Sulfur Addi ves

Thiochemical compounds (sulfur containing compounds) are common coke inhibitors added to
feedstocks to suppress coke forma on. The various commonly used thiochemical compounds are:

Table 1:Commonly used thiochemical compounds

DMDS Dimethyl disulfide
DBS Dibenzyl sulfide
DES Diethyl sulfide
Thiophene C4H4S
CS2 Carbon sulfide
DMS Dimethyl sulfide
DBDS Dibenzyl disulfide
H2S Hydrogen sulfide
B-Thiophene Benzothiophene
1-Buthanethiol

Sulfur related addi ves and pretreatment have been found to be able to repress surface reac ons and
thus reduce coke forma on [5]. Coke reduc on by sulfur addi ves has been a ributed to the inhibi ng
effect caused by the layer of metal sulfides formed through the interac on of hydrogen sulfides with the
metallic wall. This layer of stable metal sulfides also serves as a passiva ng surface against cataly c
coking mechanism. For example, pretreatment with sulfur addi ves on stainless steel leads to the
forma on of metal sulfides which will then act as a “protec ve cover” on the surface. The ac ve metals
are begin “trapped” as sulfide form and thus, are unable to catalyze any coke forma on reac on with
hydrocarbons. This significantly reduces carbon forma on on the metal surfaces through the cataly c
coking mechanism [14]. This probably led researchers in ATOFINA to develop an foulant CLX which use
sulfur-containing compounds.

Figure 1:Coking rates of different addi ves [26]

However, in the recent years, other researchers found that sulfur compounds, instead of suppressing
coke forma on as thought by many, can in fact increase the rate of coke forma on. The work by Froment
et al. [28] supported the la er point and will form the main part of the discussion in this sec on.
A reduc on in CO yield in the outlet stream of the cracking furnace is o en interpreted as an indica on
of reduced coke. It has been shown however that this is not always true [28,29]. Over the years, many
different researchers who carried out research involving sulfur addi ves have reported contradictory
results. The list of researchers stated in the table below is obtained from the publica on by Froment et
al. [28].
Researches Addi ves used Coke deposi on
Crynes & Albright (1969) Elemental sulfur Reduced
Ghaly & Crynes (1976) Elemental sulfur Reduced
Dunkleman & Albright (1976) Elemental sulfur, ethane Reduced
Bajus & Vesely (1980) Elemental sulfur Reduced