Sie sind auf Seite 1von 21

Applied Catalysis, 22 (1986)

159-179

159

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FLUID CATALYTIC

CRACKING

OF HEAVY

(RESIDUAL)

OIL FRACTIONS:

A REVIEW

J.E. OTTERSTEDTa, aDepartment University b

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,

EKA AB, 445 01 Surte,

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

of shock waves searches were

the petroleum to develop latent

industry. energy

hand desperate also explore gas reserves. resulting Thus,

alternative

sources

for and develop On the other

(often off-shore)

oil and natural less oil, oil products.

hand, the world in the demand fractions

has learned patterns

to live with

in a radical

change

for the various residual

the demand while

for heavier

and the so-called

oils has steadily is increasing. rjhich cannot and are forced both

decreased, This shift adjust

that for gasoline, pattern

diesel

and such lighter

fractions

in product

has become

so compelling situation

that refineries uneconomic

and adapt quickly

to this changing

become

to shut down (e.g. Texaco Refinery


in a small country One solution like Belgium). change to the above

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

into lighter operations

distillates. [I] of 1973, high;

of such resid-cracking 1982. Furthermore,

doubled

February

1981 and October

since

the oil crisis

the ratio between

the cost of crude oil and the cost of refining

has become

0166-9834/86/$03.50

0 1986 Elsevier Science Publishers B.V.

this has created oils in general particular

a powerful

incentive

to develop cracking

processes

for upgrading

heavy in

and for fluid catalytic of heavier

(FCC) and resid-cracking poses numerous

[Z]. Cracking design

fractions, firms

however,

problems Hence

for oil companies, these three groups urgent

and engineering developing

and catalyst

manufacturers.

are naturally problems. because

several

innovations

to face these

and stupendous innovations

The purpose

of this review impact

is to draw attention for the science C3al have reviewed they have which caused and

to these

of their great Quite recently,

and relevance and Peters

and technology the special

of catalysis. adapted

Maselli

processes

or newly developed

for resid molecular

cracking;

also discussed complicate by these processing while Aalund

in detail

the large organo-metallic operation,

structures problems

the resid-cracking giant molecules,

the special

diffusion

etc., Many practical recently by Elvin

aspects

of residue

blending

have been reviewed grades

[3b], and Campagna available

et al. [3c], by

the various

of commercial process

catalysts

have been surveyed in a com-

[3d]. More general review

aspects

of FCC have been described

prehensive monograph

by Venuto

and Habib

[4a] and by Decroocq French

[4b] in 1984 in a version published if at all, in in

in English, these

translated aspects

from its original will

1978. Hence the present

process

be only briefly

mentioned,

review.

Greater metals

attention on process

is paid here to the disastrous selectivity and catalyst

consequences the in an in

of the accumulating recent breakthrough

stability,

innovations

to cope with the increased roles of matrix

coke formation

existing cracking

or new catcracker, heavier fractions,

the separate

and molecular

sieve

the new generation

of FCC catalysts SOx emissions the harmful

specially

tailored to

to give almost enhance

complete

CO combustion, number, etc.

to reduce

from FCC stacks, of Ni and V

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

them nor do they separate condition of petroleum defined

tate with measurable

rate. This pseudo-stable number

oils

that there are only a limited chemical bonds and heteroatoms

of functionalities

in terms of

in oil molecules.

Furthermore,

the distribution varies

of functionalities, .with the boiling in a low boiling indeed

but not the types

of functionalities, Hence

in an oil fraction

point of the fraction. fraction

the same compound fraction

types are present gas oil and of large

as in a high boiling fraction and metal

of vacuum

also as in the asphaltene containing point heteroatoms

[4a]. The increasing contaminants in processing are present

portion

molecules boiling Although

in fractions

of increasing [5,6]. fraction size of the

accounts

for the difficulties

of heavy oils

the same type of functionalities gas oil, the degree

in the asphaltene due to the sheer

as in e.g. vacuum molecules

of association

and due to the presence

of several

functionalities

in the same molecule

161
TABLE 1 variation in residues from 150 different crude sources

Contaminant

Residue

type

Ni/ppm

V/ppm

S/%

N/%

CCRa/%

Density /kg crnm3

API gravity 8.4-13.7 3.4-21.5

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.

is much higher catalytic

in the asphaltene of heavy feeds and molecular

fraction.

A major

reason

for the difficulties the low volatility

in of

cracking

has therefore clusters

to do with

the large molecules This causes over Table

of the asphaltene

and resin fractions. and be carried onto the catalyst. distillation of

them to be present where

on or in the catalyst

as liquids

into the reactor 1 shows typical distillation

they will make coke and deposit ranges refinery in residues operations.

metals

concentration in typical cycles

from atmospheric

and vacuum

Due to the hundreds particle

cracking-regeneration concentration

undergone

by every catalyst to hundreds

in FCC, the metal of ppm.

on the catalyst

can accumulate

or thousands

A Scdlum n Vanadiur

FIGURE Zandona

1 Surface area as a function of metal impregnated


et al. [7]).

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

concentrations the catalyst.

and will Nickel

have detrimental

effects

on the cracking nonselective

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

into the zeolite

V). Figure

1 shows the change


and subjected are usually is often

in specific

of a catalyst

contaminated Nickel

with metals

to a steaming

test at 788C for 5 hours molecules and as

and vanadium Sodium

present

in porphyrine-like as a result

naphthenates. Sodium

present

in resids

of poor desalting. activity of molecular

neutralizes

the acid sites which

are so vital

for the cracking

of the catalyst, sieves

it also leads to collapse

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

was to characterize feeds increases

sulfur compounds

in crude oil. The catalytic

the SOx content

in the stack gas from the catalytic 5% of the total S is transferred

cracker.

gas-oil

cracking,

as rule of thumb,

into the coke in other stack. than of or For

on the catalyst words,

and this appears

as SO2 in the stack gas of a FCC unit; 1000 ppm SO2 in the regenerator

1 wt% S in the feed gives about the proportion

resid cracking, these values

of SO2 in the stack gas can be much higher be reduced below

C3al. Emissionshaveto by January

60 kg S per 1000 barrels are being imposed

feed in California contemplated

1, 1987. Similar also.

restrictions

in many other countries

3. Nitrogen

and oxygen of nitrogen compounds is higher in heavier feeds than in vacuum gas oil. adsorbed rate indols Hence

The content Basic nitrogen

such as pyridines resulting

and quinolines in reduced compounds

are strongly

at the acid sites of the catalyst of coke formation. and pyrrols Neutral

activity

and higher

types of nitrogen adsorbed

such as carbazoles,

are not as strongly the cracking

on the acid sites of the catalyst. of the catalyst the content very much [Sl.

they do not affect

performance

As in the case of nitrogen with the boiling

and sulfur,

of oxygen little

also increases attention catalysts. has

point of an oil fraction of oxygen

but relatively

been paid to the effect

on the performance

of cracking

4. Asphaltenes Asphaltenes functionalities recently are aggregates of several of molecules Their containing polycyclic aromatics and

types.

structures

have been discussed

quite

by Kaselli varies to accept

and Peters

C3al and Bunger i. Since

and Norman the pores

[9]. The size of of the zeolites pore structure asphaltenes are than

asphaltenes too small zeolites cracked embedded. asphaltenes

in the range 25-300 asphaltenes,

catalysts

with much

larger

are required on the matrix There

to crack asphaltenes. in which the regular

Alternatively, zeolites

can be catalysts out are

used in cracking for separating

are also commercial [IO-121.

processes

available

from crude oils

163
PETROLEUM DESIRED TRANSPORTATION FUELS

\,_;_-__ RESIDUAL OILS . / * .i 1.5

Heavy

$ 1.0
FIGURE 2

H/C ratio

2.0 feedstocks, residual oils, and

H/C ratio for heavy and light petroleum end products.

the desired

5. Resins Resins weight are polar molecules containing oxygen and nitrogen. Their molecular in paraffins.

is normally

in the range 500-1000.

They are slightly

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

1.4 to 1.8. For all usable

transportation refining ratio.

be in the range

1.8 to 2.1. All petroleum to raise the H/C

operations

may be considered

as efforts

This can be achieved the excess

in two ways: carbon as in processes like Delayed Coking [13], Flexi-

a) by rejecting coking

[14], Visbreaking

[15], or Solvent

Deasphalting

[IO-121. or hydrocracking. in detail instead in this

b) by introducing

more hydrogen are widely

as in resid hydrotreating practised

These two options the literature.

and have been described any further here,

Hence they will

not be discussed cracking

review will concentrate

on the direct

of resids.

III.

PROBLEMS Resids

FACED

BY EXISTING of resids

CATCRACKERS

IN PROCESSING

HEAVY OIL FRACTIONS in catcrackers [I71 that in the

and blends

with gas oil have been processed conducted in 1983 showed

for more than 20 years United States already

[163. A survey 47 refineries of resids

used resids boiling

as a part of their feedstock 500C in the feedstocks in con-

mix for FCC. The blending varied

at or above

from 5% to even 50%. Most of this type of cracking or revamped FCC units originally designed

has been done

ventional

for cracking

only gas oil. because of the

Such operations relatively peculiar

are possible

only at the expense

of unit capacity oil [18] and other below.

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

Introducing ordinary contains

resid or blends in several

situation

respects. Residue

less than 0.5% Conradson feed generally

(CCR). Catalytic

cracking

such conventional

a coke-make

of 4-6% based on the feed.

164 The combustion various process of this amount energy of coke will generate enough heat to satisfy the feed, the

requirements cracking

such as heat to vaporize reactions steam

heat to air adjust

carry out the endothermic and the different itself

and to heat the regeneration

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

l-15% CCR, while resid is introduced

resid may

even up to 25% CCR (Table in a higher

as part of the feed, in the rethe increased will neverseveral

this will result generator. quantity theless

coke production

and more

heat release

The increased

heat release air needed,

is partially

used in heating temperature

of regeneration rise considerably.

but the regenerator regenerator below: in traditional

This higher

temperature

causes

types of problems

in a FCC unit as described problems: The regenerator higher

a)

Metallurgical not designed exceeded the total when

FCC Units That limit

is generally is easily

for temperatures introducing

than 730-740C. of resid

even small amounts constant.

in the feed, provided

throughput

remains

b)

Deactivation FCC-catalysts regenerator A higher sequently, version

of the catalyst: is mainly temperature,

The rate of deactivation of contamination of water

of present-day

commercial

a function partial

level on the catalyst, in the regenerator faster. and time. Concon-

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)

Low catalyst/oil requirements catalyst selective

in a FCC unit, a higher

regenerator

temperature

circulation catalytic

rate. This results cracking. A higher If

in more thermal

cracking

d)

Inadequate regenerator another

regeneration: air blower.

coke make will capacity

increase

the strain

on the factor,

the air blower

is not the limiting

constraint At higher

can be the gas velocity velocities,

in the regenerator

or the flue-gas

cyclones. cyclones

more catalyst

fines will be blown out of the

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

low. This will entrain

more

fines to

when accentuated generally

by the fact that the proportion is many times higher than in

in resid crackers The increased of atmospheric

operation.

temperature nitrogen

in the regenerator

can also lead

to more fixation gases.

and consequently

more NOx in the stack

165 2. Problems with metal contaminants harmful from an operational point of + naphthenates and nitrogen compounds,

Feed contaminants view are the metal

that are especially organic compounds

such as Ni- and V-porphyrines Heteroatoms problems. such as sulfur Basic

and salts of sodium,

iron and copper.

cause more environmental however, adsorbed can temporarily on the catalyst, molecules.

than operational deactivate this will

nitrogen

the acidic

catalyst;

since they are easily

also add some extra coke from the nitrogen-

containing

High metal the following

and heteroatom respects:

levels will affect

the catcracker

performance

in

a) Poor selectivity. The selectivities dehydrogenating dramatically compressor contaminant

The metals

build up almost

quantitatively

on the Catalyst. due to the strong basis will increase

change function

toward more H2- and coke production of nickel. The gas-make on a volume

as the contamination to be the "through-put coke that is produced described

level goes up. This often limiting" part when

causes

the dry gas blends. The part

cracking metals

resid

by the contaminant

is an important

of the coke problem b) Catalyst

earlier. will mainly be deactivated by V and Na. structure, make-up

deactivations.

The catalyst

High levels of these metals especially in combination

have a destructive high regenerator activity

influence

on the zeolite Catalyst

with

temperatures. level

must be increased

to keep a reasonable

in the unit.

3. Interaction

of metals

with the catalyst characterization techniques have recently been

Some powerful employed zeolitic has shown tendency catalyst. uniformly the worst

physico-chemical insight Using

to get a better cracking

into the interactions secondary ion mass

of Ni and V with the spectrometry

catalyst.

(SIMS),

Jsrfis

[20] that,

under cracking-regeneration enriched

conditions,

V has a remarkable in the remains

to get selectively

on the molecular enrichment

sieve component

No such preferential distributed contaminant

surface

is exhibited

by Ni, which

on the sieve and matrix at low concentrations

surfaces.

But Ni is undoubtedly low concentrations

(<5000 ppm). At these content

the usual relation Ni": Equivalent as obtained

for calculating

the total metal

of a feed is "equivalent in ppm by weight

Ni = Ni + 0.2 V + 0.1 Fe, all metals analysis. Above

expressed

from elemental

5000 ppm, Ni and V are additive.

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

concentration but higher

loadings

to its surface [211 to occur

enrichment.

The segregation ways:

in the catalyst the cracking

has been found

in three

different

a) during due

stage V is deposited

on the outer

part of the catalyst complex; b) during

particle

to the polar nature

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

from the matrix [20])and

surface

(as already

shown

from SIMS studies

destroys

the crystal

structure

of the zeolite. further the

Pompe et al. [22] have applied destructive roles of the metal decompose

DTA/TGA

techniques

to elucidate

porphyrines

and naphthenates

on the FCC catalyst.

Ni- and V-porphyrines cracking conditions,

fully only after about naphthenates

30 min at 500C under are decomposed readily both

but the corresponding

and completely these classes

under those conditions. of compounds decompose

Under typical exothermally

regenerator

conditions, and/or

(could be combustion of the rare-earth to the attack

polymerization). sieve

The mechanism

of the destruction

exchanged

(REY) in the catalyst

has been attributed a low-melting

of V205 on the rareThis vanadate by V205. Ttis thus leadi?+ i.

earth component formation

of REY forming more oxygen

RE-vanadate

phase.

requires

per RE atom than what from the zeolite

can be supplied structure, [ZZ].

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

The high concentrations gases are objectionable standpoints. Finally,

of CO (even up to 10%) in older-type both from the environmental the increasing tendency

regenerator

and energy-conservation out lead from gasoline with should (both

to phase

from environmental exhaust directly cleaning

considerations catalysts)

and also for use in automobiles that higher octane numbers

noble-metal be achieved

dictates

from the FCC operation

than is possible

at present. fractions energy as FCC feedstock crisis started are in 1973. pressures,

The problems a direct These result

posed by the need to use heavier of the oil crisis sometimes resemble

and the consequent closely

problems

those arising

from environmental design and

as briefly catalyst

enumerated

above.

Luckily,

innovations

in FCC process

improvement

have sometimes Typical

been able to offer examples

simultaneous

solutions

to

both these Section IV,

sets of problems.

for these will be discussed

under

IV.. INNOVATIVE 1. Process

APPROACHES

TO PROBLEMS adaptations

OF RESIDCRACKING

and engineering Processes.

a) Modified catalyst

The oil companies,

design

and engineering

firms and

manufacturers heavier

have been quick

to react to the problems solutions

posed by the indeveloped involve

creasingly feedstock Already refinery

feedstocks

for FCC. The technical cracking

pretreatment

or resid catalytic installed Since

or a combination

of both.

in 1960, Kellogg at Borger,

a Heavy Oil Cracking

(HOC) unit at a Phillips of the HOC process

Texas.

then, a continuous

development

167

has been taking riser to reduce cracking, separation to ensure

place.

The latest

versions

of HOC involve

[23] a) a Vertical effects and overfor quick steam and

catalyst-oil

contact

time, minimizing

metal

b) the riser ending of the catalyst good and instant

at a 90"-turn

into the riser cyclone

c) multiple mixing with mode

feed injectors the catalyst,

and use of excess

d) a large regenerator temperature and e)

regeneration internal

in a counter-current coils

to avoid excessive and external

cooling

in the regenerator by Total

catalyst

coolers. [24-251 mainly

Modifications in conducting instantaneous a riser

introduced

Petroleum

in 1982 consist

both the cracking thermal cracking

and regeneration of the asphalt portion

in two steps each. zone

Here, an by

in the mixing

is followed step.

cracking

of the lighter

of the product

from the first

Similarly, ture

the first

stage of the regeneration oxygen; steam

is carried is present

out at a lower temperaat this stage, partly

(600-750C)

in insufficient and partly

from steam-stripping into H20. The CO-rich catalyst undergoes

from the combustion

of the H-content

of the coke the

flue gas is then separated regeneration

from the catalyst at 760-940C

before

the second-stage

in excess

oxygen Such

to burn off only the carbon high temperatures generator temperature burning

of the coke

still remaining

on the catalyst. outside

are possible

since the cyclones bricks, hence

are located there

the re-

and lined with refractory limit. Since there

is no metallurgical CO after-

is no steam present is protected by Ashland

and the so-called hydrothermal with

is avoided,

the catalyst [26] developed in process

against

deactivation.

The RCC process several improvements

Oil, jointly

UOP, incorporates regenerator with metals IV.3b)

design

like UOP's high efficiency activity coupled

(see Section passivation

IV.2) and in catalysts (see Section

like greater

1V.3~) and combustion

promoters

(see Section

added to the catalyst. The Ashphalt [27,28] process Residual Treating (ART) process pretreatment and metals developed process. by Engelhard Corporation

is essentially for removal

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

of the feed. Another C291, combining Such typical

is the new Hycon process and hydroconversion however, or resid Since will

of Shell

demetallization, fixed-bed

into one process.

hydrogenative

not be discussed

any further

in this review

of FCC of heavy oil

fractions. the conditions to innovate in no two refineries are identical, every refinery is in

a way forced encountered

and find its own solutions heavier feedstocks.

to its specific

problems seldom find

when processing

Many such solutions Some of these refineries. efficiency

their way to patent may be applied some catcrackers to process

literature

or scientific ways

journals. in different

solutions For instance, if they want the so-

in quite will

contradictory

have to increase This

their regeneration

heavier

feeds.

is achieved

by using catalysts

containing

168 called combustion promoters, or by using a high efficiency Sections). regenerator, or by

using oxygen-enriched

air (see the following situation:

Some other catcrackers coke may

may face just an opposite lead to excessive constraints. of coke will imperative

the combustion cannot

of any additional because

heat generation

which

be allowed

of metallurgical combustion makes it

In such cases,

sometimes

even a deliberate

incomplete

have to be resorted

to. The resultant

high CO production

to have a costly pollution

CO after-boiler

if loss of CO as a valuable Thus,

fuel gas and

and environmental acceptability innovations

with CO are to be avoided. catcracker

the suitability

for any particular will depend

of the recent

process

and catalyst of that FCC at present.

very much on the specific applicable

characteristics is available

unit. No general

panacea,

for all units,

disengaging vessel combustion riser

FIGURE

The high efficiency

regenerator

of UOP (from 1303).

b) UOP's high efficiency application advanced

regenerator

(HER).

The HER is the result engineering

of a unique and

of the basic principles

of chemical

in a very elegant [30].

way to the problem

of coke combustion regenerator

on the catalyst

In a conventional escapes

fluidized-bed

in its bubbling-bed

form, oxygen

from the catalyst

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.

If all the combustion

in the catalyst

not be any CO left for after-burning. by the catalyst special catalyst tonne. for the cracking promoters

All the heat generated It is precisely

proper.

for this purpose

combustion

(like ppm levels of Pt) are added

to the catalyst by $100-200

manufacturers,

but it increases

the price of the catalyst

169 A closer examination from the chemical engineering standpoint by UOP revealed catalyst-

the crux of this problem air mixing, Bubbling break-through

to be the bubbling and escape

bed leading

to insufficient

of air (oxygen) to the design geometries,

and hence the after-burning. of the air distributor, and all of these problems Even if the mixing

beds are notoriously

sensitive

the catalyst are magnified was perfect temperatures, combustion,

bed level, and other with increasing

internal

diameter

of the regenerator. the combustion

in this type of regenerator, hence CO escapes it will increase

of CO is slow at low to complete the

from the bed. If formation

more air is added

bubble solution

and loss of the catalyst. is an ideal plug-flow to the same extent, the

The chemical regenerator. residence

engineering

to this problem

To reduce

the coke content

on the catalyst reactor

time required

in an ideal plug-flow reactor.

system

is only about onein residence time

tenth of that in an ideal back-mixed allows much smaller catalyst

This decrease

inventories advantage:

of only about the catcracker

50%. Decreasing plant responds

the catalyst more

inventory quickly

gives an operational control,

to process

the whole achieved

unit becomes

easier

and safer to operate.

The complete

CO combustion

eliminates

the need to have an expensive in a synergetic (Figure manner, are

CO after-boiler. achieved

All these advantages,

inteA-related

by incorporation occurs

of a riser tube in the regenerator during the plug-flow movement

3). Most of

the coke burning

of catalyst portion

and air through of the heat and thus becomes apart

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

of the FCC plant,

from all the other during

gains mentioned

above.

In the 20 new FCC units built in Europe


regenerator. to crack of The trend and necessity bring invariably

the last ten years, enrichment

13 units have the high-efficiency air.

c) Oxygen heavier more

of regeneration

fractions,

as discussed

in Section

III,

the problem

coke formation without

and the need to have more substantial new capital

regeneration investment,

capacity.

But expansion

of capacity, crackers, running

is not easy in most catStates are

especially

when many refineries of their installed

in Europe capacity

and the United

only at 50-70%

and some are even completely be made capable of cracking

shut down. So the present heavier feedstock without

FCC units should any major capital

themselves investment.

One way to increase is oxygen en-

regeneration richment Products

capacity,

without

any major mechanical

alterations,

of regeneration C311. Bringing

air (from 21% in air up to about in pure oxygen into a hydrocarbon safety

25%), proposed plant of course

by Air increases

fire and explosion corporated

hazards.

Hence special

precautions

will have to be in-

along with

this system.

170 2. Catalyst adaptations out in Section

As pointed heavier

III.

4, increasing
of catalyst are briefly

energy

costs,

the need to process have led to

feedstocks,

and the tightening

environmental

restrictions

the creation features

of a new generation

technology outlined

for FCC. Some salient below. losses per day catalyst

of this new development dust emissions.

a) Reduce

Concern

of refiners through

on catalyst FCC stacks

and local restrictions manufacturers involved

on dust emissions so-called

have forced catalysts. micron-size

to develop

high-attrition-strength strength of colliding environments are often

The problems particles

in improving

the mechanical

at 500-700C adequately or inspired rare-earth

under cracking/regeneration/steam The improvements The thermal

are still not based on ad hoc trials catalysts by

understood. guesses. oxides

achieved

stabilization lesson

of alumino-silicate

is a valuable

drawn from solid-state of oxides

and ceramic

science.

b) Reduce

CO emissions.

Introduction

like Cr203 and MnO2 and ppm has become combustion quite common

levels of Pt into FCC catalyst in recent years regenerator [32]. This

as combustion

promoters complete units:

leads to an almost two expensive

of CO in the preheater and of

itself,

eliminating Since

the feedstock

the CO after-boiler.

Pt is also a powerful

catalyst

for the oxidation

so2 to so3, the fixation from the stacks one complication

of sulfur

on the catalyst

and hence reduced promoters. requires

SOx emissions is, however, in

are also achieved

by these combustion of SOx emission

There

here: the reduction

excess

oxygen

the stack. A high level of oxygen of any nitrogen generation esox air. transfer catalysts.

enhances

the emission fixation

of NOx due to oxidation of nitrogen in the re-

in the coke or even by direct

Significant

progress

has been registered

since SOx

1980 in the removal can, in principle, - feed selection - feed hydrotreating - feed-gas - catalyst

of SOx from regenerator be based on [4a, 33 a,b]: - often often

flue gas. Technology

to reduce

not much choice need heavy costs

here and rather high

investment

scrubbing I[ adaptation

operating

- the cheapest investment

alternative

today,

with no new capital

According solution

to McArthur

et al. [34] the economic is so strong

incentive

for a purely

catalytic catalyst increand

to the SO, problem at triple

that even

if an SOx transfer catalysts,

were priced mental would

the present

price for conventional

their

cost would

be lower than the operating capital

cost for flue-gas

scrubbing

also save the additional reactions

investment. of SO, via the catalyst are:

The chemical Regenerator:

involved 2 so3

in transfer +

S (in coke) + 0 so2 + 302 +

so2 + so3 (< 10%)

Formation

of metal

sulfate:

MO + SO3

MSO4

171 TABLE Active 2 ingredients of SOx transfer catalysts

Company Exxon Chevron, Arco, Amoco Union Oil Texaco Akzo-Ketjen

Active Group

ingredient IIA metal special oxides clays (Mg on SiO,-MgO)

Alumina; Oxides

Katalistiks

of Si, Zr, Mg, etc., Spinels

Na, SC, Ti, etc., Bastnaesite (rare-earth ore)

Bi on alumina

Riser

(cracker):

MS04 + 4 H2 MS + H20 in the reactor

-+ MS + 4 H20

Stripper The HpS formed ultimately modern

-+ MO + H2S section can be easily handled and removed in any

in the conventional

Claus

units and sulfur

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

In the 1981-84 and commercialized SOx emissions prominent oxide given

SOx transfer stacks.

from regenerator

As additives

ones developed

by various

companies

are shown

in Table patent

combinations in a review

and detailed by Habib

references

to the recent

[33a]. Of the above

formulations, even before

alumina

lanthanides

were already

part of FCC catalysts

SOx emissions

an environmental been described

issue. The characteristics by Baron and co-workers of regenerator

of typical

SOx getter materials

[34,35 a,bl, who have also reviewed One disturbing

in 1985 the problem

emissions.

factor emerging with the use of to be tackled

from all the above work is that often SOx transfer by research catalyst/additive in the near future. catalysts.

NOx emissions This

can increase

technology.

is a serious

problem

d) Octane-boosting in automobiles compounds cessing

Customer

demand

for higher

engine

performance

and government-imposed in an urgency

limits on the use of lead as anti-knock for higher-octane gasoline from all prooctane is

have resulted

operations

in the refinery. additives

One approach

to enhance

gasoline methyl

to use anti-knock butyl ether

not containing anti-knock

lead, e.g. ethanol, agents. States) Since

tertiaryfraction it

(MTBE), pool

and manganese

a significant

of the gasoline is only natural tailored

(about 35% in the United manufacturers

comes from FCC units, develop

that catalyst the octane

and oil companies

catalysts

to enhance

number of FCC-derived

gasoline.
by Mcdaniel since and Maher 1966. But it catalysts

The ultra-stable

Y (USY) type of zeolites,

developed

C361, was already being used by Davison


was only in 1976 that the modern

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

The structural this review, NMR, a fairly has evolved thermal

of ultrastable

except

just to mention

that, with the advent

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.

The mechanism [38-391

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

of a stronger zeolites. in olefins

exchanged

Y (REY) richer Since

Consequently,

significantly in aromatics.

at the expense

of paraffins,

and slightly

both these factors

will minimize

the well-known

hydrogen-transfer

reaction,

olefins

+ naphthenes

paraffins

+ aromatics

less paraffins there is also

are produced

ultimately.

Since

the hydrogen

transfer

is impeded, aromatic yield are

less likelihood and finally

of aromatics

condensing

to form polynuclear aromatics cracking

coke precursors secondary

coke. Thus

less coke and improved acid sites enhance more likely rather

benefits. Hence

Furthermore,

the strong

over hydroproducing up as

gen transfer. aromatics

large alkly aromatics in the gasoline components

would

dealkylate than ending

and olefins

or LPG range,

high-molecular-weight aromatic

in the light cycle

oil (LCO) range or polynuclear

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].

< 6i. They catalyze isomerization,

secondary

reactions and

like re-cracking, hydrogen transfer,

and skeletal

polymerization

the primary

products

from cracking

on the X- or Y- sieve over that of branched

component.

The ease of reaction pores

of straight

chain molecules cracking

ones in the narrow straight-chain

lead to a preferential

away of the low-RON the formation

paraffins.

At the same time, the narrow polyaromatic

pores prevent

of larger molecules

like typical sieves

coke precursors.

Hence the addition produces

of these shape-selective

(usually a few wt%)

to the FCC catalyst by the faujasite

little or no extra coke over and above that produced and the matrix of the catalyst. to predict

component

It is not difficult may try to combine ly different by which reasonably

that in the near future, additives,

octane-boosting working

catalysts

both the above octane-booster As Magee

by such entire-

mechanisms.

et al. C39] point out in 1985, cracked-product gasoline

"the mechanisms number are

these two families well understood,

enhance

octane

but commercial

exploitation

of this understanding

has only just started".

173
3. Metals passivation One way to minimize the harmful effect of accumulating Ni on the

2) Nickel. catalyst

is to use the Phillips organometallic

metal

passivation compound

procedure

[411. Very low levels along with in which Ni metal bismuth

of a soluble

antimony

are added continuously

the feed. ESCA studies the Sb is highly area

have shown that Ni and Sb readily on the surface

form an alloy

enriched

[42]. In this way the active conditions.

is effectively

covered

up by Sb under the process as potential metal

Boron,

and tin have also been claimed literature. b) Vanadium. studies [20-221 As discussed

passivators

in recent

patent

in Section

III.

3, SIMS, ESCA, DTA/TGA


the mechanism This understanding, the effects

and other destruction has

in recent years

have revealed

of selective

of zeolites

by V accumulating

on the catalyst. strategies

in turn, of V: towards

led to the development - by selecting zeolite - by adding passivators

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.

- by providing Typical examples

a suitable

dumping

for these three different

As Pompe et al. [22] have shown, mixture X-ray can be reduced

in a reducing

atmosphere,

V205 in a REY/V205 (450-750C). Y is not to the

in two steps to V204 (50-450C) by the same authors

and V203

diffraction

studies

show that the zeolite V relatively

affected zeolite

by V204 or

V203. Hence,

one way to render

harmless

in the FCC catalyst conditions,

is to operate

the regenerator that there

as close

as possible oxygen. seem to V, e.g.

to reducing Patent favour

or at least to ensure

is no surplus

literature

of the last few years additives

indicate

that oil companies can immobilize

the use of metal patented

or passivators

which

formulations diluent,

by Ashland by Gulf

Oil [43J, or tin additives [44,453. is aimed

and a Mg-containing

both developed

The strategy

of catalyst

manufacturers

at providing metals

a large dumping

area on the catalyst separate the cracking lesson

to accommodate function learned

the accumulating

and preferably (This is apparentcatalysts as an for

of zeolite

from this metal

sink.

ly a valuable residual additive oils

from the development Thus,

of hydratreating

in the 1970's).

the use of non-dispersive [46] of Akzo-Ketjen. of particle

sepiolite

has been proposed suggest

by De Jong

Otterstedt sizes:

et al. [47]

of Katalistiks Particles activity, amorphous emissions

the use of two ranges u contain

the larger the cracking of kaolin and SO, take

in the range 80-100 while the smaller

the zeolite

component

with

particles

(30-60 u) comprise other additives

a matrix

silica-alumina, and/or catalyzing

and possibly

for minimizing

CO oxidation.

The principle

here is that it will the zeolite

a longer time for V to penetrate crystallites or distributed embedded

the larger particles if these were

and reach

in them than

located

in the smaller

particles

uniformly

in particles

of all sizes activity

in the catalyst.

The idea of by Wear

using a vanadium

sink with [48].

no catalytic

has also been proposed

of W.R. Grace/Davison

174 TABLE 3 in fluid catalytic cracking 1951 designs (from O'Dea [50]).

Improvements

1960's zeolite catalysts

1970's high temp. regeneration 33 732 378 126 200 ppm to 5%

Regenerator

pressure/psig

9 607

20 677 351 94 11

Temperature/"C Flue gas: Enthalpy/Btu Available lb-' lb-'

318 49 IO

shaft energy/Btu

CO in flue gas/vol%

C on regenerated

catalyst/wt%

0.7

0.3

<O.l

Leuenberger predicting

[49] has quite

recently

provided

some very useful FCC catalysts.

correlations

for

the activity

of vanadium-contaminated

4. Net improvements The mutually last 30 years sumption,

in FCC [50] improvements in FCC process and catalysts economy over the con-

synergetic have

led to important in Table 3.

gains

in the process

and energy

as summarized

V. THE ROLES OF MATRIX Catalysts order

AND SIEVE

IN RESIDCRACKING

CATALYST stability in

for cracking activity

heavy oils must have high hydrothermal under severe regenerator conditions Normal

to maintain

and selectivity consists

for lighter

products

such as gasoline matrix

and diesel.

FCC catalyst

of an alumino-silicate crystallites, vary

of spherical

particles

of 20-80 u. The zeolite The zeolite content may than riser

l-4 u size, are embedded in the catalyst.

in the matrix.

from 5 to 25 wt% This

It is IOO-10,000

times more active

the matrix. crackers,

high activity

has led to the present-day less sensitive to metal

short-contact-time contaminants. have an active

which make suitable

the catalysts

A matrix surface

for a heavy oil cracking for the following will

catalyst

should

and larger

pores

reasons:

a) rapid transport and coking); increase

of large b) large

molecules,

(since slow transport pore collapse

lead to overcracking c) small pores

pores minimize

and sintering; as liquids

the carrythey

over of heavy molecules will decompose the dispersion

present

into the regenerator

[51] where

to coke; and d) large pores and low surface of contaminant composition metals and thereby increase

area matrix the metal

decrease

resistance

[52]. The chemical with Na and

of the matrix the detrimental

is also important, effects

e.g. it may react It has been

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

of H2 and coke, or zirconia

compared

matrix.

Free alumina, of catalysts

on the matrix will

resistance

[54], but alumina Resid cracking zeolitic active

give more coke higher

also requires

component.

For this, the Na20 content content is more Y which

in the zeolite

has usually than

to be below for thermal low sodium thermal

0.5%. The rare-earth stability content

important contains

for hydrothermal

[56]. Ultrastable

no rare earth

and very hydro-

has extremely [57].

high thermal

stability

but only moderate

stability

Different

types of zeolites

have different strength

selectivity

for lighter

products in-

[58]. The distribution fluences the selectivity

of the acid

of the active ion-exchange,

sites decisively the desired

[59]. By suitable

selectivity secondary

can be achieved. cracking

Very strong

acid sites are undesirable into light gases and surface

since

they cause

of the desired nature

products

increased

coke formation. matrix

The acidic will

of the matrix produce matrix

is also important: with lower octane

thus a SiO*/MgO number

for instance

more gasoline [58].

and more diesel

than a Si02/A1203 The specific changes

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

at high temperatures rehydration of catalyst with

converts

acid sites, while reaction. Transfer atmosphere

steam

in the stripper atmosphere

leads to the reverse in the cracker

from the reducing may change

to the oxidizing metals.

in the regenerator changes can affect

the oxidation selectivity

state of deposited and stability

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

The upgrading the interactions The general detail

system:

Feedstock

- Process-

aspects

in normal

FCC have been discussed aspects pertaining

by Venuto and Habib will

[4a]. Hence only some special here.

heavy oil cracking

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

Much work has gone vacuum

gas oil with additions

deep vacuum for cracking

oils, atmospheric

resids and vacuum process,

such oils are the Kellogg process. The Kellogg

the RCC process,

the Total

process,

the ART

and Total

processes

can be used to upgrade quality.

the first two The KC process

types of oil and atmospheric is claimed resids

resids

of high to medium resids

to be able to handle to poor quality

atmospheric

in general.

For atmospheric is

of medium

and for vacuum

resids,

the ART process

176
necessary developed fractions as a pre-treatment before the feed enters work one of the other processes of oil

for heavy oil cracking. in the boiling point

No systematic 300-750C

on the crackability

region

has been published.

2. Catalyst

- feedstock

interactions present in heavy oils have low volatility, operation. In most processes The fraction which creates of

The large molecules special problems

in the cracking catalyst

the temperature

the regenerated above which will

does not exceed

750C.

of heavy oil boiling as a liquid material as coke.

750C will not vaporize will be difficult therefore

and will be present

on the catalyst

to strip from the catalyst. over into the regenerator

The high boiling where it will between

be carried

behave

Early studies

of stripability

did not show any correlation is probably

pore structure for large nonlarge pore

and ease of stripability. volatile structure molecules will

The situation

very different with an open

and one can expect readily.

that a catalyst

strip more

The yield gets heavier.

of heavy cycle oils will

for a given

catalyst

increase

as the oil must The

In order to crack the heavy cycle oil fraction,


surface either accessible to the large molecules large pore matrix have an active smectites

the catalyst

have an active catalyst phase, must

of the HCO fraction. large pore

or an active

e.g. crosslinked

[60]. more V than Ni, it is important to attack to develop a

Since most matrix-zeolite

heavy oils contain system which

is resistant system

by V or a passivating

system

for V, analogous manufacturers

to Phillips

based on Sb for passivating and Davison have claimed

Ni. FCC catalyst the development

like Katalistiks, catalysts

Ketjen

of such metal-resistant Sulfur problem. in heavy feeds ARC0

in recent years. problem than an operational methods, based

is more of an environmental

[61], Chevron

[62] and Union Oil [63] have developed by an active ingredient,

on adsorption or bastnasite,

of SOx in the regenerator which reduces

such as alumina stack. SOx-catalysts.

the emission

of SOx from the regenerator of so-called

Here also, catalyst Andersson absence alumina

manufacturers

claim the development

et al. [64] have just pointed in order

out that the presence sufficient

of 02 and the of SO, on of FCC units to be operated

of CO are necessary at 700C. This

to obtain with

adsorption experience

is in accordance

the general

that the use of y-alumina in the total CO combustion

for SOx transfer mode.

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

[19]. The replacement

of amorphous

alumino-silicate catalysts

catalysts

and selective design,

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

but not necessarily

hydrothermal

stability.

The rapid development however, if

of efficient present

catalysts designs

for heavy oil cracking can make

raises

the question,

process

full use of the properties

of such catalysts.

4. Some unsolved Much progress catalytic

problems has been made in the development Further of processes and catalysts for

cracking

of heavy feeds.

development

work will be stimulated

and assisted

when more

is known about: and non-crackable of increasing fractions. molecular

a. Characterization b. The crackability weight.


C.

of heavy oil in terms of crackable of fractions

of heavy oil as function

The state of the largest mixing zone.

and most

non-volatile Possible

molecules separation

of heavy oils

in the

Extent of vaporization.

of these in a pre-

treatment d. Differences cracking

of the feedstock. between standard catalyst and special catalysts for heavy oil

in terms of physical of metal ageing

and catalytic

properties.

e. The mechanism f. Steps

in the regenerator. cracking of heavy oils which are specially

in the process

of catalytic

sensitive

or insensitive

to catalyst

performance. when the catalyst and process are

9. How to prevent adapted

NOx emissions

increasing

to reduce

SOx emissions.

ACKNOWLEOGEMENT The authors express their thanks National to the Swedish Board for Technical Development support.

(STU) and the Swedish

Energy Administration

(STEV) for financial

REFERENCES P.G. Thiel, Davison Catalogram, No. 66, 1983. Advances in Residual Cracking, NPRA Annual Meeting, San Francisco, March 20-22, 1983. a. J.M. Maselli and A.W.Peters, Catal. Rev. -Sci. Eng., 26 (1984) 525. b. F.J. Elvin, Oil & Gas J., May 9, 1983, p. 100. c. R.J. Campagna, AS. Krishna and S.J. Yanik, Oil & Gas J., Oct. 31, 1983, p.129. d. L.R. Aalund, Oil & Gas J., Nov. 26, 1984, p. 104. a. P.B. Venuto and E.T. Habib, Catal. Rev. Sci. Eng., 18 (1978) l-150. b. 0. Decroocq, Catalytic Cracking of Heavy Petroleum Fractions, Editions Technip, Paris 1984. F.J. Elvin and K.V. Krikorian, Katalistiks 4th Annual FCC Symposium, Amsterdam, May 18-19, 1983 (Hereafter referred to as Katalistiks-4 (1983)). J.S. Magee and S.D. Griffith, in Katalistiks-4 (1983). O.J. Zandona, L.E. Busch and W.P. Hettinger, NPRA Meeting, San Antonio, Texas, March 1982; W.P. Hettinger, H.W. Beck, E.B. Cornelius, P.K. Doolin, R.A. Kmecak and S.M. Kovach, Oil & Gas J., April 9, 1984, p.102. D-R. Latham and H.W.E. Okanol, Non-Basic Nitrogen Compounds in Petroleum, API-RP-52, report 34. J.W.Bunger and C.L. Norman, Chemistry of Asphaltenes, Advances in Chem. Series,

178 195 (1981); see also: B. Tissot, Connaissances actuelles sur le produits lourds du petrole. Revue Institut Francais du Petrole, 36, NO. 4, p.429 (1981). L. Garwin and J.A. Gearhart, Oil & Gas J., p.63 ff, June 14, 1976; Hydrocarb. Proc., May 1976. A. Billon and E.L. Fehr, Oil & Gas J., p-43, Jan. 24, 1976. J.A.Gearhart and W.L. Wermilion, Katalistiks-4 (1983). R.A. Busch, J.J. Kociscin, H.F. Schroeder and G.N. Shaw, Hydrocarb. PrOC., 58 (1979) 136. D.E. Allen, D.E. Blaser and M.M. Lambert, Oil & Gas J., May 17, 1982, p. 93. D.E. Allen, C.H.Martinez, C.C. Eng and W.J. Barton, Chem. Eng. Progr., 79 (1983) 85. J.B. Rush, Chem. Eng. Progr., 77 (1981) 29. P.G. Thiel, Davison's Catalogram, No. 66 (1983). D.F. Barger and C.B. Miller, NPRA Annual Meeting, San Francisco, March 1983. L.L. Upson, I. Dalin and W.R. Withers, Katalistiks-3 (1982). S. Jgr&, Applied Catal., 2 (1982) 207. S.L.T. Andersson, S.T.Lundin, S. J?irds and J-E. Otterstedt, Applied Catal., 9 (1984) 317. R. Pompe, S. JZir& and N-G. Vannerberg, Applied Catal., 13 (1984) 171. J.R. Murphy, Katalistiks-3, Amsterdam 1982. R.R. Dean, J.L. Mauleon and W.S. Letzsch, Oil & Gas J., 80 (40) Oct. 4, 1982; 80 (41), Oct. 11, 1982. R.R. Dean, J.L. Mauleon and R.W. Pfieffer, U.S. Pat., 4,331,533 (May 1982); 4,332,674 (June 1982); 4,336,160 (June 1982). C.W. Strother and D.ALomas, Katalistiks-4, 1983. D.B. Bartholic, U.S. Pat., 4,243,516 Jan. 1981. R.P. Haseltine, A.K. Logwinuk and D.L. Caldwell, NPRA Annual Meeting, March 1983. J. Heard, Chem. Eng., Nov.12, (1984) p-20-1. C.A. Cabrera and R.W.Mott, Katalistiks-3, 1982. F.J. Elvin and R. Milne, Oil & Gas J., 81 (9), Feb.28, 1983. F.D. Harzell and A.W. Chester, Hydrocarb. Proc., (July 1979) 137. a. E.T Habib, Oil & Gas J., Aug. 8, 1983, p. Ill. b. J.D. Wall, Hydrocarb. Proc., Oct. 1984, p. 45. D.P. McArthur, H.D.Simpson and K. Baron, Oil & Gas J., Feb. 23, 1981, p- 55. a. K. Baron, A.H. Wu and L.D. Krenzke, Preprints, ACS Div. Petr. Chem., 28 (4) (1983). b. E.J. Aitken, K. Baron and D.P. McArthur, Katalistiks 6th Symposium, Munich, May 1985. and P.K. Maher, First Zeolite Symposium, Sot. Chem. Ind., C.V. McDaniel London, 1967. U.S. Pat. 3,402,996 (1968). J. Klinowski, Progress in NMR Spec., 16 (1984) 237. J.S. Magee and R.E. Ritter, Symposium on Octane in the 1980's, ACS Div. Petr. Chem., Sept. 10-15, 1978, p. 1057. J.S. Magee, W.E. Cormier and G.M. Wolterman, Katalistiks-6, Munich, 1985. Mobil, Euro. Pat. Appl., 21 (1981) 787, CA 94 (1981) 159,539; see also S.J. Miller and K.C.Bishop, U.S. Pat., 4,340,465 (1982). G.D. Parks, ACS Div. Petr. Chem. Preprints, Houston, March 23-28, 1980. G.D. Parks, Appl. Surf. Sci., 5 (1980) 92. Ashland Oil, U.S. Pat., 4,432,890 (1982). Gulf, U.S. Pat., 4,465,779 (1984). See NPRA Panel Discussion, Oil & Gas J., July 15, 1985. J.I. de Jong, U.S. Pat., 4,519,897 (1984). J.E. Otterstedt, S.G. Jar&, R. Pudas and L.L. Upson, U.S. Pat., 4,515,903 (1984). C. Wear, Oil & Gas J., March 4, 1985, p.106. E.L. Leuenberger, Oil & Gas J., July 15, 1985. D.M. O'Dea, Chem. Eng. Progr., 76 (1980) 59. A. Bondi, R.S. Miller and W.G. Schlaffer, Ind. Eng. Chem., Proc. Des. Dev., 1 (1962) 196. H.R. Grane, J.E. Connor and G.P. Masalogites, Petroleum Refiner, 40, No. 5 (1961) 168.

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35

36 37 38 39 40 41 42 43 44 45

46
47 48 49 50 51 52

179
53 54 55 56 57 :: H.E. Swift, J.J. Stanulonis and E.H. Reynolds, U.S. Pat., 4,158,621 (1979); 4,179,358 (1979). E. Em. Gladrow, U.S. Pat., 4,147,613 (1979). B.C. Gates, J.R. Katzer and G.C.A. Schuit, Chemistry of Catalytic Processes, McGraw Hill Inc., New York, 1979. A.D.N. Wallace, ACS Symp. Series No. 164 (1981). J.J. Blazek and J.S. Magee, Zeolite Chemistry and Catalysis, 976, Chapter 2. J.S. Magee, J.J. Blazek and R.E. Ritter, Oil & Gas J., July 19 3, p. 48. H. Otouma. Y. Arai and H. Ukihashi. Bull. Chem. Sot. Jaoan. 42 (1969) 2449. A.J. Shabtai and A. Lahav, U.S. Pat., 4,216,188 (19801.' . T.J. Nelson, U.S. Pat., 2,032,947 (1980). W.A. Blanton and R.L. Flanders, U.K. Pat., 1,540,205 (1977). D.P. McArthur, U.S. Pat., 4,259,175 (1981). S. Andersson, R. Pompe and N.-G. Vannerberg, Appl. Catal., 16 1985) 49.

62 63 64