com-
ponent is selectively oxidized and dissolved under the particular
operating conditions. For example, Alloy C-276 is prone to deal-
loying of either its chromium or nickel content under SCWO
conditions depending on the pH [23,24].
• Pitting – this localized and aggressive form of corrosion has
been observed in a number of stainless steel and nickel-based
alloys (e.g., 600, 625, C-276) in the presence of chloride [25–27]
and sulfate [28] under subcritical conditions, and even under
supercritical conditions in some cases with chloride exposure.
Nickel-based alloys are generally better than stainless steels with
respect to this type of corrosion, but even they are not always
immune. It is interesting to note that titanium does not exhibit
pitting under similar conditions with these same species [25], but
will in the presence of phosphate or fluoride [29].
• Stress corrosion cracking (SCC) – requires the presence of a
mechanical stress component in addition to the usual aggressive
chemical species component. Internal pressure stress is inherent
in a SCWO system, but stresses also arise from a variety of other
87
circumstances such as bend points in tubing or piping, through
welding, from weight loads and from thermal expansion. SCC has
been seen with some nickel-based alloys (625, C-276) in the pres-
ence of high chloride concentrations under subcritical but not
supercritical conditions [25], and with some ferritic/martensitic
stainless steels (e.g., HT-9) under supercritical conditions [2]. In
general, nickel-based alloys are more resistant to SCC than stain-
less steels [30]. Once again, no SCC was seen in titanium under
similar conditions, either sub- or supercritical. SCC is of particular
concern because it has the potential to cause catastrophic failure
in a relatively short period of time.
• Intergranular corrosion – occurs by definition along metal grain
boundaries. It has been observed in Alloy 625 under subcritical
conditions [26,28,31], in a batch subcritical/supercritical process
with both Alloy 625 and Alloy 617 [32], and with 316L stainless
steel [33] and some ferritic/martensitic stainless steels (e.g., HT-
9 [2]) under supercritical conditions. Intergranular corrosion has
been observed to occur in the presence of chloride, sulfate, and/or
nitrate.
• Hydriding – associated mainly with titanium. While titanium has
shown very good resistance to other localized forms of corro-
sion in the presence of chlorides, it undergoes a combination
of corrosion and hydrogen embrittlement in the presence of
phosphate salts [6]. It is postulated that the phosphate reacts
with the normally protective titanium dioxide surface layer [34],
exposing bare titanium metal that in turn reacts with water to
reform the oxide, with some of the resulting hydrogen pene-
trating into the titanium to form a hydride. The result is not
only a net loss of titanium but also a swelling of the remaining
metal from the added volume of hydrogen, further weaken-
ing the structural integrity of the metal. Hydriding has been
observed to occur under a layer of salt, where the isolated
microenvironment between the salt and metal may explain the
formation of hydrogen in the otherwise highly oxidizing and
supercritical conditions that prevail in the bulk fluid phase in the
reactor.
• Crevice corrosion – small crevices can experience concentration
differences from the bulk solution that result in corrosion. The
most common example is oxygen depletion within the crevice
causing a potential difference and hence electron flow from the
crevice area to the bulk metal surface. The net result is metal
dissolution in the crevice area. In addition, the solution within the
crevice may develop high concentrations of aggressive ions [35].
Crevice corrosion under SCWO conditions has been reported by
Gloyna and Li [36] for 316 stainless steel, Alloy C-276, and Monel
400.
• Under-deposit corrosion – similar to and sometimes grouped with
crevice corrosion. The presence of precipitated salts on a metal
surface such as in a SCWO reactor can create a microenviron-
ment between the salt and metal where conditions are distinct
from that of the bulk fluid phase and more conducive to corrosion.
Thus, materials that normally exhibit good corrosion resistance
under SCWO conditions may be prone to both general and local-
ized forms of corrosion. This may be due to physical changes such
as lower temperatures or easier movement of charged species
beneath the insulating salt layer. Under-deposit corrosion has
been reported for Alloy 625 [37,38] and titanium [29,39]. Another
example is provided by titanium hydriding in the generally
highly oxidizing SCWO environment as mentioned above. Under
some conditions, deposits may protect against rather than cause
corrosion [40].
• Galvanic corrosion – occurs when dissimilar metals are electrically
coupled while exposed to an electrically conductive medium. Gal-
vanic corrosion has been reported by Wood and Baker [41] at
conditions relevant to SCWO preheating and cool-down oper-
ations. Galvanic corrosion could also occur within the SCWO
88 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103

Table 1
SCWO corrosion control approaches.

Category Approach Purpose Examples

Prevent corrosive species from
reaching a solid surface
Form a
corrosion-resistant
barrier
Manage/minimize
corrosion
Adjust process conditions to
avoid or minimize corrosion
Transpiring wall/film-cooled
wall reactor
Adsorption/reaction on
fluidized solid phase (assisted
hydrothermal oxidation)
Vortex/circulating flow reactor
(conceptual)
Use of high corrosion
resistance materials
(long-term applications)
Liners (corrosion-resistant
material)
Coatings
Liners (sacrificial material)
Use of adequate corrosion
resistance materials
(short-term applications)
Pre-neutralization
Cold (ambient temperature)
feed injection
Feed dilution with
non-corrosive wastes
Effluent dilution/cooling
(quench water addition)
Optimization of process
operating conditions
Avoidance of corrosive feeds
Pretreatment to remove
corrosive species
Use of thin film water barrier to protect reactor wall
surface
Corrosive species formed during reaction retained and
neutralized on solid particles
Use of rotating fluid motion to keep hot (less dense)
reacting fluid away from reactor wall
Choice of primary construction material with
acceptable strength and good overall corrosion
resistance, typically nickel-based alloys
Corrosion-resistant solid barrier installed to protect
underlying structural or more permanent component;
often used in pressure-balanced environment so only
needs to withstand temperature and process fluid
chemistry
Protective layer applied or formed on surface; usually
thin and intimately bonded to surface.
Inexpensive and disposable solid barrier that corrodes
at predictable and acceptable rate while protecting
underlying structural or more permanent component;
usually pressure-balanced
Choice of primary construction material with
acceptable strength and adequate corrosion resistance
for expected duration of use; may be able to use less
expensive materials such as stainless steel alloys
Typically involves addition of a base to the feed or
entrance of reactor to neutralize corrosive acidic
species as they form in the reactor. Alternatively, acid
may be added to alkaline feeds.
Introduction of waste feed to the reactor without
preheating; used to protect upstream feed lines
Mixing of highly corrosive waste feeds with less
corrosive waste feeds to reduce the overall
concentration of aggressive species without increasing
process time
Addition of cooling water and/or base solution at
reactor exit to reduce concentrations of aggressive
species and rapidly drop temperature below range
where corrosion is most severe; used to protect
downstream effluent and heat exchanger lines
Use of equilibrium and process-gathered data to adjust
feed composition and/or operating parameters to
region where corrosion is minimized
Constraint of system operation to non-aggressive feeds
(i.e., CHON compounds) with minimal or no salts
For certain feeds, corrosive constituents are amenable
to separation prior to the reactor
Foster Wheeler [6,47,82], FZK [84–86],
ETH [90,91,95,96], CEA [92,93],
University of Valladolid [87–89]
SRI International [101,105], Mitsubishi
Heavy Industries [108]
Barber [109]
Base case for corrosion control often
used in conjunction with other
methods; Kane [43] and Kritzer [12]
provide guidelines for material choice
Modar [39], General Atomics
[6,46,56,57], Chematur [63,64], Los
Alamos [49,58,59], FZK [38,66], CEA
[62]
Modar [39,77], General Atomics [74]
General Atomics [6,48]
Hayward et al. [42]; Kane [43] and
Kritzer [12] provide guidelines for
material choice
Modar [111,112], General Atomics
[115], Foster Wheeler [82]
Modar [114], General Atomics
[6,48,115], Foster Wheeler [6,47],
Chematur [63,64], Organo [116]
General Atomics [48]
Modar [39], General Atomics
[6,48,115], Foster Wheeler [6,47,82],
Chematur [63,64]
Advocated by Latanision and
co-workers [9,11,24]
MODEC [121], HydroProcessing [122],
EcoWaste Technologies [123,124],
General Atomics [4,125]
Modar [113]

reactor if dissimilar metals are in common contact with an ionic
melt or brine phase.
• Noncoupled corrosion – Kriksunov and Macdonald [10] discuss
this form of corrosion in which undissociated species may react
directly with metal substrates in low density SCWO environ-
ments, i.e., without an electrochemical coupling of different
surface sites. Examples of such corrosive species include undis-
sociated HCl, Cl2 , O2 and SO2 [14]. However, this mode of attack
appears to be relatively low at a typical SCWO reactor tempera-
ture of about 650 ◦ C.
3.4. Corrosion control approaches
Because of the combination of high temperature, highly oxidiz-
ing conditions, and the frequent presence of heteroatoms and the
associated low pH that often are part of typical SCWO waste feeds,
corrosion is a significant concern and risk for any SCWO system. In
fact, unless one is absolutely sure that the feed will be restricted to
only the elements CHON (with the exception of nitric acid), corro-
sion in some part of the system will be inevitable over time in the
absence of any mitigating actions. As a result, some means of cor-
rosion control is usually essential for operation of an economically
viable and versatile SCWO process.
Over the years, a number of strategies for corrosion control in
SCWO systems have been developed (Table 1). These approaches
can be arbitrarily divided into four categories according to their
primary objective:
• Prevent corrosive species from reaching a solid surface
• Form a corrosion-resistant barrier (allows corrosive species to
reach surface but no corrosion)
• Manage/minimize corrosion (allows corrosive species to reach
surface and corrosion to occur, but in a controlled, acceptable
manner)
• Adjust process conditions to avoid or minimize corrosion
Each of the corrosion control approaches is described and dis-
cussed in more detail below. The approaches presented cover a
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
wide variety of characteristics — some involve a specific reactor or
system component design while others deal primarily with mod-
ifying process operating conditions; some are purely physical in
nature while others are chemical; some have been developed by a
specific commercial firm and are an integral part of that company’s
SCWO process while others are non-process specific and utilized in
some form by many different SCWO vendors. It should be noted that
based on experience, there is no “right” approach that works better
than all the others or works in all cases. The particular approach
that is best for a given application depends mainly upon the nature
of the feed type. It is also possible to use more than one of these
approaches in a given SCWO process. Since salt precipitation and
corrosion issues are often present together, a complete approach to
SCWO operation can include one or more of the approaches for cor-
rosion control used in conjunction with methods for salt handling
discussed elsewhere [8].
3.4.1. Use of high corrosion resistance materials
Choosing a material of high corrosion resistance as the primary
structural material of construction in a SCWO system is the sim-
plest and most basic means of corrosion control. This approach
is used (explicitly or not) in all SCWO systems (commercial or
research) and at all scales (bench to full). In some cases, such as
with SCWO systems designed specifically for non-aggressive feeds,
this approach may be all that is necessary for adequate corrosion
control. In most cases, however, this approach is not sufficient by
itself to effectively control corrosion in all parts of the system and
is used in conjunction with one or more of the other approaches
described below.
Often more than one material is chosen for use in different parts
of the system in order to optimize material properties with process
conditions in a given zone. In general, nickel-based alloys (e.g., 600,
625, 718, C-276) are the most common base material of construc-
tion for SCWO system components, particularly those at elevated
temperature and pressure such as the reactor. These alloys are usu-
ally chosen because of their good overall strength and corrosion
resistance to a wide range of substances and conditions. However,
nickel-based alloys can exhibit unacceptable corrosion in certain
environments and thus are not always a viable choice. As a rule of
thumb, Alloy 625 is generally more corrosion resistant at super-
critical temperatures and Alloy C-276 is generally more corrosion
resistant at subcritical temperatures. As always, the best material is
dictated by the process environment that it must withstand. Even in
more complex reactor designs or when using other corrosion bar-
riers such as liners or coatings, nickel-based alloys are often used
as the base, pressure-bearing shell material.
In contrast to nickel-based alloys, stainless steel alloys are much
less expensive, easier to obtain, and easier to fabricate. As a result,
Table 2
Solid wall liner options.
Placement Material Reactivity
Fixed Metal Corrosion resistant
Fixed Ceramic Corrosion resistant
Fixed Metal Sacrificial
Fixed Ceramic Sacrificial
Removable Metal Corrosion resistant
Removable Ceramic Corrosion resistant
Removable Metal Sacrificial
Removable Ceramic Sacrificial
89
stainless steel can be a more economical choice for the primary
material of fabrication for SCWO components [42]. Because stain-
less steel alloys exhibit a wider and more variable range of corrosion
resistance than nickel-based alloys even in pure supercritical water
[33], they are riskier and more restricted in their use in SCWO sys-
tems. Nevertheless, stainless steel can be an adequate material in
certain cases, particularly if the feeds are not aggressive or if the
expected system lifetime is limited. It can also be used safely for
components that do not see high temperatures. Resistance of both
stainless steels and nickel-based alloys to stress-related corrosion
mechanisms (SCC and hydrogen embrittlement) can be improved
by annealing heat treatment for stress relief [35].
While other metals may have a better corrosion resistance than
nickel-based or stainless steel alloys, they typically have inade-
quate physical strength and/or are too expensive to be used for the
primary, pressure-bearing material of construction. This is the case
with materials such as gold or platinum. Some materials carry other
risks that limit their use in SCWO systems as the primary material of
construction. While titanium is not prohibitively expensive, its use
in large quantities such as for the reactor shell is not recommended
because of the risk of fire when in contact with high concentrations
of oxidant, particularly when pure oxygen is used as the oxidant.
Many of these materials, however, can be used effectively in much
smaller quantities as liners (see below). Kane [43] provides an over-
all survey of base materials for use in SCWO environments. Wellig
[44] provides a summary of many of the materials that had been
tested in SCWO environments through 2001.
3.4.2. Liners
Liners are an effective way to provide customized corrosion pro-
tection to a specific part of a SCWO system. Liners are designed to
protect the main structural material of a SCWO component when
the structural material does not have sufficient corrosion resis-
tance to the environment in question. Because the liner overlays the
structural material, it does not have to withstand system pressure
by itself and therefore does not usually require a large thickness.
The separation of the corrosion resistance and strength require-
ments from the same material is a significant advantage and opens
up the potential use of a greater number of materials with high
corrosion resistance but poor strength properties, high cost, and/or
other compatibility constraints.
Liners can be used in any part of the SCWO system, but are most
often used in the reactor. They are particularly well-suited to vessel
type reactors as opposed to pipe or tubular reactors because there
is a relatively small area to be protected by the relatively expen-
sive liner material or assembly. Another popular location for liners
is in the heat exchanger, particularly those of double pipe design.
Liners come in a variety of types, and can be classified according to
Notes
Most often used combination for fixed liner since it can be permanently
attached to pressure shell
Unlikely combination since it is difficult to bind ceramic to metal pressure shell
Not viable; sacrificial liner needs to be easily removable
Not viable; sacrificial liner needs to be easily removable
Represents case where infrequent liner replacement is expected; typical
materials are noble metals (thin layer on backing material) and nickel-based
alloys
Represents case where infrequent liner replacement is expected; typical
materials are alumina and partially stabilized grades of zirconia
Requires periodic liner replacement and economically acceptable corrosion
rates; material must be inexpensive and corrosion solids must not create a
transport problem (e.g., titanium)
Unlikely combination since ceramics failure modes (e.g., delamination,
disintegration) can be unpredictable
90 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
Fig. 2. Removable liner assembly housing (in foreground) and inner titanium pipe
liner (in background).
whether they are metal or ceramic, fixed or removable, corrosion
resistant or sacrificial, and solid or porous (Table 2). For the pur-
poses of this discussion, the remainder of this section is restricted
to solid wall liners. Porous liners are discussed under the section
pertaining to transpiring wall reactors (Section 3.4.4). Liners are
distinct from coatings (see Section 3.4.3) in that they are installed
as a solid form, while coatings are applied in liquid or gaseous form.
Fixed liners are those that are permanently installed and not
meant to be removed. They are often bonded or welded into
place, in close contact with the structural (i.e., pressure-bearing)
shell material. Because of the nature of this type of liner, the
only practical types of fixed liners consist of corrosion-resistant
metals. Modar, Inc. (the first commercial SCWO vendor) had suc-
cessfully utilized a tantalum-lined cool-down heat exchanger for
many years in the 1980s [45]. General Atomics (GA) has utilized
a fixed liner in their SCWO reactors [46] along with a remov-
able liner [47,48] for destruction of chemical agent and energetic
hydrolysates. Researchers at Los Alamos National Laboratory have
utilized a non-removable, titanium (grade 2) lined, stainless steel
tube reactor for destruction of chlorinated hydrocarbons [49].
Removable liners have more variety of form and material than
fixed liners. They typically are designed to be concentric with the
vessel or tubing to be protected, which creates an annular region of
some finite thickness between the liner and structural shell. A fluid
or other insulating material is often contained within the annular
region to pressure balance the liner. Thus the liner contains the
hot corrosive fluid but not pressure, while the chemically isolated,
cooler shell only needs to withstand the pressure and can therefore
be fabricated from a less expensive material. Such a design is often
referred to as a cold wall or dual shell reactor. There are several
examples of this type of design, such as that described by Fassben-
der [50], Hazlebeck [51], McBrayer et al. [52], and Joussot-Dubien
et al. [53]. Fig. 2 shows an example of a removable pipe liner and
its housing used in the pilot-scale treatment of chemical agent and
energetic hydrolysates.
Metal removable liners are manufactured with either a
corrosion-resistant or sacrificial material. Liners designed to be
corrosion resistant often are made of expensive noble or rare met-
als such as platinum, gold, niobium, or tantalum. Because they
do not have to withstand pressure, these liners can be of mini-
mal thickness (e.g., <3 mm thick). Very thin liners may need to be
mounted to a thicker backing of less expensive material to pro-
vide support during handling or rapid depressurization events (i.e.,
unplanned system shutdown). Platinum is an example of a mate-
rial that requires a support because its high cost restricts its use
as a liner to a very small thickness when designed for use in a
pilot- or full-scale reactor (i.e., several meters in length). Test-
ing has shown platinum to be highly corrosion resistant to most
SCWO environments except in the presence of hydrochloric and
sulfuric acids [25,54,55] and neutral chloride salts [56]. GA has
utilized a platinum removable liner for bench and pilot-scale reac-
tors in destruction of chemical agent (GB and VX) [57] and agent
hydrolysates. Researchers at Los Alamos National Laboratory have
utilized a gold lined SCWO reactor for destruction of explosive
materials, where it was found to have good corrosion resistance
except at low pH values and with chlorides [58,59]. Niobium [60]
and tantalum [61] exhibit the unusual behavior of good corrosion
resistance at subcritical but not supercritical conditions (attributed
to a change in oxide structure at higher temperatures), which make
them better liner materials for preheaters or heat exchangers rather
than reactors.
In contrast to corrosion-resistant metal liners, sacrificial liners
are designed to use inexpensive materials that can be periodically
accessed and replaced easily. No effort is made to avoid corrosion
of the sacrificial liner, although the corrosion rate has to be pre-
dictable and reasonable enough that the replacement frequency
is not so high as to make system operation uneconomical. Thus,
nickel-based alloys can function as good sacrificial liners. In this
case, the liner can be of the same material as the pressure shell,
with the benefit of it being easier to replace than the shell. One also
has to be careful that the products of liner corrosion are not of a size,
quantity, or toxicity that will create a solids transport or effluent
disposal problem. Titanium (grades 2 and 7) is another good choice
for use as a sacrificial liner because of its relatively low cost and
the fine and nontoxic nature of its oxide solid corrosion product. In
many cases, the designation of a liner as being corrosion resistant
or sacrificial depends on the environment to which it is exposed.
For example, titanium may be considered corrosion resistant when
exposed to chloride feeds but sacrificial when exposed to phos-
phate feeds. Researchers at the Commissariat a l’Energie Atomique
(CEA) in France have designed and utilized a SCWO system with a
removable titanium liner for nuclear contaminated organic wastes
[62]. The liner could be considered either corrosion resistant or sac-
rificial depending on the feeds with which it was tested (e.g., sulfur
or phosphorus-containing, respectively). GA has utilized metal sac-
rificial removable liners of both Alloy C-276 and titanium as its
main form of corrosion control in its SCWO reactor for use with
high-salt feeds [6,47]. Chematur AB has also described the use of
titanium removable liners (referred to as a mixing pipe) in its feed
injection and effluent cooling zones [63,64]. Although the mixing
pipe is described as being of a corrosion-resistant material, it is also
designed to be easy to replace in case of excessive corrosion.
While their brittle nature makes them unsuitable as structural
materials for SCWO reactors, ceramics have been utilized as lin-
ers because of their good inertness to many forms of chemical
attack and good thermal stability. Based on test results of a wide
variety of oxide and non-oxide ceramics in a SCWO environment
with HCl, alumina (Al2 O3 ) and partially stabilized zirconia (ZrO2 )
have been identified as good candidates for liners [65]. They are
also the most frequently used ceramic materials in SCWO systems.
Researchers at the Forschungszentrum Karlsruhe (FZK) in Germany
have developed and utilized a SCWO system (referred to as the
SUWOX process) that functions at very high pressure (to keep salts
dissolved) and uses a removable alumina liner for corrosion control
[38,66]. Lee et al. [67] also built a SUWOX system with an alu-
mina liner for use with halogenated feeds. In long-term tests with
2,4-dichlorophenol, there was no evidence of corrosion of the alu-
mina tube reported. Zirconia was used successfully as a filter media
for hot SCWO effluent from the Modar SCWO reactor without evi-
dence of corrosive attack [68]. The particular stabilizing element
(e.g., magnesia, yttria, calcia) used in zirconia-based ceramics can
have a significant impact on their stability in a SCWO environment
and should be chosen carefully to be compatible with the type of
feeds to be processed [69]. Zirconia stabilized with a small amount
of magnesia or both magnesia and yttria has shown the best sta-
bility in an oxidizing and chlorinated environment [65]. Silicon-
and boron-based ceramics suffered severe corrosion in the same
environment and do not appear to be viable for SCWO applications.
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
3.4.3. Coatings
Coatings perform the same function as liners in that they protect
a less corrosion resistant underlying structural material. However,
coatings are usually much thinner than liners (on the order of tens
to hundreds of microns) and are bonded intimately to the host sur-
face. These properties make coatings more versatile in where they
are utilized in a SCWO system. They can be applied to components
with small surfaces and/or difficult geometries (e.g., thermocou-
ples, valve stems, feed nozzle tip) in addition to larger surfaces such
as the reactor or liner interior.
Coatings can be made of metal or ceramic applied to a surface, or
can be generated from the base material itself by means of an oxide
coating formation. The latter is one of the simplest ways to form a
protective coating because it happens naturally when metals are
exposed to highly oxidizing conditions such as exist in the SCWO
environment. Nickel-based alloys in particular form strong oxide
coatings on their surface under these conditions through passiva-
tion (provided that pH is not too low), which in fact is what accounts
for their corrosion resistance.
Rather than allow exposed surfaces to passivate during oper-
ation, SCWO reactor or system components can be preoxidized
before use by heat treatment in air at high temperatures [70], or by
exposure to SCW containing an oxidant. For example, Frayret et al.
[71] suggest improving titanium corrosion resistance in SCWO by
using a preoxidation process. However, preoxidation can also result
in degraded performance if not performed carefully or under the
right conditions. Preoxidized nickel-based alloy samples (heated
up to 900 ◦ C for 800 h) showed mixed results with respect to cor-
rosion resistance when exposed within a SCWO reactor operating
with methylene chloride feed at 420 ◦ C [72].
For coating materials that are different from the base metal,
there are several means of application. Metal coatings can be
applied via such processes as chemical vapor deposition, ther-
mal spraying, and electroplating. An example of a metal that
has been proposed and tested as a coating is iridium. Testing
of iridium and iridium alloys with platinum and rhodium in a
SCWO reactor exposed to chloride and sulfate acids and salts
above 600 ◦ C showed excellent corrosion resistance [73]. Plat-
inum/iridium alloys have also been used successfully by GA as
thermocouple coatings (sheaths) in SCWO reactors processing
high-salt feeds [74]. The main drawback to use of these metals is
their high cost, although their good performance in harsh envi-
ronments may still justify judicious use as coatings under certain
conditions.
Ceramic coatings are typically applied via a form of thermal
spraying. To be effective, they must be free of surface defects and
must flex with the base material as it expands and contracts with
temperature. The greatest concern with ceramic coatings is for-
mation of fractures or delamination, as both can provide access
by corrosive species and/or oxygen to the base metal. The larger
volume of corrosion products that form can in turn cause further
breakdown of the ceramic material. To avoid cracking caused by
the differences in thermal conductivity between the ceramic and
base metal, a “bond coat” consisting of a metal–ceramic compos-
ite material may be added first as a primer. The ceramic is then
applied often in layers of varying composition to further avoid
degradation caused by thermal cycling. Ceramic materials that have
been proposed as coatings for SCWO reactors are zirconia [69], tita-
nia [75], and diamond [76]. Extensive testing was performed with
yttria stabilized zirconia, magnesia stabilized zirconia, and titania
coatings (and various mixtures of these) on Alloy 625 and tita-
nium (grades 2 and 12) base metals by Modar and Idaho National
Engineering Laboratory (INEL) [77]. Samples were exposed to sul-
fate and chloride environments (to simulate a mixture of machine
cutting fluid and radioactive mixed wastes) over a range of tem-
peratures from 300 to 650 ◦ C. Although none of the coatings were
91
able to adequately protect the Alloy 625 samples, the combination
of titania on titanium showed no degradation and good resistance
to the challenging environment. Modar subsequently fabricated
and tested a version of their reactor liner with a titania coating
with generally good results [39]. As far as the authors are aware,
however, there are no commercial SCWO systems currently oper-
ating with a coated surface as the primary means of corrosion
protection.
3.4.4. Transpiring wall/film-cooled wall reactors
The main concept behind these types of reactors is to pass a
continuous thin film of clean water over the reactor wall surface to
prevent both corrosive species and solid salt particles from reaching
the wall. This benefit is probably due to a combination of dilution
and physical transport through the momentum of the water flow.
The temperature of the water can be either subcritical or supercriti-
cal, but is usually less than that achieved in the center of the reactor
where oxidation takes place. The cooler water barrier generally
allows a hotter temperature to exist in the center of the reactor
than could be tolerated with a solid wall reactor, improving waste
destruction kinetics, though it can potentially trap incompletely
oxidized material near the wall.
In transpiring wall reactors (TWRs), the water flow is introduced
through a liner material that extends the length of the reactor
over the pressure shell. One of the earliest examples of a TWR
was that developed by Foster Wheeler Development Corporation in
collaboration with Aerojet General Corp. and Sandia National Lab-
oratory [78,79]. The cylindrical liner is formed from several thin
metal sheets or platelets that are bonded together. Each platelet is
etched in a specific pattern such that a three dimensional network
of channels is formed when the platelets are combined to form
the liner [80]. The channels are designed to meter clean water to
the inner surface of the liner in a specific distribution pattern. The
water exiting the inner surface forms the protective film as it flows
to the bottom of the vertically oriented reactor. After initial tests
with a bench-scale system (2.5 cm reactor ID) [81], a pilot-scale sys-
tem was fabricated (0.152 m reactor ID; 1.6 m in length) and tested
extensively with a challenging variety of Navy shipboard wastes
[82] and chemical agent and energetic hydrolysate mixtures [6,47].
The platelet material of construction was Alloy 600. Transpiration
water flow rates ranged from 381 to 417 kg/h for waste feed rates
ranging from 113 to 227 kg/h. Short-term tests (i.e., <100 h) showed
little or no evidence of corrosion despite an aggressive environ-
ment of chloride, sulfate, and phosphate. Although longer term
testing (∼500 h) revealed some evidence of corrosion, it was sig-
nificantly less than that experienced by a solid wall reactor tested
with similar feeds. Thus the transpiration water was able to either
avoid corrosion or at least substantially extend the lifetime of the
liner. Disadvantages to the platelet-type liner design are that it is
not easily removable and it exhibited problems with mechanical
integrity during testing. A full-scale version was constructed for
the U.S. Army at Pine Bluff Arsenal (AR), but neither this nor the
pilot-scale system is currently in operation.
A simpler and less expensive TWR design utilizes a porous liner
made of sintered metal or ceramic [83]. Heated transpiration water
is fed into the annulus between the liner and shell, and then enters
the reactor through the porous liner. Several systems have been
constructed with this type of design. TWR pilot-scale systems have
been built and operated at FZK in Germany (0.06 m ID × 0.95 m
length; 20 kg/h waste feed rate) [84–86], the University of Val-
ladolid (UVa) in Spain (0.074 m ID × 1.5 m length; up to 40 kg/h
waste feed rate) [87–89], the Swiss Federal Institute of Technology
(ETH) in Switzerland (0.022 m ID × 0.375 m length preceded by a
coaxial burner for hydrothermal flame generation; 10 kg/h waste
feed rate) [90,91], and CEA in France (0.015 m ID × 0.50 m length;
waste feed rate of 3 kg/h) [92,93]. Each has utilized a different mate-
92 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
rial of construction for its porous liner: stainless steel (FZK), Alloy
600 (UVa), Alloy 625 (ETH), and ␣-alumina (CEA). A similar TWR
system is designed and offered by Turbosystems Engineering [94],
which has collaborated with FZK on TWR technology. More spe-
cific details on each system are summarized elsewhere [88]. Most
of the emphasis in the reported testing performed to date in these
systems has focused on ensuring good organic destruction effi-
ciency. Although the presence of a cooler fluid flow near the reactor
wall creates a risk of incomplete or inconsistent waste destruction,
none of the studies performed in these systems has observed poor
destruction efficiency. Most of the studies to date have utilized rela-
tively benign feeds (e.g., alcohols, organic acids) but several studies
have been performed with up to 10% salt solutions. In all cases, some
salt accumulation was observed, but minimal or no evidence of cor-
rosion was observed in the area protected by transpiration water.
In particular for the FZK system, corrosion was found to be sup-
pressed or strongly reduced relative to comparable tests conducted
in a solid wall (pipe) reactor.
Another variation of the water barrier design is a solid wall
tubular reactor with water film cooling. In this version, the flow
of clean water that functions as the protective film is introduced
at the top of a solid wall reactor instead of through the liner wall
itself. The most notable example of this reactor is that developed
at ETH [95,96]. A subcritical “by-pass” water flow is injected
coaxially with the oxidant and organic feeds at the reactor top.
The by-pass water flow envelops the supercritical reaction zone in
the center of the reactor, keeping corrosive species and salts away
from the reactor wall surface. The ETH reactor design has typically
been operated with waste feed concentrations high enough to
support a hydrothermal flame. However, significant corrosion
has been observed at the center tube tip and inner surface of the
coaxial tubes after tests with this design, although these parts are
replaceable [97]. More recently, ETH researchers have focused on
the porous liner TWR design cited above.
The biggest risk with any TWR system is a loss of transpira-
tion water. While the use of transpiration water allows for the use
of less corrosion resistant and therefore less expensive materials,
interruption or blockage of this water flow leaves the liner and reac-
tor exposed to severe corrosive attack. Such a situation can be a
problem even if water is deprived from a small section of the liner.
3.4.5. Adsorption/reaction on fluidized solid phase (Assisted
Hydrothermal Oxidation)
In this approach, corrosive species formed during oxidation are
prevented from reaching the reactor wall by their adherence on
to solid particles within the reactor. Such is the basis for the pro-
cess developed by personnel at SRI International and referred to as
Assisted Hydrothermal Oxidation (AHO) [98–102]. The AHO pro-
cess, which is a variation of SCWO, utilizes a fluidized bed of solids
that functions as both a reactive and adsorptive surface. The solid
material is a basic salt, usually sodium carbonate, that is insoluble
at the relatively low temperatures (380–450 ◦ C) at which the pro-
cess operates. The process is most often associated with destruction
of chlorinated wastes. Testing has shown that oxidation of several
chlorinated and aromatic compounds is significantly accelerated in
the presence of sodium carbonate particles [103,104]. The effect of
the carbonate is probably due to a combination of its functioning
both as a catalyst and neutralizing agent [105].
In the process, organic feed and oxidant are fed to a reactor con-
taining a fluidized bed of sodium carbonate. The organic species
adsorbs to the particles, where it is oxidized, and any resulting acids
such as HCl are neutralized by the Na2 CO3 . Because the surface area
provided by the pre-determined carbonate loading is much greater
than that offered by the reactor wall, product salts such as NaCl are
more likely to adhere to the carbonate particles instead of the wall.
To minimize caking of the carbonate salt and maintain the neces-
sary high surface area, the use of subcritical pressures and agitation
has been suggested [102]. This immobilization of aggressive species
is the key to corrosion protection (as well as salt precipitation con-
trol) provided by this approach. As a result, less expensive materials
of construction can be used for the reactor pressure shell. Testing
results have verified the reduction in corrosion achieved by this
process [104,106].
Mitsubishi Heavy Industries (MHI), a licensee of the AHO pro-
cess, has patented a version of the AHO process for polychlorinated
biphenyls (PCBs) where the sodium carbonate is generated and
replaced in-situ during operation by addition of sodium hydroxide
[107]. MHI recently constructed the first full-scale AHO plant for a
Japanese government agency in Tokyo Bay, Japan for destruction of
PCBs [108]. The plant consists of three reactor systems each hav-
ing a capacity to process 1814 kg (2 tons) of PCB/day and 90,718 kg
(100 tons) water/day. It has a treatment requirement to achieve
<3 ppb PCB in the liquid effluent, representing a target of six 9s
(99.9999%) destruction efficiency. The plant began operation in late
2005.
3.4.6. Vortex/circulating flow reactor
Most of the specific reactor designs to mitigate corrosion that
involve separation of high temperature and process flow from the
pressure shell do so through the use of a physical barrier such as
a liner or coating. Another option that has been proposed is to use
the fluid motion itself to constrain the hottest environment away
from the shell. In one example of this design [109], a combined feed
is introduced into a cylindrical or toroidal shape reactor through a
single perforated tube near the reactor wall. The feed flow out of the
tube openings is directed tangentially (relative to the wall), caus-
ing the fluid to rotate or spiral toward the center of the reactor in
a vortex-like manner. The fluid exits the reactor through a simi-
larly perforated exit tube located in the reactor center. Oxidation
takes place as the fluid circulates between the entrance and exit
tubes, generating heat from the reaction. The hotter and therefore
less dense reacting fluid (and presumably the aggressive species
formed during reaction) is forced to the center of the reactor vessel
by centrifugal force, leaving cooler fluid in contact with the reactor
wall. As a result, the pressure shell can be designed for a lower tem-
perature and therefore with less expensive materials. This design
would not be viable for feeds containing salts, as these precipitating
solids would likely be forced to the reactor wall. Another proposed
design utilizes a circulating flow pattern in a batch reactor [110].
The efficacy of this design depends on how well the rotating fluid
motion can constrain corrosive species away from the reactor wall
and how cool the fluid is which is in contact with the wall. Recall
that a high subcritical temperature fluid can be worse from a corro-
sion perspective than a hotter supercritical temperature. Also, there
will still be some sections of the reactor, such as the center top and
bottom surfaces and the feed and exit tubes, that will require addi-
tional corrosion protection, since they will be in contact with the
reacting fluid. Thus this design limits but does not completely elim-
inate the areas that need corrosion protection. In addition, reliance
on specific fluid flow patterns as the primary means of corrosion
protection can be risky if the required flow pattern deviates for any
reason from what is expected or is not achieved. It may be difficult
or impossible for an operator to identify any flow deviations until
it is too late. To the authors’ knowledge, there has been no com-
mercially tested or available version of this type of SCWO reactor.
3.4.7. Pre-neutralization
The use of a base to pre-neutralize the feed stream is one of
the simplest and most popular approaches to corrosion control in
a SCWO system [111,112]. Unlike all of the previously described
options which involve a specific equipment-based approach for
corrosion control, base pre-neutralization represents a process-
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
based approach, where the control action occurs by modifying
some aspect of process operating conditions.
In this approach, a base such as sodium hydroxide is added to
the waste feed flow prior to entering or once within the SCWO
reactor. The waste feed is known to contain species that will gen-
erate acids during the oxidation reaction (e.g., materials containing
halogens, sulfur, or phosphorus). If added to the waste feed before
reaching the reactor, the addition is usually done in-line at some
point just before or at the feed nozzle. In this case, there may also
be a hydrolysis reaction in addition to neutralization that occurs
before reaching the reactor [113], which is useful if the waste is
being preheated and/or is prone to degradation. If added directly
to the reactor, the base solution is often injected through a sepa-
rate feed line and mixes with the waste feed soon after entering
the reactor. The amount of base to be added is pre-determined to
approximately balance the expected acid concentration based on
the feed composition. Too much base is undesirable because it will
combine with carbon dioxide to make a carbonate salt, which can
exacerbate corrosion or cause plugging.
Once acid-forming species are liberated from the organic feed
compound as it is oxidized within the reactor (e.g., Cl from C2 HCl3 ),
the resulting acids (HCl) are immediately neutralized by the base
(NaOH) to produce the corresponding salt (NaCl). The corrosive
ions are hence locked up in the salt in its non-dissociated form
because of the low solubility of salts in SCW. A potential prob-
lem to this approach is that it converts a corrosion issue into a
salts transport issue. Thus, one must be capable and ready to han-
dle the precipitating salts that will occur in the reactor due to
base pre-neutralization. If not, the amount and rate of salt forma-
tion and precipitation can lead to rapid plugging of the reactor.
Methods available to control salt accumulation and transport that
can be used in combination with this corrosion control approach
are summarized elsewhere [8]. Neutralization significantly reduces
but does not eliminate corrosion. There may still be corrosion that
occurs beneath the salt layer that forms, meaning that other meth-
ods of corrosion control may have to be utilized along with this
one.
3.4.8. Cold (ambient temperature) feed injection
This approach is applicable to protect only the process feed sec-
tion of a SCWO system. Many SCWO system designs, particularly
those consisting of pipe reactors, use continuous feed preheating
to ensure that that the waste feed enters the reactor at the desired
supercritical temperature and will react immediately when coming
in contact with oxidant in the reactor. While this may be beneficial
in terms of the system energy balance, corrosion problems can be
encountered when aggressive species such as halogens or sulfur are
present or liberated during the preheat, as previously exemplified
with methylene chloride preheating (see Section 2). The presence
of these species occurs in one of the most susceptible zones for
corrosion as feed passes through the hot subcritical temperature
regime in the preheater. Also, many typical waste compounds of
large molecular weight pyrolyze or decompose when heated, which
leads to char formation and fouling in the preheater and feed lines
that can be difficult to remove. Thus, a significant incentive exists
to avoid preheating the feed.
There are two varieties of cold feed injection, one in which the
cold (i.e., unheated) feed is introduced into the reactor along with
a preheated stream and the other in which all of the feed streams
enter the reactor cold. In either case, cold feed injection eliminates
the need for preheating and consequently alleviates the concern for
corrosion in the feed lines and components in all but the portion in
immediate proximity to the reaction chamber. The key to successful
operation with cold feed injection, especially for the case where all
feed streams are unheated, is achieving sufficient mixing within
the reactor to utilize the heat of reaction to quickly bring incoming
93
feed up to the required temperature. By careful design of the feed
nozzle or feed injection ports, this can be done in minimal time and
without any loss of organic destruction efficiency.
Many commercial SCWO vendors utilize cold feed injection
because of the reduction in corrosion and consequent material cost
savings in a major section of the SCWO system. The downside to
this approach is that without an independent heat source for the
feed, the system becomes much more sensitive to mixing of all feed
components and this becomes more critical to achieving viable sys-
tem operation. Also, it may be necessary to use an auxiliary fuel
to maintain temperature in the reactor if the feed does not have
a high enough heat of combustion (i.e., heating value). However,
with proper consideration given to the method of feed injection,
implementation of cold feed injection has not proven to be diffi-
cult. Examples of companies that have utilized cold feed injection
as part of their SCWO process include Modar [114], GA [6,48,115],
Chematur [63,64], Organo [116], and Foster Wheeler [6,47].
3.4.9. Feed dilution with non-corrosive wastes
Because the extent of corrosion is dependent on the amount
of aggressive species present, reducing the concentration of these
species should slow the corrosion rate, ideally to an acceptable
value. While feed dilution with water is easily accomplished, it has
the significant drawback of increasing the total volume of waste
that must be treated and the time needed to do so, which may
not be economically viable. However, if there are multiple waste
streams of different composition available that must be processed,
it may be possible to “dilute” the more corrosive feeds with those
that are less corrosive (e.g., those containing only carbon, hydrogen,
and oxygen), provided that there are no mixing incompatibilities.
This combination of feeds effectively reduces the concentration of
corrosive species without increasing the total amount of feed to be
processed or the total process time. How successful this approach
is depends mainly on how many less corrosive feeds are available
to blend and how much less corrosive these feeds are relative to
the others. The greater the number and/or concentration of low
corrosion feeds, the greater the ability to reduce system corrosion.
Conversely, this approach is less effective or ineffective for feeds
that are all of comparable and high corrosivity.
The option of whether or not this corrosion control approach can
be used clearly depends on the particular application and cannot
be used in all cases. This approach may also require some creativ-
ity in how feeds are mixed to achieve the greatest impact while
avoiding feed delivery impairment. However, when applicable, this
approach can be a relatively simple way to achieve a dramatic
reduction in corrosion without any further cost. An example of
the effects achievable with feed dilution can be seen when com-
paring the results of processing highly corrosive chemical agent
hydrolysates alone compared to processing a mixture of chemi-
cal agent hydrolysate and non-corrosive energetic hydrolysate. The
chemical agent hydrolysates contained one or more of chlorine, sul-
fur, and phosphorus elements, while the energetic (explosive and
propellant) hydrolysates contained only carbon, hydrogen, oxygen,
and nitrogen. Testing was performed in a titanium-lined solid wall
reactor system by GA for the US Army in separate SCWO test pro-
grams. Use of the blended feed resulted in a reduction in corrosion
rate by as much as a factor of six when compared to that observed
when processing the corresponding chemical agent hydrolysate
alone [6,48].
3.4.10. Effluent dilution/cooling (quench water addition)
In contrast to the previous two approaches, this approach is
designed to minimize corrosion in the downstream effluent sec-
tion of a SCWO system. The addition of quench water is primarily
intended as a means of quickly redissolving salts at the end of the
reactor so as not to clog the reactor exit and the smaller diame-
94 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103

ter downstream piping. However, it also has a significant effect on

minimizing corrosion as well. Through dilution, the cooler quench
water drops the temperature of the reactor effluent quickly and
reduces the concentration of the now-soluble aggressive species.
From a corrosion perspective, this reduces the length of down-
stream piping and heat exchanger that are exposed to hot but
subcritical temperatures and are needed to return the effluent to
ambient temperature. Note that the benefit is to reduce the extent
of the corrosive region, not eliminate it, since there is always a finite
length necessary for cooling. Thus, this approach alone may not be
sufficient to eliminate downstream corrosion, particularly at the
end of the reactor. Another variation of this approach to achieve
more effective corrosion reduction with acidic reaction products is
to add a base such as sodium hydroxide to the quench water.
The more water that is added, the greater the temperature drop
achieved, and the shorter the zone most susceptible to corrosion. Fig. 3. Generic depiction of the stable region for a material on an E vs. pH (Pourbaix)
Just as with adding dilution water to the feed, however, the more plot.
water that is added, the greater the volume of effluent that must be Reprinted with permission from Kritzer [12], copyright (2004) Elsevier.
processed downstream. If the effluent cannot be discharged directly
to a local sewer line (e.g., if heavy metal concentrations exceed reg-
tion under supercritical conditions [117,118]. Analysis of process
ulatory limits), the higher effluent volume to dispose of can result
effluent for metal species can also yield information to help iden-
in a significant increase in cost. Increased costs can also result if
tify location on the Pourbaix diagram. Once the starting point is
the SCWO system is located in an area where water costs are high.
determined, the goal is to find a region on the Pourbaix diagram
While the effluent water can be recovered and reused in these cir-
where stable oxides of the major alloy component elements co-
cumstances, the water recovery equipment necessary to do this
exist. With this information, one can then adjust E and/or pH to get
(e.g., evaporator or reverse osmosis) has higher capital and operat-
to the region of maximum stability in the reactor (or system com-
ing costs. Nevertheless, when water constraints are not significant,
ponent in question) at the desired temperature. The most common
the use of quench water is a simple and effective option. Sev-
way to adjust pH is by addition of base to the feed or directly to
eral SCWO vendors have utilized quench water (with and without
the reactor or effluent. Potential can be increased or decreased by
base) as part of their corrosion and salt transport control strategy,
utilizing cathodic or anodic protection, respectively, or to a cer-
including Modar [39], GA [6,48,115], Chematur [63,64], and Foster
tain extent by adjusting oxidant concentrations. Additives such as
Wheeler [6,47,82].
corrosion inhibitors or nickel, chromium, or iron salts can change
the Pourbaix diagram and are another way to optimize conditions.
3.4.11. Optimization of process operating conditions
However, organic-based inhibitors are likely to be destroyed in the
Since aqueous corrosion is an electrochemical phenomenon, it
SCWO reactor.
should be possible in principle to limit its occurrence by adjust-
As an example of how this approach might be used with a
ing the values of key chemical and electrochemical parameters.
SCWO system, Fig. 4 shows overlaid Pourbaix diagrams for nickel,
This approach therefore involves manipulating process chemistry
chromium, and molybdenum (the principal elements of Alloys C-
to steer operating conditions toward a region resulting in the low-
est possibility of corrosion. The variable values to be optimized
typically involve the following: temperature (affects thermody-
namic equilibrium as well as kinetics), pH (e.g., through addition
of base), electrochemical potential (e.g., through oxidant concen-
tration), and feed composition (e.g., concentration of aggressive
species). For most SCWO applications, the feed composition is fixed
based on the waste to be treated, and thus there may be limited
opportunity to make major adjustments without adding to the cost
or treatment time.
A key factor in adjusting process conditions for low corrosivity
is the range of electrochemical potential and pH values for which at
least one major alloy component in the chosen material of construc-
tion is stable (i.e., exists in insoluble as opposed to soluble form).
Insight into elemental stability can be provided by electrochemi-
cal potential-pH (Pourbaix) diagrams. Because of the typically high
electrochemical potential in SCWO systems caused by the high oxi-
dant concentrations, it is unlikely that the stable form of metals will
be their reduced (i.e., metallic) form. Thus, the goal is to search for a
region (or “stability island” as referred to by Kritzer [12]; see Fig. 3)
where the stable form for at least one major alloy component is an
insoluble, protective oxide.
To use this approach, one needs to determine the approximate
location of system operation on the appropriate Pourbaix diagram
(e.g., nickel and chromium for nickel-based alloys). Both the pH
Fig. 4. Combined Pourbaix diagram for nickel, chromium, and molybdenum at
and the electrochemical potential (E) of the process are difficult 300 ◦ C.
to measure at the elevated temperature and pressure conditions Reprinted with permission from Mitton et al. [24], copyright (2000) American Chem-
in the reactor. However, sensors have been developed to func- ical Society.
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
276 and 625) at 300 ◦ C. Point 1 indicates a potential operating
point for an acidic (or acid-forming) feed in a SCWO reactor, pre-
heater, or heat exchanger. Here, chromium is stable (exists as the
solid oxide CrOOH) but nickel is not (exists as soluble Ni2+ ). If
the chromium passivating layer were to be breached, dealloying
of nickel would therefore be expected under these conditions. By
increasing pH, one could move to Point 2 on the graph. Here, nickel
is stable (exists as solid NiO), but chromium is not (exists as solu-
ble HCrO4 − ), although the strong protective surface coating formed
by NiO would likely limit dissolution of Cr and Mo. By dropping the
potential to reach Point 3, however, one enters a region where both
chromium and nickel are stable (as CrOOH and NiO, respectively).
This zone defined by the overlap of CrOOH and NiO stability rep-
resents the predicted optimal operating conditions with respect to
corrosion (but not necessarily for waste oxidation) for use with this
feed and reactor material.
Though straightforward in theory, this chemistry adjustment
approach can be difficult to implement. Pourbaix diagrams are
either not available or not applicable at many of the conditions
of interest to SCWO. Most are available from ambient temperature
up to only 300 ◦ C, although some have been developed for nickel
[118] and iron [119] up to 450 ◦ C and 500 ◦ C, respectively, albeit at
sufficiently high pressures (500–1000 bar) to retain liquid-like den-
sities. Furthermore, application of concepts such as pH and data on
soluble species at lower temperatures frequently does not apply
because of the lack of dissociation of ionic species at many SCW
operating conditions. However, it must be borne in mind that in
salt-containing systems, ionic liquid phases may be encountered
throughout the range of typical SCW operating conditions, mean-
ing that Pourbaix diagrams would be relevant in such cases. At the
nonionic conditions frequently encountered at temperatures above
∼400 ◦ C, other types of thermochemical diagrams (e.g. Ellingham
diagrams [free energy of formation vs. temperature]) rather than
Pourbaix diagrams are more appropriate [120]. An example of such
a diagram is provided in Section 4.5.
Finally, it must be borne in mind that Pourbaix diagrams are
based only on thermodynamic data, and as such, provide no infor-
mation on reaction rates or how good a solid oxide may be in
forming a protective surface layer (i.e., whether it is dense or
porous, and how well it adheres to the base metal). Thermochem-
ical diagrams cannot predict the type of corrosion, particularly
where the more dangerous localized corrosion may occur. In gen-
eral, one can only gain a rough idea of where to operate using these
thermochemical tools. Nevertheless, this approach can still yield
useful information and provide general guidance as to the direc-
tion of change to improve performance with respect to corrosion.
However, it is important to closely monitor operating conditions
and feed composition when utilizing this approach because inad-
vertent changes to the feed or mistakes in operation may result in a
move to a less desirable operating regime and expose the otherwise
unprotected system to severe corrosion.
3.4.12. Avoidance of corrosive feeds
One of the simplest and most obvious ways to prevent corro-
sion in a SCWO system is to avoid processing feeds that have or
will generate corrosive species or salts. This approach limits opera-
tion to processing feeds containing only carbon, hydrogen, oxygen,
and most forms of nitrogen (CHON). Examples of feeds that may fall
into this category include sewage sludge, waste hydrocarbons and
oxygenated hydrocarbons, and wastewater from explosives man-
ufacturing (pink water). However, corrosion can never be entirely
avoided, and some thought must be given to materials selection
even when following this approach.
Over the years, several SCWO vendors have utilized the benign
feed approach, targeting their SCWO systems for low corrosion,
low salt wastes. For example, both MODEC [121] and HydroPro-
95
cessing [122] focused on low corrosivity sludge applications. The
first commercial SCWO system built in the U.S. for Huntsman Corp.
by EcoWaste Technologies (later acquired by Chematur) operated
successfully for several years on laboratory waste consisting pri-
marily of alcohols, glycols, and amines [123,124]. This system was
designed to process only CHON feeds with low solids. Other com-
panies have developed separate, less expensive versions of the
SCWO system for handling more benign wastes. General Atomics
has developed a simpler version of its SCWO process, referred to as
industrial SCWO or iSCWO, for less corrosive though still high-salt
wastes such as hydrolyzed energetics [125].
The benefit to this approach is the significant savings in cost
of materials and in operation from being able to avoid specialty
materials of construction and components, complex control mech-
anisms, and added maintenance associated with handling corrosive
feeds. The downside to this approach, however, is that the system is
at risk to suffer severe corrosion if waste composition changes and
no other control options have been taken. Thus it requires particular
attention be paid to monitoring feed composition and parameters
such as pH at all times.
3.4.13. Pretreatment to remove corrosive species
Certain feeds may be amenable to removal of corrosive species
by pretreatment, thereby moderating the demands on downstream
materials. As an example, it was noted previously that some feed
materials may hydrolyze during preheating, yielding corrosive
species. In view of this phenomenon, Hong et al. [113] describe
a dechlorination pretreatment in which HCl is removed by neutral-
ization and phase separation prior to the SCWO reactor. Depending
upon the feed, various other pretreatment separations may be pos-
sible.
4. Supercritical water gasification (SCWG)
4.1. SCWG background
Gasification refers to the process in which organic materials
are reacted with water or steam to form light gases, in particular
methane, hydrogen, carbon dioxide and carbon monoxide. Use of
biomass as the organic material is currently of great interest due to
the dual concerns of energy security and global warming. As with
SCWO, the unique properties of SCW impart several potentially
useful features to its use as a gasification medium, in particular:
- High transport rates conducive to high reaction rates at a given
temperature.
- High operating pressure translates to a compact gasifier with low
heat loss.
- High solvation of organic materials conducive to reducing the for-
mation of higher molecular weight condensation products, i.e.,
reduced tar and char.
- High water density encourages the gasification reactions.
- High density medium conducive to heat recovery.
- Compatible with high water content feeds such as sludges and
biomass; reduces or eliminates the need for feedstock drying
required for conventional gasifiers.
- Inherent scrubbing action during the cool-down process as the
water condenses, reducing, or eliminating the need for gas
cleanup prior to usage or further processing.
- Product gases available at high pressure facilitates compact stor-
age.
- High pressure facilitates CO2 removal and sequestration.
Likewise in similarity to SCWO, the potential technical difficul-
ties inherent in the application of SCWG include operation at high
pressure, solids accumulation, and corrosion.
96 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
The earliest work on SCWG was carried out at MIT in the 1970s
[126–129], where it was reported that the use of supercritical con-
ditions prevented the formation of char when reforming aqueous
mixtures of glucose, cellulose, coal and sawdust to gaseous and liq-
uid products. SCWG is currently being investigated by dozens of
research groups worldwide, and a number of recent review arti-
cles are available in the literature [130–134]. In contrast to SCWO,
however, there are very few corrosion observations published in
the literature, and only FZK has reported long-term corrosion data.
To some degree this is a matter of the particular feeds investigated.
Many SCWG researchers to date have focused on model compounds
containing only carbon, hydrogen, and oxygen. The most striking
corrosion rates in SCWO were observed with chlorinated feed-
stocks, which are not a major focus of SCWG applications. The
general practice for SCWG has been to rely on stainless steel and
nickel-based alloys that have proven generally applicable in SCWO,
but the strong difference in oxidative (electrochemical) potential
between the two types of systems suggests that very different
behaviors may occur. Oxide surface layers are responsible for the
corrosion-resistant properties of stainless steel and nickel-based
alloys, and given the reducing nature of SCWG environments, the
effectiveness of such a corrosion protection mechanism is open to
question.
4.2. SCWG process description
Gasification systems in general are divided into two types, indi-
rectly heated and directly heated, depending on whether the heat
for attaining reaction temperature is generated external to the pro-
cess or within it, respectively. Both types of processes are classified
as SCWG, although when a portion of the feed material is oxidized
within the gasifier to provide heat (directly heated), the process
is also known as supercritical water partial oxidation (SWPO). In
SWPO as in SCWO, the oxidation reactions take place very rapidly,
so that the region of high oxidation potential is very limited. Thus,
SCWG reactors of any type are dominated by reducing conditions
and no distinction between the indirectly and directly heated pro-
cesses will be made in the discussion that follows.
Fig. 5. Generic SCWG process flow diagram.
A typical SCWG process flow diagram (PFD) for processing
biomass is shown in Fig. 5. Slurried biomass is pumped to the sys-
tem operating pressure of approximately 25 MPa and preheated in
two stages — first, in a heat recovery heat exchanger and then in
a gas-fired trim heater. The hot flue gas from the gas-fired heater
is used to produce steam for export or other in-plant uses. Hav-
ing been preheated to the gasification temperature of 650 ◦ C, the
process stream enters the gasification reactor. In the reactor, the
feed is converted primarily to CH4 , CO2 , H2 , and CO. Upon leaving
the gasifier, the process stream gives up part of its heat to preheat
the feed in the heat recovery heat exchanger, and is then cooled
to near-ambient temperature in a steam generator. The condensa-
tion of liquid in the gasifier effluent is a highly efficient scrubbing
mechanism, partitioning salts and particulates into the liquid phase
and yielding a clean product gas. Subsequent to cooling, but still
at essentially full pressure, the process stream enters a gas–liquid
separator. The liquid phase, comprising water, a significant fraction
of the CO2 , residual liquid organics, and dissolved or suspended
mineral matter and char, exits from the bottom of the separator
and is depressurized. The depressurized liquid effluent is sent to a
wastewater treatment plant for final discharge. The clean product
fuel gas exits from the top of the separator and is sent to storage or
to further processing or usage.
Process objectives and economics will frequently vary greatly
for SCWG as opposed to SCWO, and this affects the viability of vari-
ous corrosion control approaches. In many SCWO applications, the
material to be processed is a difficult-to-treat waste such as PCBs
[135] or chemical agent byproducts [6] and the economics are jus-
tified by disposal cost alone. Alternatively, a high value primary
product such as precious metal catalyst can be recovered [136] to
justify the economics. In either case the primary objective is con-
version of waste, with energy or byproduct recovery of secondary
concern and not a necessity for process economic viability. On the
other hand, processing of lower heating value materials such as
sewage, drinking water or paper mill sludge by SCWO necessar-
ily involve recovery of energy or steam [137] or byproducts such
as iron, aluminum and phosphate [138] or carbon dioxide [139]
for acceptable economics. SCWG has an economic advantage over
 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
SCWO in that no oxidant need be supplied to the system (or much
less oxidant in the case of SWPO). SCWG effluent, however, has
high organic content, and it is not a useful process for obtaining the
clean, mineralized products desired in the above-mentioned SCWO
waste treatment applications. Rather, the objective of SCWG pro-
cesses is typically the preservation of feedstock energy as fuels or
chemicals, and the process energy balance is paramount. Regen-
erative heat exchange as shown in Fig. 5 is essential to acceptable
economics. While SCWG feedstock may in some instances be neg-
ative value, e.g. sewage sludge or municipal solid waste, a more
usual scenario is processing of a feedstock such as biomass that
must be purchased. Because net energy is required to bring the
feed materials and any accompanying water up to the processing
temperature of ∼650 ◦ C, SCWG of biomass materials only makes
economic sense if the feed material has at least ∼20% dry content
[140]. This economic restriction limits the applicability of corrosion
control approaches that involve dilution.
4.3. Key location areas for corrosion
As with SCWO, the primary areas of corrosion concern are where
liquid-like densities (>0.2 kg/L) occur at elevated temperatures.
With reference to Fig. 5, the heat recovery heat exchanger and
the cool-down heat exchanger are particularly vulnerable. Regions
in the fired heater and gasifier where liquid-like phases may be
present are also of high concern, e.g., near the inlet of the fired
heater and in areas where brines, melts, or slag may be present.
4.4. Common types of corrosion encountered or anticipated
As previously noted, many of the corrosion phenomena
observed in SCW are tied to the properties of the water medium
itself, so that their occurrence would be expected under either the
oxidizing conditions of SCWO or the reducing conditions of SCWG.
There are however some important differences as noted below.
• General corrosion – For the low electrochemical potentials present
in SCWG, oxide film instability may be anticipated. General corro-
sion will take place via active dissolution rather than transpassive
dissolution as with SCWO. Kritzer et al. [14] note that active dis-
solution of many metals, including Fe, Ni, Cr and Ti, will occur
under reducing conditions. D’Jesús et al. [141] note that an estab-
lished layer of NiO on the surface of Alloy 625 is converted to
metallic nickel at SCWG conditions.
• Dealloying – Dealloying reactions may differ from SCWO due to
the different attacking species. Mitton et al. [142] report dealloy-
ing of Ni in an acidic chloride environment, while Habicht et al.
[143] report dealloying of Ni and Mo in the presence of the alka-
line compound K2 CO3 . Kruse et al. [144] report dealloying of Cr
and Mo believed to be due to reactions with sulfide.
• Pitting – No reports of pitting under SCWG conditions have been
found in the literature. This may partly be a reflection of the
limited number of environments and materials tested to date.
However, as pitting is a result of localized attack on a gener-
ally passive oxide layer, lack of pitting observations may simply
reflect the lack of such oxide layers.
• Stress corrosion cracking (SCC) – SCC in chlorinated SCWG environ-
ments has been reported by Mitton et al. [142] and Fujisawa et al.
[145]. Interestingly, in the latter case increased partial pressures
of H2 reduced the tendency for SCC.
• Intergranular corrosion – Intergranular corrosion has been
reported under SCWG conditions by Mitton et al. [142]. This took
the form of dealloying at grain boundaries.
• Crevice corrosion – As with SCWO, crevices could be subject to
concentration differences from the bulk fluid leading to corro-
97
sion when ionic fluids are present. However, no reports of crevice
corrosion in SCWG environments have yet appeared.
• Under-deposit corrosion – Deposit formation in SCW is largely a
function of the solvation properties of the water, and is expected
to be common in SCWG as it is in SCWO. For example, Boukis et
al. [146] report SCWG reactor plugging due to salt precipitation.
Thus, under-deposit corrosion is expected to occur in SCWG as it
does in SCWO. Under-deposit corrosion may have played a role
in the results reported by Boukis et al. [147,148], where potas-
sium carbonate deposits were present on the corrosion sample
surfaces.
• Hydriding – With H2 as a major reaction product in SCWG, metal
hydriding is an obvious concern. However, after more than 1000 h
of testing, Boukis et al. [146] report only thermal embrittlement
with Alloy 625, with no apparent accelerated embrittlement due
to hydrogen. It thus appears that hydrogen embrittlement is not
a concern for the nickel-based alloys. As previously noted, hydro-
gen embrittlement of titanium has been observed in strongly
oxidizing SCWO environments at around 600 ◦ C, and is thus to
be expected in SCWG environments at similar temperatures.
Based on SCWO experience, the rate of titanium hydriding drops
strongly at lower temperatures, and it is possible that titanium
is acceptable in SCWG environments at low supercritical tem-
peratures. Vogel [149] reports use of a titanium vessel in SCWG
environments for ∼100 h with no apparent degradation.
• Galvanic corrosion – Galvanic corrosion has not been reported to
date for SCWG environments. As with SCWO, galvanic corrosion
is possible when dissimilar metals are in common contact with
an ionic melt or brine phase.
• Noncoupled corrosion – As with SCWO, noncoupled corrosion
should be of relatively minor importance at SCWG conditions of
650 ◦ C. Some caution is in order due to the presence of differ-
ent potentially corrosive species, e.g. H2 S and NH3 . In addition,
higher operating temperatures are sometimes used for SCWG
(e.g., 800 ◦ C [150]), which can accelerate any corrosion reactions.
However, no reports of noncoupled corrosion in SCWG environ-
ments have yet appeared.
4.5. Materials
Table 3 presents literature corrosion observations and data for
various materials that have been used or tested in SCWG envi-
ronments. The table is limited to materials that have been used
or tested for tens of hours, but is not restricted to corrosion stud-
ies. In some cases, no detailed material examinations were done
or no observations were reported. However, the fact of usage for
a substantial period of time indicates at least a modest corro-
sion resistance. The preponderance of nickel-based alloys in the
table is evident, due to their generally superior corrosion resis-
tance, strength at elevated temperatures, and prior experience with
SCWO. (Note that a similar table was not previously presented
for SCWO due to the large size of the database. For the interested
reader, Kritzer [12] has provided a useful, concise summary of the
SCWO corrosion database.) It will be noted in Table 3 that model
SCWG environments containing only carbon, hydrogen and oxygen
are fairly benign, while the inclusion of heteroatoms such as potas-
sium, sulfur or chlorine can result in significant corrosion. As was
the case with SCWO, it is anticipated that a combination of material
selection with other corrosion control strategies will yield accept-
able corrosion control solutions for SCWG. For example, Boukis et
al. [148] found that compared to Alloy 625, low-molybdenum alloys
show much lower corrosion in environments containing the rep-
resentative biomass salt potassium bicarbonate (KHCO3 ), although
the tests reported to date were not carried out in the presence of
organic.
 98
Table 3
Summary of corrosion experience under SCWG conditions.

Material Feed T (◦ C) P (MPa) Exposure (h) Corrosion results Reference

316SS Coal 363–399 0.5–27 ∼100 (est.) No observations reported [151]

316SS Ethanol + K2 CO3 , pyroligneous 650–700 25 140 Tube failure [152]
Alloy C-276 acid + K2 CO3 300
Alloy C-276 Methylene chloride 150–350 25 45–104 Tube failure; dealloying; SCC [142]
Alloy C-276 Potato waste 720 28 NA Corrosion product deposits show all [153]
constituents of Alloy C-276
Alloy 625 Glucose, biomass, sewage 700 34.5 >400 No observations reported, but later [140,153,154]
sludge, paper sludge publications indicate significant corrosion of
both Alloy 625 and Alloy C-276.

P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103

Alloy 625 Methanol 600 25 1011 No corrosion; normal embrittlement; no [146]
apparent hydrogen embrittlement
Alloy 625 Methanol + K2 CO3 700 40 423 Dealloying; Ni and Mo depleted [143]
Alloy 625 Glucose, K2 CO3 500 30 NA Corrosion product particulates show all [155]
constituents of Alloy 625
Alloy 625 Glucose + K2 CO3 , carrot/potato 500 30 NA Severe corrosion sometimes observed with [144,156]
puree, rice/chicken puree protein-containing biomass (rice/chicken)
believed due to the high sulfur content
reacting with Cr and Mo
Alloy 625 Corn silage 300–700 25–40 280 (biomass) General corrosion; leakage; NiO surface layer [141]
1520 (water >500 ◦ C) reduced to Ni; 490 mg/kg potassium in feed
Alloy 625 Ethanol/methanol + KHCO3 350–700 25–40 146–775 Rapid general corrosion with Mo dealloying [147]
with 100–1696 mg/kg potassium in feed
Alloy 625 Methanol + KHCO3 600–700 30 289–340 No weight loss with 78 mg/kg potassium in feed [148]
Alloy 617
316SS (12Ni–18Cr–2.5Mo)
Alloy C-276 (Ni–16Cr–16Mo)
At reducing conditions with and without HCl,
Alloy 625 (Ni–21.5Cr–9Mo) Formic acid, HCl 350–550 25 50–100 [157]
higher Mo content reduces weight loss
MC-alloy (Ni–45Cr–1Mo)
MAT 21 (Ni–19Cr–19Mo)
316SS
Alloy C-276 Increased Cr reduces susceptibility to SCC;
Formic acid, HCl 400 25 15–60 [145]
Alloy 625 increased H2 reduces susceptibility to SCC
MC-alloy
Alloy C-276 (Ni–16Cr–16Mo)
Alloy 625 (Ni–21.5Cr–9Mo)
Higher Mo test alloy most stable, gives least
MC-alloy (Ni–45Cr–1Mo) Formic acid, NaOH 400 25 50 [158]
weight change
MAT 21 (Ni–19Cr–19Mo)
Test alloy (Ni–21Cr–21Mo)
Gold plating Ethanol, formic acid, acetic 360–500 30 ∼300 No apparent corrosion though some coating [149,159]
acid, phenol, anisole detachment
Titanium Gr. 5 Ethanol, KNO3 , Na2 SO4 , K2 CO3 , 390–500 25–30 ∼100 No apparent corrosion [149]
K3 PO4

NA: not available.

 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
Fig. 6. Phase stability diagram for the Ni–H–O system at 650 ◦ C.
As in the case of SCWO, thermochemical data can help pro-
vide guidelines for suitable materials and conditions for SCWG. As
noted previously, thermochemical diagrams other than Pourbaix
diagrams are appropriate in cases where nonionic conditions pre-
vail. Fig. 6 gives an example of such a diagram, referred to as a phase
stability diagram, calculated using HSC Chemistry 6.0 software, and
illustrates both the usefulness and uncertainties associated with
such diagrams. The plot represents the behavior of nickel in a SCWG
environment as expressed by the following reaction equations and
equilibrium constants (Ki ) in terms of partial pressures (Pj ):
NiO + H2 O = Ni(OH)2 K1 = 1/PH2 O
NiO + H2 = Ni + H2 O K2 = PH2 O /PH2
Ni(OH)2 + H2 = Ni + 2H2 O K3 = 2
PH /PH2
2O
For each equation, the standard Gibbs free energy of reaction G◦
is calculated from the thermochemical data at the desired temper-
ature (T) of 650 ◦ C, which then allows calculation of the equilibrium
constant (K) from Eq. (4):
G◦ = −RT ln K
For the equilibrium calculations that define the stable phases,
solid phases are assumed to have unit activity and gases to have unit
fugacity coefficients, although water thermochemical properties
are corrected for 200 bar. The horizontal axis of Fig. 6 shows water
partial pressure while the vertical axis shows hydrogen partial
pressure. (The total system pressure would be the sum of the two
partial pressures.) In the band of typical SCWG operating pressures
(225–350 bar), nickel hydroxide (Ni(OH)2 ) is the predicted stable
solid phase at hydrogen partial pressures below about 100 bar. This
is consistent with the analyses summarized by Sun et al. [160] and
Was et al. [161], where both nickel oxide (NiO) and nickel hydroxide
have been observed at the surface of nickel-based alloys exposed
to high temperature water. Given that the actual phase stability
boundaries may be in somewhat different locations due to non-
idealities, and that nickel oxide may persist as a metastable phase
from lower temperatures and pressures, the nickel oxide and nickel
hydroxide phases appear to be reasonably represented by the dia-
gram. Furthermore, nickel hydrides are predicted to not be stable
until hydrogen pressures in excess of those shown on the diagram
are attained, consistent with experimental observations [146]. On
the other hand, the reduction to metallic nickel at hydrogen par-
tial pressures in excess of 100 bar seems to be well off the mark, as
D’Jesús et al. [141] observed such conversion at only a few bars of
hydrogen partial pressure.
In addition to the materials listed in Table 3, investigations of
SCWG catalysts provide insights into material compatibility with
99
SCWG environments. Raney nickel catalyst has been found to deac-
tivate by sintering in the range of 400 ◦ C. Titania in rutile form is
stable at subcritical temperatures [162,163], although it may be
unstable above ∼400 ◦ C [164,165]. The passivating titania layer on
titanium metal becomes nonprotective above ∼650 ◦ C [166]. ␣-
Alumina is stable in the range of 400 ◦ C for at least 100 h at neutral or
moderately acid conditions, but dissolves fairly quickly under alka-
line conditions [149,159]. Ruthenium has good catalytic activity for
gasification, but reacts and is deactivated quickly by both oxidized
(sulfite, sulfate) and reduced (sulfide) forms of sulfur [149].
In contrast to SCWO, the compatibility of many materials
with SCWG has not been established. Several references suggest
or indicate that higher molybdenum content increases corrosion
resistance in SCWG environments [12,157,158]. Kane [43] has
suggested that cobalt alloys may have performance superior to
nickel-based alloys. Takeshita et al. [167] decomposed polyvinyl
chloride at SCWG conditions in a cobalt alloy reactor, however no
corrosion observations were reported. Metals that fail by rapid oxi-
dation under SCWO conditions, e.g., tantalum and zirconium, may
prove useful under SCWG conditions.
Other than alumina as a catalyst support, no literature refer-
ences have been found discussing the compatibility of ceramics
with SCWG environments. While the long-term stability of oxide
ceramics is doubtful, non-oxide ceramics such as silicon carbide
would appear to have good prospects. Furthermore, as char is slow
to gasify in SCWG systems, graphite may be a useful material of con-
struction. In this regard, Antal et al. [140] reported good stability
for activated carbon catalyst in SCWG environments.
(1) 4.6. Corrosion protection methods
(2) Table 4 considers the corrosion control approaches that have
(3) been utilized or suggested for SCWO with regard to their applicabil-
ity to SCWG. Further comments on certain approaches are provided
below.
As previously mentioned in Section 4.2, corrosion control
schemes involving dilution impart a significant disadvantage to
SCWG processes. For example, use of the transpiring wall technique
for SCWG is generally uneconomical. The large flow of transpiring
(4)
water would have to be heated either prior to entering the reac-
tor (for high temperature transpiring flow) or heated up within the
reactor (for ambient temperature transpiring flow). In either case,
the energy necessary for such heating is highly detrimental to the
process energy balance. Similarly, cold slurry feed injection and
quench cooling to dilute corrosive species in the feed and effluent
and minimize the extent of the high corrosion temperature regime
are not generally useful in SCWG as they hinder the necessary heat
recovery from the reactor effluent stream.
For certain feedstocks, removal of corrosive species prior to
the reactor may be an option. The removal may take place at
milder conditions than present in the reactor. Matsubara et al.
[168] describe a process for dechlorination of chlorinated plastics at
250–350 ◦ C prior to SCWG of the organic portion of the plastic. This
process is analogous to the dechlorination pretreatment described
by Hong et al. [113] for SCWO.
As with SCWO, additives may be useful for corrosion reduction,
primary examples being the usage of acids or bases to obtain a more
favorable pH. For large volume feedstocks, however, such additives
may represent an unacceptable economic burden. For example,
processing of biomass will typically result in production of useful
potash (potassium carbonate) byproduct. Reducing alkaline corro-
sion by adding acid (sulfuric for example) leads to additional costs
for acid and also reduces the value of the byproduct.
Unlike SCWO, which can generate much or all of its required
heat internally, SCWG processes require heat transfer into the pro-
cess at one or more locations to bring the feed up to gasification
100 P.A. Marrone, G.T. Hong / J. of Supercritical Fluids 51 (2009) 83–103
Table 4
SCWG corrosion control approaches.
Category Approach
Prevent corrosive species from Transpiring wall/film-cooled wall reactor
reaching a solid surface
Adsorption/reaction on fluidized solid phase (AHO)
Vortex/circulating flow reactor (conceptual)
Form a corrosion-resistant barrier Use of high corrosion resistance materials (long-term
applications)
Liners (corrosion-resistant material)
Coatings
Manage/minimize corrosion Liners (sacrificial material)
Use of adequate corrosion resistance materials
(short-term applications)
Adjust process conditions to avoid Pre-neutralization
or minimize corrosion Cold (ambient temperature) feed injection
Feed dilution with non-corrosive material
Effluent dilution/cooling (quench water addition)
Optimization of process conditions
Avoidance of corrosive feeds
Pretreatment to remove corrosive species
temperatures. Also, while the gasification reactions are not highly
endothermic, provision for some heat transfer into the reactor is
generally provided. Liners and coatings typically interfere with
heat transfer and thus are of reduced utility in SCWG. However,
graphite and silicon carbide have thermal conductivities an order
of magnitude higher than the nickel-based alloys, helping to reduce
interference with heat transfer.
One approach to improving the energy balance for SCWG is the
use of catalysts to permit gasifier operation at lower temperatures,
e.g. 400 ◦ C instead of 600 ◦ C. As is clear from the preceding discus-
sion, this approach will reduce some forms of corrosion but may
exacerbate others.
In general, mechanical and process design options for corro-
sion control are more constrained in the SCWG process than in
the SCWO process. This translates to an increased reliance upon
corrosion-resistant materials. The existence of such materials is still
in the process of being established.
5. Conclusions
The SCW process environment involves elevated temperatures
and pressures, and for a given application may be oxidizing, reduc-
ing, acidic, basic, nonionic, or highly ionic. No single material or
design can withstand the effects of all feed types under all condi-
tions, but acceptable approaches do appear to be generally available
on an application-specific basis. Corrosion in SCWO systems has
been successfully handled through a combination of resistant mate-
rials, chemistry control, mechanical design, and process design.
Corrosion control via mechanical and process design is more con-
strained in SCWG systems than in SCWO systems due to the need
for minimal dilution and the need for heat transfer surface associ-
ated with the reactor. While fairly limited SCWG material testing
has been carried out to date, it is anticipated that as for SCWO
a combination of resistant materials, chemistry control, mechan-
ical design, and process design will yield acceptable solutions to
corrosion control.
Acknowledgment
The authors would like to thank Dr. Frederic Vogel of the Paul
Scherrer Institut for providing unpublished corrosion data.
Applicability to SCWG
Limited usefulness in SCWG due to adverse effect of dilution on system
energy balance
Limited usefulness in SCWG as chlorinated hydrocarbons are not a
significant target feed
Applicable to SCWG
Applicable to SCWG
Reduced usefulness in SCWG due to need to transfer heat into reactor
Reduced usefulness in SCWG due to need to transfer heat into reactor
Reduced usefulness in SCWG due to need to transfer heat into reactor
Applicable to SCWG
Applicable to SCWG
Reduced usefulness in SCWG due to need to preheat feed for optimum
system energy balance
Limited usefulness in SCWG as primary feed is typically high volume
Limited usefulness in SCWG due to adverse effect of dilution on system
energy balance
Applicable to SCWG
Limited usefulness in SCWG
Some feeds may be amenable to heteroatom removal prior to SCWG
processing
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