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Ch.

1 Catalyst

Chapter 1
Catalyst
1.1 Introduction
Catalyst plays an important role in large no. of important
processes in chemical engineering especially in hydrotreating
because it is a catalytic process. As the catalyst change we can
meet any required specification and/or do treating for any
process.
The following examples will well illustrate this idea.
A new sulfur specification of gas of 50 ppm. was imposed at
the end of 2004 in Japan. However most of Japanese refineries
marketing and distributing 50 ppm. Sulfur gas oil since April
2003, ahead of legislation. This was an ongoing process with
the Japanese refineries developing strategies to produce and
market sulfur free gas oil [less than 10 ppm.] at the end of
2005.
On December 2000, the U.S. environmental protection agency
(EPA) administrator signed a final rule on heavy duty engine
and vehicles standards and high way gas oil sulfur control.
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The final rule mandates that refineries and importers of gas oil
reduce the sulfur content to 15 ppm. at June 2006.
In April 2001 the European commission adopted directive
2001, this introduced amendments to the Euro standard of gas
oil and gasoline specifications. Sulfur specification of gas oil
is 50 ppm. In 2005 and 10 ppm. in 2009.
Catalyst suppliers have been putting intensive efforts to
develop new catalysts to meet stringent regulations of
petroleum products.

1.2 Types, composition and structure of

the used catalyst


1.2.1 Catalyst types
Catalysts used and developed for hydrotreating include
metals oxides as shown in the table 1.1 on alumina or
alumina silica support, the shown percentages means
that there is more than one choice according to the
application we do.
The selection of CoMo / Al2O3 catalyst due to its highly
selective, easy to generate and resistance to poisoning.
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Catalyst
Compositio
n
Range %

NiO CoO MoO3 WO3 P2O5 Al2O3 SiO2


0:13 0:6 0:30 0:30 0:10 40:95 0:45

Table 1.1: catalyst composition ratios

1.2.2 Catalyst design and structure


Hydrotreating catalysts are (as the common use) either Mo or
W promoted with Co or Ni and supported on a gammaalumina carrier and sometimes mixed with silica, K, P, B or
rare earth oxide promoters may be added to lower the acidity
of the catalyst and / or improve Mo sulfidability. Addition of P
is known to increase the activity of Ni-Mo catalysts for HDN;
whether P increases Mo dispersion is controversial.
While Co and Ni sulfides have relatively low HDS or HDN
activity relative to Mo sulfide, when combined in solid
solution with Mo lead to increase the specific gravity of Mo
by factors of (2-10). CoMo is generally more expensive and
used principally for special applications in which high
saturation and moderate cracking of low sulfur feed stocks are
desired.
A key specific of catalyst design in hydrotreating is the
optimization of pore structure. The ability to adjust pore size
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to concentrate pores around a particular diameter has a great


impact on hydrotreating activity both start of run (SOR) and as
catalyst ages. Reactions taking place in hydrotreting of gas oil
(200: 566 o C) generally requires a minimum pore size to
overcome most diffusional restrictions. Pores that are larger
than necessary lend little to improving diffusional
characteristics and as the pore diameters of the catalyst
increase the surface area decreases (at constant pore volume).
Activity generally with surface area and loss in pore volume
occurs in smallest diameter pores first. Highest activity
retention is maintained if pore volume is concentrated in very
narrow range of pore diameters. At the hydrotreating severity
to reduce sulfur in light cycle oil (LCO) to 0.05 wt. % the
performance of high activity catalysts NiMo and CoMo appear
to be equivalent. For middle distillate fractions crude oil
containing high concentration of nitrogen reduction is
achieved by using a catalyst charge of 90% (Ni-Mo) and 10%
(Ni-W), where the nitrogen has been implicated in sludge
formation and light instability of gas oil.
The following figures show the micro structure of different
catalysts.

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Figure 1.1 : Catalyst for hydrodemetallation

Figure 1.2

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Figure 1.3 : STM Scanning Tunneling Microscopy

Mo

Co

Figure 1.4

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Figure 1.5

1.3 Catalyst processing


1.3.1 Loading the catalyst
Loading the catalyst in the reactor is an important step because
the mass of catalyst loaded in relation to a definite reaction
volume depends on how well packed it is. Packing depends
not only on catalyst characteristics (specific gravity, grain
shape and size) but also on the loading method. The catalyst
must be uniformly packed all throughout the volume, both
vertically and radially in order to prevent channeling. The
tighter the packing, the more catalyst is required and
consequently the greater the activity of the reaction volume.
However, there is also a greater risk of pressure loss problems.
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The two main methods of catalyst loading are the "sock"


method that gives loose packing and the "dense" method that
usually causes an increase of 15% in packing density.

1.3.2 Sulfiding the catalyst


The catalyst in oxide form must be activated by converting the
hydrogenation metals from oxide form to sulfide form.
The catalyst was sulfided either by H2S /H2 mixture or using
dimethyl disulfide (H3C-S-S-CH3) {DMDS} in presence of
hydrogen. Sulfiding the catalyst with DMDS/H2 instead of
H2S/H2 yielded more acidic and hydrogenolysing properties
for the C-S bond but less hydrogenating capacity. Sulfidation
by DMDS/H2 is applied by injecting the sulfiding chemical
into oil feed during star up. The sulfiding reaction is highly
exothermic and care must be taken to prevent excessive
temperature during activation.
The origin of promotion exist in the catalyst, due to presence
of a second metal, gives activities greater than the simple one
based on the binary sulfides, such as the Co and Ni promoted
MoS2 or WS2. The relation suggested that the promotional
effect exists between the two activities of the will Co and Ni
promoted MoS2, Ws2 catalyst and periodic trends for the
binary sulfides. Studies of promotion have led to the idea of
(contact synergy) for sulfided catalysts containing Co or Ni
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together with Mo or W, but there is another correct idea said


that Ni/Mo , Co/Mo, Co/W and Ni/w can behave as ( synergic
pairs), work together or cooperate.
The bulk binary phases or these elements, Ni8S2, Co9S8, MoS2
and WS2 are present in the unsupported catalyst but the rent
work provide their presence in both supported and
unsupported catalysts. Although Co9S8 and Ni3S2 have been
described as a promoter of MoS2 or WS2. These phases
themselves have activates which are of the same order as
MoS2. The synergic pairs of active sulfides give enhancement
of activity far greater than would be expected by simultaneous
presence of non interacting phases. The relation between the
activity of these synergic pairs and the periodic trends for
binary sulfides appear by examining the average heats of
formation of the sulfides of the synergic pairs. The most active
catalyst has a heat of formation between 30: 50 Kcal/mol.
There is a correlation between Hf for sulfides, and are
linearly correlated with heats of adsorption of sulfur on
transition metal surface. This reflects under catalytic condition
and the optimum metal sulfur bond strength on surface of
catalyst, the elements in the periodic table can divided into :1- Left of periodic table sulfides have high Hf bind sulfur
too strongly so it poisoned by sulfur.
2- Right of periodic table sulfides has low Hf and sulfur
bearing molecules are likely bound too weakly for reaction
to occur.
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Thus the sulfides have intermediate Hf bind S occur bearing


molecules neither too strongly nor too weakly, are effective
catalysts. So the synergic pairs of the elements from the
hydrotreating catalyst (CoMo-) have intermediate heat of
formation. The average heat of formation of the synergic pairs
falls in the 35:50 Kcal/mol rang known as promoters. And any
other elements fall outside this range not known as promoters.
The general surface areas of synergic pairs are lower than
those of pure phases (15-25m2/g) where as MoS2 prepared in
similar manner have surface area in the rang of 50 m2/g.
This suggests that in the synergic pairs the number of active
sites is not increasing but rather that the quality of the active
sites may be enhanced.

1.3.3 Regeneration the catalyst


Hydrotreating catalysts become deactivated with time mainly
because of coke deposition. Deactivation is rapid at beginning
of a run and then slows down afterward. Carbon deposits are
promoted by a high reaction temperature and low hydrogen
pressure. This type of deactivation is reversible since the
carbon can be burned during regeneration.
Another important source of deactivation is the deposit of
metallic impurities such as Ni,V,Si,Pb,As, etc. These poisons
are irreversible but are generally laid down at top of the bed
because of reactivity. Consequently, the top of the bed can be
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"skimmed off" and new catalyst can be added if the aim is to


save on catalyst.
,
One way of measuring a hydrotreating catalyst s resistance to
deactivation is the duration of the run. It usually lasts several
years for light cuts such as gasoline, kerosene and gas oil but
is considerably shorter for heavier cuts or cuts that are
seriously polluted by metallic impurities Table 1.2
Distillate hydrotreating catalysts are regenerated several times
during their lifetime. Regeneration consists in burning the
coke "CxHy" and the sulfur and nitrogen it contains, and
removing the sulfur from the sulfide phase "Co0.5 Mo2.5" by
oxidation as shown below in the overall reaction:
Co0.5 Mo2.5 +CxHy + [(17+y+4x)/ 4] O2
0.5CoO + MoO3 + 0.5YH20 + xCo2 + 2.5So
When regeneration is carried out in the hydrotreating unit
reactor, the combustion stages must be very carefully
controlled. Combustion is performed by injecting of steam and
air or nitrogen and air. In both cases the oxygen content must
be very low to prevent runaway combustion due to the very
highly exothermic combustion reactions. The procedure is
generally to increase the oxygen concentration and the
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temperature very gradually. Ex-situ regeneration is


increasingly practiced. Since it shortens downtime for the
units and simplifies shut-down procedures. It also guarantees
better control of combustion. With regeneration, the lifetime
of a hydrotreating catalyst can be extended up to ten years
Table 1.2
Petroleum cut
Run duration ( Year)
Gasoline / Kerosene
2:4
Gas oil / Vacuum Gas
1:2
oil
Rrsidue
3 months : 1year

Life times ( Year )


4:10
2:6
3 months : 1year

Table 1.2 : Run duration and life time for hydrotreating catalysts.

1.4 Different applications of catalyst in

hydrotreating processes
The hydrotreaing of fractions such gas oil proceeds mainly
through two steps; hydrogenation and hydrogenolysis for
removal sulfur as H2S and nitrogen as NH3, but H2S is the
most abundant. Generally hydrogenation steps are slightly
inhibited or unaffected by H2S. Whereas activity for sulfur is
strongly depressed at high level of H2S. Conversely, H2S
promotes the C-N bond breaking of saturated amines where
the other types of nickel containing catalysts are efficient in
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hydrodenitrogenation and composed of Ni-CoMo or NiMo


which are more efficient in HDN and more difficult than HDS.
For the most important part, hydrodesulfurization catalyst
technology has been used to accomplish hydrodenitrogenation.
Although such catalysts are not ideally suited to nitrogen
removal H2S may promotes the C-N bond breaking, although
inhibition was found in the HDN of carbazole cracking and
isomerization enhanced by H2S.

1.4.1 Catalyst for gas oil desulfurisation


It is known that straight run gas oil contains various sulfur
compounds with different reactivity. Isoda ET. Al. has shown
the relative reactivity of different refractory sulfur species in
deep desulfurization reaction1. For example relative reactivity
of 4,6 Dimethyldibenzothiophen (4,6 DMDBT) is about one
fifth of Dibenzothiophen (DBT). In order to achieve an ultra
low sulfur product, those refractory species such as 4,6
DMDBT must be effectively removed. Thus catalyst must be
designed to enhance removal of such refractory compounds.
Lower reactivity of 4, 6 DMDBT is mainly due to the stearic
hindrance of methyl branches that hinder sulfur atom from
accessing to active sites 2. Thus methyl branches need to be
isomerised to other locations which develop less
stearic hindrance or they must be dealkylated to obtain
sufficient accessibility of sulfur atom to active sites.

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In order to enhance those reactions the catalyst surface needs


acidic sites. Another possibility to remove such refractive
sulfur compounds is to enhance hydrogenation of the aromatic
ring structure so that cleavage of the ring structure takes place
easily followed by sulfur removal. The rate of sulfur removal
of the reaction is accelerated by hydrogenation of aromatic
rings and hydrogenation activity of the catalyst is critical.
Thus the design concept of the catalyst for refractive sulfur
compounds is different from that of a catalyst for reactive
sulfur compounds, which is mainly desulfurised by direct
access of sulfur atom to active sites.
The reactivity of conventional CoMo and NiMo catalysts were
compared with gas oil feedstock having different sulfur
content of 16,230 and 303 ppm. The sulfur compound of
Middle East straight run gas oil having 16,230 ppm. sulfur
contains reactive sulfur and refractive sulfur. Another gas oil
having 303 ppm. sulfur is a hydrotreated gas oil, thus the
sulfurspecies are mainly refractory compounds. The result is
shown in Figure 1.6. The CoMo catalyst showed higher HDS
Feed
S = 330than
ppm. the NiMo catalyst
Feed for
S = 330
activity
gasppm.
oil having 16,230 ppm.
sulfur while the NiMo catalyst. showed higher HDS activity
than the CoMo catalyst for gas oil having 303 ppm. sulfur.

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Figure 1.6 : the effect of different catalyst on different types of sulfur


compounds

HDS reaction over CoMo catalysts primarily takes the direct


HDS route, in which sulfur compounds access an active site
directly. Because the reactive sulfur compounds are easily
desulfurised via the direct route, the CoMo catalyst showed
higher activity. However the direct HDS route is not effective
for refractory compounds. The NiMo catalyst, over which
sulfur compounds are desulfurised via a hydrogenation route
showed higher activity than the CoMo catalyst for the
refractory sulfur dominant gas oil. The NiMo catalyst
desulfurises refractory sulfur compounds in the presence of
poisoning materials such as hydrogen sulphide and ammonia.

Catalyst *RelayTM technology

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Based on the above observation, Catalyst RelayTM, a


combination technology of Cobalt Molybdenum catalyst and
Nickel Molybdenum catalyst has been developed to enhance
removal of both reactive and refractory sulfur compounds. The
Catalyst RelayTM converts sulfur species in two steps as is
shown in Figure 1.7. The first bed of CoMo catalyst
(**HOP-467) achieves desulfurisation of reactive compounds
and the second bed of NiMo catalyst (HOP-414) plays the
main role of desulfurisation of refractory compounds. The
combination of two catalysts enables the conventional units to
produce ultra-low sulfur diesel. The reaction temperature to
achieve 50 ppm. sulfur is 14C lower than that of conventional
HOPTM catalysts. The Catalyst RelayTM system has been
applied to several working units in Japan without any major
revamp of the unit. Those units have
* Trade name for a catalyst produced by ARTCo. (Advanced refining
technologies co.)
** Type of catalysts

been successfully operated to achieve ultra low sulfur diesel


for more than a year.

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Figure 1.7 : effect of using two bed catalysts

1.4.2 Combination of HDM/HDS catalysts for


residue.
Atmospheric residue desulfurisation units are commonly
operated to desulfurise residue not only to produce low sulfur
fuel oil for power station but also as a preparatory measure for
feeding low sulfur vacuum gas oil feed to FCC and
hydrocrackers, and low sulfur residue feed to delayed coker
units. Fixed bed hydrotreating units for residual oil normally
employ one to four reactors in series and are operated for six
months to two years. The catalyst combination technology is
known to be advantageous in residue HDS because different
catalysts having different functions can be combined in a
system.
The main purpose of the HDM catalyst is to remove feed
metals and to protect high activity downstream catalysts of
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HDS and HDN. HDM catalysts are loaded in the guard


reactors as well as in the first main reactor of a multi reactor
system. Residual oils used as a feedstock have a wide range of
molecular weight distribution from around 500 to 10,000
although the average molecular weight of the whole fraction is
about 1,000. The vanadium is mainly concentrated in heavier
fractions as vanadyl porphyrins and is associated with other
large molecules containing condensed poly-aromatic rings.
The pore structure of HDM catalysts is designed to handle
these metal compounds of large molecular size. The function
of HDS catalysts is to remove sulfur compounds from
demetallated feedstock to produce low sulfur compounds.
Thus the pore structure of HDS catalysts is designed to show
high desulfurization activity but HDS catalysts are susceptible
to deactivation by metal deposition due to its fine pore
structure. In order to protect HDS catalysts HDM catalysts
need high intrinsic activity of HDM to remove vanadium and
nickel in the feed while the catalyst need large metal uptake
capacity to maintain its HDM activity throughout the whole
operation. Catalysts of high surface area and less pore volume
are active in hydrotreating due to more dispersed active site of
metals through their fine pores. However they are susceptible
to deactivation due to pore mouth plugging. On the other hand
catalysts with low surface area and large pore volume are less
active but more resistant to pore plugging. Deactivation
behaviour of both catalysts is shown in Figure1.8
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Figure 1.8 : Relation between catalyst activity and metal


accumulation

Thus pore structure of HDM catalysts must be well designed


to have optimum balance of metal uptake capacity and
intrinsic HDM activity from the activitys point of view. Care
Must be taken in the design of pore structure to have sufficient
crash strength because large pores often leads to lower crash
strength of the pellet.

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