HR 500 series with ACE technology

Axens advanced catalytic engineering (ACE) technology has been applied to the manufacture of a new series of hydrotreating catalytic materials the HR 500 series of CoMo, CoMo-Ni, NiMo and hydrocracking pretreatment catalysts. Comprehensive adsorption modeling studies coupled with detailed feedstock and effluent analyses have led to the adaptation of manufacturing facilities to enable sub-micron level control in hydrotreating catalyst production. The ACE concept has afforded a new class of dual-activity products with significantly enhanced desulfurization activity and, as a bonus, enhanced denitrogenation activity. Axens HR 500 series catalysts, with ACE technology, exhibit a powerful attraction for organosulfur compounds. Used in combination with EquiFlow reactor internals and Catapac dense-loading technology, HR 500 series catalysts provide strong performance improvements for long-lasting, ultra-low-sulfur diesel (ULSD) production and vacuum gasoil (VGO) hydrotreatment.

Our advanced catalytic engineering has powerful attraction

Axens Procatalyse Catalysts & Adsorbents 89 bd Franklin Roosevelt BP 50802 92508 Rueil-Malmaison, France Tel: +33 1 47 14 21 00 Fax: +33 1 47 51 87 95

Axens North America, Inc. Procatalyse Catalysts & Adsorbents 1800 St James Place, Suite 500 Houston, Texas 77056-4199, USA Tel: +1 713 840 1133 Fax: +1 713 840 8375

www.axens.net

HR 500 series catalysts

Advanced catalytic engineering (ACE) technology

Dual-activity hydrotreating catalysts

Dual-activity

HR 500 series Effluent sulfur content, ppm 50 40 30 20 10 0

7

Previous series

Stepping up HDS activity

ACE technology provides a major step-up in hydrodesulfurization (HDS) activity that enables the attainment of ULSD diesel specifications, whether they are less than 50-, 15- or 10-ppm product sulfur objectives. Catalyst evaluations have been carried out at 7-ppm product diesel specification and below, i.e., ULSD7, to ensure compliance with the most severe constraints. In many cases, revamping from current sulfur targets to ULSD7 can be achieved through the addition of supplementary catalyst volume to current operations with equipment revamping. The HDS activity gain with ACE technology is indicated in Figure 1. Compared with previous-generation catalysts, the operating temperature reduction for diesel desulfurization, as a function of product sulfur, improves substantially. The maximum activity gains are obtained at the lowest product sulfur specifications. The tougher the job, the better the HR 500 series performs.

known to inhibit the adsorption of sulfur compounds, thereby reducing HDS activity. The superior HDN activity offered by these engineered materials provides an added boost in HDS activity by liberating active sites. A schematic representation of the dual-activity function is shown in Figure 2. The elimination of nitrogen-containing inhibitors becomes particularly important for ULSD applications where the objective is to eliminate trace amounts of sulfur. Nitrogen inhibition is an important consideration at low sulfur target levels because the nitrogen content can be substantially higher than the sulfur content. The dual-activity function of the ACE series provides an added, indirect boost in HDS activity by freeing the sites needed to remove unwanted sulfur species.

WABT

Figure 1: HR 500 catalysts step up HDS activity. The gain in relative volume activity is indicated.

ACE

Boost in HDS activity

Boost in HDN activity

Figure 2: The dual activity of ACE technology.

Material engineering on the small scale

Mixed sites involving at least one Mo atom in close proximity to one promoter atom (Co or Ni) are required to generate the synergy effects needed to reach high HDS turnover frequencies. Engineering the shape of the mixed crystallites has produced new materials that provide enhanced activity per volume. ACE technology has enabled the best utilization of each gram of molybdenum.

Dual activity boosts HDS

Not only does ACE technology directly boost the HDS activity of HR 500 series catalysts, it also simultaneously provides improved hydrodenitrogenation (HDN) activity. Organonitrogen compounds are

y hydrotreating catalysts

Modeling simulations at the atomic level have provided insights into the superior HDS activity of the ACE materials. The commercial catalysts contain crystallite shapes of active metals with sites that are particularly suited to the adsorption of organonitrogen species. An atomic representation of the two crystallite structures, with and without ACE-type active sites, is shown in Figure 3. The crystallite sizes shown are provided only for illustration and do not represent an accurate size comparison.

temperature (WABT) over time for the HR 526 catalyst (CoMo) and the previousgeneration product shows a major activity gain for HR 526 and retention of the same benchmark stability. Stability testing under various VGO service conditions, including VGO HDS, mild- and full-conversion hydrocracking pretreatment confirms the results obtained under ULSD7 operation. In all cases, ACE technology materials outperformed all the other catalysts tested on an activity per volume basis and in expected cycle length. Easy to use ACE catalysts can be loaded directly into commercial units without nitrogen blanketing. The mechanically tough HR 500 products rely on conventional sulfiding procedures and are readily regenerated for reuse. They require no special postregeneration chemical treatment. For most units, dense loading reactors with Catapac technology afford the maximum catalyst volume activity. In addition, EquiFlow reactor internals ensure optimized flow distribution for maximum catalyst effectiveness. The combination of HR 500 series catalysts, dense loading and EquiFlow internals can easily lead to a reduction in WABT of 10 to 20C for ULSD applications.

Strong, stable and simple

Cycle length HR 500 series catalysts have the key combination of high initial activity and low deactivation rate that enables them to achieve superior cycle lengths. Since cycle lengths are not just a matter of initial activity, the new series builds on the same manufacturing principles that provided high levels of stability to previous HR products. The results of a stability test performed over more than 1700 hours under ULSD7 conditions are shown in Figure 4. This test was based on a typical straight run/ cracked-stock feed mixture at moderate pressure. The effluent sulfur content was maintained at 7 ppm throughout the test. A comparison of the weighted average bed

Mo

Co (Ni)

Sulfur Conventional sites

ACE sites

Figure 3: An atomic representation of the two crystallite structures, with (top) and without (bottom) ACE-type active sites.

HR 426 WABT

New HR 526

300

1000 Time, hr

1700

Figure 4: Change in WABT over time for CoMo catalysts under ULSD operation.

Optimizing hydrotreating costs with ACE catalysts

In the catalyst replacement market, the outstanding HDS activity and dualactivity boost provided by the new HR 500 series ACE technology materials make it possible to operate at lower temperatures and obtain longer cycles for a given HDS performance and equivalent hydrogen requirements. Alternatively, it is typically possible to include additional, lower-cost refractory cracked stocks in the feed. For revamping and debottlenecking projects when additional reactor volume is required, the HR 500 products provide the activity necessary for employing smaller reactors, thereby saving on capital costs. For grassroots projects, ACE technology products make it possible to design units to operate at lower pressure. ULSD and conventional diesel applications HR 526 (CoMo) and HR 548 (NiMo) catalysts are ideal for diesel hydroprocessing objectives. In some cases, the association of both products is advantageous. The ACE family also includes the new HR 568 (CoMo-Ni) catalyst that exhibits impressive

performance on refractory feedstocks while limiting hydrogen consumption. This CoMo catalyst is provided with promoted hydrogenation activity through the addition of some nickel, which is advantageous for the treatment of refractory stocks. VGO applications The fourth ACE catalyst in the 500 series, HRK 558, is specifically developed for hydrocracking pretreatment applications. HRK 558 employs similar manufacturing principles to those that made the previous NiMo product so successful in HDN service. The porosity of HRK 558 is ideally suited for VGO feeds. The ACE sites provide ultra-high denitrogenation rates upstream of zeolite and amorphous hydrocracking catalysts. HRK 558 shows exceptional pre-conversion activity and also enables the production of outstanding quality lube oil bases from hydrocracked residue. For VGO applications where limited conversion objectives apply, as in mild hydrocracking, HR 548 is ideal for low-to-medium-severity feeds. For fluid catalytic cracking hydrotreaters with VGO-based feeds, HR 568 is well adapted for many applications, depending on the refractory nature of

the feedstock, sulfur objectives and hydrogen availability. Naphtha applications For mild service needs, such as kerosene/jet fuel hydrotreating and sweetening, naphtha reforming pretreaters, and second-stage pyrolysis gasoline desulfurization, HR 506 is the product of choice.

Advanced catalytic engineering has powerful attraction

When sulfur elimination is the critical objective, our hydrotreating technology toolbox has the competitive edge for cost-effective performance improvement. Axens supplies a complete set of benchmark sulfur-removal technologies:

ACE technology engineered materials: HR 506, HR 526, HR 548, HR 568 and HRK 558 ACT top-bed grading materials EquiFlow reactor internals Catapac dense-loading technology.