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)

PROCESS DESCRIPTION

The UOP Merox process accomplishes mercaptan extraction and mercaptan conversion
at normal refinery rundown temperatures and pressures. Depending on the application,

*Trademark and/or service mark of UOP.

11.31
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 UOP MEROX PROCESS

11.32 SULFUR COMPOUND EXTRACTION AND SWEETENING

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.

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
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.

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 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 120C (248F). 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.

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 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.

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 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 120C (248F). 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 230C
(446F).
The various applications of the Merox process on different hydrocarbon streams are
summarized in Table 11.3.1.

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 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.

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 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.

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 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
2RSR
2RSH
O2 2RSSR
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.

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 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

TABLE 11.4.2
Feed Type
Characteristics Gases, FBR Jet Heating
LPG, NGL NGL, LN MN, HN gasoline fuels Kerosene Diesels oils
Feed:
Mercaptan sulfur, wt ppm 5010,000 502,000 505,000 505,000 301,000 301,000 50800 50800
H2S, wt ppm* 10 10 10 10 1 1 <1 1

11.40
Acid oil, wt % .... .... 0.01 0.01 0.01 0.01 0.01 0.01
Products:
Mercaptan sulfur, wt ppm 510 510 510 510 10 10 30 30
UOP MEROX PROCESS

Mercaptan sulfur
disulfide sulfur, wt ppm 1020 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.

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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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