Gasoline Desulfurization: Douglas A. Nafis and Edward J. Houde

Source: HANDBOOK OF PETROLEUM REFINING PROCESSES
CHAPTER 11.6
GASOLINE DESULFURIZATION
Douglas A. Nafis and Edward J. Houde
UOP LLC Des Plaines, Illinois
INTRODUCTION
Both government and private industries are actively involved in the search for less polluting or nonpolluting alternatives to the conventional hydrocarbon-fueled internal combustion engine. Unfortunately, issues regarding the economics, infrastructure requirements, and consumer acceptance of these alternatives suggest that for the foreseeable future, automobiles will continue to rely on the internal combustion engine as their primary power source. To reduce automobile emission levels, governments have begun to implement fuel reformulation and emission limits. Automobile manufacturers, meanwhile, argue that current gasoline quality is inadequate for the advanced engine and catalytic converter designs required to meet the new emission standards, citing sulfur as the major deterrent to their ability to further reduce engine emissions. Governments have responded to these issues by legislating that refiners produce lowand ultralow-sulfur gasoline. A survey of U.S. refiners conducted in the mid-1990s indicated the average refinery gasoline pool contained approximately 350 wt ppm sulfur.1 By January 2005, U.S. tier II regulations will establish a maximum standard gasoline sulfur content of 30 wt ppma more than 90 percent reduction in gasoline sulfur content. Geographic phase-in has been provided for U.S. refiners located in PADD IV (Colorado, Idaho, Montana, and Utah) where, because of the large number of small refineries, 300 wt ppm sulfur gasoline will be allowed during 2004 to 2006, with an 80 wt ppm cap being implemented by 2006. As Fig. 11.6.1 indicates, although the timing may vary, other countries around the world are also imposing gasoline sulfur limits. In Europe, a 150 wt ppm gasoline sulfur specification has been enacted as an intermediate step prior to the implementation of a 50 wt ppm limit by 2005. Other European countries including the United Kingdom and Germany have introduced tax incentives for the production of 50 wt ppm sulfur gasoline, with Germany also intending to introduce incentives for 10 wt ppm sulfur gasoline in 2003. In addition, Japan will implement a 50 wt ppm gasoline sulfur specification in 2005, with the potential for a further reduction to 10 wt ppm by 2008. This legislation will require refiners to make numerous technical and economic decisions. For the decision process to be most effective, refiners must become familiar with the various methods for reducing gasoline sulfur content, the variety of gasoline desulfurization technologies that
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GASOLINE DESULFURIZATION 11.58

SULFUR COMPOUND EXTRACTION AND SWEETENING
1000 U.S. Gasoline Sulfur Content, wppm Europe 100 Japan Europe U.S. Japan
10
1 1999 2000 2001 2002 2003 2004 2005 2006 Year

FIGURE 11.6.1 Gasoline sulfur limits.
2007 2008 2009 2010
are available, and the often subtle differences between them. The first step in this process involves a review of the origins of the sulfur present in gasoline.
WHY FCC NAPHTHA?

Most refinery gasoline desulfurization strategies have focused on the FCC naphtha component of the refinery gasoline pool. As illustrated in Fig. 11.6.2, a survey of U.S. refiners conducted in the mid-1990s identified FCC naphtha as the largest single contributor of sulfur to the gasoline pool, accounting for more than 90 percent of the pools total sulfur content.1 This survey also provided insight into the magnitude of the effort that would be required to meet lower gasoline sulfur targets since, as indicated in Fig.11.6.3, FCC naphtha was shown to represent almost 40 percent of the typical refinery gasoline pool. For these reasons, any strategy for reducing gasoline sulfur content clearly must focus on desulfurizing the FCC naphtha component of the gasoline pool. An effective gasoline desulfurization strategy should begin with an examination of the general features of FCC naphtha. Table 11.6.1 provides a summary of the properties of several commercially produced FCC naphtha samples, representing a wide range of FCC feedstock quality and FCC operating severity. The FCC naphthas molecular structure, as represented by its GC-PIONA analysis, and the types and amounts of sulfur within FCC naphtha can vary significantly. Closer inspection of Table 11.6.1 indicates the sulfur distribution in FCC naphtha is also not uniform. Rather, as Fig. 11.6.4 illustrates, the majority of the sulfur is contained in the naphthas heavier fraction. In addition, the types of sulfur compounds and their distribution within the FCC naphtha vary with boiling range. The naphthas light fraction contains predominantly mercaptan-type sulfur, while the naphthas intermediate-range fraction contains primarily thiophenic-type sulfur and its heavy fraction contains mostly benzothiophenic-type sulfur compounds. Figure 11.6.5 also highlights another unique feature of FCC naphtha. The two major components that influence the naphthas octaneolefins and aromaticsare not evenly distributed. Rather, similar to sulfur, the naphthas aromatic components are concentrated
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FCC Naphtha 93% Coker Naphtha 3%
Other 4%
FIGURE 11.6.2 Sulfur sources in U.S. gasoline pool.
FCC Naphtha 39% Other 44%
Coker Naphtha <1% SR Naphtha 4%

FIGURE 11.6.3 U.S. gasoline pool composition.
Alkylate 13%
in its heavy fraction, while the lighter naphtha contains primarily olefinic compounds. As a result of the octane differences between these components, and their distribution within the FCC naphtha, the Road octane of the intermediate fraction of FCC naphtha typically is lower than that of either the naphthas light or heavy fractions.
REDUCING THE SULFUR CONTENT OF FCC NAPHTHA

Before new processing units are added, other options for reducing the sulfur content of the FCC naphtha should be considered. For example, FCC manufacturers have claimed the ability to reduce the sulfur content of FCC naphtha by 20 to 30 percent.2 These additives tend to reduce the amount of thiophenes and alkylthiophenes in the FCC naphtha,
GASOLINE DESULFURIZATION 11.60 TABLE 11.6.1

Properties of Commercial FCC Naphtha FCC gasoline sample A B 42.4 127 287 476 2.2 12.5 10.6 15.4 56.7 2.6 100.0 1 12 331 43 147 0 0 534 C 58.0 35 232 465 4.9 21.0 8.0 33.0 32.0 1.1 100.0 57 29 217 128 312 2 0 745 D 49.6 120 264 402 3.2 19.4 10.4 26.3 39.7 1.0 100.0 17 73 885 43 40 7 39 1104 E 57.6 28 219 475 7.0 31.1 9.5 19.3 31.2 1.9 100.0 29 51 468 223 654 3 0 1428 F 58.1 50 224 471 4.5 24.2 7.8 30.1 32.1 1.3 100.0 84 64 599 251 628 4 36 1666 G 54.3 41 253 477 3.5 21.8 6.5 30.3 34.4 3.5 100.0 30 71 701 463 1559 2 242 3068 H 53.6 55 230 484 5.5 17.4 7.6 28.5 38.9 2.1 100.0 257 61 3498 30 244 30 235 4355
API gravity Boiling range, D2887 IBP, F 50%, F EP, F PIONA types, wt % n-Paraffins iso-Paraffins Naphthenes Olefins Aromatics C12 nonaromatics
57.0 38 231 447 3.1 22.1 10.4 33.8 26.8 3.8 100.0
Sulfur types, wt ppm, D5623 Mercaptans 0 Thiophene 31 Subst. thiophenes 305 Benzothiophene 61 Subst. benzothiophenes 82 Sulfides, disulfides 2 Other sulfur 8 Total sulfur 489
while having little effect on the heavier benzothiophenes and alkylbenzothiophenes which are typically very stable at FCC operating conditions. Adjusting the FCC units operating severity or its catalyst activity can also affect the quality of the resulting FCC naphtha. As Fig. 11.6.6 illustrates, increased FCC operating severity alters the naphthas molecular distribution, converting more of the heavier olefins and producing an FCC naphtha with a lower overall olefin content. LPG production will increase at the higher operating severity, while the yields of gasoline, light cycle oil (LCO), and clarified oil will decline. Assuming the units gas concentration section can process the additional LPG, higher severity provides an attractive route to increased alkylate or poly gas production, offsetting MTBE removal and improving the gasolines driveability index. Finally, as a result of additional aromatic and iso-alkane production, the FCC naphtha octane will increase at the higher operating severity, although the sulfur content of the FCC naphtha will also increase as a result of increased LCO conversion. Reducing the endpoint of the FCC naphtha will also lower its sulfur content. For example, lowering the naphthas endpoint by 50F (from 430 to 380F) can reduce the sulfur content of an FCC naphtha by as much as 40 percent while also reducing its aromatic content by up to 25 percent. Unfortunately, this approach tends to have a negative impact on refinery economics since both the yield of gasoline and the octane of the gasoline decline, being replaced by increased production of lower-valued diesel (LCO) product. Generally, the levels of sulfur reduction that can be achieved by the above techniques will not be sufficient to meet the new, ultralow-sulfur gasoline specifications that are being legislated. Consequently, although these methods may play a role in a refiners overall sulfur reduction strategy, additional sulfur reduction techniques will typically also be required. Technology licensors have responded to this need by developing a wide range of
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100000 Wppm Sulfur in Overhead Fraction Benzothiophene S 10000 Mercaptan S C1Th C2Th C3Th C4+Th Thiophene S C1BzTh BzTh
1500 Cumulative Sulfur in Feed, wppm
1200
1000 C1SH C2SH
900
Th C3SH
100
600 Total S -> C4SH
10
300
50
100
150
200
250
300
350
400
0 450
Overhead Temperature, F
FIGURE 11.6.4 Sulfur in FCC naphtha.
92 91 90 Road Octane, (R+M)/2 89 88 87 86 85 84 83 82 100 150 200 250 300 350 400 Road Octane wt% Olefins wt% Aromatics
100 90 80 wt% by GC PIONA 70 60 50 40 30 20 10 0 450
50% pt. of Cut, F

FIGURE 11.6.5 FCC naphtha octane distribution.

12 Moderate - severity FCC operation Total Olefins = 30 wt-% (R+M)/2 = 86 10 Olefin Content, wt-% 8 6 4 2 0 C5
FIGURE 11.6.6
High - severity FCC operation Total Olefins = 24 wt-% (R+M)/2 = 89
C6
C7
C8 C9 Carbon Number
C10
C11+
Impact of FCC operating severity.
technologies designed to reduce the sulfur content of FCC naphtha. These processes fall within two broad general categories:

Those that remove sulfur from the FCC units feedstock (pretreating) Those that process the naphtha after it is produced in the FCC unit (posttreating)
FCC NAPHTHA PRETREATING

Pretreating the feed to an FCC unit, whether by hydrotreating or low-severity hydrocracking, has been shown to be an economical way to reduce the sulfur content of FCC naphtha.3 Pretreating also allows the refiner to benefit from increased gasoline and LPG yields, reduced coke make, and significantly lower SOx emissions from the FCC. Typical hydrotreating requirements for FCC pretreating and posttreating units are summarized in Table 11.6.2. The most obvious difference between these two approaches is the significantly larger hydrotreating capacity required for the pretreating option, since the entire feed to the FCC unit must be processed. Due to its higher operating severity, the pretreating unit also has significantly greater catalyst and hydrogen requirements. Higher pretreating severity, however, reduces the nitrogen contents of the FCCs naphtha and LCO products and makes them easier to hydrotreat. In addition, pretreating becomes even more attractive if the refiner can benefit from the incremental FCC capacity that becomes available as a result of conversion in the pretreating unit. The economics of FCC feed pretreating are often very attractive. Unfortunately, capital restrictions frequently limit the refiners ability to implement these projects. Instead, despite the fact that naphtha posttreating tends to reduce refining margins, refiners often choose the posttreating route since it offers the lowest-capital route to gasoline desulfurization.
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TABLE 11.6.2
Pretreating versus Posttreating Severity FCC feed pretreat FCC naphtha desulfurization 30,000 0.3 (Base) 50200 23
Feed rate, BPSD Reactor pressure H2 consumption, SCFB ISBL EEC, $ million
55,000 Base 600 170
FCC NAPHTHA POSTTREATING

Refiners early attempts at reducing gasoline sulfur levels focused on conventional naphtha hydrotreating units because they were very efficient at removing sulfur, particularly when processing less-olefinic feedstock such as straight-run naphtha. When these units were required to process olefinic feedstock such as coker and FCC naphtha, however, the typical hydrotreating catalysts and processing conditions that were used also promoted other reactions, including olefin saturation. Because olefins have higher octane than their paraffinic counterparts, this approach reduced the octane of the FCC naphtha. Because FCC naphtha represents such a large portion of a refinerys gasoline pool, it is also usually the refinerys largest octane-barrel contributor. Since both the olefinic and aromatic components of the FCC naphtha contribute to its octane, proper octane management involves preserving as much of the aromatic and olefinic components as possible. Fortunately, aromatic preservation during posttreating is generally not an issue since the processing conditions required for typical posttreating operations have little impact on the aromatic components. Olefin management, however, is a critical issue that must be considered. The actual octane reduction that can occur during hydrotreating is influenced by many factors, including the desired level of desulfurization, the types and amounts of olefins present in the FCC naphtha, and interactions between the naphthas various hydrocarbon components. As Figs. 11.6.7 and 11.6.8 indicate, the octane loss observed when saturating pure olefinic components can range from 5 to 70 RONC depending upon the olefins structure and its molecular weight. Octane loss is greater for normal olefins than for branched olefins, while heavier olefins lose more octane than lighter olefins and internal double bonds lose more octane than terminal ones. As Fig. 11.6.9 illustrates, the rate of olefin saturation also varies with molecular weight and structure, with heavier olefins being more reactive than lighter olefins and normal olefins being more reactive than iso- and cyclic olefins. In practice, however, the octane that a component can contribute to the gasoline blend can differ significantly from its pure component octane. Figure 11.6.10, which illustrates the effect of olefin saturation for a typical FBR FCC naphtha, indicates the naphthas Road octane declines approximately 0.2 to 0.5 (R M)/2 for each weight percent of olefins saturated. For this reason, conventional hydrotreating of this naphtha would typically not be acceptable since the octane loss from total olefin saturation would be excessive. Although the lighter olefins tend to lose less octane when hydrotreated, Fig. 11.6.5 indicates the olefin distribution within a typical FBR FCC naphtha is significantly weighted toward lighter olefins. Consequently, although the sulfur in the light FCC naphtha is primarily mercaptan sulfur, significant octane loss can occur if this fraction is hydrotreated. Fortunately, as Table 11.6.3 indicates, splitting FCC naphtha provides the opportunity to improve olefin management by exploiting the natural segregation of sulfur and olefinic components that occurs within the naphtha. Table 11.6.3 compares the economics of hydrotreating an FBR FCC naphtha to a flow scheme that involves fractionating the FBR naphtha, caustic-extracting the mercaptan-rich lighter fraction, and hydrotreating the less-olefinic heavy naphtha fraction. For the condi-

140 120 n-Olefins 100 1C5= 80 RONC 60 40 n-Paraffins 20 0 20 C2 1C8= t2C6= 1C6= t2C7= 1C7= t3C7= t3C8=
t2C8=
C3
C4
C5
C6
C7
C8
C9
Carbon Number
FIGURE 11.6.7 Octane loss from saturation of n-olefins.
120 iso-olefins 100 80 60 RONC 40 20 0 20 40 C4 iso-paraffins 2Mt3C7= 6Mt3C7= 2M1C6= 2Mt2C7= 3M1C6= 3MC5 5M1C6= 2M1C7= 2MC5 3EC5 6M1C = 7 3MC6 3EC6 2MC6 3MC7 2MC7 2Mt3C6= 2Mt2C6=
C5
C6
C7 Carbon Number
C8
C9
C10
FIGURE 11.6.8
Octane loss from saturation of iso-olefins.
11.65
1.0 C5 n-Olefins Olefin Product Olefin Feed Olefin Product Olefin Feed C6 n-Olefins 0.1 C7 n-Olefins C8 n-Olefins C9 n-Olefins 0.10 i-C6 = Product i-C6 = Feed
Relative olefin reactivities.
1.0 C5 iso-Olefins C6 iso-Olefins C7 iso-Olefins C8 iso-Olefins
0.1
0.01 0.01
1.00
0.01 0.01
C9 isoOlefins C10 iso-Olefins C11 iso-Olefins 1.00
0.10 i-C6 = Product i-C6 = Feed
FIGURE 11.6.9
90 88 86 84 Road Octane 82 80 78 0.5 Rd Loss/% Olefin 76 74 72 0

FIGURE 11.6.10
FBR FCC Naphtha Sulfur = 2265 ppm, wt-% Olefins = 26.3, Road Octane = 85.4, 10/50/90% = 115/250/393 F
0.2 Rd Loss/% Olefin
10
15
20
25
30
Wt-% Total Olefins (PIONA)

Octane loss during olefin saturation.
tions established in Table 11.6.3, splitting the naphtha into its light and heavy fractions resulted in a $0.36 per barrel improvement in posttreating economics. The improved economics were primarily due to the lower hydrogen demand and reduced octane loss that resulted from elimination of the light olefins from the hydrotreaters feed. This example highlights a key advantage that naphtha splitting provides when used in an integrated posttreating approach: the ability to separate olefin and sulfur types by their boiling ranges. This ability provides refiners with additional processing flexibility, enabling them to approach desulfurization and octane management from virtually the molecular level.

TABLE 11.6.3 No splitter
Economics of Naphtha Splitting Splitter
Capital $680/bbl Capital $700/bbl H2 200 SCFB H2 125 SCFB Octane loss 2.1 Octane loss 1.4 Economic advantage due to reduced H2 consumption and octane loss* $0.36/bbl
*Basis $0.25/octane bbl, $250/MSCF H2.
OLEFIN MANAGEMENT IN LIGHT FCC NAPHTHA PROCESSING

Removing mercaptans from light FCC naphtha without incurring an octane loss can be costeffectively achieved by several methods. These include caustic extraction and mercaptan sweetening technologies. The choice of technologies is influenced by many factors, including the amount and types of sulfur in the naphtha, feed stability (polymerization potential), product sulfur specifications, and existing equipment.
Caustic Extraction of Light FCC Naphtha In the preceding example, a caustic extraction unit was used to remove a significant portion of the extractable mercaptan sulfur from the light FCC naphtha. This is arguably the most common approach to mercaptan removal. The extraction of mercaptans from gasoline dates from the time when lead additives, such as TEL and TML, were used to improve gasoline octane. By reducing the gasoline components sulfur content, its susceptibility to lead additives increased and refiners were able to reduce the additive rate needed to achieve a given octane. Today, with the virtual elimination of lead additives, interest in caustic extraction technology has shifted to removal of the gasolines mercaptan sulfur to help meet tighter gasoline sulfur specifications. Predominant among the caustic extraction processes is UOPs Merox extraction technology.4 This technology is based on the ability of an organometallic catalyst to promote the oxidation of mercaptans to disulfides. The flow scheme of an extractive Merox unit, illustrated in Fig. 11.6.11, employs a single multistage vertical extraction column that utilizes proprietary high-efficiency, high-velocity extraction trays to achieve mercaptan extraction efficiencies approaching 100 percent when processing light mercaptans. The low-molecular-weight mercaptans are removed by contacting them with a regenerated caustic solution and a small amount of caustic-soluble reagent. Spent caustic is regenerated by oxidizing with air, which also converts the recovered mercaptans to disulfides. These disulfides can then be recovered by naphtha washing, producing an essentially mercaptanfree, doctor sweet naphtha for gasoline blending. The disulfide oil and wash naphtha stream is decanted and then sent for reprocessing. Because olefins are not saturated in the Merox unit, it is desirable to recover as many olefins as possible in the naphtha splitters light overhead fraction. Unfortunately, since mercaptan extraction efficiencies decline as the molecular weight and branching of the mercaptan increase, the amount of light FCC naphtha that can be processed in an extractive Merox unit will decline as the desired gasoline sulfur level decreases. Optimal olefin management involves maximizing the amount of nonextractable sulfur components, and
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Extracted Product
Extractor
Excess Air Air Disulfide
Feed Disulfide Separator
Oxidizer Recycle Caustic

FIGURE 11.6.11 UOP Merox process flow scheme.
therefore the amount of olefins, contained in the product from the Merox unit consistent with satisfying the required product sulfur content. This approach also minimizes the amount of olefins in the splitters heavy naphtha fraction. Because sulfur species exhibit varying degrees of nonideal behavior during fractionation, operational and experimental data play key roles in establishing the optimal endpoint of the light naphtha. A light naphtha endpoint of approximately 150F is usually considered adequate for recovering a light naphtha fraction that contains primarily mercaptan-type sulfur components, as well as some thiophenic sulfur.
Sweetening Light FCC Naphtha Sweetening technology may also be used to remove the mercaptans from light FCC naphtha. Unlike caustic extraction, sweetening reactions involve catalytic oxidation of two mercaptan sulfur components and the formation of a nonodorous disulfide sulfur compound. In a typical sweetening application, the disulfide compound would be allowed to remain in the gasoline. Although this would not actually reduce the naphthas sulfur content, it would produce a doctor sweet naphtha. As illustrated in Fig. 11.6.12, UOPs Sweetfrac technology can be used to reduce the sulfur content of light FCC naphtha by simply repositioning the Merox sweetening unit upstream of the naphtha splitter. This approach allows the disulfide compounds formed in the sweetening process, which have significantly higher boiling points than their respective mercaptan components, to be recovered in the splitters heavy naphtha fraction. Since these newly formed disulfides are easily hydrotreated, they are readily converted to H2S in the downstream hydroprocessing unit. Consequently, the light naphtha fraction recovered from the naphtha splitter will be essentially mercaptan-free and can be sent to gasoline blending without further treating. In addition, because mercaptan oxidation is not limited by mercaptan extraction efficiency or reentry sulfur concerns, sweetening the FCC naphtha upstream of the naphtha splitter enables the refiner to extend the light naphthas endpoint, recovering more olefins in the light naphtha fraction and further improving olefin management.

LCN
To Gasoline Blending
Naphtha Splitter FBR FCC Naphtha Merox Sweetening
HCN
To Downstream Processing
FIGURE 11.6.12
UOP Sweetfrac process flow scheme.
OLEFIN MANAGEMENT IN HEAVY FCC NAPHTHA PROCESSING

As discussed previously, naphtha splitting allows the bulk of the FCC naphthas sulfurcontaining species to be concentrated into a smaller stream. The resulting heavy naphtha, which contains significantly fewer olefins, can then be processed independently of the lighter naphtha. This approach also provides some control over the octane of the posttreated naphtha since hydrotreating only the heavy naphtha reduces the octane loss caused by light olefin saturation. Although several processing options are available to remove the mercaptan sulfur from light naphtha without saturating the naphthas olefinic components, the naphthas nonextractable thiophene component and the required degree of desulfurization frequently limit the amount of light naphtha that may be recovered. For these reasons, several technologies have been developed to selectively convert sulfur while minimizing olefin saturation.
Selective Hydrotreating of Heavy FCC Naphtha Predominant among the processes designed to reduce olefin saturation during hydrotreating are the selective hydrotreating technologies.5,6 These technologies reduce olefin saturation by adjusting the catalyst formulations, process configurations, and process conditions used in typical conventional hydrotreating units. In fact, early applications of these technologies used a single-stage process configuration very similar to that of a conventional hydrotreater. However, because olefin saturation reactions have a stronger pressure dependency than desulfurization reactions, lower pressures (200 to 400 lb/in2 gauge) and lower catalyst metals levels are used. Figure 11.6.13 illustrates the relationship between desulfurization and olefin saturation rates for both conventional and selective hydrotreating processes. Of particular interest is the shape of these curves which, rather than being linear, vary with desulfurization level. Consequently, because olefin saturation increases more quickly at the higher desulfurization levels, refiners are forced to tolerate increasingly higher octane losses at the more severe desulfurization levels required to satisfy ultralow-sulfur gasoline specifications. An additional concern of selective hydrotreating is the tendency to promote mercaptan recombination reactions that occur when H2S produced in the desulfurization reactions combines
11.69
100 Olefin Saturation, wt-% by GC-PIONA 90 80 70 60 50 40 30 20 10 0 75 80 85 90 95 100 Selective Hydrotreating Conventional Hydrotreating
Desulfurization, wt-% by XRF

FIGURE 11.6.13 Selective hydrotreating performance.
with unreacted olefins to form new, higher-molecular-weight mercaptans. Unfortunately, these recombined mercaptans contribute to the overall sulfur content of the hydrotreated product, since heavy mercaptans are not easily removed by caustic extraction. When hydroprocessing catalyst is present, mercaptan recombination reactions occur very fast and approach an equilibrium that increases with higher product olefin content and H2S partial pressure, and lower reactor outlet temperature. Since the primary goal of selective hydrotreating involves maximizing the products olefin content, once the unit is operating, the only factors that can appreciably alter the H2S partial pressure are the sulfur content of the feedstock and the required desulfurization level. Figure 11.6.14 shows the equilibrium recombination mercaptan levels that are formed at typical selective hydrotreating conditions for different FCC naphtha sulfur contents. As this figure illustrates, higher feedstock sulfur contents reduce the ability to achieve low recombination mercaptan levels at normal selective hydrotreating temperatures (500 to 650F). As a result, for certain combinations of feedstock quality and operating conditions it can be possible to produce recombination mercaptan levels that actually exceed the gasolines sulfur target, limiting the refiners ability to produce ultralow-sulfur product. Figure 11.6.14, however, also indicates that recombination mercaptan content can be reduced by increasing the reactor outlet temperature. Unfortunately, higher reactor outlet temperature increases olefin saturation, reduces product octane, and ultimately impacts processing flexibility by linking octane loss to recombination sulfur and olefin content. Regrettably, these higher temperatures also reduce operating cycles since, at higher temperatures, the same factors that favored improved olefin selectivity (reduced catalyst metals levels and lower operating pressure) also promote catalyst instability. For these reasons, selective hydrotreating operating conditions represent a compromise between olefin selectivity and acceptable catalyst life.

100 50 wppm Product Sulfur Mercaptan Sulfur in Product, wppm
10
10 wppm Product Sulfur
Feed Sulfur Content 500 wppm 1000 wppm 2000 wppm 3000 wppm 0 450
Basis: Product Olefins = 20 wt-% P = 250 psig, H2/HC = 1500 scfb 600 650 Reactor Temperature, F 700 750
500
550
FIGURE 11.6.14
Equilibrium recombination sulfur.
Second-Generation Selective Hydrotreating Processes Several approaches have been introduced to reduce the recombination mercaptan levels observed at the higher desulfurization levels required for ultralow-sulfur gasoline production. Some address the problem by adding a second selective hydrotreating stage, a liquid separator located between the two stages, and a recycle gas scrubber.7 The resulting second-generation two-stage configuration reduces H2S partial pressure at the second-stage reactor outlet by removing the H2S produced in the units first stage. Although this approach offers a slight improvement in desulfurization selectivity, since H2S inhibits desulfurization reactions more than olefin saturation reactions, the combined cost of the second reactor, separator, recycle gas scrubber, and additional heat integration required for the two-stage configuration can increase capital cost by 30 to 40 percent relative to a single-stage design. Rather than adding another desulfurization stage, another approach for achieving increased desulfurization rates at acceptable recombination mercaptan levels involves the addition of a caustic extraction step, utilizing an ethanol solutizer, to a single-stage selective hydrotreating flow scheme.8 Mercaptan removal rates of up to 90 percent have been reported, although the additional capital requirement is equivalent to 35 to 50 percent of the cost of the single-stage selective hydrotreater.
Reactive Distillation Still another approach for reducing the level of olefin saturation during hydrotreating involves reactive distillation, and the natural temperature gradient that exists within a catalytic distillation column, to promote selective hydrotreating reactions.9 In this approach, the lighter FCC naphtha is hydrotreated at the top of the reactive distillation column
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where the mildest (lowest-temperature) hydrotreating conditions exist. Because this material contains the more readily hydrotreated sulfur and a large portion of the naphthas olefins, these mild conditions reduce olefin saturation and octane loss. Conversely, the less olefinic heavy naphtha, which contains the more refractive sulfur compounds, is selectively hydrotreated at the progressively higher severities (higher temperatures) in the lower sections of the column. Similar to conventional hydrotreating, the required reactive distillation reaction temperatures are dependent upon such factors as the types of sulfur present, their relative desulfurization rates, and the desired product sulfur content. For mild hydrotreating applications, the capital requirement for reactive distillation is often less than that for alternative approaches since the column acts as both a naphtha splitter and a reactor. At the higher desulfurization levels required to produce ultralow-sulfur gasoline, however, more heat must be added to the reactive distillation column to promote the necessary desulfurization reactions. Since reaction temperature and column temperature are the same in this technology, these higher temperatures unfortunately increase olefin saturation and reduce the products octane. To circumvent excessive olefin saturation at higher desulfurization levels, an additional reactor must be added to the flow scheme when desulfurization levels greater than approximately 90 percent are required. Although other reactive distillation techniques such as recovery of intermediate product fractions and independent processing of these fractions have been suggested, these modifications will further increase the cost of the process.
Selective Hydroconversion Lower recombination sulfur levels can be achieved by reducing the concentration of either of the two reactants, olefins or H2S, required for the recombination reactions. In selective hydrotreating, this is achieved by adding a second reaction stage and a recycle gas scrubber to reduce H2S partial pressure. Another approach to lower recombination sulfur levels involves reducing the concentration of the olefinic reactant. Unfortunately, this approach can lead to significant octane loss since none of the reactions that are promoted by conventional hydrotreating catalysts will restore lost octane. Technologies have been developed to allow refiners to regain the octane lost from olefin saturation. The ISAL hydroconversion technology illustrated in Fig. 11.6.15 has been jointly developed by UOP and PDVSA-Intevep to simultaneously achieve desulfurization and octane control through the use of a fixed-bed, dual-catalyst system that operates within a single-stage process configuration very similar to that of a conventional hydrotreater. The dual-catalyst system saturates the feedstocks olefinic components, then regains lost octane by promoting octane-enhancing reactions. With this technology, the operating severity required to achieve a particular product octane depends upon several factors, including the feedstocks molecular structure and its olefin content. Similar to reforming, higher operating severity promotes increased product octane at the expense of additional conversion to light hydrocarbon, primarily LPG-range, product. This yield/octane relationship enables the units operation to be optimized to meet the refiners particular octane requirements. Recombination sulfur issues are eliminated with this technology since olefins are saturated in the process. Commercial operations have produced doctor sweet gasoline products with total sulfur contents of less than 5 wt ppm. Depending upon the required octane recovery, however, conversion to lighter products may not be acceptable. Consequently, it is preferable to fractionate the feed to remove light olefins, which both reduces operating severity and improves product yield.

FCC Naphtha Reactor Recycle Gas Compressor Quench Heater Wash Water Off Gas
Stabilizer Hydrogen Makeup Makeup Compressor

FIGURE 11.6.15 UOP/Intevep ISAL process flow scheme.
Sour Water
Low Sulfur Product
RECOVERING INTERMEDIATE-RANGE FCC NAPHTHA

Separating an FCC naphtha into its light and heavy fractions was previously shown to improve posttreating economics by reducing both octane loss and hydrogen consumption. In the context of a fully integrated refinery, naphtha splitting plays a critical role in the overall gasoline posttreating scheme since it provides the ability to separate olefin and sulfur types by their boiling ranges, enabling desulfurization, octane management, and recombination sulfur issues to be approached from virtually the molecular level. Unfortunately, the amount of light naphtha that can be recovered is often limited not by the splitters design, but rather by the amount of nonextractable sulfur present in the splitters feed. A review of the sulfur types present in FCC naphtha indicates the lightest sulfur component that is not extractable in caustic is thiophene. With a true boiling point of 183F, thiophene should boil within the range of the heavier, caustic-extractable C3 and C4 mercaptans (163 to 208F). Similarly, the next-heavier thiophenes, substituted C1 and C2 thiophenes, have boiling points ranging from approximately 235 to 300F, and should boil well outside the range of these heavier mercaptans. In reality, as Fig. 11.6.16 indicates, commercial FCC operations have shown that thiophene and lighter substituted thiophenes actually boil over a very wide range, beginning at temperatures as low as 40F below their true boiling points. This nonideal distillation behavior imposes two major restrictions on the refiner. First, since these thiophenic components can often account for up to 25 percent of the total sulfur in an FCC naphtha, it limits the amount of light naphtha that can be recovered for a given product sulfur level. Second, it limits the light naphthas endpoint, forcing more olefins into the heavy naphtha fraction. The splitters heavy naphtha fraction will contain primarily thiophenic- and benzothiophenic-type sulfur as well as a significant amount of olefins. Hydrotreating this fraction while preserving olefins is difficult due to the wide range of desulfurization rates that these sulfur species exhibit. As Fig. 11.6.17 illustrates, while the sulfur atom in a thiophene molecule is relatively easily hydrotreated, desulfurization rates decline as access to the sulfur atom decreases. The desulfurization rate of a sterically hindered substituted thiophene such
11.73 275 F
100 90
185 F
Total Olefins Thiopene Boiling Point 70 Wt-% Recovery 60 50 40 30 20 10 0 120 140 160 180 200 220 240 Thiophene Methyl-Thiopene Boiling Point CH3 CH3 1.00 80
Methyl-Thiophene
Overhead Cut Point, F

FIGURE 11.6.16 Fractionation of thiophenic sulfur.
1.0 2-Methylthiophene Sulfur Product Sulfur Feed S CH3 0.10 Thiophene CH3 S 3-Methylthiophene 0.01 0.01 0.10 Thiophene Product Thiophene Feed 1.00 Sulfur Product Sulfur Feed
1.0 2,5-Dimethylthiophene CH3 S CH3 0.10 Thiophene
0.01 0.01
S 3,4-Dimethylthiophene 0.10 Thiophene Product Thiophene Feed
FIGURE 11.6.17
HDS reactivities of thiophenic sulfur.
as 2-methyl thiophene, for example, can be as little as one-hundredth that of a substituted thiophene with a methyl group located farther from the sulfur atom. Similarly, although the desulfurization rate of benzothiophene is more than 1000 times higher than that of thiophene, some substituted benzothiophenes are actually harder to desulfurize than thiophene. Clearly, the amount and type of sulfur species in the heavy FCC naphtha will have a significant influence on its required hydrotreating severity and, consequently, on the amount of olefins saturated during the hydrotreating process. Again, a review of the boiling points of the various sulfur species present in FCC naphtha is helpful. While more easily hydrotreated thiophene boils toward the front end of the FCC naphtha, the more refractive substituted thiophenes (b.p. 235 to 290F) are con-

centrated in the naphthas mid-boiling range. Based on a typical FCC naphtha olefin distribution, it is logical to conclude that fractionating thiophene from the more refractive sulfur species would significantly reduce the olefin content of the heavy naphtha. Recovery of the naphthas thiophene component, which can easily be accomplished by the addition of a side draw stream to the naphtha splitter design, will cause fewer olefins to be saturated during the hydrotreating of the more refractive sulfur species and will result in less overall octane loss.
OLEFIN MANAGEMENT IN INTERMEDIATE FCC NAPHTHA PROCESSING

An understanding of the unique characteristics of thiophene and light substituted thiophenes has encouraged the development of several technologies specifically designed to desulfurize intermediate-range FCC naphtha. While the objective of each of these technologies involves preserving the olefins in the intermediate naphtha, the approaches the y use vary widely, ranging from selective hydrotreating to conversion or extraction of the thiophenic components.
Mid-Cut Selective Hydrotreating The nonlinear olefin and sulfur distributions of an FCC naphtha typically produce an intermediate FCC naphtha that contains much less sulfur than the heavy naphtha and fewer olefins than the light naphtha. Unfortunately, since this midrange naphtha will usually still contain an appreciable amount of olefins, conventional hydrotreating of this fraction can result in significant octane loss. Depending upon the sulfur content of the midrange naphtha fraction and the final gasoline sulfur specification, it may be possible to selectively hydrotreat this fraction while preserving a significant amount of its octane. In actual application, this midrange selecti ve hydrotreating operation might be implemented either as a stand-alone unit or, as illustrated in the split-feed (SF) ISAL processing configuration of Fig. 11.6.18, as part of the hydroprocessing unit treating the heavy naphtha fraction. Regardless of how it is imple-
LCN
Merox
FBR FCC Naphtha
SF-ISAL Unit MCN LowSeverity
To Gasoline Blending
HCN
HighSeverity
FIGURE 11.6.18 Application of SF-ISAL process.
11.75
mented, selective hydrotreating of the midrange fraction produces much less H2S, which reduces H2S partial pressure and minimizes recombination reactions. Thiophene Conversion Under the appropriate processing conditions, an acid-based catalyst can promote the reaction of thiophene with olefins to produce heavier, alkylated thiophenes.10 Because these heavier sulfur compounds boil beyond the range of typical gasoline, they can be separated from the midrange naphtha by fractionation, thus producing a gasoline product with a lower sulfur content. The higher-boiling-range sulfur compounds recovered in the fractionation can then be sent to the refinerys diesel pool or, if necessary, hydrotreated before blending to distillate. Although sulfur removal rates of more than 99 percent have been claimed with this approach, compounds other than thiophene may also be alkylated. The relative reaction rates for alkylation of benzene- and thiophene-based components are close enough that some loss of gasoline-range aromatics is inevitable. Kinetic calculations suggest that this could result in a potential yield shift from gasoline to distillate of up to 4 percent, which will result in the need for incremental distillate hydrotreating capacity. Consumption of some olefins also impacts the yield and octane of the gasoline product. Finally, the need to acid-wash the units feed to protect the solid acid catalyst from organic nitrogen compounds, combined with the catalysts general physical and chemical characteristics, magnifies the complexity, operability, and environmental impact of the process.
Thiophene Extraction Extraction methods that employ solvent such as tetramethylene sulfone (Sulfolane) to recover the aromatic components of reformed naphtha have been used in the petrochemical industry for decades. A comparison of the physical properties of thiophene and Sulfolane reveals they have similar molecular structures, but significantly different boiling points. By exploiting these characteristics, UOPs Sulfur-X solvent extraction technology provides the ability to extract sulfur from the midrange FCC naphtha and also separate the solvent from the recovered sulfur.11 As Fig. 11.6.19 illustrates, with this technology naphtha is introduced into a vertical extractor vessel where it flows upward, countercurrent to the incoming solvent. Thiophene, as well as mercaptans and light substituted thiophenes, selectively dissolves into the solvent, producing a low-sulfur, high-olefin extracted product for gasoline blending. A steamreboiled recovery column is used to separate solvent from the extracted sulfur and hydrocarbons. The recovered fresh solvent is recycled to the extractor, while the small hydrocarbon stream from the column, which contains the majority of the sulfur present in the original midrange naphtha, is recovered for downstream processing. Because this technology removes sulfur by physical separation, rather than by catalytic conversion, no hydrogen is consumed. Liquid yields are essentially 100 percent, and extraction rates of thiophene and the light substituted thiophenes exceed 95 percent. Table 11.6.4 provides a summary of the performance of the process when treating a 100 to 260F midrange FCC naphtha containing 400 wt ppm sulfur and 45 percent vol % olefins. As this table indicates, more than 98 percent of the sulfur can be removed from the midrange fraction while retaining more than 90 percent of the fractions olefinic components. This is superior to selective hydrotreating where typically one-third or more of the olefins would be saturated at a similar desulfurization level. In addition, since no H2S is produced in the extraction process, mercaptan recombination is not an issue.

Feed Surge Drum Feed
Vent Gas Raffinate Extractor Water Extract Receiver
Wash Column Recycle Solvent
Recovery Column
Water Stripper
FIGURE 11.6.19 UOP Sulfur-X process flow scheme.
TABLE 11.6.4
Performance of UOP Sulfur-X Unit Feed Raffinate 93.0 9 45 Extract 7.0 4900 45
Yield, vol % feed Sulfur, wt ppm Olefins, vol % Sulfur removal 98 wt % Olefin retention 90 vol %
100 400 45
INTEGRATED SOLUTIONS FOR GASOLINE DESULFURIZATION

Because history plays a key role in the learning process, valuable insight into the future direction of gasoline desulfurization can be gained by reviewing the development sequence of gasoline desulfurization technologies over the last few years. Initially, licensors regarded tighter gasoline sulfur regulations as an issue of simply determining the best catalyst, or the additional severity, needed for their existing process units. Once the limitations of that approach were fully realized, other techniques were proposed. In an attempt to reduce desulfurization costs, these techniques generally focused on single-technology solutions intended to process the entire FBR FCC naphtha. Unfortunately, as tighter gasoline sulfur regulations emerged, revisions to these singletechnology solutions were generally required. Some revisions were fairly minor, involving adjustments to catalyst formulations or operating conditions. Others were tolerable, requiring additional process equipment or the inclusion of pre- or postfractionation facilities. Still other revisions were major, including significant flow scheme revisions or the inclusion of other process units to treat their products. Interestingly, although feed fractionation was once considered a major impediment, it has now become a common feature of virtually every licensors gasoline desulfurization offering.
11.77
In recent years, another shift in the direction of gasoline desulfurization has occurred. This shift has evolved from deeper understanding of the unique characteristics of the components of FCC naphtha, the relationship between olefin structure and octane loss, and the wide differences in desulfurization reactivities between the naphthas various sulfur species. As a result, single-technology solutions are being replaced by gasoline desulfurization solutions that incorporate multiple technologies, with each technology being chosen based on the unique characteristics of the FCC naphtha. An example of a gasoline desulfurization solution that incorporates several of the posttreating technologies that have been discussed is illustrated in Fig. 11.6.20. Initially, fractionation of the treated naphtha allows the naphthas various olefin and sulfur components to be separated by boiling range. Then, depending upon the desired product quality, these fractions may be further processed or sent directly to the gasoline pool. If gasoline mercaptans are a concern, sweetening or caustic extraction of the light naphtha may be employed. If octane control is critical, the intermediate naphtha can be solvent-extracted to remove sulfur while minimizing olefin loss, with the extract from the solvent extraction unit being processed along with the low-olefin-content heavy naphtha for both desulfurization and octane control. While each of the technologies used in Fig. 11.6.20 provides its own distinct set of processing advantages, it is the combination of these technologies that maximizes their posttreating contributions. Ultimately, this multitechnology approach provides the ability to desulfurize FCC naphtha and to control product octane, while offering the potential to improve feedstock and product flexibility, increase on-stream efficiencies, reduce operating costs, and enhance product blending capabilities.
SUMMARY
Recent legislation regarding significant reductions in the sulfur content of gasoline has forced refiners and technology licensors to focus on ways to reduce the sulfur content of FCC naphtha. In some cases, this legislation may be satisfied with adjustments to conventional process units. More often, however, new technologies designed around the unique characteristics of FCC naphtha will be required. In those cases, the selection of the most appropriate gasoline desulfurization approach will be a complicated process, involving a wide range of issues.
LCN
Merox
FBR FCC Naphtha
MCN
Sulfur-X Extract
To Pool
HCN
FIGURE 11.6.20
ISAL
Integrated gasoline desulfurization solution.

For the selection process to be most effective, refiners will be required to become familiar with a variety of different technologies and the often subtle differences between them. The first step in the selection process will then involve determining whether adjustments to the operating severity, catalyst activity, or additive usage of the existing FCC unit will enable the new sulfur specification to be met. If posttreating of the FCC naphtha is necessary, a detailed review of the quality of the FCC naphtha, focusing specifically on the types and quantities of sulfur and olefin species present, must be conducted. This evaluation will identify the required degree of desulfurization and any specific fractionation requirements while allowing technologies that do not meet the refiners specific processing requirements, such as octane value and hydrogen availability, to be eliminated. The remaining technologies can then be evaluated based on their other characteristics, considering such factors as capital requirements, feedstock flexibility, and operating reliability. Ultimately, the refiner must be aware that no one technology will typically satisfy all these requirements. Instead, it is highly likely that some combination of technologies, possibly including both pre- and posttreating, may provide the best overall desulfurization solution.
REFERENCES
1. Final Report, 1996 American Petroleum Institute/National Petroleum Refiners Association, Survey of Refining Operations and Product Quality, July 1997. 2. J. A. Francis, C. W. Kuehler, J. A. Gonzalez, and A. P. Humphries, Catalytic Technology Helps Resolve the Gasoline Sulfur Problem, 21st JPI Refining Conference, Tokyo, Oct. 2223, 2002. 3. S. W. Shorey, D. A. Lomas, and W. H. Keesom, Exploiting Synergy between FCC and Feed Pretreating Units to Improve Refinery Margins and Produce Low-Sulfur Fuels, AM-99-55, NPRA Annual Meeting, San Antonio, Tex., Mar. 2123, 1999. 4. R. A. Meyers, Handbook of Petroleum Refining Processes, McGraw-Hill, 1986. 5. T. R. Halbert et al., Technology Options for Meeting Low Sulfur Mogas Targets, AM-00-11, NPRA Annual Meeting, San Antonio, Tex., Mar. 2628, 2000. 6. J. L. Nocca and Q. Debuisschert, Prime G : From Pilot to Startup of Worlds First Commercial 10 ppm FCC Gasoline, AM-02-12, NPRA Annual Meeting, San Antonio, Tex., Mar. 1719, 2002. 7. T. R. Talbert et al., Scanfining: A Commercially Proven Technology for Low Sulfur Gasoline, NPRA Annual Meeting, San Antonio, Tex., Mar. 1719, 2002. 8. ExomerSM Low Sulfur Gasoline Technology, Technical Information sheet from Merichem, www.merichem.com. 9. R. Gardner et al., Canadian Refinery Starts Up First-of-a-Kind Gasoline Desulfurization Unit, Oil Gas J., 5458 (June 18, 2001). 10. BP Announces New Cleaner Gasoline Technology, Press Release, Nov. 16, 2000. 11. L. Zhou et al., FCC Naphtha Desulfurization by Solvent Extraction, AIChE 2002 Spring Meeting, Mar. 1014, 2002.

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Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

GASOLINE DESULFURIZATION 11.58

1 1999 2000 2001 2002 2003 2004 2005 2006 Year

2007 2008 2009 2010

WHY FCC NAPHTHA?

FCC Naphtha 93% Coker Naphtha 3%

FCC Naphtha 39% Other 44%

Coker Naphtha <1% SR Naphtha 4%

REDUCING THE SULFUR CONTENT OF FCC NAPHTHA

GASOLINE DESULFURIZATION 11.60 TABLE 11.6.1

1500 Cumulative Sulfur in Feed, wppm

1000 C1SH C2SH

600 Total S -> C4SH

100 90 80 wt% by GC PIONA 70 60 50 40 30 20 10 0 450

50% pt. of Cut, F

GASOLINE DESULFURIZATION 11.62

High - severity FCC operation Total Olefins = 24 wt-% (R+M)/2 = 89

Impact of FCC operating severity.

FCC NAPHTHA PRETREATING

55,000 Base 600 170

FCC NAPHTHA POSTTREATING

GASOLINE DESULFURIZATION 11.64

Octane loss from saturation of iso-olefins.

1.0 C5 iso-Olefins C6 iso-Olefins C7 iso-Olefins C8 iso-Olefins

C9 isoOlefins C10 iso-Olefins C11 iso-Olefins 1.00

0.10 i-C6 = Product i-C6 = Feed

90 88 86 84 Road Octane 82 80 78 0.5 Rd Loss/% Olefin 76 74 72 0

0.2 Rd Loss/% Olefin

Wt-% Total Olefins (PIONA)

GASOLINE DESULFURIZATION 11.66

TABLE 11.6.3 No splitter

Economics of Naphtha Splitting Splitter

OLEFIN MANAGEMENT IN LIGHT FCC NAPHTHA PROCESSING

Excess Air Air Disulfide

Feed Disulfide Separator

Oxidizer Recycle Caustic

GASOLINE DESULFURIZATION 11.68

Naphtha Splitter FBR FCC Naphtha Merox Sweetening

UOP Sweetfrac process flow scheme.

OLEFIN MANAGEMENT IN HEAVY FCC NAPHTHA PROCESSING

Desulfurization, wt-% by XRF

GASOLINE DESULFURIZATION 11.70

100 50 wppm Product Sulfur Mercaptan Sulfur in Product, wppm

10 wppm Product Sulfur

Equilibrium recombination sulfur.

GASOLINE DESULFURIZATION 11.72

Stabilizer Hydrogen Makeup Makeup Compressor

Low Sulfur Product

RECOVERING INTERMEDIATE-RANGE FCC NAPHTHA

Overhead Cut Point, F

1.0 2,5-Dimethylthiophene CH3 S CH3 0.10 Thiophene

S 3,4-Dimethylthiophene 0.10 Thiophene Product Thiophene Feed

HDS reactivities of thiophenic sulfur.

GASOLINE DESULFURIZATION 11.74

OLEFIN MANAGEMENT IN INTERMEDIATE FCC NAPHTHA PROCESSING

FBR FCC Naphtha

SF-ISAL Unit MCN LowSeverity

FIGURE 11.6.18 Application of SF-ISAL process.