Catalytic Hydrotreatment - Société Chimique de · PDF fileCatalytic...

Catalysis in France: an Adventure 2007, July 1 / 16

Christophe Geantet, IRCELyon ([email protected]) and

Michèle Breysse, Université Pierre et Marie Curie ([email protected])

Hydrotreatment processes permit, by hydrogen treatment, the purification of

petroleum cuts by reducing the amounts of sulfur containing compounds

(hydrodesulfurization), of nitrogen containing compounds (hydrodenitrogenation), of

oxygen containing compounds (hydrdeoxygenation) and for heavy cuts also the amounts

in metals containing compounds (hydrodemetallation). These processes are utilised for

the treatment of all kinds of petroleum cuts, light products such as gasoline and heavy

products such as vacuum residues. Depending on the nature of the feed, various

conditions are used. The world capacity for hydrotreating is presently circa 1 Gt/year

of petroleum cuts for circa 2000 units and an annual consumption of catalysts of

100 000 t/year which represents almost 10% of the worldwide market of catalysts.

The elimination of sulfur compounds has constituted the main objective during many

years. Sulfur is present in important amounts in crudes in various heteroatomic

compounds which nature and concentration depends strongly on their geographical

origin. Desulfurization is essential for allowing the utilisation of noble metals catalysts

(Pt) in some refining process, such as catalytic reforming, the main process leading to

gasoline production with high octane number. Nowadays, all transportation fuels

(gasoline, kerosene, gas oils), heating and industrial fuels are desulfurized in order to

limit sulfur oxides formation and allowing a good working of the devices of purification

of car exhausts gas. More and more stringent limitations of the concentration of sulfur

containing compounds in transportation fuels have been applied for more than twenty

years in EU, USA and Japan (Table 1).

Table1 – Maximal amount (in ppm S) in gasoline and gasoil in EU Before1996 1996 2000 2005 2009

Gasoline, ppm S 350 350 150 50 10 Gasoil, ppm S 2000 500 350 50 10

Catalytic Hydrotreatment

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mailto:[email protected]


Taking into account the predictable rarefaction of light crudes containing rather low

amounts of impurities, heavy crudes and cuts issued from coal and biomass will have to

be utilised. They contain higher amounts of nitrogen, oxygen and metals, which imply the

adaptation of the present catalysts and processes.

In 1977, just after the first oil crisis, a French thematic program on the

hydrodesulfurization of petroleum fraction started at the Institut de Recherches sur

la Catalyse (IRC in Lyon) under the direction of L. de Mourgues. This programme also

involved three academic laboratories (Lille - J.-P. Bonnelle, Montpellier - P. Geneste and

Toulouse - B. Gilot). This collaboration went on in 1979 within a DGRST contract

associating the IRC, Lille, Montpellier and in addition IFP (Y. Jacquin) and the

University of Caen (D. Cornet). The field of interest was extended to

hydrodenitrogenation and the preparation of unsupported or carbon supported

catalysts, in order to get a better understanding of the synergetic effect. Thus, the

federative organisation of this research theme appeared and was materialised after

the arrival of M. Breysse in the HDT group of IRC, in 1983. Then, thanks to the

continuous support of industrial partners (Elf, Total, Procatalyse, IFP) and of CNRS

programmes (Ecotech and Ecodev), a hydrotreating community was born, associating new

catalysis laboratories (Poitiers, G. Perot) and occasionally some specialists from sold

state chemistry, organic chemistry and chemical engineering. An illustration of the

activity of this community was given by two issues of Catalysis Today gathering studies

dedicated respectively to NiW sulfide1 and hydrodenitrogenation2. Taking into account

the considerable interest of this subject, at the industrial and academic levels, other

teams, like that of M. Ledoux in Strasbourg worked also on these subjects outside the

federate organisation mentioned above.

Topics and references given below have selected among hundreds of publications

incoming from these groups.


1 - Mechanisms, kinetics and reactivity in hydrotreatment

Catalytic hydrotreatment is a direct inheritance of coal technologies developed in

Germany at the beginning of the twentieth century. BASF researchers identified

transition metal sulfides as catalysts of coal hydro-liquefaction and from 1924 used

molybdenum sulfide in their processes. Then, just after the world war II,

hydrotreatment processes, involving mixed molybdenum and cobalt sulfides supported

on alumina, were developed in USA. Since that time, the refining industry has utilised

this combination of sulfides and developed new associations of supported sulfides

(NiMo and NiW) for more specific applications.

The initial demand of French industrial laboratories to academic people dealt with the

evaluation of catalyst performances in a fundamental approach utilising model

reactants.

Chronologically, the first topic dealt with kinetic and mechanistic studies on HDS. M.

Vrinat’s review about the kinetic of hydrodesulfurization is still very often cited3. This

Langmuir-Hinshelwood approach initially limited to competitive adsorption of the

reactant and H2S, now takes into account hydrogen and/or H2S activation and then

contributes to the understanding of inhibiting effects in HDT4. Depending on the H2S

partial pressure and on the catalyst type, the limiting step of the reaction (often the

activation of hydrogen) might be modified.

Factors influencing the reactivity of organic molecules (aromaticity, C-S or C-N

bondings) were then studied5,6. In the 90s, the evolution of environmental constraints

required the understanding of deep desulfurization. The refractory molecules being

identified, mechanistic studies of the conversion of model molecules such as 4,6-

dimethyldibenzothiophene (4,6-DMDBT) permitted to clarify the two desulfurization

routes7 (hydrogenation HYD and direct desulfurization HDS, Figure 1) and to determine

the main role of Co or Ni dopants on the selectivity8,9. Finally, it has been shown that,


among the family of refractory compounds, the reactivity changes dramatically from

one molecule to another10 and that important competitive phenomena with aromatics or

nitrogen containing molecules have to be taken into account11. Besides, the ultimate

elimination of these compounds can be performed by alternative routes, different from

conventional hydrotreating, and a recent review summarizes these new aspects12.

Figure 1: Hydrodesulfurization scheme of dibenzothiophenes

In parallel to these studies about desulfurization, an analogous approach was devoted to

hydrodenitrogenation. The introductory works about HDN, summarized at the time in

two review articles13, 14 were followed by studies implying substituted molecules. These

last studies evidenced several types of reactions mechanisms for the cleavage of the C-

N bond, depending on the nature of the unsupported sulfide catalyst implied15. These

studies are considered as reference tools in the field. Taking into account the evolution

of the regulations and the appearance of two stages processes, considering using noble

metals in the second reactor, kinetic studies of hydrodenitrogenation reactions in the

presence of Pt supported catalysts have been carried out16.

Aromatics hydrogenation in the presence of H2S, often used as an evaluation method

for catalytic properties17, is now the topic of new studies, considering its influence on

cetane number18. Similarly, the selective opening of cyclic aromatics in the presence of

bi-functional catalysts has recently been explored19.

M -

M -H -

M -H S -

H2 +

S2 -

H S - S

2 - H Y D

E 2 - D D S

S2 - H S-

M

M - + H2

+

S2 - M - H -

+ H S -M- +

H 2 S + S 2- M - S H-

+ H S -

Heterolytic dissociation S

S

M S

M

SH

H

S-

H 2 M - =

Coordinatively

unsaturated site

+ H 2 S

H -

M

H S - S 2 -

M

SH


The studies related to the activation of hydrogen on sulfide catalysts, a field where the

French contribution is of major importance, have been summarized in a recent review20.

In these studies, the heterolytic dissociation of hydrogen21, the influence of the

dispersion of the catalyst on this activation22, the roles of the support23 and the

dopant24 have been shown.

The drastic political pressure for the decrease of the sulfur amount in gas oils has

similarly led to a decrease in the sulfur amount of gasoline. In the gasoline pool, sulfur

comes mainly from FCC blends which contribute to 99% of the total sulfur amount as

mercaptans, thiophenes and benzothiophenes. The new regulations applied in 2000

required the introduction of gasoline desulfurization units in the refining scheme. A

conventional hydrotreatment process can easily solve this desulfurization problem but

simultaneously leads to the hydrogenation of olefins and consequently to a decrease of

octane number and an increase of hydrogen consumption. IFP (AXENS) has developed a

very efficient process named PRIME G®for this selective desulfurization . This subject

has been also addressed by academic researchers25 and a review has been recently

published26 . Finally, deep desulfurization of gasolines or gas oils can also be achieved by

alternative processes avoiding the use of expensive hydrogen. Thus, the formation of a

charge transfer complex (CTC) between the 4,6-DMDBT and an acceptor such as the

dichlorodicyanobenzoquinone (DDQ) or the tetranitrofluorenone (TENF) can occur with

the refractory compounds containing sulfur or nitrogen27,28 by means of a simple

separation step.

In the context of the deep desulfurization of gasolines, the alkylation of sulfur

containing molecules by an olefin followed by a distillation which allows the extraction

of these unwanted compounds has also been addressed in academic study29.


2 - Active phases in hydrotreating

Industrial catalysts are composed of a sulfide active phase, usually Mo sulfide (more

rarely W sulfide) doped by Ni or Co and supported on a high surface oxide like � alumina

(150 to 270 m2/g). The metal amounts are typically around 10% for Mo and 2.5 % for Co

or Ni. The catalysts are often doped by phosphorus (a few weight %). Their preparation

involves numerous steps, all of them important for the activity of the catalysts. In

general, there is at first, an impregnation step, and then a calcination step leading to an

oxidic state and finally a sulfidation step carried out in-situ or ex-situ (Sulficat® ot

Totsucat® processes)30.

In order to get a better understanding of the active phases properties and synergetic

effects, it was necessary to get on one hand, a precise characterization of industrial

catalysts, and on the other hand a fundamental approach involving unsupported

catalysts31.

Each step of the preparation of industrial catalysts and model catalysts were tackled

with specific studies: characterization of the oxidic state of the catalyst32,33, the role

of impregnation34, the influence of P-doping35 as well as the catalyst activation by means

of gas phase sulfidation, in industrial conditions36-40 or by means of a sulfiding agent41,42.

The role of carbon on the catalytic activity43 and the poisoning effect of metals44 have

been shown. All these studies show the importance of each step on the genesis of the

catalyst and its evolution during the catalytic reaction and the origin of its deactivation.


Figure 2 : Hydrogenating (biphenyl hydrogenation) and hydrodesulfurizing (dibenzothiophene HDS) properties of transition metal sulfides.

The fundamental approach using unsupported catalysts or models supported ones (on

carbon, contribution of the University of Strasbourg, M. Ledoux) has its origin in

Chianelli’s original work concerning the “volcano curves” giving the desulfurizing activity

as a function of the position of the element in the periodic table for all the transition

metal sulfides. This trend was completed by studies for other reactions involved in the

hydrotreatment processes45,46 as illustrated in figure 2.

These studies led to the research of new active phases. Thus, numerous studies were

devoted to ruthenium sulfide47 or niobium sulfide48 based catalysts, doped or as solid

solutions49,but also to more original compounds like molybdenum carbide50,51.

It also opened the way to new preparation methods using as precursors

heteropolymetallics compounds52 or polysulfides precipitated in the MoS2 form, under

soft conditions53.

Besides sulfides, Mo carbides were studied extensively, as hydrotreating catalysts, by

G. Djéga-Mariadassou and his team (LRS, Paris). Actually, carbides present high

hydrogenating properties which could be interesting in a two steps hydrodesulfurization

processes as well as in hydrodenitrogenation. As for sulfides, carbides can be supported

by alumina54 and doped by phosphorus55. In the presence of very small amounts of H2S,

they are more active than sulfides55. Moreover, they can be supported on carbon56,


which simplifies their preparation. Many recent works utilize mesoporous composites

carbons as supports57,58.

3 - Characterisation techniques of hydrotreating catalysts

Improvement in the knowledge of these extremely complex catalysts requires the use

and development of physical and chemical characterization techniques, especially in situ

techniques. In this field, the hydrotreating community was very early involved in the use

of XPS 59 and Raman60 spectrocopies, solid state NMR61 and the development of the IR

technique with molecular probes for site counting62 et characterizing acid-base

properties63. All these techniques benefit from evolutions such as the use of

mercaptans64 as probe molecules and the possibility of studying dispersed unsupported

sulfides. Transmission microscopy (and related techniques such as EDS, EELS, HAADF),

which first allowed to visualize MoS2 nanoparticles, remains a unique tool for analysing

and imaging nanoobjects65. This technique allows an atomic resolution of RuS266

supported nanoparticles morphology (Figure 3). In situ and time-resolved X-ray

absorption gives unique structural information on the evolution of the catalyst during

the sulfidation step67. Inelastic diffusion of neutrons was utilized for characterizing

hydrogen and ammoniac adsorption on sulfide catalysts68. Very recently, the use of last

generation XPS spectrometer has permitted the discrimination of the various Co

species (CoMoS, Co9S8, Co aluminate)69.

Experimental image Simulated image (Ru large circles, S small circles)

Figure 3: RuS2 nanoparticle supported on silica and simulation of images of the

atomic columns.


4 - Support effect in hydrotreatment

As mentioned above, industrial hydrotreating catalysts are composed of an active

sulfide phase usually supported on alumina. The almost exclusive use of alumina is

related to its mechanical and textural properties and to its relative low cost. However,

it was recognized in the very first studies related to these catalysts by H. TopsØe in

Danemark70, that alumina is not an inert carrier and that the promoter ions, Co or Ni,

can react with the support and occupy octahedral and tetrahedral sites in the surface

layers of the support depending on the reaction conditions. The existence of strong

interactions between the precursor salt of Mo (or W) and alumina has been also

evidenced by X. Carrier et al.71,72 and characterized by Raman73 spectroscopy. The

substitution of alumina by other supports would allow to get rid of these interactions,

to increase the dispersion of the active phase and to modify its morphology and possibly

its electronic properties. Lastly, for some reactions, the acid-base properties of the

support could play a beneficial role.

Utilization of other supports was addressed very early by the French researchers and

it is still a very active domain. The use of titanium oxide74, zirconium oxide75,76, nickel or

magnesium aluminates77 was examined by the French teams who published the first

reviews articles related to this field of research 78,79.

These studies had several aspects: i) the development of supports of enhanced textural

properties in order to compete with alumina, ii) the development of new methods of

preparation of the active phase and detailed understanding of the observed

phenomenon, particularly in the case of titanium oxide. For this last oxide, the recent

contribution of theoretical chemistry has been determining (see next paragraph).

Then, numerous developments of mixed oxides allowing at the same time the

stabilization of the textural properties and the modification of the acid-base


properties have been proposed, especially thanks to the melted nitrates bath synthesis

methods80. A review article was recently published on these subjects81. Considering the

context of deep desulfurization, zeolitic supports have been also investigated82,83 and

the influence of the support acidity on the reaction schemes and the active phase

properties studied84,85. However, due to the present tendency to treat more man more

heavy petroleum cuts, the utilization of zeolites as acid supports is limited due to the

fact that the biggest molecules cannot enter into the microporous cavities of the

supports. Thus, the study of mesoporous supports such as MCM-41, MCM-48 or SBA-15,

with larger ordered pore structure has also been undertaken with the hope to solve this

dfficulty86,87. New materials combining the acidity of a conventional zeolite with the

open structure of a mesoporous solid could be also envisaged88.

5 - Modelling and theoretical approach

By comparison to other fields of catalysis, hydrotreatment is, with catalysis by metals,

one of the favourite subjects of theoretical and modelling studies. Thus, hydrotreating

community had benefited from the wealth of the French catalytic field in theoretical

chemistry and modelling teams: at the Institute of Research on Catalysis (B. Bigot and

P. Sautet), at the laboratory of Lille (J.-F. Paul, S. Cristol) and at IFP (H. Toulhoat and

P. Raybaud).

Modelling of sulfides catalysts began with a geometrical approach89, but soon benefited

from more and more efficient theoretical tools. For example, the study of the

activation of hydrogen by ruthenium sulfide confirmed experimental results90,91. Recent

approaches are based on the density functional theory combined with thermodynamic

and microkinetic models92. This theoretical approach has been used first for elucidating

the properties of active phases of industrial catalysts Co(Ni)MoS: localization and role

of the promoter, electronic properties and morphological changes induced by the

reaction conditions or by promoter addition (Figure 4)93, 94.


Similarly, the modelling of the supports surface such as alumina and titanium oxide in

conditions close to those of the hydrodesulfurization reactions has been achieved (PH2O,

PH2S, PH2 and T) 95,96. DFT simulation have recently been shown to give new insights at

the atomic scale on the interface between MoS2 and the support while any available

techniques, even the most advanced ones have shown to reach their limits of

sensitivity97.

The theoretical approach has also led to a better understanding of the adsorption mode

of hydrogen98,99, as well as those of sulfur containing molecules and to the elucidation of

the determining steps of their conversion mechanisms. These studies are related to

thiophene100,101, and also DBT 102.

In parallel to these studies related to Mo based systems, DFT simulation combined to

microkinetic models help to rationalize “volcano-curve” type relationship between

hydrodesulfurization or hydrogenation activities and the sulfur-metal bond energy103 104.


Figure 4. (a) TEM image of layers of active phase supported on alumina-γ. Representation at the atomic scale (b) of the hydroxylated surface (110) of alumina-γ and (c) of a monolayer of CoMoS in HDS conditions.

6 - Conclusion

For more than thirty years, the French hydrotreating community has largely

contributed to the development and knowledge in this research area and in all the

various aspects it involved. This community has been involved in the synthesis of new

solids (supports and active phase), and in the characterisation and deep understanding

of catalytic phenomena and catalysts. Most advanced techniques and modelling have

been utilised and developed. It is important to mention that these academic researches

have been carried out in close collaboration with industrial partners which has

permitted a constant confrontation of the results obtained at the laboratory scale with

the complex reality of the industrial process. Although, it is sometimes considered that

hydrotreatment is a mature subject, the demand from the industry for enhanced

(a)

γ-Al2O3 CoMoS (b)

(c)

OxygèneHydrogèneAluminium

OxygèneHydrogèneAluminium

MolybdèneSoufreCobalt

MolybdèneSoufreCobalt


fundamental knowledge of the catalysts, conventional or new active phases, and for

more efficient and selective processes is still very strong.

Acknowledgments:

The authors thank Pascal Raybaud for having kindly transmitted Figure 4, which

illustrates the modelling part.

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