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Ultra Low SulfuF> Gasoline:
Overview and Comparison of Gasoline Sulfur Reduction Technologies
Steve McGovern and CK Lee
PetroTech Consultants
3 Chambord Lane, Voorhees, New Jersey 08043
Key Words: Ultra Low Sulfur Gasoline, Gasoline Sulfur Reduc ion Technologi, s
Prepared for presentation at the AIChE Spring National Meet g 2001
Fourth International Conference on Refinery Processing
April 22-26, 2001, Houston, Te
Copyright, Steve McGovern and CK Lee, Petro ech Consultants
January 22, 2001
Unpublished
AIChE shall not be responsible for statements or opinions containe in the paper or pr ted
publications " \
Abstract
Over the last few years, motor fuel sulfur level has become the most pressing environmental
the worldwide refining Ne,: regulations have th,
maXImum sulfur level allowed In both gasolIne and dIstIllates. For example, cUI\ent CalIfornIa CARp'\:Y
gasoline requires an average of.30 A similar regulati.on. has been recently by EP1 ifr
the rest of the US to be phased In begInnIng In 2004. In Europe, sImIlar been to
reduce sulfur from the current 150 ppmw to 50 ppmw in 2005. Gennany is incentives for
refiners to produce 10 ppmw sulfur gasoline starting in 2003. "',-
Refiners have many options to choose from to reduce the sulfur in their gasoline. There are many
competing technologies available in the market, including pretreatment, post-treatment, and FCC catalyst
additives. Some of the technologies are commercially proven and some are still in various stages of
development.
In this tutorial session, an overview of the gasoline sulfur reduction technologies will be presented and
compared. Sometimes, more than one technology may be required to produce the ultra low sulfur gasoline.
However, the optimal technology or combination of technologies for a refinery is very much site-specific.
Introduction
In most parts of the world, sulfur oxide emissions from automobiles are not a serious problem. They are
not a significant contributor to global atmospheric SOX levels. Gasoline sulfur contents are generally lower
than those of most other fuels. The impetus to lower gasoline sulfur content comes from the poisoning
effect that sulfur has on the onboard catalyst systems that are used to control automotive tailpipe emissions
of Carbon Monoxide, Hydrocarbons and Nitrogen Oxides.lhese pollutants contribute to the formation of
atmospheric ozone and haze.
Numerous studies, summarized in a recent US EPA Staff Paper (USEPA 1999), have clearly demonstrated
the deleterious effect of gasoline sulfur content on catalyst performance in automobile emission control
systems. Although the magnitude of the impact is a function of both absolute fuel sulfur level and catalyst
and emission control systems in use, lowering fuel sulfur level, lowered tailpipe emissions in all studies.
The combination of advanced onboard emission control systems and lower fuel sulfur levels results in a
very cost effect method for lowering emissions from new vehicles. Furthermore, lowering fuel sulfur
levels will immediately lower emissions from the existing fleet of vehicles currently on the road.
In light of these results, many government agencies, worldwide, have proposed or implemented regulations
that will lower the maximum allowable sulfur content of automotive gasoline. A few of these regulations
are summarized below:
Table 1 Gasoline Sulfur Regulations
MaXlmum Allowable GasorIne SuIfur Cont ent,ppmw
Current Implementation
Date
Corporate
Annual Average
30
Per Batch Cap 80
California Air Resources Board
2003 2005
15 15
60 30
U.S. Environmental
Protection Aeency (1)
. European
Community
2004
-
2006 2005
120 30 50 (2)
300 80
(1) Sulfur specs are phased in over time with full implementation by 2008
(2) Not yet finalized
The regulations noted above are typical of those being considered in other parts of the world as well. Most
currently proposed limits are for sulfur contents of 30-50 ppmw; however, the state of California has
already lowered its limit from 30 to 15 ppnlw. In addition to regulatory limits, some countries such as
Germany are proposing tax incentives for gasoline sulfur contents as low as 10 ppmw and auto emission
studies have shown additional benefits down to as low as 5 ppmw, the practical limit for measuring and
controlling gasoline sulfur contents. This paper will primarily focus on US gasoline regulations,
production, and composition outside of California (OC). The situation in other countries is very similar,
however the large number of FCC units in the US n1akes the problem somewhat more severe.
Current Gasoline Composition
Gasoline is a blend of many different refinery streams that are produced on different process units under
different conditions. These are blended together to produce gasolines with the desired properties. Process
unit operating conditions are varied along with blend compositions to maximize refinery profitability while
meeting the required gasoline specifications. Since all crudes contain some sulfur, which is distributed
throughout the entire crude boiling range, all gasoline components contain some amount of sulfur.
Until the mid 1980's, the sulfur content of gasoline in the US was essentially unregulated. It was limited to
0.5 wt% (as it currently is in some countries), but this limit was almost never reached. The limit was then
reduced to 1000 ppmw, and further reduced as a result of Reformulated Gasoline regulations. In 1998,
total US gasoline production (OC) averaged about 270 ppmw. The sulfur content of individual batches
varied from <20 ppmw up to almost 1000 ppmw, the ASTM limit for pipeline transport. There were three
refineries with 1998 average sulfur contents below 30 ppmw, while 14 refineries had average gasoline
sulfur levels greater than 500 ppmw (USEPA 1999).
This wide variability in gasoline sulfur content is due to: the sulfur contents of the crudes processed, the
type and operating conditions of the refinery process units, and the amount of each blend component used
in the final blends. The typical range of sulfur contents for the common gasoline blend components are
listed below:
T hi e 2 G r c eve s
Percent of Pool
<5
<1
20-70
0-10
0-50
0-15
0-15
a aso Ine omponent SuIfur L
Stream
Light Straight Run Naphtha
Light Coker Gasoline
Reformate
Alkylate
FCC Gasoline
Oxygenates
Others (1)
Sulfur Content, ppmw
1-500
1-3000
<5
5-100
50-2000
1-30
1-1000
(1) Includes Butanes, Natural Gas Liquids, Hydrocrackate, Dimate, lsomerate, Poly gasoline and
Petrochemical rej ect streams
In 1998, almost 40 percent of the US gasoline pool was FCC gasoline with an average sulfur content of 650
ppmw. The other 60 percent had an average sulfur content of 30 ppmw. Typically, the FCC gasoline
contributes over 90 percent of the total gasoline sulfur. It is clear, that in most refineries, the FCC gasoline
must be desulfurized. In refineries with significant sulfur in their non-FCC streams, they must weigh
desulfurizing the non-FCC streams against over desulfurizing the FCC gasoline. Ifthe non-FCC streams
are sulfur free, then the FCC gasoline can have about 75 ppmw sulfur. If the non-FCC streams contain 30
ppmw sulfur, then the FCC gasoline must be 30 ppmw sulfur or less.
FCC Gasoline Composition
Typical FCC gasoline has a (R+M)/2 octane of about 86-88 and has good volatility properties, thus it is an
excellent gasoline blend stock. The good octane is derived from its olefin, iso-paraffin and aromatic
content. These components, however, are not distributed uniformly throughout the boiling range as shown
below for a typical high sulfur FCC gasoline (Nocca et al. 1995).
Fraction
Boiling Range, F
Boiling Range, C
Vol %
Sulfur, ppmw
Olefins, %
Aromatics, %
(R+M)/2
. a
T bl e 3 FCC Gaso Ine r ComllOS}'fIon
LCN ICN HCN Full Ran2e
C5 360+
C5
C6-360
182+
24
C6-182
100
50
64 12
1100 2500
50
3800
26.5 9.3 30
0 30 75 30
88 85.5 86 86.3
Although all components are distributed throughout the boiling range, the olefins are concentrated in the
lighter fractions, while the aromatics and sulfur increase with boiling point.
There are four major types of sulfur compounds in FCC gasoline: Mercaptans, Sulfides, Thiophenes and
Benzothiophenes. The sulfur in the LeN (Light Cat Naphtha) is mostly mercaptans. There can be small
amounts of carbonyl sulfide and carbon disulfide, but their total is usually less than 5 ppmw. Depending on
the actual cut point and the quality of fractionation, the LCN can also contain some thiophene (b.p.
84C/184F). The dominant sulfur type in the ICN (intermediate Cat Naphtha) is the thiophene homologous
series, wrttTJesser amounts (about 10% oftotal sulfur) of sulfides (primarily cyclic) and mercaptans. The
sulfur in the HCN (Heavy Cat Naphtha) is predominantly Benzothiophene (b.p. 221C/43OF) and ifhigh
enough end point, Methyl benzothiophenes. The total sulfur content of FCC gasoline is primarily a
function of FCC feed sulfur content and the end point of the FCC gasoline.
@
Methods for Lowering FCC Gasoline Sulfur
The sulfur content of FCC gasoline can be lowered by one of three methods: 1) removing sulfur from the
FCC feed, 2) modifying FCC operating conditions or catalyst/additives, or 3) post-treating the FCC
gasoline. All three of these methods have been successfully used commercially to lower FCC gasoline
sulfur. Since FCC units normally operate for 4-5 years between major maintenance turnarounds, any
process chosen to lower gasoline sulfur should be capable of running for at least 2 years between
shutdowns. Each major type, along with important sub-types, will}Je discussed below.
FCC Feed Pretreatment To produce FCC gasoline with less than 100 ppm sulfur, the FCC feed must
contain less than 0.1 wt% sulfur. The only commercially viable process for lowering the feed sulfur to that
level is Catalytic Feed Hydrotreating (CFHT) (Danzinger 1999 and Shorey 1999). To produce low sulfur
product over the desired 2 year cycle, high pressures (> 1200psi) are normally required. These high
pressures also improve overall FCC feed quality and can have a significant beneficial impact on FCC
yields. Additionally, CFHT lowers the .sulfur content of all other FCC products, including regenerator
SOX emissions. The major disadvantage of CFHT is the high cost, both capital and operating. In some
special cases, where the FCC feed quality is particularly poor and both diesel sulfur and regenerator SOX
emission reductions are anticipated, the improvement in FCC yields and alternate cost avoidance can justify
the higher costs associated with CFHT.
FCC Modifications The simplest FCC modification to reduce gasoline sulfur is to lower the end point of
the FCC gasoline. The FCC main product fractionator produces gasoline as an overhead product, with
LCO as a side draw product (sometimes a HCN sidedraw is taken between the gasoline and LCO). The
quality of fractionation is usually not high, hence, there can be a significant amount of benzothiophene and
even methylbenzothiophenes in the FCC gasoline. Adjusting the FCC gasoline end point (or increasing
reflux to improve fractionation) can reduce FCC gasoline sulfur content by up to 50%, with minimal loss of
gasoline to LCO. Other FCC operating conditipn changes have minimal impact on FCC gasoline sulfur
levels.
Gasoline sulfur reduction additives have been developed by some of the major FCC catalyst vendors. For
example Grace is offering their GSR additive, which is claimed to lower FCC gasoline sulfur by up to 25A
with no other effects on FCC operation (Wormsbecher 1993, AKZO 2000). In some situations, this might
be adequate for meeting the required sulfur levels. The use of ZSM-5 additive in the FCC does not lower
gasoline sulfur, but can change the olefin distribution so that other gasoline desulfurization methods are
more effective (Smith and Evans 1998).
FCC Gasoline Desulfurization By far, the most active area for new process development currently is in
the area of FCC gasoline sulfur removal technology. Removing sulfur from the FCC gasoline (rather than
the FCC feed) gives a much smaller, lower cost unit than treating the FCC feed. Furthermore, the critical
gasoline specification, sulfur, is being controlled at the end of the processing train. USEPA estimates that
over 100 new units will be built in the US over the next 8 years (USEPA 1999). The various technologies
for removing sulfur from FCC gasoline can be divided into two major classes: physical separations and
chemical reactions. By definition, the physical separation processes do not remove the sulfur atoms from
their parent sulfur containing molecules, instead, they concentrate these sulfur compounds in a smaller
stream that must then be treated. As will be discussed later, some of the chemical reaction based
technologies are based on the same principal, concentration of the sulfur into a smaller easier to treat
stream.
The most obvious technology for removing sulfur from FCC gasoline is a simple Hydrotreating unit. This
technology has been used extensive for removing sulfur from naphtha reformer feeds and more recently for
removing sulfur from heavy FCC gasoline (HeN).. These units are relatively low cost and long run times
have been obtained at reasonably low pressures and moderate reactor temperatures. The major
shortcoming of this technology for lighter FCC gasoline is that it also saturates the olefins and lowers the
octane of the gasoline by as much as 8 or 10 numbers (Nocca et a1. 1995).
Several improvements over conventional naphtha hydrotreating have been announced over the past several
years. These new technologies will be discussed below.
Optimal Hydrotreating conditions Both ExxonMobil (Greeley et a1. 1999) and IFP (Kasztelan et
a1.1999) currently offer fixed bed, FCC gasoline hydrotreating processes that are based on the concept of
optimizing process conditions and catalyst choice (Scanfining and Prime G, respectively). Kinetic studies
of naphtha hydrotreating have shown that.at typical conditions thiophene desulfurization and olefin
saturation have similar rate constants, however, olefin saturation has a higher activation energy. Lowering
the reaction temperature and pressure and increasing contact time will favor desulfurization over olefin
saturation. The lower operating temperature limit is set by the equilibrium between mercaptans and H
2
S
plus olefins. This limit can be circumvented using a multistage process with interstage H
2
S removal. The
equilibrium limit on the low temperature side and the increased olefin saturation and higher aging rates on
the high temperature side give a rather narrow operating window. Neither process can tolerate significant
amounts of benzothiophene in the feed. Benzothiophene is more difficult to desulfurize and essentially
complete olefin saturation is experienced at the conditions required to remove substantial amounts of
benzothiophene.
Although the Phillips S-Zorb process (Phillips 2000) is marketed as an adsorption process, it is really a
moving bed hydrotreating unit with optimized operating conditions and continuous catalyst regeneration.
The continuous catalyst regeneration, allows it to operate at lower pressure and hydrogen circulation rates
, (to minimize olefin saturation), without encountering the catalyst deactivation limitation of a fixed bed unit.
Furthermore, the catalyst contains a second component with high affinity for sulfur (the absorbent) to
reduce the H
2
S concentration in the reaction zone. This shifts the mercaptan/olefin equilibrium away from
the mercaptan. Although this process should be able to handle a higher level ofbenzothiophene (BT) in the
feed than the fixed bed units, increasing the level of BT in the feed will increase olefin saturation.
Hydrotreating with Octane Recovery Both ExxonMobil (Tryjankowski et a!. 1999) and UOP/lntevep
(Salazar et a1. 1999) offer processes (Octgain and ISAL, respectively) that use more conventional
hydrotreating conditions, but recover some or all of the octane by isomerizing and cracking the normal
paraffins that are formed from the olefins via hydrotreating. This octane recovery comes at the expense of
some loss in yield. The yield loss is a function of feed quality and target product octane. These processes
are especially suited for refineries that are octane constrained or would like to increase their octane
capabilities. Since the hydrotreating conditions are more severe, these processes can handle higher levels
ofbenzothiophene.
The ultimate process for hydrotreating with octane recovery is to severely hydrotreat the FCC gasoline and
then reform the hydrotreated product. This could be the lowest capital solution for a refinery that has
excess reforming capacity. The hydrotreated ICN is also an above average reformer feed, so this
processing combination can actually result in an increase in total gasoline production at constant pool
octane.
Extraction/ Adsorption GTC Technology Corporation (Gentry and Lee 2000) has recently announced a
technology for extracting the sulfur containing compounds from FCC gasoline. The process is similar to
those used to recover aromatics from reformate, so the aromatics in the FCC gasoline are also extracted
along with the sulfur compounds. This gives a much smaller stream that must be hydrotreated to ultimately
convert the sulfur compounds to H
2
S. Furthermore, the olefms in the FCC gasoline bypass the HDT unit,
eliminating the octane loss that results from their saturation. Favorable economics for this process are
dependent on obtaining high value for the recovered aromatics.
Black and Veach, Pritchard have also announced the IRVAD process (Irvin et a1. 1999). This is a moving
bed adsorption process that is claimed to use a circulating bed of solid adsorbent.to, removethe sulfur
containing molecules from the FCC gasoline. Continuous regeneration ofthe adsorbent produces a small
high sulfur stream that must be further treated.
Sulfur Concentation Processes As was discussed earlier, removal of the heaviest portion of the FCC
gasoline via Distillation can reduce the sulfur content of the remaining gasoline. Additionally, producing a
light cat naphtha via distillation, yields a stream that is high in oletins and contains essentially only
mercaptan type sulfur. The column must be designed and operated to keep thiophene in the bottoms.
Higher fractionation efficiency gives higher overhead yield. These mercaptans can easily be extracted
using caustic based extraction processes such as DOP's Merox or Merichem's extractive sweetening to
produce a sulfur free LCN with no yield or octane loss. Both of these extraction processes produce a small,
high sulfur reject stream that must be treated in another unit. Since most refiners currently sweeten their
FCC gasoline, the cost of conversion to an extractive sweetening unit is very low.
CDTech's CDHydro process combines distillation and sulfur removal into a single catalytic distillation
column (Rock et al. 1998). The catalyst pronlotes the reaction of mercaptans with diolefins, forming
heavier sulfur compounds that leave with the fractionator bottoms. The overhead is eS,sentially sulfur free.
Small amounts of hydrogen are also added to the column to saturate any remaining diolefins. Like the
conventional distillation column, conditions must be closely controlled to eliminate thiophene from the
overhead product. The bottoms product must be desulfurized using another technology. CDTech
advertises their CDHDS process for this service, however, any other desulfurization process will also work.
Another new process recently announced by BP/Amoco is called the OATS process (BP 2000). This is
essentially a thiophene alkylation process. A proprietary catalyst and process conditions are used to react
some of the olefins or diolefins with thiophene homologues. These are higher boiling anq can be
concentrated via distillation in the low olefin content heavy naphtha. There is no mention in literature
about what happens to the mercaptans and sulfides in the light gasoline.
Comparative Economics
There are two major components to the cost of lowering gasoline sulfur content, fixed costs and variable
operating costs. The fixed costs, which include capital recovery, depreciation, taxes, insurance, manpower,
etc. are determined by the type and size of unit that is built. Once the decision is made on the type and size
of unit, these costs will remain unchanged until the unit.is modified in some way. Even if the unit is not
operating. Variable operating costs include utilities, catalysts and chemicals, yield and quality changes, etc.
and are related to the actual amount of feed processed by the unit.
The US EPA has estimated and reported the average cost for the US of producing 30 ppm sulfur gasoline at
1.7 cent per gallon (USEPA This cost is based on a blend of proven and unproven technologies with
operating costs accounting for over 75% of the total cost. Several other studies, summarized in the EPA
report, estimate the cost at 2.4-5.7 cents per gallon. These cost differences are due to differences in
technology choice, capital cost estimate and the rate of return assumed for the capital employed. EPA
assumed a 7% rate of return, before taxes. The average capital investment per refinery was $44 million.
Furthermore, operating costs are dominated by energy cost, ie utilities, hydrogen and yield or octane loss.
Energy costs have increased significantly since the report issued.
Some of the new technologies might have hidden costs that have not yet been revealed by long term
operation, while other costs might be loeer than current estimates. California has demonstrated that
sustained production of low sulfur gasoline is feasible, but much greater attention to good operating
practices and process monitoring is required. Furthermore, unscheduled down time makes it much more
difficult to blend finished product.
Summary
Removing sulfur from gasoline is a worldwide problem. While there are several viable technologies for
accomplishing that objective, including some promising technologies that are not yet commercially
demonstrated, each refmery situation is different. At this time, there is no te.chnalogy for all
refiners. Sometimes a combination oftechnologies might provide the best solution. The optimal
technology or combination of technologies for each refinery is very much site specific.
References
AKZO-Nobel, Resolve Technology for FCC Gasoline Sulfur Reduction, www.akzonobel-catalysts.com
2000
BP/Amoco Press Release, BP Announces New Cleaner Gasoline Technology, November 16,2000
Danzinger, F., et al. Revamping OMV's FCC Pretreater to a MAKFining MPHC Hydrocracker for
Maximun Operational Flexibility and Profit, NPRA 1999 Annual Meeting
Gentry, J.C., Lee, F.M., Novel Process for FCC Gasoline Desulfurization and Benzene Reduction to Meet
Clean Fuels Requirements, NPRA 2000 Annual Meeting
Greeley, J.P., Zaczepinski, S., Selective Cat Naphtha Hydrofining with Minimal Octane Loss, NPRA 1999
Annual Meeting \
Irvin, Robert L., et aI., IRVAD Process-Low Cost Breakthrough for Low Sulfur Gasoline, NPRA 1999
Annual Meeting
Kasztelan, S., et aI., Improving Motor Fuel Quality, NPRA 1999 Annual Meeting
Nocca, J.-L., et aI., Sulfur and Olefin Management in the FCC Gasoline, NPRA 1995 Annual Meeting
Phillips Petroleum, S-Zorb Technology, www.fuelstechnology.com/szorbgas.htm
Rock, Kerry L., et al , Improvements in FCC Gasoline Desulfurization via Catalytic Distillation, NPRA
1998 Annual Meeting
Salazar, J.A., et al. The ISAL Process: A Refiner's Option to Meet RFG Specifications, NPRA 1998
Annual Meeting
Shorey, S.W., et aI., Exploiting Synergy between FCC and Feed Pretreating Units to Improve Refinery
Margins and Produce Low-Sulfur Fuels, NPRA 1999 Annual Meeting
Smith, G.A., Evans, M., Meeting Changing Gasoline Specifications and Variable Propylene and Butylene
Demand Through the Use of Additives, NPRA 1998 Annual Meeting
Tryjankowski, D.A., et aI., Mobil's Octgain Process: FCC Gasoline Desulfurization Reaches a New
Performance Level, NPRA 1999 Annual Meeting
United States Environmental Protection Agency, Regulatory Impact Analysis - Control of Air Pollution
from New Motor Vehicles: Tier 2 Motor Vehicles Emissions Standards and Gasoline Sulfur Control
Requirements, EPA420-R-99-023, www.epa.gov/otag/tr2home.htm1999
Wormsbecher, R.F., et aI., Emerging Technology for the Reduction of Sulfur in FCC Fuels, NPRA 1993
Annual Meeting