Beruflich Dokumente
Kultur Dokumente
CHAPTER-2
MEROX PROCESS-THEORY & PRINCIPLES
2.1
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.
CHAPTER-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)
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.
CHAPTER-2
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.
CHAPTER-2
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.
CHAPTER-2
Antioxidant
Barrel
BPD
Caustic
C/H
Delta P (DP)
Differential pressure.
Disulfide
EP
Extraction
GC or GLC
Gas chromatography
GPH
GUM
Polymerized hydrocarbon.
Hydroperoxide
IBP
Inhibitor
LHSV
Mercaptan
CHAPTER-2
PW
Pre wash
RX
Reactor.
SCFH
Sweetening
Stability
Thiol
Thiophenol
Vol. Vol-%
Wt. Wt%
CHAPTER-2
[]
CHAPTER-2
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.
###########################
CHAPTER-2