Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 11.4

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

David Legg and Jason Gislason
ConocoPhillips Petroleum Company Bartlesville, Oklahoma

INTRODUCTION
The need for improving the environment has resulted in a continuing worldwide effort to produce cleaner-burning fuels. The reduction of sulfur in gasoline is considered to be a means for improving air quality because of the impact on performance of sulfur-sensitive items such as automotive catalytic converters. The presence of oxides of sulfur in automotive engine exhaust inhibits and may irreversibly poison noble metal catalysts in the converter. Emissions from an inefficient or poisoned converter contain levels of noncombusted, nonmethane hydrocarbons, oxides of nitrogen, and carbon monoxide. Such emissions are catalyzed by sunlight to form ground-level ozone, more commonly referred to as smog. As the concern over the impact of automotive air pollution continues, it is clear that further effort to reduce the sulfur level in automotive fuels will be required. Governments around the world are moving to mandate lower allowable sulfur levels in transportation fuels. In the United States, the U.S. Environmental Protection Agency has promulgated regulations that require refiners to achieve an average pool target of 30 ppm sulfur in gasoline with phase-in beginning in 2004. In Canada, refiners will have to lower sulfur levels in two steps: The first was to 150-ppm level by the year 2002, and then down to 30-ppm level by the year 2005. In Europe, gasoline sulfur levels are required to be below 50 ppm by 2005 and to less than 10 ppm between 2005 and 2008. In conjunction with the need to be able to produce low-sulfur-content gasoline, there is a need for a process that will not negatively impact the important properties of the gasoline. Any acceptable sulfur reduction process must have a minimal effect on the olefin content of the feed since saturation of olefins greatly affects the octane number (both research and motor octane number). Such adverse effect on the olefin content is generally due to the severe conditions normally employed, such as during hydrodesulfurization, to remove thiophenic compounds, which are some of the most difficult sulfur-containing compounds to remove from cracked gasoline. In addition, there is a need to avoid a system wherein the conditions are such that the aromatic content of the cracked gasoline is lost through satu11.43 Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE 11.44

SULFUR COMPOUND EXTRACTION AND SWEETENING

ration. ConocoPhillips Petroleum has developed such a process with its S Zorb sulfur removal technology (SRT), which is a commercialized, economically competitive process to remove sulfur from hydrocarbon streams.

TECHNOLOGY DEVELOPMENT
Affected as all other refiners by the new regulations, ConocoPhillips began searching early for the solution, but was unsatisfied with existing and developing technologies. During an intensive research and development effort initiated in early 1998, ConocoPhillips researchers, aided by extensive experience in the areas of sulfur chemistry, hydrotreating, olefin processes, and sorption, were successful in developing a superior process, S Zorb SRT. The S Zorb process can economically reduce the sulfur content of gasoline to ultralow levels with minimal octane loss, minimal hydrogen consumption, and near-zero volume loss. These results are obtained through the use of a novel sorbent that selectively removes sulfur from hydrocarbon molecules. In conjunction with the sorbent development, a reliable plant design was developed that allows continuous operation paralleling major refining units such as the fluidized catalytic cracker (FCC), thus reducing operation and maintenance costs. To develop and prove the new technology within the time frame mandated by upcoming regulations, ConocoPhillips decided to fast-track the design and construction of the first commercial S Zorb SRT unit at its Borger, Texas, refinery. Implementation of the S Zorb technology at the Borger refinery was conducted by an integrated group, which included research and development, process operations, maintenance, safety, environmental, and construction teams. Through the application of creative engineering approaches, a clear focus on schedule and deliverables, and full support of upper management, the technology was moved from conceptual flow sheet to a fully operational plant in less than 18 months. The vertical start-up (feed in to on-specification production within 72 hours) and high throughput of the S Zorb unit at the Borger refinery are testimony to the efficacy of the S Zorb sorbent and engineering design. Within 72 hours of unit start-up, product gasoline with only 10 ppm sulfur was produced, and within a week after start-up, the plant was processing full-range FCC naphtha at 110 percent of the design capacity. The plant continues to produce low-sulfur, full-range FCC naphtha with minimal octane loss exceeding the gasoline sulfur removal requirements for the Borger refinery (Fig. 11.4.1).

PROCESS
S Zorb SRT is not a modified hydrogenation technology. It uses a revolutionary new sorbent that operates in a fluidized-bed reactor (sorber), allowing optimal conditions to attain the required sulfur removal while minimizing undesired reactions and results. In the sorber, a stream of vaporized sulfur-containing feed and hydrogen is passed over the sorbent, yielding a low-sulfur product with little octane loss and no volume loss. The sorbent circulates between the sorber and a regeneration section with on-line regeneration, allowing for steadystate performance with very selective, deep sulfur removal and extended run lengths. The ConocoPhillips S Zorb process is a continuous operation, with the sorbent moving between three vessels in a pseudocontinuous process (Fig. 11.4.2). Sulfur is chemically removed from the gasoline stream in the sorber and stored on the sorbent. The effluent stream from the sorber is a low-sulfur gasoline blendstock with minimal octane loss, minimal hydrogen consumption, and little to no volume loss (Tables 11.4.1 and 11.4.2). The sorbent is removed from the sorber in a continuous process and regenerated in an oxygen-containing atmosphere to produce sulfur dioxide, a small amount of carbon dioxide, and a fresh sorbent.

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THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

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FIGURE 11.4.1 First S Zorb SRT Gasoline Commercial Unit in Borger, Texas.

The sulfur dioxide produced in this process can be separated from this regenerator effluent stream in a number of ways depending on the configuration of the refinery. The primary benefit of the absorptive process is the elimination of hydrogen sulfide from the reactor. The lack of hydrogen sulfide allows the S Zorb process to remove as much as 99 percent of the sulfur from a gasoline stream without the need for an additional reactor to remove mercaptans formed from olefin recombination. After oxidative regeneration, the sorbent is transferred to a small holding vessel, where it is reduced by using a hydrogen stream that can have as little as 50 percent purity. The S Zorb sorbent reduction is highly invariant to reduction temperature and pressure. Therefore, the reduction vessel is primarily treated as a surge vessel and requires minimal oversight by the operators. The S Zorb SRT process has many control parameters that allow for treating various streams and conditions by changing the operating conditions while controlling octane loss. A few of these parameters include adjustments in sorber temperature or pressure, sorbent circulation rate, and sorbent sulfur loading. One of the unique features of the S Zorb process is that selectivity toward sulfur removal increases with an increase in temperature, as shown in Fig. 11.4.3. The result of this increased selectivity is improved octane retention at a given product stream sulfur level. Octane protection and olefin conversion are closely related for gasoline. Because of the decoupling of the olefin loss from sulfur removal activity, S Zorb SRT produces much higher-octane gasoline for a given sulfur level than hydrotreating, as shown in Fig. 11.4.4. One key aspect to operation of the S Zorb unit is the ability to shut down the regeneration section of the unit for periods of time while the sorber continues to operate. This abil-

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THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

PRODUCT

LOCK HOPPER

REDUCER

TO SRU

SORBENT RECEIVE

REGENERATOR

SORBENT STORAGE

AIR

H2

FEED + H2

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FIGURE 11.4.2

The S Zorb process.

R e a c t o r

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

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TABLE 11.4.1 General Operating Conditions for the Gasoline S Zorb Process Reactor temperature Reactor pressure Space velocity Hydrogen purity 650775F (343413C) 100300 lb/in2 gauge (7.021.1 kg/cm2) 410 WHSV 50%

TABLE 11.4.2 Example Case Studies Showing the Performance of S Zorb SRT When Processing Full-Range FCC Naphthas Feed properties Unit capacity, BPD Sulfur, wt ppm Product properties Sulfur, wt ppm Volume yield RVP change (R M)/2 loss Utilities Chemical hydrogen consumption, ft3/bbl Fuel, Btu/bbl Electricity, kW/bbl Cooling water, gal/bbl Steam, MP, lb/bbl Nitrogen, ft3/bbl Economics Capital cost (ISBL) Operating cost* Case 1 35,000 300 10 99.9% None 0.3 Case 2 35,000 1500 10 99.9% None 1.0

25 33,000 0.8 115 12 4

70 33,000 1.1 115 12 16

U.S. $1100/bbl U.S. $1200/bbl 0.9 cents/gal 1.2 cents/gal

*Includes utilities, 4 percent per year maintenance and sorbent costs.

ity to isolate the regeneration section of the unit gives operators the flexibility to perform maintenance on the unit without interrupting the production of low-sulfur gasoline. As will be shown in the chemistry section, the S Zorb sorbent can be regenerated with no appreciable loss in sulfur removal activity or selectivity. Because of this unusual regenerative capacity, the sorber runs at start-of-run conditions, and there is no reason to remove sorbent from the unit to optimize unit activity, as done in other fluidized-bed processes, for example, in an FCC unit. The advantage of the sustained high activity is that the need for adding fresh sorbent is based only on losses due to attrition; therefore S Zorb SRT units are designed to minimize attrition. This is accomplished through minimization of lift velocities (which also explains the absence of any erosion issues), elimination of 90 bends in transfer lines, and specifically designed vessel internals. Due to these efforts and continuing improvements in sorbent characteristics, the attrition rate of the sorbent from the S Zorb SRT process is significantly lower than in other fluidized-bed processes, thereby reducing operating costs of the unit. The attrited fines produced from the unit are removed from the system between the regeneration and reduction steps in the process. At this point the fines produced are in the oxidative state and are essentially identical in composition to the fresh sorbent. The Environmental Protection Agency (EPA) has stated, The

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THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE 11.48

SULFUR COMPOUND EXTRACTION AND SWEETENING

120 100 80 60 40 20 0 Temperature

FIGURE 11.4.3 Temperature impact at constant conditions.

PPM Sulfur % Olefin Loss

Conventional fixed bed Selective HDS Olefin Conversion, % 100 80 60 40 20 0 80

FIGURE 11.4.4

Selective HDS S Zorb Selectivity

85

90 Sulfur Conversion, %

95

100

Olefin retention comparisons.

spent material does not appear to be characteristically hazardous or pyrophoric. Therefore, the EPA has ruled that the K171 regulations governing spent hydrotreating catalysts do not apply to the spent S Zorb sorbent. This ruling is very significant for the technology as it allows more options in the disposal of spent sorbent and a decrease in disposal costs of 98 percent, as it is considered a nonhazardous waste.

CHEMISTRY
For many years, sorbents that remove sulfur from streams have been reported in the literature. The S Zorb sorbent is unique in that the material does not just remove sulfur from hydrogen sulfidecontaining streams, but also reacts with sulfur-containing hydrocarbon compounds forming a nonsulfur containing hydrocarbon. The sulfur is stored on the sor-

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THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

THE S ZORB SULFUR REMOVAL TECHNOLOGY APPLIED TO GASOLINE

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bent for future removal from the system. The stored sulfur is released from the S Zorb sorbent as sulfur dioxide, when the sorbent is heated in the presence of oxygen. An S Zorb Unit is comprised of three fluidized-bed reaction vessels: the reducer, sorber, and regenerator (Fig. 11.4.2). Fresh makeup sorbent is loaded into the process and mixed with regenerated sorbent directly downstream of the regenerator. The oxidized sorbent, whether it has been previously loaded with sulfur or not, is transported to the reducer, where it is contacted and reacted with hydrogen gas, forming the active sorbent. The S Zorb process is unique in that the sorbent can be regenerated without a significant loss in activity or selectivity. After reduction, the sorbent is transferred to the sorber, where it is contacted with a mixed stream of hydrogen and vaporized sulfur-containing hydrocarbon molecules. Three reactions occur during this absorption step. First, the sulfur-containing hydrocarbon molecules undergo hydrogenolysis, cleaving the sulfur from the hydrocarbon molecule. Second, the cleaved sulfur is stored on the sorbent. Concurrently with the sulfur removal reactions, some of the unsaturated hydrocarbon molecules are hydrogenated to saturated hydrocarbon molecules. Unlike hydrotreating technologies, the hydrogenation of nonsulfur containing molecules by the S Zorb sorbent is minimal, which allows for the retention of the high road and motor octane numbers of the feed stream. CnH2n CnH2n
2

H2

sorbent CnH2n
2

sorbent sorbent

(11.4.1) (11.4.2) (11.4.3)

sorbent CnH2n

sulfur

Sorbent

sulfur sulfur-containing sorbent

After the sorbent is loaded with sulfur in the sorber, it is transported to the regenerator system. In the regenerator, the sulfur-loaded sorbent is contacted with an oxygen-containing stream. The regeneration process produces two reactions. The first reaction results in the burning of the sulfur-containing sorbent to a sulfur-free sorbent and sulfur dioxide. The second reaction burns any trace carbonaceous material to carbon dioxide, carbon monoxide, and water. Sulfur-containing sorbent C xH y O2 sulfur-free sorbent H 2O CO SO2 (11.4.4) (11.4.5)

O2 CO2

The sulfur dioxide formed during regeneration is removed from the sorber and transported to a sulfur recovery unit. The sorbent is then reactivated and reintroduced to the process. The S Zorb sorbent is significantly more insensitive to poisons than typical hydrotreating catalysts. This insensitivity is due to the S Zorb sorbent being composed of mostly active components and not inert support. A poisoning event, if it does occur, can be minimized with the ability to add fresh sorbent while continuing to run. This is a significant advantage over fixed-bed systems, which must be shut down to change out catalyst.

PROCESS ECONOMICS AND OPERATIONAL FLEXIBILITY

The production of low-sulfur gasoline is a requirement refineries must meet to continue operation; however, the technology solution for each refiner is based on maximizing the specific economics. These economics are influenced by the unique configuration of the overall refinery process, utility values, blending capabilities, feedstock availability, and market conditions. The chemical mechanisms of the sorbent and the flexibility of the process are what drive the associated economic benefits of S Zorb SRT over other available technologies.

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The retention of valuable stream properties due to the sorbtion mechanisms of the sorbent is a key economic advantage of S Zorb SRT. The selectivity of the process of removing sulfur with minimal saturation of olefins allows for the maximum in octane retention. Since the process does not result in cracking any of the feed hydrocarbons, vapor pressure is unchanged and the volume of blending product across the absorber is retained. The retention of the maximum amount of octane-barrels and not increasing vapor pressure are critical to the refiners gasoline blending economics. With less olefins saturated, the demand for chemical hydrogen is reduced, which is also highly valued by refiners and is quite often of limited supply. By reducing the amount of hydrogen required, operating costs are reduced and in cases where supply is extremely limited, capital costs of adding hydrogen production can also be avoided. Flexibility in the process is inherent in the basic design. The fluidized bed and continuous regeneration allow maximum run lengths, continuous start-of-run conditions, and recovery from poisons in the feed. They also allow the refiner feed and product flexibility to adjust to variances in feed composition and/or product target properties. When the unit is designed, it is sized for a particular feed volume and worst-case feed sulfur level. However, the ultimate sulfur removal achieved can be set at the discretion of the individual refiner, providing flexibility in handling feedstocks with different sulfur concentrations or other properties. It also gives the refiner the ability to adjust product sulfur levels, should economics or future regulations dictate that is necessary. As previously mentioned, since H2S is not produced in the S Zorb process, the problem of H2S recombination reactions is avoided. These recombination reactions can prevent other technologies from achieving low sulfur levels without the addition of H2S scrubbing equipment and an additional finishing reactor, both of which increase capital costs. This is one of the key features that allows the S Zorb process to economically produce the very low product sulfur levels needed to meet the clean fuel demands of today and beyond. Another significant advantage over existing desulfurization technologies is the ability of the S Zorb SRT process to match the run lengths of the fluidized catalytic cracker (FCC). The S Zorb SRT process operates in a similar manner to the FCC in that sorbent is continuously removed from the process. Therefore, the unit avoids the need to be shut down for turnarounds due to bed compaction, attrition, or fouling as seen in hydrotreating units. With a sulfur limit for produced gasoline and minimal inventory storage available at the refinery, it will be impossible to produce gasoline during downtime of the sulfur removal process. This is avoided with the S Zorb SRT process by allowing maintenance turnarounds to be coupled with scheduled shutdowns of the FCC unit. Therefore, the S Zorb SRT unit will not limit the ability of the refinery to produce on-specification gasoline.

CONCLUSION
With a multitude of sites licensed around the world in addition to the ConocoPhillips units in operation, design, or construction, the S Zorb SRT is a viable commercialized technology for the removal of sulfur from gasoline. Benefits realized by using the S Zorb SRT process relate to the basics of the technology. Sulfur is removed to ultralow levels with minimal effect on the process stream. A continuously regenerated fluidized bed, coupled with the ability to add fresh sorbent and remove fines during operation, allows for steadystate start-of-run conditions in the sorber for extended run lengths. Coking, hot spots, channeling, and permanent poisoning of catalystall extremely detrimental occurrences associated with traditional fixed-bed systemsare minimized. The high degree of selectivity during sulfur removal decreases hydrogen consumption, because the excessive amount of olefin saturation typical of other technologies does not take place. With this olefin retention and absence of cracking reactions, the ever more valuable octane-barrel is retained.
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