Studies in Surface Science and Catalysis 130

A. Corma, F.V. Melo, S. Mendioroz and J.L.G. Fierro (Editors)

‹D 2000 Elsevier Science B.V. All rights reserved. 83

Catalysts for oil refining and petrochemistry, recent developments

and future trends

G. Martino
Institut Franpais du Petrole
1&4 avenue de Bois Preau, 92582 Rueil-Malmaison Cedex

1. INTRODUCTION

Catalysis a multidisciplinary science is a very important tool for most of the

industries.
Industrial catalysis contributes to about 259a of the whole Gross Domestic
Products (GDP) [1] and in the most developped countries the generation of a
million C added GDP is linked to the spending of about 300 C of catalysts [2].
At present, worlwide catalysts demand is at about 10 Billion C. Oil refining,
chemical and petrochemical industries and environmental protection are the
main users of catalysts as presented in table 1.

Tablel
2000Wor1widecataystsdemand(-IOGE)
Reining 257
FCC 10
HDT/HYC 10
Others 5
Chemical processing 429
Chemicals 28
Polymers 14
Emission control 33%
Motor vehicules 30
Others 3

Future projections of this demand is difficult to make but most manufacturers

[31 are looking for growth in the next five years and even beyond.
Heterogeneous catalysis remains the most important one, most of the
developments in the fields of environmental protection are based on solids, mainly
metals and oxides supported on monoliths.
A lot of new polymerization catalysts are solids and their preparation is based
on several organometallic chemistry steps.
84

The worldwide foreseen growing rates for the different domains are, rather low
for oil refining (2 to 3% per annum), reasonable for environmental protection (4 to
5'7o) and rather high for chemicals (more than 69c). Regional growths may be
significantly different, due to the contrasted starting points as presented in Table
2. The biggest growth rates are expected to take place in the Asia Pacifie area.

Table 2
2000 Estimates for specific countries (G £)
USA EUROPE AP/J*
Refining 1.1 0.5 0.4
Chemical processing 1.1 1.9 0.9
Emission control 0.7 1.0 0.5
Total 2.9 3.4 1.8
* AP/I Asia Pacific+Japan

These trends seem reasonable for the oil refining and petrochemical industries
which the present paper will be devoted to. It will be limited to the
manufacturing of hydrocarbons, cuts or pure compounds like motor fuels, olefins
and basic aromatics.

2.OILREFINING

2.1. Presezzt sltzzatiozz

At present, there are about 600 refineries running worldwide. Catalytic
reforming and hydrotreating capacities as well as the necessary flue gas
treatment are present in most of them. Thermal units like visbreaking or coking
are also used. But only about one half of the refineries have a catalytic cracking
unit and one on four only have implemented an hydrocracker.
As a consequence, only a few families of the different catalysts are largely
present in all the refineries (table 3). For each family several catalysts
manufacturers offer proprietary products [4].
For most on these catalysts, important improvements have been introduced
during the recent years but only a few catalysts, clearly different in concept of
the existing ones, have been brought up and introduced into a refinery since
1990.
These improvements have largely benefited of the tremendeous efforts made
by the catalyst community in the last 20 years ; most of it has been brought
together in the handbook edited by E. Ertl, H. Knozinger and J. Weitkamp [5].
Sophisticated physical technics, surface and material sciences as well a
molecular modeling have allowed heterogeneous catalysis to move from « black
art to atomic understanding ».
 85

Table 3
Main basic refining catalysts
Catalysts Processes
Ni, Pd, Pt/carriers Hydrogenations
Metals Pt + M/alumina Catalytic reforming
Pt/ch1orided alumina or mordenite Paraffin isomerization
Group VI + Group VIII Hydrotreating
Sulfides OH Hydrocracking
carriers
USY/carriers FCC
Solid H,P0,/silica Polymerization
Acids Resins MTBE
HF, HMSO, Alkylation
Modified aluminas CLAUS
Others
Co Phtalocyanine/carbon Sweetening

Chemical engineering has made a lot of progresses in kinetic modeling and

transport phenomena understanding [6] and has allowed an optimized use of
industrial catalysts.

2.ADrivingforces
The evolution of the refining industry is market driven but the market rules
are heavily puzzled by environmental concerns and the interference of political
decisions well ahead of scientific consensus. For instance MTBE production
peaked in 1998 [7al and was hailed as the environmentaly friendly component for
gasoline but it’s future now looks in doubt, at least in California and other states
in the USA [7b,c] and perhaps elsewhere. That means that any forecast has to be
done at our best knowledge on a « as today business » basis.

2.2.1. Product demand evolution

Worldwide oil consumption is foreseen to increase slightly beetwen now and
2010 as indicated in Table 4. For 2020, the increase may continue but it will be
linked to the introduction of new kinds of transportations vehicules. Mainly the
ratio of heavy ends to transportation fuels will continue to decrease ; natural gas and
renewable energies taking over as fuels for fixed power stations.

Table 4
World oil consumption (GT)
1995 2000 2010
Transportation fuels 1.600 1.870 2.320
Petrochemicals 0.192 0.250 0.300
Other now energy uses 0.192 0.215 0.250
Heating & ind. fuels 1.216 1.265 1.430
Total 3.200 3.600 4.300
86

An other important point for the refiners is the continuous evolution of the
ratio beetween gasoline and middle distillates as indicated in table 5. This raises
the question of the hydrogen to carbon ratio in the refinery finished products ;
the hydrogen richest product is diesel oil and in the future the hydrogen content
may even increase with the decrease of their aromatic content. The same trend is
expected for gasoline with the projected aromatics and olefins content reduction.

Table 5
World distillates demand (MT)
1995 2000 2010
Gasoline"’ 860 950 1150
Middle distillates"’ 1085 1250 1550
(1) including naphtha — (2) including heating oil

Even w)thout taking into account the most controversial concerns on climate
change arising from Greenhouse Gases (GHG) effects, motor fuels are under
pressure in order to contribute with the engine’s modification to meet the future
tighter tailpipe emissions.
This pressure has led to the implementation of new specifications all around
the world and by january 1“ 2000 in Europe where more severe ones are expected
to become mandatory by 2005.
Table 6 shows the existing specifications for gasoline. The most stringent ones
concern benzene, reduced to 1% volume, sulphur, brought down to 150 ppm. The
ban of lead in most european countries gasoline has started by the 1“ of january
2000. By 2005, vapor pressure reduction will be mandatory, aromatics content
will be limited to 359c volume. For sulphur a maximum of 50 ppm has been
decided but the possibility to move down to 30 or even to 10 ppm are under
consideration. For Canada and USA, 30 ppm average have been adopted.
The possible lowering of the specification on olefins would severely hurt all
refiners using FCC as a work horse for conversion.

Table 6
Evolution of gasoline specifications in EU
Property 2000 2005
TVR summer (Kpa) 70 60
Benzene (to vol) 1 1
Aromatics ('to vol) 42 35
Olefins (to vol) 18 (10)
O, max (%wt) 2.3
S otax ppm 150 50 (30)
Pb (max) gh 0.005

The situation for diesel oil (table 7) indicates the clear bend to reduce sulphur
in order to contribute to a reasonnable solution to NO emissions. Europe has
 87

moved from 500 ppm to 350 by january this year. Cetane number has been
increased, polyaromatics are limited to ll% wt, 959c volume distillation point has
been brought down from 370°C to 360°C.

Table 7
Evolution of diesel specifications in EU
Property 2000 2005
Sulphur max (ppm) 350 50 (30)
Cetane number min 51 - (55)
Polyaromatics max ('how) 11 - (1)
Density (Kg/1) 0.845 - (0.84)
T95 max (°C) 360 (340)

There is a definitive obligation to reach the 50 ppm level of sulphur in diesel

by 2005 in Europe. Other countries have not yet made their decision. Figures as
low as 30 or 10 ppm are, even today, requested by refiners for the design of their
new hydrotreating units.
Other properties may give rise to new specifications as indicated in column 2
under brackets. Cetane number of 55 and polyaromatics at 1% wt would need
expensive investments. Reduction of T95 and density would reduce the amount of
diesel oil available and require the implementation of several hydrocrackers.

2.2.2. Other constraints

As any industrial operation, oil refining generates different waste streams
which have to be handled and induce operating costs.
Water -up to a few cubic meter are used per ton of crude- is more and more
under scrutinizing [8].
Solids like catalysts are more and more subject to retreatments. Sulphur
which had a sales price in the past may become an issue as hydrotreating is
growing.
Gaseous streams are the main concerns today [9] . For nitrogen oxides, sulphur
dioxide, particulates and VOC’s emissions new limits have been adopted in
Europe for 2007 (table 8).

Table 8
Limits of emissions in EU (after 2007)
Pollutants Power >500 MW Power <300 MW
SO, mg/Nm° 400 1700
NO, mg/Nm’ 450 450
Particulates mg/Nm3 50 50

Other products emissions may also in the future be more strictly limited, even
though their concentrations are very low at the outlet of incinerators [10].
88

The issues concerning GHG is not yet clear ; carbon dioxide is the main
involved gas but not the only one. CO, is produced by any energy production from
hydrocarbons ; taxation will have important impacts, directly or indirectly on the
refining industry.
Inside the refinery, where 5 to more than 10% of the crude is used to make
energy or hydrogen, there will be a renewed fight for energy saving [11]. A new
insight in hydrogen production as well as its utilization [12J will come up with
technologies which could introduce new hydrogen producing routes. Any ton of
hydrogen produced starting from resids leads to 15 tons of CO, and even with
natural gas about 10 tons of CO z are generated. This could even modify
tremendously some, today, classical refining schemes and push to non hydrogen
using processes.
It could also severely impact the price of the new high hydrogen containing
fuels and fasten the implementation of a new generation of cars with high
efficiency propulsion systems like hybrid vehicules or fuel cells engined cars. A
fast evolution in that way, seems not to be the most likely ; it would bring us out
of a forecast of « business as usual »
The heavy investments required in such a case would be insustainable for
refiners faced with low margins of less than 20 Euros/Ton of crude in most cases.

2.2.3. Conclusions
Without taking into account this extreme issue of severe CO 2 taxation, refiners
will have to
1. make more and cleaner transportation fuels while reducing production costs
and coping with waste management.
2. handle the incertainties concerning the agenda of the implementation of the
new specifications not only for the motor fuels but also for the other products like
resids.
3. face competition for their resids in fixed power stations ; natural gas gives
less COC and contains less sulphur.
4. find ways to increase profitability through specialties productions as well as
petrochemical intermediates.

2.3. Recent changes and future trends

Refiners have been able to satisfy the demand of products by continuously
improving their units. Their refining schemes have been modified to cope with
the crude oils they could buy.
Until 2010 it seems that rather conventional crude oils could be available ;
this means that only a few heavy crude upgrading refineries will be erected in
the next years. As the use of heavy ends will continue to decline, new resid
conversion units will be implemented and on going R&D will be necessary in
order to reduce operating costs and investments. Resid desulphurization will be
needed before combustion ; if not, flue gas treatment will be required.
 89

As indicated before, this paper will now focus on motor fuels production in the
next decade.

2.3.1. Gasoline manufacturing

The main blends contributing to the gasoline pool are reformate, isomerate,
catalytic cracking, coking and visbreacking gasolines, polymerization and
alkylation gasolines as well as ethers. The ban of ethers (- 30 MT/year), will be
difficult to handle if other limitations, mainly on aromatics, are introduced at the
same time.

Catalytic reforming
Catalytic reforming has been questionned several years ago when limitations
on benzene were introduced. This issue has got several solutions. It is admitted
that catalytic reforming is the only cheap, almost without CO, , hydrogen
producer in a refinery. Most of the recent improvements have been dealing with
how to get a high continuous production of hydrogen in order to maintain the
whole refinery on stream. More and more refineries have implemented continuous
catalysts regeneration and catalyst have been improved as indicated in table 9
[13, 14]. The same trends will remain for the future.

Table 9
Low pressure catalytic reforming with continuous
regeneration Catalyst changes Impact
Activity Z Throughput Z
Recently Selectivity 7'I H, + aromatics >
Coke formations Benzene H
Thermal stability of carrier Z Throughput "I
Time on stream Z
Tomorrow
Same trends

Paraffin isomerization (table 10)

The use of light paraffins isomerization has grown during the last decade.
Mordenite based catalysts have been less successful than platinum on chlorinated
aluminas. For the latest, some major changes have been introduced : improved
catalysts which allow operations with very low hydrogen to hydrocarbon ratios
and which have lower sensitivity to the higher cyclo alkane concentration linked
with the benzene management [15]. The off site regeneration of some of these
catalysts has also been demonstrated.
Table 10
Paraffins isomerization
Catalyst changes
Stability of Pt/alumina Z Impact
Activity Pt/alumina Z Hz recycling
Recently Off-site regeneration Pt/alumina Cyclo alkanes in feed 7"i
New sulfated oxides Life D
Stability/impuritiesZ
No chlorides
Activity Z But activity K
Tomorrow Octane 7'i
or
Cracking N Throughput "I Treatment of C

A new generation of catalysts based on sulfated zirconia [16] has shown

interesting features : higher activity than mordenite and lower sensitivity to
poisons but, until now, lower activity than chlorinated aluminas. Nevertheless,
their operation without producing waste chlorides might save money and
certainly gives them a « green » image.
There is a lot of progress possible in that line and work is going on in
numerous laboratories for C,.s [17] but also for C„ C, and other paraffins. Zeolites
may not be forgotten on the way of treating even higher paraffins [18]. The
coupling with separations processes able to screen dibranched paraffins from
monomethyl and normal paraffins will promote other catalysts.

Fluid catalytic cracking

Fluid catalytic cracking remains the most important process to convert
vacuum distillates, deasphalted oil and partly pretreated resids into lighter ends.
It has benefited of continuous improvements as indicated in table 11. The big
recently rised issue is the sulphur content of the FCC gasoline - Several solutions
have been developped to reduce it, although limiting the octane loss.

Table 11
Fluid catalytic cracking
Catalyst changes Impact
New matrix Bottom conversion 7i
Recently Coke formation N
Zeolitie additives Olefins production Z
De SO, additives SO, formation N
Tomorrow New zeolites Olefins Z
Coke formation N Heavier feeds 71
 9

Mobil’s Octgain as well as Intevep’s Isa1 couple hydrodesulphurization with

reactions (isomerization, alkylation) which allow to recover the octane loss due
to olefins saturation.
Exxon/Akzo [19] and IFP/Procatalyse have choosen the way of selective
hydrotreating catalyst developments and their optimized use.
CDTech [20] has taken advantage of the catalytic distillation process to reach
the goal.
Adsorption has been priviledged by Phillips [21] and others [22] to eliminate
sulphur. Processes will be demonstrated soon.
Even if catalytic cracking produces a very bad diesel oil (LCO), it seems that
it will continue to be used in the future.
Feed pretreatment with more or less conversion may help to get more and
better diesel. FCC, as indicated in tableau 11, will remain as a conversion work
horse oriented to convert heavier feeds and produce more light olefins.
Cost reduction of gasoline desulphurization will remain an important issue —
mainly if hydrogen becomes more expensive.

Alkylation of light olefins (table 12)

Alkylation of light olefins with isobutane leads to good gasoline blends. The
environmental concerns about liquids acids (HF, H zSO,) have at least been
partially solved. On the other side, solid catalyst alkylation does not show,
beside
of being more environmental friendly, any significant economical advantage.-
There have been progresses, concerning mainly regeneration [23, 24] and new
solid acids [251 have been claimed.

Table 12
Light olefins alkylation
Catalyst changes Impact
HF eomplexation Vapor pressure X
Recently HMSO, on site regeneration Transport N
H, regeneration of solid acid Costs N
New Solids Investments N
Tomorrow Quality of product Z
Other solids (low cracking) Convert higher olefins

If ethers are banned, a strong need for more alkylation and more C, olefins
alkylation too will appear.

Polymerization of CJC, FCC cuts (table 13)

Polymerization, in fact, oligomerization, uses at present mainly two kind of
catalysts : supported phosphoric acid and homogeneous Ziegler type nickel. Both
have environmental drawbacks and are best suited for C 3 cuts or C, cuts without
isobutene.
92

Table 13
Polymerization of CXC, FCC cuts
Catalyst change Impact
Solid regenerable catalysts WasteS
Recently
Solid for iso C —r i CQ Replacement of MTBE
Selectivity 71 Gasoline 71
—r branched C6 - C,2
Tomorrow Selectivity 7"I Diesel Z
—r linear > C,‘‘
C,-C, olefins conversion
Selective solids

Recently the possible use of other solids have been demonstrated with long
cycles and several regenerations.
The ether ban could bring up a new demand for the use of isobutylene.
Revamping of MTBE units has been announced by Snamprogetti [26] and
indirect alkylation has been claimed [27]. Iso octenes are produced ; they can further
be hydrogenated into iso octanes.
Tomorrow, more olefins will be produced in FCC and more propylene will go to
the petrochemistry. There is a clear need to convert not only C„s but also higher
olefins into valuable products, gasoline or diesel oil.

2.3.2. Diesel ozl productioxz

The trends for diesel oil future demand as well as quantities and qualities are
concerned are clear : more and better products are needed. Although the final
specifications are not yet defined, many refiners prepare themselves to the most
stringent situation.

Deep desulphurization
A lot of efforts have been made by the refining industry with the help of
technology and catalyst suppliers to reach the 500 ppm specification as indicated in
table 14. Each catalyst manufacturer has brought up more active catalysts in order
to avoid investments [28, 29, 30] ; activity increases by factors up to 2 are claimed.
Intrinsic activities have been enhanced through better carriers, higher metal
loadings. A lot has been added by chemical engineering contributions . control of
fluid distribution in reactors [31], use of series of different catalysts, best adapted
to the chemical transformation requested, hydrogen effects on the different reactions
have been reanalyzed and mastered.
 9

Table 14
Deep desulphurization of diesel oil
Catalyst change Impact
Throughput 71
Activity 71
or
Recently
Cycle 7"l or HDS "i

Different ones HDS2

Activity 7"I HDS D
Tomorrow Stability 71 Cycle 7'i
Regenerability 7"I Life 7'I

In order to keep most investments as low as possible further improvements of

catalysts activities are needed.
These improvements may arise from changes in the active phases, nature and
porosities of the carriers but also in changes in startup procedures for instance.
There may be on important competition between catalysis and other
technologies like adsorption, oxidation followed by washing or
biodesulphurization [32].

Deep hydrogenation (table 15)

A few deep hydrogenation units, have been implemented in order to provide
city diesel. These processes are based on sulphur resistant noble metal catalysts
[33, 341 ; their main drawbacks are their cost and the need to work at rather low
sulphur levels (< 50 ppm). This has been overcome with process modification by
Lummus/Criterion with the Synsat process [35] where hydrogen flows at
counter- current to the feed and allows for the highest hydrogen pressure at the
outlet. Implementation of many deep hydrogenations will require a lot of
hydrogen units and, alternatives to reduce the large amount of noble metal
catalysts. There is a need for a better sulphur resistance or for other more active
catalysts.
There may be a place for alternative ; non hydrogen based processes.

Table 15
Deep hydrogenation of diesel oil
Catalyst change Impact
Zeolite supported metals Activity
7"I
Recently
Bimetallic noble metals Activity "I
New carrier Activity 7'i
TOIfl0I’fiOW New bimetallics Activity Z
Non noble metals Cost N
Hydroeracking (table 16)
The existing move to the erection of maxi distillates hydrocrackers, with
selective amorphous catalysts operated at high pressure in 2 stages units, fills
the gap for the increased middle distillate demand. Products are of good quality
but investments as well as hydrogen consumption are high (> 2% wt/feed) [36,
37].

Table 16
Hydrocracking
atalyst change Impact
Selectivity 71 Middle distillate yields 7"I
Recently
Stability 7'i Pressure N or cycle length 'I
Selectivity 7"I Yields 7"I
Tomorrow Stability 7"I H, consumption N
Pressure H
Selective ring opening Cetane Z

It is important to reduce the cost of investment by lowering operating

pressures and by reducing the size of units with new more active catalysts.
The processing of LCO or naphthenes rich crudes requires not only
hydrogenation but also ring opening activity [38J while minimizing hydrogen
consumption.
Competition may arise in the future from Fischer Tropsch products.

2.3.3. Conclusions
The refining industry is a mature industry where costs reduction is the day to
day issue. Important changes in quantity but mainly in quality of the demand
are foreseen. The possible GHG taxes implementation add new incertainties.
Nevertheless refiners will adapt themselves, while catalysts manufacturers
and research and development will have to play their respective roles.
Catalyst manufacturers will have to improve continuously the existing products
and find, in some cases, new solutions. Paraffins isomerization, olefins alkylation,
deep hydrogenation of diesel oil and ring opening may be the domains where some
breakthroughs can be foreseen.

3. PETROCHEMISTRY

As presented before this topic will be limited to the routes for the production of
the main basic olefins and aromatics.
 9

3.1. Present situation

At present, olefins are mainly manufactured by steam cracking of ethane,
naphtha and heavier cuts. Aromatics, benzene, toluene and xylenes are
coproduced in steam crackers when naphtha is used as a feed, but the main
source remains catalytic reforming of naphtha .
The industry uses a limited number of kind of catalysts (table 17) ; noble
metals on different carriers, solids acids like zeolites which tend to progressively
replace liquid acids and some mixed oxides, for dehydrogenation mainly.

Table 17
Main basic petrochemical catalysts
Catalysts Processes
Metals Pt+(Ml)/alumina Aromatization
on Dehydrogenation of paraffins
oxides Pd+(M2)/alumina or silica Selective hydrogenation
Metals Pt/MFI Xylenes isomerization
on Pt/H mordenite Xylenes isomerization
zeolites Ni/H mordenite Transalkylation of aromatics
Zeolites MFI Xylenes isomerization
+ HM, H beta Benzene alkylation with light olefins
other HYorMCl,
acids Iron+ alkaline oxides Dehydrogenation of ethylbenzene
Chromium oxide + alkaline oxides Dehydrogenation of light olefins
Oxides

Unlike oil refining, catalysts are tuned to each operation, this opens the need
to more specific research and developments.

3.2. Driving forces

Costs reduction of the whole production chain from raw materials to the
intermediate olefins or aromatics is the main driving force. The high required
purity is increasing in connection with the quality improvements of the final
products : polyethylenes, polypropylenes or polyterephtalates for instance.
Separation and purification operations have a very important role. The intrinsic
selectivity of the catalyst used not only saves raw materials but also decreases the
cost of purification.
The evolution of the global demand is another important driving force, olefins
demand (table 18) will grow at a rather high rate [39] . The differences of growing
rates for the different olefins, 3,5'7o for ethylene, more than 5'7o for propylene and
more than 8% for some of the higher olefins, introduce a need of different
production routes.
96

Table 18
Worldwide main olefins demand (MT)
1998 2010
Ethylene 80 120
Propylene 45 82
1 Butene 0.8 1.4
Higher o olefins i.o 2.2

Aromatics demand (table 19) is growing at a reasonnable rate of about 4' o,

paraxylene much faster (69c) and, even m xylene or dimethylnaphtalene are
supposed to grow at much higher rates.

Table 19
Worldwide main aromatics demand (MT)
1998 2010
Benzene 27 40
Toluene 13 21
p 14 30
Xylene

There are big differences in regional growing rates ; South East Asia is
expected to have the highest ones.
Increased demand and better quality at lower cost push the industry to
maintain an important research and development effort.

3.3. Recent changes and future trends

3.3.1. Olefins
Ethylene
Ethylene remains the most important olefin ; most of it is obtained from steam
cracking of ethane (40%) or of heavier hydrocarbons. Recent evolutions in steam
crackers have been devoted to cost reduction through several modifications (table
20).

Table 20
Ethylene
Millisecond furnace 1 conversion
Recently Better selective hydrogenation catalysts
Use of condensates
Increase conversion to more than 85'7o
Tomorrow New adapted hydrogenation catalysts
Use of selected feeds
New routes
 9

The use of cheaper feeds like gas condensates have brought up some concerns
on arsenic and mercury removal.
Another move to get higher per pass conversion is likely. This will lead to the
formation of more acetylenics and will requires renewed downstream
hydrogenation processes.
New routes are of interest. Oxidative dehydrogenation of ethane which is a
big challenge could have a better chance to succeed compared to the oxidative
coupling of methane to which a tremendous amount of work has been devoted
during the 80’s.
Methanol to olefins (MTO), demonstrated by Mobil [40] in the 80’s, could take
advantage of the excess capacity of methanol which could result of an MTBE ban.
UOP and Norsk Hydro have brought up a new process [411 which gives propylene
to ethylene ratios of up to 0,7 which is higher than those obtained by naphtha
steam cracking.

Propylene
More than 60% of the needed propylene is produced by steam cracking of
naphtha. In the recent years several propane dehydrogenation units have been
erected but the growing source of propylene has been FCC units. The
implementation of FCC splitters, the design of dedicated olea»s producing units
like the DCC of RIPP/Stone & Webster [42] and the use of additives, MFI type
zeolites, have helped to provide the required amount of propylene to the market.

Table 21
Propylene
Recently Propane dehydrogenation processes & catalysts
More propylene ex FCC (new catalyst + processes)
More propylene ex FCC (new catalyst + processes)
Tomorrow FCC more oriented to olefins/new additives
MTO propylene oriented
Metathesis implementation

These trends will be maintained and there is place for new additives and new
modifications of the FCC units.
Dehydrogenation may be favored in places where FCC units are too far away
[43]. Considered today as rather expensive, dehydrogenation can be expected to
be improved on both catalysts and process sides. The use of membrane reactors
as well as the introduction of oxidative dehydrogenation are considered as
possible future solutions [44].
Metathesis of ethylene and 2 butene is another alternative which helps to get more
propylene while using the low value C, cut [45] . The IFP/CPC’s low temperature
rhenium based process and the Phillips ABB Lummus, high temperature process,
have to cope with catalyst deactivation and the need of frequent regenerations.
Progresses can be expected for both processes.
98

MTO as presented previously may lead to interesting ratios of propylene to

ethylene. Some older datas obtained on mordenite at IFP have shown that yields
of up to 60' o wt of Cz to C4 olefins can be obtained with a ratio of propylene to
ethylene of more than 5.
This indicates that it may be possible to get out of MTO, the desired slate of
olefins. Further studies will allow to move in that direction.

Higher n olefins
Butene 1 can be extracted from C, cuts. It is also obtained by selective
dimerization of ethylene with homogeneous catalysts [39] ; higher o olefins are
mainly obtained via oligomerization of ethylene. As a consequence only higher ti
olefins with even numbers of carbon atoms are produced in most cases with a
Schulz Flory like distribution. Recently pure hexene-1 has been obtained with the
new Phillips catalyst.
Fischer Tropsch oriented toward olefins production gives n olefins with any
carbon atom number but their purification is difficult. Sasol has implemented a
separation for hexene 1 and has brought hexene 1 (ex FT) on the market.
Improvements in both catalysts and separations may make that route more
competitive.

3.3.2. Aromatics
BTX (table
22)
The starting point of the production of aromatics is the mixture of benzene,
toluene, xylenes (BTX) which is mainly obtained, at present, by catalytic
reforming of naphtha (60%). The other way is steam cracking of naphtha (259c).
Catalytic reforming has benefited of the improvements described in the gasoline
section (2.3.1.).

Table 22
BTX production
Improved catalytic reforming and solvent extractions
Distillations and other separation processes
Recently Specific feeds ; dedicated catalysts
- Ba, K/L C, ,C7 feeds
- Ga/MFI C , C, feeds
Tomorrow Further improvements of catalysts
Increased use of shape selectivity

Some dedicated processes based on new catalysts have been proven at large
scale and several industrial units are scheduled to start in the near future.
Platinum on baryum/potassium exchanged zeolite L initially patented by ELF
[46) and further developed by Chevron is well adapted to get more aromatics out
of C, and C, paraffins. The advantage on platinum on alumina catalysts seems
not to be as high for C, hydrocarbons.
 9

The BP/UOP cyclar process [47] based on Ga/MFI, converts LPG’s, a rather
cheap feed in some places, and produces an important amount of hydrogen as
well as fuel gas.
Both kind of catalysts could be improved. There might be place for specific
catalysts for other niche applications.

Xylenes production (table 23)

The full range BTX feed is handled in different units where benzene, toluene, g
Illixtures and heavier aromatics are separated. Only benzene and p xylene are largely
used ; the excess of the others is converted as much as possible into
benzene and p xylene through transalkylation, isomerization or dealkylation.
Several new catalysts have been introduced into the market place for xylenes
isomerization.
Mobil’s MFI based processes remain at the top for isomerization of xylenes
with dealkylation of ethylbenzene.
The mordenite based catalyst, which isomerizes ethylbenzene into xylenes is
being challenged by other zeolites based catalysts [48, 49] which lead mainly to
better selectivities toward p xylene.

Table 23
Xylenes production
Better catalysts for xylenes isomerization
Recently Improved catalysts for transalkylation
Use of shape selective catalysts to convert toluene —r p xylene
+ benzene
Tomorrow More use of shape selectivity
Integration of reaction/separation

Transalkylation of toluene with C, aromatics has been developed on

Ni/mordenite based catalysts. Their main limitation was the quantity of C, s
which could be fed to the reactor. The most recently developed catalysts seem to
overcome that difficulty ; the TAC9 process claims to be able to handle up to 70%
of C aromatics.
The better understanding of coking of this kind of catalyst can help to increase
their performances.
Toluene disproportionation is another way to get more benzene and more
xylenes. The Mobil MSTDP has been demonstrated several years ago [50]. Based
on ZSM 5, it has been continuously improved.
The two main features of xylenes production are
- the involved reactions are equilibrated and mainly catalysed by zeolites.
- products with close ebullating temperatures are obtained which makes
separation by distillation difficult.
10

The future trends take into account both these facts. Catalysts selectivity
mainly shape selectivity and integration of reactions and separations will be
main lines of improvements.

Styrene (table 24)

Styrene is produced via a two step process ; benzene alkylation with ethylene
and further dehydrogenation.

Table
24
Styrene
New alkylation catalysts/processes
Improved DH with higher conversion
Recently
Introduction of post-DH, selective hydrogenation
Tomorrow Higher conversions/selectivities in dehydrogenation
New routes

For the first step zeolitic catalysts are, since the 70’s, progressively replacing
the other catalysts.
The Mobil Badger process operates in vapor phase with MFI type catalysts.
Recent processes use liquid phase with other zeolitic catalysts. CD Tech has
introduced the use of catalytic distillation ; this allows better heat integration
and avoids polyalkylation. There is place for further improvements.
The dehydrogenation step, limited by equilibrium has been improved by
subatmospheric pressure operation and selective hydrogen removal (Styro Plus
process of UOP). These higher conversions lead to acetylenics formation and
require the addition of a specific purification.
The main expected improvements concerning the dehydrogenation step are
higher conversion and better selectivity which would help to reduce costs.
Membrane technologies have also been considered [51].
New routes have to be considered ; the most advanced one is based on
butadiene dimerization into vinyleyclohexene and further dehydrogenation into
styrene ; DSM and DOW have been the most active companies in this field ; it is
a way to use excess butadiene. These two steps processes have to be improved in
order to become competitive.

3.4. Conclusions
In the future the petrochemical industry has to face an increase in the demand
of existing products and a requirement for higher purities and for lower costs. A
rise-up of niche products can also be foreseen.
In order to tackle both these challenges, innovative solutions have to be
brought up.
More extensive use of condensates and better integration with the refining
industry will give access to lower priced feeds.
 1

More selective catalysts, more efficient catalytic and separation processes and
even integration of both kinds of processes will help in lowering capital
expenditures and operating costs.
New catalytic routes may open the road to real breackthroughs and new
products.

4. GENERAL CONCLUSIONS

Without a severe taxation of GHG, mainly carbon dioxide, it appears that both
the oil refining and the petrochemical industries will see an increasing demand
for their products ; nevertheless the average growing rate is much higher for
petrochemicals.
The production of environmental more friendly fuels and higher purity
petrochemicals creates a need for improvements in catalysts and processes.
There is a strong need for new catalytic materials with well defined sites [52]
but also a deeper integration of catalysis and reaction engineering [53] taking
into account the overall process, catalytic and separation sections. Modeling and
simulation will used more and more and be of great help.
Combinatorial methods [54] could become a must for future new solids
screening.

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ACKNOWLEDGEMENTS

I wish to thank J.F. Gruson from IFP’s strategy and economics division and
Dr. Ph. Courty for their help in preparing this paper.