Guard bed catalysts

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Introduction Particulates Pressure drop Preventing fouling Guard bed catalysts Application examples Conclusions

1. Introduction All hydroprocessing units suffer from fouling of the catalyst bed. There are many causes for fouling. Fouling of a hydrotreating reactor can be caused by: Particles present in the feed coming from outside the battery limits Particles generated inside the battery limits, upstream of the reactor Fouling generated in the reactor

2. Particulates Feedstocks for hydroprocessing units can contain particulates. Common sources of particulates are: Corrosion products from crude towers, storage tanks, piping, heat exchangers, furnaces, etc. Salt from (improper working) desalters Coke from cokers or Coke generated on hot surfaces in processing equipment Fines from FCC units

Also inside the battery limits particulates can be generated. Sources for particulates can be corrosion products or coke. The most likely places for coke formation are the heater and heat exchangers, the places with the highest (wall) temperature.

3. Pressure drop All feedstocks will generate coke inside the reactor. Usually the coke is deposited inside the catalyst particles, causing catalyst deactivation and not pressure drop build-up. However, when processing cracked feedstocks containing gum and coke precursors, more coke can be generated leading to catalyst bed fouling and pressure drop. Especially interruptions of the hydrogen supply can lead to a fast coking (compressor failure, etc.). A second cause of pressure drop increase is organic iron compounds (e.g., iron naphthenates), which are decomposed inside the reactor as iron sulfide. The iron sulfides can cause bridges between catalysts and act as a catalyst for coke generation. Both the iron bridges and the coke will increase the pressure drop in the reactor.

4. Preventing fouling All particulates, etc. entering the reactor will cause a rise in pressure drop in the hydroprocessing reactor, because the catalyst bed is a very effective filter. The best way to prevent pressure drop build-up is to remove the particulates before they enter the reactor, or preventing the particulates from being formed. Particulates can be removed form the feedstock by: Filtering the feedstock Application of a small guard reactor before the hydroprocessing unit

Methods to prevent particulates formation are: Store (cracked) feedstocks in nitrogen blanketed storage Limit the storage time for cracked feedstocks as much as possible Use of anti-oxidants and anti-fouling additives Corrosion control

5. Guard bed catalysts Preventing fouling from entering the reactor is easier said than done. In all cases some fouling/particulates will enter the reactor. The Akzo Nobel Catalysts group has developed a series of catalysts, which are aimed at either providing

storage capacity for the particulates and/or preventing particulates from being formed in the reactor. The catalysts are: Ketjenfine KG 55 Ketjenfine KG 55 is an inert pentaring support material for hold-down, bed grading and improved pressure drop stability with excellent holding capacity for contaminants and particulate matter. It has 19-mm outer diameter and has a very large void fraction (62%) for scale trapping properties without getting plugged. It serves as large size toplayer material for catalyst bed grading and as hold-down material to replace the 1 or ceramic balls in the top of first the catalyst bed.

Ketjenfine KG 1 This spherical catalyst is produced in two sizes, 3 mm (Ketjenfine KG 1-3B) and 5-mm (Ketjenfine KG 1-5B) diameter. The catalyst is especially designed to trap and store fine iron particulates and to break down organic iron compounds inside the Ketjenfine KG 1 itself, preventing pressure drop build-up and excessive coke formation. Ketjenfine 542 There are two types of Ketjenfine 542 grades: Raschig rings Extrudates

The Ketjenfine 542 Raschig rings catalysts are produced in two sizes, 5 mm and 9 mm (5R and 9R respectively). The ring shaped catalyst has a higher void fraction than solid catalysts, and is better able to store fouling compounds entering the reactor. The Ketjenfine 542 catalysts are also effective for hydrogenation of di-olefins/olefins and oxides. The extrudates are available in 5.4 mm quadralobe and a 3.2 mm cylinder (5.4Q and 3E respectively). KF 542-5.4Q/3E are guard bed catalysts which allows a more gradual change in void fraction and void size, and reduce as a result pressure drop build-up.

6. Application examples For many fouling problems a balanced combination of the above mentioned guard bed catalysts, optionally in combination with inert spherical grading material needs to be applied. Since each fouling problem has its unique characteristics, it is difficult to give a "standard" application of our guard bed catalysts. In all cases an optimal system needs to be defined by the refinery and the Akzo Nobel Technical Service group based on the observations made on the unit in question. See also our Technical Information bulletin HPC-15. Below a number of typical problem descriptions and possible solutions are given. In the loading examples, the depth of the layers is not indicated, since this depth depends strongly on the size of the reactor, the amount of fouling observed, and the unit pressure drop history. Case A: Straight run gasoil Case B: Naphtha Case C: Cracked gasoil

Case A Feedstock: Straightrun gasoil Cause of fouling: During skimming large and small scale particles were observed in the top layer of the catalyst bed. Analyses showed that the particulates consist mainly of coke, and some iron. Recommended guard bed system: In order to reduce the rate of pressure drop build-up, the layer of particulates needs to be spread out over a larger distance in the catalyst bed. Furthermore, the void fraction needs to be increased. Therefore the recommended guard bed catalyst system in the top of the reactor is: KG 55 Ketjenfine 542-9R Ketjenfine 542-5R Ketjenfine 752-3Q Ketjenfine 752-1.3Q

The size of each layer depends on the reactor size.

Case B Feedstock: Straightrun naphtha Cause of fouling: The reactor needs to be skimmed every six months. In the top 500 mm of the reactor fine powder is observed. Upon analyses the powder is mainly iron, and some coke. Recommended guard bed system: The fine iron observed is coming from either corrosion products, or from iron naphthenates, which can be present in even light feedstocks like naphtha. The recommendation is to apply a catalyst system of: KG 55 Ketjenfine 542-5R Ketjenfine KG-1-5B Ketjenfine 752-3Q Ketjenfine 7521-3.Q

The Ketjenfine KG 1 traps the iron inside its unique pore structure, and break down the iron naphthenates inside the catalyst particles. Therefore the iron will be much less deposited on the outside of the catalyst bed. This will result in a decrease in the rate of pressure drop build-up. Commercial results: The problem described in this case is a commercial case. The Akzo Nobel guard bed indicated above was installed and the operation improved considerably. In the graph the pressure drop in the cycle without the Ketjenfine KG 1 and with the Ketjenfine KG-1 are plotted. It is clearly shown that the application of the KG 1 results in a much longer cycle. The cycle was increased from an average of six months to two years.

Case C Feedstock: Blend of LCO and straight run LGO The feedstock comes mainly from storage. The unit contains a CoMo catalyst. Cause of fouling: On opening of the reactor during a skimming operation a gummy layer is observed in the top part of the catalyst, below the inert balls. Analyses showed the layer consists mainly of hydrocarbons and coke. Recommended guard bed system: In this case the fouling is most likely caused by the cracked feedstock processed in the reactor. It is unclear if the (di-)olefins cause the problem, or oxygenates formed during storage. For this case the recommended catalyst system is: KG 55 Ketjenfine 542-5R Ketjenfine 542-3E Ketjenfine 841-2E Ketjenfine 752-1.3Q

Ketjenfine 542-5R is a medium active hydrogenation catalyst, which will saturate most of the very active compounds. Further hydrogenation of the olefinsoxygenates is done on the NiMo Ketjenfine 841. Commercial application: This system was applied in a commercial unit which suffered frequently from shut

downs due to pressure drop problems. After installing the system with the Ketjenfine 542-5R active support, and replacing 20% of the CoMo catalyst with Ketjenfine 841 NiMo catalyst, the units has not suffered from pressure drop problems again.

7. Conclusions Application of the Akzo Nobel guard bed catalyst technology can decrease or completely remove pressure drop problems. Optimal solutions for pressure drop problems depend on: Detailed analyses of the nature of the fouling Application of a good grading system Applying the right type and volume of guard bed catalysts