Economic Analysis for Wet
Oxidation Processes for the
Treatment of Mixed Refinery
Spent Caustic
Raafat Alnaizy
Chemical Engineering Department, American University of Sharjah, Sharjah, UAE; ralnaizy@aus.edu (for correspondence)
Published online 20 February 2008 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ep.10261
Sodium hydroxide (caustic) continues to be one of
the primary reagents used in refineries and petro-
chemical plants to extract hydrogen sulfide, mercap-
tans, and organic acids from hydrocarbon streams. A
local refinery had accumulated
5000 m3 of spent
caustics containing cresylic and naphthenic com-
pounds. The chemical oxygen demand (COD) con-
centrations must be reduced to less than 1 g/L prior
to discharge to biotreatment. A simple and safe treat-
ment system for this high volume and high concen-
tration of COD is desired. Bench-scale treatment of
spent caustic by the Fenton’s reagent process had a
total COD removal of greater than 95%, and the
effluent COD was lower than 1 g/L. The process was
operated at a temperature lower than 808C and am-
bient pressure. The capital cost was thus lower than
that of the wet air oxidation (WAO) process that nor-
mally operates at 2008C and 28 bars. The cost of
exporting spent caustic to a full-service company in
USA was $1.21 per gallon that was competitive with
treatment at the individual generation sites on a
short-term basis. Ó 2008 American Institute of Chemical
Engineers Environ Prog, 27: 295–301, 2008
Keywords: Fenton’s reagent, cresylic, naphthenic,
sulfidic
INTRODUCTION
A typical spent caustic effluent from refineries may
contain about 5–12% by weight sodium hydroxide.
The common practice is to convert spent caustic to a
Ó 2008 American Institute of Chemical Engineers
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
form that minimizes the load on the wastewater treat-
ment plant (WWTP), or sold to chemical companies
as a process feedstock. In a typical petroleum refin-
ery, spent caustics are classified into three types: sul-
fidic, cresylic, and naphthenic caustics. The composi-
tion and strength of refinery spent caustics are highly
variable. Often plants do not have the facilities to
segregate the used caustic solutions into these various
classifications and, therefore, a mixed used caustic
stream is produced. This is considered a fourth type
of used caustic solution.
Sulfidic spent caustic is generated from fuel gas,
liquefied petroleum gas, and gasoline-treating pro-
cesses. Sulfidic is mostly just sulfides in caustic. The
composition of a typical refinery sulfidic caustic
stream is displayed in Table 1 [1]. It is not difficult to
oxidize at a high temperature (2008C), which destroys
the sulfides and mercaptans. At lower temperatures,
not all the reduced sulfur species are destroyed that
usually means a high chemical oxygen demand
(COD) load for the downstream bio-plant (mostly
from thiosulfate). On the other hand, sulfidic caustic
solutions with high quality may be sold as treating
agents to pulp and paper plants, but transportation
and handling costs can easily exceed product value
and onsite processing may be the most economical
option. Naphthenic spent caustic is generated from
caustic washing of diesel and jet fuel fractions. It con-
tains a minute amount of sulfide. Mostly it has naph-
thenic acids. Table 1 shows typical characteristics of
naphthenate streams derived from kerosene and die-
sel stocks. If naphthenic caustic solution is kept in
October 2008 295
Table 1. Characteristics of typical refinery caustic streams [1].
Naphthenic
Jet fuel/
kerosenae Diesel
NaOH, wt % 1–4 1–4
Sulfide as S2, wt % 0–0.1 Trace
Mercaptide as S1, wt % 0–0.5 0–0.5
Naphthenic acids, wt % 2–10 2–15
Carbonates as CO3, wt %
Cresylic, wt % 1–3 0–1
Ammonia
pH 12–14 12–14
pure enough form, and if there are any local plants
interested in it, then it can actually be sold, otherwise
the logistics are usually encumbrance and onsite
processing may be the most economical option. This
material tends to foam vigorously if treated at 2008C,
making the plant inoperable. So, it has to be oxidized
at higher temperatures (2608C). A moderate oxidation
rate is possible at that temperature, however the cost
is usually higher, since the pressure required to keep
water liquid at that temperature is, of course, higher
than for a low temperature system. Cresylic spent
caustic is generated from caustic washing of the gaso-
line fraction, and is comprised mostly of aromatic
acid oils. These used caustic streams contain phenols,
cresols, and other organic acids that are generally
present as water-soluble cresylates. Table 1 shows
the characteristics of a typical cresylic caustic. Cresylic
caustic solutions resulting from a strong caustic oper-
ation can be sold as a chemical feedstock for the pro-
duction of phenolic compounds. Otherwise, the low
acid oil content drastically increases transportation
and processing costs per weight of cresylate, and
may be a good candidate for onsite processing.
Spent Caustic Management
The disposition of spent caustic may result in
costly economical and environmental outcomes. Not-
withstanding the neat description above, refiners typi-
cally combine all types of used caustics in the same
storage vessel and label it as one waste stream ‘‘Re-
finery Spent Caustic’’ rendering the entire mixture
unsaleable. Such effluents are considered essentially
useless waste streams, and require significant process-
ing before disposal. Major companies that offer spent
caustic treatment systems and/or services include
UOP, Merichem, MPR, and USFilter.
MPR convert refinery spent caustics, including sulfi-
dic, naphthenic, and cresylic into a biodegradable
stream suitable for treatment in a conventional
WWTP. Details of the process specifics are not avail-
able and are difficult to obtain. It is an adaptation of
Fenton’s, which uses peroxide and a metal salt. As
such, it is relatively a low temperature process, which
means lower capital cost. But it uses peroxide as the
oxidant, which means higher operating costs. Per-
296 October 2008
Cresylic
Strong Dilute
caustic operation caustic operation Sulfidic
10–15 1–4 2–10
0–1 0–0.2 0.5–4
0–4 0–0.5 0.1–4
0–0.5 0–0.1
10–25 2–5 0–4
Trace
12–14 12–14 13–14
formance is unknown, as is its operability. The UOP
sulfide oxidation process for treating spent caustic is a
low temperature oxidation process that uses a propri-
etary UOP catalyst. It takes place over a fixed bed of
catalyst in the oxidizer column. It is questionable, if
this is an adequate process for treating high COD re-
finery spent caustic. At low temperatures, organic
compounds are not readily oxidized, and the sulfides
will only oxidize to thiosulfate. This leaves a high
COD reduced sulfur waste stream that still has to be
dealt with. Odor could be a concern, since the rates
are slow at low temperature, and there is a possibility
of stripping sulfides and mercaptans into the gas
phase. Excessive foaming could potentially be a major
concern, as it prevents the phase separator from oper-
ating properly. Also, since it is low temperature, it is
unclear how effective this process is on mercaptans.
The manufacturer claims that ‘‘the noncorrosive envi-
ronment and mild operating conditions allow for car-
bon steel construction throughout.’’ [2] UOP sulfide
oxidation units have been placed on-stream with
design capacities ranging from 16.5 to 55 gal/h. Based
on year 2003 estimates for North American supply,
UOP quoted a price of a 50 gal/h unit US $0.4 million
(630%). The direct operating costs are US $0.15 per
gallon of caustic treated (Catalyst, packing, chemicals,
and utilities) [2]. Merichem offers a full-service ap-
proach to caustic management. They offer both spot
purchase and long-term contracts for naphthenic,
phenolic, and sulfidic caustics. They convert spent
caustics into organic chemicals in many USA plants.
Merichem also offers a custom-designed modular sys-
tem to process caustic solutions in plants worldwide,
when this is the most cost-effective solution.
The well-known USFilter Zimpro is a moderate to
high temperature and high-pressure WAO technology.
Wet air oxidation is commonly used for treating spent
caustics that can be divided into three ranges of oper-
ation. A low-temperature system achieves partial oxi-
dation of sulfides to both sulfate and thiosulfate. It is
applicable for dilute sulfidic caustics, when thiosul-
fate is not a concern for downstream treatment. A
medium-temperature system achieves complete oxi-
dation of sulfides to sulfate and destroys mercaptans,
which is usually used for sulfidic ethylene spent
caustic treatment. A high-temperature system achieves
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
complete oxidation of sulfides and mercaptans, plus
destruction of organic contaminants such as cresylic
acids. Applied to refinery spent caustics, most of the
organics are oxidized with some residual acetate
formed. The oxidation products are acids, so they
neutralize the alkalinity. Since it is a high-pressure
system, it has a relatively high capital cost compared
to the other options.
Wet oxidation is a very efficient process, but it
involves high temperature and pressure conditions.
To lower this constraint, more efficient oxidizers can
be employed. The first idea developed is to use ho-
mogeneous catalyst, such as transition metal salts or
hydrogen peroxide (H2O2) in order to promote air
oxidation at a lower temperature [3]. The second
attempt is to use H2O2 as the oxidizer instead of mo-
lecular oxygen, leading to the development of
another process, wet peroxide oxidation (WPO). It is
an adaptation of the Fenton process in the event that
iron salts are used as catalyst; one of the many forms
of advanced oxidation processes. The WPO process
is derived from the classical Fenton’s reagent. It uses
H2O2 catalyzed by Fe21 as the oxidant at a pH of 3.
The operating conditions are very mild with a 90–
1308C temperature and a pressure of 15–75 psia.
High oxidation efficiencies (up to 98%) are achieved
at these conditions [4]. Under these circumstances,
the only difference between both processes would be
the temperature at which the reactions are con-
ducted. As opposed to WAO, which employs a gase-
ous source of oxidizing agent (air or oxygen) and
which is a two-step process (mass transfer plus oxi-
dation), WPO uses a liquid oxidizing agent (H2O2)
that eliminates the mass transfer problems. There are
numerous design parameters, including temperature
and pressure. Oxidation of organic waste with H2O2
is usually a slow process. However in the presence of
a catalyst, the oxidation process proceeds rapidly.
Catalysts include ferrous iron, copper, aluminum, and
chromium. Ferrous iron is a good selection, because
it is not listed as a heavy or toxic metal and its use
and subsequent precipitation does not create further
hazardous waste problems. H2O2 in combination
with a ferrous iron salt is commonly referred to as
Fenton’s Reagent. This reagent acts as an oxidizing
agent through the formation of hydroxyl free radicals.
Optimum oxidation with the Fenton Reagent nor-
mally occurs at a pH of 3–7. However, in the pres-
ence of acetate or phosphate buffers, the reaction
precedes slower in these pH ranges [5]. The ferric
iron can be precipitated by increasing the pH either
with lime or caustic. There is some coprecipitation of
the remaining organics. Depending on the effluent
discharge requirements, further treatment may be
required to reduce the COD to discharge limits. The
effluent, however, may be applicable for discharge to
a domestic sewage treatment plant or biological
industrial waste treatment plant.
SCOPE AND OBJECTIVES
The variations in spent caustic characteristics and
treatment objectives must be carefully considered
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
Table 2. Composition of the refinery spent caustic
sample.
Constituent
pH 12.6
Specific gravity 1.12
Sodium wt % 5.93
Sulfide as sulfur wt % 0.5
Oil and grease (mg/L) 4.66
Phenols (mg/L) 4,375
Total organic carbon (TOC) (mg/L) 41,600
Chemical oxygen demand (COD) (mg/L) 91,200
prior to choosing the optimal treatment option and
design. These issues can have a significant impact on
the critical design parameters, including the materials
of construction. A local refinery had accumulated

5000 m3 of spent caustics. These facilities are not
currently capable of handling spent caustic in ac-
cordance with current environmental standards.
Spent caustic treatment option must be designed to
accept naphthenic spent caustic. The test results for
the spent caustic are summarized in Table 2. The
COD levels must be reduced to less than 1000 mg/L
and less than 25 ppm phenol prior to discharge to
the biological treatment facilities. A simple and safe
treatment system for this high volume and high con-
centration of COD is desired. The overall objective
of this work is to conduct a comparative economic
analysis for onsite treatment of refinery spent caustic
and subsequent discharge of the brine effluent into
the WWTP. The study evaluates the economics of the
Zimpro process and the potential use of a Fenton-
like oxidation process based on results of bench-
scale experiments. In addition, the study compares
both treatment options to the disposing of the spent
caustic through an outside company. The principal
means of doing so is to review the published litera-
ture on WAO along with the findings from earlier
assessments under the Saudi Company for Environ-
mental Works Ltd.
METHODS AND EXPERIMENTAL PROCEDURES
A sample of the mixed spent caustic was obtained
from the refinery. The sample analyses were per-
formed by AHS independent testing laboratories. The
tests methods were Standard Test Methods for Chemi-
cal Analysis of Caustic Soda and Caustic Potash (so-
dium hydroxide and potassium hydroxide) (ASTM E
291) and Standard Methods for the Examination of
Water and Wastewater, American Water Works Assn.,
19th Edition (1995). The laboratory-scale semibatch
experiments were performed in glassware at ambient
pressure. The Fenton reactor (1 L) was equipped
with an electromagnetic stirrer, and temperature-con-
trolled hot plates were used to maintain the desired
temperature (if needed). The Spent caustic was neu-
tralized by adding 5N normality sulfuric acid to
obtain a pH around 3. Then, ferrous sulfate solution
and H2O2 (50 wt %) were added to the reactor. Sam-
ples were taken and analyzed at specified time inter-
October 2008 297
Figure 1. Process flow diagram of a typical wet air oxidation system.

vals. The off-gas was vented into the atmosphere. All Table 3. WAO processing of refinery spent caustic [7].
chemicals were laboratory-grade from Aldrich and/or
Sigma chemicals. The exothermic nature of the reac- Effluent
tion caused an increase in reaction temperature. The
reactor temperature reached about 808C under adia- Feed 2608C 2808C
batic conditions. Residence time (min) — 60 60
Each test entailed charging the Fenton reactor with COD (mg/L) 81,300 24,200 18,000
200 mL of the spent caustic. The average pH value of COD destruction (%) — 70.2 77.9
the spent caustic was around 12.98. The highly con- Total sulfur (mg/L) 7,900 9,260 8,972
centrated nature of the spent caustic called for dilu- Sulfide sulfur (mg/L) 5,024 <4 <4
tion prior to treatment at 2 parts water to 1 part spent Sulfate sulfur (mg/L) <54 6,350 6,727
caustic. The pH was reduced to about 3 by adding Mercaptans as methyl 8,680 <10 <10
H2SO4 dropwise. Once a pH of 3 was obtained, a (mg/L)
predetermined amount of FeSO4 was added (molar
ratio of FeSO4 to H2O2 is 1:7) and the contents were
stirred continuously. Subsequent to this, a pre-esti-
mated amount of 50% H2O2 was added very slowly Wet Air Oxidation
to the reactor (COD to H2O2 molar ratio of 2:1). Sub- The basic flow scheme for a typical WAO system is
stantial foaming and a little fume were observed. The illustrated in Figure 1. Spent caustic is pumped from
temperature at the start of H2O2 addition was noted the tank to the oxidizer tower. Before entering the
to be 268C. The exothermic reaction caused an tower, the caustic is first mixed with a predetermined
increase in reaction temperature (as high as 808C). amount of fresh water and/or fresh caustic depending
When the entire quantity of H2O2 was added to the on the strength of the spent caustic (TOC concentra-
Fenton reactor, the pH was noted to be around 2. tion). Then, it is preheated through feed/product
The contents were allowed to settle down and the exchangers. Air containing sufficient oxygen is added
temperature was rapidly decreased. Addition of H2O2 to meet the oxygen demand requirements. After
was accomplished over 10 min. The off-gas from the being adequately heated, the spent caustic enters the
reaction was not analyzed. It may have contained bottom of the oxidation tower. The reactor provides
NOx, SOx, and volatile organic compounds (VOCs) sufficient retention time to allow the oxidation to
such as aldehydes, ketones, and alcohols [6]. approach the design reduction in COD, see Table 3
for typical operating parameters [7].
The estimated equipment cost of the Zimpro for a
RESULTS AND DISCUSSION 10 gpm unit was $4.3 million in 2001 [7]. The quoted
The following analysis includes a preliminary eco- price for a 5 gpm, nickel 200, 2608C oxidation sys-
nomic evaluation of the Zimpro process (WAO) and tem, was $4.0 million in 2005, excluding any state or
an in-house Fenton-based process. The study also federal taxes, import or export duties, fees, or ocean
considers the costs of exporting the mixed refinery freight [8]. The cost in 2007 should be in the vicinity
spent caustic to a full-service company for treatment. of $5.5 million for the 10 gpm system based on the
This evaluation is based upon rough-order-of-magni- Chemical Engineering Plant Cost Index. This cost
tude estimates of capital and operating costs for the includes a regenerative thermal oxidizer for VOC
first two treatment options. treatment. The cost does not include installation and

298 October 2008 Environmental Progress (Vol.27, No.3) DOI 10.1002/ep

facility costs. The delivery schedule is 12–18 months.
The spent caustic flow is based on a total flow of 10
gpm through the wet oxidation unit. Depending on
the actual composition (mostly the COD) of the spent
caustic, the flow of spent caustic that can be treated
is much less than 10 gpm. The unit may not have a
total spent caustic feed throughput of 10 gpm, if the
COD of the spent caustic is too high. The oxidation
process consumes alkalinity, and to protect the mate-
rial of construction, the effluent must remain alkaline.
Fresh caustic will have to be added, if the available
alkalinity in the spent caustic is not sufficient. In
many cases, dilution of the spent caustic waste is also
required to keep the concentration of the dissolved
salts below their solubility limit. A 10 gpm (total
inflow) WAO unit treating mixed refinery spent caus-
tic with COD of 60,000–100,000 mg/L requires the
flow of about 3 gpm of dilution water and 0.5 gpm
of fresh caustic (50% NaOH) of the total flow through
the wet oxidation unit. Dilution water should be
deionized water (boiler feed quality water) to prevent
scaling in the WAO unit. Factoring in dilution fresh
water and fresh caustic (50%), the 5000 m3 will gen-
erate about 2.7 million gallons of WAO liquid efflu-
ent. The processing duration is 185 days for all
wastes based on a 10 gpm processing rate. These
times are based on 24-h, 7-day operation and will
extend about 40%, if the operation would be 5 days
per week. These durations are within the allocated
timeframe that is set by the management.
The cost analysis presented here is based on the 10
gpm processing rate. This estimate assumes the reactor
residence time of 60 min and the material of construc-
tion to be alloy Inconel 600 [7]. The equipment cost
includes engineering and design, but does not include
the cost of installation. Adding 50% of the equipment
cost for installation raises the estimate to $8.25 million.
The facility square footage is estimated to be about
3000 sq. ft. at no cost. The annual cost for maintenance
spare parts will be 1–2% of the capital costs of the WAO
system. At least two people must be available, at the
WAO unit, 24 h per day, to operate and maintain the
unit. The estimated annual operating cost is $540,000.
This operating cost includes annual labor costs of
$240,000 for eight people at $30,000 per person and
$300,000 per year for utilities. The liquid effluent gen-
erated from the WAO process will need additional
treatment. A cost of $0.05 per pound is assumed for its
disposal, which amounts to $227,000 for 4,550,000
pounds of liquid effluent. The annual operating cost is
multiplied by the processing duration in years, and the
liquid effluent disposal cost is added to arrive at the
total operating cost. The addition of capital and operat-
ing costs provided the estimate for the total cost to dis-
pose of the waste. It is estimated to be nearly $10 mil-
lion for treating the mixed refinery caustic waste by the
WAO process.
Fenton’s Reagent (H2O2/Fe21)
The experimental results of neutralization and oxi-
dation reaction of the spent caustic are shown in Fig-
ure 2. The data are the average of three replicas. The
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
Figure 2. Average COD concentration versus time of
three identical bench-scale experiments.
data indicate that the average total COD concentra-
tion is reduced to about 1 g/L. With the addition of
H2O2, the COD that of nonsulfide compounds
(mainly, phenols and emulsified hydrocarbons) is
oxidized (ring broken), which is confirmed by the
temperature rise and the drop in pH (from 3.29 to
2.17) that can only be due to formation of low MW
acids such as oxalic acid and others. A key point that
is illustrated in this reaction is that as COD is reacted,
acids are produced. This is an important considera-
tion, as NaOH depletion can lead to acidic conditions
resulting in slower reactions and corrosion in the
reactor.
The results of the bench-scale experiments indicate
that the Fenton’s reagent process is a viable option as
a pretreatment, but there are limitations that must be
addressed. COD reduction requires the pH to be
adjusted from pH 13 to 3. However, corrosion rate
increases as pH decreases. Therefore, the reactor and
others must be made of materials that offer a high re-
sistance to strong acids. The pH must be further
adjusted back to pH 5.5–9.0, before effluent is dis-
charged to biotreatment. Hence, a caustic mixing
before discharging is required. Foam formation can
be reduced by adding H2O2 very slowly as it is
observed in the bench-scale experiments. In addition,
the proposed process design, see Figure 3, has about
3 m3 head space in the reactor with a vent to a hold-
ing tank. The overflow is recycled to the spent caus-
tic containers. The temperature in the bench-scale
experiments does not go beyond 808C, which poses
no threat or need for cooling. The process conditions
and COD removal percentage is better than the ap-
proximate values reported by common WAO proc-
esses. Iron catalyst can be recycled without affecting
treatment effectiveness.
The main reactions proceed by radical mechanisms
as follows [9]:
H2 O2 þ Feþ2 ! Feþ3 þ OH þ OH (1)
H2 O2 þ Feþ3 ! Fe2þ þ Hþ þ HO2 (2)
October 2008 299
Figure 3. Schematic of the proposed Fenton’s reagent (H2O2/Fe21) process design.
A kinetic study considering a pseudo-first-order reac-
tion rate with respect to COD was carried out.
d½COD
¼ k0 ½COD
dt
where k0 is the apparent kinetic constant that includes
the initial H2O2 and ferrous ion concentration.
k0 ¼ k½H2 O2 ½Fe2þ 
Figure 2 shows a plot of ln([COD]0/[COD]) vs. time.
As can be seen, the points lied satisfactorily around a
straight line (r2 5 0.99) with positive slope and an
intercept practically zero. The apparent kinetic con-
stant k0 is 0.031 min21. The rate constant is expected
to increase with concentrations of COD and Fe21,
but this increase is not infinite. It is highly limited by
many factors including foaming and precipitation to
form sludge [9, 10]. Precipitation greatly reduces the
concentration of Fe31, as the reaction proceeds.
Finally, The values for k and k0 are system-specific.
They differ from one waste stream to another. Bench
tests must be conducted before applying this process.
As shown in Figure 3, the heart of this process
occurs in the reactor mixer, where the spent caustic
diluted with water is added into the reactor mixer. A
pH controller is required to reduce the pH of the
alkaline solution in the tank to a pH of 3 by the use
of 50% sulfuric acid. Fenton’s reagent is then added
in the form of two separate streams; one containing
ferrous solution (as catalyst) and the second stream
containing 50% H2O2 solution. Products from the re-
actor mixer are pumped to a settling tank, where fer-
rous-containing sludge is removed and the treated
spent caustic is sent through a holding tank, where
another pH controller is utilized to raise the pH of
the treated spent caustic by mixing it with fresh caus-
tic before it is sent to the biotreatment facilities. To
300 October 2008
avoid corrosion, corrosion resistant material should
be selected for the equipments, including pumps,
pipes, and tanks. The reactor mixer should contain a
vent to allow gas emissions, extra headspace to allow
for foaming, a level controller, and a second tank to
allow for overflow and recycle of any overflow that
occurs.
The results of the bench-scale experimental work
provided information on the mass ratio required for
sufficient reduction of COD in the spent caustic.
Results of the bench test show sufficient COD reduc-
tion with mass ratios of H2O2/Fe21/COD 5 2/7/1.
Temperature of the reactor contents rises to 808C.
Foaming can be controlled by feeding H2O2 at a very
low rate (dosing pump), and by increasing the
capacity of the reactor mixer. The rate constant of the
pseudo-first-order reaction is a function of both, ini-
tial concentration of Fe21 and H2O2. At the current
conditions, we estimate a space time of 2 h. It is
rather long, because, we consider many factors that
may limit the progress of the oxidation reaction such
as excessive precipitation and sludge formation.
Using a safety factor of 1.5 and head space of 4 m3,
the estimated tank size is about 15 m3 at a total influ-
ent rate of 10 gpm (spent caustic, dilution water,
H2O2, Fe21). The Fenton reactor is epoxy cast steel-
coated to make it corrosion resistant, since it has to
handle a pH range from 13 to 2. Pumps are corrosion
resistant, made of PVC/Teflon and pipes are epoxy-
coated carbon steel. The estimated total purchased
equipment cost is $200,000. The installation and facil-
ity costs need to be integrated to this estimate, as
there are additional raw material (H2O2, H2SO4, Fe21,
etc.) and utility costs associated with this equipment,
resulting in an overall cost of about $2.7 million. The
estimated cost for treating the liquid effluent from the
process onsite, using the postoxidation treatment, is
$0.3 million. At the designed treatment flow rate, it
will take
393 days to remedy the total 5000 m3 of
spent caustic.
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
Offsite Treatment
The cost of exporting spent caustic to a major full-
service company in USA for treatment and/or reuse is
evaluated using present value techniques. The offsite
disposal cost estimate is $1.21 per gallon. The total
offsite disposal cost estimate, inclusive of shipping
and handling, is $1.6 million.
CONCLUSIONS AND RECOMMENDATIONS
The estimated total cost for onsite treating of the
mixed refinery spent caustic by the WAO process is
$10 million. Treatment of the spent caustic by Fen-
ton’s reagent oxidation is found to remove over 95%
of the initial COD, and the effluent COD can be
lower than 1 g/L under the following oxidation con-
ditions: reaction time 5 120 min, T 5 808C, Fe21 5
100 mg/L, and a stoichiometric H2O2/COD 5 2 and
ambient pressure. The conditions and COD removal
percent is better than the approximate values
reported by common WAO process. Iron catalyst can
be recycled without affecting treatment effectiveness.
The estimated capital and operating cost for onsite
treating of the spent caustic and the liquid effluent
from the Fenton’s reagent oxidation process is $2.7
million. The optimum conditions of the Fenton reac-
tion such as pH, and H2O2, Fe21, and COD ratios
need to be optimized. The cost of exporting spent
caustic to a full-service company in USA for reuse is
evaluated using present value techniques. This evalu-
ation indicates that a $1.21 per gallon nominal fee is
competitive with treatment and disposal at the indi-
vidual generation sites on a short-term basis.
The total cost of the WAO process is considerably
higher than the Fenton’s reagent process or the offsite
disposal. There are numerous uncertainties regarding
the Fenton’s process, and further optimization is
needed preferably in a pilot-scale plant. The total off-
site disposal cost estimate of $1.6 million is very
attractive and a trouble-free option. Therefore, send-
ing the spent caustic for offsite treatment is the most
cost-effective approach that is preferred by the man-
agement for the time being. The refinery is advised
to review their caustic management systems and
implement measures that maximize caustic utility,
quality, and value. Also, the search for economical
Environmental Progress (Vol.27, No.3) DOI 10.1002/ep
alternatives for onsite processing of caustic solutions
is enduring.
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