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, n-
butyl mercaptans becomes 1-butanethiol, t-butyl mercaptans becomes 2-methyl-2-
propanethiol. 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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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 + H2 O (3)

NaSR + O2 + H2 O Merox NaOH + RSSR (4)

Catalyst

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. molecular weight of mercaptan

b. degree of branching of mercaptan molecule
c. caustic soda concentration
d. 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 + NaOH NaSR + H2O (5)

Oil Aqueous Aqueous

Phase Phase 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).
IBP Initial boiling point (ASTM distillation).

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 Normal cubic meter ( 1 atm 0C)

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 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 Inhibitor free radical

C Carbon
C1 Hydrocarbon with 1 carbon atom (e.g., methane)
C2 Hydrocarbon with 2 carbon atom (e.g., methane)
Cn Hydrocarbon with n carbon atom.
CaCO3 Calcium carbonate.
CO2 Carbon dioxide.
H Hydrogen
H2S Hydrogen sulphide.
Na Sodium
NaHS Sodium bisulfide.
Na2CO3 Sodium carbonate.
NaOH Sodium hydroxide (caustic)
Na2S Sodium sulfide.
NaSR Sodium mercaptide.
Na2S2O3 Sodium thiosulfate
O Oxygen
O2 Diatomic oxygen (normal form in gaseous state).
R- Alkyl1 group side chain
R Alkyl free radical
RSH Mercaptan
S Sulfur
S Elemental sulfur
-SH Thiol (mercapto functional group)
Unsaturated cyclic hydrocarbon compound

Saturated cycle hydrocarbon compound.

[] Solution concentration (moles/liter)

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 MEROX UNIT: GENERAL
2.4 PHYSICAL PROPERTIES OF MERCAPTANS AND ORGANIC DISULFIDES

S. No. Mercaptans Chemical Formula Molecular Specific Boiling Point

or Disulfides Weight Gravity C
(20/4C)
1 Methyl CH2SH 48.1 0.867 6.5
2 Ethyl CH3CH2SH 62.1 0.838 36
3 N-Propyl CH3(CH2)2SH 76.1 0.837 67.5
4 I-Propyl (CH3)2CHS 76.1 0.809 58
5 N-Butyl CH3(CH2)3SH 90.1 0.837 97.6
6 I-Butyl (CH2)2CHCH2SH 90.1 0.829 84.5
7 N-Amyl CH3)CH2)3CH2SH 104.2 0.842 70.4
8 I-Amyl (CH3)2CH(CH2)2S 0.836 119
9 N-Hexyl H 118.2 0.846 150
10 N-Heptyl C6H13SH 132.2 0.844 176
11 N-Octyl C7H15SH 146.2 0.841 199
12 Thiophenol C6H6SH 110.2 1.078 168
13 Diethyl C6H5SH
Disulfide 94.2 1.058 115
14 Diethyl (CH3)2S2
Disulfide 122.3 0.993 153
15 Dubiety (C2H5)2S2
Disulfide 150.3 0.956 193
16 Dibutyl (C3H7)7S2
Disulfide 178.4 0.937 231
17 Diphenyl (C4H9)2S2
Disulfide 218.3 1.353 310
(C6H5)2S2

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

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