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MEROX UNIT: GENERAL

CHAPTER-2
MEROX PROCESS-THEORY & PRINCIPLES

2.1

CHEMISTRY OF THE MEROX PROCESS


To fully understand the Merox process and how it can be applied to a broad range of
treating problems, it is necessary to review the basic chemical reaction of the process and
how it is applied in a variety of ways. First let us discuss the term Mercaptans, most
widely used term in treating.

2.1.1 Mercaptans
The word "Mercaptan" is a descriptive name applied over 140 years ago to organic
compound with a sulfhydryl function (-SH) and derived from the Latin mercurium captans,
due to there mercury seizing properties. Todays literature, however, assign the word
"thiol" for the functional group. In the common system used by the petroleum industry,
mercaptans are named after their analogous alcohol counterparts. Thus CH3SH, by the
common system, is methyl mercaptan just as one would name an alcohol having the
formula CH3OH methyl alcohol; the strict formal name is "methanethiol". Likewise, nbutyl mercaptans becomes 1-butanethiol, t-butyl mercaptans becomes 2-methyl-2propanethiol. The aryl mercaptans are commonly called Thiophenol, while in the formal
system as used by chemical abstracts, these compounds are benzenthiol, toluenthiol, etc.
Thioalcohols or thiols, more commonly known as mercaptans, is a family of organic
sulphur compounds frequently present in a wide range of untreated petroleum distillates
such as LPG (C3/C4), naphtha, kerosene and gas oil. Specific mercaptans found in the
petroleum distillates originate in the crude and may even from during subsequent crude
refining. The concentrations of these mercaptans in crude distillates depend upon the crude
origin and the sulphur distribution in the crude.
In chemical shorthand all mercaptans are represented by the general formula RSH where
R is a hydrocarbon radical such as an alkyl, cycloalkyl, or aryl group and SH is the
mercaptan group which typifies all mercaptans and consists of sulphur and a hydrogen
atom. For reasons which will become clearer later, mercaptan concentration is represented
in terms of the sulphur in the mercaptan molecule, for example, an analysis of 100 WPPM
mercaptan sulphur (RSH-S) in C3/C4) means that on a weight basis 100 parts of sulphur
are present per million parts or C3/C4 but the sulphur is specifically mercaptan. If an
average mercaptan molecular wt were known, which is seldom the case, the actual
mercaptan concentration could be calculated. In the previous example an assumed average
mercaptan molecular weight 54.4 allows the actual mercaptan concentration to be
represented as 170 wt PPM.

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MEROX UNIT: GENERAL


Mercaptans are undesirable for many reasons. The lower boiling mercaptans are
moderately acidic and characterized by an extremely offensive odour. These proprieties
diminish as the mercaptan molecular weight increases. Thiophenol, which is an aryl
distillates and is an aryl mercaptan and more acidic than alkyl mercaptans, is found
principally in cracked distillates. Thiophenol is undesirable in finished gasoline because it
produces an unstable gasoline by promoting the hydroperoxidation of olefins to gum. All
sulfur compounds inhibit the ability of lead alkyl compounds such as tetraethylead
mercaptan sulphur content, it becomes economically desirable to chemically remove these
mercaptans thus increasing the lead susceptibility of the gasoline.
In summary, mercaptans are undesirable in finished petroleum products to whatever extent
their presence is considered to adversely affect the products odour, stability total sulphur
content, octane lead susceptibility etc.
2.1.2

Merox Reaction
The name "Merox" originates from the function of the process itself; namely the
conversion of mercaptans by oxidation. This discussion uses the common mercaptan
terminology as practiced in the petroleum industry.
The Merox process in all of its application is based on the ability of an organometallic
catalyst to accelerate the oxidation of mercaptans to disulfides at near ambient
temperatures and pressures. The overall reaction can be written:
RSH + 1/4 O2

1/2 RSSR + 1/2H2O

(1)

R is a hydrocarbon chain that may be straight, branched, or cyclic. These chain may be
saturated or unsaturated. In most petroleum fraction, there will be a mixtures of mercaptans
to the extent that the R chain might have 1, 2, 3,.10 or more carbon atoms in the chain.
This indicated by showing R and R' in the reaction. The reaction is then written:
2R'SH + 2 RSH + O2

2 R'SSR + 2 H2O

(2)

This reaction occurs spontaneously, but at a very slow rate, whenever any sour mercaptans
bearing distillate is exposed to atmospheric oxygen. In addition, reaction (1) is required the
presence of an alkyl solution, such as sodium hydroxide. The mercaptan oxidation
proceeds at an economically practical rate at moderate refinery run down stream
temperatures.
The stiochiometry of reaction (1) is as follows:
a) The quantity of air theoretically required to oxidize on Kg of mercaptan sulphur is 0.89
NM3 @ 15C and 1 Atm. The theoretical oxygen (Air) needed is independent of the
molecular weight of structure of the mercaptan.
b) The water of reaction produced from the oxidation of 1 Kg of mercaptan sulphur is
1.42 to 2.50 liters depending upon the disulfide molecular weight.

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MEROX UNIT: GENERAL


c) The disulfides produced from the oxidation of 1 Kg of mercaptan sulphur is 1.42 to
2.50 liters depending upon the disulfide molecular weight.
2.1.3 Merox Process For Mercaptan Sweetening of Gasolene & Kerosene/ATF Stream
In Mercaptan sweetening units, the mercaptans are converted directly to disulfides, which
remain in the product; there is no reduction in total sulphur content. Because the vapor
pressures of disulfides are very low relative to those of mercaptans, their presence is much
less objectionable.
Fixed bed sweetening is normally employed with charge stocks having end points above
275-300F (135-150C) with these stocks, the heavier mercaptan types associated with the
higher end points are only partially soluble in caustic solution and are more difficult to
sweeten. Contact and residence time requirements become uneconomical for liquid liquid
designs.
Mercaptans are converted to disulfides in a fixed bed reactor system. This consists of a
reactor, which contains a bed of specially selected activated charcoal impregnated with
merox reagent and wetted with caustic solution. Air is injected into the feed hydrocarbon
stream ahead of the reactor and in passing through the catalyst-impregnated bed, the
mercaptans in the feed are oxidized to disulfides.
The hydrocarbon, air and caustic are simultaneously contacted over the charcoal bed in the
reactors where the sweetening reaction takes place in two steps.
RSH +

NaOH

NaSR +

O2 +

NaSR +
H2 O

H2 O

Merox
Catalyst

(3)
NaOH + RSSR

(4)

The mercaptans enter 1st the sodium hydroxide to form sodium mercaptide and water. This
reaction (2) is reversible. The reaction (3) is irreversible where sodium mercaptide in
oxidized over the merox catalyst to form disulfide and regenerate the sodium hydroxide.
The composite reaction is:
RSH +

O2

RSSR

H2 O

(1)

The disulfide is essentially caustic insoluble and remains in the hydrocarbon phase. Pre
treatment to remove excess water, H2S, CO2 and organic acid compounds in the
hydrocarbon feed is done in caustic pre wash. The presence of these Impurities will
hinder the merox reaction. Also post treatment is required to remove undesirable by
products due to side reactions such as the neutralization of H2S, oxidation of Phenolic
compounds, entrained caustic, etc.
Fixed bed Marcaptan sweetening process is utilized in the treatment of Gasolene and
Kerosene/ATF stream.

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MEROX UNIT: GENERAL


1.2.4 Extractive Merox Process for LPG treatment
Extraction is applied to both gaseous and liquid hydrocarbon streams. The degree of
completeness of mercaptans extraction depends upon the solubility of a mercaptan in the
alkaline solution. That, in turn, depends primarily upon the following.
a.
b.
c.
d.

molecular weight of mercaptan


degree of branching of mercaptan molecule
caustic soda concentration
temperature of the system

As the molecular weight of the mercaptan increases, solubility in the alkaline solution
decreases, and as chain branches increase, solubility decreases.
Low molecular weight mercaptans are soluble in caustic soda solution. Therefore, when
treating LPG, the Merox process can be used to extract mercaptans, thus reducing the
sulfur contents of the treated product. In the extraction unit, sulfur reduction is directly
related to the extractable mercaptan contents of the fresh charge.
The LPG Merox process utilizes liquid-liquid contacting to extract the mercaptans from
hydrocarbon with a strong aqueous alkali solvent. The mercaptan-rich solvent, which also
contains the dispersed Merox catalyst, is sent to a regeneration section where air is injected
and the mercaptans are oxidized to disulfides. The disulfides are subsequently separated
from the solvent by coalescing, gravity settling and decanting the regenerated lean solvent
is recycled back to the extractors. Thus the main process consists of two steps- mercaptan
extraction and solvent regeneration.
The following equation illustrates the mechanism of mercaptan extraction:
RSH
Oil
Phase

NaOH
Aqueous
Phase

NaSR + H2O

(5)

Aqueous
Phase

Of course, nothing can be done to control either the amount or the molecular weight of the
mercaptans present as this is a function of the crude source and distillation cut of the feed.
However, for a mercaptan of the same molecular weight, primary mercaptan will be most
completely extracted, secondary mercaptan will be less completely extracted. This, too, is a
function of the feed stock.

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MEROX UNIT: GENERAL


2.2

TERMINOLOGY GENERALLY USED IN MEROX TREATMENT


Azeotrope

A mixture of substance that behaves as a single substance in that the


vapor produced by partial evaporation has the same composition as
the liquid.

Antioxidant

Chemical additive to inhibit oxidation reaction.

Barrel

42 U.S. gallons measured at 60F.

BPD

Barrels per day (also BSD).

Caustic

Sodium hydroxide solution.

C/H

Caustic/hydrocarbon volume ratio.

Delta P (DP)

Differential pressure.

Disulfide

Class of sulphur compounds characterized by sulphur to sulphur bond


and relatively low volatility represented by the general formula
RSSR.

EP

End point (ASTM distillates).

Extraction

Removal of mercaptan sulphur from hydrocarbon.

GC or GLC

Gas chromatography

GPH

U.S. gallons per our.

GUM

Polymerized hydrocarbon.

Hydroperoxide

Compound responsible for propagation of gum forming chain


reaction (-OOH).
Initial boiling point (ASTM distillation).

IBP
Inhibitor

Compounds responsible for delaying or terminating a chemical


reaction.

LHSV

Liquid hourly spaces velocity.

Mercaptan

Common name given to class of compounds having thiol functional


groups represented by the general formula RSH.

Naphthenic acid Organic (carboxylic) acid.


NM3

CHAPTER-2

Normal cubic meter ( 1 atm 0C)

MEROX UNIT: GENERAL


Std m3

Standard cubic meters (1 atm 15C).

Organo-metallic Complex compound characterized by weak carbon to metal bonds.


PPM

Parts per million.

PW

Pre wash

RX

Reactor.

SCFH

Standard cubic feet per hour (1 atm 60F).

Sweetening

Conversion of mercaptan to disulfide without desulfurization.

Stability

Quality of a fuel to remain unchanged for long periods of time in


storage.

Thiol

Sulphur to hydrogen bond.

Thiophenol

Common name given to aryl mercaptans; also the compound C6H5SF.

Vol. Vol-%

Volume, volume percent.

Wt. Wt%

Weight, weight percent

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MEROX UNIT: GENERAL


2.3

CHEMICAL ABBREVATIONS AND SYMBOLS USED IN MEROX


A
C
C1
C2
Cn
CaCO3
CO2
H
H2S
Na
NaHS
Na2CO3
NaOH
Na2S
NaSR
Na2S2O3
O
O2
RR
RSH
S
S
-SH

Inhibitor free radical


Carbon
Hydrocarbon with 1 carbon atom (e.g., methane)
Hydrocarbon with 2 carbon atom (e.g., methane)
Hydrocarbon with n carbon atom.
Calcium carbonate.
Carbon dioxide.
Hydrogen
Hydrogen sulphide.
Sodium
Sodium bisulfide.
Sodium carbonate.
Sodium hydroxide (caustic)
Sodium sulfide.
Sodium mercaptide.
Sodium thiosulfate
Oxygen
Diatomic oxygen (normal form in gaseous state).
Alkyl1 group side chain
Alkyl free radical
Mercaptan
Sulfur
Elemental sulfur
Thiol (mercapto functional group)
Unsaturated cyclic hydrocarbon compound
Saturated cycle hydrocarbon compound.

[]

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Solution concentration (moles/liter)

MEROX UNIT: GENERAL


2.4

PHYSICAL PROPERTIES OF MERCAPTANS AND ORGANIC DISULFIDES


S. No.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17

Mercaptans
or Disulfides

Chemical Formula

Methyl
Ethyl
N-Propyl
I-Propyl
N-Butyl
I-Butyl
N-Amyl
I-Amyl
N-Hexyl
N-Heptyl
N-Octyl
Thiophenol
Diethyl
Disulfide
Diethyl
Disulfide
Dubiety
Disulfide
Dibutyl
Disulfide
Diphenyl
Disulfide

CH2SH
CH3CH2SH
CH3(CH2)2SH
(CH3)2CHS
CH3(CH2)3SH
(CH2)2CHCH2SH
CH3)CH2)3CH2SH
(CH3)2CH(CH2)2S
H
C6H13SH
C7H15SH
C6H6SH
C6H5SH

Molecular
Weight

Boiling Point
C

48.1
62.1
76.1
76.1
90.1
90.1
104.2

118.2
132.2
146.2
110.2

Specific
Gravity
(20/4C)
0.867
0.838
0.837
0.809
0.837
0.829
0.842
0.836
0.846
0.844
0.841
1.078

94.2

1.058

115

122.3

0.993

153

150.3

0.956

193

178.4

0.937

231

218.3

1.353

310

6.5
36
67.5
58
97.6
84.5
70.4
119
150
176
199
168

(CH3)2S2
(C2H5)2S2
(C3H7)7S2
(C4H9)2S2
(C6H5)2S2

Many mercaptans from azotropic mixtures with hydrocarbons of lower and higher boiling
points.

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CHAPTER-2