Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

• 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.
• 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.
• 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.
• 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.
• 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.
• the feed stock can be a whole crude.
• 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.
• 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,
• 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.
• a relatively high level i.e., 40 to 80 percent, preferably 50 to 75 percent
• 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.
• 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.
• 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.
• the invention is especially beneficial Where hydrodesulfurization is effected without concomitant cracking of the hydrocarbons present in the feed stock.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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
• 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.
• a suitable hot gas such as flue gas
• 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.
• 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.
• 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.
• 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
• 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.
• any water formed during presulfiding is preferably removed prior to recycling through the catalyst bed.
• 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.
• 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.
• 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.
• 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.
• the initial stabilized reaction temperature following initial rapid temperature increase during startup, was 726 F. after four days of operation.
• 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.
• 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.
• 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.,
• 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 catalyst was an alumina having deposited thereon 0.5 percent nickel, 1 percent cobalt and 8 percent molybdenum.
• 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.
• 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 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.
• 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:
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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.
• 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 moly

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• 1967
  • 1967-01-11 GB GB1416/67A patent/GB1122525A/en not_active Expired
  • 1967-01-16 DE DE1967G0049000 patent/DE1645750B2/de active Granted
  • 1967-01-18 ES ES0335782A patent/ES335782A1/es not_active Expired
  • 1967-01-18 CH CH71767A patent/CH487235A/fr not_active IP Right Cessation
  • 1967-01-19 DK DK33567AA patent/DK115194B/da not_active IP Right Cessation
  • 1967-01-19 BE BE692879D patent/BE692879A/xx not_active IP Right Cessation
  • 1967-01-19 FR FR91702A patent/FR1509369A/fr not_active Expired
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