Sulfrex

and Sweetening

PROCESSES TO EXTRACT AND CONVERT MERCAPTANS IN HYDROCARBONS

MERCAPTANS ELIMINATION

Air

Mercaptans (RSH) occur naturally in crude oils but

are also generated from other sulfur compounds
during crude fractionation and cracking processes.
Mercaptans are undesirable in gasoline because of
their obnoxious odor and their tendency to hydrolyze,
forming toxic and corrosive hydrogen sulfide. The
classic tests for mercaptan presence are the doctor
test and odor threshold.
Our Sulfrex and Sweetening processes eliminate
mercaptans by extraction or by their conversion into
less aggressive compounds, protecting downstream
equipment or units such as hydrotreaters as well as
meeting fuel specifications.
EXTRACTIVE SULFREX
The extractive Sulfrex process both sweetens and
reduces the total sulfur concentration.
With its moderate operating conditions of pressure
and ambient temperature, this continuous process is
ideal for C3, C4, LPG, light gasoline and NGL feeds.
The overall reaction shown below - where R
represents an aliphatic group - involves two steps,
starting with extraction and culminating in oxidation:
Overall Sulfrex reaction
4 RSH + O2 2 RSSR + 2 H2O
First step: Extraction
RSH

NaOH

NaSR + H2O

Second step: Oxidation

4 NaSR + 2 H2O + O2 4 NaOH

Aqueous phase
Hydrocarbon phase

2 RSSR

Optional
Caustic
Prewash

Extractor

Oxidizer Separator

Catalyst
Tank
Sand Filter

Disulfides

Feed
Steam/cw

Make-up
Caustic

Spent
Caustic cw

Sweet
Product

Extractive Sulfrex Process

In the flow diagram, the light mercaptans are

extracted (Extractor) by a weak caustic solution
forming water and sodium mercaptide salts (NaSR).
These salts are oxidized (Oxidizer) by air injection in
the presence of our LCPS 30 catalyst, producing an
organic disulfide (RSSR) phase that separates by
gravity (Separator) from the aqueous solution.
This phase is sent to storage or further treatment
facilities. The resulting regenerated caustic solution is
then returned to the Extractor.
The product flows through a sand filter to eliminate
traces of free water and caustic.
Pretreatment
If required, a dilute caustic prewash step is used
upstream to eliminate any H2S, COS and CO2 that
may be present in the feed.
Post-treatment
If final product quality warrants, a molecular sieve
bed downstream from the sand filter minimizes total
sulfur and residual water content. For cracked feeds,
e.g., those from FCC units, clay beds are used to
improve product color.

Alternative treatment
Washing the regenerated caustic solution with an
appropriate hydrocarbon cut minimizes RSSR
entrainment in the final sweet product.
SWEETENING
Sweetening converts RSH directly to RSSR and is
used to treat full-range or heavy gasoline. This
process also features mild operating conditions:
moderate pressure and ambient temperature.
Air

Optional
Caustic
Prewash

Make-up
Caustic

The LCPS 30 catalyst features a very high activity for

converting the RSH (removed as NaSR in the liquidliquid extraction (Extractor) step) to RSSR in the
oxidation step (Oxidizer) of the Sulfrex process or, in
the Sweetening process, in the Sweetening Column
regardless of the type of feed.
Storage and handling are problem-free, the active
agent being present in a dilute aqueous solution.
COMMERCIAL EXPERIENCE

Sweetening
Column
Sand Filter

Feed

LCPS 30 CATALYST

Separator

Catalyst
Tank

The total licensed capacity for thirty-one Sulfrex and

Sweetening units exceeds 50,000 tons per day, among
which several references are designed for processing
sour streams from FCC units and NGL feedstocks as
well.

Sweet
Product

Spent
Caustic

Sweetening Process

The reaction occurs in the presence of air and caustic

in a Sweetening Column that contains our LCPS 30
catalyst impregnated on an activated carbon packing.

For certain feed and product specifications a fullrange naphtha for example combined units can be
used.
An Extractive Sulfrex unit first converts the lighter
RSH compounds to disulfides that are then removed
from the feed to reduce its total sulfur content. A
Sweetening step next converts heavier mercaptans to
disulfides that remain in the product. If a naphtha
splitter is available, an Extractive Sulfrex unit can be
used to treat the light naphtha overhead stream while a
Sweetening unit treats the heavy naphtha tower
bottom.

March09-Sulfrex & Sweetening

COMBINED UNITS