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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 90’s 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 1990’s (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. Topsøe, 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. Topsøe, 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. Topsøe, “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 C–240°C; 392 0 F-464 0 F) and completed at temperatures greater than 300°C 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 - 200°C) 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. Gøbel, B. Hinnemann, Z. Li, K.G. Knudsen, H. Topsøe, 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. Pérot, V. Harlé, 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 (417–424°F) 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:

Hydrogen

Nitrogen

DMDS /

n-dodecane

(1% sulfur)

G.C. Flare PI P PI H 2 S analysis (Draëger tubes) FI LI FI Liquid
G.C.
Flare
PI
P
PI
H 2 S analysis
(Draëger tubes)
FI
LI
FI
Liquid
samples
Furnac

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 300°F (150°C) 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 300°F, 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 Draëger tubes. Once a constant composition in species was observed (H 2 S, methane, etc…), a liquid sample was taken at the bottom of the gas–liquid

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 18°F (10°C) and steps #5 and #6 were repeated. Hence, DMDS decomposition is described step by step at 300°F, 318°F… 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 (248-284°F) 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 (284-338°F) 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 (354-428°F) 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

(4)

9 CoO

+

8 H 2 S

+ H 2 

Ni 3 S 2

+ 3 H 2 O

+ 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 350°F and above 570°F, 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 390°F. Therefore we started our investigation of the DMDS decomposition around 350 0 F.

Starting at 356°F 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.

Temperature (°F)

356 365 374 383 392 401 410 419 428 437 446 455 464 473 482
356
365
374
383
392
401
410
419
428
437
446
455
464
473
482
100
90
DMDS
MeSH
80
DMS
70
CH4
60
H2S
50
40
30
20
10
0
180
190
200
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220
230
240
250
Products formed by DMDS decomposition (w/w %)

Figure 2:

Temperature (°C)

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

Temperature (°F)

356 365 374 383 392 401 410 419 428 437 446 455 464 473 482
356
365
374
383
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401
410
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482
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DMDS
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MeSH
DMS
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CH4
70
H2S
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40
30
20
10
0
180
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250
Products formed by DMDS decomposition (w/w %).

Temperature (°C)

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 356°F, 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 380°F before disappearing completely at 430°F. 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 300°F. 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 302°F, 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.

Temperature (°F)

302 311 320 329 338 347 356 365 374 100 DMDS 90 MeSH 80 DMS
302
311
320
329
338
347
356
365
374
100
DMDS
90
MeSH
80
DMS
CH4
70
H2S
60
50
40
30
20
10
0
150 155
160
165
170
175
180
185
190
Products formed by DMDS decomposition (w/w %)

Temperature (°C)

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, N°1, 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.

% w/w

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 450°F, irrespective of the space velocity.

H

2 S

356 374 392 410 428 446 464 482 500 100 218 psig 80 870 psig
356 374
392
410
428
446
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482
500
100
218
psig
80
870
psig
60
40
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0
180 190
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260
% w/w

DMS

356 374 392 410 428 446 464 482 500 45 40 218 psig 35 870
356 374
392
410
428
446
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482
500
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40
218
psig
35
870
psig
30
25
20
15
10
5
0
180 190
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260

(°F)

100

80

60

40

20

0

CH 4

356 374 392 410 428 446 464 482 500 40 30 20 218 psig 10
356 374
392
410
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446
464
482
500
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20
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psig
10
870
psig
0
% w/w

(°F)

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10

0

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260
(°C)
(°C)
MeSH
(°F)
(°F)
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374
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40
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psig
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870
psig
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10
10
5
0
0
0
180
190
200
210
220
230
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250
260
(°C)
(°C)
% w/w

Figure 5: DMDS decomposition on CoMo/Alumina catalyst in presence of n-dodecane (LHSV=1h -1 ), between 218 and 870 psig of hydrogen.

% w/w

% w/w

H 2 S (°F) 356 374 392 410 428 446 464 482 500 100 100
H 2 S
(°F)
356 374
392
410
428
446
464
482
500
100
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80
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60
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LHSV = 0.5 h-1
LHSV = 1
h-1
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20
LHSV = 2
h-1
0
0
(°C)
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210
220
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(°F)
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% w/w
50 LHSV = 0.5 h-1 40 LHSV = 1 h-1 30 LHSV = 2 h-1
50
LHSV = 0.5 h-1
40
LHSV = 1
h-1
30
LHSV = 2 h-1
20
10
0
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(°C)

CH 4

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LHSV = 0.5 h-1
LHSV = 1 h-1
10
LHSV = 2 h-1
0

(°F)

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20

10

0

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260
(°C)
MeSH
(°F)
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LHSV = 0.5 h-1
50
LHSV =
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30
30
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10
0
0
180 190
200
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260
(°C)
% w/w

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 300°F) to methylmercaptan and at 340°F, the presence of methane proves that methylmercaptan also start to get hydrogenolyzed to hydrogen sulphide and methane. However, at 340°F, another side reaction is observed, where methylmercaptan gets converted partially to generate dimethylsulfide and hydrogen sulphide. Finally, at 360°F, 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 430-450°F (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.

CH 3 -S-S-CH 3

H 2

CH 3 -S-S-CH 3 H 2 300-340°F 2 C H 3 - S H + 2

300-340°F

2 CH 3 -SH

+ 2 H 2

3 H 2 300-340°F 2 C H 3 - S H + 2 H 2 330-450°F

330-450°F

2 CH 4 + 2 H 2 S

320- 390° + 2 H 2 CH 3 -S-CH 3 + H 2 S 390-450°F
320-
390°
+ 2 H 2
CH 3 -S-CH 3
+ H 2 S
390-450°F

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.

% w/w

H 2 S (°F) 356 374 392 410 428 446 464 482 100 100 80
H 2 S
(°F)
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374
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482
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Calculated
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Real
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0
0
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250
(°C)
DMS
(°F)
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482
% w/w
50 50 Calculated 40 40 Real 30 30 20 20 10 10 0 0 180
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Calculated
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Real
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10
0
0
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250 (°C)
CH 4 482 (°F) 356 374 392 410 428 446 464 40 40 30 30
CH 4
482 (°F)
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392
410
428
446
464
40
40
30
30
20
20
Calculated
10
10
Real
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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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