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159
FLUID CATALYTIC
CRACKING
OF HEAVY
(RESIDUAL)
OIL FRACTIONS:
A REVIEW
S-6. GEVERTa,
S.G. JxRfiSb and P.G. I.IENONa School of Chemical Sweden. Engineering, Chalmers
of Engineering of Technology,
Chemistry,
412 96 Gbteborg,
Sweden.
(Received
16 July
1985, accepted
6 January
1986)
ABSTRACT The oil crisis of recent times has caused a drastic decrease in the total consumption of oil and changed the demand pattern for the products of petroleum refinino. The demand for heavier fractions or residual oils has steadily decreased, making it imperative to convert these into gasoline, diesel and such lighter fractions. Fluid catalytic cracking (FCC) of these heavier fractions, however, poses several serious problems, caused mainly by their much higher hetero-atom concentration, metal contents and coking tendency, as compared to earlier feedstocks. Several process and catalyst innovations have been made to tackle these problems. A new generation of FCC catalyst technology has emerged with tailor-made catalysts for higher structural stability and attrition strength, more complete CO combustion during regeneration, reducing SO, emissions from FCC stacks, enhancing the gasoline octane number, passivating the harmful effects of metals like Ni and V accumulating on the catalyst, etc., These developments contain valuable lessons for the science and technology of catalysis.
INTRODUCTION The arbitrary senia series raising and controlling through launched hitherto of crude oil prices refining since 1973 by OPEC On the one as
industry. energy
alternative
sources
(often off-shore)
to live with
in a radical
change
for heavier
oils has steadily is increasing. rjhich cannot and are forced both
diesel
fractions
in product
has become
so compelling situation
to this changing
become
in Ghent
and Chevron
Refinery
in Feluy,
in the demand
pattern
for petroleum
products
is to crack more and more of heavier In the United between States, the number
or resid fractions
doubled
February
since
has become
0166-9834/86/$03.50
a powerful
incentive
to develop cracking
processes
for upgrading
heavy in
fractions, firms
however,
problems Hence
and catalyst
manufacturers.
several
innovations
to face these
The purpose
is to draw attention for the science C3al have reviewed they have which caused and
to these
of catalysis. adapted
Maselli
processes
or newly developed
cracking;
in detail
structures problems
the special
diffusion
aspects
of residue
blending
et al. [3c], by
the various
of commercial process
catalysts
aspects
prehensive monograph
by Venuto
and Habib
in English, these
translated aspects
process
be only briefly
mentioned,
review.
Greater metals
attention on process
consequences the in an in
stability,
innovations
coke formation
existing cracking
the separate
and molecular
sieve
specially
tailored to
complete
to reduce
the gasoline
octane
to passivate
effects
accumulating
on the catalyst,
II. CHARACTERISTICS
OF HEAVY OIL FRACTIONS oils are stable substances. They do not or precipiimplies
On the time scale of man, petroleum react with the rock formations which
contain
oils
of functionalities
in terms of
in oil molecules.
Furthermore,
of functionalities, Hence
in an oil fraction
of vacuum
portion
in fractions
accounts
of heavy oils
of association
of several
functionalities
161
TABLE 1 variation in residues from 150 different crude sources
Contaminant
Residue
type
Ni/ppm
V/ppm
S/%
N/%
CCRa/%
Atmospheric Vacuum
0.5-94 1.5-120
0.3-274 5-614
O-2-4.5 0.2-5.0
0.2-0.6 0.3-1.0
0.1-15.6 4.0-25.0
840-1010 920-1050
aCCR = Conradson
carbon
residue.
fraction.
A major
reason
in of
cracking
to do with
of the asphaltene
on or in the catalyst
as liquids
they will make coke and deposit ranges refinery in residues operations.
metals
from atmospheric
and vacuum
cracking-regeneration concentration
undergone
on the catalyst
can accumulate
or thousands
A Scdlum n Vanadiur
FIGURE Zandona
in FCC catalyst
(from
1. Metals The metal Nickel content is considerably are particularly higher in heavy since oil than in vacuum they can be present gas oil. in high of leading
and vanadium
important
have detrimental
effects
performance cracking
deposited
on the catalyst
causes
162
to high hydrogen Vanadium Section will and C,-C4 gas production and high coke formation and react destructively surface on the catalyst. with it (cf. when [7].
penetrate
V). Figure
in specific
of a catalyst
contaminated Nickel
with metals
to a steaming
present
in porphyrine-like as a result
naphthenates. Sodium
present
in resids
neutralizes
are so vital
of the crystalline
structure
at high temperatures.
2. Sulfur Sulfur compounds. is present as mercaptans, of American sulfides, Petroleum thiophenes Institute and other organo-sulfur Research Project cracking No. 48 of heavy For
The objective
sulfur compounds
cracker.
gas-oil
cracking,
as rule of thumb,
as SO2 in the stack gas of a FCC unit; 1000 ppm SO2 in the regenerator
restrictions
3. Nitrogen
and oxygen of nitrogen compounds is higher in heavier feeds than in vacuum gas oil. adsorbed rate indols Hence
are strongly
at the acid sites of the catalyst of coke formation. and pyrrols Neutral
activity
and higher
such as carbazoles,
on the acid sites of the catalyst. of the catalyst the content very much [Sl.
performance
and sulfur,
of oxygen little
but relatively
on the performance
of cracking
4. Asphaltenes Asphaltenes functionalities recently are aggregates of several of molecules Their containing polycyclic aromatics and
types.
structures
quite
and Peters
[9]. The size of of the zeolites pore structure asphaltenes are than
catalysts
with much
larger
Alternatively, zeolites
processes
available
163
PETROLEUM DESIRED TRANSPORTATION FUELS
Heavy
$ 1.0
FIGURE 2
H/C ratio
the desired
5. Resins Resins weight are polar molecules containing oxygen and nitrogen. Their molecular in paraffins.
is normally
soluble
6. The H/C ratio As shown varies in Figure 2, the H/C atomic ratio,for from normal petroleum feedstocks premium
from 1.5 to 1.9, and for resids fuels this ratio in essence should
be in the range
operations
may be considered
as efforts
a) by rejecting coking
[14], Visbreaking
[15], or Solvent
Deasphalting
b) by introducing
on the direct
of resids.
III.
PROBLEMS Resids
FACED
BY EXISTING of resids
CATCRACKERS
IN PROCESSING
and blends
at or above
from 5% to even 50%. Most of this type of cracking or revamped FCC units originally designed
ventional
for cracking
are possible
high coke make per tonne of residual to resid cracking, as briefly outlined
problems,
1. Problems
of increased
coke production containing operational Carbon gives resid to a FCC Unit causes Ordinary vacuum an extragas oil of
situation
respects. Residue
(CCR). Catalytic
cracking
such conventional
a coke-make
164 The combustion various process of this amount energy of coke will generate enough heat to satisfy the feed, the
requirements cracking
kinds of process
[19]. The FCC unit will generally in the range 670-720C. a vacuum
to heat balance
at regenerator
temperatures
An atmospheric contain
resid contains
generally 1). If
resid may
coke production
and more
heat release
The increased
is partially
This higher
temperature
causes
types of problems
a)
is generally is easily
throughput
remains
b)
of present-day
commercial
a function partial
pressure
regenerator a higher
temperature catalyst
will deactivate
the catalyst
make-up
rate is needed
to keep a constant
level
in the unit. ratio: Since this ratio is set mainly by the heat balance will reduce and nonthe
c)
regenerator
temperature
circulation catalytic
in more thermal
cracking
d)
increase
the strain
on the factor,
constraint At higher
in the regenerator
or the flue-gas
cyclones. cyclones
more catalyst
into the stack. problems: If the regenerator must air is not oxygen with enriched, the gas to
e)
Environmental velocity
through
the regenerator
increase
increasing
coke-make
keep the coke on regenerated the environment, of fresh normal catalyst especially
catalyst
more
fines to
operation.
temperature nitrogen
in the regenerator
and consequently
165 2. Problems with metal contaminants harmful from an operational point of + naphthenates and nitrogen compounds,
cause more environmental however, adsorbed can temporarily on the catalyst, molecules.
nitrogen
the acidic
catalyst;
containing
the catcracker
performance
in
The metals
build up almost
quantitatively
change function
toward more H2- and coke production of nickel. The gas-make on a volume
causes
cracking metals
resid
by the contaminant
is an important
deactivations.
The catalyst
influence
with
temperatures. level
must be increased
to keep a reasonable
in the unit.
3. Interaction
of metals
Some powerful employed zeolitic has shown tendency catalyst. uniformly the worst
catalyst.
(SIMS),
Jsrfis
[20] that,
conditions,
to get selectively
sieve component
surface
is exhibited
by Ni, which
surfaces.
for calculating
expressed
from elemental
exist as Ni
ESCA studies by Anderson et al. [213 have shown quite recently that Ni may 3+ 2+ 5+ or Ni and V as V after a typical regeneration. Up to a metal of 2%, Ni is homogeneously of Ni lead distributed throughout the catalyst, of V
loadings
enrichment.
in three
different
a) during due
stage V is deposited
on the outer
particle
of the vanadium-porphyrin
the regeneration
166 V migrates to the surface because of the low melting to the zeolite point of V2OB surface (690C); c) V
also migrates
surface
(as already
shown
destroys
the crystal
structure
Pompe et al. [22] have applied destructive roles of the metal decompose
DTA/TGA
techniques
to elucidate
porphyrines
and naphthenates
regenerator
conditions, and/or
polymerization). sieve
The mechanism
of the destruction
exchanged
RE-vanadate
phase.
requires
extra oxygen
is apparently collapse
drawn
lattice
to the ultimate
of the crystalline
zeolite
structure
4. Environmental
problems
High levels of S and N in the feed will give high SOx and NO, in the regenerator flue gases. temperatures More coke deposition and relatively on the catalyst attrition loss leads to higher (dust emissions) regenerator of the catalyst. flue
higher
of CO (even up to 10%) in older-type both from the environmental the increasing tendency
regenerator
to phase
considerations catalysts)
noble-metal be achieved
dictates
than is possible
at present. fractions energy as FCC feedstock crisis started are in 1973. pressures,
posed by the need to use heavier of the oil crisis sometimes resemble
problems
those arising
as briefly catalyst
enumerated
above.
Luckily,
innovations
in FCC process
improvement
simultaneous
solutions
to
sets of problems.
under
APPROACHES
TO PROBLEMS adaptations
OF RESIDCRACKING
a) Modified catalyst
design
and engineering
firms and
manufacturers heavier
feedstocks
pretreatment
or a combination
of both.
Texas.
then, a continuous
development
167
place.
The latest
versions
of HOC involve
catalyst-oil
contact
time, minimizing
metal
at a 90"-turn
regeneration internal
in a counter-current coils
cooling
catalyst
introduced
Petroleum
in 1982 consist
Here, an by
in the mixing
is followed step.
cracking
of the lighter
of the product
Similarly, ture
the first
is carried is present
(600-750C)
of the H-content
before
the second-stage
in excess
oxygen Such
to burn off only the carbon high temperatures generator temperature burning
of the coke
still remaining
are possible
the re-
is no metallurgical CO after-
is avoided,
against
deactivation.
Oil, jointly
design
like greater
promoters
(see Section
added to the catalyst. The Ashphalt [27,28] process Residual Treating (ART) process pretreatment and metals developed process. by Engelhard Corporation
a feedstock
It is a low-conversion
of asphaltenes components
from heavy oils by vaporization process for resid conversion desulfurization processes,
of the hydrogen-rich
is the new Hycon process and hydroconversion however, or resid Since will
of Shell
demetallization, fixed-bed
hydrogenative
not be discussed
any further
in this review
fractions. the conditions to innovate in no two refineries are identical, every refinery is in
to its specific
when processing
literature
or scientific ways
journals. in different
in quite will
contradictory
their regeneration
heavier
feeds.
is achieved
by using catalysts
containing
using oxygen-enriched
may face just an opposite lead to excessive constraints. of coke will imperative
heat generation
which
be allowed
In such cases,
sometimes
even a deliberate
incomplete
have to be resorted
high CO production
CO after-boiler
the suitability
of the recent
process
characteristics is available
unit. No general
panacea,
FIGURE
regenerator
regenerator
(HER).
of a unique and
of chemical
on the catalyst
In a conventional escapes
fluidized-bed
in its bubbling-bed
form, oxygen
bed and reacts with CO at the top of the bed, causing The coke combustion, took place however, is far from complete bed, there would can then be utilized that by per
excessively or optimum.
high temperatures.
in the catalyst
not be any CO left for after-burning. by the catalyst special catalyst tonne. for the cracking promoters
proper.
combustion
manufacturers,
but it increases
169 A closer examination from the chemical engineering standpoint by UOP revealed catalyst-
bed leading
to insufficient
and hence the after-burning. of the air distributor, and all of these problems Even if the mixing
sensitive
internal
diameter
bubble solution
and loss of the catalyst. is an ideal plug-flow to the same extent, the
engineering
to this problem
To reduce
time required
system
This decrease
inventories advantage:
inventory quickly
to process
unit becomes
easier
The complete
CO combustion
eliminates
CO after-boiler. achieved
inteA-related
by incorporation occurs
3). Most of
of catalyst portion
this riser tube, most of the CO also burns here. A maximum from coke combustion available and CO combustion This increases is absorbed
by the catalyst
for cracking.
the throughput
gains mentioned
above.
of regeneration
fractions,
as discussed
in Section
III,
the problem
regeneration investment,
capacity.
But expansion
especially
in Europe capacity
only at 50-70%
themselves investment.
capacity,
without
alterations,
air (from 21% in air up to about in pure oxygen into a hydrocarbon safety
by Air increases
hazards.
Hence special
precautions
along with
this system.
As pointed heavier
III.
4, increasing
of catalyst are briefly
energy
costs,
feedstocks,
environmental
restrictions
of a new generation
technology outlined
a) Reduce
Concern
of refiners through
to develop
in improving
the mechanical
achieved
stabilization lesson
of alumino-silicate
is a valuable
and ceramic
science.
b) Reduce
CO emissions.
Introduction
like Cr203 and MnO2 and ppm has become combustion quite common
as combustion
itself,
eliminating Since
the feedstock
the CO after-boiler.
Pt is also a powerful
catalyst
of sulfur
on the catalyst
There
excess
oxygen
the stack. A high level of oxygen of any nitrogen generation esox air. transfer catalysts.
enhances
Significant
progress
since SOx
1980 in the removal can, in principle, - feed selection - feed hydrotreating - feed-gas - catalyst
to reduce
investment
scrubbing I[ adaptation
operating
alternative
today,
According solution
to McArthur
incentive
for a purely
that even
the present
their
cost would
scrubbing
involved 2 so3
in transfer +
Formation
of metal
sulfate:
MO + SO3
MSO4
Active Group
Alumina; Oxides
Katalistiks
Bi on alumina
Riser
(cracker):
-+ MS + 4 H20
in the conventional
Claus
plant existing
refinery. period, special almost all FCC catalyst catalysts manufacturers or additives or getters have developed to combat excessive for SOx, the most 2. Other metalliterature and became have C35bI are
from regenerator
As additives
ones developed
by various
companies
are shown
in Table patent
combinations in a review
references
to the recent
alumina
lanthanides
were already
SOx emissions
of typical
emissions.
from all the above work is that often SOx transfer by research catalyst/additive in the near future. catalysts.
can increase
technology.
is a serious
problem
Customer
demand
for higher
engine
performance
limits on the use of lead as anti-knock for higher-octane gasoline from all prooctane is
have resulted
operations
One approach
to enhance
gasoline methyl
tertiaryfraction it
(MTBE), pool
and manganese
a significant
catalysts
to enhance
number of FCC-derived
gasoline.
by Mcdaniel since and Maher 1966. But it catalysts
The ultra-stable
developed
in cracking
IJSY catalyst,
containing
even up to 25 wt%
172
zeolite, became commercially peculiarities available as a typical zeolites octane-boosting fall outside catalyst. the scope of Spinning
of ultrastable
except
just to mention
of Magic Angle
picture of de-alumination and the formation of USY sieve 29 . Sl NMR of faujasites after increasingly severe by following the Klinowski [37] has reviewed this area in 1984. proposed by Magee et al.
detailed
treatments.
of octane
improvement
by USY catalysts,
is as follows. acidity
In USY, the acid sites are more widely than those cracking in conventional over USY yields rare-earth a product richer
dispersed
and are
exchanged
Consequently,
significantly in aromatics.
at the expense
of paraffins,
and slightly
will minimize
the well-known
hydrogen-transfer
reaction,
olefins
+ naphthenes
paraffins
+ aromatics
are produced
ultimately.
Since
the hydrogen
transfer
of aromatics
condensing
coke. Thus
less coke and improved acid sites enhance more likely rather
benefits. Hence
Furthermore,
the strong
over hydroproducing up as
would
and olefins
or LPG range,
high-molecular-weight aromatic
coke precursors. catalytic approach to enhance the octane sieves, number of FCC gasoline by Mobil consists
Another
of the use of ZSM-5 type of shape-selective These sieves have pore-mouth double-bond using openings
developed
[40].
secondary
reactions and
and skeletal
polymerization
the primary
products
from cracking
component.
of straight
lead to a preferential
paraffins.
pores prevent
of larger molecules
coke precursors.
of these shape-selective
little or no extra coke over and above that produced and the matrix of the catalyst. to predict
component
octane-boosting working
catalysts
by such entire-
mechanisms.
enhance
octane
but commercial
exploitation
of this understanding
173
3. Metals passivation One way to minimize the harmful effect of accumulating Ni on the
2) Nickel. catalyst
metal
passivation compound
procedure
of a soluble
antimony
form an alloy
enriched
is effectively
covered
Boron,
and tin have also been claimed literature. b) Vanadium. studies [20-221 As discussed
passivators
in recent
patent
in Section
III.
in recent years
have revealed
of selective
of zeolites
by V accumulating
in turn, of V: towards
of three
to combat
more optimum
process
conditions
to render
V harmless
for
V and area or trap for the V on the catalyst. strategies are given below.
a suitable
dumping
in a reducing
atmosphere,
and V203
diffraction
studies
affected zeolite
by V204 or
V203. Hence,
harmless
is to operate
as close
or at least to ensure
is no surplus
literature
indicate
or passivators
which
formulations diluent,
by Ashland by Gulf
and a Mg-containing
both developed
The strategy
of catalyst
manufacturers
at providing metals
a large dumping
the accumulating
of zeolite
sink.
of hydratreating
in the 1970's).
sepiolite
by De Jong
Otterstedt sizes:
et al. [47]
the zeolite
component
with
particles
a matrix
and possibly
for minimizing
CO oxidation.
The principle
and reach
in them than
located
in the smaller
particles
uniformly
in particles
in the catalyst.
using a vanadium
no catalytic
of W.R. Grace/Davison
174 TABLE 3 in fluid catalytic cracking 1951 designs (from O'Dea [50]).
Improvements
Regenerator
pressure/psig
9 607
20 677 351 94 11
318 49 IO
shaft energy/Btu
CO in flue gas/vol%
C on regenerated
catalyst/wt%
0.7
0.3
<O.l
Leuenberger predicting
recently
provided
correlations
for
the activity
of vanadium-contaminated
in FCC [50] improvements in FCC process and catalysts economy over the con-
synergetic have
gains
in the process
and energy
as summarized
AND SIEVE
IN RESIDCRACKING
CATALYST stability in
heavy oils must have high hydrothermal under severe regenerator conditions Normal
to maintain
for lighter
products
and diesel.
FCC catalyst
of spherical
particles
in the matrix.
It is IOO-10,000
high activity
the catalysts
A matrix surface
catalyst
should
and larger
pores
reasons:
of large b) large
molecules,
pores minimize
the carrythey
present
[51] where
to coke; and d) large pores and low surface of contaminant composition metals and thereby increase
decrease
resistance
V and neutralize
of these metals.
175 proposed yields silica [53] that a matrix of magnesium-alumino-phosphate to an alumina-silicate will improve [55]. thermal and hydrothermal stability of the the metal will decrease the
compared
matrix.
resistance
also requires
component.
in the zeolite
important contains
for hydrothermal
[56]. Ultrastable
no rare earth
high thermal
stability
stability
Different
types of zeolites
selectivity
for lighter
products in-
of the acid
[59]. By suitable
selectivity secondary
Very strong
since
they cause
products
increased
for instance
surface
area of catalysts
decreases
by ageing.
This,
in turn,
the distribution
of acid sites and their acid strengths. Brtlnsted acid sites into Lewis
The dehydration
converts
steam
All such
the activity,
of the catalyst.
VI.
GENERAL
DISCUSSION of heavy oil by catalytic in the three component of these interactions cracking is a question of optimizing Catalyst. in to
system:
Feedstock
- Process-
aspects
in normal
be discussed
1. Process
- feedstock
interactions into the development of atmospheric resids. of processes and vacuum Commercia7 for heavy oils resids, processes such as gas of
oils, atmospheric
the Total
process,
the ART
and Total
processes
resids
atmospheric
in general.
For atmospheric is
of medium
resids,
176
necessary developed fractions as a pre-treatment before the feed enters work one of the other processes of oil
No systematic 300-750C
on the crackability
region
2. Catalyst
- feedstock
interactions present in heavy oils have low volatility, operation. In most processes The fraction which creates of
the temperature
750C.
on the catalyst
be carried
behave
Early studies
of stripability
The situation
that a catalyst
strip more
for a given
catalyst
increase
the catalyst
or an active
e.g. crosslinked
is resistant system
by V or a passivating
system
to Phillips
Ketjen
is more of an environmental
[61], Chevron
on adsorption or bastnasite,
the emission
manufacturers
to obtain with
adsorption experience
is in accordance
the general
requires
the regenerator
3. Process
- catalyst catalyst
interaction development has guided and stimulated the process with developthe more
In general
ment active, changes cracking, stable
of amorphous
alumino-silicate catalysts
catalysts
zeolite-based
has led to very significant process for heavy oil has stimulated
in process
e.g. riser
cracking. where
Total's process
on the other
hand,
is an example
development
catalyst thermal
development, stability
namely
the development
of catalysts
with extremely
high
hydrothermal
stability.
of efficient present
catalysts designs
raises
the question,
process
of such catalysts.
problems has been made in the development Further of processes and catalysts for
cracking
of heavy feeds.
development
and assisted
when more
and most
non-volatile Possible
molecules separation
of heavy oils
in the
Extent of vaporization.
of these in a pre-
of the feedstock. between standard catalyst and special catalysts for heavy oil
and catalytic
properties.
in the process
of catalytic
sensitive
or insensitive
to catalyst
NOx emissions
increasing
to reduce
SOx emissions.
ACKNOWLEOGEMENT The authors express their thanks National to the Swedish Board for Technical Development support.
Energy Administration
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