Advanced recycle paraffin isomerisation technology

An examination of how combining chlorinated catalyst, molecular sieves and well designed process configurations can maximise the value of C5/C6 streams
Bruno Domergue Axens Russell Matthews Holborn Europa Raffinerie GmbH

ight naphtha isomerisation can significantly generally proposed, both having noteworthy boost octane in light gasoline fractions. It is competitive advantages. The choice is between particularly attractive when employed in the robustness of the zeolite and the high activity conjunction with processes whose objectives are of the chlorinated alumina-based catalyst. The to meet Euro 2005 benzene and sulphur limits more rugged but less active zeolite catalyst, in gasoline. Unfortunately, many of these IP632, can be employed if feed purity prevents mandated processes have the undesirable side use of chlorinated alumina catalyst. Nevertheless, effect of reducing octane. Further complicating the zeolite operates at higher temperatures and the refiners octane deficit is uncertainty about provides a significantly lower octane boost. future MTBE regulations, highlighting the need Chlorinated aluminas lower operating temperfor isomerisation processes that produce aromat- ature results in the highest octane, although its ics and sulphur-free product. higher sensitivity to feedstock impurities requires The first half of this article presents isomerisa- strict feed pretreatment to eliminate oxygention technologies from conventional once-through (including water) containing, nitrogen- and and deisohexaniser recycle to advanced schemes sulphur-containing compounds. involving separation processes. Cost-effective The IS 614A chlorinated alumina catalyst is debottlenecking opportunities applying the unique among the chlorinated in that it is regenIpsorb or Hexorb concepts to an existing isomer- erable. Should it be poi-soned during a plant isation unit, which can improve product RON by upset, a complete shutdown is avoided by using 4 to 6 points, are also discussed. a two-bed reactor system. The contaminated bed Following the overview of isomerisation tech- is simply taken offline, the catalyst removed, nologies, Holborn Europa Raffinerie (HER), describes an industrial Processing economics programme that includes isomerisation technology with deisohexaniser recycle Once- Deisohexaniser Ipsorb Hexorb to meet Euro 2000 and prepare for through recycle Isomerate RON 83 87.5 89 91.5 anticipated 2005 gasoline specificaIsomerate MON 80.5 85.5 86.5 89 tions. Project considerations that were Operating cost, million $/yr addressed from the initial concept (utilities-catalyst-adsorbants) 0.8 3.3 3.4 4.7 through start-up and the operating Product revenue, million $/yr ( octane-barrel feed/isomerate) 11.1 16.2 17.9 20.5 results obtained are covered.
ISBL investment cost. million$ 5.9 14.2 15.2 20.8

Isomerisation routes
Catalyst: the process base

Two types of isomerisation catalyst, zeolite and chlorinated alumina, are Table 1

Economics for four processing schemes 8000bpd 40:60 C5/C6 feed Chlorinated alumina catalyst

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feed adds 4.5 octane points to the once-through scheme. Although adding the deisohexaniser is simple in concept and increases the C6 isomer content, it does not provide for recycling normal pentane (61 RON) which enters the final isomerate product via the deisohexaniser distillate.

Advanced recycle technologies

Figure 1 Deisohexaniser application to recycle low octane value C6 components Molecular sieve separation

regenerated, reloaded, and put back online. This ensures years of continuous service. The isomerisation performance for four chlorinated alumina catalyst configurations discussed in this article is summarised in Table 1, based on processing a feed having a C5 to C6 ratio of 40:60. This ratio corresponds to a feed containing benzene precursors that are typically sent to isomerisation units in order to minimise benzene production in catalytic reforming units. Operating costs and production revenue are obtained from typical utilities, catalyst, adsorbent costs and octane-barrel values for the year 2000.

Conventional isomerisation
Once-through isomerisation

For minimum capital investment, a cost effective once-through scheme is available. Going beyond the 83 RON octane limitation (Table 1) the oncethrough scheme requires recycling the unconverted lower-octane paraffins to the isomerisation reactor. Adding a deisohexaniser downstream from the reaction section is a logical next step towards octane improvement. Isomerisation with deisohexaniser In Figure 1 (on previous page), the deisohexaniser separates the higher octane and more volatile C5s and di-methylbutanes (DMBs) as a distillate that is recombined with the bottom fraction to become the final isomerate product. A side-stream from the bottom half of the column, containing higher concentrations of lower octane methylpentanes (MPs) and unconverted n-hexane, is recycled to the reactor. A recycle flow equivalent to 65 per cent of the fresh

For full conversion of all normal paraffins, recycling normal paraffins to extinction is required to convert them entirely to branched isomers. This involves separating and recovering the normal paraffins from their isomers. An efficient separation path uses molecular sieve adsorption technology. Using molecular sieves to separate normal paraffins from their isomers, either in the vapour or liquid phase, is a proven industrial technique and has been applied to isomerisation processes. This separation method relies on the pore size of the molecular sieve to adsorb normal paraffins selectively, taking advantage of their smaller molecular diameter. The adsorption step is followed by a desorption step for a net recovery of the normal paraffins. These steps are carried out cyclically or pseudo-continuously and often rely on third fluids for the desorption and delivery steps. Hydrogen can be used in processes that are integrated with the isomerisation reaction. The more volatile butanes are used in liquid phase non-integrated processes. In the latter, the use of butanes for desorption calls for two debutanisers to recover the desorbing fluid from both the isomerate and the normal paraffin extract streams. This implies a rather high reboiling duty. When using recycle hydrogen to desorb the normal paraffins, the non-chlorinated less active zeolite isomerisation catalyst is required to avoid molecular sieve degradation. As such, it cannot attain the same RON performance as does the chlorinated alumina catalyst. For the highest octane isomerate, it is best to use a chlorinated alumina catalyst with a segregated molecular sieve normal paraffin separation section.

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Two patented separation processes are offered, Ipsorb and Hexorb, enabling attainment of 89 to 92 RON.
Ipsorb

With the Ipsorb process, shown in Figure 2, a cyclic vapourphase adsorption system follows the isomerate stabiliser to remove unconverted normal paraffins from the raw isomerate. Desorption of adsorbed normal paraffins takes place Figure 2 The Ipsorb process using an isopentane-rich vapour stream to recycle the normal paraffins to the upstream deisopentaniser column. Separating isopentane from the fresh feed reduces flow to the reaction section, thereby affording increased per-pass conversion of normal pentane to isopentane. The increased per-pass conversion in turn reduces the recycle of normal pentane for conversion to extinction. The net reaction section feed rate is a maximum of 10 per cent above the fresh feed rate for a chlorin- Figure 3 The Hexorb process ated alumina catalyst system. Adsorption/desorption cycles The molecular in Table 1 for deisohexaniser recycle and Ipsorb sieve sorption system uses rugged 5 molecular are very close, with a significant RON benefit for sieves designed to give a high dynamic adsorp- the latter (+1.5 points). The Ipsorb molecular tion capacity when operating under optimised sieve system enables product RON of up to 89 to pressure swing cycles. be obtained from a typical 40:60 C5/C6 feed. Deisopentaniser A low pressure, conventional In 1994, the first Ipsorb isomerisation unit was deisopentaniser column is required in the sepa- commissioned in Italy. ration scheme as an integral part of the Ipsorb process. One feature is that it is not necessary to Hexorb attain a very sharp separation in the column Ultimately, to go beyond the 90 RON threshold, because the isopentane-rich distillate is used as substantial conversion of the methylpentanes is a desorption stream for the molecular sieve required. This can be achieved with full conversection, where any n-pentane present is sion of normal paraffins by integrating the removed. Hexorb separation process with the reaction The distillate is combined with the molecular section. This patented process provides isomersieve effluent to make the final product, which ate having over 90 RON (typically 9191.5 RON) can tolerate a reasonable concentration of n- with a 40:60 C5/C6 feed. pentane (isomerate contains less than 1 per cent The Hexorb isomerisation process shown in n-pentane). Figure 3 combines a cyclic molecular sieve Note that investment and operating costs given adsorption system with a downstream deisohex-

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Debottlenecking: Ipsorb
Isomerate RON Operating cost, million$/yr (utilities-catalyst-adsorbents) Product revenue,million$/yr ( octane-barrel feed/isomerate) ISBL investment cost for revamp, million $ Existing once- through unit Base Base Base Revamped unit Ipsorb Base + 6 Base + 2.6 Base + 6.8 9.3

Debottlenecking of a once-through unit with Ipsorb 8000bpd of 40:60 C5/C6 feed with chlorinated alumina catalyst

Table 2 Debottlenecking: Hexorb

Isomerate RON Operating cost, million $/yr (utilities-catalyst-adsorbants) Product revenue, million $/yr ( octane-barrel feed/isomerate) ISBL investment cost for revamp, million $/yr Existing DIH recycle unit Base Base Base 6.6 Revamped unit Hexorb Base + 4 Base + 1.3 Base + 4.3

feeds that have been previously hydrogenated to eliminate benzene and that contain substantial quantities of C6 isomers or naphthenes, the isomerisation feed is first sent through the molecular sieve section together with the raw isomerate. In this manner, only the n-paraffin constituents and MP from the deisohexaniser are charged to the isomerisation reaction section. The per-pass conversion to branched paraffins is greatly enhanced by the absence of the latter in the feed. In this case, the molecular sieve adsorbent volumes will be higher than in configurations where the fresh feed is fed directly to the reactors because of the substantially higher amounts of nparaffins to be removed. On the other hand, molecular sieve is much less expensive than the isomerisation catalyst.

Debottlenecking studies
From once-through to Ipsorb

The Ipsorb scheme lends itself to debottlenecking once-through isomerisation Debottlenecking a DIH recycle unit with Hexorb 8000bpd 40:60 C5/C6 feed units (especially those with chlorinated with chlorinated alumina catalyst alumina) allowing six-point product Table 3 octane increases (up to 89 RON). Indeed, because the upstream deisoaniser that splits raw isomerate from the pentaniser diverts from the reaction section a molecular sieve section into an isomerate over- quantity of isopentane equivalent to the amount head stream rich in isopentane and of unconverted normal paraffins recycled from dimethylbutanes, and poor in the lower octane molecular sieves, the new feed rate will be equivmethylpentanes (MP), from two streams contain- alent to the original one. ing higher boiling components. Practically, a revamp will consist of adding a The first is a bottoms section side-stream from deisopentaniser and sieve section without modithe deisohexaniser, containing essentially all the fying the existing unit, needing only a short MP, is recycled to the isomerisation reaction shutdown for tie-ins. system. It is also used as a desorption fluid From a layout standpoint and according to through the molecular sieve system. This desorp- space availability constraints, the construction tion fluid acts in the same manner as the phase is greatly simplified because the new isopentane rich vapour stream in the Ipsorb equipment does not need to be erected nearby. process. As shown in Table 2, the investment for debotThe second stream, a bottoms purge, is tlenecking a 8000bpd isomerisation is US$9.3 removed and combined with the isomerate prod- million and, despite an operating cost increase, uct since it is high in C6 naphthenes and C7+ the octane improvement project returns the orighydrocarbons. This avoids catalyst inhibition by inal investment in around two years. naphthenes and hydrocracking of C7s to extinction in the isomerisation reactor. From DIH recycle to Hexorb It is preferable that, particularly with fresh The deisohexaniser sidedraw, used to desorb

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normal paraffins trapped on the sieves, Gasoline specifications will be adapted so that the resulting desorption stream remains equivalent Gasoline Euro 2000 to the original recycle flow rate. (95 RON) 98 RON Accordingly, the reaction section and Min Max Min Max DVPE Summer kPa 45 60 45 60 deisohexaniser throughputs remain Winter 60 90 60 90 unchanged and no modifications are Density 15C kg/m 720 775 720 775 necessary. As only the molecular sieve RON 95.0 98.0 system is added, this revamp case is MON 85.0 88.0 Olefins vol% 18 18 even more attractive. Aromatics vol% 42.0 42.0 Table 3 displays economic informaSulphur mg/l 150 150 tion for debottlenecking an 8000bpd Benzene (Note 1) vol% 1.0 1.0 deisohexaniser recycle unit using a Total Oxygen wt% 2.7 2.7 40:60 C5/C6 feed chlorinated alumina Note: The allowed benzene content in vol% up to the end of December 1999 was 5.0 catalyst. This option economically for all gasoline grades. The marketable content in 98 RON was <1.0% achieves a significant octane gain. As in previous revamp cases, the short Table 4 payout period puts isomerisation revamping in a good position among the many Contractor/licensor selection solutions to meet future Euro 2005 The imposed time frame was extremely short, specifications. hence HER prepared an ITB which put the onus on the engineering contractor to select, offer and Case study guarantee the supply of a suitable unit on a lump Holborn Europa Raffinerie (HER) sum turnkey basis. The ITB was issued at the Late in 1995, the German market specification end of December 1997, the targeted latest feed for benzene in 98 RON unleaded gasoline was in date, 31 December 1999, was a guarantee suddenly reduced from 5 per cent to 1 per cent. requirement. Later it was announced that this would apply to all grades of gasoline by January 2000. HER Options considered launched a series of studies and actions in order Three isomerisation catalyst/technology options to meet immediate market requirements as well were available for consideration: as prepare for Euro 2000 specifications (Table a) Amorphous chlorinated alumina catalyst with 4). Several columns and operations were modi- single pass hydrogen. (All catalysts require fied and studies were undertaken to compare continuous chlorination). benzene removal by extractive distillation with b) Zeolite-based catalyst with recycled hydrogen. hydrogenation of LVN benzene to cyclohexane c) Superacid sulphated Zirconium. and isomerisation of the pentane and hexane (All catalysts in the development phase). components to isopentane and isohexane. A deisohexaniser would be included to recycle Comparison low octane methylpentanes. The decision was to Option (c) was only in the development phase use the benzene hydrogenation/isomerisation- when the technologies were compared, hence with-recycle route because it produces a high options (a) and (b) were compared and the fact octane product totally deficient in aromatics, that equipment required for option (b) lends making an excellent blending product to facili- itself for future upgrading to option (c) was tate an overall reduction in aromatics, yet taken into consideration. preserving the octane value of the stream. Both technologies fulfilled HERs requireThe following pages summarise aspects consid- ments, and have advantages and disadvantages. ered and results obtained during the conceptual, The zeolitic catalyst has a lower activity and contractor/licensor selection, engineering, requires a higher operating temperature than the construction, pre-commissioning, commission- amorphous catalyst, so giving a lower octane ing, operation and performance testing phases of isomerate product. It is however a forgiving the project. catalyst, is less sensitive to C7+, sulphur and

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Guaranteed performance vs pilot test results

Guaranteed data for industrial unit Number of reactors 2 Total isomerate MON 85 min Total isomerate yield, wt% 96.2 min

Pilot tests 1 85.1 96.9

Table 5

water, has a longer expected lifetime and can be regenerated in situ. The zeolite catalyst does not require chlorination and is therefore environmentally friendly. Option (a) was finally selected. This decision was influenced by the catalysts higher activity, supported by proven experience with a similar technology at HERs sister refinery in Switzerland. The contract was awarded to Kvaerner Process using Axens technology and Procatalyse IS 614A catalyst, which uses an eta alumina support which provides a higher surface area than gamma alumina. The subject catalyst, an evolution of previous IS612A catalyst which was in operation in several units, had not been commercially proven when the contract was awarded, and HER wanted to be convinced that it was suitable for the required service. Axens invited HER and KP to witness a pilot performance test at their research centre in Solaize. The test was carried out using representative samples provided by HER and was set up in a one-reactor unit operated under oncethrough mode. The pilot results allowed for precise evaluation of catalyst pattern like isomerisation activity, ring opening ability, C7+ cracking to simulate the deisohexaniser recycle case. For recycle operation mode, the calculation results summarised in Table 5 have shown that the licensors projections were met. It must be underlined that, the pilot tests being performed with a single reactor, show the results are on the pessimistic side as compared to the results achievable with the industrial concept of lead-lag reactor system.
Environmental restrictions

The German authorities were particularly concerned about the use of chlorinated alumina catalyst, which has to be continuously chlorin-

ated, and therefore stringent handling and emission regulations were imposed, some of which are listed below. Catalyst handling: Chlorinated catalyst loading Unloading, transport and regeneration of spent catalyst. IFP convinced HER and the German authorities that IFPs loading, transport, and unloading procedures for chlorinated catalyst met all safety regulation, and also demonstrated that the exsitu regeneration and eventual platinum recovery processes at the French catalyst recovery subsidiary were both environmentally friendly and approved by the responsible French environmental authority, including: a) Perchloroethylene (tetrachloro ethylene) handling. b) KP engineered the perchloroethylene loading and storage facilities to conform with German regulations, which prohibit discharge of perchloroethylene vapour to the atmosphere. c) Flare gas emission. The owner (HER) must guarantee and prove that no chlorides are burned at the flare or in furnace firing systems. This problem necessitated modification to the licensors standard design in which perchloroethylene is injected into the isomerisation feed stream upstream of the reactor pressure relief valves located at the inlet of the reactors. Hence perchloroethylene could be entrained in the pressure relieved stream which was designed to go to flare. HER and Axens decided to relocate the pressure relief valves from the reactor inlet to the reactor outlet to ensure that non-decomposed perchloroethylene could not be entrained in the relief valve discharge stream. An online chlorine analyser interlocked with an emergency stop was added to the off-gas line. d) Pressure relief valves discharging possible chloride contaminated hydrocarbons were routed to the caustic scrubber, entering it in the sump above the maximum liquid level. The scrubber was re-sized to accommodate the maximum possible simultaneous relief of chloride contaminated hydrocarbons. It was equipped with caustic circulation pumps connected to the emergency power supply system to ensure neutralisation capability in the event of power failure. e) Chloride in product.

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The owner (HER) must guarantee Guaranteed performance vs test run results that the isomerate is completely chloride free. Guaranteed data Guaranteed data for A chloride trap was added in the line for design feed test run feed Test run results from the stabiliser bottoms to the C5/C6 ratio, wt 65:35 55:45 55:45 Fresh feed capacity, m3/h 50 min 50 min 50 deisohexaniser. Total Isomerate MON 85 min 84.3 min 84.7 Since it was subject to drastic enviTotal Isomerate yield, wt% 96.2 min 99.5 ronmental regulation, the project proved that, thanks to licensor, contractor and owner collaboration, the Table 6 drawbacks linked to chloride handling and processing can be easily and efficiently extremely smooth and right on schedule noon solved. on 31 December 1999 a just reward for effective operator training, precommissioning and Construction, commissioning and startup commissioning. Although a very short time frame was allocated to plan, procure and construct the new facilities Performance test and despite the difficult access to the area After careful adjustment and stabilisation of the selected for the new unit the stabiliser and main operating conditions, the performance test deisohexaniser columns were crane-lifted over was run in January 2000. During three days, all operating pipe racks the construction phase necessary data were collected to evaluate and was completed as scheduled owing to the close compare the unit performance with the set of collaboration between all parties concerned. guarantees given by IFP. Table 6 shows that all The normal commissioning/startup phase, guarantees were met. function testing, control loop simulation, safety Since design feed was not available, a new set system testing, hydrogen purging, introduction of guarantees for test run feed has been agreed. of treat gas and feed etc, ran smoothly, and the main concern was isomerisation catalyst loading. Operation The catalyst was loaded in December 1999, A catalyst inhibition problem was experienced during a continuous rainy period, immediately after the unit had been producing a high octane before introduction of treat gas and feed. Since light isomerate for a week. C7 and benzene platinum alumina catalyst type is extremely concentrations had been carefully monitored in sensitive to oxygenates and moisture, it had to be the feed stream, the recycle stream could only be loaded under dry nitrogen atmosphere. monitored using the results of laboratory tests Enclosures were installed to protect catalyst on a daily sampling basis. An increase in the drum storage at the foot of the reactors, loading bottoms temperature resulted in carryover of platforms and drum loading lift, passage from heavy naphthenes to the recycle stream causing the storage tent to the foot of the lift. The refinery fire brigade ensured that all necessary safety procedures were followed during the catalyst loading phase, breathing equipment was made available at the loading platforms and the air quality in the confined loading area was continuously monitored and supplemented by air blowers. After a catalyst loading period of Figure 4 Effect of benzene concentration in reactor feed on MON (60:40 <C5:C6 four days, the startup was ratio < 55:45)

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Gasoline specifications
2000 Specification Anticipated 2005 specification (Note 2) Sulphur (Note 1), mg/l 150 5 10 Aromatics, vol% 42 35 Olefins, vol% 18 10 Oxidation stability, minutes 360 480 Min Max Min Max Density at 15C, kg/m_ 720 775 715 770 DVPE Summer, kPa 45 60 Note 3 Note 3 DVPE Winter, kPa 60 90 Note 3 Note 3
Note 1. The 2005 sulphur content of 5-10ppm maximum is based on available data on advanced technology vehicles. As more data become available, a more specific maximum will be defined. Note 2. The 2005 specifications have not been finalised, are subject to a lot of discussion and may well have to be compromised. Note 3. The DVPE will probably remain unchanged.

technology because it facilitates complete removal of sulphur, accompanied by partial instead of total saturation (octane degradation) of high octane olefins. The compensation necessary for octane loss caused by selective desulphurisation is therefore significantly less than for traditional HDS, and can be achieved by upgrading the isomerise-tion, reformer and other units.

Conclusion

Table 7

temporary catalyst inhibition. HER plans to install an online analyser (gas chromatograph) to monitor C7+ in the recycle stream. After the above mentioned unstable period, the unit has been performing very smoothly and steadily. Differences, as compared to the design, are first a higher C5/C6 ratio (as for the acceptance test run) as well as higher benzene content in the current fresh feed. Figure 4 illustrates the negative impact of increasing benzene in feed content on unit performance. Both deviations lead to a slight octane drop from 85 for design feed to an average value of about 84. After 10 months operation, IFPs design has demonstrated reliability, safety for the environment and flexibility despite appreciable changes in feed quality.
More stringent gasoline specifications 2005

Based on the World-Wide Fuel Charter (April 2000), the anticipated gasoline specification for 2005 will not change the RON and MON requirements but could require the changes shown in Table 7, necessitating major refinery modifications: HER is evaluating available technologies, compatible with the refinery infrastructure in anticipation of an accelerated market demand for sulphur free (<10ppm.) gasoline; promoted by differential tax benefits. Selective desulphurisation of cracked naphtha, the main sulphur source, has advantages over traditional HDS

In the intricate challenge of meeting the most severe Euro 2005 gasoline specifications that impose stiff limits on benzene, aromatics and olefins contents, total or partial ban of MTBE, isomerisation is recognised as the most effective means of boosting the octane value of a refinerys C5C6 streams. When a major boost in octane is required, complete conversion of normal paraffins to branched paraffins is necessary. Revamping existing isomerisation units to improve product octane is also a field in which molecular sieve separation of normal and isoparaffins (Ipsorb and Hexorb) is an attractive solution. The Holborn Europa Raffinerie deisohexaniser project was efficiently executed in a close, contractor/licensor/client - team effort and completed on schedule. Difficult environmental and permitting problems were resolved in cooperation with the responsible German authorities. The performance test was successfully run, HER is satisfied with the units operation and licensor support. The installed isomerisation unit lends itself to future modification necessary for gasoline production in accordance with the anticipated 2005 gasoline specifications.

Links
More articles from: Axens More articles from the following categories: Catalysts & Additives Reforming Design, Engineering & Construction Desulphurisation & Sulphur Handling Hydrogen Management Isomerisation

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