Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 11.5

CONOCOPHILLIPS S ZORB DIESEL PROCESS

Ed Sughrue and John S. Parsons
ConocoPhillips Fuels Technology Bartlesville, Oklahoma

INTRODUCTION
The S Zorb sulfur removal technology (SRT) diesel process removes sulfur from distillates to meet the new diesel fuel regulatory requirements around the world. Environmental concerns initiated the S Zorb concept over 20 years ago with sulfur removal from furnace exhaust. During the last several years, the S Zorb-Gasoline process for producing ultralowsulfur gasoline has been commercialized. Today ultralow-sulfur and zero-sulfur diesels are being mandated in order to allow auto manufacturers to meet the emissions standards. Advanced engine emission control technologies, in the forms of particulate matter (PM) traps and NOx adsorbers, are much less effective with high-sulfur fuel because of catalyst poisoning. To ease the impact of these regulations on the refining industry, ConocoPhillips has developed a unique and selective sulfur removal technology that applies to current onroad diesel blends and other higher-sulfur, distillate-range blendstocks. Key advantages offered by the S Zorb SRT diesel process are very low hydrogen consumption, high product yields ( 99.5 percent), and the preservation of the fuel properties such as lubricity.

CHEMISTRY
Sulfur removal in the S Zorb process is influenced by a number of feedstock properties such as boiling point range, nitrogen content, and most importantly the sulfur content. The amount of sulfur and its distribution among different organic molecules vary significantly between different types of diesel feedstocks. In Fig. 11.5.1, the concentration of sulfur is plotted against boiling point (in degrees Celsius) for diesel fuels and blendstocks from different sources. The vertical line on the plots is at 315C. Below this temperature, the sulfur molecules are primarily benzothiophenes, dibenzothiophenes, and methyldibenzothiophenes which have generally high removal rates. Above 315C the peaks represent the higher-boiling-point dimethyldibenzothiophenes which are the most difficult to remove sulfur compounds. The plot for straight-run diesels shows that two of the straight-run
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CONOCOPHILLIPS S ZORB DIESEL PROCESS 11.52

SULFUR COMPOUND EXTRACTION AND SWEETENING

10 Straight run diesels 8 Sulfur, ppm 6 4 2 0 100 10 Blended diesels 8 Sulfur, ppm 6 4 2 0 100 30 Light cycle oil Sulfur, ppm 20 10 0 100
FIGURE 11.5.1

200

Boiling point, C

300

400

200

Boiling point, C

300

400

200

Boiling point, C

300

400

Sulfur chromatograms of distillate-range hydrocarbons.

diesel feeds have very similar sulfur distributions with high concentrations of lower-boiling sulfur compounds, while the third diesel contains significant amounts of the higherboiling sulfur compounds. The third diesel is significantly more difficult to desulfurize. The blended diesels represent current on-road diesel fuels. The total sulfur concentration is lower, but previous hydroprocessing has removed all but the higher-boiling sulfur compounds. A similar sulfur distribution is seen in a light cycle oil, where the majority of the sulfur is again in the higher-boiling fraction even though this light cycle had not been previously hydrotreated. All the diesel feedstock with high concentrations of sulfur above the 315C line has been shown to require more severe process conditions to produce ultralowsulfur products. In S Zorb technology, sulfur removal occurs when the entire organic sulfur molecule sorbs onto the S Zorb particle surface in a mechanism similar to hydrodesulfurization. The sulfur atom is then separated from the remainder of the organic molecule, which is released into the bulk fluid. In standard hydrodesulfurization, the absorbed sulfur is reduced to form H2S gas. Also, there is significant hydrogenation of aromatic rings. In S Zorb, the sulfur atom remains bound to the sorbent as a metal sulfide. No H2S is observed in the product, and hydrogenation of aromatic rings is not significant. Consumption of hydrogen is minimal. The production of light hydrocarbons is also extremely low. This produces diesel-range product yields greater than 99.5 percent. The S Zorb chemistry gen-

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CONOCOPHILLIPS S ZORB DIESEL PROCESS

PHILLIPS S ZORB DIESEL PROCESS

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erates a product that has virtually the same properties as the feed. As shown in Table 11.5.1, even at very low product sulfur levels, there are no significant changes in specific gravity, distillation boiling curve, cetane number, cetane index, ASTM color, cloud point, and pour point. There is also virtually no impact on lubricity, unlike in traditionally hydrodesulfurized diesel products.

SORBENT
The S Zorb sorbent is composed of base metals commonly used in conventional refining catalysts. It contains no noble metals. The S Zorb sorbent has a significantly higher active site density than typical HDS catalysts. The higher active site density produces a material that has significantly higher sulfur removal rates and less sensitivity to poisons such as silica and chlorides. Both pilot-plant and commercial data indicate little or no loss in activity even after several hundred regeneration cycles. The sorbent particle size averages 50 to 60 m and is produced by a spray-drying process similar to the process used to manufacture catalytic cracking catalysts. These small, fluidizable particles have higher external surface areas than conventional 1 16-inch extrudate and exhibit no intraparticle transport limitations. Much effort in the sorbent development process has focused on the production of an attrition-resistant material, commercial manufacturability, and composition optimization. ConocoPhillips licenses certified catalyst vendors to manufacture and market the sorbent in commercial quantities.

PROCESS DESCRIPTION
The process scheme for the S Zorb SRT diesel process is similar to that for a low-pressure hydrodesulfurization process with the exception that a fluidized-bed reactor having continuous regeneration replaces the fixed-bed HDS reactor. Hydrocarbon is fed to a charge
TABLE 11.5.1 Feed and Product Properties of S Zorb-Treated Diesel Property Sulfur, wt ppm API gravity Hydrogen, wt % Cetane number Cetane index D86 distillation IBP 10 50 90 ASTM color Cloud point Pour point Lubricity SLBOCLE HFRR Feed 523 33.20 12.72 43.5 44.4 385F 440F 513F 604F 0.5 10.6F 13.5F 3700 385 Product 6 33.22 12.72 43.5 44.4 380F 438F 513F 603F 0.5 10.6F 13.5F 3600 315

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CONOCOPHILLIPS S ZORB DIESEL PROCESS 11.54

SULFUR COMPOUND EXTRACTION AND SWEETENING

pump and is then mixed with the recycle hydrogen stream containing a small amount of makeup hydrogen. After hydrogen addition, the combined stream is passed through a feedeffluent heat exchanger for vaporization and then to a fired heater to achieve the desired feed temperature. The vaporized feed is sent to the bottom of the reactor vessel containing a fluidized bed of the S Zorb sorbent. After passing through the sorbent bed, the hydrocarbon stream exits the top of the vessel through fines filters that remove any entrained sorbent. The desulfurized hydrocarbon product exits the reactor and proceeds through a series of heat recovery and cooling steps before entering the product separator for vapor/liquid separation. The vapor from the product separator is sent to the recycle compressor. Liquid from the product separator is passed through heat recovery and then fed to the stabilizer where light material, mainly hydrogen, is stripped out of the liquid product. The bottoms product from the stabilizer is cooled and sent to product blending. The regeneration system begins with sorbent from the reactor section draining through the reactor receiver and lock hopper system. It is then pneumatically transferred to the regenerator vessel. From there the sorbent passes through the regeneration process. Next, it drains through a regenerator receiver and lock hopper system to a reducer where hydrogen reactivates the promoter metals. Finally the sorbent is reintroduced to the reactor, completing the circuit. The regeneration section is designed to maintain sorbent integrity and to operate safely and efficiently in all situations. The oxygen content of the regeneration gas going to the regenerator is limited to control the temperature rise in the regenerator. The regeneration offgas consists primarily of nitrogen, carbon dioxide and sulfur dioxide. In most unit configurations, it is cleaned of SO2 and returned to the regenerator as diluent. The SO2 produced in the S Zorb process can be handled in several different ways. The most common include scrubbing, concentration for disposal, and elemental sulfur production. Scrubbing is performed in a traditional spray or packed tower. Caustic or ammonia can be circulated to react the SO2 out of the gas stream. The reaction products are then disposed of in the wastewater system, sent for off-site disposal or, in the case of ammonia, sold as a product. SO2 can be concentrated by using circulating solvent loops in a traditional contactor / regenerator configuration. The solvents are either complex buffer solutions or proprietary selective amines. The concentrated SO2 can then be sent to the refinery Claus unit, flue gas scrubber, or other appropriate location. Elemental sulfur can be produced at the unit by using a number of different process schemes that take advantage of the Claus reaction. Sorbent fines are generated through natural attrition. They are captured by filters in the regenerator offgas stream and exit the process in a harmless, oxidized state. The fines are collected in a vessel and stored for recycling or disposal. In a recent determination by the EPA, the material was found to not meet the Resource Conservation Recovery Act (RCRA) definition of K-171 classified waste. This allows for disposal that is dependent only on toxicity characteristics and local regulations versus being automatically classified as hazardous. Based on this analysis, the material is currently being handled as nonhazardous industrial waste with less liability and expense. A small amount of water from reduction is also produced from the process. It, along with any water from the feed, exits the process from the product separator or stabilizer overhead accumulator. This water is free of hydrogen sulfide but contains some ammonia and minor amounts of dissolved hydrocarbons. The S Zorb-Diesel process can be placed in the refinery in several different ways. A refinery that is currently producing all on-road, 500 wt ppm diesel could build a unit that treated the entire volume to ULSD quality. Another configuration is to treat a blend of 500 wt ppm on-road diesel and higher-sulfur off-road diesel. This would allow the refiner to increase the total volume of on-road quality diesel available for sale. Finally, a refiner could opt to treat any one of a number of diesel pool individual blend components. In combination with the first two cases, a refiner could consider decreasing the severity of upstream desulfurization units to save utilities and increase current unit cycle length as part of an overall optimization.

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CONOCOPHILLIPS S ZORB DIESEL PROCESS

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Operating Variables The unique nature of the ConocoPhillips S Zorb sulfur removal technology allows circumvention of several operating limitations that exist with conventional diesel hydrodesulfurization technologies. With continuous regeneration and a different sulfur removal mechanism, the S Zorb process can be operated at higher temperatures and more moderate pressures than conventional hydrotreaters. This allows the S Zorb process for distillates to operate at or near hydrogenation equilibrium conditions, which translates to minimal and, in many cases, zero net chemical hydrogen consumption. Typical operating conditions are Pressure Temperature WHSV 350500 lb/in2 gauge 725775F 16 per hour

In the fluid-bed process, the reactor operates at constant conditions with no need to raise temperature to compensate for a loss in catalyst activity. There are no start-of-run and endof-run operating conditions and yield differences. Unit shutdowns and turnarounds to replace sorbent are not needed. Instead, the reactor is operated at constant temperatures generally between 700 and 800F. Combining higher temperatures, smaller sorbent particles, and the sorbents higher active site density, sulfur removal rates are significantly higher than conventional hydrodesulfurization reaction rates. This allows the S Zorb process to operate at moderate pressures of 500 lb/in2 gauge or less and still produce very low product sulfur levels. The S Zorb sorbent is designed to minimize hydrogenation activity, however. The higher reaction temperatures and lower pressures also aid to limit hydrogenation of aromatic molecules. Figure 11.5.2 shows the chemical hydrogen consumption for a blended diesel containing 500 wt ppm sulfur. The chemical hydrogen consumption decreases with increasing temperature while sulfur levels are below 10 wt ppm over the entire temperature range. Over most of the temperature range, the chemical hydrogen consumption is actually negative (hydrogen is being produced). As the sorbent accumulates sulfur, its activity for sulfur removal decreases and regeneration is required to restore activity. For S Zorb, only 1 lb of sorbent is regenerated for every 40 to 200 lb of feed versus a catalytic cracker where 5 to 7 lb of catalyst is regenerated for every 1 lb of feed. The S Zorb regenerator is several orders of magnitude smaller than regenerators for catalytic cracking. The regeneration of the sorbent occurs in a separate vessel where temperatures are near 1000F. The metal sulfides are converted to metal oxides, and SO2 is released. The sorbent from the reactor usually contains a small amount of carbon which produces carbon dioxide. Before the sorbent is returned to the reactor, it spends a short time in a reducing atmosphere near 700F to reactivate the metals.

PROCESS ECONOMICS
Table 11.5.2 is a summary of the capital and operating cost requirements for the S Zorb Process. The utilities and unit cost are a function of both the total amount of sulfur in the feed and the types of sulfur compounds. Case B is a current on-road diesel with low-sulfur and moderately hard sulfur species. Case A is higher in sulfur with the full spectrum of sulfur species.

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CONOCOPHILLIPS S ZORB DIESEL PROCESS 11.56

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50 Hydrogen consumption, SCFB Hydrogen Consumption 0

20

15 Sulfur, ppm

50 Product Sulfur 100

10

150 675 700 725 750 Temperature, F

FIGURE 11.5.2

0 775 800 825

Chemical hydrogen consumption and product sulfur versus reactor temperature.

TABLE 11.5.2

S Zorb Process Requirements Case A Case B 40,000 500 6 3698 Tracing only 332 1870 109.6 1.44 19,085 30.60

Feed rate, BPD Feed sulfur, wt ppm Product sulfur, wt ppm Power, kWh Steam Nitrogen, million SCFD Cooling H2O, gal/min Fuel gas, million Btu/h Total hydrogen, million SCFD Sorbent makeup, lb/mo Erected equipment, million $

20,000 2600 6 2511 Tracing only 807 1835 46.5 1.24 9970 20.85

COMMERCIAL EXPERIENCE AND FUTURE PLANS

The commercial S Zorb gasoline unit in operation at the ConocoPhillips Borger, Texas, refinery has shown great flexibility for operation over a wide range of feedstock and process conditions. By operating this unit at up to 7500-BPSD feed rate and over 1400 wt ppm sulfur in feed, versus design conditions of 6000-BPSD feed rate and 1000 wt ppm sulfur, we have been able to evaluate and optimize S Zorb process operating conditions to reach sulfur levels under 15 wt ppm in the product with minimal octane loss and near-zero production of light gases. The mechanical design and operation of a diesel unit are very similar to those of the commercial gasoline unit. Since January 2002, a diesel pilot plant at the ConocoPhillips Bartlesville Technology Center in Bartlesville, Oklahoma, has been operating continuously. The pilot plant with a 2- to 4-BPD capacity contains all the major vessels that will be used in a commercial unit design.
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