GB2124252A - Treatment of metals-containing hydrocarbonaceous feeds in countercurrent moving bed reactors - Google Patents

Abstract

Demetallation of heavily metals contaminated hydrocarbonaceous feedstocks is effected by means of a demetallation catalyst in the presence or absence of added hydrogen in a countercurrent moving bed reactor in which the catalyst is contained in a moving bed and the feedstock flows in a direction countercurrent to the catalyst. By this means it is possible to reduce catalyst consumption and make more effective use of the catalyst when processing heavily metals loaded hydrocarbon feeds. <IMAGE>

Description

SPECIFICATION Treatment of metals-containing hydrocarbonaceous feeds in countercurrent moving bed reactors This invention relates to the treatment of hydrocarbonaceous feeds and is concerned with a process for demetallizing heavily metals contaminated feedstocks.

Many petroleum refineries built over the years have been designed for use with relatively high quality petroleum feedstocks. The typical and most desirable feeds have relatively low viscosities and are relatively uncontaminated with metal compounds and sulfur compounds. In recent years, however, the supply of these high quality crude oils has diminished and the price of the easily refined oils has increased dramatically. Further, many of the countries which have reserves of the high quality light petroleum oils are now requiring their customers to take quantities of cheaper, but contaminated, and heavier oils which are generally much less desirable. Countries requiring the purchase of heavy contaminated oils to get lighter, relatively uncontaminated oils include Saudi Arabia and Venezuela.

In addition, and in spite of recent heavy drilling activity, many companies and countries are looking towards the production of synthetic fuels to satisfy future needs for hydrocarbon fuels. Among the ultimate sources for synthetic fuels are oil shales, coal, tar sands, and very heavy oils or tars, such as are found in the Orinoco River Belt. A common characteristic of the liquids produced from these materials is that they are very heavy, have high viscosities, and are very heavily contaminated with metals and sulfur. The problems the petroleum refiner faces in planning for future use of these synthetic feedstocks are similar to those faced in planning for use of the very heavy crude oil feeds.

The threshold problem in dealing with these sorts of feedstocks is their very high metals content.

Metals such as nickel, vanadium and iron are present in such large quantities that if they are not removed before getting into the standard refinery processing scheme, they will foul and contaminate all downstream refinery processes. It can be appreciated that metals removal and desulfurization are problems of increasing importance and that research continues at ever increasing levels seeking new and more efficient catalysts and methods for removing these contaminants from the desirable hydrocarbon materials present in the feeds.

Many different reaction schemes and catalysts have been proposed for use in demetallizing and desulfurizing. Often, however, these processes have been proposed for treating residual oils which have contaminants that are at very much lower levels than the modern refiner must be concerned with.

U.S. 3,826,737, Pegels, et al., July 30, 1 974, discloses a continuous process and apparatus for catalytically treating residual oils. The process is disclosed as operating on a feed having a total metals content of less than 65 ppm by weight. The demetallation reactor disclosed is stated to be suitable either for countercurrent or cocurrent operation, although the patent is directed primarily to cocurrent operation. A later literature disclosure, U.S. 3,882,015, Carson, May 6, 1975, discloses a unitary multiple-stage reaction system for countercurrently contacting a fluid reactant stream with catalyst particles, primarily for reactions involving light naphtha hydrocarbons.

As noted above, most process schemes relating to desulfurizing and demetallizing heavily contaminated feedstocks, if they do not relate to fixed bed operation, related to cocurrent moving bed operation in which the feed and the catalyst both flow through the reactor in the same direction.

Examples of these sorts of schemes include: U.S. 3,730,880, Van der Toorn et al., May 1, 1973- residual oil desulfurization with cocurrent intermittent moving bed condition; U.S. 3,880,598, Van der Toorn et al., April 29, 1 975-residual oil hydrodesulfurization by intermittent cocurrent moving bed operation; U.S. 4,312,741, Jacquin, January 1982-conversion of hydrocarbons or bituminous shale in the liquid phase in semi-stationary or ebullating beds with intermittent countercurrent catalyst flow.

Fixed bed and cocurrent moving beds are easier to design and engineer than countercurrent moving beds. The ease of operation of cocurrent as opposed to counter-current moving beds is reflected in the literature and its disclosure of large numbers of reaction schemes, apparatus, and processes for adding and removing catalysts and reactants in these processes.Some examples of these disclosures include: U.S. 2,956,010, Buckner-method and apparatus for the supply of reactant and contact material to moving masses of granular contact materials; U.S. 3,336,217, Meaux, August 1 5, 1 967-method and apparatus for intermittently withdrawing particulate catalysts from the bed of a high pressure and temperature reactor; U.S. 3,547,809, Ehrlich et al., December 1 5, 1970-a process for the addition and withdrawal of solids from a high pressure reaction vessel by using a pressurized liquid transfer medium; U.S. 3,785,963, Boyd et al., January 1 5, 1 974-withdrawing uniform amounts of solids from a movable bed of solids by a system comprising a plurality of conduits equally spaced across the solids cross-sectional area;U.S. 3,849,295, Addison, November 1 9, 1 974- removal of catalysts from moving bed reactor systems having poor catalyst flow due to liquid reactants or catalyst agglomeration problems; U.S. 3,856,662, Greenwood, December 24, 1 974-solids withdrawal and transport vessels and methods for use in superatmospheric pressure systems: U.S.

4,188,283, Czajkowski et al., February 12, 1 980-start up method for moving bed reactors used in hydrogenating olefin containing hydrocarbons.

Other reaction schemes for demetallation processes include the use of ebullating or fluidized beds. In an ebullating bed, a liquid or gaseous material flows upwardly through a vessel containing a mass of solid particles. The solid particle mass is maintained in random motion by the upflowing streams and the physical space occupied by the catalyst bed is larger ("expanded") as compared either to the space occupied by the catalyst bed when no material flows through it or to a fixed or a moving bed type reaction zone.Discussions of ebullating bed reaction zones and their characteristics can be found in RE 25,770 of U.S. 2,987,465, Johansen, June 6, 1961, as well as in U.S. 3,901,792, Wolk et al., August 26, 1 975-demetallizing and desulfurizing crude or atmospheric residual oils using an ebullating bed, and, in U.S. 4,21 7,206, Nongbri, August 12, 1980-catalytically demetallizing Venezuelian crude oils using fixed and preferably ebullating beds.

The non-patent literature also has discussions relating to upgrading heavy contaminated oils. For example, LC-Fining, as described in "Hydrocarbon Processing", pg. 107, May 1979, involves the use of an ebullating bed reactor. The ebullating or expanded bed design is disclosed as allowing very heavy feedstocks to be processed while never shutting the unit down for catalyst replacement. The H-OIL Process as described in "Hydrocarbon Processing", pg. 112, September 1980, uses an ebullating bed with onstream catalyst addition and withdrawal to up-grade high-metals and high-sulfur content feeds.

The Shell-Bunker Flow Process as described in the Oil and Gas Journal, pg. 120. December 1, 1 980, involves an intermittent cocurrent flow as described in the Pegels and Van der Toorn patents discussed above.

Although one might expect that countercurrent moving beds could be very useful for demetallation and desulfurization reactions, the advantages of counter-current operation, as opposed to cocurrent or even fixed bed operation, have not been sufficient to justify tackling the engineering difficulties or to make them economically desirable. We have now discovered that countercurrent moving bed reaction zones, particularly under certain reaction conditions, are not only better than cocurrent or fixed bed operation, but are so dramatically superior to cocurrent or fixed bed operation as to justify their commercial use and development.

Thus in accordance with the invention, there is provided a process comprising: contacting a hydrocarbonaceous feed, which comprises metal compounds and wherein said metal compounds are present at a level greater than 150 ppm by weight of said feed, with a demetallation catalyst under demetallation conditions, wherein said demetallation catalyst is contained in a moving bed and wherein said feed flows in a direction countercurrent to said catalyst.

In accordance with one aspect of the invention, there is provided a process for upgrading a hydrocarbonaceous feed, comprising: (a) contacting a hydrocarbonaceous feed, which comprises metal compounds and sulfur compounds, said metal compounds being present at a level greater than 1 50 ppm by weight of said feed, with a demetallation catalyst under demetallation conditions to produce an effluent wherein said demetallation catalyst is contained in a moving bed and wherein said feed flows in a direction countercurrent to said catalyst; and (b) contacting at least part of said effluent with a desulfurization catalyst under desulfurization conditions, wherein said desulfurization catalyst is contained in a fixed bed.

In accordance with another aspect of the invention, there is provided a process for upgrading a hydrocarbonaceous feed, comprising: (a) contacting a hydrocarbonaceous feed, which comprises metal compounds and sulfur compounds, said metal compounds being present at a level greater than 1 50 ppm by weight of said feed, with a demetallation catalyst under demetallation conditions to produce an effluent wherein said demetallation catalyst is contained in a moving bed and where said feed flows in a direction countercurrent to said catalyst; and (b) contacting at least part of said effluent with a desulfurization catalyst under desulfurization conditions, wherein said desulfurization catalyst is contained in a moving bed and wherein said effluent flows in a direction countercurrent to said catalyst.

By "moving bed", as used herein is meant, a catalyst configuration in which the catalyst is added at one end of the catalyst bed in an intermittent or substantially continuous manner and is withdrawn at the other end in an intermittent or substantially continuous manner. Typically, the catalyst will be added at the top of the reaction zone and withdrawn at the bottom. A moving bed, however, is to be distinguished from fluidized, ebullating, 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 circulates throughout the reactor, often being carried out of the top of the reactor with the products.Ebullating or expanded beds are very similar to fluidized beds, except that the extent of fluidization is not quite as great and the extent of catalyst movement within the reaction zone is not quite as great. The typical ebullating bed reactor will have a mass of solid particles whose gross volume in the reaction vessel is at least 10% larger when feed is fiowing through it, as compared to the stationary mass with no feed flowing through it. Although the particles in the bed do not necessarily circulate as if they were fluids, they are separated from one another and go through random motion.

In the moving bed, on the other hand, the catalyst particles are substantially in contact with one another. The catalyst bed is not expanded when the fluid or feed is passed through it, and its physical condition, except for the addition and removal of catalyst, is susbtantially that of a fixed bed. The catalyst addition and removal rates for a typical moving bed reactor are 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 vessel will be much larger. 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 which must be balanced are the demetallation capacity of the catalyst itself as well as the metal content of the feed introduced into the reaction zone and the extent of demetallation desired.

Similar considerations are involved in choosing whether to have intermittent or continuous catalyst addition and withdrawal. Catalyst replacement rates can range from several percent of the charge per day to several percent of the charge per week, all depending on reactor size, catalyst metals capacity, feed rate and feed composition. Whether intermittent (addition and withdrawal of discrete batches of catalyst at specified times), or continuous, the catalyst addition and withdrawal method depend on these factors, and others.

The most typical and undesirable metals which are present in hydrocarbonaceous feeds are nickel, vanadium, arsenic, and iron. These metals deactivate desulfurization and other catalysts in downstream 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, those metals in any state in which they may be present in the crude oil, either as metal particles, inorganic metal compounds or as organometallic compounds. Where amounts of metals are referred to herein, the amounts are given by weight based on the metal itself.We have discovered that, the higher the metals content of the feed, the more dramatically efficient a countercurrent demetallation process is In low metal content feeds, however, cocurrent and countercurrent operations have approximately equal efficiency. For these reasons, the feed should have levels of the undesirable metals greater than about 1 50 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.

Although nickel, vanadium, arsenic, and iron are the most usual metal contaminants, other undesired metals, such as sodium and calcium, can also contribute to the metals content of the feed for purposes of this operation.

The typical feed is hydrocarbonaceous, i.e., it contains hydrocarbons. It can be derived from crude petroleum, from coal by means of coal liquefaction, from oil shale, from tar sand bitumen, from heavy oils, and from tars. It can be appreciated that the process works well on the worst materials that the refiner must deal with. These feeds are typically high boiling materials. They typically boil above 2040C, preferably above 3430C and more preferably above about 5100C.

One of the important characteristics which we have discovered is that at higher feed hourly space velocities the countercurrent process is more efficient than cocurrent processes. It can be appreciated that the faster a feed can be fed through a reactor, the smaller the reactor can be, thereby significantly lowering capital costs. The feed hourly space velocity for the process is greater than about 0.5, and preferably greater than about 1.0, in the countercurrent reactor.

The temperatures and pressures within the moving bed can be those typical for demetallation reactions. The pressure is typically above 300 psig (314.7 psia; 21.8 bar), preferably above about 500 psig (514.7 psia; 35.5 bar). The temperature is typically greater than about 31 50C, and preferably above 371 OC. Generally, the higher the temperature, the faster the metals are removed; but the higher the temperature, the less efficiently the metals capacity of the demetallation catalyst is used.

The reaction can be conducted in the presence or the absence of added hydrogen. Typically, hydrogen is used.

Catalysts which can be used in the countercurrent reaction zone are those which can be typically used for demetallation reactions. The preferred materials usually have high average pore diameters.

Examples of demetallation catalysts are disclosed in U.S. 3,947,347, Mitchell, March 30, 1 976; U.S.

4,119,531, Hopkins et al., October 10, 1978; U.S. 4,192,736, Kluksdahl, March 11, 1980; and U.S.

4,227,995, Sze et al., October 14, 1 980. These patents and others which also disclose acceptable demetallation catalysts can be found in general, in Class 208, Subclass 251.

The catalysts particularly useful herein, have a high metals capacity. The metals capacity of the catalyst is preferably greater than about 0.10 grams of metal per cubic centimeter of catalyst and is more preferably greater than about 0.20 grams metal per cubic centimeter of catalyst. The difference between cocurrent and countercurrent operation becomes more and more dramatic as the metal capacity of the catalyst increases. The catalyst can also contain a hydrogenation component.

Hydrogenation components are typically Group VIB or VIII metal compounds and are especially nickel, cobalt, molybdenum and tungsten.

One of the outstanding characteristics of our process is that it can be operated to use very high amounts of the metal capacity of the catalyst. We have discovered that very high metal loadings on a demetallation catalyst can be achieved, even at high space velocities and using high metal content feeds. Preferably, more than about 50% of the metals capacity of the catalyst is used, preferably greater than about 70% of the metals capacity is used, and more preferably, greater than about 90% of the metals capacity is used.

The effluent from the countercurrent demetallation reactor can be processed further. All or part of the effluent can go to a hydrodesulfurization reactor. Part of the effluent can be recycled, either for further demetallation or as a diluent, into the feed to the countercurrent demetallation reactor. The efficiency increase in using a countercurrent moving bed before a fixed bed desulfurization reactor is dramatic, especially when compared to other modes of operation. Further, all or part of the effluent of the countercurrent demetallation reaction zone can be fed through a desulfurization unit which is itself a countercurrent moving bed reaction zone.

Figure 1 of the accompanying drawings shows four reactor schemes used in computer simulations for processing residuum. Scheme 1 is a fixed bed reactor alone, charged with RDS (residuum desulfurization) catalyst. Scheme 2 combines a cocurrent moving bed guard reactor with a fixed bed reactor. The moving bed reactor contains HDM (hydrodemetallation) catalyst, which represents 20% of the total catalyst charged to this scheme. The fixed bed reactor contains the same RDS catalyst used in Scheme 1. Scheme 3 combines a countercurrent moving bed guard reactor with a fixed bed reactor. Again, HDM catalyst is charged to the moving bed reactor while RDS catalyst is charged to the fixed bed reactor. The HDM catalyst represents 20% of the total catalyst charged.

Scheme 4 combines fixed bed swing guard reactors with a fixed bed reactor. HDM catalyst is charged to the guard reactors and RDS to the main fixed bed reactor. Each swing guard bed contains 20% of the catalyst charged to one guard bed plus the main reactor. The total catalyst charged to each scheme is equal; the guard beds are charged with a demetallation catalyst and contain 20% of the total catalyst charged to each scheme. The fixed beds, except for the fixed guard bed, are charged with desulfurization catalyst and contain 80% (100% for fixed bed alone) of the catalyst charged to each scheme. The overall LHSV is maintained at 0.29, the guard bed LHSV is 1.45 and the product sulfur is maintained at 0.4 wt %. The feed sulfur is 1.5 wt %, except when the feed metals are 120 ppm; when the feed sulfur is 2.5 wt %. The feed's metal contents are varied from 120 ppm to 900 ppm.The catalyst removal rate for the moving bed reactors is set to maintain a six-month life for the fixed bed reactors.

Figure 2 of the accompanying drawings shows the results for the four reactor schemes, in terms of the relative catalyst consumption for the four schemes. The countercurrent moving bed plus fixed bed reactor scheme consumes the smallest amount of catalyst over the range of feed metals from 1 20 ppm to 900 ppm. The countercurrent moving bed combination is significantiy better than the fixed bed alone or the cocurrent moving bed plus fixed bed schemes. The countercurrent scheme is also better than the fixed guard bed scheme.

Based on catalyst consumption the countercurrent moving bed plus fixed bed scheme is better than the other 3 schemes studied. This is particularly true at feed metals levels greater than 300 ppm.

What is not evident from the Figures, which show relative catalyst life and catalyst consumption, is that the absolute life of a fixed bed reactor processing 500 ppm metals feed is only about one month.

It might appear that a fixed bed reactor could be used to process 500 ppm metals feeds with catalysts available now, by simply paying more for catalyst replacement. But processing 500 ppm metals feed in a fixed bed reactor is not practical for commercial operation because of the loss of throughput while the reactor is having the catalyst changed. Countercurrent moving bed guard beds allow for more flexibility in processing high metals feeds and use less catalyst than fixed beds when the feed metals are greater than about 200 ppm.

Tables I and II list the catalyst consumption and the catalyst metals loading for a number of feed metal levels and space velocities. These data are for a catalyst of moderate desulfurization activity and relatively high (0.300 g/cc) metals capacity. (Ks is the kinetic rate constant for desulfurizing; Km is the kinetic rate constant for demetallizing.) Tables Ill and IV list the catalyst consumption and the catalyst metal loading for LHSV=1.5 at three feed metals levels. These data are for a catalyst with low desulfurization activity and high (0.400 g/cc) metals capacity.

Table I shows that for a catalyst of moderate desulfurization activity and moderate to high metals capacity, cocurrent and countercurrent reactors consume the same amount of catalyst at space velocities less than about 1.5. This is true even for feed metals levels as high as 500 ppm. At space velocities of 1.5 or higher, the countercurrent reactor consumes much less catalyst. Table II shows that the countercurrent reactor is using the catalyst more efficiently that the cocurrent reactor at the higher space velocities. More of the metals capacity of the catalyst is being used.

Cocurrent operation begins to be significantly inferior when the space velocity is high enough to prevent the catalyst from being loaded to its metals' capacity. However, countercurrent operation continues to load the catalyst to its metals capacity even at high space velocities and high feed metal levels.

Tables Ill and IV show that catalyst properties are also important in assessing the relative performance of cocurrent and countercurrent reactors. A comparison of Tables I and Ill at the same space velocity (1.5 LHSV) shows that a less active catalyst having a higher metals capacity has a greater differential between cocurrent and countercurrent reactors. Again, as shown in Table IV, cocurrent operation fails to load the catalyst fully. Even countercurrent operation does not load the catalyst to capacity, however, countercurrent operation does use surprisingly more of the metals capacity of the catalyst than cocurrent operation. The result is lower catalyst consumption rates and more efficient use of the catalyst.

Table I Relative catalyst consumption for cocurrent (Co) and countercurrent (counter) moving bed reactors at three feed metal levels. Countercurrent reactor at LHSV of 0.5 and 300 ppm feed metals equals 1.00.

300 ppm 400 ppm 500 ppm LHSV feed metals feed metals feed metals 0.5 Co 1.01 1.55 2.10 Counter 1.00 1.55 2.10 1.0 Co 2.05 3.11 4.31 Counter 2.05 3.11 4.31 1.5 Co 3.11 4.85 7.06 Counter 2.99 4.56 6.48 2.0 Co 4.85 7.40 11.10 Counter 4.08 6.21 8.63 Maximum metals loading=0.300 g/cc Feed Sulfur=3.0% Product Sulfur=1.5% Product Metals=1 40 to 180 ppm Ks at 7000 F=0.25 hr-' wt %-' Km at 7000F=0.0056 hr-' ppm-' Table II Catalyst metals loading, g/cc, for cocurrent (Co) and countercurrent (Counter) moving bed reactors at three feed metal levels.

300 ppm 400 ppm 500 ppm LHSV feed metals feed metals feed metals 0.5 Co .300 .300 .300 Counter .300 .300 .300 1.0 Co .300 .300 .300 Counter .300 .300 .300 1.5 Co .297 .286 .270 Counter .300 .300 .300 2.0 Co .248 .247 .227 Counter .298 .298 .294 Maximum Metals Loading=0.300 glcc Feed Sulfur=3.0% Product Sulfur=1.5% Product Metals=1 40 to 180 ppm K5 at 7000 F=0.25 hr-' wt %-' Km at 700 F=0.0056 hr-1 ppm-l Table Ill Relative catalyst consumption for cocurrent (Co) and countercurrent (Counter) moving bed reactors at three feed metal levels. Countercurrent reactor at LHSV of 1.5 and 300 ppm feed metals equals 1.00.

300 ppm 400 ppm 500 ppm LHSV feed metals feed metals feed metals 1.5 Co 1.71 2.63 4.14 Counter 1.00 1.45 1.93 Maximum Metals Loading=0.400 g/cc Feed Sulfur=3.0% Product Sulfur=1.5% Product Metals=1 40 to 175 ppm K5 at 7000 F=0.1 5 hr-' wt. %-' Km at 700 F=0.0035 hr-l ppm-1 Table IV Catalyst metals loading, g/cc for cocurrent (Co) and countercurrent (Counter) moving bed reactors at three feed metal levels.

300 ppm 400 ppm 500 ppm LHSV feed metals feed metals feed metals 1.5 Co .202 .197 .172 Counter .346 .360 .367 Maximum Metals Loading=0.400 g/cc Feed Sulfur=3.0% Product Sulfur=1.5% Product Metals=1 40 to 175 ppm K5 at 7000 F=0.1 5 hr' wt. %-1 Km at 7000 F=0.0035 hr-l ppm-l The desulfurization catalyst life for three different feed mixtures was calculated. The feeds for the simulation are Arabian Heavy residuum, Maya residuum, and a mixture of 10% Maya/90% Arabian Heavy. The residua are 7700F+.The metals contents are Maya-600 ppm, Arabian Heavy-1 15 ppm, and mixture-i 63 ppm. The run lives calculated for fixed bed units, LHSV=0.38, product sulfur 0.6% are: Arabian Heavy 3700 hrs.

Mixture 2300 hrs.

Maya 500 hrs.

For either the Maya or Mixture feeds, a guard reactor would be necessary for demetallation to achieve commercially reasonable run lives.

Using the Mixture as the feed and the process schemes of Figure 1, the catalyst costs were calculated. The simulated operation is based on the foilowing characteristics: RDS unit LHSV of 0.38, feed rate to the reactor system of 32,000 bbl/day, product sulfur of 0.6%, RDS catalyst in main reactors, HDM catalyst in guard reactors, and operation to achieve main RDS reactor catalyst life of 6300 hrs. in schemes 2, 3, and 4. To simulate large and small guard reactor sizes, two simulations were performed (a) an HDM guard reactor in front of two RDS reactors with the HDM reactor of the same size as the RDS reactors, using a guard LHSV of 0.76 and (b) an HDM guard reactor in front of two RDS reactors with the HDM reactor one-half the size of the RDS reactors, using a guard LHSV of 1.52.Using catalyst costs of $3.00/lb for HDM catalyst and $4.00/lb for RDS catalyst, the total catalyst costs, in dollars/bbl feed are as follows: Swing Cocurrent Countercurrent Guard LHSV No guard guard beds guard bed guard bed 0.76 $1.32 $0.75 $0.66 $0.61 1.52 - $0.85 $0.70 $0.63 Over one cycle of RDS catalyst life (6300 hrs.; 262.5 days) it can be seen that even with a feed having a metals content of 1 63 ppm, countercurrent moving beds have a significant economic benefit over cocurrent moving beds as guard reactors. With a large guard reactor (LHSV=0.76) the refiner would save (32,000 bbl/day; 6300 hrs.) $420,000 just in catalyst cost by using a countercurrent guard reactor; and with a small guard reactor (LHSV=1.52) the refiner would save $588,000. It can be appreciated that these significant savings become even more dramatic as the feed metals content increases.

Claims (37)

Claims

1. A process comprising: contacting a hydrocarbonaceous feed having a metals content greater than 1 50 ppm by weight of said feed with a demetallation catalyst under demetallation conditions, wherein said catalyst is contained in a moving bed and wherein said feed flows in a direction countercurrent to said catalyst.

2. A process according to Claim 1, wherein said feed comprises one or more of iron, nickel, vanadium and arsenic.

3. A process according to Claim 1 or 2, wherein said feed further comprises one or more organosuifur compounds.

4. A process according to Claim 1,2 or 3, wherein the metals content of the feed is greater than 200 ppm by weight of said feed.

5. A process according to Claim 1, 2, 3 or 4, wherein said demetallation conditions include desulfurizing conditions.

6. A process according to any preceding claim, wherein said contacting takes place in the presence of added hydrogen.

7. A process according to any preceding claim, wherein said contacting takes place at a feed hourly space velocity greater than 0.5.

8. A process according to Claim 7, wherein said feed hourly space velocity is greater than 1.5.

9. A process according to any preceding claim, wherein said contacting takes place at a temperature greater than 31 50C (6000F).

1 0. A process according to Claim 9, wherein said contacting takes place at a temperature greater than 371 0C (7000F).

11. A process according to any preceding claim, wherein said contacting takes place at a pressure above 300 psig (314.7 psia; 21.7 bar).

12. A process according to Claim 11, wherein said contacting takes place at a pressure above 500 psig (514.7 psia; 35.4 bar).

13. A process according to any preceding claim, wherein said feed boils above 2040C (4000 F).

14. A process according to Claim 13, wherein said feed boils above 3430C (6500F).

15. A process according to Claim 14, wherein said feed boils above 51 OOC (9500 F).

1 6. A process according to any preceding claim, wherein said feed is derived from crude petroleum.

1 7. A process according to any one of Claims 1 to 1 5, wherein said feed is derived from coal.

18. A process according to any one of Claims 1 to 15, wherein said feed is derived from oil shale.

19. A process according to any one of Claims 1 to 15, wherein said feed is derived from tar sand bitumen.

20. A process according to any one of Claims 1 to 1 5, wherein said feed is derived from heavy oil.

21. A process according to any preceding claim, wherein said catalyst contains a hydrogenation component.

22. A process according to Claim 21, wherein said hydrogenation component is at least one Group VIB or VIII metal compound.

23. A process according to any preceding claim, wherein said catalyst has a high metals capacity.

24. A process according to Claim 23, wherein the metals capacity of said catalyst is greater than 0.10 g metals per cubic centimeter catalyst.

25. A process according to Claim 24, wherein the metals capacity of said catalyst is greater than 0.20 g metals per cubic centimeter catalyst.

26. A process according to Claim 23, 24 or 25, wherein said catalyst has low desulfurization activity.

27. A process according to Claim 23, 24 or 25, wherein more than 50% of said metals capacity is used.

28. A process according to Claim 27, wherein greater than 70% of said metals capacity is used.

29. A process according to Claim 28, wherein greater than 90% of said metals capacity is used.

30. A process according to any preceding claim, wherein said moving bed is contained in a reactor, wherein the direction of movement of said moving bed is downward, and wherein said feed flows upward through the entire portion of said reactor occupied by said moving bed.

31. A process for upgrading a hydrocarbonaceous feed comprising: (a) contacting a hydrocarbonaceous feed which comprises metal compounds and sulfur compounds, said metal compounds being present at a level greater than 1 50 ppm by weight of said feed, with a demetallation catalyst under demetallation conditions to produce an effluent wherein said demetallation catalyst is contained in a moving bed and wherein said feed flows in a direction countercurrent to said catalyst; and (b) contacting at least part of said effluent with a desulfurization catalyst under desulfurization conditions, wherein said desulfurization catalyst is contained in a fixed bed.

32. A process for upgrading a hydrocarbonaceous feed, comprising: (a) contacting a hydrocarbonaceous feed, which comprises metal compounds and sulfur compounds, said metal compounds being present at a level greater than 1 50 ppm by weight of said feed, with a demetallation catalyst under demetallation conditions to produce an effluent wherein said demetallation catalyst is contained in a moving bed and wherein said feed flows in a direction countercurrent to said catalyst; and (b) contacting at least part of said effluent with a desulfurization catalyst under desulfurization conditions, wherein said desulfurization catalyst is contained in a moving bed and wherein said effluent flows in a direction countercurrent to said catalyst.

33. A process according to Claim 31 or 32, wherein the pressure in step (a) and step (b) is greater than 300 psig (314.7 psia; 21.7 bar).

34. A process according to Claim 31,32 or 33, wherein step (a) and step (b) are conducted in the presence of added hydrogen.

35. A process according to Claim 31, 32, 33 or 34, wherein the feed hourly space velocity of step (a) is greater than 0.5.

36. A process according to Claim 31,32, 33, 34 or 35, wherein said demetallation catalyst has a metals capacity greater than 0.10 g metal per cubic centimeter of catalyst.

37. A process according to any one of Claims 31 to 36, wherein the compounds present in said feed are nickel, vanadium, or iron compounds or mixtures thereof.