Novel Coker Naphtha Hydrotreating Technology

by Rasmus Breivik and Rasmus Egebjerg Haldor Topse A/S, Lyngby, Denmark

Introduction
In recent years, the application of residue upgrading technologies has grown in a market with increasing prices for light sweet crudes and a decreasing demand for heavy residual fuel oil. Carbon rejection technologies such as delayed cokers have been the preferred choice in the market, since the crude quality typically declines with increasing metal content and Conradson Carbon Residue.

Installation of a new coker unit, resulting in an increase in cracked distillate, poses some additional challenges to the downstream hydrotreaters. This is especially the case for naphtha hydrotreaters, since the properties of coker naphtha are very different from those of straightrun naphtha.

Typically, coker naphtha contains 10-20 times more sulphur and has high contents of olefins, nitrogen and silica as compared with straight-run naphtha. Target levels of nitrogen in the reformer feed are typically around 0.10.5 wt ppm to avoid ammonium chloride deposition. This implies that high severity operating conditions of the coker naphtha hydrotreater are necessary to fulfil the required product specifications on nitrogen. However, it is usually practically impossible to increase the operating severity by increasing the temperature since sulphur recombination takes place at high temperatures.

The origin of silica can be traced back to the silicone oil added to the heavy residue feed to the coker. Because of gas formation, silicone oil is added to the coker drums to suppress foaming. Excess quantities of silicone oil will crack or decompose to form modified silica gels and fragments. These gels and fragments are mostly distilled in the naphtha range and are therefore carried to the downstream hydrotreaters together with the coker naphtha.

-2Unfortunately, silica poisoning of the catalyst in the downstream hydrotreaters greatly reduces the HDN activity and results in very large catalyst volumes being required to ensure simultaneous removal of nitrogen and silica. The required space velocity to match the turnaround schedule of the reformer/coker unit will often be below 0.2 hr-1 when using standard hydrotreating technology and catalyst.

Another important consideration to be made for coker naphtha hydrotreating is control of the temperature increase from saturation of olefins, since this reaction takes place readily and is highly exothermic. When olefin saturation is not controlled properly, this may lead to a premature shutdown as excessive coke formation will take place due to gum formation/polymerization in the top layer of the catalyst bed.

Topse has in recent years spent considerable time and money on offering a variety of technologies and catalysts to overcome the above described challenges. This has been done in preparation of a future, where there will be a higher ratio of cracked components in the refinery slate.

For new grassroots units, a three-reactor lay-out is typical. In the first reactor, mainly diolefins are saturated at low temperature. In the second reactor section, silica is adsorbed on high-surface area catalysts known as a silica guard. Simultaneously, most of the olefins are saturated, while a relatively large degree of HDS and a small degree of HDN takes place. Finally, a reactor with high HDS and HDN activity catalyst ensures that the sulphur and nitrogen specifications are met. Even when operating with only two reactors, these three steps saturating conjugated di-olefins, removing silica and removing sulphur and nitrogen must be carried out. In this paper, the challenges of each of these process stages as well as overall process conditions will be discussed. Recent fundamental studies will be used to show how optimum process and catalyst technology can help find the optimum unit lay-out and operating conditions.

Controlled Removal of Conjugated Olefins

Formation of olefins is a result of high-temperature conversion reactions in the delayed coker. Upon contact with air, olefins and di-olefins may form gum that complicates the transportation and processing of coker naphtha. Di-olefins and in particular conjugated di-

-3olefins present in coker naphtha must be saturated in order to stabilise the feed. The stabilisation typically takes place in a separate reactor since the required operating conditions are quite different from those of the HDS and HDN reactions. The saturation of di-olefins is a very fast reaction and can therefore be carried out at high LHSVs and at low temperatures. Conjugated di-olefins polymerise at normal hydrotreating temperature conditions, and the polymers cause fouling of the reactor resulting in pressure drop build-up. The polymer formation potential of coker naphtha is about 300 times the potential for straight-run naphtha. A generally accepted way of controlled saturation of conjugated olefins is to use a hydrotreating catalyst operated at low temperature (160-220C) in the presence of hydrogen.

With the growing market for coker technology, increasing focus is put on the reliability of the coker unit, resulting in more coker units being designed with ISBL facilities to remove conjugated olefins. The main benefit of making the removal of conjugated olefins independent of the coker naphtha hydrotreater is the possibility of sending the coker naphtha directly to storage if the coker naphtha hydrotreater has an unforeseen shutdown.

Nowadays, many units are designed independently of the coker naphtha hydrotreater with once-through hydrogen, which facilitates the change of catalyst online to increase the reliability of the coker unit.

Since the exothermic di-olefin saturation reactions produce large amounts of heat, it is necessary to operate at low temperatures and to use a selective catalyst to control the temperature increase. High selectivity means that the catalyst should saturate di-olefins only and not mono-olefins, which might lead to a too high temperature increase in the reactor. Topse has carried out studies of catalyst selectivity by processing a model feed containing 1,3-hexadiene. The di-olefin to olefin reaction selectivity was studied as a function of diolefin conversion as shown in Figure 1A. As expected, the selectivity decreased with conversion, since the two reactions (saturation of 1,3-hexadiene to hexenes and saturation of hexenes to hexane) are consecutive.

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B Figure 1: Selectivity of di-olefin saturation reaction

The effect of pressure was also investigated. In Figure 1B, the selectivity is shown as a function of the reactor pressure for two different catalysts. At all conditions, the hexadiene is completely converted, but as can be seen, the selectivity towards hexene increases with decreasing pressure. Furthermore, the two catalysts tested have different selectivity and slightly different responses to changes in pressure. This means that even though the saturation reactions are very fast, there are still a number of knobs that can be turned to control the reactions to ensure that both complete saturation of di-olefins and high selectivity towards olefins are achieved. Topse uses this knowledge to optimise the selection of catalyst and process conditions to maximise the run length.

Silica Removal and Olefin Saturation

The simultaneous removal of silica by adsorption and saturation of olefins requires a proper design of both the catalyst system and process schemes to control temperature increases and pressure drop build-up.

The amount of silicon in coker naphthas is dependent on the economics of the coker unit. Typically, a coker naphtha fraction contains about 5 wt ppm silicon but silicon contents of up to 10 wt ppm can be seen on some occasions. Unfortunately, silica poisoning of the catalyst in the downstream hydrotreaters reduces the HDN activity of the catalyst to a large degree.

Typically, when processing feedstocks in the past with low silica contents, the approach was to allow the silica to be absorbed on the bulk catalyst, since only a small amount of catalyst was required to remove silica. However, with the increasing amount of coker material to be processed, the content of silica and nitrogen content has increased, and it is nowadays

-5desirable to confine the silica deposition to the guard material to allow the use of a high activity catalyst as bulk catalyst.

Different configurations can be selected for the silica reactors dependent on feedstock and refinery specific considerations (Figure 2):

Bypass silica reactor Lead/lag reactor system

Typically, the bypass reactor configuration is selected for hydrotreaters operating with a low content of coker naphtha and a high amount of silica. The main problem with a bypass reactor is that the heat integration should be prepared for switching the temperature increase from the silica guard reactor to the main hydrotreater reactor during catalyst change-out. This limits the fraction of coker naphtha to be processed with this reactor configuration.

In a lead/lag reactor configuration, two reactors are connected in series (Figure 2). When the lead reactor is saturated with silica, the catalyst may be replaced, whilst still running the unit at full capacity. The flow is then redirected to have the fresh catalyst in the lag position and the partially saturated silica guard in the lead position. The lead/lag reactor system is preferred for hydrotreater units processing high amounts of coker naphtha. This solution has the advantage that a very high temperature increase can be allowed across the silica guard system. With the lead/lag reactor system it is possible to process a larger fraction of coker naphtha than with the bypass reactor configuration. Typically, the fraction of coker naphtha is controlled by recycling part of the product in order to dilute the coker naphtha fraction. Allowing a larger fraction of coker naphtha to be processed would therefore decrease the actual throughput of the high pressure reactor section, reducing both investment and operating cost. Another benefit would be the full utilisation of the silica guard since a large silica slip can be tolerated to the lag reactor, ensuring that the maximum silica pick-up in the lead reactor is reached before the catalyst change-out.

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Figure 2: Silica guard configurations: Bypass silica reactor (left) and lead/lag reactor system (right)

Topse has conducted extensive studies to determine the mechanism of catalyst deactivation when subjected to coker naphtha feedstocks containing silicon. These studies aimed at investigating the nature of the silicon deposition chemistry and the effect of silica contamination on HDS and HDN activity.

Silica in coker naphthas originate from silicone oil added to the heavy residue feed in upstream processes. Typically, the silicone oil is a polydimethylsiloxane (PDMS). At the elevated temperature of the delayed coker, PDMS decomposes, and Topse has identified a homologue series of cyclic siloxanes in coker naphthas, examples of which are shown in Figure 3.

-7Polydimethylsiloxane

CH3 H3C Si O H3C Si O H3C CH 3

Hexamethylcyclotrisiloxane

CH 3 O CH 3 Si

H3C
Si

Si

CH3 O CH3
Si

H3C O Si H3C O CH3

CH3

Octamethylcyclotetrasiloxane

Figure 3: Structure of silicone oil (PDMS) and typical decomposition products (cyclic siloxanes) present in coker naphthas.

The amounts of these siloxanes causing the catalyst deactivation are determined by a quantitative Si-sensitive GC analysis. Furthermore, the interaction of these siloxane species with the catalyst surface as well as a characterisation of spent catalysts, have shed light on the deactivation mechanism. The cyclo-siloxanes are quickly adsorbed on the catalyst surface. A detailed characterisation of the Si deposits on aged coker naphtha HDT catalysts was carried out by NMR spectroscopy. Si is present in the form of modified silica gels consisting partly of bulk SiO2 with surface groups SiOH and Si(OH)2 and partly of modified silica gels with methylated surface species. The deposition of Si is similar to the deposition of coke. No chemical bonds to the alumina or metal sulphides are formed. The deactivation is caused by adsorption on surface reaction sites reducing the amount of active sites that the sulphur and nitrogen species have access to. However, the loss of activity due to Si is irreversible and cannot be restored by catalyst regeneration.

The deposition has been shown to be an activated and diffusionally controlled reaction catalysed by the surface alumina sites. This means that the silicon uptake capacity is higher for catalysts with higher specific surface areas and that, at higher bed average temperatures, the silica capacity of the catalyst will be higher (Figure 4). In order to fully utilise the silica capacity of the guard, it is thus necessary to design the heat profile of the entire unit properly from SOR to EOR.

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Figure 4: Influence of catalyst specific surface area (left) and operating temperature (right) on the Si uptake capacity.

The influence of Si deposition on catalyst activity is more pronounced for HDN than for HDS (Figure 5), and the HDN activity can thus be followed to track the silicon contamination.

Figure 5: Influence of SiO2 deposition on HDS and HDN catalyst activity These findings have implications for the design of catalysts with respect to maximising Si capacity and HDS/HDN activity. Since the surface alumina sites are responsible for the decomposition of the siloxane species, a low metal loading and a high surface area are

-9optimum for Si uptake. However, low metal loadings result in a low HDS/HDN activity. The knowledge acquired from fundamental studies of silicon deposition chemistry combined with canister tests in industrial coker naphtha hydrotreaters has led Topse researchers to the development of the TK-431, TK-437, and TK-439 catalysts, allowing an optimum design of the silicon guard catalyst system. This catalyst series consists of catalysts with varying silica capacities and HDS/HDN activities. Depending on feedstock reactivity and operating conditions, the correct catalyst system can be selected, maximizing the cycle length.

Interbed Cooling
The combination of high olefin content and the low end boiling-point of coker naphtha results in large temperature increases, which are typically seen across the first catalyst bed. For high concentrations of olefins, temperature increases of more than 100C have been observed in industrial units. The combination of a high temperature increase and the possibility of sulphur recombination, which requires a low temperature, results in a substantial need for interbed cooling.

In the past, interbed cooling was carried out either by quenching with cold gas or liquid. However, with the increasing energy prices, alternative ways of cooling need to be considered.

Topse recently developed a new technology utilising the high temperature increase to improve heat integration by applying interbed heat exchangers. This new concept not only improves heat integration but also increases the catalyst activity, since the treat gas rate and fugacity can be controlled independently of the required cooling requirements. The concept has already been applied in the design of several coker naphtha hydrotreaters.

Grading
The high olefin content of coker naphthas increases the risk of coking on the catalyst, and good grading becomes more important in order to avoid excessive pressure drop build-up. Typically, a hard crust layer leading to rapid pressure drop build-up would be experienced in the top part of the catalyst bed if the grading and reactor dimensions were not designed to

- 10 handle the higher amount of olefins. The solution to the problem comes from a fundamental understanding of crust formation with respect to the following:

Graded catalytic activity Heat transfer Bed void size Rate of olefin saturation versus temperature

Typically, in the past, part of the solution was to grade the top of the catalyst bed by catalytic activity only, i.e. gradually increasing catalytic activity from the inert top layer down to the main bed by several increments instead of having one step from inert to maximum activity.

This is, however, not sufficient for high olefinic feedstocks since only a very small activation energy is required, resulting in a high temperature increase in the topmost part of the catalyst bed even when utilising low activity catalysts. The key to solving this challenge, in combination with the activity grading, is to design the reactors and the rate of treat gas to allow a sufficient heat transfer in the axial direction thereby avoiding hot spots and resulting crust formation. This problem has typically been overlooked in the past but is becoming more important as the amount of olefins in feeds increases.

However, even with the best activity grading, some crust and coke formation will still occur in combination with contaminants introduced with the feedstock. This call for additional protection to make sure that there is a sufficient void for these types of contaminants. Typically, this is done by controlling the bed void size. Controlling the bed void size is done by loading the reactor with different sizes and shapes of grading material: high void topping material followed by larger rings on top of smaller rings and underneath these, the bulk catalyst. The reason for using rings of different sizes is to create a loading, which has a differentiated filtering effect, so that the largest contaminants introduced with the feed, are trapped in the upper layers, and the smaller particles are deposited in the lower layers.

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Achieving Sub-ppm Sulphur and Nitrogen Levels

After removal of silica and saturation of olefins, the removal of sulphur and nitrogen to very low product levels remains. The light-boiling sulphur components present in coker naphthas are generally quite readily removed. However, mercaptan formation through recombination of olefins and H2S may limit the HDS conversion. For nitrogen removal, a high-activity HDN catalyst should be used to obtain reformer-grade naphtha. The catalyst selection depends on feedstock and product specifications. Major challenges are to select the correct pressure level and to avoid recombination to limit the cycle length.

Hydrogen partial pressure One of the key parameters to define is the minimum required hydrogen partial pressure. Below a certain hydrogen partial pressure it becomes impossible to reduce the product nitrogen to the level required for the reformer feedstock even when increasing the operating temperature.

The actual reactor outlet hydrogen partial pressure is a function of several parameters:

Total pressure Degree of feedstock vaporization Amount of circulated treat gas Type of quench, liquid product or treat gas

All these parameters need to be considered along with the ammonia inhibition and fugacity of the reaction components to reach the optimum catalyst activity.

In the past, hydrogen partial pressure was considered to be basically the only factor affecting the catalyst activity. However, it should also be taken into account that the fugacity of the sulphur components is highly dependent on the amount of treat gas being circulated. Since the treat gas to oil ratio has pronounced effects on the fugacities of all reacting molecules, a more thorough analysis in the design phase is needed to define the optimum treat gas amount that results in maximum catalyst activity.

- 12 Sulphur recombination The reaction of H2S with olefins to form mercaptans is known as recombination and is of particular importance in coker naphtha hydrotreating due to the high amounts of olefins and organic sulphur in these feedstocks. The formation of olefins from dehydrogenation of paraffins is an endothermic reaction. At high reactor outlet temperatures, mercaptans may thus be encountered in the product, even though the recombination reaction itself is exothermic. Thus, contrary to common practice, it may be necessary to lower the reactor temperature to reach the product S specification. The recombination reaction may then limit the cycle length, since an increase in reactor temperature cannot make up for the loss in catalyst activity when approaching end-of-run. To understand the fundamental chemistry behind the recombination reactions, Topse has carried out a number of pilot plant experiments.

Using 1-hexene as representative of olefins in the liquid feed and a H2S/H2 treat gas mixture, it was observed that three different mercaptans were formed: 1-, 2- and 3-hexanethiol. This observation strongly implies that both a radical addition pathway and an electrophilic addition pathway are possible reaction routes. To prove that not only terminal olefins may undergo recombination, an experiment with cyclohexene was carried out, and only a single thiol (cyclohexanethiol) was observed. It is thus necessary to take all olefin isomers present in the reactor into account when modelling the recombination reactions. As was experimentally demonstrated, 1-hexene readily isomerizes into the more stable 2- and 3-hexenes at typical reaction conditions.

The recombination reactions may reach equilibrium at high temperatures as demonstrated in Figure 6, where the measured equilibrium constant (Pthiol / Phexene PH2S ) is shown and compared with the theoretical equilibrium line. At low temperatures, the reaction is kinetically limited, whilst at high temperatures, the reaction is controlled by equilibrium.

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Figure 6: Recombination of H2S and hexene as a function of temperature. At low temperatures, the reaction is kinetically controlled. At high temperatures, the reaction is equilibrium controlled.

Such fundamental studies enable Topse to determine to what extent recombination reactions take place in the reactor effluent train and to take measures to avoid these.

Conclusion
Hydroprocessing of coker naphtha material requires specialised catalysts and technologies to overcome the challenges of the high olefin and silica content and to produce a product meeting the very stringent sulphur and nitrogen specifications. As provider of both technology and catalyst, Topse is in the unique position of being able to supply the most optimised solutions for both existing and new coker naphtha hydrotreaters. Topse combines the knowedge acquired from fundamental studies of di-olefin saturation, of silica deposition and of recombination reactions to develop optimised catalysts and to implement new technologies for the best utilisation of the catalysts. A careful selection of process conditions as well as a proper integration of the different sections within the unit make longer runs possible and ensure a better profitability. Topses strong market position is reflected by the fact that during the last two years alone, we have designed more than 10 units processing coker naphtha feedstocks.