OXIDATIVE DESULFURIZATION: A NEW improve the economics of these regulations-driven projects relative to

TECHNOLOGY FOR ULSD current HDS technology.

Eni S.p.A. recognized the advantages of lower capital and
Ron Gatan, Paul Barger, and Visnja Gembicki operating cost that oxidative desulfurization can offer and started
research efforts to develop new catalysts. UOP LLC had previously
UOP LLC developed process technology for integrating oxidative
Des Plaines, Illinois, USA desulfurization units with hydrotreating units that could be applied to
1,2
the new catalysts. In 2002, EniTecnologie S.p.A. and UOP LLC
Agostino Cavanna embarked on a collaborative research effort that combined each
companys catalyst and process technology expertise to develop the
Eni S.p.A. Refining and Marketing Division UOP/Eni Oxidative Desulfurization Process, a new sustainable
Rome, Italy oxidative desulfurization technology that is targeted for
commercialization in 2005.
Daniele Molinari The question that needs to be addressed is how best to meet
future low sulfur fuel regulations such as the upcoming off-road
EniTecnologie S.p.A., diesel specifications in the United States and the potential for zero
Milan, Italy sulfur fuels at some point in the future. The preference has been to
make the most with what is available, and a revamp solution is
Abstract preferable to building new units. Hydrotreating is expensive,
Oxidative desulfurization is an innovative technology that can particularly for an existing low pressure unit. These units generally
be used to reduce the cost of producing ultra-low sulfur diesel have been revamped to meet ULSD specifications by adding a large
(ULSD). The key to successful implementation of this technology in quantity of catalyst and reducing the available operating cycle.
most refinery applications is effectively integrating the oxidative Hydrogen consumption is increased at the higher severity needed for
desulfurization unit with the existing diesel hydrotreating unit in a ULSD, which can result in product quality give-away in some
revamp situation. instances. The spent catalyst from these units represents a solid waste
The economics of applying oxidative desulfurization technology disposal issue, which combined with the additional CO2 emissions
are dependent on the operating pressure of the existing hydrotreating associated with increased hydrogen demand, points to the need for a
capacity. A case study has been developed to illustrate how this more sustainable technology.
innovative new route can be effectively utilized as an alternative to A typical feedstock will contain about 30% LCO or other
revamping existing hydrotreaters. cracked blendstocks, with the balance being straight run diesel.
Substantially higher severity is required to produce ULSD in
Introduction intermediate and low pressure units. A summary of the process
Regulations regarding the sulfur content of motor fuels continue
conditions typically required for modern HDS catalysts is shown in
to be enacted worldwide in response to the need for cleaner air.
Table 1. Generally, a significant increase in catalyst volume is
Today, most industrialized countries have regulations in place to
required, combined with a shorter process cycle and higher hydrogen
reduce diesel fuel sulfur to either 15 or 10 ppm by 2009. Developing
circulation.
countries are progressing environmental quality improvement
programs as well, with most electing to enact fuel quality regulations Table 1. Process Conditions Required for ULSD
similar to those in place in Europe.
Intermediate Pressure Low Pressure
Refiners will meet the challenge of these new regulations at a Original vs. New Original vs. New
significant cost. Technology licensors and catalyst manufacturers Specifications Specifications
have continued to progress conventional hydro-desulfurization
technology to reduce the capital and operating expense required. Product S, ppm 500 <10 500 <10
Revamping existing intermediate and lower pressure units will LHSV, 1/hr 3.0 1.0 1.5 0.5
typically require addition of significant catalyst volume and Gas/Oil Ratio, SCFB 1500 2000 1000 1500
equipment modifications to increase the hydrogen purity and Cycle Length, months 36 18 24 8
circulation rate. However, there is a limit to the cost reduction that
can be achieved as hydro-desulfurization (HDS) chemistry requires Installation of a new high pressure (750+ psi) hydrotreating unit
elevated temperature and pressure for deep desulfurization and, of is expensive, which is generally avoided unless there is no other
course, consumes hydrogen in the process. Hydro-desulfurization option. Typical capital costs for a new 30,000 BPD diesel
also cannot readily achieve the very low sulfur levels envisaged for hydrotreating unit for ULSD will be $35-$45 MM on a US Gulf
future zero sulfur fuels. Coast (USGC), inside battery limits (ISBL) basis. High pressure units
There are alternatives to using conventional hydrotreating can typically be easily revamped to make ULSD by changing to a
technology for producing ULSD, including biodesulfurization, modern HDS catalyst and installation of improved reactor internals,
physical separation, and oxidative desulfurization. Both such as UOPs Ultramix internals, for better flow distribution.
biodesulfurization and physical separation processes have not been Intermediate pressure (600 psi) units may require a significant
shown to be economically viable on a commercial scale. Oxidative revamp depending on the difficulty of the feedstock. A major revamp
desulfurization technology, however, has progressed to the state in these cases will typically include a new reactor for additional
where it is nearing commercialization. Oxidation chemistry catalyst, modification or replacement of the compressors, a hydrogen
represents an alternative route to diesel desulfurization that purification system, and a recycle gas scrubber. This is a relatively
complements HDS chemistry. The integration of an oxidative high cost revamp, $10-$25 MM for a 30,000 BPD unit on the USGC,
desulfurization unit with a conventional hydrotreating unit can ISBL basis used by UOP. Operating cost is also higher, ranging from
$0.25/bbl to $0.50/bbl or higher. The largest cost element is increased

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004, 49(2), 577
hydrogen consumption in these units. The revamped unit generally The oxidant from the oxidant supply section is first mixed with
operates with a shorter catalyst cycle which translates into higher hydrotreated diesel and then sent to the sulfur reaction section. The
catalyst cost. sulfur reaction section operates at low temperature and pressure, less
Low pressure (450 psi) units will require either a major revamp than 200F and less than 100 psig. The reaction occurs in the
or replacement with a new high pressure hydrotreating unit presence of a proprietary heterogeneous catalyst in a conventional
depending on the feedstock available. A major revamp for such a unit fixed bed reactor. The use of an organic peroxide as the oxidant
will include a new, much larger reactor, new recycle gas avoids the need to recycle corrosive organic acid catalysts that are
compressors, a recycle gas scrubber, and equipment to increase needed when hydrogen peroxide is used. Very high conversion is
make-up hydrogen purity such as a Polybed PSA unit. These are obtained in the sulfur reaction section, in excess of 98% conversion
high cost revamps, ranging from $15-$30 MM for a 30,000 BPD unit. of organic sulfur compounds.
Operating costs are significantly increased, ranging from $0.50/bbl to The final step is the sulfone separation section. The sulfones are
$0.75/bbl. As in the intermediate pressure case, the operating cycle is polar molecules so they are easily separated by either extraction or
typically dramatically shorter in the revamped units and hydrogen adsorption. UOP and Eni have evaluated both routes, and have
consumption is increased. The difficulty of processing cracked concluded that the adsorption route is more cost-effective. The
feedstocks at low pressure also decreases the flexibility of the unit. adsorption section also serves to remove any trace by-products
It is clear in this discussion that while hydrotreating is relatively formed during the oxidation and reaction steps. The sulfones that are
expensive, a new technology has to be cost-effective to be considered separated can either be processed in a coker or can be blended
as an alternative to revamping existing HDS units to meet ULSD directly into the heavy fuel oil pool in some locations.
specifications. It is easier to justify a new technology in those
instances where the competitive option is a new grassroots unit, but Oxidant Sulfur Sulfone
HCBN ULSD
that is only a consideration in about 25% of refineries. UOP and Eni Supply Reaction Separation
have set development targets for the UOP/Eni Oxidative
Desulfurization Process at a capital cost of $15 MM or less for a
O2 or Hydrotreated Extracted
30,000 BPD unit and an operating cost of $0.25/bbl or less in order to Peroxide Diesel Sulfones
be competitive as an alternative to a major revamp of moderate to ~500 ppm S
low pressure hydrotreaters. Oxidative desulfurization is not a Figure 2. UOP/Eni Oxidative Desulfurization Process
competitive option for high pressure units where only a minor
During development of the process flow scheme, a number of
revamp or a simple catalyst replacement is required.
key economic issues surfaced that are essential for the oxidative
desulfurization process to compete with revamping conventional
Oxidative Desulfurization Technology
hydrotreating units for ULSD production. The major hurdles
Oxidative desulfurization is not a new concept and has been
addressed were:
discussed for several years in previous publications.3,4 The advantage
that oxidative desulfurization has over conventional HDS is that the Oxidant cost
difficult-to-desulfurize, refractory-substituted dibenzothiophenes Minimize equipment
(DBT) are easily oxidized under low temperature and pressure
Minimize operating costs
conditions to form the corresponding sulfones. This reaction is shown
Maximize ULSD yield
in Figure 1. The oxidant can be supplied by either hydrogen
peroxide/peracid4 or organic peroxide. Note that there is no hydrogen Disposition of the sulfone extract
consumed in this reaction. The sulfones are highly polar compounds An engineering analysis of the operating and equipment costs
and are easily separated from the diesel product by either extraction for all sections was conducted that highlighted where innovations
or adsorption. were needed to meet the development targets of <$0.25/bbl operating
cost and <$15 MM capital cost. The sections that have the largest
Catalyst
+ ROOH impact on cost of the unit are the oxidant supply and sulfone
S S separation sections. This was not too surprising, as these sections
= =

R R R O O R have the largest number of equipment items and require product

Figure 1. Dibenzothiophene Oxidation Chemistry fractionation. Efforts were then focused on reducing the cost of these
two sections.
This oxidation chemistry is complementary to hydrotreating, as There are a number of issues associated with using purchased
other sulfur compounds such as disulfides are easy to hydro- organic peroxides in the process, the chief being the high cost and
desulfurize, but oxidize slowly. For this reason, oxidative limited availability of these materials. The purchase cost adds $0.30
desulfurization is best utilized as a second stage after an existing to $0.40/bbl to the operating expense, in excess of the required target
HDS unit, taking a low sulfur diesel (~500 ppm) down to ULSD (<10 operating cost. Other safety issues associated with handling and
ppm) levels. In this situation, the diesel product has been depleted of storage of organic peroxides on-site can be addressed technically but
difficult-to-oxidize sulfur species and has a high concentration of the will add significant capital cost to the unit. Eni and UOP have
more refractory DBT constituents. decided that the best solution to this problem is to generate the
The UOP/Eni Oxidative Desulfurization Process is shown peroxides in situ using an easily oxidizable hydrocarbon and air. We
schematically in Figure 2. The process consists of three process steps; have identified catalysts that are active for the oxidation reaction and
an oxidant supply section, a sulfur reaction section, and finally a are completing the process development necessary for
sulfone separation section. The UOP/Eni technology uses an organic commercialization.
peroxide as an oxidant. The oxidant supply section can consist either A number of different designs were evaluated for the sulfone
of the handling equipment associated with purchased organic separation section, including liquid-liquid extraction and several
peroxide such as t-butyl-hydro-peroxide, or the peroxide can be different adsorber configurations. Extraction is technically viable, but
generated internally via direct oxidation of a hydrocarbon with air.

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004, 49(2), 578
has a high capital and operating cost, and can be difficult to operate. was estimated for the unit, which is equivalent to $533/bbl. The
A high capacity adsorbent was identified that made the adsorption operating cost was estimated at $0.31/bbl over the base case
section technically feasible. UOP based the adsorber design on our operation. While both values are slightly above the development
commercial experience with similar separation applications in other target values, the economics are attractive relative to the conventional
technologies. The configuration used has a low capital cost, low revamp. The calculated incremental net present value (10% interest
diesel yield loss, and nearly complete sulfone removal from the diesel rate and 10 year project life) was $10 MM higher for the oxidative
product. desulfurization case. This significant improvement in economics is
due to eliminating the additional hydrogen consumption by
Oxidative Desulfurization Economics installation of the oxidative desulfurization section.
UOP and Eni conduct extensive techno-economic feasibility
studies as part of the development process to ensure that the The Future of Oxidative Desulfurization
technologies in development are competitive with alternatives that The study presented in this paper has demonstrated that
are available to refiners. A case study was selected to illustrate how oxidative desulfurization can play an important role in future
oxidative desulfurization can be effectively applied as an alternative technical strategies to produce ULSD. This technology can be
to revamping conventional hydro-desulfurization technology. The considered to be a viable option for new ULSD projects that will be
utility and product values used in this analysis were based on energy implemented in 2006 and beyond. Oxidative desulfurization
pricing current in 4Q03. technology also holds promise for both reducing operating cost and
The value of hydrogen is critical in any comparisons of improving the sustainability for low pressure units where substantial
hydroprocessing technology options. In the case studies considered investments have already been made. The key to success is that the
here, the hydrogen value used was $2.25/MSCF. This value was oxidative desulfurization process must be cost-effective versus the
calculated based on a 4Q03 Henry Hub natural gas price of HDS revamp alternatives available to refiners.
$4.50/MM BTU.5 Typical hydrogen plant operating costs were used Over this coming year, UOP and Eni will continue to conduct
to calculate the hydrogen value used based on this assumed natural studies in our continuous pilot plants to fully demonstrate the
gas feedstock price. UOP/Eni Oxidative Desulfurization Process. The key aspects to be
demonstrated include long-term catalyst stability in an integrated
Case Study operation over a range of commercial feedstocks. We will continue to
The scenario assumed is an existing diesel hydrotreater, optimize our engineering design to improve the cost-effectiveness of
designed for processing 30 MBPD of a 70% straight run/30% LCO the process.
blend at 600 psi, producing 400 ppm low sulfur diesel. The unit Eni is considering implementation of an oxidative
design parameters are listed in Table 1 for intermediate pressure desulfurization unit as an alternative to revamping an existing
revamps. The changes required are: intermediate pressure hydrotreater at an Eni refinery in Italy. The
basic design of this unit is scheduled to start at the end of 2004, with
Decrease LHSV from 3 to 1 hr-1 construction starting in the second half of 2005. This will be a full
Reduction in process cycle from 36 to 18 months scale commercial unit to produce ULSD meeting the 2009
33% increase in hydrogen consumption ( 150 SCF/bbl) regulations in Europe.
Requires new reactor, compressors, and recycle gas scrubber
Summary
The critical performance parameters and economic values are Oxidative desulfurization technology offers a non-hydrogen
summarized in Table 2 for both the base case operation at 400 ppm consuming, lower capital cost, more sustainable alternative to
sulfur and the requirements for ULSD. A capital cost estimate for this conventional hydrodesulfurization technology. The technology can
revamp was $18.5 MM on a USGC, ISBL basis. The operating cost be applied as part of an effective strategy for both an alternative to
increased $0.45/bbl over the base case operation, nearly all due to the revamping intermediate and low pressure HDS units to produce
increased hydrogen consumption. ULSD, or as a means to reduce the operating cost of low pressure
units that have already been revamped. Oxidative desulfurization can
Table 2. 600 psi Diesel Hydrotreater Revamp Case Study also be considered as an attractive revamp opportunity for any
existing unit where construction of new high-pressure HDS units is
Base Conventional Oxidative
Parameter Operation Revamp Desulfurization
the alternative.

Diesel Sulfur, wt-ppm 400 <10 <10 References

Diesel Yield, lv-% 98.5 97.0 97.0 (1) Cabrera, C.A.; Imai, T., US Patent 6,171,478 assigned to UOP
Capital Cost, $MM 18.5 16.0 LLC.
(2) Kocal, J.A.; Brandvold, T.A., US Patent 6,638,495 assigned to
Hydrogen Cost, $MM/yr 10.0 13.4 10.0 UOP LLC.
Utilities Cost, $MM/yr 0.8 1.0 2.5
(3) Liotta, F.J.; Yuan, Z.H., Production of Ultra-low Sulfur Fuels
Catalyst Cost, $MM/yr 0.3 1.3 1.5
Total Operating Cost, $MM/yr 11.1 15.7 14.0 by Selective Hydroperoxide Oxidation, AM-03-23, NPRA
Delta Product Value, $MM/yr 1.7 2.0 1.7 2003 Annual Meeting.
Total Operating Cost, $bbl 0.97 1.42 1.28 (4) Levy, R.E.; Pappas, A.S.; Nero, V.P.; DeCanio, S.J., Unipures
ASR-2 Diesel Desulfurization Process: A Novel, Cost-Effective
NPV, (10%, 10 yr), $MM <41> <31>
Process for Ultra-low Sulfur Diesel Fuel, AM-01-10, NPRA
The alternative to the conventional revamp is to install an 2001 Annual Meeting.
oxidative desulfurization unit. In this case, the original HDS unit (5) Oil and Gas Journal, Vol. 101, Number 41, October 27, 2003,
continues to produce 400 ppm sulfur product, with the oxidative Industry Scoreboard, pg. 4.
desulfurization unit used to make ULSD. A capital cost of $16 MM

Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem. 2004, 49(2), 579