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Reduce alkylate costs with solid-acid catalysts | Hydrocarbon Processing | October 2007

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Reduce alkylate costs with solid-acid catalysts

1 0.05.2 007 | Mukherjee, M., Exelus, Inc., Liv ingston, New Jersey ; Nehlsen, J., Exelus Inc., Liv ingston, New Jersey

New dev elopm ents in alky lation processes m itigate risk while reducing operating costs Key words:

T?he phase-out of methy l tertiary buty l ether (MTBE) leav es refiners searching for methods to keep octane and Reid v apor pressure (Rv p) of blended gasoline within specifications. The required inclusion of ethanol for reformulated gasoline blends has raised Rv p of summer gasoline. More alky late is needed to offset the octane losses while meeting v apor pressure requirements. Y et, the alky lation process has safety issues due to the liquid-acid cataly sts used to process alky late. New dev elopments in solid-acid cataly sts (SACs) remov e most safety concerns for this refining operation. Sev eral ex amples illustrate possible options for alky lation technologies to meet blending requirements of "cleaner" gasoline. Changes in gasoline pool. Ethanol is replacing MTBE as a blending stock in gasoline. Unfortunately , ethanol increases v apor pressure of blended gasoline. Alky late can be used to reduce the v apor pressure of ethanol-containing blends; it also replaces octane loss and v olume due to the remov al of MTBE from the gasoline pool. Result: In the US, alky late usage is ex pected to double ov er the nex t few y ears. Alky late is currently produced using either sulfuric acid or hy drofluoric acid (HF) as the cataly st. Both acids are dangerous and can lead to corrosioninduced accidents and impede firefighting efforts. Figs. 1 and 2 illustrate sev eral dangers associated with liquid-acid alky lation units. 1 ,2 HF is particularly dangerous due to its ability to form stable aerosols in an accidental release. HF is prone to corrode metallic equipment. Sulfuric acid is less dangerous, but its use still requires brick-lined v essels and it has high consumption rates. Storage of fresh and spent acid poses additional safety concerns. Sulfuric acid units also require costly refrigeration to maintain the proper reaction temperature.

Fig. 1

Accidents result from using liquid acids in alky lation processes. A ruptured sulfuric-acid tank killed an operator and spilled 99,000 gallons of acid. 1

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Fig. 2

In another accident, a corroded v alv e on an isostripper led to a fire at an HF alky lation unit. 2

SAC alky lation eliminates the hazards and costs associated with using and regenerating corrosiv e liquid acids. Key to the economic v iability of a SAC paraffin alky lation process is adequate cataly st stability . Unfortunately , most solid-acid technologies are significantly more ex pensiv e than liquid-acid sy stems and require complex reactor sy stems to compensate for short cataly st life. A new engineered SAC has demonstrated significantly higher stability ; thus enabling solid-acid alky lation as a competitiv e alternativ e to conv entional liquid-acid technologies. 3 Engineered SAC design. Liquid acids are well-defined chemical compounds with fix ed properties. Conv ersely , SACs hav e many properties that can be tuned. For many y ears, solid acids hav e promised safer and cleaner alky lation. Howev er, the short lifetimes of most solid acids inv olv e ex pensiv e processes with complex reactors and large cataly st inv entories; thus making SACs uncompetitiv e with liquid-acid technology . To compete with liquid acids, new SACs must be engineered for optimum performance, rather than selected from ex isting materials. Furthermore, these cataly sts should be designed to work with practical reactor designs to control final process costs. 4 SACs need a long serv ice life while still producing alky late with an octane rating higher than that achiev ed in liquid-acid sy stems. To achiev e these results, a new SAC has been engineered on multiple lev els as illustrated in Fig. 3. 5 The cataly st particle shape and size are controlled to prov ide the proper reaction env ironment by manipulating the rate of inter-phase and intra-pellet mass transport. Accordingly , the cataly st reduces constraints on reactor design, simplifies the process and lowers total costs. The cataly st pore structure has been optimized on both the macro- and microscale to enhance diffusion of large coke molecules out of the cataly st pores, thus reducing cataly st deactiv ation from pore blockage.

Fig. 3

The new engineered SAC sy stem promotes alky lation production and mitigates coke formation on the cataly st.

The strength and distribution of the activ e cataly st sites are tuned to promote alky lation ov er coke formation. The activ e sites are adjusted to facilitate the formation of 2,3,3- and 2,3,4-trimethy lpentaneboth compounds hav e octane ratings abov e 1 00. Cracking and isomerization to dimethy lhex anes (DMH) are minimized to maintain a high total alky late octane. By carefully tuning the cataly st properties at multiple lev els, all desired processing attributes can be achiev ed: long serv ice life, high product octane and simple process design. SAC perform ance. As discussed earlier, long cataly st serv ice under commercially relev ant process conditions are essential for the economic v iability of SAC alky lation processes.4 We hav e quantified the cataly st serv ice life using a stability parameter (SP), which is an intrinsic property of a cataly st that depends on the number and density of av ailable activ e sites and their resistance to deactiv ation. The effects of SP on operating costs and capital ex penses is shown in Fig. 4. The higher the SP v alue, the lower are the operating costs and capital ex penses. Essentially , a higher SP v alue indicates a more robust cataly st that relax es processing conditions, which allows using a less ex pensiv e process design. In relation to the sulfuric-acid alky lation process, a solidacid alky lation cataly st with an SP v alue of 0.002 or lower is not economical.

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Fig. 4

Operating and capital costs for v arious SP v alues.

To compete fav orably with liquid-acid cataly zed alky lation processes, solid-acid processes must hav e an SP > 0.002. Howev er, most SACs hav e SP v alues that are significantly lower (about 0.0005??0.001 ). This ex plains why solid-acid alky lation has been uneconomical as compared to liquid-acid sy stems. New engineered SACs must outperform conv entional solid acids to compete with liquid-acid sy stems. Fig. 5 compares the engineered cataly st to many different conv entional solid acids. All isoparaffin alky lation tests were conducted in the same reactor under identical feed composition, space v elocity , reactor pressures and particle sizes but ov er a range of temperatures since the modified zirconia and chlorinated alumina cataly sts work best at 20C?? 30C, while the zeolite cataly sts perform best around 7 0C??90C.

Fig. 5

Long cataly st serv ice life can be obtained when using an engineered SAC.

The new engineered cataly st sy stem ex hibits an SP > 0.004. It can achiev e a better operating performance ov er conv entional SACs and ev en reduce costs compared to sulfuric acid sy stems. The engineered SAC produces alky late with a high octane rating ov er a wide range of olefin feeds, operating temperatures (60C??90C), olefin space v elocities (0.1 to 0.5 1 /hr) and feed composition (I/O ratios from 1 0 to 1 5). As summarized in Table 1 , the process robustness minimizes feed pretreatment requirements. The octane v alues were computed using gas chromatograph product analy sis, and v erified with independent engine testing. 6 ?The cataly st's unique design allows processing a wide v ariety of feedstocks while maintaining high total product quality .

Alky lation with isobuty lene. Alky lation using isobuty lene has posed technical challenges for many y ears. Although HF units are capable of processing isobuty lene into high-quality alky late, sulfuric acid sy stems do not. Isobuty lene-containing feeds contribute to high acid consumption and as much as an eight-point drop in RON in conv entional sulfuric-acid alky lation sy stems. Ex cess isobuty lene supplies from the MTBE phase-out hav e caused some producers to switch to olefin dimerization or indirect alky lation (dimerization followed by hy drogenation). An alky lation process capable of handling isobuty lene-containing feeds offers considerable adv antages ov er these process options. Using isobuty lene can offer a 1 0- to 1 2-point MON adv antage ov er the dimerization product, and can double production capacity for a giv en amount of olefin. This leads to a tremendous gain in octane-barrels. Such an adv antage is particularly important to MTBE producers now facing declining demand and considering switching to another technology to utilize isobuty lene. The ability to directly alky late isobuty lene into a high-quality product has great potential. The engineered SACs hav e the capability to process feeds containing from 0% to 1 00% isobuty lene at temperatures of 7 0C??90C. As shown in Fig. 6, the resulting alky late maintains a high octane rating.

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Fig. 6

Alky late octane y ielded when reacting isobuty lene-containing feeds.

T he process. The new alky lation process using the engineered SAC is shown in Fig. 7 . Two multi-staged fix ed-bed reactors are used in the reaction section. One reactor is used for reaction while the other is being regenerated. The olefin stream is mix ed with isobutane returning from the distillation section and with the reactor effluent recirculation stream before being fed to the reactor. The alky lation reaction is mildly ex othermic. The robust cataly st is insensitiv e to small changes in temperature; the heat of reaction is remov ed by a heat-ex changer located on the recy cle loop outside the reactor. Table 2 summarizes ty pical process conditions for the SAC process.

Fig. 7

The SAC alky lation process uses two fix ed-bed reactorsone online and the second on regeneration.

Cataly st regeneration is done using a circulating loop of hy drogen/hy drocarbon mix ture at an elev ated temperature of 250C. The SAC does not require any neutralization or washing equipment to post-treat the alky late product. Corrosion-resistant materials are not required. This simple flow scheme results in low capital costs and the flex ible ability to retrofit ex isting plants. Alky lation cy cle lengths are designed for 1 2?24 hours to simplify reactor operation. After the alky lation cy cle, the reactor is taken off stream and the SAC is regenerated. During this time, the second reactor maintains the constant alky late production. Due to the small coke buildup on the cataly st surface, hy drogen consumption is kept to a minimum. Econom ic and env ironm ental benefits. The engineered SAC can also offer significant capital cost sav ings relativ e to liquid-acid unitsespecially sulfuric acid. The sav ings are from multiple sources. First is eliminating corrosiv e acid from the process. Remov ing the liquid acid eliminates the acid neutralization equipment, product washing v essels and storage tanks for fresh and spent acids. Equipment design is also simplified, thus eliminating the need for brick-lined v essels and proprietary contactors. Second is the change in process conditions. The SAC operates at 50C??1 00C, and the heat is supplied by the chemical reaction. Sulfuric-acid units require refrigeration and operate around 5C, which requires ex pensiv e compressors and refrigeration loops. Eliminating refrigeration also considerably lowers power costs. Table 3 summarizes capital ex penses, raw material consumptions and utility requirements.

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Differences in cataly st regeneration procedures y ield considerable sav ings, which may be considered either capital or operating costs. The SAC is regenerated in the reactor with hy drogen; thus, no waste is generated. Sulfuric acid requires a large regeneration plant that is either operated onsite (large capital cost) or by another party (large operating cost). Compared to other solid-acid technologies, engineered SACs can offer sav ings due to simplify ing operation and less processing equipment required. For ex ample, the engineered SAC requires only two reactors due to the long onstream cy cle time. Longer cy cle times enable complete regeneration of the off stream reactor, thus lowering equipment cost. The ability to perform a complete regeneration (at 250C) after each cy cle also reduces the precious-metal content of the cataly st to a fraction of that required by other SACs, which are ty pically reactiv ated at reaction temperatures of 25C??80C. The reduction in precious-metal content contributes capital sav ings of $50 million for a 1 0,000-bpsd plant and reduces the financial risk associated with large precious metal inv entories. Low cataly st stability hinders the total process design. Hav ing additional reactors or cy cling the solid cataly st in and out of the reactor are methods to artificially reduce the space v elocity . 8 ,9 Howev er, compensating for poor cataly st performance using these methods cannot ultimately result in better economics. Rather, additional capital costs v ia using more or complex v essels occurs, and higher operating costs result due to v ery high cataly st inv entories. Another important, but more abstract, sav ings is the reduced risk. SACs are inherently safer than liquid acids since they are noncorrosiv e. The transport, storage and use of sulfuric acid for alky lation hav e led to numerous accidents and fatalities. The presence of sulfuric acid is responsible for the direct risk of ex posure and complicates firefighting efforts. Spill control protocols and equipment must be in place when using sulfuric acid. HF is ev en more dangerous. A SAC eliminates these risks and the associated equipment, planning and liability . Process dem onstration. The engineered SAC performance was v alidated in a pilot unit designed to simulate a commercial reactor design. 1 0 The key to successful piloting is not simply using a large reactor or processing v ast amounts of feed. Rather, a well-designed pilot plant must achiev e the same behav ior as the commercial unit as represented by matching a number of key reaction and transport parameters. The pilot plant for this process was dev eloped to match the ex pected commercial conditions. Table 4 compares the critical scale-up parameters for the two reactors. From Table 4, the scaleup parameters are perfectly matched enabling a seamless scale-up from the pilot unit to the first commercial-scale plant. 1 1

The product octane and cataly st activ ity obtained ov er the pilot test is shown in Fig. 8. V ariations in octane resulted from altering process conditions including feed composition and olefin space v elocity . The octane v alues obtained are slightly lower than those reported in Table 1 because the test was done using an untreated MTBE raffinate feed that contained ov er 3,500 ppm of di-olefins, 7 00 ppm of ox y genates and 0.6 ppm of acetonitrile. Cataly st stability was confirmed by measuring the cataly st performance through multiple cy cles of alky lation and regeneration using hy drogen. Alky lation cy cles were ty pically 1 2 hours, followed by a two-hour regeneration cy cle. The onstream time reported here refers to the cumulativ e time for the alky lation cy cles only .

Fig. 8

The results of the pilot study indicate high octane product at v arious process conditions.

As ev ident from Fig. 8, there is no activ ity loss ov er repeated cy cles of alky lation/regeneration as measured by olefin conv ersion, product octane or alky late y ield. The product octane is significantly higher than that obtained with liquid-acid processes under similar operating conditions and feedstocks. Rev am p opportunities. The small-capital requirements of this process lead to numerous opportunities to replace older units: Liquid-acid alky lation units can be conv erted to SAC operations by replacing the reaction section with two fix ed beds. The separation train is retained. An added attraction of the SAC process is the ability to use some feedstocks without pretreatment. Cat-poly and olefin dimerization units are particularly well-suited for retrofit. The ex isting reactors can be used with only minor modifications. A deisobutanizer is added to the separation train. MTBE unit replacement. Alky lation is a v aluable addition to any MTBE facility by conv erting the unused n-butenes into additional high-v alue product. Howev er, MTBE is being phased out in certain countries, notably the US. Current isobuty lene producers can replace MTBE production with alky lation without sacrificing capacity . The SAC process is capable of directly alky lating isobutane with isobuty lene to produce high-octane alky late.

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Giv en the current push for eco-friendly processes to produce ultra-clean fuels, the engineered SAC technology can cov er the v oid in the gasoline market. HP Nom enclature = Cataly st effectiv eness factor kIn t = Intrinsic kinetic rate constant, 1 /s = Residence time, s d p = Particle diameter, m v = Superficial v elocity , m/s = Fluid v iscosity , kg/m/s

= Fluid density , kg/m 3 Cp = Fluid specific heat, J/kg/K k = Fluid thermal conductiv ity , W/m/K ks = Inter-phase mass transfer coefficient, m/s D = Fluid diffusiv ity , m 2 /s h = Fluid heat transfer coefficient, W/m 2 /K Dz = Ax ial dispersion, m 2 /s L = Reactor length, m LIT ERAT URE CIT ED
1 US Chemical Safety and Hazard Inv estigation Board, "Inv estigation Report: Refinery Incident, Motiv a Enterprises, LLC," Report No. 2001 -05-I-DE,

2002.
2 US Chemical Safety and Hazard Inv estigation Board, "Case Study : Oil Refinery Fire and Ex plosion," Report No. 2004-08-I-NM. 2005. 3 D'Aquino, R. and L. Mav ridis, "Solid-acid cataly sts shape up for alky lation," Chemical Engineering Progress, January 2007 , pp. 89. 4 Mukherjee, M. and J. Nehlsen, "Consider cataly st dev elopments for alky lation production," Hydrocarbon Processing, September 2006, pp. 8596. 5 Nehlsen, J., M. Mukherjee and R. Porcelli, "Apply an integrated approach to cataly tic process design," Chemical Engineering Progress, February

2007 , pp. 31 38.

6 Hutson, T. and R. Logan, "Estimate alky late y ield and quality ," Hydrocarbon Processing, September 1 97 5, pp. 1 07 1 1 0. 7 "Refining Processes 2002," Hydrocarbon Processing, Nov ember 2002, p. 86. 8 D'Amico, V ., et al., "Consider new methods to debottleneck clean alky late production," Hydrocarbon Processing, February 2006, pp. 657 0. 9 Meister, J. M., et al., "Optimize alky late production for clean fuels," Hydrocarbon Processing, May 2000, pp. 637 5. 1 0 Mukherjee, M., et al., "Scale-up strategy applied to solid-acid alky lation process," Oil & Gas Journal, No. 1 04, V ol. 26, 2006, pp. 4854. 1 1 Jackson, K., "HPIn Construction," Hydrocarbon Processing, March 2007 , p. 28.

T he authors Mitrajit Mukherjee is the founder and president of Ex elus. He has spent the better part of his 1 7 y ear career dev eloping v iable SAC solutions for isoparaffin alky lation processes. Prior to starting Ex elus, he held positions at Cataly tica and ABB Lummus Global. Mr. Mukherjee holds a BS degree in chemical engineering from the Indian Institute of Technology and an MS degree from Southern Illinois Univ ersity . He is a member of the American Chemical Society and the American Institute of Chemical Engineers. He can be reached by e-mail at mmukherjee@ex elusinc.com. Jam es Nehlsen is a senior research engineer at Ex elus specializing in the dev elopment of new cataly tic processes. He holds a PhD in chemical engineering from Princeton Univ ersity , where he dev eloped new desulfurization technologies. Dr. Nehlsen is also a New Jersey Science and Technology Fellow. He has authored or co-authored sev en technical publications on desulfurization and fuel cell dy namics, and is a member of the American Chemical Society and the American Institute of Chemical Engineers. He can be reached by e-mail at jpnehlsen@ex elusinc.com.

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