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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
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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
$M Equivalent/Yr.
environmental building blocks. The end result is a
customized, integrated environmental solution that optimizes 15000
5000
Utilities
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.
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
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4. CONCLUSIONS
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