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1.0 INTRODUCTION Isomerization technologies can be used across a wide spectrum of refining applications.

According to Robinson and Hsu (2006), isomerization occurs has a side-reaction in all conversion processes, but in refining, “isomerization process” refers specifically to the onpurpose isomerization of n-butane, n-pentane, and n-hexane. There are two distinct processes of isomerization; butane isomerization and pentane/hexane isomerization (C5/C6). Butane isomerization found initial commercial application during the World War II for making highoctane aviation gasoline components and additional feed for alkylation units. Isomerization of C5 and C6 alkanes was commenced towards the end of World War II, to provide additional blending stock for aviation gasoline (Weitkamp, Kno¨zinger and Ertl, 1997). However, there was a decline in the demand of alkylate and this led to majority of the butane isomerization units shut down. In recent years, new isomerization units have been installed due to greater demand for high-octane motor fuel. The n-paraffin components of the lighter gasoline fraction especially butane (C4) to hexane (C6) have poor octane ratings. Isomerization is the conversion of these n-paraffins to their isomers that yield to high gasoline components of high octane rating. Isomerization process is carried out in the presence of a catalyst. This report would focus on C5/C6 isomerization giving a detailed Universal Oil Products (UOP) Penex process description. It would further discuss the important process variables and the impact on the process when these variables are changed. This report will also discuss the technical differences of two C5/C6 isomerization licensors and finally, discuss the important factors considered in selecting a catalyst for the process.

2.0 PENTANE/HEXANE ISOMERIZATION PROCESS In C5/C6 isomerization process, low octane straight-chained n-pentane is converted into a high octane iso-pentane while hexanes are converted into branched form with double side chains. According to Magee and Dolbear (1998), the C5/C6 refinery feed in isomerization units are more complex than the n-butane feed for isobutene production. This is because the C5/C6 feed contains some benzene and naphthenes (cycloalkane). Conversion is achieved in the presence of a catalyst. This catalyst could be a chlorinated-alumina based catalyst, a

There are diverse flow schemes used commercially for isomerization processes. which remove water to protect the catalyst. The stabilizer overhead vapours are caustic scrubbed for removal of HCl formed from organic chloride added to the reactor feed to maintain catalyst activity. The reactor operates at about 120oC-180oC. Isomerization process is reversible and slightly exothermic. The chlorinatedalumina based catalyst is used in this process. It is pre-treated before reaching the isomerization unit through hydrotreating processes to avoid catalyst poisoning. The dried feed is then mixed with the hydrogen and passed through a heat exchanger against the reactor effluent. These vessels are filled with molecular sieves. desired octane number. . It then enters a charge heater where it is heated to the reactor temperature before entering the reactors. and the available capital. After scrubbing. the overhead gas flows to the fuel gas system. The light naphtha feed and the hydrogen are charged to two different dryer vessels.zeolite based catalyst or a sulphated metal oxide based catalyst. The bottom product from the stabilizer is the isomerate and it is sent for gasoline blending. The choice of which to use depends mainly on the feed composition.1 UOP PENEX PROCESS DESCRIPTION The feed to the isomerization unit is light naphtha. CH3CH2CH2CH2CH3 n-Pentane CH3CH2CH(CH3)CH3 Isopentane 2. The reactor effluent is cooled and sent to the product stabilizer where separation takes place.

even at low temperatures.2 PROCESS VARIABLES Temperature The operating temperature is the most effective influence on the equilibrium of the process. Low temperature favours C5/C6 yield. If the temperature is increased undesired hydrocracking reactions would occur. complete conversions in one pass over catalyst is not possible (Magee and Dolbear 1998). If the feed is poisoned it would affect the overall product yield. Although. However. Pressure The system pressure considered in conjunction with the hydrogen flow rate to the reactor. However. Feed This is the most important process variable. drier chloride injection stabilizer . Chlorided-alumina catalyst is more active at higher pressures. the catalyst activity must be high to achieve meaningful conversion levels. 2004) 2.off-gas to scrubber Reflux drum hydrogen reactors drier feed isomerate Figure 1 UOP Penex process flow diagram (Tine. Pressure has very little or no effect on C5/C6 isomerization.

This high-activity catalyst allows low operating temperatures that favour better isomerisation yields. However. the Axen Ipsorb process uses a deisopentanizer upstream to separate isopentane distillate from the reaction. At lower LHSVs. it is resistant to water and sulphur in the feed. Hydrogen-to-Hydrocarbon Ratio (H2/HC) Operating at lower hydrogen to feed ratio can increase conversion. Both processes can use either one or two .Liquid Hourly Space Velocity (LHSV) LHSV is set during the design phase of any isomerization project and reflects the compromise between residence time and overall catalyst cost. As a result lower temperature operation is possible. Hexorb Isomalk 2 KBR Isomerization BP Isomerization UOP Penex uses a high activity chloride-promoted catalyst (Pt/chlorinated Al2О3). Table 1 C5/C6 isomerization licensors and their processes LICENSORS UOP Axens GTC Technology Kellogg Brown & Root BP PROCESSES Penex. The zeolite catalyst is not very active and therefore needs higher operating temperatures. However. an increase in hydrogen could prevent coke formation on the catalyst. Par-Isom Ipsorb. The process flow sheets for the two licensors are different. 2005). Table 1 shows some of these licensors. Unlike the UOP process. more catalyst is loaded resulting in a longer residence time. This enhances the n-pentane equilibrium conversion while reducing reactor throughput (Domergue and Watripont. Axens Ipsorb could either use a zeolite based catalyst or the high activity chloridepromoted catalyst depending on the feed.0 PROCESS LICENSORS COMPARISON There are various licensors for C5/C6 isomerization process. 3. resulting in higher product.

0-4. For instance.reactors. The catalyst in one reactor can be replaced while operation continues in the other. This is because only a small amount of hydrogen needs to be present to drive the reaction. In both processes. On the other hand. Mpa LHSV. the operating reactor temperature for the isomerization reactors for both processes is 120oC-180oC. both processes would operate at almost the same conditions. there no recycle gas compressor is needed. a fired heater is not required in the two processes. h -1 o UOP (PENEX) 120-180 3. Table 2 Comparison of UOP Penex and Axens Ipsorb (with a chlorinated-alumina based catalyst) PARAMETER Temperature.3-0. C Pressure.5 (0. Hence.0 1. the Axens Iposrb reactor product is sent to a molecular sieve separator. The reactor product for the UOP Penex process is sent to a stabilizer for separation. Figure 2 Ipsorb Process (Dormergue and Matthews 2001) If the catalyst used in the Ipsorb process is the chlorinated-alumina based catalyst. The two reactors are in series and are used to achieve high on-stream efficiency.5):1 Absent AXENS (IPSORB) 120-180 2 2 <1 Mole Ratio H2:CH Compressor Chlorine compound injection and caustic soda wash Feed drying Fire-heater (Yasakova and Sitdikova 2010) Is necessary Is necessary Absent .

the larger the surface area and thus.  Catalyst Size: The optimum size of the catalyst should be considered. To avoid this pressure drop. The cost of the catalyst for different suppliers should be compared. .0 ISOMERIZATION CATALYST SELECTION CRITERIA Selecting the right catalyst is very significant for a process. It is important to contact more than one catalyst supplier. Catalyst selection has a major impact on the plant efficiency. the plant rate and. UOP processes differ with the catalyst used for the process. The following factors can be used to select the right catalyst for an isomerization process. 4. The suppliers should recommend the catalyst to operate in this envelope because these factors may vary. Catalyst particle size influences the rate of isomerization.  Catalyst Vendor: The information on factors such as the feed. The smaller the particles. a porous catalyst should be used as the feed would pass through the pores. The catalyst supplier should be able to provide references of clients who have used the catalyst for a number of years with good results. the achievement of desired turnaround schedule.  Reliability: It is significant to know the catalyst is reliable. its temperature and pressure should be given to a minimum of two catalyst suppliers. The catalyst could be hired or paid for in instalments. However.The major difference between the Axens Ipsorb and Hexorb process is that the Ipsorb uses a deisopetanizer upstream while Hexorb uses a deisohexaniser downstream. if the catalyst is too small it could cause pressure drop in the vessel.  Cost: The cost of the isomerization catalyst is an important selection criteria. The catalyst supplier should be able to give a guarantee for the catalyst life. the activity per unit mass of the catalyst.

 Catalyst Recycle/Reprocess: It is important to know if the catalyst can be used after it has been deactivated. In addition to stability. Catalysts become deactivated with time on-stream. catalysts would be poisoned after some.  Supply/Delivery time/Availability: The supply time. . in most cases. It is significant to know if the vendor can supply the catalyst in short notice.  Catalyst Shape: The shape of the catalyst also affects the surface area. The catalyst must be selective to avoid unwanted side reactions. the catalyst should be delivered in such a way that loading it into the vessel would not be difficult. some isomerization catalysts can be regenerated but others cannot.  Performance: Long term stability of the catalyst is significant. activity and selectivity are also important performance factors. However. Furthermore.  Catalyst Strength: The catalyst has to be strong to avoid breakage when loading into the vessel. Also. If the catalyst is not strong enough it would break in the vessel and produce dust which would plug up vessel and other equipment downstream.  Catalyst Longevity: The catalyst should be able to last for a long time without completely losing its activity or stability. However. Even the regenerable catalysts gradually lose their initial properties and would have to be replaced. Activity of the catalyst is very important for isomerization process due to the low temperature operating condition. it is the easiest shape for the catalyst vendor to make and it is cheaper than other shapes. delivery time and availability of the catalyst has to be known. A spherical catalyst is the wrong shape to use in an isomerization process because it would hold the maximum volume per surface area. the strength of the catalyst should not decrease within a short period of time.  Poison Resistance: The catalyst should be able to withstand poisons without significant change in performance. The spent catalyst then has to find utilization instead of causing environmental problems.

UOP is the leader in licensing of isomerization technology. different equipment may be used by the process licensors to make their processes more efficient. Low temperature favours C5/C6 yield. However. 2010). selectivity and activity.0 CONCLUSION Light naphtha isomerization has become increasingly significant in helping refiners improve octane number and meet the production demands for reformatted gasoline. it is important to use a high activity catalyst. when a zeolite based catalyst is used feed drying is not required as the catalyst is resistant to water. Catalyst Handling: The risks involved in storing the catalyst should be understood before purchase. Process flow schemes for the isomerization process differ with respect to the catalyst used. Selecting the best catalyst for the process is significant. . 5. For example. Hence. more than 220 units in the world are operating by its technology currently (Yasakova and Sitdikova. The catalyst must have high stability.