Technology advancements in benzene saturation

BRIAN J. SCHIAVONE, UOP LLC, Des Plaines, Illinois

Refiners once again face challenges
to address benzene in the gasoline pool.
The EPA has rolled out new regulations
under Mobile Sources Air Toxics Phase
2 (MSAT2) to reduce the annual average benzene content in the US gasoline
pool, except California, to 0.62 vol%
effective January 1, 2011. Additional
regulations of MSAT2 include a maximum benzene content of 1.3 vol% in
the gasoline pool effective July 1, 2012.
The regulations include the ability for
refiners to generate credits under the
averaging, banking and trading (ABT)
program, which allows refineries to
trade credits to meet the 0.62 vol%
specification. These new regulations
will require most refiners to implement
post-fractionation strategies to meet the
new lower benzene limit.
As shown in Table 1, the largest contributor of benzene in the gasoline pool
is reformate.
Refiners will not be able to meet
the proposed MSAT2 limits without
addressing the benzene content in reformate. There are two basic approaches
to benzene management in reformate:
prevention of the formation of benzene
and removal of benzene from the reformate.
Dehydrogenation of six-carbon
naphthenes, cyclo-hexane or methyl-cyclo pentane and de-alkylation of heavy
aromatics are two routes that lead to the
formation of benzene in a reforming
unit. The dehydrogenation route is the
largest contributor to benzene formation and is best controlled using prefractionation strategies to remove C 6
naphthenes from reforming unit feed,
as well as the benzene present in the
straight-run naphtha.
The approach of preventing the
formation of benzene by pre-fractionation and use of a low pressure reforming will reduce the gasoline benzene to
about 1 vol%, but in most cases this
approach will not achieve the MSAT2
target benzene level of 0.62 vol%. Prefractionation processing strategies that
include saturation of benzene in light
naphtha and low pressure reforming, as
shown in Fig. 1, will meet the MSAT2
benzene level, but with little or no
compliance margin. A change in feed
or product slate could force the refinery
out of compliance. Most refiners, even
those with low pressure reformers, will
need to consider the post-fractionation
options.
The post-fractionation approach
will need either benzene conversion
or benzene removal. Refiners with
high pressure reforming units produce
enough benzene that post-fractionation
solutions will be required to meet the
MSAT2 targets. Refiners with low pressure reformers can benefit, through the

Isomerization

Light naptha
benzene, C6
naphthenes

Saturation

Straight run
naphtha

0.60 vol%
benzene in
gasoline pool

Naphtha
splitter

Low pressure
reforming
unit
FIG. 1. Pre-fractionation with low pressure reforming and benzene saturation or
isomerization

Makeup

Vent
gas

SG

Light
ends

Reactor

Stablizer
Reformate
splitter
Reformate

Product
Heavy
reformate

FIG. 2. UOP BenSat process unit flows scheme.

Table 1. Typical sources of benzene contributions to gasoline

Process stream Range of benzene
Influencers

concentrations, vol%

Benzene contribution
to the pool, %

Reformate
0.28

Feed PONA, Feed

IBP, pressure

7580

FCC naphtha
0.51.3

Mode of operation
and crude source

1015

Crude source

25

Conversion of VGO to
naphtha, feedstock

15

Light straight run

naphtha C5220F

0.88

VGO hydrocracked to
1 to 5
C5 + 380F naphtha

TABLE 2. BenSat process economics with the H-18 catalyst

LHSV

BenSat unit with
H-8 catalyst

Base

BenSat unit with 2.5 * Base

H-18 catalyst

Catalyst
requirements

Pt
requirements

Base

Base

40% * Base
(by vol)

22% * Base
(by wt)

ABT program from the additional compliance margin that post-fractionation

will provide.
The simplest post-fractionation solution is saturation of the benzene. UOPs
BenSat process with the UOP H-8 catalyst has been the industry standard for
benzene saturation for over 25 years.

Pt
savings

$ 1,548,000

The BenSat process has been updated in

response to demand for improved economics. The new BenSat process uses a
new catalyst, the H-18 catalyst, resulting in lower catalyst volume, reduced
recycle and lower precious metal
requirements. The new BenSat process,
as shown in Fig. 2, still uses a platinum

catalyst for robust operations, highest

yield and minimal hydrogen consumption. Unlike nickel-based catalysts,
platinum-based saturation catalysts are
not permanently poisoned by sulfur or
heavies upsets and do not cause cracking to light ends. More then 10 BenSat
process units are in operation and many
of those units with the same catalyst
load for over 11 years. No BenSat unit
has ever required a catalyst reload due
to catalyst deactivation.
The BenSat process will allow refiners to target benzene levels well below
the 0.60 vol% limit of MSAT2. Lower
levels of benzene will allow greater
flexibility in the case of pool benzene
limits. Table 2 compares the economics of the BenSat process with the new
H-18 catalyst for a typical 8,000 bpsd
unit processing a light reformate stream
of 19 vol% benzene. The benefits are
based on Pt at $1,270 per tr. oz.
Benzene separation and saturation
will result in an octane loss. For most
refiners, this octane loss can be offset
by ethanol blending. A common solution for the pre-fractionation approach
is to process SRN including benzene
precursors in an isomerization unit to
saturate the benzene. The post-fractionation option is to process SRN
plus light reformate in an isomerization
unit. UOP offers a wide range of light
naphtha isomerization technologies.
The most common process is the UOP
Penex process with over 100 units in
operation. The Penex process can process up to 5 vol% benzene in the feed.
Penex process unit feed severity is
likely to increase beyond 5 vol% benzene, in a low benzene world, increasing the probability that a Penex-Plus
process will be required. A revamp of a
Penex process to a Penex-Plus process
would allow greater levels of benzene
to be saturated.
The proposed lower gasoline benzene specifications will require modification of most refineries. The target
benzene levels can be obtained by focusing on the benzene produced in the
reformer. Most solutions will require
separation and conversion of benzene.
Benzene saturation either in a standalone benzene saturation unit such as
the BenSat process or in a light naphtha
isomerization unit such as the Penex
process or the Penex-Plus process are
well-established, robust, economical
technologies for new benzene management solutions.
Brian Schiavone is the product line manager
for gasoline technologies in UOPs Process Technology and Equipment business in Des Plaines, Illinois.
In his 15 years of experience with UOP, Brian has
worked in a variety of roles, most recently as manager of the Platforming Technology Center in UOPs
Engineering Department. Brian holds a B.S.Ch.E
degree from The Ohio State University.

Article copyright 2008 by Gulf Publishing Company. All rights reserved.

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