SULPHUR & RECOVERY

Sulfur and Its Chemistry

Sulfur is an odorless, tasteless, light yellow solid. It is a reactive element that given favorable
circumstances combines with all other elements except gases, gold, and platinum. Sulfur
appears in a number of different allotropic modifications: rhombic, monoclinic, polymeric, and
others.
The rhombic structure is the most commonly found sulfur form. Each allotropic form differs in
solubility, specific gravity, crystalline, crystalline arrangement, and other physical constants.
hese various allotropes also can exist together in equilibrium in definite proportions, depending
on temperature and pressure.
Types : 4 naturally occurring types exist
Rhombic And Monoclinic Sulfur
Both the rhombic and monoclinic crystalline modifications of sulfur are made up of eight sulfur
atoms arranged in a puckered-ring structure. At one atmosphere pressure and temperatures
less than 95.4ºC, rhombic is the stable crystalline form. Above 95.4ºC to the melt temperature of
118.9ºC, the monoclinic crystalline structure is dominant.
Polymeric / plastic Sulfur
At 160ºC and higher, the eight-member-ring sulfur molecule is energized and ruptures. The
open-chain sulfur molecule that takes shape combines to make long unbranched polymer
chains by a free radical mechanism.
Sulfur vapor
contains both eight-membered rings and diatomic sulfur; the blue color of the vapor
is due to diatomic sulfur. Like diatomic oxygen, diatmic sulfur is paramagnetic and
has two unpaired electrons.
Boiling Point: 444oC
Freezing/Melting Point: 110-119oC
Flashpoint: 207.2 oC

SULFUR RECOVERY

Currently only two methods are available for dealing with large quantities of H2S:

• Disposal of the gas by injection into underground formations

• Conversion of the H2S into a usable product, elemental sulfur

However, more commonly, H2S is converted into elemental sulfur, much of which goes
into sulfuric acid production. As late as 1950, over half of the world’s sulfur supply came
from “voluntary producers,” that is, companies whose principal purpose was to produce
elemental sulfur. Now, these producers furnish less than 5% of the world’s supply and
“involuntary producers ( Gas processing Industries),” primarily petroleum refineries and
natural gas plants, are the major source of the element Sulfur.

The most common method of converting H2S into elemental sulfur, is the Claus
process or one of its modifications.
According to available literature, the most commonly used processes are Shell Claus
Offgas Treating (SCOT), SUPERCLAUS, and cold-bed adsorption (CBA). This
discussion will be limited to these processes.

CLAUS PROCESS
All Claus units involve an initial combustion step in a furnace. The combustion
products then pass through a series of catalytic converters, each of which produces
elemental sulfur.

Basic Chemistry

The Claus process consists of the vapor-phase oxidation of hydrogen sulfide to

form water and elemental sulfur, according to the overall reaction:

The above overall reaction does not represent the reaction mechanism or
show intermediate steps. In practice, the reaction is carried out in two steps:

The first reaction is a highly exothermic combustion reaction, whereas the second is a
more weakly exothermic reaction promoted by a catalyst to reach equilibrium.

Figure 11.2 shows the equilibrium conversion obtained for H2S into elemental sulfur by
the Claus reaction.

Unusual shape of the equilibrium curve is caused by the existence of different sulfur
species at different reaction temperatures. They point out that at a sulfur partial
pressure of 0.05 bar and temperatures below 370°C, the vapor is mostly S6 and S8, but
at the same partial pressure and temperatures over approximately 540°C, S2
predominates.
This shift in species causes the equilibrium constant in the reaction to shift from a
downward slope to an upward slope, as shown in Figure 11.2. This behavior has a
significant effect on the operation of the Claus process.
The melting point of amorphous sulfur is 248°F (120°C), and its normal boiling point is
832°F (445°C). Figure 11.2 shows that the maximum conversion to sulfur by reaction
11.1 is obtained at temperatures near the melting point of sulfur, but to maintain sulfur in
the vapor state, relatively high temperatures are required. Consequently, if the catalytic
converters are to operate under conditions in which the sulfur does not condense on the
catalyst, they cannot operate at optimum equilibrium conversion.

This is the reason for having a series of converters, with the sulfur product withdrawn
from the reacting mixture between converters. Withdrawing the sulfur product causes
the reaction 11.3 to shift to the right, which results in more sulfur product.