Publication / Presented:

NPRA Annual Meeting

Date:

1998

MAXOFINTM: A NOVEL FCC PROCESS

FOR MAXIMIZING LIGHT OLEFINS USING 

A NEW GENERATION ZSM-5 ADDITIVE

Authors:

Rik B. Miller - KBR

Phillip K. Niccum - KBR

Alan Claude - KBR

Michael A. Silverman - KBR

Nazeer A. Bhore - Mobil Technology Company

Girish K. Chitnis - Mobil Technology Company

Stephen J. McCarthy - Mobil Technology Company

Ke Liu - Mobil Technology Company
MAXOFINTM: A Novel FCC Process

for Maximizing Light Olefins

Using a New Generation ZSM-5 Additive

by

Rik B. Miller, Phillip K. Niccum, Alan Claude, and Michael A. Silverman

Kellogg Brown & Root, Inc.

Houston, Texas USA

and

Nazeer A. Bhore, Girish K. Chitnis, Stephen J. McCarthy, and Ke Liu

Mobil Technology Company

Paulsboro, New Jersey USA

Presented at:

1998 NPRA Annual Meeting

San Francisco, California USA

 16 March 1998
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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ABSTRACT

The Mobil-Kellogg FCC Alliance announces MAXOFINTM -- a remarkably flexible FCC process

that produces maximum light olefins from traditional feedstocks without resorting to severe

operating conditions. MAXOFINTM is based on commercially proven technology and is now

available for grassroots or revamp FCC application. 

A new generation, higher ZSM-5 content additive and proprietary FCC hardware provide the

flexibility to produce either maximum olefins or conventional fuels based on market

demands. This paper shows an example where MAXOFINTM can produce between 6 and 18

wt% propylene from Minas vacuum gas oil.

The key features of the MAXOFINTM FCC process are:

 # A new generation, high ZSM-5 content MAXOFIN-3TM additive that produces maximum

light olefins without catalyst dilution

 # No requirement for large amounts of riser steam or severe operating conditions

 # A cost-effective ZSM-5 additive that is only now being offered to the industry

 # Proprietary Mobil-Kellogg Hardware:

 T New ATOMAX-2TM feed nozzles to provide superior atomization and greater riser

coverage

 T Second Riser or lift zone for re-cracking of Naphtha

 T Closed Cyclones for olefin generation with minimum associated dry gas

production

BACKGROUND

a. Demand for propylene increasing

Light olefins, propylene and butylenes, have long been basic building blocks for the

manufacture of a variety of petrochemical products and fuels. Today, light olefins are used

for the production of gasoline, polymers, antifreezes, petrochemicals, explosives, solvents,

medicinals, fumigants, resins, synthetic rubber, and many other products. Propylene is

second in importance to ethylene as a raw material for petrochemical manufacture.

The largest source of petrochemical propylene on a worldwide basis is that produced as the

primary byproduct of ethylene manufacture by thermal cracking. Ethylene plants charging

liquid feedstocks typically produce about 15 wt% propylene and provide about 70 percent

of the propylene consumed by the petrochemical industry. Petroleum refining, nearly all

from FCC, is by far the next largest supplier of worldwide propylene production, supplying

about 30 percent of the petrochemical requirement. In the U.S., FCCU's supply about

one-half of the petrochemical propylene demand.
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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The demand for propylene is expected to more than double, primarily driven by the rapidly

increasing market for polypropylene. Propylene demand by the petrochemical industry is

projected to increase more rapidly than the demand for ethylene. Since ethylene plants

produce more ethylene than propylene, and furthermore, since many of the new ethylene

plants in construction are based on ethane feed with no propylene co-produced, significant

increases in propylene from FCC will be required to meet the increased demand. This will

be accomplished by increasing FCC propylene selectivity, and by increasing the percentage

of FCC propylene sent to petrochemical manufacture. Dehydrogenation of propane is

expected to supply a much smaller proportion of the increased propylene demand, due to

its higher production costs.

Although propylene demand is high, refiners are still cautious about committing large capital

investments for propylene production alone because of the large swings in propylene-fuels

margins. To mitigate these risks, the MAXOFINTM process can switch from a maximum

propylene mode to a fuels mode to meet the marketplace demands. The key to the flexibility

of MAXOFINTM process is the high ZSM-5 content additive that was previously unavailable

to the FCC industry.

b. ZSM-5 additive evolution

Mobil invented ZSM-5 zeolite in 19721. Since its invention, ZSM-5 has been commercially

used in a wide variety of catalytic applications including petrochemicals (ethylbenzene,

xylene isomerization, etc.), synthetic fuels (Methanol to Gasoline), and petroleum upgrading

(lube and distillate dewaxing, gasoline octane enhancement, etc.). 

In 1983, Mobil demonstrated that ZSM-5 increased gasoline octane in a moving bed

Thermofor Catalytic Cracking (TCC) Unit2. In 1986, GRACE-Davison, working with Mobil,

developed the first ZSM-5 additive for use in FCC. Mobil licensed GRACE and other catalyst

manufacturers to market and sell ZSM-5 additives containing 25 wt% or less ZSM-5 crystal

for use in fluid and moving bed cracking processes. Within a few years, the industry

embraced ZSM-5 additives for octane enhancement and maximizing alkylate.

More recently the industry has looked to ZSM-5 additives for incremental production of

propylene from FCC. However, current ZSM-5 additives are best suited for increasing FCC

propylene yield by 50-100%. Extensive pilot plant studies by Mobil, GRACE, and others show

that further increases in propylene (up to 300%) require an additive with more than 25 wt%

ZSM-5 crystal content to minimize dilution of the base catalyst activity3. Mobil conducted

commercial trials of its own proprietary high ZSM-5 additive as early as 1992, validating this

approach.

With propylene demand increasing, Mobil will now allow catalyst manufacturers to produce

high ZSM-5 content additives pursuant to Mobil’s patent position. The MAXOFINTM FCC

process couples these new additives with proprietary hardware to produce either maximum

olefins or conventional fuels, as the market demands, from traditional FCC feedstocks

without resorting to severe operating conditions.
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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DESCRIPTION OF KEY MAXOFINTM FEATURES

The MAXOFINTM process brings together a new generation high ZSM-5 content additive and

proprietary FCC hardware to economically produce high yields of light olefins from

traditional FCC feedstocks such as gas oils, deasphalted oil, and residual oil feedstocks. All

these features are commercially proven and provide flexibility to alternate between light

olefin maximization and traditional maximum gasoline operations. The next few sections

provide details of the MAXOFINTM technology.

a. MAXOFIN-3TM Additive

The MAXOFINTM process is built around a family of proprietary additive formulations

containing higher levels of ZSM-5 than previously available. The formulation can be tailored

to the refiner’s needs based on the extensive data base compiled by Mobil during ZSM-5

development. The result is a new generation of additives that exhibit superior activity, high

propylene selectivity, and excellent attrition resistance. Furthermore, these additives exploit

the synergies with the Mobil-Kellogg hardware to produce maximum propylene from

FCCU’s.

Table 2 shows a comparison between conventional ZSM-5 additives and MAXOFIN-3TM

additive at the same crystal level in the inventory. The large amount of conventional additive

would dilute the base catalyst activity and produce lower conversion, higher bottoms yield,

and fewer C6+ gasoline olefins. It is the C6+ gasoline olefins that subsequently react over

ZSM-5 to produce propylene and butylenes.

TABLE 2: MAXOFIN-3TM Additive Achieves High Propylene Yield

Without Significant Conversion Penalty

Additive D Propylene yield, wt% D Catalyst MAT Activity

MAXOFIN-3TM Additive Base Base

Conventional Additive -1.2 -4.0

b. ATOMAX-2TM Feed Injection System

The feed injection system plays a key role in the yield performance of the MAXOFINTM

process because a large fraction of the ZSM-5 cracking precursors, C6-C12 olefins, is formed

in the feed-catalyst mixing zone. By minimizing bacmixing in the riser, an efficient feed

injection system protects the C6-C12 olefins from deleterious bimolecular hydrogen transfer

and makes them available for ZSM-5 to crack into light olefins. 
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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-20 -10 0 10 20

0.4

0.6

0.8

1.0

1.2

Distance from Center of Spray, inches

Relative Sauter Mean Diameter

ATOMAX-1

 Avg. SMD = 1.0

ATOMAX-2

Avg. SMD= 0.57

Wider Spray Angle

and More Uniform

Atomization

DROPLET SIZE ACROSS SPRAY

ATOMAX-2 vs. ATOMAX-1

Figure 3

In 1992, Mobil and Kellogg commercialized the ATOMAXTM feed nozzle, which provided a

significant advancement in FCC feed injection technology. Although the original ATOMAXTM

nozzle quickly became

the market leader,

Mobil and Kellogg

were not willing to rest

on this accomplishment. 

In 1996, we began work

to develop the nextgeneration feed nozzle.

A custom feed nozzle

test rig was built at the

Kellogg Technology

Development Center to

evaluate nozzle prototypes. This rig incorporates a state-of-theart Laser Dopplerimeter that can measure droplet size,

velocity, and liquid flux

at any point in the spray pattern. Each of these parameters is key to developing a wellintegrated feed injection system.

Our successful development efforts have led to the commercialization of the ATOMAX-2TM

nozzle, representing a significant step forward in feed nozzle technology. As shown in

Figure 3, ATOMAX-2TM produces a significantly smaller Sauter mean droplet size than the

industry-leading ATOMAXTM nozzle at all points in the fan-shaped spray.

ATOMAX-2TM produces a “spray-averaged” Sauter mean droplet size that is about 43%

smaller than ATOMAXTM. For a given volume of spray, the new nozzle produces about six

times more droplets than its predecessor!
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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Closed

Cyclone

System

ATOMAX-2

Fresh Feed

Injection

Primary

Feed

Riser

2nd Riser

for Naphtha

Recycle

Recycle

Naphtha

Injection

CounterCurrent

Regenerator

Two-Stage

Stripper

MAXOFINTM FCC with Dual Risers

Figure 4

c. Second Riser for Naphtha Cracking

FCC naphtha, preferably light cat naphtha,

can be re-cracked in the presence of ZSM-5,

high cat-to-oil ratios, and high riser outlet

temperatures to produce olefins. For clients requiring maximum olefin yields, a

second riser can be installed that processes

recycled naphtha and operates at a riser

outlet temperature of approximately 1100°F.

A dual riser MAXOFINTM FCC configuration

is depicted in Figure 4

The combination of high temperature and

high levels of ZSM-5 allow the gasolinerange light olefins and light paraffins to

crack. The high riser outlet temperature

and the high heat of reaction produce a

cat-to-oil ratio close to 25-to-1, thus maximizing the effectiveness of MAXOFIN-3TM

additive.

At lower cost than a second riser, naphtha

can also be recycled to the "lift zone" at the

base of the riser and below the fresh feed

nozzles. This location produces the highest

temperature possible in a unit with only one

riser. However, in this scenario gasoline

cracking is less than with a separate riser

due to reduced residence time and inefficient gas-solid contacting. As a result, olefin yields are slightly lower and selectivity is better

for lift-zone naphtha cracking than for separate-riser naphtha cracking. However, the second

riser gives more operating flexibility, especially when it is desirable to maximize the distillate

and light olefins with minimum gasoline produced. Thus, the choice between a lift-zone and

a second riser depends on the need for operating flexibility and capital availability.

d. Choice of base catalyst and feedstock

In addition to the MAXOFIN-3TM additive, the propylene yield from a given feedstock can be

optimized by proper choice of the base catalyst. The base FCC catalyst is optimized to

minimize hydrogen transfer and produce maximum C6-C12 olefins, which will convert to light

olefins in the presence of ZSM-5. Reaction pathways4-8 for cracking over base catalyst and

ZSM-5 are depicted in Figure 5.
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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FCC REACTION PATHWAYS

for production of C3-C4 olefins with base catalyst & ZSM-5

Feed Component Intermediate Product

Paraffin

& Side

Chains

Naphthene

Aromatic

C6 - C12

 Olefins

Paraffin

Coke

C3 - C4 

 Olefins

ZSM-5

Cracking

Condensation

Cracking

Cracking

Cracking

H Transfer

H Transfer

Polymerization

Figure 5

FEATURES OF CLOSED CYCLONES

Closed Cyclones

Excellent catalyst / vapor separation

97+% of riser product vapors flow directly 

to overhead line

Very brief vapor residence time

Very little thermal cracking

No dilute phase catalytic cracking

Yield benefits:

less dry gas

higher propylene yield

less bottoms yield

improved coke selectivity

Figure 6

The feedstock can be optimized among the available feed components. As mentioned

earlier, recycle of naphtha to a

second riser or lift zone can be

used to produce incremental

propylene. 

Mobil and Kellogg have pilot

plant and commercial test

data on cracking streams of

various unfinished gasoline

streams. These include virgin

naphtha, coker gasoline,

visbreaker gasoline, and

hydrotreated naphtha. The

optimum feedstock and catalyst are identified by using a

proprietary compositional FCC

yield model that tracks more

than 3000 components in the

FCC feed and products.

Unlike competing processes,

the MAXOFIN-3TM additive and base catalyst combination obviates the need for low riser

hydrocarbon partial pressure and high amounts of riser steam.

e. Riser Termination

(Closed Cyclones)

The MAXOFINTM process uses

relatively high riser outlet

temperatures to optimize the

yield of propylene. In this environment, modern riser termination technology is essential.

Closed Cyclones minimize the

residence time of hydrocarbon vapor and catalyst in the

disengager vessel. By eliminating post riser thermal and

catalytic cracking, Closed Cyclones reduce the yield of dry

gas, reduce coke formation on

the catalyst, and increase the yield of more valuable products, as depicted in Figure 6. 
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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Slide

Valve

Catalyst

Return

Fluidization

Air

Catalyst In Tubesheet

Tubesheet

Inner

Tube

Scabbard --

Outer Tube

Water In

Water &

Steam Out

Figure 7 - Dense Phase Catalyst Cooler

Closed Cyclones have been in commercial service since 1985 and have proven to minimize

thermal cracking in the disengager while being both operationally and mechanically reliable.

f. Dense Phase Catalyst Cooler

For processing heavy

resid-containing feedstocks the MAXOFINTM

process offers a Dense

Phase Catalyst Cooler to

control regenerator temperature and optimize

catalyst-to-oil ratio.

The unique design of the

system allows complete

turndown by adjustment

of the catalyst circulation

rate through the cooler.

By placing the tube bundle on top of the cooler

shell as shown in Figure 7,

the fluidization air distributors within the cooler shell are located well below the tubes,

eliminating the possibility of tube erosion and failure due to impingement of air jets. Since

1989, eleven Kellogg dense phase catalyst coolers have been licensed and three are now in

operation.

MAXOFINTM PROCESS EXAMPLE

a. Basis and Yields

As a case study, we have illustrated the flexibility of the MAXOFINTM process by studying

three different modes of operation:

T Maximum propylene

T Maximum fuels

T An intermediate case

While this technology can be easily applied to revamp cases, the illustrations below cover

a grassroot FCC processing 600-1000°F TBP boiling range gas oil feed derived from Minas

crude oil. The unit is designed to process 30 MBPSD of gas oil in the maximum propylene

mode at 1000°F riser top temperature and 400°F combined feed temperature. 
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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Table 3 shows that the propylene yield / fuels yield tradeoffs can be selected to suit the

current market needs. For example, the propylene yield can be changed from 6.2 wt% in the

fuels mode to 18.4 wt% in the maximum propylene mode. The maximum propylene case

produces about 300,000 tons of propylene per year for a downstream world scale

polypropylene facility.

TABLE 3: MAXOFINTM Process Yields and Operating Conditions

DESCRIPTION

OPERATING MODE

Maximum

Propylene Case

Intermediate

Case 

 Fuels Mode

Case

Propylene Yield, wt.% 18.4 14.4 6.2

Feed VGO & Light

Naphtha Recycle VGO VGO

Catalyst RE-USY + ZSM-5 RE-USY + ZSM-5 RE-USY Only

Reactor Configuration Dual Riser Single Riser Single Riser

Riser Top Temp, °F 1000 / 1100 1000 1000

Catalyst / Oil 8.9 / 25 8.9 8.9

Feed Rate, MBPSD 30.0 30.0 44.1

YIELDS, wt%

 Hydrogen Sulfide 0.03 0.02 0.01

 Hydrogen 0.91 0.18 0.12

 Methane & Ethane 6.61 2.07 2.08

 Ethylene 4.30 1.96 0.91

 Propane 5.23 3.90 3.22

 Propylene 18.37 14.38 6.22

 n-Butane 2.25 2.16 2.17

 i-Butane 8.59 8.52 7.62

 Butylenes 12.92 12.33 7.33

 Gasoline 18.81 35.53 49.78

 Light Cycle Oil 8.44 7.33 9.36

 Decant Oil 5.19 5.24 5.26

 Coke 8.34 6.38 5.91

The extraordinary propylene yield is accomplished with a combination of high ZSM-5

content additive and re-cracking of gasoline in a second riser. The optimal top temperature,

gasoline recycle ratio, and residence time in the second riser depends on gasoline

composition, incremental propylene and gasoline prices, metals on equilibrium catalyst, and
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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FCCU constraints such as air rate, main fractionator, wet gas compressor, and gas

concentration section bottlenecks.

The second riser converts essentially all the gasoline range olefins and naphthenes in the

recycled gasoline. Both the fresh feed riser and the gasoline re-cracking riser are operated

at conventional steam rates (2-5 wt%). For purposes of the example, and to more clearly

show the effects of the ZSM-5 additive and the effects of the second riser, a 1000°F primary

riser temperature is used for all three cases. In a commercial application, depending on unit

constraints and other operating objectives, the primary riser temperature would be

optimized in each case. 

Also listed in Table 3 is an intermediate case that provides up to 14.4 wt% propylene yield

without the use of the second gasoline re-cracking riser. In this intermediate case, the

increased coke yield relative to the fuels case is due to the heat requirement for C6+ olefin

re-cracking and lack of hydrogen transfer.

An additional 5-7 wt% propylene yield can be obtained by secondary processing of ethylene

and butylenes through olefin interconversion processes, thereby producing a net propylene

yield of up to 25 wt% on a fresh feed basis.

b. Fuels Mode

The use of MAXOFIN-3TM additive can be discontinued if market conditions change and the

production of fuels becomes more economic than the productioni of propylene. The third

column of Table 3 outlines a maximum fuels operating mode, which uses a conventional FCC

catalyst (without ZSM-5 additive) and employs the second riser for gas oil feed. The fresh

feed rate is increased to take full advantage of the available capacity of the air blower

required for producing maximum propylene. For simplicity we show the incremental feed

quality to be the same as the base feed. However, depending on the refiner's configuration,

this incremental feed could be light gas oil, vacuum tower overflash, or vacuum tower

bottoms.

Detailed investigations indicate that all the equipment can be designed to operate at the

extremes of both cases (high vapor loads at the top of the main fractionator for the

maximum propylene case and high liquid loads for the debutanizer in the fuels operation).

Although these examples show a maximum conversion FCC operation, the MAXOFINTM

process can also be used for providing maximum propylene in a low-conversion, highdistillate mode of operation. Distillate mode consists of low riser temperature, high feed

preheat temperature, and high recycle of bottoms.

c. Utilities

Mobil/Kellogg can assist in evaluations of propylene production costs for the various catalyst

and hardware options. The production costs should always include the visible catalyst and
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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additive expenses as well as the life cycle effect of the less visible utility costs. The life cycle

costs can be significant, especially if a large amount of steam is necessary to maintain low

hydrocarbon partial pressures. Surprisingly, the cost of steam may actually exceed the cost

of the ZSM-5 additive!

To allow a quick comparison of utilities requirements, Table 4 outlines the estimated utilities

requirements for three different operating modes: 1) MAXOFINTM maximum propylene case,

2) MAXOFINTM fuels case, and 3) A process using 20 wt% dispersion steam.

The MAXOFINTM process provides high yields of propylene with only 4 wt% dispersion steam

on a fresh feed basis. The cost of this steam is estimated to be approximately 7 cents per

barrel of fresh feed when main fractionator condensing costs and sour water treating costs

are included along with the cost of producing the steam. The cost per barrel of fresh feed

would be approximately 5 times higher if 20 wt% dispersion steam were required. The

difference in steam costs, approximately 28 cents per barrel, is typically more than the cost

of ZSM-5 additive.

Table 4 shows that consuming large amounts of dispersion and stripping steam in the

converter can also lead to significant costs for condensing the steam and for treating the

subsequent sour water. In addition to the increased steam consumption and production of

sour water, the high dispersion steam case requires an increase in air blower capacity to

burn the extra coke required to heat the dispersion steam to riser outlet temperature. The

extra coke production must come at the expense of liquid product yield, a factor that has not

been considered in this analysis.

CONCLUSIONS

As worldwide demand for polypropylene has increased, refiners have looked to FCC to

produce incremental propylene for petrochemical feedstock. The Mobil-Kellogg MAXOFINTM

FCC process, based on a new MAXOFIN-3TM ZSM-5 additive and proprietary hardware

technology features, is available for maximizing the production of light olefins from FCC

feedstocks. 

The key feature of this technology is its flexibility to respond to market demands by

effectively operating in maximum olefin mode, maximum fuels mode, or anywhere between.

The MAXOFINTM FCC process can produce propylene yields approaching 20 wt% of feed

while retaining the ability to operate as a conventional fuels FCC. This flexibility is provided

by using the highly active MAXOFIN-3TM additive and FCC hardware components designed

for maximum operating flexibility. Mobil’s extensive database can be used to optimally

match the selection of FCC feedstock components, base FCC catalyst, and MAXOFIN-3TM

additive.
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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1. R.J. Argauer and G.R. Landolt; US Patent 3,702,886; Nov 14, 1972 to Mobil.

2. C.D. Andersen, F.G. Dwyer, G. Koch, P. Niiranen; 9th Ibero American Symp. Catal.;

Lisbon, Portugal; 1984.

3. Y.G. Adewuyi, J. Klocke, J.S. Buchanan; Appl. Catal. A,131 (1995), 121.

REFERENCES

4. J. S. Buchanan and Y. G. Adweyi, Applied Catalysis, 134 (1996) 237.

5. D. A. Pappal and P. H. Schipper, ACS Symposium Series 452, 1990.

6. R. J. Madon, J. Catal. 73 (1991) 275.

7. J. S. Buchanan, Appl. Catal. 74 (1991), 83.

8. P.H. Schipper, F.A. Dwyer, P.T. Sparrell, S. Mizrahi, S.P. Donnelly, J.A. Herbst; ACS

Symp. Series 375 (1982) 364.
MAXOFINTM: A Novel FCC Process for Maximizing Light Olefins

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TABLE 4: Estimated Utilities

OPERATING MODE

Max Propylene

Case

Fuels Mode

Case

High Dispersion Steam

Case

Feed Rate, BPSD 30,000 42,350 30,000

Dispersion Steam, wt% Fresh Fd 4.0 3.0 20.0

High Pressure Stm (600 psig)

 Production, lb/hr

 Flue Gas Cooling 98,000 104,600 102,300

 Consumption, lb/hr

 Air Blower Turbine (99,300) (99,300) (103,600)

 Wet Gas Comp. Turbine (91,700) (50,500) (91,700)

 C3 Drier (11,700) (6,600) (11,700)

Med Pressure Stm (250 psig)

 Production, lb/hr

 Main Frac P/A’s 30,000 34,400 45,700

 Consumption, lb/hr

 Converter (28,800) (26,000) (89,000)

 Main Frac Stripping (1,600) (2,400) (1,600)

 Amine Stripper (600) (300) (600)

Low Pressure Stm (50 psig)

 Consumption, lb/hr

 VRU Reboilers (244,000) (152,800) (244,000)

Condensate Return, gpm 894 619 903

Boiler Feedwater, gpm 264 286 305

Cooling Water, gpm (20EF rise) 54,500 42,100 55,700

Main Frac Wash Water, gpm 60 85 60

Sour Water Produced, gpm 121 141 241

Electric Power, kW 2,300 2,100 2,500

Main Frac Ovhd Duty, MMBtu/hr 126 138 192