UOP MEROX PROCESS

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 11.3
UOP MEROX PROCESS
G. A. Dziabis
UOP LLC
Des Plaines, Illinois

INTRODUCTION

The UOP* Merox* process is an efficient and economical catalytic process developed for
the chemical treatment of petroleum fractions to remove sulfur present as mercaptans
(Merox extraction) or to directly convert mercaptan sulfur to less-objectionable disulfides
(Merox sweetening). This process is used for liquid-phase treating of liquefied petroleum
gases (LPG), natural-gas liquids (NGL), naphthas, gasolines, kerosenes, jet fuels, and heat-
ing oils. It also can be used to sweeten natural gas, refinery gas, and synthetic gas in con-
junction with conventional pretreatment and posttreatment processes.
Merox treatment can, in general, be used in the following ways:

 To improve lead susceptibility of light gasolines (extraction)

 To improve the response of gasoline stocks to oxidation inhibitors added to prevent
gum formation during storage (extraction and sweetening)
 To improve odor on all stocks (extraction or sweetening or both)
 To reduce the mercaptan content to meet product specifications requiring a negative
doctor test or low mercaptan content (sweetening)
 To reduce the sulfur content of LPG and light naphtha products to meet specifications
(extraction)
 To reduce the sulfur content of coker or fluid catalytic cracking (FCC) C -C olefins
3 4

to save on acid consumption in alkylation operations using these materials as feed- stocks
or to meet the low-sulfur requirements of sensitive catalysts used in various chemical
synthesis processes (extraction)

El proceso de UOP * Merox * es un proceso catalítico eficiente y económico desarrollado

para el tratamiento químico de las fracciones del petróleo para eliminar el azufre presente
como mercaptanos (extracción de Merox) o directamente convertir sulfuro de mercaptano
para menos objetable disulfuros (endulzamiento Merox). Este proceso se utiliza para
tratamiento de gases licuados de petróleo (GLP), fase líquida calor-ing aceites, NAFTAS,
gasolinas, kerosenes, combustibles de jet y líquidos de gas natural (NGL). También puede
ser utilizado para endulzar el gas natural, gas de refinería y gas sintético en unión con los
procesos convencionales de pretratamiento y post-tratamiento. Tratamiento merox, en
 UOP MEROX PROCESS
general, utilizable en los siguientes aspectos:

- A mejorar la sensibilidad de plomo de gasolinas ligeras (extracción)-

- para mejorar la respuesta de las existencias de gasolina a los inhibidores de
oxidación añadido para evitar la formación de la goma de mascar durante el
almacenamiento (extracción y específico del producto edulcorante)
- Para mejorar el olor en todas las poblaciones (extracción o endulzamiento o
ambos) –
- para reducir el contenido de mercaptano –
- para cumplir con las especificaciones del producto que requiere un examen médico
negativo o mercaptano bajo contenido (edulcorantes) –
- para reducir el contenido de azufre de LPG y luz nafta los productos a cumplir con
las especificaciones (extracción)-
- para reducir el contenido de azufre de coker o fluido catalítico craqueo (FCC) C3-
C4 olefins para ahorrar en el consumo de ácido en las operaciones de alquilación
usando estos materiales como alimento-acción o para cumplir los requisitos de
bajo azufre de sensible catalizadores utilizados en procesos de síntesis química
(extracción)

PROCESS DESCRIPTION

The UOP Merox process accomplishes mercaptan extraction and mercaptan conversion at
normal refinery rundown temperatures and pressures. Depending on the application,
extraction and sweetening can be used either singly or in combination. The process is based
on the ability of an organometallic catalyst to promote the oxidation of mercap- tans to
disulfides in an alkaline environment by using air as the source of oxygen. For light
hydrocarbons, operating pressure is controlled slightly above the bubble point to ensure
liquid-phase operation; for heavier stocks, operating pressure is normally set to keep air
dissolved in the reaction section. Gases are usually treated at their prevailing system
pressures.

El proceso de Merox UOP logra mercaptano extracción y conversión de mercaptano

en refinería normal Resumen temperaturas y presiones. Dependiendo de la
aplicación, extracción y edulcorantes pueden utilizarse solos o en combinación. El
proceso se basa en la capacidad de un catalizador organometálicos para promover la
oxidación de mercap-broncea a disulfuros en un ambiente alcalino usando aire como
fuente de oxígeno. De hidrocarburos ligeros, presión de operación se controla un
poco por encima del punto de burbuja para asegurar la operación de la fase líquida;
para acciones más pesadas, presión de servicio normalmente se establece en
mantener el aire disuelto en la sección de reacción. Gases son tratados generalmente
en sus presiones del sistema imperante.

Merox Extraction

Low-molecular-weight mercaptans are soluble in caustic soda solution. Therefore, when

treating gases, LPG, or light-gasoline fractions, the Merox process can be used to extract
mercaptans, thus reducing the sulfur content of the treated product. In the extraction unit
(Fig. 11.3.1), the sulfur reduction attainable is directly related to the extractable-mercap-
tan content of the fresh feed.
In mercaptan-extraction units, fresh feed is charged to an extraction column, where
mercaptans are extracted by a countercurrent caustic stream. The treated product passes
overhead to storage or downstream processing.
The mercaptan-rich caustic solution containing Merox catalyst flows from the bottom
 UOP MEROX PROCESS
of the extraction column to the regeneration section through a steam heater, which is used
to maintain a suitable temperature in the oxidizer. Air is injected into this stream, and the
mixture flows upward through the oxidizer, where the caustic is regenerated by converting
mercaptans to disulfides. The oxidizer effluent flows into the disulfide separator, where
spent air, disulfide oil, and the regenerated caustic solution are separated. Spent air is vent-
ed to a safe place, and disulfide oil is decanted and sent to appropriate disposal. For exam-
ple, the disulfide oil can be injected into the charge to a hydrotreating unit or sold as a
specialty product. The regenerated-caustic stream is returned to the extraction column. A
small amount of Merox catalyst is added periodically to maintain the required activity.

FIGURE 11.3.1 Merox mercaptan-extraction unit.

Mercaptanos de bajo peso molecular son solubles en la solución de soda cáustica.

Por lo tanto, para el tratamiento de gases, LPG o fracciones de gasolina liviana, el
proceso de Merox puede utilizarse para extraer mercaptanos, reduciendo así el
contenido de azufre del producto tratado. En la unidad de extracción (Fig. 11.3.1), la
reducción de azufre alcanzable está directamente relacionada con el contenido de
extraíbles-mercap-tan de la alimentación fresca.
En la unidad extracción de mercaptano unidades, la alimentación es cargada en la
columna de extracción, donde mercaptanos son extraídos por un flujo de Soda
cáustico a contracorriente. El producto tratado pasa al almacenamiento o
procesamiento aguas abajo. La solución cáustica de mercaptano rico que contiene
catalizador Merox fluye desde la parte inferior de la columna de extracción a la
sección de regeneración a través de un calentador de vapor, que se utiliza para
mantener una temperatura adecuada en el oxidante. Se inyecta aire en esta corriente,
y la mezcla fluye hacia arriba a través de oxidazer, donde se regenera la soda cáustica
al convertir los mercaptanos en disulfuros.
El efluente del oxidazer fluye al separador de disulfuro, donde se separan el aire
gastado, aceite de disulfuro y la solución cáustica regenerada. Aire gastado es
venteado a un lugar seguro, y aceite de disulfuro es decantado y enviado a disposición
apropiada. Por ejemplo, el aceite de disulfuro puede inyectar como carga de la unidad
de hidrotratamiento o vendido como un producto específico. La corriente cáustica
regenerada es devuelta a la columna de extracción. Una pequeña cantidad de
catalizador Merox se añade periódicamente para mantener la actividad requerida.
 UOP MEROX PROCESS

UOP MEROX PROCESS 11.33

Merox Sweetening

In sweetening units, the mercaptans are converted directly to disulfides, which remain in
the product; the total sulfur content of the treated stock is not reduced.
Merox sweetening can be accomplished in four ways:
 Fixed-bed processing with intermittent circulation of caustic solution (Fig. 11.3.2)
 Minimum-alkali fixed-bed (Minalk*) processing, which uses small amounts of caus-
tic solution injected continuously (Fig. 11.3.3)
 Caustic-Free Merox* treatment for gasoline (Fig. 11.3.4) and kerosene (Fig. 11.3.5)
 Liquid-liquid sweetening (Fig. 11.3.6)

Fixed-Bed Sweetening (Conventional). Fixed-bed sweetening (Fig. 11.3.2) is normally

employed for virgin or thermally cracked chargestocks having endpoints above about
120°C (248°F). The higher-molecular-weight and more branched mercaptan types
associated with these higher-endpoint feedstocks are only slightly soluble in caustic
solution and are more difficult to sweeten. The use of a fixed-bed reactor facilitates the
conversion of these types of mercaptans to disulfides.
Fixed-bed sweetening uses a reactor that contains a bed of specially selected activated
charcoal impregnated with nondispersible Merox catalyst and wetted with caustic solution.
Air is injected into the feed hydrocarbon steam ahead of the reactor, and in passing through
the catalyst bed, the mercaptans in the feed are oxidized to disulfides. The reactor is fol-
lowed by a settler for separation of caustic and treated hydrocarbon. The settler also serves
as a caustic reservoir. Separated caustic is circulated intermittently to keep the catalyst bed
wet. The frequency of caustic circulation over the bed depends on the difficulty of the feed-
stock being treated and the activity of the catalyst.
An important application of this fixed-bed Merox sweetening is the production of jet fuels
and kerosenes. As a result of the development of the Merox fixed-bed system, jet fuels and
kerosenes (also diesel and heating oils) can be sweetened at costs that are incomparably low-
er than those of the simplest hydrotreater. The same basic process flow just described is used.
However, because of other particular jet-fuel quality requirements, some pretreatment and
posttreatment are needed whenever any chemical sweetening process is used.

Fixed-Bed Sweetening (Minalk). This Merox sweetening version is applied to feedstocks

that are relatively easy to sweeten, such as catalytically cracked naphthas and light virgin
naphthas. This sweetening design achieves the same high efficiency as

*Trademark and/or service mark of UOP.

FIGURE 11.3.2 Fixed-bed Merox sweetening unit.

 UOP MEROX PROCESS

11.34 SULFUR COMPOUND EXTRACTION AND SWEETENING

conventional fixed-bed sweetening but with less equipment and lower capital and operating
costs.

The UOP Merox Minalk process (Fig. 11.3.3) relies on a small, controlled, continuous
injection of an appropriately weak alkali solution rather than the gross, intermittent alkali
saturation of the catalyst bed as in conventional fixed-bed Merox sweetening. This small
injection of alkali provides the needed alkalinity so that mercaptans are oxidized to disul-
fides and do not enter into peroxidation reaction, which would result if the alkalinity were
insufficient.

Caustic-Free Merox. A different version of the Merox family is the Caustic-Free Merox
process for sweetening gasoline and kerosene (Figs. 11.3.4 and 11.3.5). This technology
development uses the same basic principles of sweetening in which the mercaptans are
catalytically converted to disulfides, which remain in the treated hydrocarbon product.
The Caustic-Free Merox catalyst system consists of preimpregnated fixed-bed cata-
lysts, Merox No. 21* catalyst for gasoline and Merox No. 31* catalyst for kerosene, and a
liquid activator, Merox CF.* This system provides an active, selective, and stable sweet-
ening environment in the reactor. The high activity allows the use of a weak base, ammo-
nia, to provide the needed reaction alkalinity. No caustic (NaOH) is required, and fresh-
caustic costs and the costs for handling and disposing of spent caustic are thus elim- inated.
The actual design of the Caustic-Free Merox unit depends on whether it is used on
gasoline or kerosene. The reactor section is similar to the previously mentioned fixed-bed
systems, conventional and Minalk, except for the substitution of a different catalyst, the
addition of facilities for continuous injection of the Merox CF activator, and replacement
of the caustic injection facilities with ammonia injection facilities, anhydrous or aqueous.
For kerosene or jet fuel production, the downstream water-wash system is modified to
improve efficiency and to ensure that no ammonia remains in the finished product. Other
posttreatment facilities for jet fuel production remain unchanged.

Liquid-Liquid Sweetening. The liquid-liquid sweetening version (Fig. 11.3.6) of the

Merox process is not generally used today for new units as refiners switch to the more

*Trademark and/or service mark of UOP.

FIGURE 11.3.3 Fixed-bed minimum-alkali Merox

sweetening unit.
 UOP MEROX PROCESS

UOP MEROX PROCESS 11.35

FIGURE 11.3.4
Caustic-Free Merox sweetening for gasoline.

FIGURE 11.3.5 Caustic-Free Merox sweetening for kerosene jet fuel.

active fixed-bed systems. Hydrocarbon feed, air, and aqueous caustic soda containing
dispersed Merox catalyst are simultaneously contacted in a mixing device, where
mercaptans are converted to disulfides. Mixer effluent is directed to a settler, from which
the treated hydrocarbon stream is sent to storage or further processing. Separated
caustic solution from the settler is recirculated to the mixer. A small amount of Merox
catalyst is added periodically to maintain the catalytic activity.
In general, liquid-liquid sweetening is applicable to virgin light, thermally cracked
gasolines and to components having endpoints up to about 120°C (248°F). The mercaptan
types associated with catalytically cracked naphthas are easier to oxidize than those con-
tained in light virgin or thermal naphthas, and therefore liquid-liquid sweetening has been
successfully applied to catalytically cracked gasolines having endpoints as high as 230°C
(446°F).
The various applications of the Merox process on different hydrocarbon streams are
summarized in Table 11.3.1.
 UOP MEROX PROCESS

11.36 SULFUR COMPOUND EXTRACTION AND SWEETENING

FIGURE 11.3.6 Liquid-liquid Merox sweetening unit.

TABLE 11.3.1 Merox Process Applications

Hydrocarbon stream Merox type

Gas Extraction
LPG Extraction
Natural gas liquids Extraction, extraction plus sweetening
Light naphtha Extraction, liquid-liquid sweetening, Minalk
sweetening, caustic-free sweetening
Medium or heavy naphtha Liquid-liquid sweetening
Caustic-free sweetening
Full-boiling-range naphtha Extraction plus sweetening, Minalk sweetening,
fixed-bed sweetening, caustic-free sweetening
Kerosene or jet fuel Fixed-bed sweetening
Caustic-free sweetening
Diesel Fixed-bed sweetening

Merox Process Features

Relative to other treating processes, the Merox process has the following advantages.

Low Operating Cost and Investment Requirement. The noncorrosive environment in

which the process operates requires no alloys or other special materials, thus
minimizing investment. In many applications, investment is essentially nil because of the
ease of converting existing equipment to Merox treating.

Ease of Operation. Merox process units are extremely easy to operate; usually, the air-
injection rate is the only adjustment necessary to accommodate wide variations in feed rate
or mercaptan content. Labor requirements for operation are minimal.

Proven Reliability. The Merox process has been widely accepted by the petroleum
industry; many units of all kinds (extraction, liquid-liquid, and fixed-bed sweetening) have
been placed in operation. By early 2002, more than 1700 of these UOP Merox units had
been licensed.
 UOP MEROX PROCESS

UOP MEROX PROCESS 11.37

Minimal Chemical-Disposal Requirements. Caustic consumption by atmospheric CO2,

excessive acid in the feedstock, and accumulation of contaminants are the only reasons for
the occasional replenishment of the caustic inventory.

Proven Ability to Produce Specification Products. Product deterioration as a result of side

reactions does not occur nor does any addition of undesirable materials to the treated
product. This fact is especially important for jet-fuel treating. In the Merox process,
sweetening is carried out in the presence of only air, caustic soda solution, and a catalyst
that is insoluble in both hydrocarbon and caustic solutions and cannot therefore have a
detrimental effect on other properties that are important to fuel specifications.

High-Efficiency Design. The Merox process ensures high catalyst activity by using a high-
surface-area fixed catalyst bed to provide intimate contact of feed, reactants, and catalyst
for complete mercaptan conversion. The technology does not rely on mechanical
mixing devices for the critical contact. State-of-the-art Merox technology has no
requirement for continuous, high-volume caustic circulation that increases chemical
consumption, utility costs, and entrainment concerns.

High-Activity Catalyst and Activators. Active and selective catalysts are important in
promoting the proper mercaptan reactions even when the most difficult feedstocks are
processed. For the extraction version of the process, UOP offers a high-activity, water-
soluble catalyst, Merox WS,* which accomplishes efficient caustic regeneration. As a
result, chemical and utility consumption is minimized, and mercaptans are completely
converted. For the sweetening version of the Merox process, UOP offers a series of
catalysts and promoters that provide the maximum flexibility for treating varying
feedstocks and allow refiners to select which catalyst system is best for their situation.

PROCESS CHEMISTRY

The Merox process in all its applications is based on the ability of an organometallic
catalyst to accelerate the oxidation of mercaptans to disulfides at or near ambient tem-
perature and pressure. Oxygen is supplied from the atmosphere. The reaction proceeds only
in an alkaline environment. The basic overall reaction can be written:
Merox catalyst
4RSH O2  2RSSR 2H2O (11.3.1)
Alkalinity

where R is a hydrocarbon chain that may be straight, branched, or cyclic and saturated or
unsaturated. Mercaptan oxidation, even though slow, reportedly occurs whenever
petroleum fractions containing mercaptans are exposed to atmospheric oxygen. In effect,
the Merox catalyst speeds up this reaction, directs the products to disulfides, and minimizes
undesirable side reactions.
In Merox extraction, in which mercaptans in the liquid or gaseous feedstocks are high-
ly soluble in the caustic soda solution as solvent, the mercaptan oxidation is done outside

*Trademark and/or service mark of UOP.

 UOP MEROX PROCESS

11.38 SULFUR COMPOUND EXTRACTION AND SWEETENING

the extraction environment. Therefore, a mercaptan-extraction step is followed by oxida-

tion of the extracted mercaptan. These steps are:
RSH NaOH NaSR H2O (11.3.2)
Oil phase Aqueous phase Aqueous phase

Merox catalyst
4NaSR O2 2H2O 4NaOH 2RSSR (11.3.3)
Aqueous phase Aqueous phase Oil phase (insoluble)

According to these treating steps, the treated product has reduced sulfur content corre-
sponding to the amount of mercaptan extracted.
In the case of Merox sweetening, in which the types of mercaptans in the feedstocks are
difficult to extract, the sweetening process is performed in situ in the presence of Merox
catalyst and oxygen from the air in an alkaline environment. UOP studies have shown that
the mercaptan, or at least the thiol (—SH) functional group, first transfers to the aqueous
alkaline phase (Fig. 11.3.7) and there combines with the catalyst. The simul- taneous
presence of oxygen causes this mercaptan-catalyst complex to oxidize, yielding a disulfide
molecule and water. This reaction at the oil-aqueous interface is the basis for both liquid-
liquid and fixed-bed sweetening by the Merox process and can be written:
Merox catalyst
4RSH O2  2RSSR 2H2O (11.3.4)
Oil phase Alkalinity Oil phase

Merox catalyst
2RSR 2RSH O2  2RSSR 2H2O (11.3.5)
Oil phase Alkalinity Oil phase

Equation (11.3.5) represents the case in which two different mercaptans may enter into
this reaction. Petroleum fractions have a mixture of mercaptans so that the R chain may
have any number of carbon atoms consistent with the boiling range of the hydrocarbon
feed.

FIGURE 11.3.7 Mercaptide at inter-

face.
 UOP MEROX PROCESS

UOP MEROX PROCESS 11.39

Because the process is catalytic, essentially catalyst and caustic soda are not consumed.
This fact is borne out by commercial experience, in which actual catalyst consumptions are
low. Consumption is due mainly to fouling by certain substances and loss through an
occasional purge of dirty or diluted caustic solution and a corresponding makeup of fresh
caustic to maintain effective caustic concentration.

PRODUCT SPECIFICATIONS

The only product specification applicable to Merox treating is the mercaptan sulfur content
of the product because the Merox process per se has no effect on the other prop- erties of
the feedstock being treated. Generally, therefore, the Merox process is used to reduce the
mercaptan sulfur content, and thereby the total sulfur content, when the process is applied
to gases and light stocks in the extraction mode of operation. In the case of heavier
chargestocks that require the sweetening mode of operation, the only product specification
applied is the mercaptan sulfur content (or sometimes also the doctor test); the total sulfur
contents of the untreated feed and the treated product are the same.
Merox-treated products may be finished products sent directly to storage without any
further processing or intermediate products that may require either blending into finished
stocks or additional processing for making other products.
Table 11.3.2 lists typical quality specifications for treating applications of the Merox
process.

PROCESS ECONOMICS

Sample economics of the UOP Merox process in 2002 dollars on the basis of 10,000 barrels
per stream day (BPSD) capacity for various applications are given in Table
11.3.3. The capital costs are for modular design, fabrication, and erection of Merox plants.
The estimated modular cost is inside battery limits, U.S. Gulf coast, FOB point of
manufacturer. The estimated operating costs include catalysts, chemicals, utilities, and
labor.

PROCESS STATUS AND OUTLOOK

The first Merox process unit was put on-stream October 20, 1958. In October 1993, the
1500th Merox process unit was commissioned. Design capacities of these Merox units
range from as small as 40 BPSD for special application to as large as 140,000 BPSD and
total more than 12 million BPSD.
The application of the operating Merox units is distributed approximately as follows:
 25 percent LPG and gases
 30 percent straight-run naphthas
 30 percent FCC, thermal, and polymerization gasolines
 15 percent kerosene, jet fuel, diesel, and heating oils
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TABLE 11.3.2 Quality Specifications for the Merox Process

Feed Type

UOP MEROX PROCESS

Characteristics Gases, FBR Jet Heating
LPG, NGL NGL, LN MN, HN gasoline fuels Kerosene Diesels oils
Feed:
Mercaptan sulfur, wt ppm 50–10,000 50–2,000 50–5,000 50–5,000 30–1,000 30–1,000 50–800 50–800
11.40

H2S, wt ppm* <10 <10 <10 <10 <1 <1 <1 <1
Acid oil, wt % .... .... <0.01 <0.01 <0.01 <0.01 <0.01 <0.01
Products:
Mercaptan sulfur, wt ppm <5–10 <5–10 <5–10 <5–10 <10 <10 <30 <30
Mercaptan sulfur disulfide sulfur, wt ppm 10–20 <50

*After caustic prewash, if any, before Merox process. LPG = liquefied petroleum gas; NGL = natural gas liquid; gas = natural gas, refinery gas, or synthesis gas; LN = light naph-
thas; MN and HN = medium and heavy naphthas; FBR = full boiling range.
 UOP MEROX PROCESS

UOP MEROX PROCESS 11.41

TABLE 11.3.3 Merox Process Economics

Est. operating
Merox Est. capital, costs,
Product type million $ cents/bbl
LPG Extraction* 1.8 0.4
Gasoline Minalk 0.9 0.3
Caustic-free 0.9 2.5
Kerosene Conventional fixed-bed 2.1 2.5
Caustic-free 2.1 6.0
*Includes pretreating and posttreating facilities.

The Merox process has been thoroughly proved and well-established commercially. Its
popular acceptance by the petroleum industry is based on its simplicity, efficiency, low
capital and operation costs, and proven reliability. Many refiners have two or more Merox
units. Even though the process is approaching 45 years of use, its technology is by no
means stagnant, thanks to continuing research and development efforts to ensure an
excellent outlook for this remarkably successful process.

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 UOP MEROX PROCESS

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Any use is subject to the Terms of Use as given at the website.