Octane and Benzenze

Management for
Reformulated Fuels

J.L. Ross

Axens North America, Inc

650 College Road East, Suite 1200
Princeton, NJ 08540 - USA
Tel.: + 1 609 243 8700
Fax: + 1 609 987 0204

Octane and Benzene Management for

Reformulated Fuels
BY JAY ROSS
Axens North America

The octane challenge will continue due to

aromatics limits, low sulfur regulations and octane loss
in selective hydrotreating processes, and future
regulatory pressure on olefins in gasoline. Oxygenates
can be used to partially compensate the octane loss,
but isomerization of light reformate is the leading-edge
answer to add octane to the gasoline pool, especially for
octane-short refineries. In light of all of these issues, a
clear and efficient strategy to achieve current and near
future RFG specifications concerning octane and
benzene content will consider the synergies of the key
process blocks within the RFG processing chain.

SUMMARY
As a result of the continuous trend for stricter
environmental regulations mandated world-wide,
refiners will be producing cleaner fuels. Nowhere is the
impact of the ever-greening regulations more strongly
felt than in the gasoline market. High octane gasoline is
one of the answers to smaller, more efficient, high
compression ratio engines.
Among the main issues in gasoline reformulation
are a near complete sulfur removal and a severe
benzene reduction in gasoline. Both of these factors
impact directly on gasoline quality, requiring
compensatory action to restore the octane requirement.

INTRODUCTION

Reformulation of gasoline to attain moving

environmental targets is the subject of much debate and
concern for the refiner. One major dilemma is how to
maintain high octane gasoline production while reducing
sulfur and high octane value components such as
aromatics and benzene in particular. Whereas the
complete phase-out of leaded additives was
compensated readily with environmentally acceptable
substitutes, benzene reduction is not as straightforward.

Oxygenated octane enhancers, such as MTBE and

TAME, have led the way to replace leaded compounds.
They also contribute clean-burning qualities to gasoline
and are generally required in reformulated gasoline
(RFG). However, the future of oxygenated components,
MTBE in particular, is bleak in California and may be
problematic elsewhere due to a fear that MTBE could
find its way into drinking water.
Benzene, long recognized as a carcinogen, is
controlled to 1.0 vol% in the U.S. and the European
Community (EC). Since the major contributor of
benzene to the gasoline pool is reformate (i.e., over
80%), its reduction is primarily achieved by decreasing
benzene precursors going to the reforming process.
Added reductions to meet RFG specifications will
require reducing further its formation in cat reformers
and its removal from reformate, either by hydrogenation
or extraction before it enters the gasoline pool.

October 2002

Benzene is an unavoidable component of the

refining process and a valuable gasoline octane
component.
Benzene extraction for use as a
petrochemical feed can be economic when refining and
petrochemical complexes are integrated; however, this
reduces gasoline yield and may impose additional
constraints on the refinery if it is octane short.
Converting benzene to cyclohexane by hydrogenation
slightly increases liquid volume yield but imposes an
octane penalty on the gasoline pool. It also reduces the
hydrogen availability from the reformer. The strategies

Octane and Benzene Management for Reformulated Fuels

which may be employed to achieve RFG benzene

targets are well established, as are the processing
technologies involved. In the classical benzene
reduction strategy for an octane-short refinery with
limited oxygenates addition (i.e., up to 2.0 wt%), three
interactive processing segments in the RFG production
chain are concerned:
Catalytic reforming
Benzene removal
Octane restoring isomerization

Proven and reliable technologies and catalysts are

available to significantly increase yields, capacity and
severity.

Recent technological advances in these three

segments will be discussed as they relate to octane and
benzene management in the RFG production chain.

AXENS CCR REFORMING

A novel combination of SR and CCR technology,

called Dualforming, has been employed by Axens to
provide staged investment and increased capacity
options to our clients. The addition of a CCR loop to an
existing SR unit can increase capacity and severity to
attain increase unit performance and profitability.
The Octanizing and Aromizing CCR reforming
processes are the workhorses of Axens refining and
petrochemical technology sectors respectively. Both
processes have a long track record of successful
performance as can be attested with more than 35
operating units worldwide.

CATALYTIC REFORMING FOR RFG

Catalytic reforming is the technology of choice for

the production of high octane gasoline and is usually the
main source of refinery hydrogen. The increasing need
for hydrogen and the desire to limit benzene production
in transportation fuels favors the implementation of low
pressure units and the use of catalysts which afford
superior performance under severe operating
conditions, i.e., low hydrogen recycle to hydrocarbon
ratio, high space velocity, low pressure and high
regeneration frequency.

Flowscheme and process features

The Axens CCR reforming process is schematically

represented in Figure 1. This advanced technology for
the production of high octane gasoline or C8 aromaticsrich petrochemical streams from naphtha, offers
excellent product yields and an exceptional on-stream
factor at moderate investment and operating costs. The
key features of the CCR process are described below.

The vast majority of newly installed reforming

capacity employs continuous catalyst regeneration
(CCR) technology. For the foreseeable future, catalysts
developed for use in these units will operate in the 3090 psig range with recycle H2 to feed ratios from 1.5 to
2.5, and attain regeneration frequencies of up to 200
times per year. These operating conditions have
implications for the process and the catalyst. Axens has
developed new processing schemes and catalysts to
meet these challenges.

Continuous catalyst regeneration

The Octanizing and Aromizing catalyst circulation
systems are designed to ensure long, active catalyst
service and ease in operation and maintenance. The
smooth operation of the lift system ensures
homogeneous, non pulsating and gentle lifting of the
catalyst and therefore low catalyst attrition.
Catalyst is continuously transferred to the
regenerator where the coked catalyst undergoes a
sequence of steps involving controlled coke
combustion, oxy-chlorination, and calcinations to restore
the catalyst activity and metals redispersion. The
proprietary RegenC dry-burn loop regeneration system
has several features that provide complete catalyst
restoration, such as two separate and distinct burning
zones. Catalyst circulation and regeneration operations
are highly automated and require minimal operator
attention.

There is also a large installed based of semiregenerative (SR) reforming capacity that will continue
to contribute to the gasoline pool. With the changing
regulatory environment and cost constraints, these units
are being called upon to increase capacity, reformate
yield and hydrogen production. Obviously, performance
from fixed-bed units will never be comparable that
obtained from ultra-low pressure CCR units.
Nevertheless, what is achievable today in fixed-bed
units is dramatically better than a few years ago.

Octane and Benzene Management for Reformulated Fuels

Booster
Compressor

Reactors and Heaters

R-1

R-2

R-3

Hydrogen-Rich

Gas

RegenC

Regenerator

Recovery

System

Reformate to
Stabilization

Recycle
Compressor

Feed

Figure 1 Axens CCR reforming process

highly efficient
consumption.

Side-by-side reactor design

The side-by-side reactor arrangement has

several advantages over the stacked design. Access
for construction, inspection, and future modifications
to the reactors as well as to the internals is greatly
increased in the side-by-side configuration. In
addition, thermal expansion problems are minimized
and the reactor structure is lighter and lower to the
ground. This enables optimal reactor design without
height constraints. The reactor placement also
provides for shorter catalyst transfer lines between
reactors and heaters and a reduction in the nonflowing heel catalyst volume to less than 1% of the
catalyst inventory. These advantages, which are not
always taken into consideration in the early stages of
a project, translate into significant savings in
investment, construction, and maintenance costs.

process

with

limited

utilities

RegenC - Catalyst Regeneration Technology

A key to high performance and long catalyst life
in CCR reforming is the regenerator. To this end and
in conjunction with the family of Axens catalysts, the
commercialization of a high performance regenerator
design is Axens answer to meet the reforming
challenges for the next decade. The RegenC
regenerator benefits from significant technology and
monitoring improvements of the burn and
oxychlorination zones, which results in increased
catalyst life and improved operation flexibility.
RegenC consists of four independent zones
depicted in the block flow diagram shown in Figure 2.
These zones include:
a primary burn zone equipped with a dry burn
loop which minimizes the moisture level during
combustion;
a finishing zone with oxygen and temperature
modulation;
an oxychlorination zone;
a calcination zone.

Optimum operating conditions and design

The continuous regenerative unit is designed to

maximize hydrogen and gasoline or C8 aromatics
production and to minimize operating costs. With a
low pressure, high severity, CCR reforming system,
low hydrogen recycle to hydrocarbon ratios are
required. The minimal pressure drop in the reactor
section limits the power requirement of the recycle
compressor. In addition, the heat recovery is
optimized to limit fuel consumption. The result is a

The principal innovations of the RegenC

regenerator and the corresponding economics
3

Octane and Benzene Management for Reformulated Fuels

benefits have been recently reviewed at the 1998

NPRA Annual Meeting (AM-98-39).

chloriding agent addition during oxychlorination

to compensate for the dechlorination during coke
burning is reduced.

Spent Catalyst

Primary
Combustion
Gas

Primary
Burn
PrimaryBurn
Burn
Primary

Secondary
Combustion
Gas

Finishing Burn

To Dry Burn
Loop

Oxychlorination

To Effluent
Treatment

Oxychlorination
Gas

The hydrothermal sintering of the alumina carrier,

which occurs during regeneration and in particular
during coke burning, results in a decrease of the
specific surface area of the catalyst. As is the case
for dechlorination, the leading factors involved in
carrier aging are the moisture level, temperature and
combustion time. Consequently, it is of paramount
importance that the water content be maintained as
low as possible in the combustion gases. This
observation has led to the incorporation of the dry
burn loop in the RegenC regenerator.

Chloriding
Agent
Calcination
Gas

The benefits of a dry burn loop are shown in the

Figure 3 where catalyst surface area retention is
plotted against number of regeneration cycles for the
same catalyst in three different regeneration systems:
Hot-burn loop recirculating burning gas is hot
and wet ( 35,000 ppm moisture)
Cold-burn loop recirculating gas is washed but
not dried ( 10,000 ppm moisture )
Dry-burn loop recirculating gas is washed and
dried ( < 2,000 ppm moisture )

Calcination

Regenerated Catalyst

Figure 2 : RegenC Regeneration Block Flow

Coke burning is the principal function of a

catalyst regeneration system. It is essential that this
step is carried out to completion. However, the coke
burning step is the primary contributor to three
negative factors concerning catalyst performance and
life:
metallic phase sintering, which lessens catalyst
performance, in particular stability;
partial dechlorination of the carrier, which
reduces catalytic activity;
hydrothermal sintering of the carrier, which
decreases ultimate catalyst life.

Relative Surface, m /g

Base

20

Dry Burn Loop

Unit A
Unit B
Cold Burn Loop

40

Unit C
Hot Burn Loop

60

In normal operation, the metal dispersion is

reconditioned in the oxychlorination zone. The
dechlorination that occurs in the coke burning section
is predominantly the result of the moisture level in the
burn zone. Accordingly, a reduction of the moisture
content during combustion lowers catalyst
dechlorination, which has three advantages:
equipment required for chloride treatment in the
combustion effluents is reduced;
corrosion potential downstream of the
combustion effluent treatment is reduced;

Unit D
Unit E

Number of Regenerations

Figure 3 : Surface Area Decline vs

Regenration Cycles in Commercial Units

The RegenC regenerator affords the following

advantages over other systems:
extended catalyst life - an increase of at least
70% in catalyst life compared to the hot burn
loop;
reduced catalyst attrition via controlled
temperature and less severe thermal cycling;

Octane and Benzene Management for Reformulated Fuels

units. CR401 has been specifically developed for

reactor pressures of 30-90 psig.

more stable catalyst performance through

optimization of the oxychlorination operating
parameters throughout the catalyst life;
improved regenerator operation flexibility due to
the separation of the burn and oxychlorination
gas loops.
reduced downstream corrosion due to better
chloride retention & management

Axens also offers a range of low density catalysts

CR 701 and 702 for catalyst replacement when
reduced catalyst loading is required.

Catalyst Performance
The superior stability and stength of the AxensProcatalyse catalysts have been recently
demonstrated in a competitors CCR unit. After the
changeout to CR 702, the catalyst attrition reduced by
50%, Figure 4, resulting in improved catalyst
circulation and reduction in catalyst makeup costs.

Axens has just completed a value engineering study

of the RegenC system and found ways to streamline
the design while retaining the superior process
performance. The result of this effort is the new
RegenC-II regeneration system with an overall CCR
cost reduction of 5% - and a reduction in operating
costs. New designs now incorporate RegenC-II.

80

Previous
Catalyst

CCR Cat Fines, lb/day

CCR Cat Fines 5 Day Avg

60

Axens CCR Catalysts

Axens provides customized catalyst formulations

to meet the specific needs of gasoline and aromatics
production: CR 401 and AR 400/500 series
respectively. These are supplied in the calcined state
or reduced state upon request. The principle
characteristics of CR401 are shown in Table 1.

CR 702 Catalyst

40

20

Figure 4 : Reduced Fines Production

(Attrition) with CR 702

0.65 ( 40 )
200
0.27 0.30

In terms of catalyst stability, the chloride addition

rate was reduced by a factor of 4, Figure 5, thereby
reducing operating costs and fouling/corrosion of
downstream equipment.

1.5
>5

1.6

* Particle Crushing Strength

Previous
Catalyst

1.4

Chloride Injection, wt%

Table 1 : CR401 Typical Properties

Most of the recent CCR reforming units operate

under severe conditions in terms of WHSV, recycle
ratio and pressure. Low hydrogen partial pressures
favor the principal octane-improving reactions:
naphthene
dehydrogenation
and
paraffin
dehydrocyclization. Gasoline and hydrogen yields
are also improved with lower benzene production due
to the lower operating temperatures associated with
low pressure operation. The development of the
CR401 catalyst follows and anticipates the trend for
low pressure operation, either for new or for existing

1.2
1
0.8
0.6

CR 702 Catalyst

0.4
0.2

20
3/ 00
1/
20
00
4/
1/
20
00
5/
1/
20
00
6/
1/
20
00
7/
1/
20
00
8/
1/
20
00
9/
1/
20
10 00
/1
/2
0
11 00
/1
/2
12 000
/1
/2
00
0
1/
1/
20
01
2/
1/
20
3/ 01
1/
20
01
4/
1/
20
01
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01
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20
01
7/
1/
20
01
8/
1/
20
01

20

99
/1
/1
12

00

0
2/
1/

Physical properties
Density, g/cm3 (lb/ft3)
Surface area, m2/g
Platinum content (wt%)
Mechanical properties
Minimum PCS* (kg)
Average PCS (kg)

Spherical
1.8 (0.070)
calcined (reduced on request)

1/
1/

Shape
Size, mm (inch)
State

12
/1
/1
99
9
1/
1/
20
00
2/
1/
20
00
3/
1/
20
00
4/
1/
20
00
5/
1/
20
00
6/
1/
20
00
7/
1/
20
00
8/
1/
20
00
9/
1/
20
10 00
/1
/2
0
11 00
/1
/2
0
12 00
/1
/2
00
0
1/
1/
20
01
2/
1/
20
3/ 01
1/
20
01
4/
1/
20
01
5/
1/
20
01
6/
1/
20
01
7/
1/
20
01
8/
1/
20
01

Figure 5: Reduced Chloride Use with CR 702

Octane and Benzene Management for Reformulated Fuels

C5+ Yield, vol %

Pilot results comparing the yield performance of

CR 702 to a competitors catalyst confirm the
improved performance with an initial yield advantage
of 1 vol% - Figure 6. This differential expands to 3-4
vol. % as the run length is extended which confirms
the yield stability and performance of the Axens
catalysts

Feed Effluent Exchanger

It is not unusual of find reaction section

feed/effluent exchanger networks consisting of four,
eight, or even 12 exchangers. This design results in
high pressure drop, poor heat recovery, and hence
large fuel consumption in the first heater. In such
cases, the installation of a high efficiency feed/effluent
exchanger can result in significant improvements:
reduction in the thermal duty of the first heater
reduction in the duty of the reformer reactor
effluent air cooler
large reduction in the pressure drop through the
reaction section
large reduction in the power consumption of the
recycle compressor.

85
80
75
Cat A CR-701/702

70
65

Constant Octane 102 RONC

125

250

375

Time, hours

With the installation of a high-efficiency weldedplate type exchanger ( Figure 8 ) manufactured by

Packinox the temperature approach can be reduced
by 50% and the pressure drop by 30 psi or more.
This translates into a furnace duty reduction of 40%
and recycle compressor power reduction of 25%.
These improvements can then be used to increase
throughput and/or reduce the unit pressure to
enhance the yield selectivity.

Figure 6 : Improved Yield with CR 701/702

SEMI-REGEN REFORMING OPPORTUNITIES

In conventional Semi-Regen (SR) reforming

units, there are many different reactor designs and
operating conditions vary widely from about 150 to
450 psig. The higher pressure and hydrogen recycle
rates are required to suppress coking and attain an
acceptable run length before period in-situ
regeneration. The higher pressure results in lower
reformate yield and lower hydrogen production.
Modifications to SR units, hardware and catalyst, can
still provide significant performance improvements.
Axens has licensed over 50 SR reforming units and
has gained considerable insight into how to maximize
the performance of these units.

Figure 7: Semi Regen Reformer

Figure 8: Welded Plat F/E Exhanger

Octane and Benzene Management for Reformulated Fuels

moulds to the shape of the top of the bed - Figure 10.

The flow-guide settles along with the bed so there is
no further need to design dead space; the formerly
dormant catalyst section is now completely active.
The reactor pressure drop is reduced now that the
reactants flow through a greater catalyst bed crosssection. Or, viewed differently, the reactor can accept
15 per cent more feed.

Radial Reactor Performance Improvement

Fixed bed radial flow reactors are used whenever

low-pressure drop is critical to good performance,
such as in fixed-bed reforming units. It has been
standard design practice in radial reactor design to
effectively waste the top 15% or so of the catalyst bed
with a baffle arrangement designed to avoid reactants
short-circuiting the bed as the bed settles.

Figure 10 : Texicap Industrial Installation

Texicap is an engineered composite of refractory

fibers and fillers containing no asbestos. It is
impermeable and withstands the severe operating
conditions of multiple regenerations encountered in
reformers as well as the hydrogen/hydrocarbon
atmosphere. Installation and removal are easy,
requiring about one-tenth the manpower and time
required to remove and replace the shroud and cover
assembly.

Figure 9 : Texicap Radial Reactor Installation

Catalyst settling during the course of the run

generates a gap between the top of the bed and
cover plate. Were it not for the shroud extending
down into the bed, the reactants would pass
preferentially through the gap Figure 9. In addition,
because of the very high residence time due to poor
flow dynamics in the shroud volume, the catalyst
loaded at the shroud level attains very high coke
levels, much higher than the average. The coke,
found in the shroud region, is very difficult to burn
during regeneration. Consequently, center pipe grid
damage is frequently observed in the top of the bed.
This is due to the final coke burn at high oxygen
content. Therefore, expensive reforming catalyst
(unused platinum inventory) and reactor volume are
wasted.

Texicap improves the unit performance and

economics due to a better fluid dynamics and shorter
down time for removal and installation:
Cycle lengths are improved at the same severity
Severity can be increased at constant cycle
length
Platinum inventory can be reduced at same
effective throughput
Coke burning is complete
Center-pipe maintenance is reduced
Downtime for catalyst change out is reduced, due
to rapidity of installation and removal; turnaround
time reduced by at least 50 hours for a four
reactor reformer, with a corresponding gain in
throughput.

Responding to this problem, Axens in the early

nineties developed a cost-effective way to recover
unused bed volume. The conventional metal shroud
is replaced by TexicapTM, a flexible flow-guide that

Octane and Benzene Management for Reformulated Fuels

The first Texicap was installed in 1992 at the IES

refinery in Italy. Since then, this application has been
extensively implemented. In Europe alone, nearly 40
radial reactors in major refineries (Agip, Elf, Repsol,
Shell, TotalFinaElf, etc.) were upgraded with this
technology.

third promoter metal and is now recognized as a

definite breakthrough by the industry. The results are:
Improved yield
Increased stability
Increased activity
Improved ease of regeneration

New RG 682 Catalyst

The third metal moves the yield profile

directionally toward that achieved with tin or
germanium but without any of the disadvantages
noted above. To the contrary, yield and stability are
excellent, and regeneration is easy.

Axens second generation platinum-rhenium

catalyst, RG 582, was the first industrial PtRe multimetallic catalyst, providing maximum C5+ and
hydrogen yields combined with excellent stability in
both semi-regenerative and cyclic reformers. RG 582
has shown outstanding results in a wide variety of
commercial applications worldwide in over 50
industrial units.

RG 682 uses new technology to improve the

interaction of the catalytic metal species on the
alumina carrier, impacting the catalytic properties at
the nanometer scale to produce the results outlined
above. Axens nanotechnology has enabled
optimization of the metal phase interaction and the
surface characteristics of the alumina carrier.

Axens is currently introducing a new platinum

rhenium multi-metallic catalyst into the market RG 682.
This catalyst is designed for semiregenerative reformer applications, but can also be
applied to cyclic reforming service. RG 682
represents an important development within our
reforming catalyst portfolio.

Mid East Naphtha

P = 140 psig, H2/HC = 5 mol/mol,
LHSV = 3, RONC = 96

Pt-Sn or Pt-Ge

RG-682

C5 +
Yield

The addition of rhenium to a platinum/alumina

catalyst dramatically improves the stability (cycle
length) of the catalyst by decreasing both the rate of
coke formation and its toxic effect on catalyst activity.
RG 682 exhibits excellent yields and activity even at
higher coke levels. Other promoter metals, such as
tin or germanium, enhance hydrogen and C5+ yields
by suppressing hydrogenolysis of paraffins and alkyl
aromatics to light gases, but these catalysts show
poor stability, i.e. similar to platinum monometallic
catalysts. This is due to reduced hydrogenolysis of
coke precursors resulting in the deposition of coke in
a mono-layer over the metallic species.

RG-582

Pt

Pt-Re
Bimetallic

Cycle life

Figure 11 : Improved Yield & Stability with

RG 682 Over a Typical Full Cycle
Figure 11 shows typical full cycle C5+ yield
profiles for various catalyst formulations. A balanced
Pt/Re catalyst such as first generation RG 482 has a
start of cycle (SOC) yield equivalent to a
monometallic platinum catalyst. But as the cycle
progresses, it shows greatly improved average yield
and a longer cycle length. The impact of the rhenium
metal is described above. The addition of tin (Sn) or
germanium (Ge) improves SOC yield, but has zero
impact on yield stability, thus these catalysts exhibit
cycle lengths similar to the mono-metallic catalyst.
However, the addition of the third metal in RG 582
adds approximately 1 wt % higher yield at SOC and a
comparable cycle length as a standard Pt/Re

Commercial attempts to use promoter metals

such as tin and germanium for fixed bed applications
have either failed to meet the yield and stability
objectives, or they have not had sufficient activity or
they have been exceedingly difficult to regenerate.
Now with RG 682, a moderated tri-metallic catalyst, it
has been demonstrated that these performance
barriers have been overcome. RG 682 is a
moderately skewed Pt/Re catalyst that combines a

Octane and Benzene Management for Reformulated Fuels

reformate yield and especially hydrogen yield. It is

also known that lower pressure operations in fixed
bed units increases coke formation on reforming
catalyst and significantly reduces cycle life. The
Axens Dualforming process addresses both the
positive and negative factors of lower operating
pressure.

bimetallic catalyst. RG 682 provides 0.6 to 1.0 wt %

increase in C5+ yield over RG 582. As it is a
moderately skewed catalyst, it brings, in addition, a
greater resistance and tolerance to coke thereby
extending the cycle life by more than 35 % over a
classical balanced bimetallic Pt/Re catalyst.
When comparing RG 682 to previous generation
catalyst, the performance improvement is clear. The
data shows that RG 682 is truly a step out in terms of
performance. The increased yields, improved stability
and increased activity make this the catalyst of choice
for all semi-regenerative reformer applications Table
2.
Yields (wt%)
H2
C1+C2
C3+C4
C5+
Aromatics
Benzene
Temp. SOR*
Stability

Standard
PtRe
Base
Base
Base
Base
Base
Base
Base
1.0

RG 582
Series
Base + 0.12
Base 0.5
Base 0.7
Base + 1.0
Base + 0.4
Base 0.2
Base
1.0

A significant advantage of the Dualforming

process is the maximum utilization of existing reactor
section equipment in a semi-regenerative catalytic
reformer. The revamp includes the addition of a new
reactor that operates with continuous catalyst
circulation. The new reactor and regenerator are
integrated into the existing reactor train of the
conventional reformer and operate at the same
pressure. The revamp also includes replacement of
the feed/effluent heat exchanger, an additional
interheater and a booster compressor for export
hydrogen. Upstream of the reformer, a liquid phase
sulfur guard bed is installed to extend cycle length of
the fixed bed reactors. A diagram of the Dualforming
process is shown in Figure 12.

RG 682
Series
Base + 0.18
Base 0.5
Base 1.2
Base + 1.6
Base + 1.4
Base 0.2
Base 3C
1.35

*Activity improvement is directly proportional to the reduction in the start of

run temperature (SOR). Pressure = 10 barg, RONC = 98, WHSV = 3/h,
H2/HC = 3, PNA = 52/33/15

Table 2 : Comparison of RG 682 to Previous

Generations

DUALFORMING A HYBRID DESIGN

Axens has developed and commercialized a
process that allows the refiner to revamp a
conventional reformer and achieve the goal of higher
octane at the minimum capital cost. This process is
called DualformingTM. The Dualforming process
allows for the maximum utilization of existing
equipment, while improving both reformate yield and
hydrogen production compared to a semiregenerative unit.
In many cases, significant
improvement in catalytic reforming flexibility may be
realized at less than 50% of the capital investment
costs of a new continuous regeneration catalytic
reformer. There are currently 5 Dualforming units in
operation.

Figure 12 : Dualforming Flow Diagram

This configuration allows for the operating

pressure to be reduced in the semi-regenerative
section of the unit. The amount of the pressure
reduction is limited primarily by pressure drop through
the unit and by limitations of the existing recycle
compressor. The semi-regenerative section is then
operated at a lower reaction temperature in order to
satisfy cycle length requirements. In one example,
the average reactor pressure of the reformer was
reduced from 375 psig to 220 psig.

It is well known that reducing operating pressure

in a catalytic reforming unit substantially improves the

Octane and Benzene Management for Reformulated Fuels

The new reactor, with its continuous regeneration

section, is designed and operated to increase the
reformate octane number from the outlet of the fixed
bed portion of the unit to that desired in the finished
product. This is an important feature of the process.
Because of the use of continuous catalyst
regeneration, the new reactor has the ability to
operate at high severity in order to achieve the
desired reformate octane while the existing fixed-bed
reactors may be operated at more moderate severity
to extend their run length and/or increase their
throughput.

BENZENE MANAGEMENT FOR RFG

Benzene Regulations

Benzene is carcinogenic and has been identified

in automotive evaporation and refueling vapors, as
well as in exhaust emissions. Benzene content in
gasoline is limited to 1.0 lv% in the U.S. and EC. It is
very likely that stringent benzene regulations will also
be imposed in other geographical zones.

Benzene Production

The overall result of the Dualforming process is

an improvement in reformate yield, hydrogen yield
and octane performance, which approach those of a
continuous regeneration process at a lower capital
cost. In a variation on this design, a separator can be
installed after the fixed bed reactors and the new
reactor-regenerator system operated at very low
pressure Dualforming Plus.

Benzene is a high octane gasoline component

(RON=106, MON=100), and its reduction will
significantly impact the overall octane value of the
pool. Since the cat reformer is the principle benzene
generator, this is the main process block which will be
targeted for benzene control, Figure 13
FCC
N a p h th a
17%

To complete the spectrum of processing options,

one can consider a new Octanizing CCR unit as the
upper limit. An overall comparison of Operating
conditions and yields from a SR unit, Dualformer
revamp, Dualformer Plus revamp, and new CCR are
presented in Table 3.
Scheme:
100 RON
Cycle length- Mo.
Yields
H2 , SCF/BBL
H2 , wt%
C5+, wt%
Revamp
Investment
Million US$
Cat & Utilities
Million US$/yr
Prod. Revenue
Million US$/yr

SR Unit

Dualforming

Dualform
ing Plus

Octanizer
CCR

12 / Cont.

12 / Cont.

Continuous

830
1.7
76.3

1170
2.4
81.9

1270
2.6
83.8

1510
3.1
87.4

Base Unit

+ 18

+ 22

+ 40

3.1*

5.3

7.0

7.8

14.1

17.4

28.4

R e fo r m e r
81%

Figure 13 : Source of Benzene in Gasoline

The first issue involves reducing benzene exiting the

reformer. The three major reformate benzene
contribution routes involve:
native benzene present in the straight run
naphtha,
benzene generated from precursors in the
reformer feed, such as methylcyclopentane and
cyclohexane,
benzene production from hydrodealkylation
reactions of C7+ aromatic compounds.

*In the conventional case, the catalyst was not replaced.

Table 3 : Yield Summary, Revamp Investment,

and Utilities Costs for 20,000 BPD

Benzene production from the reformer can be

substantially decreased by removing benzene
precursors via pre-fractionation and by lowering
reformer pressure.

10

Octane and Benzene Management for Reformulated Fuels

feed to the downstream isomerization unit, when

present, with little additional equipment. Axens has
designed more than 20 benzene saturation units.

When oxygenates are added to the gasoline

pool, fractionating the benzene precursors from the
reformer feed is the least expensive, albeit least
flexible, method of decreasing benzene content. Prefractionation can reduce the benzene production of
the reformer by more than half, the other fraction
being produced in the reformer by hydrodealkylation
reactions.

Conventional Benzene Reduction

This solution permits the use of idle fractionators

as reformate splitters. The unit processes the
benzene rich light reformate. The heat of reaction is
removed through a pump-around system equipped
with a cooler. The pump-around stream dilutes the
benzene concentration at the reactor inlet and thus
decreases the temperature rise through the reactor.
The reactor temperature is accurately monitored by
cooling of the recycle stream. A feed/effluent
exchanger system is not required adding to the safety
of the system and minimizing the reboiling duty of the
downstream stripper. Low hydrogen excess over
stoichiometry is employed and neither recycle
compressor nor furnace is required. This process
enables the attainment of a light reformate benzene
content below 0.1% ! Benzene saturation units lend
themselves to modular construction which can
significantly reduce both the overall project schedule
and capital costs.

Post-fractionation allows further elimination of

benzene from the gasoline pool. This may involve
benzene extraction for sales or for cumene or
cyclohexane production. Many refiners have chosen
the option of hydrogenating the benzene in the light
reformate to cyclohexane which avoids a liquid
volume loss of gasoline.

Benzene Saturation for RFG

With benzene production minimized in the

reformer, the next step in the benzene reduction
strategy is to significantly reduce the benzene content
of the reformate. The reformate is first split to isolate
a benzene concentrated light reformate distillate.
This fraction is sent to the benzene saturation unit,
where benzene is converted to cyclohexane.
The reaction system is based on a proven, highly
active catalyst operating in liquid phase at mild
temperature. Noble metal or non-noble metal based
catalyst may be used.
Although Axens has
commercial experience with both catalysts for this
service, the non-noble metal is generally the best
solution because of its lower cost and higher activity.

Benfree Benzene Saturation

The latest in benzene saturation technology

employs a novel patented distillation reaction
concept. Benfree combines within the same unit, a
reformate splitter and benzene saturation Figure 14.
Hydrogenation of benzene to cyclohexane in a
distillation environment produces a light, benzenepoor reformate free of C7s. Unlike benzene,
cyclohexane does not form low boiling azeotropes
with C7 hydrocarbons. In addition, Benfree may be
operated in order to minimize the amount of
naphthenic compounds in the light reformate.
Naphthenes are known for their inhibiting impact on
isomerization catalysts while C7 alkanes have a
tendency to hydrocrack when contacted with
isomerization catalysts.
The Benfreed light
reformate thus generates a significantly improved
isomerization feed than a light reformate processed in
a conventional benzene saturation unit.

Benzene is converted to cyclohexane and olefins

(if present) are hydrogenated to the corresponding
paraffin. Under optimized operating conditions, no
cracking reactions take place. This results in a
volumetric yield exceeding 100% due to the lower
specific gravity of cyclohexane.
Two processing schemes may be employed: a
conventional fixed bed reactor based process
installed downstream of the reformate splitter or an
integrated reformate splitter/benzene saturation
process (Benfree). The patented Benfree process
advantageously incorporates an external side reactor
associated with the withdrawal of a benzene rich
sidestream from the splitter affording a better quality

11

Octane and Benzene Management for Reformulated Fuels

Conventional "once-through" Isom

Light Ends

C5-C9
Reformate

Conventional once-through C5/C6 isomerization

processes employ zeolite or alumina catalysts in the
presence of hydrogen to convert low-octane normalC5/C6 feed components to the thermodynamic
equilibrium concentration of normal and branched
paraffins. Lower isomerization reaction temperatures
favor the equilibrium concentration of highly
branched, higher-octane isomers, especially those in
the C6 cut. The lower temperatures are achieved by
employing a highly active chlorinated alumina
catalyst..

To Isomerization
H2

C5-C6

Low Benzene
Reformate to
Gasoline Pool

Figure 14 : Benfree Process

Benfree requires somewhat higher reformate

reflux than a conventional splitter. However, its
overall cost is significantly lower than that of a
grassroots reformate splitter plus a stand-alone
benzene saturation unit. If no towers can be
reutilized as a conventional splitter, Benfree is the
lowest cost option. Benfree operates with no
hydrogen excess therefore eliminating any
requirement for a hydrogen recycle compressor.
Although integration of reaction and distillation
functions reduces capital cost, it should not be at the
expense of flexibility.

Isom Performance

Even with the use of a highly active isomerization

catalyst, the ultimate octane attained with simple
once-through isomerization processes is limited by
thermodynamics. From a 70 RON feed, a 13 RON
increase can be expected in a once-through
chlorinated alumina catalyst scheme. However, the
use of the sensitive chlorinated catalyst requires strict
feed pretreatment to eliminate water, elemental
oxygen and sulfur. To exceed these octane imitations
requires separating the lower octane components
from the isomerate and recycling them to the
isomerization reactor.

Although very clean, benzene containing streams

such as reformate, light hydrocrackate and light
straight run naphtha may contain traces of
contaminants which irreversibly poison benzene
saturation catalysts. The Benfree design allows for
rapid catalyst change-out while maintaining
continuous operation of the distillation column. This
may not be the case for conventional catalytic
distillation system and is not the case for systems
where the catalyst is incorporated inside the column.

Normal Paraffins Recycle

Attaining higher light reformate octane numbers

is possible by recycling all of the normal paraffins to
the isom unit to extinction, rather than adopting once
through or partial recycle options. The most
demanding requirement is the separation and
recovery of the normal paraffins from their isomers.
Molecular sieve technology is the answer to this
requirement. The use of molecular sieves on either
vapor or liquid phase streams is a proven technique
with a good industrial track-record. Molecular sieve
separation technology exploits the difference in sizes
of the various molecular components in the stream by
contacting the stream with zeolite sieves of calibrated
pore size thereby affording selective adsorption of
certain components. The normal paraffins are
retained in the sieves due to their smaller molecular
diameter while the larger diameter isomeric or
branched molecules are excluded. The adsorption
step is followed by a desorption step enabling a
complete recovery of the normal paraffin.

ISOMERIZATION FOR RFG

The light reformate from the Benfree column and

the light straight-run naphtha cut from the reformer
prefractionation column are destined for the gasoline
pool. Octane numbers are relatively low in these two
streams. Isomerization makes it possible to increase
their combined octane number by as much as 22
points which should fulfill the refinerys gasoline pool
octane requirements. The resulting octane-barrel
increase in the gasoline pool gives the refiner much
greater flexibility in reducing benzene in the gasoline
pool and some margin to offset any gasoline octane
loss due to hydrotreatment. Axens has designed
more than 20 C5/C6 isomerization units.

12

Octane and Benzene Management for Reformulated Fuels

Deisopentanizer
A low pressure conventional de-isopentanizer
column is required in the separation scheme as an
integral part of the Ipsorb process. The deisopentanizer does not require a very sharp
fractionation since the iso-pentane rich distillate is
generally passed through the molecular sieve section
which eliminates n-pentane. The desorption vapor
together with the desorbed n-paraffins are cooled by
heat exchange then pumped back to the deisopentanizer where the normal paraffins are isolated
in a bottoms stream and recycled to the isomerization
reactor. Another advantage of the front end deisopentanizer is its ability to dehydrate the raw feed
by distillation. This eliminates the requirement for a
full scale molecular sieve fresh feed dehydration
system which is normally mandatory for chlorinated
alumina catalyst isomerization units.

Improved Recycle Process

Liquid phase adsorption/desorption exhibits poor
mass transfer dynamics compared to vapor phase
mechanisms. Thus molecular sieve paraffin recycle
processes employ vapor phase with either the zeolite
or chlorinated alumina isomerization catalyst system.
Axens has two versions of this normal/iso paraffin
separation process: Ipsorb and Hexorb. The Ipsorb
version relates to a novel use of iso-pentane vapor to
desorb normal paraffins from the molecular sieves by
pressure swing techniques. The Hexorb version
employs iso-hexane.

Ipsorb Isomerization
The Ipsorb isomerization process consists of a
fresh feed de-isopentanizer column which feeds the
de-isopentanized bottoms to the isomerization
reactor. The raw isomerate is then fed to the
molecular sieve sorption system, located downstream
of the isomerate stabilizer, where the unconverted
normal paraffins are separated from the raw
isomerate by adsorption/desorption cycles.
Desorption of the adsorbed normal paraffins
takes place using an iso-pentane rich vapor stream,
Figure 15. The desorbed n-paraffin-rich stream is
then recycled upstream to the de-isopentanizer
column. This lowers the recycle to the isomerization
section to as low as 20 to 30% of the fresh feed when
a chlorinated alumina catalyst is employed in the
reactor section.

Isomerization
The isomerization system can be any design
using any commercial catalyst with or without recycle
hydrogen. Depicted in the simplified schematic in
Figure 15 is an isomerization catalyst system without
hydrogen recycle. The Ipsorb process utilizes
chlorinated alumina catalyst, IS-614A. Due to its very
high activity, isomerization is achievable at relatively
low temperature and high space velocity with
negligible hydrocracking of C5/C6 molecules.
Because of this high activity at low temperature, a
very high equilibrium conversion rate of normal
alkanes to higher branched isomers is realized. In
particular, the once-through C6 isomers formed are
more concentrated in the desirable dimethylbutanes
at the expense of methylpentanes than with an
equivalent zeolite based catalyst.

Figure 15 : Ipsorb Isomerization Process

Reaction Section
The dehydrated (by distillation) de-isopentanizer
bottoms or condensed molecular sieve desorption
effluent (in Hexorb mode) is pumped and mixed with
dry make-up hydrogen at a suitable reaction pressure
and is passed through a feed/effluent heat
exchangers and a final feed heater to the reaction
section. The reaction system could be maintained in
the liquid phase at the moderate reaction temperature
required. Commonly, two reactors are used in series
with inter reactor cooling to remove the exothermic

Adsorption/Desorption Cycles
The molecular sieve sorption system uses
rugged molecular sieves designed for high dynamic
adsorption capacity when operating under optimized
pressure swing cycles.

13

Octane and Benzene Management for Reformulated Fuels

heat of reaction from the first reactor. In the first

reactor, any residual feed benzene is completely
hydrogenated and the majority of the isomerization
reactions take place. The final isomerization
equilibrium is achieved in the second reactor, which is
operated at lower temperature to favor the conversion
to higher octane components.

CONCLUSIONS

For the foreseeable future gasoline reformulation

will remain an important issue for the refiner. Global
RFG specifications are expected to become more
stringent, particularly concerning gasoline benzene,
sulfur and olefins content. These will all put pressure
on the gasoline octane and means of preserving or
enhancing octane will be paramount. Environmental
constraints, minimum investment, octane short/long,
petrochemical integration are all key factors which
must be judiciously taken into account when
considering improving segments in the RFG
processing chain.

After heat exchange, the reactor effluent can be

passed directly to the stabilizer column operating at
moderate pressure. The stabilizer removes dissolved
residual hydrogen as well as the light ends that are
present in the raw isomerate. When the fresh feed
contains some C7 and heavier alkanes, these
components are hydrocracked to produce propane
and butanes which can be removed as a stabilizer
LPG distillate stream. A medium pressure steam
heated reboiler is used to provide the stabilizer reboil
heat. The same reboiler can also be used to vaporize
the stabilizer bottoms.

Advances in CCR reforming ( Octanizing ) using

the latest CR401/CR702 catalysts and incorporating
the new RegenC-II regenerator significantly reduces
CCR reforming operating costs by lowering catalyst
deactivation and attrition and chloride consumption.
The process enable the production of less benzene
by operating at lower pressure, affords high liquid
yields and maintains high co-production of hydrogen
to satisfy the increase in hydrotreatment in the
refinery.

New ATIS 2L Catalyst

Axens and Akzo Nobel Catalysts have jointly
developed a new high activity chlorinated alumina
alkane isomerization catalyst after a significant
combined program of development, testing and
production. The new product offers a major boost in
isomerization activity while significantly reducing total
fill weight, platinum content, and cost. The new ATIS2L reflects the combination and improvement of Akzo
Nobels AT and Axens IS series catalysts.

92

RON
88

84

NEW Catalyst
Breakthrough!
+ 1 to 1.5 RON

Semi-regen reforming units can also benefit from

the new RG 682 catalyst to increase reformate and
hydrogen yield. Hardware modifications can greatly
increase the efficiency and throughput of many SR
units: Low pressure drop Packinox feed/effluent
exchanger to debottleneck a unit and reduce reactor
pressure, and Texicap for added catalyst volume and
better catalyst utilization in radial reactors. For large
increases in severity and/or capacity, a novel hybrid
design utilizing an additional reactor with CCR loop
can combine some of the attributes of a CCR system
while maximizing the reuse of existing SR equipment.

Hexorb
Ipsorb

In order to control the gasoline pool benzene

content with certainty, post treatment or benzene
saturation is required. The benzene saturation in
post-fractionated light reformate can be complete,
simple and cost effective. Additionally, the recently
commercialized Benfree process is the simple, low
cost answer to benzene saturation with a reduction in
the number of equipment required. The process also
affords a light reformate, essentially free of benzene
and C7+ components, thereby ensuring excellent

DIH
Once through
Investment Cost

Figure 16: Higher Octane with New ATIS 2L

14

Octane and Benzene Management for Reformulated Fuels

gasoline yield in an isomerization unit by avoiding

hydrocracking of these heavier components.
Light naphtha isomerization processes are
versatile enough to co-process a very naphthenic light
reformate together with light straight run naphtha.
Axens isomerization technology, combining the new
higher active ATIS 2L catalyst with advanced recycle
schemes such as Ipsorb and Hexorb, afford an
octane boost which should more than compensate
the octane loss due to sulfur and benzene reductions
in RFG.
Axens has the experience and know-how to help
refiners select the right combination of process
technologies, flow schemes, operating conditions,
and advanced control strategies to optimize the
solution to the RFG and regulatory puzzle.
Acknowledgement: this article has drawn upon
several presentations and publications prepared by Axens
and IFP technical staff: C. DuPraz, B. Domergue, JL
Nocca, J. deBonneville, L. Mank, PY LeGoff, M.Schmidt,
and M. Pike.

15