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Activation of Hydroprocessing Catalysts: An in depth understanding of

Dimethyldisulfide (DMDS) decomposition chemistry on


Hydroprocessing Catalysts during their activation via Sulfiding

Francis Humblot
R&D Manager, Thiochemical Division, Arkema, France

Vijay Srinivas
Principal Research Scientist, Thiochemicals Division, Arkema Inc., USA

Paper # 293309


Abstract: The progress in the improvement of hydroprocessing catalysts has been impressive
since the discovery of Type-II acid sites. Strict regulations on the sulphur and nitrogen levels
in finished transportation fuels are being enforced globally, and this has promulgated the need
to capture all the available activity of these new catalysts. The new generations of CoMo and
NiMo catalysts have to be carefully activated via sulfiding to accomplish this task. Dimethyl
disulfide (DMDS) has been and continues to be the agent of choice to sulphide in-situ, and
obtain optimal activity from these catalysts. The decomposition of DMDS, while verified under
laboratory conditions, has not been clearly understood under actual refinery unit conditions.
The DMDS decomposition chemistry under a range of commercial unit conditions has been
investigated. Experimental data obtained have been used to build a kinetic model based on
the fundamental decomposition mechanism. The data can be used beneficially to fine tune
existing sulfiding procedures established by Catalyst Manufacturers and Refining Companies so
as to make them optimal for and applicable to different types of units in the refinery.
Additionally, this information can be used to ascertain essentially complete use of the sulfur
introduced via DMDS and prevent SO
2
excursions due to inadvertent loss of sulphur
intermediates to the flare or flue gas, during the catalyst sulfiding and activation. Being the
leader in DMDS manufacture, Arkema has recently introduced a new formulation, DMDS
Evolution

E2 that has an improved user-friendly odor. Details of this formulation and of the
Carelflex

Service that Arkema provides to sulfide these catalysts in-situ will be described.

1. Introduction
For more than 20 years, the refining industry has greatly improved the refining process
to be able to convert the bottom-of-the-barrel to valuable fuels and to drastically
decrease or exclude the deleterious impurities present
1,2
. Thanks to this effort and
particularly the reduction of sulfur content in gasoline and gasoil, the acid rain
phenomena observed in Europe and United-States in the 90s has just about disappeared.
Furthermore, the deactivating effect of sulfur compounds in gasoline and diesel on the
noble metal catalysts used in catalytic converters on cars to reduce hydrocarbon and NOx
in tail pipe emissions prompted Europe and the United States to promulgate regulations
targeting 10-15 PPM sulfur in these fuels. This trend is now progressively being adopted
all around the world.
To meet this challenge for cleaner fuels, the refining industry and catalysts
manufacturers have worked diligently hand-in-hand on developing new hydroprocessing
technologies and new generations of catalysts
3
. While the metals used in todays
hydroprocessing (HDP) catalysts are still the same as those used in the 1990s (bimetallic
Cobalt-Molybdenum or Nickel-Molybdenum, Nickel-Tungsten) their relative activities have
been drastically improved. These improvements have been made possible by the
development in sophisticated catalyst characterization techniques that have resulted in a
deeper understanding of the catalyst structure and the nature of their active sites.
Invoking mixed sulfide structures such as CoMoS
4,5,6
and their interaction with the
carrier or support, leading to the concept of Type-I and Type-II active sites
7,8
has
allowed catalyst manufacturers to introduce the current line of highly active catalysts with
defined specificity via the use of templates provided by organic molecules such as glycol
ethers
9,10,11
.

1
H. Topsoe, B.S. Clausen, F.E. Massoth, Hydrotreating catalysts Science and Technology, Ed. Springer, 1996
2
World wide fuels regulations: United States, Canada, Europe, Japan, India
(http://www.dieselnet.com/standards/)
3
A. Stanislaus, A. Marafi, M.S. Rana, Recent advances in science and technology of ultra low sulfur diesel
production, Catal. Toady, 153, 1-68 (2010)
4
H. Topse, B.S. Clausen, Importance of cobalt-molybdenum-sulfur type structures in hydrodesulfurization,
Catal. Rev.-Sci. Eng., 26, 395 (1984)
5
P. Ratnasamy, S. Sivasanker, Structural chemistry of cobalt-molybdenum-alumina catalysts, Catal. Rev.-Sci.
Eng., 22, 401 (1980)
6
B.S. Clausen, H. Topse, R. Candia, J.V. Villadsen, B. Lengeler, J.Als. Nielsen, F. Christensen, Extended X-ray
Absorption Fine Structure Study of Co-Mo Hydrodesulfurization Catalysts, J. Phys. Chem., 85, 3868 (1982)
7
B. Hinnemann, J.K. Norskov, H. Topse, A density functional study of the chemical differences between type I
and type II MoS2-based structures in hydrotreating catalysts, J. Phys. Chem. B, 109, 2245, (2005)
8
E.J.M. Hensen, V.H.J. de Beer, J.A.R. van Veen, R.A. van Santen, A refinement on the notion of type I and
type II (Co)MoS phases in hydrotreating catalysts, Catal. Letters, 84, vol. 1-2, 59 (2002)
9
S. Eijsbouts, L.C.A. van den Oetelaar, R.R. van Puijenbroek, MoS2 morphology and promoter segregation in a
commercial type II Ni-Mo/Al2O3 and Co-Mo/Al2O3 hydroprocessing catalysts, J. Catal., 229, 352 (2005)
10
D. Nicosai, R. Prins, The effect of phosphate and glycol on the sulfidation mechanism of CoMo/Al2O3
hydrotreating catalysts: an in situ QEXAFS study, J. Catal., 231, 259 (2005)
Hydroprocessing catalysts are manufactured as a mixture of active metal oxides on a
support, typically alumina. These have to be converted to their corresponding active
metal sulfides prior to use. The metal oxides are fully converted to metal sulfides, which
are dispersed on the carrier surface to create nano-scale crystals by treating them with a
sulfiding agent. This activation is generally performed on site (in-situ sulfiding), in the
catalytic reactor to avoid the handling of metallic sulfides, which are known to be
pyrophorric. Sulfiding is an exothermic process thus needing careful monitoring to
control the temperature and avoid deleterious side reactions such as metallic oxide
reduction by hydrogen and coke formation that reduce the final catalyst activity. These
side reactions are minimized if the sulfiding process is started in the temperature range
(200
0
C240C; 392
0
F-464
0
F) and completed at temperatures greater than 300C or
572
0
F. Metal oxides react readily with hydrogen sulfide (H
2
S) to form the corresponding
sulfides, however the use of H
2
S on a large scale poses a high safety risk due to its
toxicity. Hence most refiners and catalyst manufacturers around the world prefer to
activate their catalysts using a sulfiding agent that efficiently generates and delivers H
2
S
in-situ.
For several decades, dimethyldisulfide (DMDS) has been recognized as an efficient,
relatively safe and convenient sulfiding agent for HDP catalysts
12,13
. It is a liquid that
contains 68% sulfur, which efficiently converts to H
2
S on the HDP catalysts in the
presence of hydrogen at relative low temperatures (180
0
C - 200C) thus being optimally
suited for in-situ sulfiding of HDP catalysts
14,15,16
. Produced for more than 30 years by
Arkema and available worldwide, it has become the reference standard for the sulfiding
agent market. Until recently, DMDS decomposition data on HDP catalysts was known
under ambient pressure conditions only. There was a need to understand the DMDS
decomposition chemistry under a range of commercial unit operating conditions. Arkema
embarked on an investigation to obtain such data and establish a mechanism of DMDS
decomposition supported by a kinetic model as well. This data and information can now
be used beneficially to fine tune existing sulfiding guidelines established by catalysts
manufacturers as needed and maximize sulfur transfer from DMDS to the catalyst.

11
T.S. Nguyen, S. Loridant, C. Lorentz, T. Cholley, C. Geantet, Effet of gloycol on the formation of active
species and sulfidation mechanism of CoMoP/Al2O3 hydrotreating catalysts, Appl. Catal B: Environmental,
107, 59 (2011)
12
H. Hallie, Experience reveals best presulfiding techniques for HDS and HDN catalysts, Oil and Gas J., pp 69-
74, (Dec. 20, 1982)
13
A. Tuxen, H. Gbel, B. Hinnemann, Z. Li, K.G. Knudsen, H. Topse, J. Lauritsen, F. Besenbacher, An atomic-
scale investigation of carbon in MoS2 hydrotreating catalysts sulfided by organosulfur compounds, J. Catal.,
281, 345 (2011)
14
C. Brun, T. Saint-Pierre, Thiochemicals as sulfiding agents for hydrotreatment catalysts, Hydrocarbon Eng.,
pp26-30, Jan-Feb. 1997
15
S. Texier, G. Berthault, G. Prot, V. Harl, F. Diehl, Activation of alumina-supported hydrotreating catalysts by
organosulfides: comparison with H2S and effect of differents solvents, J. Catal., 223, 404 (2004)
16
F. Humblot, Agent of change: choose of sulfiding agents for hydrotreating catalysts, Hydrocarbon Eng.,
pp41-46, Aug. 2007
2. Experimental
2.1. Catalysts and Chemicals
Latest generation CoMo and NiMo commercial catalysts were used for this study
(trilobe extrudates). The metal loadings are confidential, however, the catalyst
manufacturer indicated that the sulfur uptake expected for these catalysts after
sulfiding is the following:
- CoMo/alumina catalyst : 11.0% sulfur
- NiMo/alumina catalyst : 10.5% sulfur
Synthetic liquid feed (n-dodecane, from Merck, purity > 99.0%) was used for this
study as a surrogate for straight run gasoline/gasoil (SRG/SRGO) typically employed
for industrial sulfiding. The n-dodecane used was sulfur-free and allowed for a more
accurate determination of the sulfur species present in the gas and liquid exiting the
reactor to perform a sulfur balance. Additionally, the boiling point (417424F) of n-
dodecane falls within the boiling point range for gas oil.
Pure hydrogen (purity > 99.995%) was supplied by Linde.
Dimethyldisulfide was manufactured by Arkema, at Lacq in France (Purity 99.82-
99.85%).
Silicon Carbide powder (diameter 1.68 mm) was supplied by VWR.
2.2. Hydrotreating Pilot Unit Description
This pilot was designed by Vinci technology (see Figure-1). It is capable of handling
pressures of hydrogen up to 100 bars (1450 psig). The liquid feed is injected in the
up-flow mode into a 100 cm3 reactor (diameter 19 mm, 524 mm of total height). The
Catalyst temperature is measurement with 3 thermocouples located at different
heights in the center of the reactor. Silicon carbide is placed at the bottom and at the
top of the catalyst bed so that catalyst bed is located in the isothermal zone of the
reactor. The pressure is monitored by a control valve after the catalytic reactor and
before the Gas liquid separator.
2.3. Procedure
In order to study the impact of Liquid Hourly Space Velocity (LHSV) on the DMDS
decomposition chemistry, different catalyst volumes were loaded in the reactor:
- 0.5 h
-1
LHSV : 80 cm
3
catalyst volume

- 4.0 h
-1
LHSV : 10 cm
3
catalyst volume
Catalyst was always loaded in the middle of the reactor, between 2 beds of silicon
carbide. During the study, the ratio of hydrogen / n-dodecane flow rates was
maintained at 250. The hydrogen pressure ranged from 217 psig to 870 psig. The
following steps were taken:


Figure 1 : Hydrotreating Pilot used to study the decomposition of DMDS during the
sulfiding of CoMo or NiMo catalyst

1. Catalyst drying was done at 300F (150C) with a down flow of nitrogen at low
pressure (30 psig)
2. Catalyst wetting with n-dodecane was performed at a low pressure (2 bars) of
nitrogen, until it was observed in the gas liquid separator.
3. The nitrogen was slowly displaced with hydrogen flowing at 10 L to 20L/hr. The
pressure was allowed to build up to the value that needed to be tested.
4. Once pressure was stabilized and the temperature of the catalyst bed was fixed at
300F, a solution of DMDS (1.47% w/w) in n-dodecane was injected.
5. After about 2 hours, the outlet hydrogen was analysed on-line for 2 hours by gas
chromatography. The H
2
S concentration in the hydrogen can also be measured
using Drager tubes. Once a constant composition in species was observed (H
2
S,
methane, etc), a liquid sample was taken at the bottom of the gasliquid
F
u
r
n
a
c
G.C.
Flare
PI
FI
FI
P
PI
LI
Liquid
samples
H
2
S analysis
(Drager tubes)
Hydrogen
Nitrogen
DMDS /
n-dodecane
(1% sulfur)
separator and analyzed by gas chromatography. Liquid and gas compositions were
then used to established DMDS conversion and selectivity.
6. The reactor temperature was then increased by 18F (10C) and steps #5 and #6
were repeated. Hence, DMDS decomposition is described step by step at 300F,
318F up to the full conversion of DMDS into H
2
S and methane
Sulphur balance (sulphur introduced with DMDS compared to the sum of the sulphur
species analyse in gas and liquid) was done for each test at each temperature. The
results were found to be inside +/- 10% of the expected value showing that all the
compounds were detected and appropriately quantified by gas chromatography.
2.4. Kinetic Model
Specific experiments in gas phase only (without n-dodecane) have been done for the
kinetic estimation in order to avoid the liquid phase in the reactor. The hypothesis to
establish the model were the following :
1. The reactor is isothermal
2. The reactions take place only in gas phase
3. The flow is not dispersive
Each reaction was modelled as a Power law and the chemical equilibrium was treated
as two reversible reactions. The software gPROMS

was used to develop the reactor


model and estimate the kinetic parameters. The methodology to define the kinetic of
the reactions was the following:
1. The low temperature of the specific experiments (248-284F) were used to
estimate the parameter of the first reaction
2. To define the kinetics of the equilibrium, other experiments were done by injecting
a mix of H
2
S and DMS under Helium pressure to avoid the two last reactions. The
middle range temperature (284-338F) of the gas phase experiment were also
used to estimate those kinetic parameters
3. The two last reactions (Methane and H
2
S formation) were estimated by using the
results from high temperature (354-428F) gas phase experiments
The results from the kinetic model and the parameters established with gas phase
experimental tests successfully matched the tests performed in presence of n-
dodecane.
3. Results and discussion
The sulfiding reactions of molybdenum oxide and tungsten oxide have been established for
a long time and can be described bythe following equations:

(1) MoO
3
+ 2 H
2
S + H
2
MoS
2
+ 3 H
2
O

(2) WO
3
+ 2 H
2
S + H
2
WS
2
+ 3 H
2
O

The exact stoichiometry of the cobalt and nickel sulfides formed during sulfiding has not
been well established. However, equations (3) and (4) below are generally accepted
because they adequately correlate to the observed sulfur uptake of the catalyst.


(3) 3 NiO + 2 H
2
S + H
2
Ni
3
S
2
+ 3 H
2
O

(4) 9 CoO + 8 H
2
S + H
2
Co
9
S
8
+ 9 H
2
O

The transformation of metallic oxides to the corresponding sulfides is facile and
temperature dependent. The reaction is relatively slow below 350F and above 570F,
essentially complete conversion is obtained. Hence, most sulfiding procedures and
guidelines for commonly used HDP catalysts recommend starting the injection of sulfiding
agent at about 390F. Therefore we started our investigation of the DMDS decomposition
around 350
0
F.

Starting at 356F and at each subsequent temperature thereafter, we obtained stable
concentrations of all sulphur species in both gas (H
2
) and liquid (n-dodecane) phases
within 2 hours of stabilization. The composition and concentration of the sulphur species
changed with each temperature used in the study. The figures 2 and 3 show the DMDS
conversion to the various sulphur species on CoMo and NiMo respectively, at a pressure of
362 psig of hydrogen. One important observation was that between 430
0
F and 450
0
F, the
DMDS is completely converted to methane and hydrogen sulphide exclusively on both
CoMO and NiMo catalysts, as depicted by the following equation:

(5) CH
3
-S-S-CH
3
+ 3 H
2
2 CH
4
+ 2 H
2
S

Most catalysts manufacturers recommend performing the primary sulfiding in the 430
0
F
to 450
0
F range and wait for the breakthrough of H
2
S. Most HDP catalysts are about 55%
to 60% sulfided when H
2
S breakthrough occurs. This renders the catalyst robust enough
for the temperature to be further increased at a prescribed rate while DMDS injection is
continued, albeit at a reduced rate. Presence of an active form of sulphur such as H
2
S in
sufficient amounts ensures the appropriate oxidation state of the active metal to maintain
and avoid reduction by hydrogen present in the system. Some of the more active and
selective catalysts are known to be stable to reduction up to a temperature of 480
0
F, thus
the catalyst is never at this temperature without at least 3000-5000 ppm of H
2
S being
present in the recirculating hydrogen gas.

The results obtained in our study confirm that DMDS/E/E2 decomposes completely and
exclusively to H
2
S and CH
4
at these temperatures, thus providing excellent protection for
these catalysts while activating them at the same time. Some of the intermediates
formed at lower temperatures are good sulfiding agents in their own right and thus
DMDS/E/E2 provides active sulphur species in a wide range of temperatures spanning
both the primary and secondary stages of sulfiding.



0
10
20
30
40
50
60
70
80
90
100
180 190 200 210 220 230 240 250
Temperature (C)
P
r
o
d
u
c
t
s

f
o
r
m
e
d

b
y

D
M
D
S

d
e
c
o
m
p
o
s
i
t
i
o
n

(
w
/
w

%
)
356 365 374 383 392 401 410 419 428 437 446 455 464 473 482
Temperature (F)
DMDS
MeSH
DMS
CH4
H2S

Figure 2: DMDS decomposition on CoMo/Alumina catalyst under 362 psig of hydrogen
and in presence of n-Dodecane (LHSV=0.5 h
-1
)


0
10
20
30
40
50
60
70
80
90
100
180 190 200 210 220 230 240 250
Temperature (C)
P
r
o
d
u
c
t
s

f
o
r
m
e
d

b
y

D
M
D
S

d
e
c
o
m
p
o
s
i
t
i
o
n

(
w
/
w

%
)
.

356 365 374 383 392 401 410 419 428 437 446 455 464 473 482
Temperature (F)
DMDS
MeSH
DMS
CH4
H2S

Figure 3: DMDS decomposition on NiMo/Alumina catalyst under 362 psig of hydrogen
and in presence of n-Dodecane (LHSV=1h
-1
)

At temperatures as low as 356F, DMDS is completely decomposed. A mixture of
methylmercaptan, dimethyl sulphide, hydrogen sulphide and methane are formed. Methyl
mercaptan decreases steadily as the temperature is increased whereas dimethylsulfide
(DMS) reaches a maximum at around 380F before disappearing completely at 430F.
Methane and hydrogen sulphide are formed by the hydrogenolysis of methylmercaptan.
Dimethylsulfide, known to be more stable needs a higher temperature to be converted to
methane and hydrogen sulphide via sulfhydrolysis.

In order to establish the onset temperature of DMDS decomposition, the reaction
conditions were changed to a space velocity of 2 hr
-1
and a temperature of 300F.
Stabilization of the reactor effluent composition took a longer time (6 to 12 hours) due to
an overall lower reaction rate. Results of this experiment are shown in Figure-4. Even at
302F, the conversion of DMDS was 80% and the primary product was
methylmercaptan, formed by the hydrogenolysis of the sulphur-sulphur bond in DMDS.
Dimethylsuphide is a secondary product obtained from methylmercaptan
17
. This reaction
is described as equilibrium, catalyzed by the acid sites on the catalyst:

(6) CH
3
-S-CH
3
+ H
2
S 2 CH
3
SH

Internal experience corroborates this hypothesis: DMS is a by product in the manufacture
of methyl mercaptan.

0
10
20
30
40
50
60
70
80
90
100
150 155 160 165 170 175 180 185 190
Temperature (C)
P
r
o
d
u
c
t
s

f
o
r
m
e
d

b
y

D
M
D
S

d
e
c
o
m
p
o
s
i
t
i
o
n

(
w
/
w

%
)
302 311 320 329 338 347 356 365 374
Temperature (F)
DMDS
MeSH
DMS
CH4
H2S


17
V.Yu. Mashkin an S.N. Koshelev, Kinetic studies of methylmercaptan production from dimethyl sulphide and
H
2
S, React. Kinet. Catal. Lett., 46, N1, 187-192 (1992)
Figure 4: DMDS decomposition on CoMo/Alumina catalyst under 507 psig of hydrogen in
presence of n-dodecane (LHSV=2h
-1
) and at low temperatures.

We continued this study by extending the range of hydrogen pressure and space velocity
used to the following:
- Hydrogen pressure: from 217 and 870 psig (see figure 5)
- Space velocity: 0.5 to 2.0 hr
-1
(see figure 6)

Increasing the hydrogen pressure from 218 to 870 psig., increases the DMDS conversion,
as expected and similar amounts of hydrogen sulphide, and methane are formed at 20
0
F
lower temperatures at 870 psig compared to that at 217 psig. It is believed that the
catalyst surface gets saturated with adsorbed hydrogen even at 217 psig, thus increasing
pressure further has only a limited impact on the hydrogenolysis of DMDS.

The effect of varying the space velocity, however, is more pronounced. Decreasing it from
2 hr
-1
to 0.5 hr
-1
has the same effect as increasing the temperature 30
0
F. In these tests,
hydrogen to n-dodecane volumetric flow ratio was kept constant. As a consequence, an
increase of Liquid Hour Space Velocity - LHSV (n-dodecane flow rate) is accompanied by an
increase of hydrogen flow rate, leading to a significant change in residence time thus
affecting the hydrogenolysis of DMDS. It was however observed that DMDS was totally
converted to hydrogen sulphide/methane at about 450F, irrespective of the space velocity.

H
2
S
0
20
40
60
80
100
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
20
40
60
80
100
356 374 392 410 428 446 464 482 500
(F)
218 psig
870 psig
CH
4
0
10
20
30
40
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
10
20
30
40
356 374 392 410 428 446 464 482 500
(F)
218 psig
870 psig
DMS
0
5
10
15
20
25
30
35
40
45
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
5
10
15
20
25
30
35
40
45
356 374 392 410 428 446 464 482 500
(F)
218 psig
870 psig

MeSH
0
10
20
30
40
50
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
10
20
30
40
50
356 374 392 410 428 446 464 482 500
(F)
218 psig
870 psig

Figure 5: DMDS decomposition on CoMo/Alumina catalyst in presence of n-dodecane
(LHSV=1h
-1
), between 218 and 870 psig of hydrogen.
H
2
S
0
20
40
60
80
100
180 190 200 210 220 230 240 250 260 (C)
%

w
/
w
0
20
40
60
80
100
356 374 392 410 428 446 464 482 500
(F)
LHSV = 0.5 h-1
LHSV = 1 h-1
LHSV = 2 h-1

CH
4
0
10
20
30
40
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
10
20
30
40
356 374 392 410 428 446 464 482 500
(F)
LHSV = 0.5 h-1
LHSV = 1 h-1
LHSV = 2 h-1

DMS
0
10
20
30
40
50
180 190 200 210 220 230 240 250 260
(C)
%

w
/
w
0
10
20
30
40
50
356 374 392 410 428 446 464 482 500
(F)
LHSV = 0.5 h-1
LHSV = 1 h-1
LHSV = 2 h-1

MeSH
0
10
20
30
40
50
60
180 190 200 210 220 230 240 250 260 (C)
%

w
/
w
0
10
20
30
40
50
60
356 374 392 410 428 446 464 482 500
(F)
LHSV = 0.5 h-1
LHSV = 1 h-1
LHSV = 2 h-1

Figure 6: DMDS decomposition on CoMo/Alumina catalyst under 60 barg of hydrogen and
in presence of various n-dodecane (LHSV 0.5 hr
-1
to 2 hr
-1
).

The proposed hydrogenolysis mechanism for the decomposition of DMDS is supported by
the data presented in Figure 4. The low temperature experiments clearly indicate that the
hydrogenolysis of sulphur-sulphur bonds as the primary reaction. DMDS is converted at
low temperature (below 300F) to methylmercaptan and at 340F, the presence of
methane proves that methylmercaptan also start to get hydrogenolyzed to hydrogen
sulphide and methane. However, at 340F, another side reaction is observed, where
methylmercaptan gets converted partially to generate dimethylsulfide and hydrogen
sulphide. Finally, at 360F, which is generally the temperature where some refiners start
to inject DMDS, about half of the introduced sulphur is converted to hydrogen sulphide
from both the partial hydrogenolysis of dimethyldisulfide and from the methylmercaptan
dimethylsulfide equilibrium. At this temperature, this hydrogen sulphide reacts rapidly with
hydrotreating catalyst and initiates its conversion to the active metal sulfides. As the
temperature is increased, at 430-450F (see Figures 2 and 3), no more methylmercaptan
or dimethylsulphide are formed, with methane and hydrogen sulphide being exclusively
produced from DMDS. All these reactions from dimethyldisulfide are summarized in the
Figure 7 below.



Figure 7: Mechanism of DMDS decomposition on CoMo or NiMo/Alumina catalyst with
hydrogen (200 900 psig).

In order to provide a theoretical basis for our proposed mechanism (Figure 7) of DMDS
decomposition under hydroprocessing conditions via hydrogenolysis on CoMo and NiMo
catalysts, we attempted to build a kinetic model. Pre-exponential factor, partial orders and
activation energy were estimated for each reaction shown by obtaining extensive data at
different temperatures. Some specific data had to be obtained and evaluated for the DMS-
methylmercaptan equilibrium on partially sulfided HDP catalysts in order to more precisely
get the rate of reaction. Figure 8 depicts a check of the accuracy of our best fit model on
one set of experiments on CoMo catalyst, under conditions of 290 psig of hydrogen and
1 hr
-1
LHSV. Methane and hydrogen sulphide were particularly well estimated. Minor
differences remain for the methylmercaptan and dimethylsuphide, especially when their
concentrations are low. At least partially, these differences could be due to analytical
limitations (detection limit). The kinetic model should however, predict better estimations
of the concentrations of these species.



2 CH
4
+ 2 H
2
S
300-340F
330-450F
CH
3
-S-S-CH
3

2 CH
3
-SH
CH
3
-S-CH
3

+ H
2
S
320-
390
H
2

+ 2 H
2

+ 2 H
2

390-450F
H
2
S
0
20
40
60
80
100
180 190 200 210 220 230 240 250 (C)
%

w
/
w
0
20
40
60
80
100
356 374 392 410 428 446 464 482
(F)
Calculated
Real
CH
4
0
10
20
30
40
180 190 200 210 220 230 240 250
(C)
%

w
/
w
0
10
20
30
40
356 374 392 410 428 446 464 482
(F)
Calculated
Real
DMS
0
10
20
30
40
50
180 190 200 210 220 230 240 250
(C)
%

w
/
w
0
10
20
30
40
50
356 374 392 410 428 446 464 482
(F)
Calculated
Real
MeSH
0
10
20
30
40
50
60
180 190 200 210 220 230 240 250
(C)
%

w
/
w
0
10
20
30
40
50
60
356 374 392 410 428 446 464 482
(F)
Real
Calculated

Figure 8: Example of kinetic model results, in comparison with experimental data of
DMDS decomposition on CoMo/Alumina under 290 psig of hydrogen and 1 h
-1

LHSV.

4. Summary and conclusion
DMDS is one of the most commonly used thiochemical for sulfiding HDP catalysts insitu.
DMDS belongs at the top of the list of sulfiding agents recommended by all catalyst
manufacturers. The results from our study clearly indicate that DMDS is an excellent
surrogate for H
2
S in the activation of hydroprocessing catalysts via sulfiding, from both the
safety and efficiency points of view. The sulfur contained in DMDS is all efficient sulfur.
All of this sulfur is transferred on to the catalyst during the process of insitu sulfiding.
DMDS decomposes via hydrogenolysis, first to methyl mercaptan (CH
3
SH)

and then as the
temperature increases, the methyl mercaptan is converted to methane and H
2
S, a small
portion of it via DMS. The catalyst manufacturers have innovatively improved the intrinsic
activity of the HDP catalysts steadily in the last decade. All of these catalysts can be
activated to exhibit the expected optimum activity via sulfiding with DMDS. The
decomposition of DMDS can be controlled by the conditions employed and thus eliminates
unplanned exotherms and excursions that could compromise safety.

Refineries, especially those located close to residential neighborhoods and public places like
schools etc are under greater pressure to keep the odors to a minimum. Innovation by
Arkema to incorporate a new fragrance in DMDS to impart a user-friendly odor to DMDS in
their current offering DMDS-E2, has essentially helped refiners avoid unpleasant odor
outages. In fact the original version, DMDS-E has been doing so for well over a decade.
The Carelflex

service offered by Arkema assists in delivering the DMDS-E2 to the refinery


in a safe and reliable manner and safely introducing it into the HDP reactor. This service
has now been expanded to inject DMDS at elevated pressures.

Increasing hydrogen pressure during sulfiding and decreasing the LHSV, decreases the
temperature at which DMDS decomposition to the intermediates and eventually to H
2
S
takes place. The more pronounced effect seems to be that of decreasing the LHSV. The
corroboration of results between the Kinetic Model and the Pilot Tests further goes to show
that DMDS is perfectly suitable for both liquid and gas phase sulfiding of HDP catalysts.
The low temperatures at which DMDS starts to generate H
2
S allows it to protect the
catalyst from undergoing reduction by hydrogen. Since maintaining a healthy concentration
of H
2
S in the recycle hydrogen gas at relatively low temperatures, is seen as the key to
obtaining an optimally active catalyst, DMDS is well positioned to satisfy this need in an
efficient and controlled manner.







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