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Publication numberUS3383301 A
Publication typeGrant
Publication dateMay 14, 1968
Filing dateJan 20, 1966
Priority dateJan 20, 1966
Also published asDE1645750A1, DE1645750B2
Publication numberUS 3383301 A, US 3383301A, US-A-3383301, US3383301 A, US3383301A
InventorsBeuther Harold, Bruce K Schmid
Original AssigneeGulf Research Development Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Residue desulfurization with catalyst whose pore volume is distributed over wide range of pore sizes
US 3383301 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,383,301 RESIDUE DESULFURIZATIUN WITH CATALYST WHOSE FORE VOLUME IS DISTRIBUTED OVER WIDE RANGE OF PURE SIZES Harold Beuther, Gihsonia, and Bruce K. Schmid,

McCandless Township, Allegheny County, 1321., assignors to Gulf Research & Development Company, Pittsburgh, Pa., a corporation of Delaware No Drawing. Filed Jan. 20, 1966, Ser. No. 521,816 8 Claims. (Cl. 208-216) ABSTRACT OF THE DISCLOSURE The disclosure relates to the hydrodesulfurization of sulfur-containing petroleum oils containing residual components and metallic contaminants employing catalyst comprising a hydrogenating component composited on an alumina base whose pore volume is distributed over a wide range of pore sizes.

This invention relates to desulfurization of petroleum oils containing residual components and having high sulfur contents and more particularly to a catalytic hydrodesulfurization process for reducing high sulfur content petroleum oils containing residual components by the use of catalytic compositions that are especially effective for such purpose.

Residual petroleum oil fractions containing relatively high proportions of sulfur as well as high sulfur crude oils are relatively less salable than the corresponding oils of low sulfur content. In fact, high sulfur residual fuels may be entirely unsalable in some localities, since they cannot be used as low grade fuel in municipalities that have adopted maximum sulfur specifications for fuels burned in their jurisdictions. Such residual fuels may be still more difiicultly disposable when their viscosities and/ or heavy metals content are so great as to require dilution with the relatively large proportions of cutter stocks of relatively greater value.

It has been proposed to improve the salability of high sulfur content, residual-containing petroleum oils by a variety of hydrodesulfurization processes. However, difficulty has been experienced in achieving an economically feasible catalytic hydrodesulfurization process, because notwithstanding that the desulfurized products may have a wider marketability, the manufacturer may be able to charge little or no additional premium for the low sulfur desulfurized products, and since hydrodesulfurization operating costs have tended to be relatively high in view of the previously experienced, relatively short life for catalysts used in the hydrodesulfurization of residual-containing stocks. Short catalyst life is manifested by inability of a catalyst to maintain a relatively high capability for desulfurizing charge stock with increasing quantites of coke and/or metallic contaminants which act as catalyst poisons. Satisfactory catalyst life can be obtained relatively easily with distillate oils but is especially diificult to obtain in desulfurizing petroleum oils containing residual components, since the asphaltene or asphaltic components of an oil, which tend to form disproportionate amounts of coke, are concentrated in the residual fractions of a petroleum oil, and since a relatively high proportion of the metallic contaminants that normally tend to poison catalysts are commonly found in the asphaltene components of the oil.

The present invention relates to a process for the catalytic hydrodesulfurization of sulfur-containing petroleum oils containing residual components and containing metallic contaminants in the presence of a catalyst having an unusual tolerance for the coke and metallic contaminants that accompany processing of residual-containing stocks, :as evidenced by a continued high level of desulfurization activity, notwithstanding a relatively heavy deposition of coke and metal contaminants. In accordance with the process of this invention a sulfur-containing petroleum oil that contains residual components and metallic contaminants normally tending to act as catalyst poisons, is contacted with hydrogen at hydrodesulfurization conditions in the presence of a catalyst comprising at least one hydrogenating component composited with an alumina base, said composite catalyst having not more than 15 percent of the volume of the pores having a radius in the range of 0 to 300 Angstrom units in any 10 Angstrom unit incrernent of pore radius in the range of pores having a 0 to 120 Angstrom unit radius, and also having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least 15 percent of such pore volume in pores having a radius greater than 30 Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units. Catalysts of the class indicated that also have a surface area of at least 100 square meters per gram are preferred. The hydrodesulfurization reactions of the present process can be effected at a hydrogen partial pressure in the range of about 500 to 4000 p.s.i.g., preferably about 1000 to 2000 p.s.i.g., a temperature, after startup, in the range of about 600 to 850 F., preferably about 650 to 800 F., at a space velocity in the range of 0.1 to 10, preferably about 0.5 to 5, volumes of liquid per volume of catalyst per hour, using a hydrogenzoil ratio in the range of about 1000 to 15,000, preferably about 5000 to 10,000 s.c.f. of hydrogen per barrel of oil. Especially advantageous results are obtained by the present invention in the desulfurization of petroleum oil stocks containing at least 2 percent sulfur and at least 10 ppm. vanadium, and when the operating conditions of the process are so selected and maintained as to produce a constant reduction in sulfur content of about 40 to 80 percent, preferably 50 to percent.

The feed stock to the desulfurization reaction zone of the present process can be any sulfur-containing petroleum stock containing residual materials. Since the catalysts of the class disclosed herein have an especially high tolerance for feed stocks containing metallic contaminants normally tending to act as catalyst poisons, the present process is especially advantageous in connection with crude oils containing at least 10 p.p.m. vanadium and with residues containing at least 20 ppm. vanadium. Since an important advantage achieved by the present invention is the maintenance of a relatively high level of desulfurization, notwithstanding a relatively large accumulation of coke deposits and metallic contaminants, the invention is especially useful in connection with crude oils containing at least 1.5 percent sulfur and with residues containing at least 2 percent sulfur. From what has been said, it will be clear that the feed stock can be a whole crude. However, since the high sulfur content components of a crude oil tend to be concentrated in the higher boiling fractions, the present process more commonly will be applied to a bottoms fraction of a petroleum oil, i.e., one which is obtained by atmospheric distillation of a crude petroleum oil to remove lower boiling materials such as naphtha and furnace oil, or by vacuum distillation of an atmospheric residue to remove gas oil. Typical residues to which the present invention is applicable will normally be substantially composed of residual hydrocarbons boiling above 900 F. and containing a substantial quantity of asphaltic materials. Thus, the charge stock can be one having an initial or 5 percent boiling point somewhat below 900 F., provided that a substantial proportion, for example,

about 40 or 50 percent by volume, of its hydrocarbon components boil above 900 F. A hydrocarbon stock having a 50 percent boiling point of about 900 F. and which contains asphaltic materials, 3 percent by weight sulfur and 15 ppm. vanadium is illustrative of such charge stock.

The hydrodesulfurization reactions effected pursuant to the process of this invention are carried out at a temperature that is maintained, after the relatively rapid elevation of temperature employed during startup, in the range of about 600 to 850 F. Hydrodesulfurization at temperatures in the range of about 650 to 800 F. are preferred, since notwithstanding that the same given degree of desulfurization can be maintained at higher temperatures, relatively larger proportions of gaseous products are produced, which products involve a disproportionate consumption of hydrogen.

The desulfurization reactions are effected in the presence of uncombined hydrogen partial pressures in the range of about 750 to 4000 p.s.i.g. The process of this invention is especially useful in connection with desulfurizations in which the degree of desulfurization is maintained at a relatively high level, i.e., 40 to 80 percent, preferably 50 to 75 percent, and in which hydrogen consumption is minimized. To this end we prefer to carry out the process of this invention at hydrogen partial pressures in the range of 1000 to 2500 p.s.i.g.

The desulfurization reactions of the subject process are carried out at a liquid hourly space velocity in the range of 0.1 to 10, preferably about 0.5 to 5 liquid volumes of oil per volume of catalyst per hour.

The hydrogen gas which is used during the hydrodesulfurization is circulated at a rate between about 1000 and 15,000 s.c.f./bbl. of feed and preferably between about 5000 and 10,000 s c.f./bbl. The hydrogen purity may vary from about 60 to 100 percent. If the hydrogen is recycled, which is customary, it is desirable to provide for bleeding off a portion of the recycle gas and to add makeup hydrogen in order to maintain the hydrogen purity within the range specified. Satisfactory removal of hydrogen sulfide from the recycled gas will ordinarily be accomplished by such bleed-off procedures. However, if desired, the recycled gas can be washed with a chemical absorbent for hydrogen sulfide or otherwise treated in known manner to reduce the hydrogen sulfide content thereof prior to recycling.

As indicated, the invention is especially beneficial Where hydrodesulfurization is effected without concomitant cracking of the hydrocarbons present in the feed stock. To achieve this objective, the temperature and space velocity are selected within the ranges specified that will result in the reduction in the sulfur content of the feed stock of about 40 to 80 percent, preferably 50 to 75 percent, and so that no more than about 1 to 5 gram moles of hydrogen will be consumed per gram atomic weight of sulfur removed from the feed stock.

As indicated, it has been found that the nature of the catalyst employed in the process is very important with respect to the results achieved. The class of catalysts useful for purposes of the present invention comprises those containing at least one hydrogenating component composited with an alumina carrier, which composite catalyst has not more than 15 percent of the volume of the pores having a radius of 0 to 300 Angstrom units in any Angstrom unit increment of pore radius in the range of pores having a 0 to 120 Angstrom unit radius. Furthermore, the pore volume should be more or less uniformly distributed over this range so that at least about 10 percent of the above pore volume of the pores having a radius in the range of 0 to 300 Angstrom units is in pores having a radius of less than 30 Angstrom units, at least percent of such pore volume is in pores having a radius of greater than Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume is in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units.

It will be appreciated that for most porous catalyst supports, the major portion of the pore volume will be in pores of less than 300 Angstrom units radius and that by far the major portion of the total pore volume in these relatively small pores will be found in pores having a radius from 0 to 120 Angstrom units. Since the chief portion of the total pore volume of a given porous catalyst support material is normally made up of pores in the 0 to 120 Angstrom unit radius range, it is these pores that are considered to be chiefly responsible for the behavior of a given catalyst. Although the present invention is based on the discovery of a correlation between the hydrodesulfurization of petroleum residues and the distribution of the pore volume in the 0 to 120 Angstrom unit radius range, the pore volume fractions set forth herein have been stated in terms of the volume of the pores having a radius in the 0 to 300 Angstrom unit radius range, since pore volume distribution, as measured by conventional nitrogen adsorption-desorption techniques, is normally reported in these terms.

For most porous catalytic supports, particularly those considered to be especially effective in the hydrodesulfurization of distillate stocks, it has been observed that a very high concentration of the pore volume will be concentrated in pores of about the same size, and it has been postulated that there is a correlation between the catalytic effect of a catalyst, the diameter or radius of the most frequently occurring pore size, and the average molecular diameter of the feed stock. While this theory may hold true for the desulfurizing activity of catalysts with respect to distillate feed stocks, it has now been found that contrary to supposition, what is needed for greater effectiveness in the desulfurization of residual stocks is not a catalyst having a large concentration of pores of any particular size range, but rather a catalyst having a relatively uniform, wide distribution of pores over the entire 0 to 120 Angstrom radius range.

While the mechanism by which the catalysts of this invention function has not been conclusively established, it is considered that their unusual effectiveness may be due to the fact that there are sufficient large pores present to accommodate the preferentially adsorbed large molecules without blocking, so that the pores in other size ranges, which would normally tend to become blocked by the coked residue of large molecules, remain relatively free to effect desulfurization of small and intermediate sized molecules. This hypothesis is supported by the fact that catalysts of the class disclosed herein show superior aging characteristics as compared to catalysts having a disproportionate pore volume distribution, even though the latter catalysts show higher initial desulfurizing activity.

Thus, the class of catalysts included by the present invention comprises those containing at least one hydrogenating component composited with a porous alumina support, which composite catalyst has not more than 15 percent of the volume of the pores having a radius in the range of 0 to 300 Angstrom units in any 10 Angstrom unit increment of pore radius in the range of pores having a 0 to 120 Angstrom unit radius, and also having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least 15 percent of such pore volume in pores having a radius greater than 30 Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units. Such catalysts also should have a surface area of at least square meters per gram.

Catalysts of the class indicated can be obtained in any convenient way, for example by impregnation of a suitable alumina support with solutions containing the desired hydrogenating component or components, drying and calcining. Suitable alumina supports, like the finished catalysts, are those having not more than 15 percent of the volume of the pores having a radius in the range of 0 to 300 Angstrom units in any Angstrom unit increment of pore radius in the range of pores having a 0 to 120 Angstrom unit radius, and also having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least percent of such pore volume in pores having a radius greater than 30 Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units. Such supports can be obtained as articles of commerce or they can be prepared in any convenient manner. An example of a suitable commercial support are selected batches of Filtrol Grade 86 alumina having the indicated pore Volume distribution.

Alternatively, a support having the desired pore volume distribution can be prepared by precipitation, at a pH in the range of about 4.5 to 6.0 of aluminum hydroxide from an aqueous solution of aluminum sulfate, at a temperature in the range of about 160 to 210 F., preferably 180 to 200 F., by addition of ammonia gas or ammonium hydroxide. The pH of the mixture can be raised as high as 8 to minimize peptization or colloid formation. The mixture is preferably allowed to age for a period of at least 4 to 6 hours or longer, preferably with stirring, in order to complete the reaction as far as possible. The elevated temperature is maintained throughout the aging period. After aging, the precipitate is filtered and washed free of sulfate ions and dried. The thusobtained mixture Will comprise a crystalline alumina mixture containing principally boehmite and bayerite aluminas. This material is then calcined with a suitable hot gas, such as flue gas, at a temperature in the range of about 1000 to 1250 F. and suflicient to obtain a temperature in the solids such as to effect substantial dehydration of the water of constitution. The calcined product will have the pore size distribution characteristic of the class of supports useful for the purposes of the present invention.

It is emphasized that the hydrogenating components need not be deposited on the support after calcination, and, if desired, can be deposited on the dried uncalcined support, prior to calcination.

The hydrogenating component of the class of catalysts disclosed herein can be any material or combination thereof that is effective to hydrogenate and desulfurize the charge stock under the reaction conditions utilized. For example, the hydrogenating component can be at least one member of the group consisting of Group VI-B and Group VIII metals in a form capable of promoting hydrogenation reactions, especially effective catalysts for the purposes of this invention are those comprising molyb denum and at least two members of the iron group metals. Preferred catalysts of this class are those containing nickel, cobalt and molybdenum, but other combinations of iron group metals and molybdenum such as iron, nickel and molybdenum and iron, nickel and molybdenum and iron, cobalt and molybdenum, as well as combinations of nickel and molybdenum, cobalt and molybdenum, nickel and tungsten or other Group VI-B or Group VIII metals taken singly or in combination. The hydrogenating components of the catalysts of this invention can be employed in sulfided or unsulfided form; however, the use of catalysts whose hydrogenating component is in sulfided form is preferred.

Although the hydrogenating components indicated above can be employed in any proportions with respect to each other, especially effective catalysts for the purposes of this invention are those in which the hydrogenating component is selected from the group consisting of sulfides and oxides of (a) a combination of about 2 to 25 percent, preferably 4 to 16 percent, by Weight molybdenum and at least 2 iron group metals where the iron group metals are present in such proportions that the atomic ratio of each iron group metal with respect to molybdenum is less than about 0.4, and (b) a combination of about 5 to 40 percent, preferably 10 to 25 percent, by weight of nickel and tungsten where the atomic ratio of tungsten to nickel is about 1:01 to 5, preferably 1:03 to 4.

When the use of a catalyst in sulfided form is desired, the catalyst can be presulfided, after calcination, or calcination and reduction, prior to contact with the charge stock, by contact With a sulfiding mixture of hydrogen and hydrogen sulfide, at a temperature in the range of about 550 to 650 F., at atmospheric or elevated pressures. Presulfiding can be conveniently effected at the beginning of an onstream period at the same conditions to be employed at the start of such period. The exact proportions of hydrogen and hydrogen sulfide are not critical, and mixtures containing low or high proportions of hydrogen sulfide can be used. Relatively low proportions are preferred for economic reasons. When the unused hydrogen and hydrogen sulfide utilized in the presulfiding operation is recycled through the catalyst bed, any water formed during presulfiding is preferably removed prior to recycling through the catalyst bed. It will be understood that elemental sulfur or sulfur compounds, e.g., mercaptans, that are capable of yielding hydrogen sulfide at the sulfiding conditions, can be used in lieu of hydrogen sulfide.

Although presulfiding of the catalyst is preferred, it is emphasized that this is not essential as the catalyst will normally become sulfided in a very short time by contact, at the process conditions disclosed herein, with the high sulfur content feed stocks to be used.

EXAMPLE 1 In a specific embodiment, a catalyst representative of the class disclosed herein was prepared by deposition of the desired hydrogenating components on a commercial, calcined alu-rnina base having a density of 39.0 pounds per cubic foot, a surface area of 299.6 square meters per gram, a pore volume of 0.79 milliliter per gram and an average pore radius of 79.1 Angstrom units. A typical sample of the calcined base had a pore volume distribution over the range of pores having a radius from 0 to 300 Angstrom units as follows:

Pore radius, A.: Pore volume, percent The hydrogenating components comprised a combination of 8 percent molybdenum, 1 percent cobalt and 0.5 percent nickel. The atomic ratios of these metals were as follows: 0.2 Co and 0.1 NizMo. A catalyst of equivalent makeup and properties is suitably prepared by impregnating an alumina base having the pore volume distribution indicated with a solution of ammonium paramolybdate in an aqueous ammoniacal solution. The amount of ammonia used in the solution was sufficient to yield ammonium monomolybdate. The catalyst base is impregnated with the ammonium molybdate solution using the incipient wetness technique. Following the initial impregnation, the material is dried for 24 hours at a temperature above that required to evaporate water of impregnation.

After drying, the nickel and cobalt metals are deposited on the molybdenum-alumina from a water solution of the metal nitrates. The thus-impregnated base is then dried as described and calcined at 900 to 1000 F. in an oxygen-containing gas, whereby the hydrogenating metal components are converted to the oxide form.

The finished catalyst employed in the runs described below had a total pore volume of 0.46 ml./g., a surface area of 165.8 m. /g., and an average pore radius of 74.5 Angstrom units and a pore volume distribution, over the range of pores having a radius from to 300 Angstrom units, as follows:

Pore radius, A.: Pore volume, percent The above-described catalyst was used in the catalytic hydrodesulfurization of a Kuwait crude oil containing approximately 2.5 percent sulfur and approximately 30 p.p.m. vanadium. The sulfur content of the residual fuel oil component of the crude (650 F. plus residue) was 4.0 percent. The conditions employed in the reaction were 2400 p.s.i.g. total reaction pressure (2000 p.s.i.g. hydrogen partial pressure) and a space velocity of 3.28 liquid volumes of oil per volume of catalyst, while maintaining a hydrogen to oil ratio of 5000 s.c.f./bbl. In this operation, the initial stabilized reaction temperature, following initial rapid temperature increase during startup, was 726 F. after four days of operation. At that time the sulfur content of the residual fuel oil component of the product (650 F. plus residue) was approximately 1.16 percent. The reaction was allowed to continue with temperature elevation as required to maintain the sulfur content of the residual fuel oil component of the crude oil feed stock below 1.3 percent sulfur. After 56 /2 days of continuous operation, the sulfur content of the residual fuel oil component of the product had not exceeded 1.3 percent and the temperature of the reaction had not exceeded 760 F.

By way of contrast, in a similar aging run carried out at 2400 p.s.i.g. total reactor pressure (2000 p.s.i.g. hydrogen partial pressure), a space velocity of 3.0 liquid volumes of oil per volume of catalyst per hour, while maintaining a hydrogen to oil ratio of 5000 s.c.f./bbl. oil, using a catalyst containing the same quantities of nickel, cobalt and molybdenum deposited on a commercial alumina carrier, where the finished catalyst had 28.4 percent of the pore volume of pores having a radius of 0 to 300 Angstrom units in pores having a radius of 30-40 Angstrom units and 28.8 percent of such pore volume in pores having a radius of -30 Angstrom units, but only 7.1 percent of such pore volume in pores having a radius of 50 to 60 Angstrom units, 2.4 percent in the 60 to 70 Angstrom unit range, 0.5 percent in the range of 70 to 80 Angstrom units, 0.4 percent in the range of 80 to 90 Angstrom units, 0.2 percent in the range of 90 to 100 Angstrom units, and which was known to be very effective for desulfurization of petroleum distillate fractions, the percent sulfur in the residual fuel oil component of the product was 1.1 percent at 704 F. after two days. After 20 days the temperature had been raised to 769 F.,

and the percent sulfur in the residual fuel oil component of the product was 1.52 percent.

Similarly, still another aging run was carried out with the same Kuwait crude oil charge stock at a total reaction pressure of 2300 p.s.i.g. (2000 p.s.i.g. hydrogen partial pressure), a 3.1 liquid hourly space velocity, using a hydrogen to oil ratio of 9000 s.c.f./bbl. wherein there was employed a catalyst containing the same portions of nickel, cobalt and molybdenum as in the above-indicated catalyst, deposited on a commercial alumina having 20.2 percent of the pore volume of the pores having a radius of 0 to 300 Angstrom units in pores having a radius of 10-20 Angstrom units and 25.2 percent of such pore volume in pores having a radius of 20-30 units, but only 6.9 percent in the range of 50 to 60 Angstrom units, 3.2 percent in the range of 60 to Angstrom units, 1.9 percent in the range of 70 to Angstrom units, 1.5 percent in the range of 80 to Angstrom units, and 1.0 percent in the range of 90 to Angstrom units. Although this catalyst had been found highly effective for desulfurization of petroleum distillates, the sulfur content of the residual fuel oil component of the product increased from about 1.16 percent at two days and a temperature of 735 F. to 1.64 percent after 20 days, in spite of an increase in temperature to 765 F. during that time.

EXAMPLE 2 In another specific embodiment, the charge stock of Example 1 is hydrodesulfurized at the conditions of Example 1 with a catalyst of 6 percent nickel and 19 percent tungsten, in sulfided form, deposited on the alumina of Example 1.

The unusual coaetion during hydrodesulfurization, between catalysts of the class disclosed herein and highsulfur petroleum oils containing residual components, has been demonstrated by comparative experiments in which separate samples of a Kuwait crude oil containing 2.50 percent sulfur and approximately 30 p.p.m. vanadium were hydrodesulfurized at the same process conditions, over an alumina-supported catalyst representative of the class disclosed herein and another catalyst containing the same hydrogenating components in the same proportions. In both runs the hydrodesulfurization was effected at a hydrogen partial pressure of 1000 p.s.i.g. at a temperature of 790 F. and at a space velocity of 2.0 liquid volumes of oil per volume of catalyst per hour, while maintaining a hydrogen to oil ratio of 10,000 s.c.f./bbl. In each instance the catalyst was an alumina having deposited thereon 0.5 percent nickel, 1 percent cobalt and 8 percent molybdenum. In each case the catalyst was obtained by impregnation of the calcined alumina base with aqueous solutions containing the metallic impregnants in soluble form, followed by drying and calcining to the oxide form. The physical properties of the respective catalysts, including the pore volume distribution, is indicated in the following table in which Catalyst A is a catalyst representative of the class disclosed herein and in which Catalyst B is a catalyst obtained from another commercial alumina base.

Pore Radius, Angstrom Units Catalyst A, Catalyst 13,

Volume, percent Volume, percent 1.3 0. 1 3. 1 0.2 9. 8 0. 4 14. 5 0.3 8. 7 0. 2 6. 8 0.2 6. 7 O. 2 6.4 0. 4 6. 5 0. 5 5.2 2.4 5. 5 7. 1 5.0 19.3 3.8 28.4 4. 9 28. 8 11.9 11.5 0.0 0. 0 0. 47 0. 27 Surface Area, mfl/q 221. 2 175. 5 Average Pore Radius, A 91. 7 33.2

tained as bottoms from the vacuum distillation of the atmospheric residue of a Kuwait crude oil was hydrodesulfurized at equivalent conditions over a catalyst of the class disclosed herein and a similarly prepared catalyst temperature during startup. Thereafter, in order to inhaving identical hydrogenating components deposited duce accelerated aging of the catalysts, the same samples thereon but which did not have the pore volume dison which initial activity with the Kuwait crude charge tribution of the herein disclosed catalysts. In each instock referred to above had been deter-mined were then stance the catalyst was an alumina having deposited therecontacted with a Ceuta crude oil feed stock at 2,000 p.s.i.g. on 0.5% nickel, 1% cobalt and 8% molybdenum. In each hydrogen partial pressure, 790 F., and a space velocity 10 case the catalyst was obtained by impregnation of the of 2 liquid volumes of oil per volume of catalyst per calcined alumina base with aqueous solutions containing hour, while maintaining a hydrogen to oil ratio of 10,000 the metallic impregnants in soluble form, followed by s.c.f./bbl. of oil. The Ceuta crude charge stock used for drying and calcining to the oxide form. In these runs aging the catalysts had a gravity of 335 API, a sulfur the Catalysts were Pfesulfided y contaflt With a hydrogen" content of 1.10 percent, a nitrogen content of 0.15 perhydrogen sulfide mixture at the reaction conditions. The cent by weight, a carbon residue of 3.39, a vanadium conphy lcal gwpertles of typical samples of the respective tent of 104 p.p.1n., and a nickel content of 13 ppm. Cont y lnchldlng F P Volume qlstnbutwn, are tact of the catalysts with the Ceuta crude was continued dlcated the fOHQWmg table, wherein Catalyst 0 15 a at the o dition i di t d fo 17 d O i to h catalyst representative of the class disclosed herein and high metals content and high coke-forming tendencies of 20 111 Catalyst D 15 a catalyfst p p f in equivalent the Ceuta crude, this period of time was equivalent to fashlofl from another Commefclal alumina baseabout 70 days of contact with the Kuwait crude. After Catalyst C, catalystD, this accelerated aging period with the Ceuta crude feed Pore Radius, Angstrom Units Pore Vol., Poi-e Vol., stock, the catalysts were again contacted with the Kuwait percent percent crude charge stock described above, without intermediate 300-250 1.2 0.2 regeneration of the catalyst, to determine what activity re gggfigg kg 3:? mained in the respective catalysts for desulfurization of %0 2.8 0.4 the Kuwait crude. Analyses of the aged catalysts were also 1,83 3; 8% obtained to determine the amount of coke and vanadium g g deposited thereon. The results of these experiments are F set forth in the following table: 60-50 9.5 32.9 50-40 9.5 27.1 Desulfurization, Deposits on Aged -30 8.0 15.5 Catalyst percent by Wt. Catalyst, percent by wt.

% 12.3 Fresh Aged Coke Vanadium 35 04123 0:0 0 Total Pore Vol., mL/g. 0. 5128 Catalyst A 79. 2 47. 0 is. s 6.4 Surface Area, /s 165. 0 190. 9 Catalyst B 88, 0 24. 0 14. 0 2. 2 Average Pore Radius, 71. 6 53. 2

The hydrodesulfurization conditions employed in the C i z g f gi g gi g gggg g yg% fi iifi 4O comparative runs and the significant product inspections, a ays i y along with the corresponding charge stock inspections, catalysts having a relatively uniform pore volume d1str1- are set fo1tl1 in the following table. bution 1n the range of pores having a radius of 0 to 120 Angstrom units, i.e., catalysts of the class disclosed herein, have poorer initial desulfurization activity for residual fuel Chara Catalyst Catalyst Stock 0 D oils than conventional alumina-supported desulfurizanon 45 catalysts having a high concentration of pores of about opegltmg Cmlditjons:

. ressure, p.s.Lg l, 000 1, 000 the same particular s1ze, 1.e., catalysts representatlve of Average Tempe flture F 792 791 the type found useful for desulfurizing distillates. Surgydmgen Rateisicif'lbbl 9,284 9,759

un Length, hours 80 80 prisingly, however, it W111 be noted that after severe Liquid Hourly SpacoVelooity, aging, Catalyst A retained sufficient activity still to re- C t move 47 percent of the sulfur from the charge stock, l oy 28.39 15.88 whereas Catalyst B had lost so much activity through q f mspectlonsI ravity, API 5.5 19.5 17.2 aging that it was capable of removing only 24 percent of ISqulfur, percent by wt 5.45 0. 88 1. 24

t 'etb 0.43 0.32 0.30 the sulfur from the charge stock, at the same conditions. g ggs g g g f Not only is this surpnsing, taking into consideratlon the percent by wt 23.11 10.19 11.61 fresh activities of the respective catalysts, but also these G%E m 102 icliel, p.p.m 32 8. 4 13. 6 results are further unexpected in view of the fact that Liquid ProgiuctFractions: Gasoline Catalyst A had accumulated markedly greater amounts 5 9 F3 Yleldi Percent by 01. of charge 9. 3 6. 1 of coke and vanadium during the accelerated aging cycle Flllornafli Oifl(}1100670) Yield,percent i 17.9 15.3 than had Catalyst B i f g o 33 As indicated prevlously, the catalysts of the class dis- Yield,pe1'cent by vol. of charge 71.1 77.9 closed herein are also advantageous as compared with i gg y, API 13.5 12.3 catalysts normally considered superior for hydrodesul- Viscosity, SUV, sec.: furization of distillates in that they produce a total liquid $88., g %22 product of higher API gravity and which is lower in v nadiuinj'pfpiifn 5.8 9.6 sulfur, nitrogen, carbon residue and metals. In addition, Nlckel'pp'm cfltalysts of the disclosed herein Produce S P' From a comparison of the inspections of the products tlally larger quantifies P gasoline t furnace 011 obtained over Catalyst C with the corresponding product late, and the desulfurized residue yields are relatively inspections obtained from Catalyst D, it will b Seen that smaller, of higher quality and of markedly lower viscosity. in the case of the run carried out with Catalyst C, a The latter feature is important since lower viscosity residcatalyst representative of the class disclosed herein, the ual oils require smaller proportions of cutter oil to render total liquid product had a higher API gravity and was them useful as residual fuels. lower in sulfur, nitrogen, carbon residue and metals than The advantages indicated above have been demonstrated the product obtained in the run in which Catalyst D, a by comparative experiments in which a residual oil obcatalyst representative of the class of catalysts known to be useful for hydrosulfurization of distillates is utilized. In addition, it will be seen that the total liquid product obtained with Catalyst C contained relatively larger proportions of gasoline and furnace oil, and correspondingly lower yields of residue. Finally, the residue produced with Catalyst C is of higher quality than that produced with Catalyst D. All of these results are the more surprising in view of the fact that Catalyst C at the end of the run had accumulated a markedly greater carbon content than had Catalyst D.

\Ve claim:

1. A process for catalytically hydrodesulfurizing a sulfur-containing petroleum oil that contains residual components and metallic contaminants normally capable of acting as catalyst poisons, comprising contacting said oil with hydrogen at hydrodesulfurization conditions in the presence of a catalyst comprising a hydrogenating component composited with an alumina base, said composite catalyst having not more than 15 percent of the volume of the pores having a radius in the range of to 300 Angstrom units in any Angstrom unit increment, starting at 0 Angstrom units, of pore radius in the range of pores having a 0 to 120 Angstrom unit radius, and a'so having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least percent of such pore volume in pores having a radius greater than Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units.

2. A process for catalytically hydrodesulfurizing a sulfur-containing petroleum oil'that contains residual components and metallic contaminants that are normally capable of acting as catalyst poisons, comprising contacting said oil with hydrogen at a partial pressure in the range of about 500 to 4000 p.s.i.g., at a temperature, after startup, in the range of about 600 to 850 F, at a space velocity in the range of about 0.1 to 10 volumes of liquid per volume of catalyst per hour, while maintaining a hydrogenzoil ratio in the range of about 1000 to 15,000 s.c.f./bbl. oil, in the presence of a catalyst comprising a hydrogenating component composited with an alumina base, said composite catalyst having not more than 15 percent of the volume of the pores having a radius in the range of 0 to 300 Angstrom units in any 10' Angstrom unit increment, starting at 0 Angstrom units, of pore radius in the range of pores having a 0 to 120 Angstrom unit radius, and also having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least 15 percent of such pore volume in pores having a radius greater than 30 Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units.

3. The process of claim 2 wherein the hydrogen partial pressure is in the range of about 1000 to 2000 p.s.i.g., the temperature, after startup, is in the range of about 650 to 800 F., the space velocity is in the range of about 0.5 to 5 volumes of liquid per volume of catalyst per hour, and the hydrogenzoil ratio is in the range of about 4000 to 10,000 s.c.f./bbl. oil.

4. The process of claim 2 wherein the catalyst also has a surface area of at least 100 square meters per gram.

5. The process of claim 2 wherein the hydrogenating component of the catalyst is at least one member of the group consisting of metals of Group VI-B and Group VIII in a form capable of promoting hydrogenation reactions.

6. The process of claim 5 wherein the hydrogenating component is selected from the group consisting of sulfides and oxides of (a) a combination of about 2 to 25 percent by weight molybdenum and at least two iron group metals where the iron group metals are present in such proportions that the atomic ratio of each iron group metal with respect to molybdenum is less than about 0.4, and (b) a combination of about 5 to 40 percent by weight of nickel and tungsten where the atomic ratio of tungstenznickel is about 110.1 to 5.

7. The process of claim 6 wherein the hydrogenating component is selected from the group consisting of sultides and oxides of (a) a combination of about 4 to 16 percent by weight molybdenum and at least two iron group metals, where the iron group metals are present in such proportions that the atomic ratio of each iron group metal with respect to molybdenum is less than about 0.4, and (b) a combination of about 10 to 25 percent by weight of nickel and tungsten where the atomic ratio of tungstenmickel is about 1:03 to 4.

8. A process for catalytically hydrodesulfurizing a sulfurcontaining petroleum oil that contains residual components and metallic contaminants that are normally capable of acting as catalyst poisons, comprising contacting said oil with hydrogen at a hydrogen partial pressure in the range of about 1000 to 2000 p.s.i.g. at a temperature, after startup, in the range of about 650 to 800 F., at a space velocity in the range of about 0.5 to 5 volumes of liquid per volume of catalyst per hour, while maintaining a hydrogenzoil ratio in the range of about 1000 to 15,000 s.c.f./bbl. oil, in the presence of a catalyst comprising a hydrogenating component composited with an alumina base, said composite catalyst having not more than 15 percent of the volume of the pores having a radius in the range of O to 300 Angstrom units in any 10 Angstrom unit increment, starting at 0 Angstrom units, of pore radius in the range of pores having a 0 to Angstrom unit radius, and also having at least about 10 percent of such pore volume in pores having a radius of less than 30 Angstrom units, at least 15 percent of such pore volume in pores having a radius greater than 30 Angstrom units and less than 70 Angstrom units, and at least 30 percent of such pore volume in pores having a radius of greater than 70 Angstrom units and less than 120 Angstrom units, and where the hydrogenating component is selected from the group consisting of sulfides and oxides of (a) a combination of about 4 to 16 percent by weight molybdenum and at least two iron group metals, where the iron group metals are present in such proportions that the atomic ratio of each iron group metal with respect to molybdenum is less than about 0.4, and (b) a combination of about 10 to 25 percent by weight of nickel and tungsten where the atomic ratio of tungsten to nickel is about 1:03 to 4, the reaction temperature and the space velocity being so controlled as to efiect hydrogen consumption in the range of about 1 to 5 gram mols of hydrogen per gram atomic weight of sulfur removed from said oil.

References Cited UNITED STATES PATENTS 3,264,062 8/1966 Kehl et al 252463 3,297,588 1/1967 Kehl et a1 252-465 3,322,666 5/1967 Beuther et al 208-216 3,340,180 9/1967 Beuther et al. 208-216 SAMUEL P. JONES, Primary Examiner.

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3471399 *Jun 9, 1967Oct 7, 1969Universal Oil Prod CoHydrodesulfurization catalyst and process for treating residual fuel oils
US3907668 *Mar 25, 1974Sep 23, 1975Gulf Research Development CoHydrodesulfurization of petroleum distillates
US3954673 *Feb 1, 1972May 4, 1976Chiyoda Kako Kensetsu Kabushiki KaishaAdding a molybdate to an aluminum complex, hydrothermal treatment, molybdenum or tungsten, calcining
US4012340 *Apr 10, 1975Mar 15, 1977Chiyoda Kako Kensetsu Kabushiki KaishaCoordination catalysts
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Classifications
U.S. Classification208/216.0PP, 208/251.00R, 208/216.00R, 502/439, 208/217, 502/314
International ClassificationC10G45/04, B01J35/10
Cooperative ClassificationB01J35/10, C10G2300/107
European ClassificationB01J35/10