NL8302580A - MOVING BED REACTORS AND COUNTERFLOW CATALYST. - Google Patents

Description

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Moving bed reactors with countercurrent catalyst

Many petroleum refineries built over the years are designed for use with relatively high quality petroleum feeds. * The usual and most desirable feeds have a relatively low viscosity and are relatively uncontaminated with metal compounds and sulfur compounds. However, in recent years, the supply of this high quality crude oil has declined and the price of easily refined oil has increased dramatically. Furthermore, many of the countries which have reserves of high quality light petroleum require their customers to take grades of cheaper, yet contaminated, and heavier oil, which are generally much less desirable. Countries demanding the purchase of heavy contaminated oil to get lighter, relatively unpolluted oil include 15 Saudi Arabia and Venezuela.

In addition to and despite recent heavy drilling activity, many firms and countries are looking at the production of synthetic raw materials to meet their future needs for hydrocarbon fuels. Among the latest synthetic oil sources are oil shale, coal, tar sands and very heavy oils or tars, as found in the Orinoco River area. A common feature of the liquids prepared from these products is that they are very heavy, have a high viscosity and are highly contaminated with metals and sulfur. The problems faced by the petroleum refiner in planning for a future use of this synthetic feed are similar to those faced in planning for the use of the very heavy crude oil supplies.

The threshold problem of treating this type of feeds is their very high metal content. Metals such as nickel, vanadium and iron are present in such large amounts that if they are not removed before entering the standard refining processing schedule they will clog or contaminate all subsequent refining processes. It will be appreciated that metal removal and desulfurization problems are of increasing importance 35 and research continues to progress with the search for new and more efficient catalysts and methods for removing these impurities from the desirable hydrocarbon products which are the feeds are present.

Many different reaction schemes and catalysts have been proposed for use in demetallization and desulfurization. Often 8302580 i 4 i 2, however, these methods have been proposed for the treatment of residual oils, which contain impurities with a much lower content than that which modern refiners must deal with. U.S. Pat. No. 3,826,737 describes a continuous process 5 and equipment for the catalytic treatment of. residue oils. The method is used at a feed with a total metal content of less than 65 ppm by weight. The demetallization reactor described would be suitable for both countercurrent and direct current operation, although the patent is primarily directed to direct current operation. In a later literature,

US Pat. No. 3,882,015 discloses a unitary multistage reaction system for countercurrently contacting a liquid reactant stream with catalyst particles primarily for reactions involving light naphtha hydrocarbons.

As mentioned above, most process schemes, which relate to the desulfurization and demetallization of heavily contaminated feeds, when they do not relate to a fixed bed operation, involve a moving bed operation and a DC catalyst. the feed and catalyst both flow through the reactor in the same direction. Examples of these types of schemes include: U.S. Patent 3,738,880, moving bed desulfurization desulfurization and intermittent DC catalyst; United States Patent 3,880,598,25, hydrodesulfurization of moving bed residual oil and intermittent DC catalyst; U.S. Patent 4,312,741, converting liquid phase hydrocarbon or bituminous shale into semi-stationary or boiling beds with an intermittent countercurrent catalyst stream.

A fixed bed and moving beds with a DC-brought catalyst are easier to design and implement than moving beds with a counter-flowed catalyst. The ease of operation of direct current moving beds as opposed to countercurrent catalysts is shown in the literature and description of large numbers of reaction schemes, equipment and methods of adding and removing catalysts and reagents in this process. Examples of these descriptions include: U.S. Patent 2,956,010, method and apparatus for supplying reagent and contact material to moving masses of granular contact materials; US Patent 8302580 3 * - * Λ 3,336,217, method and apparatus for intermettering extraction. particulate catalysts on the bed of a reactor operating at high pressure and temperature; US Patent 3,547,809, a process for adding and withdrawing solids from a high pressure reaction kettle using a pressurized liquid transfer medium; US Pat. No. 3,785,963, withdrawing uniform amounts of solids from a movable bed of solids by a system comprising a plurality of conduits equidistant in the cross-sectional area of the solids; U.S. Patent 3,849,295, removing catalysts from moving bed reactor systems with poor catalyst flow due to agglomeration problems of liquid reagents or catalyst;

United States Patent 3,856,662, solids extraction and transfer boilers and methods for use in superatmospheric pressure systems; U.S. Patent 4,188,283, process for starting moving bed reactors used in the hydrogenation of olefin-containing hydrocarbons.

Other reaction schemes for demetallization processes include the use of fluidized or fluidized beds. In a fluidized bed, a liquid or gaseous product flows upstream through a kettle containing a mass of solid particles. The mass of solids is kept in random motion by the upward currents and the physical space occupied by the catalyst bed is greater ("expanded") compared to either the space occupied by the catalyst bed when no material flows through it either a fixed or moving bed type reaction zone. Discussions of the fluidized bed reaction zones and their properties can be found in RE 25,770 of U.S. Pat. No. 2,987,465 as well as in U.S. Pat. No. 3,901,792, demetallization and desulfurization of crude or atmospheric residual oils using a fluidized bed and in U.S. Pat. 4,217,206, catalytic demetallization of Venezuelan crude oil using solid and preferably fluidized beds.

The non-patent literature also includes discussion regarding quality improvement of heavy contaminated oil. For example, LC refining, as described in "Hydrocarbon Processing", pages 107, May 1979, involves the use of a fluidized bed reactor. The design of a swirl or expanded bed is discussed, where 40 very heavy feeds can be processed, while the unit is never 3302580

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Λ 4 for catalyst replacement is discontinued. The H-oil process, as described in "Hydrocarbon Processing", page 112, September 1980, uses a fluidized bed with catalyst addition and extraction in operation for the quality improvement of high metal and high sulfur feeds. The Shell-Bunker Flow Process as described in Oil and Gas Journal, page 120, December 1, 1980, involves the use of an intermittent direct current as described in U.S. Pat. Nos. 3,826,737, 3,730,880, and 3,880,598.

While it could be expected that rebooted moving beds could be very suitable for demetallization and desulfurization reactions, the advantages of the countercurrent operation, unlike the DC operation or even the fixed bed operation, are not sufficient. to address implementation difficulties or make them economically desirable.

Reaction conditions were found, including moving bed and countercurrent catalyst reaction zones, which are not only better than the fixed bed or DC catalyst bed but also so much better that their economical use and development is justified.

The present invention relates to a process characterized by contacting a hydrocarbonaceous feed containing metal compounds and wherein these metal compounds are present in an amount greater than about 150 ppm by weight with a demetallization catalyst under demetallization conditions, where the demetallization catalyst is contained in a moving bed and the feed flows in a direction countercurrent with the catalyst.

The present invention also relates to a process for improving the quality of a hydrocarbonaceous feed, characterized by contacting (a) a hydrocarbonaceous feed containing metal compounds and sulfur compounds with a demetallization catalyst under demetallization conditions while producing of a effluent stream, wherein the demetallization catalyst is in a moving bed and wherein the feed flows in a direction countercurrent to the catalyst and (b) contacts at least a portion of the effluent with a desulfurization catalyst desulfurization conditions, wherein the desulfurization catalyst is in a fixed bed.

The present invention further relates to a process 8302580 w% 5 for improving the quality of hydrocarbonaceous feeds, characterized in that (a) a hydrocarbonaceous feed containing metal compound and sulfur compounds is contacted with a demetallization catalyst under demetallization conditions to generate a effluent stream, wherein the demetallization catalyst is contained in a moving bed and the feed flows in a direction countercurrent to the catalyst and (b) contacts at least a portion of the effluent with a desulfurization catalyst under desulfurization conditions, the desulfurization catalyst being contained in a moving bed and the effluent flowing in a direction countercurrent with the catalyst.

By "moving bed" here is meant a catalyst configuration, with the catalyst being added at one end of the catalyst bed in an intermittent or substantially continuous manner and withdrawn at the other end in an intermittent or substantially continuous manner. Usually the catalyst will be added at the top of the reaction zone and withdrawn at the bottom.

However, a moving bed should be distinguished from fluidized, swirling and expanded beds. In fluidized beds, the flow rates of gas or liquid as compared to the particle size of the catalyst are such that the catalyst behaves as if it were a fluid and circulating through the reactor and often discharged from the top of the reactor with the products. Swirling or expanded beds are very similar to fluidized beds, except that the degree of fluidization is not ζδ high and the amount of catalyst movement within the reaction zone is not very high. The conventional fluidized bed reactor will contain a mass of solid particles, the gross volume in the reaction vessel of which is at least 10% greater when the feed flows through it compared to the stationary mass, when no feed flows through it. Although the particles in the bed do not necessarily circulate as if they were fluids, they are separated from one another and they move randomly.

On the other hand, in the moving bed, the catalyst particles are substantially in contact with each other. The catalyst bed is not expanded when the fluid or feed passes through and its physical state, except for the feed and removal of the catalyst, is essentially that of a fixed bed. The degree of catalyst addition and removal for a conventional moving bed reactor is a matter of design choice. In a larger reactor, less catalyst will have to be added during operation, but the capital costs of the reaction boiler will be much higher. On the other hand, in a small reactor, more catalyst will have to be replaced during operation, but the capital cost of the reactor will be much lower. Among the other factors to be balanced are the demetallization capacity of the catalyst itself as well as the metal content of the feed introduced into the reaction zone and the desired degree of demetallization.

Similar considerations are involved in choosing whether to add and withdraw the catalyst to be intermittent or continuous. The degree of catalyst replacement can vary from a few percent of the charge per day to a few percent of the charge per week, all depending on the size of the reactor, the metal capacity of the catalyst, the feed rate and the feed composition. Intermittently (addition and withdrawal of individual catalyst charges at set times) or continuously, the method of catalyst addition and withdrawal depends on these factors and others.

The most common and undesirable metals present in the hydrocarbon feeds are nickel, vanadium, arsenic and iron. These metals deactivate desulfurization and other catalysts in later reaction zones and must be removed. These metals are often present as organometallic compounds. Thus, the use of the terminology "iron, nickel, arsenic, or vanadium compounds" means that these metals are in any state in which they may be present in the crude, either as metal particles, inorganic metal compounds, or as organometallic compounds . When amounts of metal are indicated, the amounts in weight amounts based on the metal itself are given. It has been found that the higher the metal content of the feed, the more effective a countercurrent demetallization process. However, when feeding with a low metal content, direct current and counter current operations have substantially the same efficiency. For these reasons, the feed should have an unwanted metal content greater than about 150 ppm by weight of the feed, preferably greater than about 200 ppm by weight of the feed, and more preferably greater than about 400 ppm by weight .

While nickel, vanadium, arsenic, and iron are the most common metal impurities, other unwanted metals, such as 8302580% sodium and potassium, can also contribute to the metal content of the feed for the purposes of the present operation.

The usual feed is hydrocarbon containing, i.e. the feed contains hydrocarbons. The feed can come from crude oil, from coal by liquefaction of the coal, from oil shale, from tar sands bitumen, from heavy oils and from tar products. It will be understood that the present process works well with the worst products the refiner has to deal with. These feeds are usually high boiling products. They usually cook above 204 ° C, preferably above 343 ° C, and more preferably above about 510 ° C.

One of the most important features is that it has been found that at higher feed hourly space velocities, the present countercurrent process is more efficient than DC processes. It will be clear that the faster a feed can be fed through a reactor, the smaller the reactor can be, which entails considerably lower capital costs. The hourly space feed rate for the present process is greater than about 0.5 and preferably greater than about 1.0 in the counterflow reactor.

Temperatures and pressures within the moving bed can be those temperatures and pressures common to demetallization reactions. The pressure is usually greater than 2180 kPa and preferably greater than about 3550 kPa. The temperature is usually higher than about 315 ° C and usually higher than 371 ° C. In general, at higher temperatures, the metals are removed more quickly; but the higher the temperature, the less efficiently the metal capacity of the demetallization catalyst is used.

The reaction may or may not be carried out in the presence of hydrogen. Hydrogen is usually added.

Catalysts used in reaction with countercurrent are those commonly used for demetallization reactions. The preferred products usually have high average pore diameters. Examples of demetallization catalysts are described in U.S. Pat. Nos. 3,947,347, 4,119,531, 4,192,736, and 4,227,995.

The catalysts, which are particularly suitable in the present process, have a high metal capacity. The metal capacity of the catalyst is preferably greater than about 0.10 grams of metal per cc of catalyst and more preferably is greater than about 0.20 g of metal per cc of catalyst. The difference between the direct current and counter-current processing increases as the metal capacity of the catalyst increases. The catalyst can also contain a hydrogenation component. Hydrogenation components are usually metal compounds of groups VIB or VIII of the periodic table and in particular are nickel, cobalt, molybdenum and tungsten.

One of the special features of the present process is that it can be carried out using very large amounts of the metal capacity of the catalyst. It has been found that very high metal loads on a demetallization catalyst can be achieved even at high space velocities and using high metal feeds. Preferably more than about 50% of the metal capacity of the catalyst is used, preferably more than about 70% of the metal capacity is used and more preferably more than about 90% of the metal capacity is used.

The effluent from the counter-catalyzed demetallization reactor can be further processed. All or part of the effluent can go to a hydrodesulfurization reactor. Part of the effluent can be recycled, either for further demetallization or as a diluent in the feed to the demetallization reactor with the countercurrent catalyst. The increase in efficiency when using a moving bed with countercurrent catalyst for a fixed bed desulfurization reactor is enormous, especially in comparison to the other embodiments. Furthermore, all or part of the effluent from the countercurrent catalyst demetallization reaction zone may be passed through a desulfurization unit, which itself is a moving bed reaction zone and a countercurrent catalyst.

30 Example 1 and figures

Figure 1 shows 4 reactor diagrams used in computer simulations for residue processing. Scheme 1 is only a fixed bed reactor filled with RDS (residue desulfurization) catalyst. Scheme 2 combines a moving bed monitoring reactor and a DC powered catalyst with a fixed bed reactor. The moving bed reactor contains HDM (hydrodemetallization) catalyst, which is 20% of the total catalyst fed to this scheme. The fixed bed reactor contains the same BDS catalyst as used in scheme 1. Scheme 3 combines a moving bed monitoring reactor and countercurrent reactor with a fixed bed 8302580 9 reactor. Again, HOH catalyst is added to the moving bed reactor, while RDS catalyst is added to the fixed bed reactor. The HDM catalyst constitutes 20% of the total added catalyst. Scheme 4 combines fixed bed swing monitoring reactors with a fixed bed 5 reactor. HDM catalyst is added to the monitoring reactors and BSS to the main fixed bed reactor. Each rocking guard bed contains 20% of the catalyst added to a guard bed + the main reactor. The total amount of catalyst added to each schedule is the same; the guard beds are filled with a demetallization catalyst and contain 20% of the total catalyst added to each schedule. The fixed beds, except the fixed guard bed, are filled with desulfurization catalyst and contain 80% (100% for the fixed bed only) of the catalyst added to each schedule. The total space velocity is maintained at 0.29, the space velocity of the guard bed is 1.45, and the sulfur content of the product is maintained at 0.4 wt%. The sulfur content of the feed is 1.5 wt%, except when the metals supplied are 120 ppm, the sulfur supplied is 2.5 wt%. The metal contents of the feeds are varied from 120 ppm to 900 ppm. The catalyst removal rate for the moving bed reactors is adjusted to maintain a life of 6 months for the fixed bed reactors.

Figure 2 shows the results for the four reactor schemes expressed in relative catalyst consumption for the four schemes. The moving bed and countercurrent catalyst + fixed bed reactor scheme consumes the smallest amount of catalyst over the feed metal range from 120ppm to 900ppm. The moving bed with countercurrent catalyst is clearly better than just the fixed bed or the moving bed schemes with DC-powered catalyst + fixed bed. The counterflow scheme is also better than the fixed guard bed scheme.

Based on catalyst consumption, the moving bed and countercurrent catalyst + fixed bed schedule is better than the three other schemes studied. This is particularly the case at metal feed levels greater than 300 ppm.

What is not clear from the figures, which show the relative catalyst life and catalyst consumption, is that the absolute life of a fixed bed reactor handling a 500 ppm metal feed is only about 1 month. It may appear that a fixed bed reactor could be used to process feedstocks containing 500 ppm of metals with currently available catalysts by simply paying more for the catalyst replacement. However, processing a 500 ppm metal feed into a fixed bed reactor is not practical for a commercial run 5 due to the loss of processed amount while the reactor is undergoing catalyst change. Moving bed and countercurrent catalyst monitoring reactors allow more flexibility in processing high metal content feeds and use less catalyst than fixed beds when the metal content in the feed is greater than about 200 ppm.

Example 2

Tables A and B list the catalyst consumption and the metal loading of the catalyst for a number of metal contents of the feed and space velocities. These data are for a catalyst with moderate desulfurization activity and a relatively high (0.300 g / cm 2) metal capacity. (Ks is the kinetic velocity constant for desulfurization; Kq is the kinetic velocity constant for metallization).

Tables C and D list the catalyst consumption and the metal loading of the catalyst for the space velocity = 1.5 at 3 metal contents of the feed. These data are for a catalyst with low desulfurization capacity and high (0.400 g / cm 2) metal capacity.

Table A shows that for a catalyst with medium desulfurization capacity and medium to high capacity for metals, reactors with DC and countercurrent catalysts consume the same amount of catalyst at space velocities below about 1.5. This is even the case for feed metal contents up to 500 ppm. At space velocities of 1.5 or higher, the countercurrent catalyst uses much less catalyst. Table B shows that the reactor with countercurrent catalyst uses the catalyst more efficiently than the reactor with countercurrent catalyst at the higher space velocities. More of the metal capacity of the catalyst is used. The DC-powered catalyst begins to deteriorate significantly when the space velocity is high enough to prevent the catalyst from being loaded to its metal capacity. However, the countercurrent catalyst embodiment continues to charge the catalyst to its metal capacity, even at high space velocities and high metal contents of the feed.

Tables C and D show that the catalyst properties are also important in determining the relative behavior of reactors with DC and countercurrent catalysts * 5 A comparison of Tables A and C at the same space velocity (1.5) shows see that a less active catalyst with a larger metal capacity has a greater difference between reactors with a direct current and a countercurrent catalyst. Again, as can be seen from Table D, the DC-catalyst mode fails when the catalyst is fully charged. Even the countercurrent catalytic converter does not load the catalyst to capacity, however, the countercurrent catalytic converter uses surprisingly much more of the metal capacity of the catalyst than the DC-catalytic converter. The result is lower catalyst consumption rates and more efficient use of the catalyst.

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8302580. 16

Example 3

The desulfurization catalyst life for three different feed mixes was calculated. The feeds for the preparation are Arab heavy residue, Mayan residue and a mixture of 10% Maya / 90% Arab heavy residue. The residues are 371 ° C +. The metal contents for Maya residue are 600 ppm, Arabian heavy residue 115 ppm and the mixture 163 ppm · The lifetimes, calculated for fixed bed units, space velocity = * 0.38, sulfur content of the product 6% are 10 Arabic heavy residue 3700 hours mixture 2300 hours

Mayan residue 500 hours

For both Maya residue and mixture feeds, a demetallization monitoring reactor would be necessary to achieve commercially reasonable life spans.

Catalyst costs were calculated using a mixture as the feed and process schemes of Figure 1. The simulated version is based on the following features: the space velocity of the RDS unit is 0.38, the feed rate to the reactor system is 17,400,000 l / day, the sulfur content of the product is 0.6%. , RDS catalyst in the main reactors, HDM catalyst in the monitoring reactors and the implementation to achieve a catalyst life of 6300 in the main RDS reactor are according to schemes 2, 3 and 4. To accommodate large and small sizes of the monitoring reactor to simulate 2 simulations were performed (a) an HDM monitoring reactor before two RDS reactors with the HDM reactor of the same size as the RDS reactors using a monitoring space velocity of 0.76 and (b) an HDM monitoring reactor before 55 RDS reactors with the HDM reactor half the size of the RDS reactors using a guard room velocity of 1.52. Using catalyst costs of $ 3 / lb for the HDM catalyst and $ 4 / lb for the RDS catalyst, the total catalyst cost in dollars / barrel feed is as follows 8302580 m 17 guard room no swing guard bed guard bed speed guard guard beds with catalytic converter with catalytic converter in rectifier in counter-current _ 0.76 1.32 0.75 0.66 0.61 1.52 - 0.85 0.70 0.63

During 1 cycle of the life of the RDS catalyst (6300 hours; 10 262.5 days) it appears that even with a feed with a metal content of 163 ppm, moving beds with a countercurrent catalyst have a clear economic advantage over moving beds with DC-powered catalysts as monitoring reactors. A large monitoring reactor (space velocity = * 0.76) would save the 15 refiner (17,400,400 1 / day; 6,300 hours) $ 420,000 in catalyst costs by using a countercurrent catalytic monitoring reactor with a small monitoring reactor (space velocity * 1.52) would save the refiner $ 588,000. It will be appreciated that these significant savings become even more violent as the metal content of the feed increases.

8302580

Claims (39)

Process according to claim 1, characterized in that the feed contains iron, nickel, arsenic or vanadium compounds or mixtures thereof. Method according to claim 1 or 2, characterized in that the feed also contains organic sulfur compounds. Method according to claims 1 to 3, characterized in that the metal compounds make up more than about 200 ppm by weight of the feed. Method according to claims 1 to 4, characterized in that the contacting is carried out under demetallization conditions. 6. Process according to claim 5, characterized in that demethylation conditions are used, which comprise desulfurization conditions. 7. Process according to claims 1 to 6, characterized in that the contacting is carried out in the presence of added hydrogen. 8. Process according to claims 1 to 6, characterized in that the contacting is carried out in the absence of added hydrogen. 9. Process according to claims 1 to 8, characterized in that the contacting is carried out at an hourly feed rate of more than about 0.5. Process according to claim 9, characterized in that a space velocity greater than about 1.0 is used. II. Process according to claim 10, characterized in that a space velocity greater than about 1.5 is used. Method according to claims 1 to 11, characterized in that the contacting is carried out at a temperature above about 315 ° C. 13. Process according to claim 12, characterized in that the contacting is carried out at a temperature above about 371 ° C. 8302580 .- * '19 Method according to claims 1 to 13, characterized in that the contacting is carried out at a pressure greater than about 2170 kPa. 15. Process according to claim 14, characterized in that the contacting is carried out at a pressure greater than 3540 kPa. Process according to claims 1 to 15, characterized in that a feed is used, a substantial amount of which boils above 204®C. 17. Process according to claim 16, characterized in that a feed is used, a considerable amount of which boils above 343 ° C. Process according to claim 17, characterized in that a feed is used, a substantial amount of which boils above 510®C. Process according to claims 16 to 18, characterized in that a feed is used which comes from crude oil. Process according to claims 16 to 18, characterized in that a feed is used which comes from coal. 21. Process according to claims 16 to 18, characterized in that a feed is used which comes from oil shale. Process according to claims 16 to 18, characterized in that a feed is used which comes from tar sand biturns. Process according to claim 19, characterized in that a feed is used which comes from heavy oil. 24. Process according to claims 1 to 23, characterized in that a catalyst is used which contains a hydrogenation component. 25. Process according to claim 24, characterized in that a hydrogenation component is used selected from metal compounds of at least Sen group VIB or VIII of the periodic table. 26. Process according to claims 1 to 25, characterized in that a catalyst is used with a high demetallization activity. 27. Process according to claim 26, characterized in that a catalyst is used, the metal capacity of which exceeds approximately 0.10 g of metals per cm 2. catalyst. 28. Process according to claim 27, characterized in that a catalyst is used with a metal capacity of more than about 0.20 g metal cm3 catalyst. 29. Process according to claims 26 to 28, characterized in that a catalyst with a low desulfurization activity is used. A method according to claims 26 to 28, characterized in that 8302580 uses more than about 50% of the metal capacity. A method according to claim 30, characterized in that more than about 70% of the metal capacity is used. A method according to claim 31, characterized in that more than about 90% of the metal capacity is used. A method according to claims 1 to 32, characterized in that the moving bed is present in a reactor, the direction of movement of the moving bed is downward and the feed flows upwards through the whole part of the reactor through the moving bed 10 is taken. 34. Process for improving the quality of a hydrocarbon-producing feed, characterized in that (a) a hydrocarbon-containing feed containing metal compounds and sulfur compounds is contacted with a demetallization catalyst under demetallization conditions to form a effluent, the demetallization catalyst being in a moving bed and the feed flowing in a direction countercurrent to the catalyst and (b) contacting at least a portion of the effluent with a desulfurization catalyst under desulfurization conditions, the desulfurization catalyst in a fixed bed is available. 35. A process for improving the quality of hydrocarbonaceous feeds, characterized in that (a) a hydrocarbonaceous feed containing metal compounds and sulfur compounds is contacted with a demetallization catalyst under demetallization conditions to form a effluent stream, the demetallization catalyst in a moving bed and the feed flows in a direction countercurrent to the catalyst and (b) contacts at least a portion of the effluent with a desulfurization catalyst under desulfurization conditions, the desulfurization catalyst being in a moving bed, and the effluent flowing in a direction countercurrent with the catalyst. A method according to claim 34 or 35, characterized in that a pressure at step (a) and step (b) is used which is greater than about 2170 kPa. 37. Process according to claim 34 or 35, characterized in that steps (a) and (b) are carried out in the presence of added hydrogen. 8302580 A method according to claim 34 or 35, characterized in that a space velocity of the feed in step (a) is greater than about 0.5. 39. Process according to claim 34 or 35, characterized in that nen 5 uses a demetallization catalyst, with a metal capacity greater than about 0.10 g of metal cm 2 catalyst. 40. Process according to claim 34 or 35, characterized in that a feed is used in which nickel, vanadium, arsenic or iron compounds or mixtures thereof are present. 41. Process according to claim 34 or 35, characterized in that a feed is used, the metal compounds of which form more than about 150 ppm by weight. % 8302580