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8O JOURNEES SCIENTIFIQUES ET TECHNIQUES

Hilton Hotel, 18 to 19 November 2008, Algiers, Algeria

DUPONT CLEAN TECHNOLOGIES APPROACHES FOR MODERN REFINING


SULFUR MANAGEMENT, EMISSION REDUCTION AND CLEAN FUELS
NEEDS
Carlos Cavalca(1), Tom Hightower(1), Glenn Liolios(2), Andrew Tyas(2), Nick Confuorto(3), Ronan Goff(4) and
Stuart Thomas(4)
DuPont Clean Technologies
cleantechnologies.dupont.com
(1)
E. I. DuPont de Nemours 4417 Lancaster Pike, Wilmington DE 19805 U.S.A.
Phone (302)992 3413 Fax (302)992 5084 E-mail : carlos.a.cavalca@usa.dupont.com
Phone (225)755 3717 Fax (225)755 8340 E-mail : thomas.c.hightower-jr@usa.dupont.com
(2)
DuPontTM STRATCO® Clean Fuel Technologies 11350 Tomahawk Creek Pkway, Leawood KS 66211 U.S.A.
Phone (913)327 3544 Fax (913)338 0003 E-mail : glenn.c.liolios@stratco.dupont.com
Phone (44)1252 816796 Fax (44)1252 812665 E-mail : andrew.tyas@stratco.dupont.com
(3)
DuPontTM BELCO® Clean Air Technologies 7 Entin Road, Parsippany NJ 07054 U.S.A.
Phone (973)515 8903 Fax (973)884 4774 E-mail : confuorto@belcotech.com
(4)
DuPont de Nemours International 2 chemin du Pavillon, Geneva CH-1218 Switzerland
Phone (33)1 4197 4555 Fax (33)14197 4533 E-mail : ronan.goff@fra.dupont.com
Phone (22)717 5392 Fax (22)717 6159 E-mail : stuart.m.thomas@che.dupont.com

Abstract - The world-wide refinery industry is faced with 1. INTRODUCTION


increasingly difficult and challenging sulfur management
needs, tougher emission reduction targets and progressively The world-wide refining industry is facing an increasing
restrictive fuel specifications. These trends, which developed challenge to minimize and control refinery emissions while
over time, have often been addressed as one-off problems simultaneously addressing production of low sulfur-
within a refinery resulting in sub-optimized solutions. containing fuels. A catalyst for these transformations is the
DuPont Clean Technologies provides customized sulfur & regulatory environment becoming increasingly stringent. At
ammonia recovery, clean fuels (alkylation and the same time, the high value of sulfur in today’s market
hydroprocessing) and gas scrubbing environmental solutions demands the optimization of the refinery sulfur management
to refiners which are designed to address in an integrated scheme and the extension of the refinery sulfur conversion
and sustainable form the above challenges. These integrated chain beyond typical elemental sulfur, to production of
solutions are optimized to maximize synergies between sulfur-derivatives for industrial and agricultural markets.
technologies, minimizing cost to the refiner and offering the
lowest environmental footprint.

Keywords: sulfur management, sulfur recovery, spent acid 2. OVERVIEW OF DUPONT CLEAN
regeneration, nitrogen management, ammonia, ammonium TECHNOLOGIES
sulfate, sulfuric acid, scrubbing, alkylation, hydroprocessing,
hydrotreating, hydrocracking, diesel, fuel switching, boiler, DuPont Clean Technologies provides integrated, customized
heater, steam, emission reduction. environmental solutions for refiners’ sulfur management,
nitrogen management, emission control and clean fuels

1
needs. The building blocks for DuPont’s integrated that the DuPont SAR-SGR acid plant provided a lower cost
environmental solutions include DuPont Sulfur Gas for sulfur recovery (compared at constant NPV over 10
Recovery (SGR) and Spent Acid Regeneration (SAR) years) compared to a conventional Claus SRU approach.
Technologies, DuPont™ Clean Fuel Technologies
(STRATCO® alkylation and IsoTherming® hydroprocessing), 25000
Variable cos t Operating Fixed Costs
and DuPont™ BELCO® Clean Air Technologies. DuPont’s SGR Capital Investment DuPont Gas Fee
science-based solutions to environmental problems are based Acid Regeneration Steam Value Offs et

on 200 years of experience in chemistry, process know-how, 20000

and on the effective integration of these recognized

$M Equivalent/Yr.
environmental building blocks. The end result is a
customized, integrated environmental solution that optimizes 15000

synergies between technologies, offers the lowest


environmental footprint and provides optimized savings in
operating cost and capital investment to the refiner1,2,3. 10000

5000

3. INTEGRATED ENVIRONMENTAL SOLUTIONS


0
3.1 DuPont SAR-SGR Sulfuric Acid Technology Refiner Best DuPont On-Site
DuPont’s sulfur management takes place via conversion of Alternative SAR/SGR
sulfur gases (amine gas, SWS gas, gasifier gas, etc.) in an
on-site spent acid regeneration and sulfur gas recovery unit Figure 2 – Cost comparison for sulfur recovery case study showing DuPont
SAR-SGR plant providing improved benefits to the refinery compared to
(SAR-SGR) located on or adjacent to a refinery. This plant refiner’s best alternative.
provides total or partial sulfur gas recovery (SGR) to the
refinery at the lowest emission levels and cost compared to
alternative technologies, producing sulfuric acid and high
pressure steam as products. This sulfur management 3.2 DuPontTM STRATCO® Alkylation Technology
capability can be effectively integrated to alkylation, where Integrated to SAR-SGR Acid Plant
the acid plant provides spent acid regeneration (SAR) to the As one of DuPont’s strategies for clean fuels involves the
refinery sulfuric acid alkylation units. Five SAR-SGR plants production of alkylate, DuPont Clean Fuels Technologies
were successfully deployed by DuPont at three refinery deploys STRATCO® sulfuric acid alkylation technology,
facilities in the U.S. Figure 1 shows this acid plant-refinery which is recognized as the safest and most mature alkylation
integration concept technology. The effective integration of DuPont SAR-SGR
DuPont On-Site
sulfuric acid plant with STRATCO® alkylation technology
Refinery yields a reduction in capital investment and optimization of
SGR/SAR Plant
operating cost and energy integration. Figure 3 shows this
Sulfur Gases (SGR) on-site acid plant – alkylation integrated solution.
SAR Service DuPont On-Site Integrated
SGR/SAR & Alkylation Plants
Utilities Close Coupled by
Refinery Pipelines
Steam (High Pressure)
Sulfur Gases (SGR)
Close Coupled by Steam (High Pressure) Fresh Non-Fuming
Pipelines
SAR

Utilities

Sulfur Products to Olefins & isobutane


Merchant Market
Tolled Alkylate Product
Figure 1 – On-site DuPont SAR-SGR sulfuric acid plant. Alkylate by-Products

The bar chart presented in Figure 2 shows the result of a


case study for an on-site SAR-SGR acid plant. For this case Sulfur Products to
Merchant Market
study, a DuPont SAR-SGR plant was designed to improve
Figure 3 – Integration of an on-site DuPont SAR-SGR sulfuric acid plant to
control of refinery emissions, increase reliability and free up a DuPont STRATCO® sulfuric acid alkylation plant.
sulfur recovery capital from the refinery. The study shows

2
3.3 DuPont IsoTherming® Hydroprocessing Technology
The second DuPont strategy for clean fuels involves
hydroprocessing. DuPont IsoTherming® technology
provides the petroleum refiner the most cost-effective means
to meet conversion, product sulfur and product nitrogen
specifications in an increasingly competitive and demanding
environment. The DuPont IsoTherming® process
technology is a commercially proven, flexible, breakthrough
technology that allows a refiner to meet their increased
hydroprocessing capacity needs at a significantly reduced Table 1 – Capital cost comparison in $/bbl (30,000 bbl/day – 4,750 m3/d
basis) between DuPont IsoTherming® technology and conventional
capital and operating costs over conventional hydrotreating for various applications.
hydroprocessing technologies. This technology can be
customized, including catalyst selection, to meet a particular
needs In each case, reactor design and operating
refiner needs.
conditions are optimized around a catalyst system. 3.4 DuPont NH3 SWS Gas Scrubbing / Ammonium
IsoTherming® technology has been successfully practiced on Sulfate Technology and Its Integration with a DuPont
a commercial scale in several ULSD units and has been SAR-SGR Sulfuric Acid Plant
licensed for several Mild Hydrocracking services. This technology comprises the separation (reactive
scrubbing) of ammonia from sour water stripper (SWS) gas
Figure 4 shows a simplified diagram of the IsoTherming® and its conversion, using sulfuric acid, to ammonium sulfate
process4. For the case example of ULSD revamp, not only a solution. The resulting ammonia-free, dry, SWS-scrubbed
significant capital savings can be realized with gas can be fed into a Claus unit freeing additional sulfur
IsoTherming® vs. a conventional revamp but the net result is recovery capacity and improving downstream SRU
a unit that offers considerably more flexible operation. operation. It is expected that up to 3.75 tons of additional
sulfur capacity per ton of ammonia can be obtained by
scrubbing ammonia from the SWS gas feed. The resulting
ammonium sulfate liquor product can be used as liquid N, S
-containing fertilizer feedstock or further crystallized for
solid bulk use. This technology is very suitable for
refineries that process crudes with a high level of nitrogen-
bound species and/or larger amounts of sour water.

This SWS gas NH3 scrubbing / ammonium sulfate process


can be readily integrated to an on-site SGR sulfuric acid
plant. As the SGR plant converts sulfur gases providing
incremental or total sulfur recovery capacity and/or SRU
backup to the refinery, it produces non-fuming sulfuric acid
and steam which become feedstock for the ammonium
Figure 4 – DuPont IsoTherming® hydroprocessing simplified process
diagram.
sulfate plant. Figure 5 depicts the integration of these
technologies. DuPont On-Site SAR-
Refinery SGR Acid Plant
The relative costs of IsoTherming® process technology in Sulfur Gases (SGR)
mild hydrocracking service will vary depending on the SAR Service
refiner need and the existing infrastructure capability. For a Utilities
30,000 BPD 2,000 psi application the capital cost for
Steam (High Pressure)
IsoTherming® is substantially lower as compared to the
conventional trickle bed process. Fuel gas and power DuPont Ammonium
Sulfate Plant
requirements are slightly lower and steam generation is
higher4.
SWS gas
(H2S, NH3, H2O) Fresh
Table 1 presents a capital cost comparison between Acid
IsoTherming® and conventional hydrotreating. DuPont Scrubbed SWS gas
IsoTherming® hydrotreating technology offers the lowest (H2S, H2O) Ammonium Sulfate Liquor to Sulfuric Acid to
cost per barrel for severe gas oil hydrotreating, mild Fertilizer Merchant Market Merchant Market
hydrocracking, and diesel (revamp and grassroots) Figure 5 – DuPont NH3 SWS gas scrubbing / ammonium sulfate on-site
applications. facility integrated to a DuPont SAR-SGR sulfuric acid plant.

3
DuPont Unit:
3.5 DuPontTM BELCO® Scrubbing Technology and Its
Integration with a DuPont SAR-SGR Acid Plant and SRU SAR-SGR Acid Plant or
Units Dual Alkali Scrubber
DuPontTM BELCO® scrubbing technologies are well known Product
in the refining industry for their use as emission control units To Market
on fluid catalytic cracking units to abate the PM, NOx and
SOx emissions. BELCO® systems are also used for other
applications such as emission control on fired heaters and SO2 (98+%) SO2 (98+%)
Acid Gas
boilers to allow for the use of high sulfur fuels in these units.
CLAUS
®
BELCO®
One challenge for the refining industry today is the Tail Gas LABSORB®
management of the bottom of the barrel components. SO2 Regenerative
Traditionally these streams were blended and sold, at a large Incinerator Scrubber
discount to crude oil, as bunker fuels. An alternative use for
these materials is to use them as fuel sources for steam SOx, NOx, PM
production and to fire process heaters. Significant economic Process
advantages can be derived through this approach: reduced Heavy Oil Fired Heater Heat
use of expensive natural gas, on-site value for distressed
stocks, and the economic value derived by redirecting the Figure 6 – Integration of a DuPontTM BELCO® LABSORBTM regenerative
diluents needed to blend with bottoms materials to produce scrubber with a DuPont SAR-SGR sulfuric acid plant and Claus unit for
marketable bunker fuels. emission control and sulfur management on refineries using high sulfur
fuels for heaters and boilers.
Given the increased level of sulfur in bottoms materials, a In a comparison case study conducted by DuPont Clean
robust emission abatement system must be included to Technologies on alternative SO2 scrubbing options for
reduce PM and SOx emissions. The long experience of refineries implementing “fuel switching” (e.g., use of
BELCO® scrubbers lends itself well to these applications cheaper high sulfur fuels instead of natural gas to fire heaters
and depending on the local environmental regulations, the and boilers) it was found that larger flue gas conversions
scrubbing system could be a once through caustic scrubber favor regenerative scrubbing systems (e.g., LABSORBTM).
or regenerative in nature using either a dual alkali approach Furthermore, it was found economically favorable to convert
or an SO2-capture buffer. DuPont Clean Technologies will both unit heaters and facility level boilers to high sulfur fuel
work with the refinery to provide a customized service feeds using the appropriate SO2 scrubbing and sulfur gas
offering to regenerate the scrubbing solution and market the conversion integrated sulfur management configuration.
resulting products (sulfuric acid or gypsum). In this way the Figure 7 shows the results of the study, depicting the
refinery can focus on core activities and capture value from comparison of scrubbing options and its impact on
distressed refinery stocks. investment NPV and fuel savings.
Figure 6 shows how a DuPontTM BELCO® LABSORBTM 250
CAUSTIC DUAL ALKALI LABSORB(TM) FUEL SAVINGS
regenerative scrubber can be integrated to a Claus unit and
to a DuPont SAR-SGR sulfuric acid plant or Dual Alkali 200
Scrubber to replace a SRU tail gas unit and enable the use of
high sulfur fuels on site. Effective sulfur management is
NPV OR SAVINGS, $MM

150
provided while minimizing emissions and producing
valuable chemicals such as sulfuric acid or gypsum for
market sales. 100

50

0
1000 2000 4000 8000

-50 BURNER FEED RATE, BPD

Figure 7 – Comparison of scrubbing options depicting its impact to NPV


and fuel savings for a refinery fuel switching case.

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4. CONCLUSIONS

The effective integration of sulfur management, nitrogen


management, emission control and clean fuels technologies
allows the design and implementation of customized
environmental solutions that take full advantage of
technology synergies and offers the lowest environmental
footprint while maximizing benefit to the refiner.

DuPont offers extensive know-how on diverse and


innovative environmental and clean fuels technologies and
processes as well as a demonstrated broad operations
expertise and environmental stewardship track record.
DuPont environmental solutions include diverse capital and
operations options, offering customized, flexible and cost
effective sulfur & nitrogen recovery, scrubbing and clean
fuels solutions to the refining community.

REFERENCES
1- J. Skurla, S. Thomas and E. Hartstein “The Acid Test – Holistic
Approaches to Refinery Sulfur Management” Hydrocarbon
Engineering 10, 3, March 2005
2- C. Cavalca, M. Davis, N. Confuorto, G. Liolios, T. Hightower and S.
Thomas “ Solutions for a Cleaner Future – Integrated Environmental
Solutions for Refinery Sulfur, Nitrogen and Clean Fuel Challenges”
Hydrocarbon Engineering 12, 8, August 2007
3- www.cleantechnologies.dupont.com
4- C. Pereira, “Mild Hydrocracking Using IsoTherming® Technology”
2008 NPRA Annual Meeting, San Diego, CA

DuPontTM BELCO® and BELCO® are trademarks of BELCO Technologies


Corp.
LABSORBTM is a trademark of BELCO Technologies Corp.
DuPontTM STRATCO® and STRATCO® are trademarks of DuPont
IsoTherming® is a trademark of DuPont