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AquaCritox ® SC: Next Generation Hydrothermal Oxidation of Spent Caustic

Technical Report · March 2020

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 AquaCritox® SC:
Next Generation Hydrothermal Oxidation
of Spent Caustic
March 2020

Sandra Kaspar John O’Regan Jeff Broderick

H+E GmbH SCFI Limited H+E GmbH
Ruppmannstr. 33b Rubicon Centre Ruppmannstr. 33b
70565 Stuttgart Bishopstown, Cork 70565 Stuttgart
Germany Ireland Germany

Abstract
AquaCritox® SC is a high temperature hydrothermal oxidation technology specifically adapted for the
treatment of spent caustics to allow disposal through a conventional wastewater treatment plant or
to the sewer. Spent caustic is a noxious and toxic waste product generated by the oil and gas
industry. The main oxidable compounds (COD) found in spent caustic include sulphides, mercaptans,
phenols, cresylic salts and naphthenic salts. In order to study the effectiveness of AquaCritox® SC
compared with conventional treatment methods, laboratory and pilot scale testing of both,
synthesised and industrial spent caustic solutions was undertaken and will be presented. COD
reduction rates in excess of 90% were achieved for almost all samples, resulting in effluent COD
concentrations of 3 mg/l and below. Both, sulphides and phenols were successfully oxidised by the
process and AquaCritox® SC treatment showed a positive effect on biodegradability.
1. Introduction
AquaCritox® is a high pressure, high temperature hydrothermal oxidation technology originally
designed to operate at supercritical water conditions which is above 221 bar and 374 °C. The design
employs a multistage tubular reactor and a novel pressure control system. Based on the demand for
an efficient and reliable solution for spent caustic treatment, the AquaCritox® SC system was
modified to achieve improved oxidation performance in the treatment of spent caustics. In order to
overcome issues with high salt content associated with spent caustic the original AquaCritox®
concept technology was modified to operate at near critical conditions but below the critical point,
and so the AquaCritox® SC process was conceived.
The AquaCritox® technology is owned by and developed by Super Critical Fluids International (SCFI)
Ltd. in a joint venture with H+E Group. With the aim of proving the feasibility and application of
AquaCritox® SC, SCFI have undertaken extensive testing, the results of which are presented in this
paper. Based on these results, a demonstration plant was commissioned and has been deployed to a
working refinery to test the technology in nearly full scale and in continuous operation. The results
from this next phase of testing will be published in the future.
1.1. Spent Caustic
In refinery, caustic solutions are used to extract acidic compounds from various hydrocarbon
streams. Once the solutions have reached a certain level, they must be replaced and become so
called “Spent Caustics” [1, 2]. Depending on the components present, there are two typical
classifications of spent caustics:
• Sulphidic Spent Caustic: This spent caustic come from processes aiming to remove H2S and
therefore mainly contains sulphides and mercaptans. Treated streams are for example light
petroleum gas streams or cracked gas from the ethylene plant [1 – 6].
• Refinery Spent Caustic: Those spent caustics are sometimes categorized as Phenolic/Cresylic
and Naphthenic Spent Caustics [3 – 5]. Source of refinery spent caustics is the mercaptan
oxidation process which is used to remove mercaptans from gasoline or kerosene/jet fuel
products. Phenol mainly origins from gasoline products, naphthenic acids are present
especially in kerosene/jet fuel cuts. Mercaptans and sulphides are also present in refinery
spent caustic [1 – 5].
In some cases, spent caustic of different types are collected in the same vessel and therefore mixed
[3, 4].
Even though spent caustics are classified as spent, they still contain high concentrations of caustic,
resulting in high pH-value [3] and depending on the outlet requirement, neutralisation may be
necessary [2]. Spent caustic COD can vary significantly from just a few grams per litre up to several
hundred grams per litre [5]. Spent caustic solutions can be very odorous, this is typically due to the
presence of sulphides, mercaptans and phenols which are most prevalent when spent caustics are
neutralized [1, 4]. Many components in spent caustic are toxic and biorefractory, especially phenols
and naphthenic acids [1, 4, 7]. Foaming can be enforced by naphthenic compounds [4].

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 2

1.2. Treatment of Spent Caustics
The properties of spent caustic solutions presents challenges in both handling and disposal. Many
strategies exist for the treatment of spent caustic solution which include [1, 2, 4 – 6, 8, 9, 10]:
Reuse of Spent Caustic: The spent caustic can be reused within or outside the refinery. Spent caustic
may replace fresh caustic streams for pH-control or may be sent to chemical recovery companies
who reclaim phenols or sulphides from the spent caustic. This strategy is not applicable for all
refineries, for example if the phenol concentration is not high enough for economic recovery.
Incineration and Drying: These strategies may be interesting for spent caustics with very high COD
(>> 50 g/l) but become uneconomic for more dilute streams. As well, dry residuals must be safely
disposed.
Neutralisation and Stripping: By adding acid, for example sulfuric acid to the spent caustic, sulphides
will be released as H2S and can be stripped out from the solutions. Organics like phenols, cresols,
mercaptans and naphthenic acid will form a separate phase if the pH is reduced which can be
removed from the spent caustic. This will significantly lower the COD. To achieve low effluent COD
values, further treatment like oxidation is still required.
Chemical Oxidation: Oxidizing agents such as hydrogen peroxide are used to oxidise the COD in the
spent caustic. This may be supported by a suitable catalyst, especially for treatment of refinery spent
caustic. Due to the high demand of chemicals in this process, this strategy is in some cases
considered as a final treatment step [8].
Biological Treatment: Spent Caustic can be added to the existing wastewater treatment plant and
therefore diluted. Due to the characteristics of Spent Caustic, this strategy can create many issues in
the wastewater treatment: Due to its high COD, the biological stage can be overloaded. Since spent
caustic often comprise toxic compounds such as phenols, spent caustic solutions may inhibit or
poison the biological process. Odour can be a result of adding sulphides-containing spent caustics to
the biological treatment plant.
Electro-oxidation: Electro-oxidation aims to destruct the COD in the spent caustic using electricity to
generate hydroxyl radicals. This technology is mainly suited for small COD load applications since the
electrical demand increases with increasing COD load [11].
Wet (Air) Oxidation: Wet oxidation is a general description of oxidation processes which take place
in the liquid phase at elevated temperatures and pressures. Wet Air Oxidation (WAO) utilises
compressed air for the oxidation of the COD in the spent caustic, next generation high efficiency wet
oxidation systems use concentrated oxygen for increased mass transfer and efficiency.
Operating temperature is critical for wet oxidation processes [4, 6, 10]. Below 150 °C, sulphides will
be oxidised and form thiosulfate and sulfate while oxidation of organics is low. With temperatures
above 200 °C, problematic compounds like phenols and naphthenic acids can be destroyed. Effluent
from high and low temperature wet oxidation may still contain COD in the range of several g/l and
further treatment such as biological treatment may be necessary. WAO can be enhanced by the use
of catalysts.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 3

2. AquaCritox® SC Technology for Spent Caustic Treatment
2.1. Process Description
The AquaCritox® SC technology is a hydrothermal oxidation process. Based on the terms that can be
often found in literature, AquaCritox® SC can be categorised as Wet Oxidation Process. Operating at
temperatures up to 300 °C AquaCritox® SC is at the cutting edge of wet oxidation technology, and
exceeds the limits of other systems currently available [9]. Employing pressures up to 165 bar
ensures the oxidation reactions take place in the liquid phase even at high temperature. The
AquaCritox® SC process uses purified oxygen as the oxidant which is directly injected at several
points along the tubular reactor. The effluent is depressurised by a pressure release system which
employs coils instead of a control valve.
2.2. Comparison with other Treatment Technologies
As with all oxidation and incineration strategies, AquaCritox® SC offers the potential to destroy
recalcitrant and problematic COD. Other strategies such as neutralisation will transfer the COD to
other phases and waste streams which need further processing (compare [4]).
In general, wet oxidation addresses waste streams that are on one hand too toxic or harmful for
biological treatment and on the other hand too dilute for incineration [9]. Compared to incineration,
wet oxidation can avoid environmental issues by dust and incomplete combustion as well as the
necessity to evaporate the water phase [12].
Chemical oxidation requires addition of chemicals [8] while electro-oxidation consumes electricity for
the treatment [11]. For wet oxidation, oxygen is consumed and the system must be heated to ensure
sufficiently high temperature in the reactor which may be aided by the exothermic reaction which
takes place within the reactor. When COD is oxidised, heat is released and therefore compensates
temperature losses. By using the hot reactor effluent for preheating the feed stream, energy is
recovered and the heating demand can be minimised. If the feed COD is sufficiently high the system
becomes autothermal and is self-sufficient in terms of heating energy [12].
2.3. Wet Oxidation Systems
Wet oxidation systems have been recognised as an efficient and practical treatment option for many
years, their use is widespread petrochemical and refinery plants worldwide. Different systems are
available on the market [13 – 16].
2.3.1. Crucial Parameters in Wet Oxidation Systems
Ellis and Lawson [6] defined four primary parameters in the design of wet air oxidation systems,
following parameters are defined for wet oxidation systems in general:
• Reactor temperature
• Reactor pressure
• Hydraulic retention time
• Oxygen concentration in gas phase (formerly: Oxygen partial pressure)
The reactor temperature is crucial for the degree of oxidation that can be achieved. As shown in
literature [4, 6], low temperatures (110 – 120 °C) are not sufficient for complete oxidation of reduced
sulphur contaminants like sulphides; sulphides and mercaptans are oxidised and form thiosulfates
and only insufficient oxidation of organic pollutants is observed. Higher temperatures (200 – 220 °C)
will result in a complete oxidation of sulphides and mercaptans, phenols will be partly oxidised. To

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 4

achieve destruction of both, phenols and naphthenic compounds, temperature must be even higher
(240-260 °C). In general, literature review shows that higher temperatures will lead to higher COD
reduction [4]. The solubility of oxygen is a function of temperature: at around 100 °C, solubility of
oxygen in water shows a minimum. Increasing temperature results in increased oxygen solubility
until at the critical point of water [4, 6, 16, 17] the solubility becomes infinite [4, 6, 16, 17].
Reactor pressure is directly related to the reactor temperature: the pressure in the reactor is set to
control the evaporation of the liquid by ensuring the system pressure is higher than the vapour
pressure at reaction temperature [6].
Increased temperature results in increased reaction kinetics and therefore allows shorter retention
times, and in general, lower operating temperatures will result in the need for longer retention times
[6, 10, 14].
The oxidation of dissolved COD requires the transfer of oxygen from the gas into the liquid phase.
Due to rapid diffusion inside the gas phase, the limiting step is the transport of the oxygen at the gas
liquid interface [12]. The concentration of oxygen in the liquid is influenced by the oxygen partial
pressure and its solubility. As previously discussed, increasing the temperature from near 100 °C up
to the critical point will result in higher solubility of oxygen.
The partial pressure of oxygen is influenced by the overall system pressure and the oxygen
concentration in the gas phase [6]. Since the system pressure is already defined as key parameter for
Wet Oxidation Design, the Parameter “oxygen partial pressure” as proposed by Ellis and Lawson [6]
can be replaced by oxygen concentration in gaseous phase.
2.3.2. Comparison of Wet Oxidation Systems with AquaCritox
Most current wet oxidation systems employ a conventional pressure vessel as the reactor. Air is
typically injected at a single point at the base of the reactor which will lead to an intense churning of
the liquid phase by the rising gas bubbles [10, 12 – 16]. Often these systems are referred to as
“bubble column reactor [10, 12].
In comparison AquaCritox® SC uses a plug flow tubular reactor arranged spirally to allow compact
arrangement. The exothermic nature of the oxidation reaction results in a rise in temperature when
oxygen is introduced and if left unchecked the temperature rise can easily exceed the reactor design
temperature. In order to limit the temperature rise, the reaction is undertaken in stages. Injection of
oxygen at the first injection point is limited and controlled to below the required stochiometric
amount, thus limiting the temperature rise to an acceptable level. The fluid is then cooled using
quench water prior to injection oxygen at the next reactor stage.
Injecting oxygen and quench water in a step wise manner along the reactor allows a high degree of
control and optimisation of the oxidation reaction which cannot be replicated in a traditional wet
oxidation system utilising a conventional / bubble column / pressure vessel reactor [18, 19]
Compared to the bubble column, back mixing in a tubular reactor is minimal. This is favourable
especially if high conversion rates shall be achieved [20, 21].
The AquaCritox® SC tubular reactor has a significantly thinner wall than a comparable system
operating with a pressure vessel. This design advantage is key to enabling the AquaCritox® SC system
to push the pressure envelope beyond that attainable by most wet oxidation systems and allows
operation at higher temperature [9], with higher oxygen partial pressure and crucially a more
complete oxidation of harmful components and COD.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 5

Regarding the shortcomings of tubular reactors compared to bubble column vessels, issues in wet air
oxidation in other applications than spent caustics are reported from plants commissioned before
2000 [12]. The operating issues comprise problematic scale up, lack of turbulence, sedimentation and
high maintenance demands which are not described in detail. It is assumed that these issues will not
apply for AquaCritox® SC due to the reactor and system design and the properties of spent caustic as
feed stock. The performance of the system will be studied during demonstration test runs with
continuous operation.
Addressing maintenance issues, AquaCritox® SC uses a valveless pressure control system. The
pressure drop is caused when the treated effluent flows through a set of capillary tubes, as well
referred to as coils. The coils are very long with small diameter, the resulting gradual pressure drop
along the length of the coil eliminates the need for conventional control valves which are prone to
erosion and cavitation associated with high pressure multi-phase flows [18, 19]. In order to maintain
constant reactor operating pressure with fixed coil dimensions additional make up water is pumped
into the system directly upstream of the coils at a controlled rate.
In comparison to other wet oxidation systems [5, 10, 13, 14] AquaCritox® SC uses pure oxygen or
oxygen with very low content of inert gases. This will result in a higher partial pressure of oxygen and
therefore in a higher oxygen concentration in the liquid [12] as the amount of inert gases in the
system is reduced or even eliminated if purified oxygen is used. Using high purity oxygen rather than
atmospheric air significantly reduces the amount of gas to be compressed [6]. When air is used, the
high volume of insoluble nitrogen (approximately 79%) results in increased vaporization of water
which reduces the temperature in the reactor and increases the heat content which leaves the
system with the gas [12]. Gas bubbles which mainly consist of nitrogen mixed with the effluent will as
well affect the performance of the heat recovery and cooling heat exchangers. In general, the
amount of off-gas is increased if air is used instead of highly pure oxygen. The main disadvantage of
using oxygen as the oxidiser is the supply; oxygen can be delivered to site as a cryogenic liquid or can
be generated in-situ which requires additional equipment and power. The benefits of oxygen and this
aspect must be compared for the individual project, depending on the conditions on site.
When compared with conventional systems the AquaCritox® SC process combining the benefits of a
plug flow reactor, the usage of pure oxygen, higher operating pressures and higher temperatures is
very promising, and allows shorter retention times and much smaller reaction volumes. As shown in
our experimental data the retention time is typically less than 20 minutes, in comparison literature
for standard wet air oxidation systems show that reaction times between 45 and 90 minutes are
typical [6, 10, 14] and can even reach 480 minutes at temperatures below 150 °C [14]. Additionally, it
is expected that the demand in oxygen will be smaller than for systems working with air or at lower
temperatures [6], mainly due to reduced off-gas production and improved oxygen transfer into the
liquid.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 6

2.4. Further Basics
2.4.1. Oxidation Reaction of Typical Spent Caustic Contaminants
The cited set of equation is presented in literature [5]. The equations for mercaptan and organic
oxidation are not balanced since the composition of the organic chain R is variable. It must be noted
that the reaction products are pH dependant, therefore the given equations are used to give a
general idea on how the oxidation reaction occurs.
Sulphide: + 2 + → +
Mercaptans + + → + +
Organics + + → + +
The organic chain R’ in the reaction products typically is acetate or oxalate.
2.4.2. Properties of Near-critical Water
At normal conditions, water is a strong polar solvent thus a very good solvent for inorganic salts. The
polarity is primarily attributed to the dielectric constant which in the case of water is very sensitive to
temperature and decreases as temperature increases. The dielectric constant is approximately 90 at
0 °C and at the critical temperature of 374 °C decreases to almost 0, the dielectric constant of water
at about 300 °C is similar to ethanol at normal conditions and at supercritical temperature similar to
n-heptane at normal conditions. Thus, the solubility of inorganic salts decreases as temperature rises
and precipitation of inorganic salts may occur at near critical temperature [22].
Studies about behaviour of salts in near and supercritical water showed that there are two main
types of salts. Sodium chloride is a type I salt that has a high solubility in near and even supercritical
water and will form a brine. Opposed to that, sodium sulfate or sodium carbonate are type II salts
which will tend to precipitate and directly stick to the reactor walls. More detailed description can be
found in the review by Voisin et al. [22]. In practice precipitation of salts is a complex problem and
the high content of inorganic salts present in spent caustic, which comprise amongst others sodium
sulphate or sodium carbonate, treating spent caustic at supercritical conditions would result in
severe blockage of the system. Hence, AquaCritox® SC applies subcritical conditions.
2.4.3. Corrosion Resistance
Due to the harsh conditions in wet oxidation processes, the selection of material for reactor
construction is crucial [6]. SCFI in conjunction with University College Dublin, Ireland performed
extensive corrosion testing and material evaluation to determine the optimum materials of
construction. Ultimately Alloy 600, a high nickel alloy, was chosen as the material of construction for
all hot wetted parts for spent caustic applications. Alloy 600 offers exceptional corrosion resistance
under alkaline processing conditions. In general, corrosion will be most likely to occur at lower pH
[6]. Therefore, the pH in the system is a crucial parameter to avoid corrosion.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 7

3. Experimental Setup
3.1. Plant
3.1.1. Laboratory Scale Plant
The AquaCritox® Hydrothermal Laboratory Test Rig is a simple format test rig, which allows the
adjustment many variables including pressure, temperature, residence time and oxygen addition to
achieve varying levels of oxidation.
The system consists of a feed tank connected to a high-pressure pump, feeding a ¼ inch SWG metal
tube, which flows to the pressure reactor. The heated vertical 1-inch Sch40 reactor, constructed of
625 Alloy, is where the feed will mix with oxygen present in the reactor. This process initiates the
oxidation reaction.
Heating of the reactor is achieved using heater bands attached to the reactor tube. Pulse-width
modulation is used, i.e. turning on and off a relay using an appropriate frequency.
The residence time in the tubular reactor can be varied depending on the pressure, temperature, and
flow rate. The oxygen flow, at 250 bar of pressure, is controlled separately.
The liquid stream, upon exiting the reactor is cooled by passing the stream through two sets of ¼
inch coiled SWG tubing. The first set of coils is exposed to air only, with the second set of cooler coils
being submerged in water to provide the desired cooling.
After exiting the cooler, the now cool (<50 °C) effluent stream passes through a back-pressure
regulator where the pressure of the stream is reduced from the set system pressure back down to
atmospheric pressure. The multiphase stream is then separated in the gas/liquid separation vessel
and finally the liquid effluent is collected at the end of the process.
3.1.2. Pilot Scale Plant
The AquaCritox® pilot plant can process 250 kg/h as nominal throughput and was originally designed
for supercritical water oxidation; the system has now been adapted to process samples at subcritical
conditions. Due to constraints associated with system set-up, it is not possible to operate with
complete flexibility of operating pressure, and all plant tests were performed at 190 bar or higher.
The sample is filled into a stirred feed tank. From there, a high-pressure pump will bring the feed up
to the desired pressure level. The feed then enters a heat exchanger where it is preheated by the
reactor effluent for heat recovery. In the next step, the feed is further heated by a heater if necessary
and then enters the reactor.
Oxygen can be introduced to the reactor at two different positions, and oxidation takes place in two
stages. Before the second oxygen injection point, quench water can be added to the system to limit
the temperature rise due to exothermal reaction. The oxygen supply is realised by using liquid
oxygen which is vaporised before being injected into the reactor.
Effluent exiting the reactor is used to preheat the feed. The final effluent temperature is achieved in
a following cooler. The pilot plant is equipped with the AquaCritox® valveless pressure relief system
using coils and choke water to control the pressure drop in the system. The last process step is the
gas liquid separator.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 8

3.1.3. Demonstration Unit
The Demonstration Unit is especially designed for the treatment of spent caustic. The unit consists
one 40ft and two 20ft standard shipping containers and is therefore transportable and easy to install
on site, requiring only mains water and electrical hook-up. The process is shown in Figure 3-1.
The system can treat 80 l/h of spent caustic with up to 50 g/l COD concentration. The spent caustic
feed as well as water required for the process are stored in a separate tank room. From there, it is
transported to the reactor unit where a high-pressure pump generates the pressure required for the
process. Two heat exchangers are installed to heat the feed by recovering heat taken from hot
effluent downstream of the tubular reactor. Additional heating, for operation with low COD and at
start-up, is provided by an electrical heater, this eliminates the necessity to provide steam to the
unit.
The reactor is double insulated to maximise energy retention and recovery. Oxygen can be
introduced incrementally at 4 separate points along the length of the reactor whilst there are 2
different injection points for quench water. Sensors provide a full profile of the temperature along
the entire length of the tubular reactor.
After leaving the reactor, the effluent is cooled to 70 °C by the air cooler before entering the
valveless pressure control system consisting of 4 sections of coiled tubes. To achieve the required
flow and pressure profile, the arrangement of these coils can be varied and in front of the coils,
choke water is added. By adjusting the length of the flow path and the volume flow or more precisely
the velocity through the coils, the pressure drop in the system is adjusted.
The treated effluent and the off gas which mainly consists of surplus oxygen are separated in the gas
liquid separator. The surplus oxygen is monitored and oxygen supply to the plant is continuously
adjusted to achieve minimal oxygen off gas.
The oxygen required by the process is produced in a separate unit which employs pressure swing
adsorption. Almost pure oxygen and nitrogen for tank blanketing and off gas measurement are
produced simultaneously. Compressed air is also produced in this unit, therefore no utilities (except
from the mains water and electricity) are required and the plant can operate independently from
most other site operations with minimal site installation requirements.
The plant is fully automated and is operated from a control room integrated into one of the supplied
containers. All system parameters therefore are continuously monitored and logged. To ensure safe
operation at any time, effective safety procedures have been implemented and tested.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 9

Figure 3-1: Simplified process flow scheme of the AquaCritox® SC demonstration unit

3.2. Spent Caustic Solutions

3.2.1. Synthetic Spent Caustics
Different synthetic solutions were prepared to study the effect of AquaCritox® SC on typical
compounds in spent caustic solutions. To create the synthetic solutions, following chemicals were
used:
Component in Spent Caustic Product used Manufacturer
Sodium hydroxide Sodium hydroxide prill material Solvay
Sulphide Sodium sulphide Guangxin Chemical
Phenols Cresol liquor Solvechem
Mercaptans Mercaptans in ethanol solution Ocon Chemicals
Naphthenates Crude sodium naphthenate solution Parchem

3.2.2. Real Spent Caustics

The performance of AquaCritox® SC for various spent caustics from different refineries was studied.
Original samples were used for those trials.
3.3. Measurements
Chemical oxygen demand (COD) was measured according to Standard Methods for the Examination
of Water and Wastewater, 21th Edition, Section 5220D, with the dichromate method and
photometric measurement. For determining the biological oxygen demand (BOD) the procedure
5210 B from above mentioned standard methods was used. This employs and incubation period of 5
days. Total organic carbon (TOC) was measured by applying procedure 5310 C of the standard
methods.
For the measurement of sulphide, a cuvette test procedure adapted from standard method 4500-S2-
D was used. Sulphate was measured applying the EPA Method 9038. Mercaptans were determined
with method ASTM D3227 – 16. Phenols were measured using EPA method 420.1: Phenolics and free
caustic was detected with method ASTM E291-18.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 10

3.4. Calculations
The retention time describes the time taken by the feed to pass through the reactor. The length of
the reactor is taken as the distance between the first injection point of oxygen and the final injection
point for choke water. To determine the retention time, the volume of one reactor part is divided by
the flow rate in that reactor part. Since the flow varies due to the injection of quench water, each
reactor part is calculated separately and the time is added in the end to find the retention time.
When calculating COD removal rates and effluent concentrations, the volume of water added to the
process must be considered. During processing water is added to the system as quench water and
upstream of the coils for pressure release. Therefore, the effluent gets diluted.

, ∗
Effluent concentration without dilution: =

, ∗
Removal rate R without dilution: = 1− =1−
∗

With
concentration in the effluent without dilution

, measured concentration in the effluent

feed concentration

feed volume flow

effluent volume flow, including dilution water

The oxygen supply is given as percent of the oxygen needed theoretically to destroy the COD
completely. It is determined by the load of COD entering the system.
!"
Oxygen supply Os: =
#!$, ∗

With
%& oxygen mass flow

'&(, feed COD concentration

feed volume flow

To evaluate the biodegradability of a solution, the ratio of BOD and COD was used. If the ratio is low,
e.g. lower than 0.3, the solution is categorised as not or hardly biodegradable. Ratios above 0.5
indicate good to very good biodegradability.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 11

4. Results and Discussion
4.1. Trials with Synthetic Solutions
Three synthetic solutions were prepared for evaluating the feasibility of spent caustic treatment with
AquaCritox. The composition of the solutions is given in the following table.
Sulphide Mercaptans Phenol Naphthenate
Solution pH COD [mg/l]
[mg/l] [mg/l] [mg/l] [mg/l]
#1 13,8 50 000 22 000 0 1 400 0
#2 13,8 42 000 22 000 230 1 500 0
#3 13,8 26 000 0 0 0 present

The solutions were treated with the laboratory test rig operating at 290 °C, 160 bar and 130% of the
stochiometric oxygen demand. The retention time was varied between 30 and 16 minutes the
following results were obtained:

• Greater than 90% COD destruction was achieved for all solutions with greater than 98% for
solution #1 and greater than 96% for solution #2.
• Sulphide, mercaptans and phenols were destroyed. In the effluent, the concentrations of
these contaminants were below the detection limit of 1.0 mg/l for sulphide and 2.0 mg/l for
mercaptans and phenols.
• For the mixture with crude sodium naphthenate solution with sodium hydroxide, COD
reduction of more than 90% were achieved.
• The ratio of BOD to COD was raised from nearly 0 (not biodegradable) to more than 0.5 for
all solutions. Therefore, biodegradability can be significantly increased.
• Retention time had no significant impact on the performance in the studied range of 30 and
16 minutes.
The synthetic solutions were then used in the next step to test the performance of the plant when
the oxygen supply was lowered to 120% of theoretical demand and retention time was set to 12
minutes. Pressure was 190 bar. With these adaptions, the same results as obtained from the
laboratory test rig were found: COD reduction was above 90%, biodegradability was increased and
sulphides, mercaptans and phenols were destroyed.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 12

4.2. Trials with Real Spent Caustic
To further study the effects of temperature and retention time on the destruction of COD, real spent
caustic was treated with the pilot plant. Initially diluted spent caustic with 16 g/l COD was used, this
was then followed by undiluted spent caustic with 32 g/l COD.
The results for the diluted spent caustic are shown in the table below:

Retention Time (Minutes) Temperature (°C) COD Reduction (%)

11 240 84
16 245 88
11 285 88
14 285 90

The results show that at lower temperatures, retention time affects the achievable COD reduction.
Increasing temperature will lead to increased COD reduction.
The undiluted spent caustic was treated at around 300 °C. At this point, variation of retention time
from 10 to 15 minutes did not lead to higher COD reduction which stabilised at around 94 %.
The results show that working at elevated temperatures (above 280 °C) offers the possibility to
shorten the retention times down to 10 – 15 minutes while simultaneously achieving higher COD
destruction rates.
4.3. Trials with Various Spent Caustic Solutions
Based on the results obtained with the preceding trials, different samples of spent caustic were
treated with both, the laboratory test rig and the plant. The samples were taken from different
refineries and therefore vary in their composition. The operation conditions are given in the
following table.

Temperature 290 – 300 °C

Pressure 160 – 190 bar
Oxygen Supply 120 – 130 %
Retention Time 12 – 15 minutes
COD 10 – 54 g/l

The results obtained in the test runs are given in the diagrams below.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 13

Figure 4-1: COD concentration in feed and effluent for various spent caustic samples

Figure 4-2: COD reduction for various spent caustic samples

In summary, the different samples of spent caustic were treated successfully with the AquaCritox® SC
technology. The COD in the effluent was in all cases 3 g/l or less, with an average below 2 g/l. The
reduction rate was clearly above 90 % except for one sample (sample ID 1). The sample ID 1 has the
lowest COD in this test series and the effluent COD was in the same range as for the other samples
tested.
The phenol concentration in the effluent of the AquaCritox® SC system was below 2 mg/l for the
streams 5,6,7,8,10,12 and 13. It was 2 mg/l for stream 1 and 9, 3 mg/l for stream 4 and 6 mg/l for
stream 2. It must be pointed out that the concentration of phenol in the feed stream 2 was very high
(1730 mg/l). No data is available for the streams 3 and 11.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 14

For the streams 2,4-10 and 12, mercaptans were measured in the effluent. It was shown that
mercaptans always were below 3 mg/l in the effluent and even below the detection limit for the
streams 4-9 and 12.
BOD was measured for several streams in the effluent. The BOD:COD ratios vary between 0.33 and
0.86, therefore biodegradability of the effluent is assumed to be good or even very good which
makes the effluent amendable for conventional biological treatment.
Combining all findings, following conclusions can be taken from the test runs:
• AquaCritox® SC is suitable for the treatment of different types of spent caustic.
• High COD reduction rates are achieved for spent caustics with both low and high COD
concentrations.
• In all cases, phenols that are known to be hazardous to biological treatment are been
reduced to near zero levels.
• Biodegradability is significantly improved; therefore it is assumed that compounds that are
inhibitory or harmful to biological processes were successfully destroyed.
4.4. Comparison with other Wet Oxidation Processes
The results obtained from the various test runs with the AquaCritox® SC will be compared to
information published in literature for other wet oxidation processes. To ensure meaningful
comparison we will only consider data where the operating temperature exceeds 250 °C.
The publications by Kumfer, Felch and Maugans [4], Huaman, Villar, Felch, Maugans and Olsen [5]
and Carlos and Maugans [10] present their results for both, small and full-scale testing of wet air
oxidation systems. It should be noted that with the exception of one test run by Kumfer et al. all of
the inlet COD concentrations were greater than 60 g/l and COD reduction rates between 72% and
90% were achieved, resulting in effluent concentrations between 7 and 15 g/l. In comparison,
AquaCritox® SC achieved effluent concentrations below 3 g/l for all tested samples and COD
reduction for most cases well above 90%. This indicated that AquaCritox® SC achieved a more
complete oxidation than the wet air oxidation systems.
For all reported cases, the sulphide oxidation is very far reaching, resulting in very low effluent
concentrations. Phenol concentration was significantly reduced by hydrothermal oxidation as well.
This is true for both, wet air oxidation systems and AquaCritox® SC.
Kumfer, Felch and Maugans [4] studied the effect of wet air oxidation on biodegradability and found
that wet air oxidation helps to improve the biodegradability of spent caustic. This matches very well
with the findings from AquaCritox® SC test runs which also proved a significant increase in the
BOD:COD ratio.
One important aspect that should be pointed out is the retention time. From the presented papers,
only Carlos and Maugans [10] mention the retention time for their process. With a retention time of
one hour Carlos and Maugans [10] achieve a COD reduction of 79.1% whereas AquaCritox® SC
achieves 79% reduction with a retention time of only 12 minutes, even higher reduction rates were
possible within 15 minutes for most of the tested samples. This already indicates that the
AquaCritox® SC offers the possibility to significantly reduce residence time and therefore reactor
volume compared to existing systems.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 15

4.5. Further Aspects
The oxidation reactions outlined in section 2.4.1 [5, 6] consume sodium hydroxide, during testing we
noted a decrease in pH and free caustic as would be expected. This is a very important aspect since a
decrease in pH will increase the risk of corrosion in the system. Therefore, as proposed in literature
[6], the pH must be prevented of becoming acidic by allowing sufficient hydroxide in the feed
solution.
Spent caustic containing naphthenate are reported to have a high foaming tendency [4], this
property complicates both handling and processing of these solutions. Experimental results from
naphthenate containing solutions confirmed that the feed solution to the AquaCritox® SC system did
indeed have a high foaming tendency whereas the effluent stream showed little or no foaming.
Another aspect is the generation of sulphate which originates from the oxidation of sulphide and
sulphur-containing contaminants. Sulphate was measured in the feed and the effluent of the
AquaCritox® SC system for different types of spent caustic. As would be expected the sulphate
concentration in the effluent was always higher than in the feed.
To test the effect of the sulphate generation, samples of spent caustic were processed at increasing
temperature. Once the temperature reached 329 °C, a blockage occurred within the reactor system
which then cleared rapidly once the temperature was lowered to 320 °C. This observation matches
well with information found in literature [22], where Na2SO4 is described as “sticky salt” which tends
to rapidly plug the process once precipitation occurs. Solubility of Na2SO4 rapidly decreases when the
temperatures approach the supercritical point. To avoid plugging of the system, a maximum
allowable temperature must be defined for the solution to be treated.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 16

5. Conclusions
The numerous tests with a wide range of spent caustics showed that the AquaCritox® SC technology
is capable of processing a wide range of effluent compositions whilst achieving very high destruction
rates for COD and harmful components like phenols and odour precursors like sulphides.
Additionally, biodegradability was increased significantly which makes further treatment by
biological systems feasible.
6. Next Steps
The data presented in this paper are limited by the spent caustic samples which could be processed
at our laboratory in Cork, Ireland. To test the plant in continuous operation, the demonstration unit
is currently deployed at a site where spent caustic is treated on an industrial scale.
In the next phase, the spent caustic on that site will be extensively tested. While doing so, many
parameters will be monitored and used for substantial evaluation of the capabilities, feasibility and
benefits of the technology and establishing a reliable base for full-scale applications.
It is expected that AquaCritox® SC will achieve significant reduction in COD, eliminate all sulphide and
all inhibitory compounds from the spent caustic solution rendering it suitable for neutralisation and
further treatment by biological processes.
The results from the demonstration test run will be published separately.
7. About Us
The AquaCritox® SC process is presented by the H+E Group in conjunction with Super Critical Fluids
International (SCFI) Ltd.
SCFI Ltd. now part of the H+E Group is an Irish company specialising in solving disposal problems
faced by wet waste generators and processors. Their proprietary technology AquaCritox® undergoes
continuing optimisation and improvement and has matured over several years. The company began
in early 2011 to examine the existing technologies deployed within the oil and gas market to deal
with spent caustics and adapted a variation of the AquaCritox® technology to achieved improve
oxidation performance for almost all types of spent caustic.
The H+E Group, headquartered in Stuttgart, has already implemented in excess of 30,000 water
treatment and recovery plants for the Oil and Gas, industrial and wastewater sectors. This makes the
company one of the world’s leading plant manufacturers.
In 2017, SCFI Ltd. and the H+E Group joined forces n to further develop the AquaCritox® SC
technology for spent caustic by designing and constructing a transportable Demonstration Unit which
can be deployed on clients site to prove the performance of the technology. After extensive testing
and design optimisation, the Demonstration Plant is now approved and operational.

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 17

8. Sources
[1] IPIECA: Petroleum refining water/wastewater use and management. IPICEA Operations Best
Practice Series, 2010
[2] Barthe, P.; Chaugny, M.; Roudier, S.; Delgado Sancho, L.: Best Available Techniques (BAT)
Reference Document for the Refining of Mineral Oil and Gas. Industrial Emissions Directive
2010/75/EU (Integrated Pollution Prevention and Control, JRC Science and Policy Reports,
2015
[3] Suarez, F.J.: Pluses and minuses of caustic treating. Hydrocarbon Processing, 1996, 75 (10),
117-123
[4] Kumfer, B.; Felch, C.; Maugans, C.: Wet Air Oxidation Treatment of Spent Caustic in
Petroleum Refineries. Presented at the National Petroleum Refiner’s Association Conference
Phoenix, AZ; March 21-23, 2010
[5] Huaman, F.; Villar, N.; Felch, C.; Maugans, C.; Olsen, S.: Disposal of Spent Caustic at the
Repsol YPF Refinery in La Pampilla, Peru. Presented at the Environmental Conference Austin,
TX; September 24-25, 2007
[6] Ellis, C.E.; Lawson, R.J.: Wet Air Oxidation of Ethylene Plant Spent Caustic. Prepared for the
American Institute of Chemical Engineers Sixth Annual Ethylene Producers Conference, 1994
[7] Aljuboury, D.A.D.A.; Palaniandy, P.; Abdul Aziz, H.B., Feroz, S.: Treatment of petroleum
wastewater by conventional and new technologies - A review. Global NEST Journal, 2017,
19(3), 439-452
[8] McGehee, J.F.: MERICON™: A Practical Low Cost Solution to Spent Caustic Treating, 2013,
available on http://www.merichem.com/MERICON-Low-Cost-Spent-Caustic-Treating-
Solution (11.02.2020)
[9] Nielsen, R. P.: Near- and Supercritical Water. In E. G. Søgaard (Ed.), Chemistry of Advanced
Environmental Purification Processes of Water: Fundamentals and Applications, 2014, 171-
197
[10] Carlos, T.; Maugans, C.: Wet Air Oxidation of Refinery Spent Caustic: A Refinery Case Study.
Presented at NPRA Conference San Antonio, TX; September 2000
[11] Siemens Energy Inc.: A Lower-cost Approach to Treating Low-volume Refinery Spent Caustic
Streams. White Paper Zimpro® Electro-oxidation, 2016
[12] Debellefontaine, H; Foussard, J.N.: Wet air oxidation for the treatment of industrial wastes.
Chemical aspects, reactor design and industrial applications in Europe. Waste Management,
2000, 20, 15-25
[13] Siemens Water Solutions: Zimpro® Wet Air Oxidation Systems. 2013 available on
https://new.siemens.com/global/en/markets/oil-gas/water-solutions.html (visited at
12.02.2020)
[14] The Linde Group: Wet Air Oxidation.
[15] Leonhäuser, J. et al: Sulfidische Ablaugen durch Niederdruck-Nassoxidation behandeln.
Chemie Technik, April 2012, available at https://www.chemietechnik.de/sulfidische-
ablaugen-durch-niederdruck-nassoxidation-behandeln/ (visited at 12.02.2020)
[16] 3V Green Eagle: TOP® - Wet Air Oxidation for Spent Caustic.
https://www.3vgreeneagle.com/en/technologies/top-wet-air-oxidation-for-spent-caustic
(visited at 12.02.2020)

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 18

 [17] Pray, H.A.; Schweickert, C.E.; Minnich, B.H.: The Solubility of Hydrogen, Oxygen, Nitrogen,
and Helium in Water at Elevated Temperatures. Chemistry – General, Batelle Memorial
Institute, Report No. BMI-T-25, 1952
[18] Vadillo, V.; Sanchez-Oneto, J.; Portela, J.R.; Martinez de la Ossa, E.J.: Problems in
Supercritical Water Oxidation Process and proposed Solutions. Ind. Eng. Chem. Res., 52 (23),
7617-7629, 2013
[19] Gidner, A.V.; Stenmark, L.B.; Carlsson, K.M.: Treatment of Different Wastes by Supercritical
Water Oxidation. Presented at the Twentieth IT3 Conference, Philadelphia; May 2001
[20] Winterbottom, J.M.; King, M.B.: Reactor Design for Chemical Engineers. Cheltenham:
Stanley Thornes (Publishers) Ltd., 1999
[21] Hagen, J.: Chemiereaktoren. Grundlagen, Auslegung und Simulation. Weinheim: WILEY-VCH
Verlag, 2017
[22] Voisin, T.; Erriguible, A; Ballenghien, D.; Mateos, D. Kunegel, A. et al.: Solubility of inorganic
salts in sub- and supercritical hydrothermal environment: Application to SCWO processes.
Journal of Supercritical Fluids, 120, 18-31, 2017

AquaCritox® SC: Hydrothermal Oxidation of Spent Caustic, 2020 19

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