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Reforming & Isomerization Pretreatment

INTRODUCTION The latest generations of reforming and isomerization catalysts are sensitive to feed impurities, in particular sulfur and nitrogen compounds. Pretreatment of reforming or isomerization feeds is therefore required to reduce sulfur and nitrogen contents to levels typically around 0.1 - 0.5 wt ppm. Traditionally, the feeds to be processed have been straight-run naphthas (SRN) containing mainly sulfur as the feed contaminant; however, there is a growing trend to blend SRN with cracked materials origination from visbreakers, cokers or FCC units. Cracked feeds are characterized by much higher nitrogen contents and the presence of olefins, diolefins and, occasionally, silicon. Hydrotreating SRN and cracked feed blends requires different catalyst combinations compared to those used for SRN pretreatment alone. Our extensive hydrotreating catalyst portfolio enables us to offer the most suitable solution corresponding to each case. Catalysts were developed with technology used in the HR 500 catalyst series. The main features of these materials are: High desulfurization / denitrogenation activities Ultra high stability during commercial operations Excellent mechanical properties, i.e. perfectly designed for dense loading and catalyst regeneration operations SRN HYDROTREATMENT Straight run naphthas contain only sulfur as the main impurity; unsaturated components such as olefins and diolefins are normally not present and the nitrogen content is very low, typically below two ppm. For this case, the objective of the pretreatment unit is mainly sulfur removal. For SRN hydrotreatment, we recommend the latest generation, high desulfurization activity CoMo catalyst HR 516. CoMo catalysts are well known to have high desulfurization activities and HR 516 is
Balls '' 150 mm Balls ''

particularly well adapted for this type of service. HR 516 is a high surface area gamma alumina material with optimized pore structure. This high surface area affords superior active phase dispersion resulting in high activity. A typical reactor loading plan is shown below. Note the use of the grading materials ACT 069, ACT 078 and ACT 139 to enable the trapping of particulate matter and improve the resistance of the unit to pressure drop build up.
SR Naphtha 100 ppm < S < 5000 ppm typically

ACT 069 150 mm ACT 078 150 mm ACT 139 150 mm

HR 516

S < 0.5ppm typically

BLENDS OF SRN WITH CRACKED NAPHTHA FROM FCC, COKER OR VISBREAKER UNITS When cracked material is added to the reformer feed, the hydrotreating reactor loading configuration is

quite different. This is required to account for the presence of unsaturated components such as diolefins and olefins, and a significantly higher amount of nitrogen compounds. It is well established that nitrogen is significantly more difficult to remove than sulfur. For effective nitrogen removal, the catalyst must possess sufficient hydrogenation activity. Consequently, for sulfur and nitrogen removal from blends containing cracked material, HR 538 or HR 548 NiMo catalysts are recommended. These products are expressly designed for this type of service. As denitrification is the dominant duty for such different feeds, the higher hydrogenation activity of NiMo catalysts provides much higher denitrogenation activity on very refractory nitrogen compounds. MANAGEMENT OF UNSATURATED COMPONENTS In addition to denitrogenation requirements, diolefins and olefins in the feed must be hydrogenated. The HR 945 NiMo catalyst is ideally suited for this application due to its unique neutral carrier. The support ensures that the most reactive unsaturated components are hydrogenated with minimal risk of polymerization. Should the feed diolefin content be too high for direct treatment in the HDT section, a specific diene elimination reactor can be added. In this case, HR 945 is employed to saturate diolefins in the liquid phase under mild conditions. HR 945 greatly reduces the potential of pressure drop build-up that could result from the polymerization of unsaturates.

PRESSURE DROP MANAGEMENT Reactor cycle lengths are frequently shortened for reasons that do not have anything to do with catalyst performance. It often happens that a rapid increase in reactor pressure drop is the reason for ending a run. In order to avoid, or at least limit, the risk of inadvertent pressure drop problems during the cycle, we provide different grading materials for pressure drop management. These materials trap iron scale and other entrained solids thereby extending the zone of insoluble deposition at the top of the reactor bed. This avoids rapid crust formation from particulate matter carryover. Inert ceramic ACT 069 grading material, in the form of penta-rings, replace inert ceramic balls for more efficient hold-down power and higher void fraction. High porosity grading materials such as inert ACT 078 and ACT 139 are very effective for trapping fines and other entrained solids. A typical reactor loading plan is shown below.
SR + Cracked naphtha 100 ppm< S < 5000ppm typically 2 ppm < N < 100 ppm typically

ACT 069 ACT 078 ACT 108 ACT 139 HR 945

150 mm 150 mm 150 mm 250 mm

ACT 961

SILICA MANAGEMENT When processing coker naphtha, the end of run (EOR) is most often linked to the limited silicon adsorption capacity of the hydrotreating catalyst. Silicon breakthrough in the hydrotreating reactor will carry over to the downstream reforming and isomerization catalysts causing irreversible damage to these high performance products. Our ACT 961 (NiMo) is specifically designed for silicon trapping. With its optimized texture and porosity, ACT 961 has very high silicon retention, resulting in significantly longer cycle times.

HR 538

Balls '' 150 mm Balls ''


Mars08-RefIsomPretr

S < 0.5 ppm typically

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