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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