EP0112667B1 - Catalyseur et procédé d'hydrotraitement - Google Patents

Catalyseur et procédé d'hydrotraitement Download PDF

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EP0112667B1
EP0112667B1 EP19830307379 EP83307379A EP0112667B1 EP 0112667 B1 EP0112667 B1 EP 0112667B1 EP 19830307379 EP19830307379 EP 19830307379 EP 83307379 A EP83307379 A EP 83307379A EP 0112667 B1 EP0112667 B1 EP 0112667B1
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catalyst
range
component
metal
calculated
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EP0112667A1 (fr
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Jeffrey Templeton Miller
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BP Corp North America Inc
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BP Corp North America Inc
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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 hydrotreating catalysts having a desirable combination of activity and high temperature stability and to processes for preparation and use thereof.
  • Catalytic hydrotreating involves contacting a feed with hydrogen at elevated temperature and pressure in the presence of catalysts having hydrogenation activity.
  • sulfur and nitrogen in the feed are converted largely to hydrogen sulfide and ammonia which are easily removed.
  • Aromatics saturation and, to a lesser extent, cracking of larger molecules often take place to convert high boiling feed components to lower boiling components.
  • Metals content of the feed decreases as a result of deposition of metals on the surface of the hydrotreating catalyst.
  • Hydrotreating of low quality hydrocarbon feeds often is conducted under conditions more severe than those used in conventional hydrotreating of lighter hydrocarbon feeds in order to achieve suitable levels of nitrogen, sulfur and/or metals removal and/or conversion of high boiling components to lower boiling materials.
  • removal of nitrogen from high nitrogen feeds such as whole shale oils or fractions thereof, typically requires higher temperatures and pressures and lower space velocities than those used in catalytic hydrotreating of low nitrogen feeds.
  • hydrotreating heavy petroleum crude oil fractions such as vacuum or atmospheric resids and particularly those containing significant quantities of sulfur, metal and/or asphaltenes, usually requires operation under condctions more severe than those employed in hydrotreating lighter feeds.
  • Hensley et al., US-A-4,297,242 have disclosed catalysts consisting of at least one active original hydrogenation metal selected from Group VIB deposed on a catalytically active support comprising alumina and use thereof with highly desirable results in hydrodesulfurization of heavy hydrocarbon feeds containing sulfur, nitrogen, metals and asphaltenes. Hensley et al. also disclose that such catalysts exhibit lower deactivation and improved lifetime, even under severe operating conditions, as compared to catalysts containing a Group VIB metal component promoted by a cobalt component.
  • the first stage of the process comprises contacting the feedstock in a first reaction zone with hydrogen and a demetallation catalyst comprising hydrogenation metal selected from Group VIB and/or Group VIII deposed on a relatively large-pore, high surface area inorganic oxide support.
  • the second stage of the process comprises contacting the effluent from the first reaction zone with a catalyst consisting essentially of hydrogenation metal selected from Group VIB deposed on a relatively small pore, catalytically active support comprising alumina.
  • the second stage catalyst has a surface area within the range of about 150 m 2 /gm to about 300 m 2 /gm, a pore volume within the range of about 0.4 cc/gm to about 0.9 cc/gm, an average pore diameter within the range of about 90A to about 160A, and a majority of its pore volume in pore diameters within the range of about 80A to about 130A. More particularly, the pore volume distribution is such that less than 40% of its pore volume is in pores having diameters within the range of about 50A to about 80A, about 45% to about 90% of its pore volume is in pores having diameters within the range of about 80A to about 130A, and less than about 15% of its pore volume is in pores having diameters larger than 130A.
  • the catalyst disclosed has a pore volume distribution summarized as follows:
  • the pores of the disclosed catalyst having diameters within the range of about 80A to about 130A preferably contain about 90 to about 180 m2/gm, and more preferably contain about 120 to about 180 m 2 /gm, of surface area.
  • the invention comprises the preparation of stabilized aqueous solutions which comprise an aqueous solvent having dissolved therein catalytically active compounds containing at least one element from Group VI of the periodic table and one element from Group VIII".
  • organic oxyacids of phosphorous are included among the disclosed stabilizers, and the examples of Pessimisis illustrate preparation of various cobalt-molybdenum, nickel-molybdenum, and nickel-tungsten catalysts using phosphorus and other acids as stabilizers. Hydrodesulfurization results with certain of the cobalt-molybdenum catalysts are presented, and the patentee suggests that the use of the stabilized solutions may lead to improved hydrodesulfurization activity in some instances.
  • Colgan et al., US-A-3,287,280 discloses the use of phosphoric acid as an impregnation aid in preparation of nickel-molybdenum catalysts and that such use can result in catalysts having improved hydrodesulfurization activity.
  • Kerns et al., US-A-3,446,730 disclose hydrodenitrogenation catalysts comprising at least one of a nickel component and a Group VI metal component, supported on a specific alumina, such catalysts being promoted with 0.1 to 2.0 wt.% of a promoter selected from compounds of phosphorus, silicon and barium.
  • a promoter selected from compounds of phosphorus, silicon and barium.
  • Hilfman, US-A-3,617,528 discloses hydrotreating catalysts comprising coextruded nickel and phosphorus components and an alumina-containing support.
  • the catalysts also may contain a Group VIB metal component.
  • the disclosed catalysts are more tolerant of nitrogen than catalysts prepared without an aluminosilicate component.
  • Examples 10-13 of both patents illustrate catalysts exhibiting improved hydrodenitrogenation activity as compared to catalysts prepared without an aluminosilicate component. Reported hydrodesulfurization activity is slightly worse.
  • Colgan et al., US-A-3,840,472 disclose catalysts prepared by impregnation of an alumina support with stabilized solutions of molybdic oxide and certain cobalt or nickel salts dissolved in aqueous phosphoric acid although the patentees suggest that the presence of certain amounts of a phosphorus component in the ultimate catalyst may harm performance, stating the following at column 2, lines 23-28:
  • Kerns et al. patent teaches that hydrodenitrogenation activity of cobalt-containing catalysts in general, and nickel-molybdenum-cobalt catalysts in particular, decreases when the specific alumina support disclosed therein is employed and when a phosphorus promoter is used.
  • a further object of the invention is to provide a catalyst of improved stability and lifetime under high severity hydrotreating conditions.
  • Another object of the invention is to provide for such improvements by simple and inexpensive methods for catalyst preparation and without the need for expensive reactants or complicated preparative techniques.
  • a more specific object of the invention is to provide a catalyst of improved activity and stability for hydrotreating high nitrogen hydrocarbon feeds under severe conditions as well as methods for the use of such catalyst.
  • the catalytic composition of the present invention comprising a hydrogenating component supported on the surface of a porous refractory inorganic oxide support, wherein the hydrogenating component consisting essentially of (1) a metal component in which the metal is selected from Group VIB of the Periodic Table and (2) a phosphorus component and wherein the support is free of a zeolite component, the Group VIB metal component being at a concentration within the range of from 1 wt.% to 30 wt.%, calculated as the metal oxide and based on the weight of the catalyst, and the phosphorus component being at a concentration within the range of from 0.1 wt.% to 5 wt.%, calculated as elemental phosphorus and based on the weight of the catalyst, and the catalyst composition having a pore volume within the range of from 0.4 cc/gm to 0.9 cc/gm, a BET surface area within the range of from 130 m 2 /gm to 300 m 2 /gm, an average pore diameter
  • the aforesaid catalyst has a pore volume within the range of 0.4 cc/gm to 0.9 cc/gm, a BET surface area within the range of 130 m2/gm to 300 m 2 /gm, an average pore diameter within the range of 90A to 160A (9-16 nm), and a pore volume distribution such that less than 40% of its pore volume is in pores having diameters within the range of 50A to 80A (5-8 nm), 45% to 90% of its pore volume is in pores having diameters within the range of 80A to 130A (8-13 nm), and less than 15% of its pore volume is in pores having diameters larger than 130A (13 nm).
  • the catalysts comprise from 8 wt.% to 22 wt.% product of the Group VIB metal component, calculated as the metal oxide, and from 0.5 wt.% to 3 wt.% of the phosphorus component, calculated as elemental phosphorus and based on the weight of the catalyst.
  • the aforesaid catalyst has a pore volume within the range of from 0.3 cc/gm to 1.2 cc/gm, a surface area within the range of from 100 m 2 /gm to 350 m 2 /gm, and an average pore diameter within the range of from 70 ⁇ to 120 ⁇ (7 ⁇ 12 nm).
  • the catalyst comprises from 15 wt.% to 22 wt.% of the Group VIB metal component, calculated as the metal oxide and based on the weight of the catalyst, and from 0.5 wt.% to 3 wt.% of the phosphorus component, calculated as elemental phosphorus and based on the weight of the catalyst.
  • the hydrogenation component consists essentially of the Group VIB metal component, the phosphorus component, and optionally a Group VIII metal component.
  • the Group VIB metal component is at a concentration within the range of from 1 wt% to 30 wt.% calculated as the metal oxide and based on the weight of the catalyst.
  • the phosphorus component is present at a concentration of from 0.1 wt.%, preferably 0.5 wt.% to 5 wt.%, preferably 3 wt.%, calculated as elemental phosphorus and based on the weight of the catalyst.
  • the Group VIII metal component is present at a concentration up to 15 wt.%, preferably 0.5 wt.% to 12 wt.%, calculated as the metal oxide and based on the weight of the catalyst.
  • the present invention also provides a process for hydrotreating a hydrocarbon feed comprising contacting the hydrocarbon feed with hydrogen under hydrotreating conditions and in the presence of a catalyst comprising a hydrogenating component consisting essentially of (1) a metal component in which the metal is selected from Group VIB and (2) a phosphorus component, deposited on the surface of a support component comprising a porous refractory inorganic oxide and free of zeolite component, the Group VIB metal component being at a concentration within the range of from 1 wt.% to 30 wt.%, calculated as the metal oxide and based on the weight of the catalyst, and the phosphorus component being at a concentration within the range of from 0.1 wt.% to 5 wt.%, calculated as elemental phosphorus and based on the weight of the catalyst, and the catalyst composition having a pore volume within the range of from 0.4 cc/gm to 0.9 cc/gm, a BET surface area within the range of from 130 m 2 /gm
  • the present invention further provides a process for the hydrodemetallation and hydrodesulfurization of a hydrocarbon feedstock containing asphaltenes and a substantial amount of metals, said feedstock comprising at least one member selected from the group consisting of crude oil, topped crude oil, petroleum hydrocarbon resids, oils obtained from tar sands, resids derived from tar sands oils, hydrocarbon streams derived from coal, and blends of any of the aforesaid resids with lighter boiling materials, which process comprises:
  • Stability and activity maintenance of the catalysts of the present invention are comparable or superior to those of high stability catalysts, such as those of Hensley et al. '242, in which the original active hydrogenation metal is selected from Group VIB, as well as those of Quick et al. '602, '284 and '635 and Hensley et al. '144, '566 and '965, in which a stabilizing chromium component is incorporated into hydrogenating components comprising another metal of Group VIB or combinations thereof with a metal of Group VIII.
  • the catalysts of the present invention exhibit activities comparable or superior to those of conventional catalysts wherein the hydrogenating component contains a Group VIB metal component alone or promoted by a Group VIII metal component.
  • the invented catalysts are particularly well suited for hydrotreating feeds containing nitrogen, sulfur, metals and/or high boiling components under severe hydrotreating conditions.
  • the improved hydrotreating catalysts of this invention comprise a hydrogenating component consisting essentially of (1) a metal component in which the metal is selected from Group VIB and (2) a phosphorus component, such hydrogenating component being deposed on the surface of a support component comprising a porous refractory inorganic oxide and free of a zeolite component.
  • Preferred catalysts are those in which the phosphorus component is a phosphoric acid residue, the same most preferably being prepared by impregnation of a support component comprising a porous refractory inorganic oxide with an impregnating solution containing phosphoric acid and one or more precursors to the aforesaid metal component.
  • Such catalysts are used in hydrotreating hydrocarbon feeds containing nitrogen, sulfur, metals and/or high boiling components wherein the feed is contacted with hydrogen under hydrotreating conditions, particularly severe hydrotreating conditions, in the presence of the catalyst.
  • the hydrogenating component of the invented catalyst comprises (1) a metal component in which the metal is selected from Group VIB and (2) a phosphorus component.
  • the Group VIB metal can be molybdenum, chromium, tungsten or a binary or ternary combination thereof.
  • the Group VIB metal is present in the metal component in elemental form, as an oxide or sulfide, as an oxygenated phosphorus species or as a combination thereof.
  • the Group VIB metal of the metal component is molybdenum alone or in combination with chromium or tungsten, because molybdenum exhibits superior hydrogenation activity when promoted by a phosphorus component.
  • a molybdenum component is the sole Group VIB metal component in the metal component of the hydrogenation component.
  • the hydrogenating component also contains a phosphorus component which is present in a form effective to promote the activity of the Group VIB metal component.
  • a preferred phosphorus component is a phosphoric acid residue remaining in the hydrogenation component as a result of simultaneous or sequential impregnation of support component with a solution or solutions consisting essentially of a precursor to the metal component and phosphoric acid in a suitable solvent, for example, water.
  • phosphoric acid residues present in the hydrogenating component are present in the form of one or more oxides, a phosphate anion, compounds of the Group VIB metal or metals of the hydrogenating component and/or polymeric species containing recurring phosphorus-oxygen units and/or phosphorus-oxygen-Group VIB metal groups.
  • preferred catalysts according to the present invention comprise about 1 to about 50 weight percent hydrogenating component and about 50 to about 99 weight percent support.
  • the Group VIB metal content preferably ranges from about 1 to about 30 weight percent, calculated as the metal oxide, that is, Mo03, W0 3 , Cr 2 0 3 .
  • the phosphorus component is present in an amount effective to promote the activity, the amount preferably ranging from about 0.1 to about 5 weight percent, calculated as elemental phosphorus, in order to promote the activity without adversely affecting the strength and other important catalyst physical properties. It is to be understood that the weight percentages set forth herein are based upon total catalyst weight after calcination.
  • the support on which the aforesaid hydrogenating component is deposed comprises at least one porous refractory inorganic oxide, specific examples of which include silica, alumina, silica-alumina, zirconia, titania, magnesia, boria and the like.
  • porous refractory inorganic oxide specific examples of which include silica, alumina, silica-alumina, zirconia, titania, magnesia, boria and the like.
  • metal oxides also are contemplated.
  • Modified porous refractory inorganic oxides such as fluorided aluminas and chlorided silica-alumina also are contemplated.
  • Supports containing minor amounts of one or more oxides of phosphorus, for example, up to 2 wt.%, calculated as phosphorus, in combination with one or more of the aforesaid porous refractory inorganic oxides also can be employed although the same are not preferred, because the presence of phosphorus oxide in the support can be detrimental to promotion of the hydrogenating metal component with phosphorus.
  • the presence of a zeolite component in the support of the catalyst of this invention changes the essential character of the catalyst and hence is not contemplated for the catalyst of this invention.
  • the support preferably is calcined prior to any impregnation in which phosphorus component precursor is to be present as hydroxyl groups of the support may react with the precursor and thereby hinder incorporation of sufficient phosphorus component into the hydrogenating component.
  • the support can be used in any suitable form, for example, as extrudates, spheres or powder. From the standpoint of attaining desirable hydrotreating performance, presently preferred supports are aluminas and silica- aluminas containing up to 50 wt.% of silica. More preferably, the support is an alumina or a silica-alumina containing up to 50 wt.% of silica.
  • the finished catalysts have a BET surface area of at least 100 m 2 /gm, a pore volume of 0.3 to 1.7 cc/gm, both as determined by nitrogen desorption, and an average pore diameter within the range of from 70A to 350A.
  • the catalyst of this invention When the catalyst of this invention is used in a hydrotreating operation in which removal of sulfur is a major concern, for example, with a feed comprising a vacuum or atmospheric resid, it is highly preferred that the catalyst has a pore volume within the range of 0.4 cc/gm to 0.9 cc/gm, a surface area within the range of 130 m 2 /gm to 300 m 2 /gm, an average pore diameter within the range of 90A to 160A, and a pore volume distribution such that less than 40% of its pore volume is in pores having daimeters within the range of 50A to 80A, 45% to 90% of its pore volume is in pores having diameters within the range of 80A to 130A, and less than 15% of its pore volume is in pores having diameters larger than 130A.
  • the catalyst of this invention has a pore volume distribution summarized as follows: Most preferably, the catalyst of this invention has a pore volume within the range of 0.5 cc/gm to 0.7 cc/gm, a surface area within the range of 140 m ⁇ /gm to 250 m 2 /gm, an average pore diameter within the range of 110A to 140A, and a pore volume distribution summarized as follows:
  • the catalyst pores having diameters within the range of 80A (8 nm) to 130A (13 nm) preferably contain 90 m 2 /gm to 180 m 2 /gm, and more preferably contain 120 m 2 /gm to 180 m 2 /gm, of surface area in order to attain maximum desulfurization activity.
  • the catayst of the present invention preferably comprises from 8 wt.% to 22 wt.% of the Group VIB metal component, calculated as the metal oxide and based on the weight of the catalyst, and from 0.5 wt.% to 3 wt.% of the phosphorus component, calculated as elemental phosphorus and based on the weight of the catalyst.
  • the catalyst of this invention When the catalyst of this invention is used in a hydrotreating operation in which removal of nitrogen is a major concern, for example, with a feed comprising a whole shale oil or shale oil fraction, it is highly preferred that the catalyst has a pore volume within the range of 0.3 cc/gm to 1.2 cc/gm, a surface area within the range of from 100 m z /gm to 350 m 2 /gm and an average pore diameter within the range of from 70A (7 nm) to 120A (12 nm).
  • the catalyst comprise from 15 wt.% to 22 wt.% of the Group VIB metal component, calculated as the metal oxide and based on the weight of the catalyst, and from 0.5 wt.% to 3 wt.% of the phosphorus component, calculated as elemental phosphorus and based on the weight of the catalyst.
  • the catalyst of this invention When the catalyst of this invention is used in a hydrotreating operation in which removal of metals is a major concern, for example, with a feed comprising a high metals resid, it is highly preferred that the catalyst has a pore volume within the range of from 0.7 cc/gm to 1.7 cc/gm, a surface area within the range of from 100 m 2 /gm to 400 m 2 /gm, an average pore diameter within the range of from 125A to 350A, a Group VIB metal component concentration from 1 wt.% to 30 wt.%, preferably to 20 wt.%, calculated as the metal oxide and based on the weight of the catalyst, a Group VIII metal component concentration of up to 15 wt.%, preferably from 0.5 wt.% to 12 wt.%, calculated as the metal oxide and based on the weight of the catalyst, and a phosphorus component concentration of from 0.5 wt.% to 3 wt.%
  • the invented catalysts are prepared by impregnation of a support comprising at least one porous refractory inorganic oxide with a solution or solutions consisting essentially of precursors to the metal and phosphorus components of the final catalyst in a suitable solvent and calcination of impregnated support.
  • a support comprising at least one porous refractory inorganic oxide with a solution or solutions consisting essentially of precursors to the metal and phosphorus components of the final catalyst in a suitable solvent and calcination of impregnated support.
  • simultaneous impregnation of a support with phosphorus and metal component precursors, followed by calcination of the impregnated support is conducted in order to maximize the promotional effect of the phosphorus component of the final catalyst.
  • sequential impregnation with phosphorus and metal component precursors also gives good results.
  • a preferred sequential impregnation involves impregnation of support with phosphorus component precursor followed by calcination, followed by impregnation with metal component precursor
  • the mechanics of impregnating a support are well known to persons skilled uf the art.
  • a technique preferred for the sake of simplicity involves forming a solution or solutions of appropriate compounds in a suitable solvent and contacting a support with an amount or amounts of solution or solutions sufficient to fill the pores of the support.
  • Useful precursors to the metal component of the invented catalysts also are well known to persons skilled in the art. Specific examples include ammonium chromate, ammonium dichromate, chromium(lll) nitrate, chromium acetate, ammonium heptamolybdate, ammonium paramolybdate, molybdic anhydride, phosphomolybdic acid and ammonium tungstate.
  • Phosphorus component precursors useful in preparation of the invented catalysts include phosphoric acid, phosphorous acid, hypophosphorous acid and pyrophosphoric acid. Esters of such acids also can be used although they are not preferred. Phosphorus oxides, such as P 2 0 5 and P 4 0 6 , also can be used. Salts of the aforesaid acids and esters also are contemplated. Specific examples of these include ammonium phosphate, diammonium hydrogen phosphate and ammonium dihydrogen phosphate. As the preferred catalysts according to this invention are those in which a phosphoric acid residue is present, phosphoric acid is the preferred phosphorus component precursor.
  • dilute or concentrated aqueous phosphoric acid is used as an impregnating solvent for the Group VIB metal component precursor.
  • Other phosphorus component precursors can be employed in the form of a solution in a suitable solvent, such as water or alcohol, or the same can simply be dissolved in a solution or solutions containing one or more Group VIB metal component precursors.
  • Phosphorus compound concentrations vary depending on solubility, amount of phosphorus component desired in the ultimate catalyst and amount of solution that can be accommodated by the particular support to be used as can be appreciated by persons skilled in the art.
  • a Group VIII metal component precursor can be used in place of, or in addition to, the Group VIB metal component precursor in the impregnation process.
  • the impregnated support is calcined. Calcination preferably is conducted at temperatures of at least 425°C and more preferably at least 535°C for a period of at least 1/2 hour. The calcination is conducted in the presence of a gas containing molecular oxygen, air being preferred from the standpoint of convenience and cost. While not required, it is desirable to dry the impregnated support at a temperature high enough to drive off excess solvent from the impregnation step prior to calcination. When water is used as the solvent in impregnation, preferred temperatures are at least about 120°C. Drying times of at least 1/2 hour are preferred.
  • sulfiding can be conducted to sulfide and partially reduce the metal or metals of the hydrogenating component.
  • a sulfiding treatment that is preferred from the standpoint of convenience comprises heating the catalyst to from 120°C to 180°C and contacting the catalyst with a flowing gaseous mixture of hydrogen sulfide and hydrogen under pressure for from 1/2 to 2 hours, raising the temperature to from 175°C to 235°C with continued flow of the gaseous mixture for an additional 1/2 to 2 hours, raising the temperature to from 340°C to 400°C, and contacting with additional hydrogen-hydrogen sulfide gas mixture for an additional period of time, preferably from 1/2 to 2 hours.
  • the gas should be employed in an amount effective to provide at least 110 percent of the stoichiometric amount of hydrogen sulfide needed to sulfide the metal or metals of the hydrogenating component.
  • concentration of hydrogen sulfide in the gaseous mixture is not critical.
  • the catalyst can be contacted with carbon disulfide or a hydrocarbon oil containing sulfur can be passed over the catalyst for a time sufficient to convert the hydrogenating component to sulfide form.
  • sulfiding treatment is conducted while the catalyst is disposed in a hydrotreating reaction zone because on conclusion thereof, the flow of hydrogen sulfide or other source of sulfide can be discontinued and hydrogen partial pressure and temperature adjusted to operating levels. Once operating conditions are achieved, hydrocarbon feed is simply introduced into the reaction zone.
  • Hydrotreating according to the present invention can be conducted in either fixed bed or expanded bed operations.
  • Preferred catalysts for use in fixed bed processes are those having an average particle size of from 0.8 millimeter to 3.2 millimeters effective diameter. Pellets, spheres, and/or extrudate are contemplated for fixed bed use. In addition, more complicated shapes, such as clover leaf, cross-shaped or C-shaped catalyst are contemplated.
  • Preferred catalysts for expanded bed use are spheres or extrudates having diameters of from 0.8 millimeter to 1.6 millimetres.
  • Hydrocarbon feeds to be hydrotreated according to this invention are those containing sufficiently high levels of nitrogen, sulfur, metals or high boiling components as to hinder direct use in more conventional refining operations, such as catalytic cracking or hydrocracking.
  • feeds that can be treated according to this invention include petroleum hydrocarbon streams, hydrocarbon streams derived from coal, hydrocarbon streams derived from tar sands and hydrocarbon streams derived from oil shale.
  • Typical examples of petroleum hydrocarbon streams include petroleum distillates, virgin gas oils, vacuum gas oils, coker gas oils and atmospheric and vacuum resids.
  • Hydrocarbon streams derived from oil shale, such as whole shale oil or a fraction thereof, are also particularly well suited.
  • Preferred feeds are those containing at least 0.1 wt.% nitrogen or resids containing high concentrations of sulfur and/or metals.
  • the conditions employed in operation of the process of the present invention will vary with the particular hydrocarbon stream being treated, with mild conditions being employed in the hydrotreating of light distillates, such s naphtha and kerosene, typically 232°C to 316°C and about 690 kPa to 4,137 kPa of hydrogen partial pressure.
  • Heavier materials can be treated under conditions of 3.45 MPa to 20.76 MPa'of hydrogen partial pressure, an average catalyst bed temperature within the range of 315°C to 443°C, with an LHSV (liquid hourly space velocity) within the range of 0.1 to 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of 89 m 3 /m 3 to 3,560 m 3 /m ' .
  • LHSV liquid hourly space velocity
  • hydrodenitrogenation conditions are preferred for the removal of nitrogen from feeds containing at least 0.1 wt.% nitrogen. Best results in removing nitrogen from whole shale oil are obtained under hydrodenitrogenation conditions comprising 8.3 MPa to 17.3 MPa total pressure, average catalyst bed temperatures within the range of 388°C to 427°C, an LHSV of 0.3 to 2 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of 178 m 3 tm 3 to 1780 m'/m 3 .
  • hydrodemetallation conditions are preferred and include a temperature of from 371°C to 454°C, a pressure of from 7 MPa to 21 MPa, a hydrogen addition rate of from 178 m 3 /m 3 to 1780 m 3 /m 3 and a space velocity of from 0.1 to 5 volumes of feed per volume of catalyst per hour.
  • hydrodesulfurization conditions are preferred for the removal of sulfur from feeds containing at least 0.1 wt.% sulfur. Best results in removing sulfur from a vacuum or atmospheric resid are hydrodesulfurization conditions comprising 12.4 MPa to 20.7 MPa total pressure, 399°C to 427°C average catalyst bed temperature, 178 m 3 /m 3 to 1780 m 3 /m 3 hydrogen rate and 0.1 to 5 volumes feed per volume catalyst per hour LHSV.
  • resid includes, a resid which has been subjected to a prior treatment such as a hydrodemetallation treatment.
  • a demetallation catalyst is employed in the first stage and provides demetallated effluent which is contacted in the second stage with a desulfurization catalyst.
  • a catalyst of the present invention having the aforesaid preferred pore volume, surface area, average pore diameter and pore size distribution is employed as the desulfurization catalyst in the aforesaid two-stage hydrotreatment process.
  • such preferred embodiment of the present invention comprises a two-stage process for the hydrodemetallation and hydrodesulfurization of a hydrocarbon feedstock containing asphaltenes and a substantial amount of metals.
  • feedstock generally contains asphaltenes, metals, nitrogen compounds and sulfur compounds.
  • the feedstocks that are to be treated by the preferred two-stage hydrotreatment process of the present invention contain from a small amount of nickel and vanadium, for example, from 40 ppm up to more than 1,000 ppm of the combined total amount of nickel and vanadium, up to 25 wt.% of asphaltenes.
  • This preferred two-stage hydrotreatment process is particularly useful in treating feedstock with a substantial amount of metals, for example, one containing 150 ppm or more of nickel and vanadium, and with a sulfur content in the range of 1 wt.% to 10 wt.%.
  • Typical feedstocks that can be treated satisfactorily by the preferred two-stage hydrotreatment process of the present invention also contain a substantial amount of components that boil appreciably above 538°C.
  • Examples of typical feedstocks are crude oils, topped crude oils, petroleum hydrocarbon resids, both atmospheric and vacuum resids, oils obtained from tar sands and resids derived from tar sands oil, hydrocarbon streams derived from coal, and blends of any of the aforesaid resids with lower boiling materials.
  • Such hydrocarbon streams contain organometallic contaminants which create deleterious effects in various refining processes that employ catalysts in the conversion of the particular hydrocarbon stream being treated.
  • the metallic contaminants that are found in such feedstocks include, but are not limited to, iron, vanadium and nickel.
  • the first-stage catalyst and the second-stage catalyst can be employed in a single reactor as a dual bed or the two catalysts can be employed in separate, sequential reactors, and various combinations of these two basic reactor schemes can be employed to achieve flexibility of operation and product upgrade.
  • the feed is contacted with the demetallation catalyst first and then with the desulfurization catalyst.
  • either of the basic reactor schemes described can comprise multiple parallel beds of the catalyst.
  • the direction of flow of the feedstock can be upward or downward.
  • the volumetric ratio of first-stage catalyst to second-stage catalyst can be within a broad range, preferably within 5:1 to 1:10 and more preferably within 2:1 to 1:5.
  • the first-stage, demetallation catalyst in the method of the present invention comprises a hydrogenation component and a large-pore, high surface area inorganic oxide support.
  • Suitable demetallation catalysts comprise catalytic amounts of a hydrogenation component typically including a Group VIB metal, a Group VIII metal or a mixture of Group VIB and Group VIII metals deposed on a relatively large-pore, high surface area porous inorganic oxide support, suitably alumina, silica, magnesia, zirconia and, similar materials.
  • This first-stage catalyst has a surface area of 100 m 2 /gm to 400 m 2 /gm, an average pore diameter of 125A to 350A, and a pore volume of 0.7 cc/gm to 1.7 cc/gm.
  • the composition of the demetallation catalyst comprises from 1 wt.% to 30 wt.% of the Group VIB metal, calculated as the oxide, and/or from 0.5 to 12 wt.% of the Group VIII metal, calculated as the oxide, based upon the total weight of the composition.
  • the Group VIB and Group VIII classifications of the Periodic Table of Elements can be found on page 628 of Webster's Seventh New Collegiate Dictionary, G. & C. Merriam Company, Springfield, Massachusetts, U.S.A. (1965). While calculated as the oxide, the hydrogenation metal components of the catalyst can be present in the elemental form or as the sulfide or oxide thereof.
  • first-stage, demetallation catalyst Commercially available catalysts that are suitable for use as the first-stage, demetallation catalyst include American Cyanamid's 1442B and Amocat 1A@, both bimodal.
  • embodiment of the catalyst of the present invention which is described hereinabove as employed in a hydrotreatment operation in which demetallation is a major concern, can also be employed as the first-stage demetallation catalyst.
  • the first-stage catalyst used in the process of the present invention can be prepared by the typical commercial method of impregnating a large-pore, high surface area inorganic oxide support.
  • Appropriate commercially available alumina preferably calcined at 426°C to 872°C for 0.5 to 10 hours, can be impregnated to provide a suitable lead catalyst having an average pore diameter of 125A (12.5 nm) to 350A (35 nm), a surface area ranging from 100 m 2 /gm to 400 m 2 /gm, and a pore volume within the range of 0.7 cc/gm to 1.7 cc/gm.
  • the alumina can be impregnated with a solution, usually aqueous, containing a heat-decomposable compound of the metal(s) to be placed on the catalyst, and the impregnated material is then dried and calcined.
  • the drying can be conducted in air at a temperature of 65°C to 204°C for a period of 1 to 16 hours.
  • the calcination can be carried out at a temperature of 426°C to 648°C for a period of from 0.5 to 8 hours.
  • the finished second-stage catalyst that is employed in the process of the present invention has a pore volume within the range of 0.4 cc/gm to 0.9 cc/gm, a surface area within the range of 130 m 2 /gm to 300 M 2 /gm, and an average pore diameter within the range
  • the catalyst possesses a pore volume within the range of 0.5 cc/gm to 0.7 cc/gm, a surface area within the range of 140 m 2 /gm to 250 m 2 /gm, and an average pore diameter within the range of
  • the second-stage catalyst should have less than 40% of its pore volume in pores having diameters within the range of 50A (5 nm) to 80A (8 nm), 45% to 90% of its pore volume in pores having diameters within the range of 80A (8 nm) to 130A (13 nm), and less than about 15% of its pore volume in pores having diameters that are largerthan 130A(13 nm). More preferably, the second-stage catalyst has a pore volume distribution summarized as follows: Most preferably, the second-stage catalyst has a pore volume distribution summarized as follows:
  • the catalyst pores having diameters 80° (8 nm) to 130A (13 nm) preferably should contain from 90 m 2 /gm to 180 m 2 /gm, and more preferably 120 m 2 /gm to 180 m 2 /gm, of surface area in order to attain maximum activity.
  • operating conditions for the hydrotreatment of heavy hydrocarbon streams comprise a pressure within the range of 7 MPa to 21 MPa, an average catalyst bed temperature within the range of 371°C to 454°C, a LHSV within the range of 0.1 volume of hydrocarbon per hour per volume of catalyst to 5 volumes of hydrocarbon per hour per volume of catalyst, and a hydrogen recycle rate or hydrogen addition rate within the range of 178 m 3 /m 3 to 2,671 m 3 /m 3 .
  • the operating conditions comprise a total pressure within the range of 10 MPa to 18 MPa; an average catalyst bed temperature within the range of 387°C to 437°C; a LHSV within the range of 0.1 to about 1.0; and a hydrogen recycle rate or hydrogen addition rate within the range of 356 m 3 /m' to 1,780 m 3 /m 3 .
  • a control catalyst identified hereinafter as Catalyst I and containing 15.0 wt.% Mo03 supported on gamma-alumina, was prepared as follows.
  • 300 gm gamma-alumina obtained from Continental Oil Company and identified as Catapal
  • the calcined product having BET surface area of 230 m 2 /gm, pore volume of 0.65 cc/gm as determined by nitrogen adsorption using a Digisorb@ 2500 instrument and average pore diameter of 113A calculated as (4Vx104)/A was placed in a desiccator until used.
  • Catalyst II A catalyst according to the invention, identified hereinafter as Catalyst II and containing 15.0 wt.% Mo03 and 1.3 wt.% P, was prepared as follows.
  • Example II Following the procedure of Example I, 18.40 gm ammonium heptamolybdate and 4.83 gm 85.% phosphoric acid dissolved in 46 ml water were added to 82.02 gm of the calcined gamma-alumina from Example I. After standing for one hour at ambient temperature, the impregnated support was dried, calcined and crushed and screened as in Example I. The resulting catalyst was tested for activity according to Example IV.
  • a second control catalyst identified hereinafter as Catalyst III and again containing 15.0 wt.% Mo03, was prepared by a two-step impregnation as follows.
  • Example II To 85.00 gm of the calcined gamma-alumina from Example I were added 9.2 gm ammonium heptamolybdate dissolved in 52 ml water. After standing for an hour at ambient temperature, the impregnated support was dried and calcined as in Example I. To the result were added 9.20 gm ammonium heptamolybdate dissolved in 52 ml H 2 0 and the result again was allowed to stand, and then dried and calcined as in Example I. The calcined catalyst was crushed and screened to 14/20 mesh as in Example I and tested according to Example IV.
  • the catalysts from Examples I ⁇ III were tested in a 81 cm long, 0.95 cm inner diameter, vertical reactor equipped with automatic controls for monitoring temperature, feed rate and hydrogen partial pressure.
  • 15.00 cc catalyst were loaded into the reactor and sulfided by passing 8 vol.% H 2 S in hydrogen over the catalyst at about 0.03 m'/hr and total pressure of about 2 MPa at 148°C for one hour, followed by 204°C for one hour, and then 375°C for one hour.
  • temperature was increased to 404°C
  • the feed was introduced via a positive displacement Ruska pump at a liquid hourly space velocity (LHSV) of 0.64 volume feed per volume catalyst per hour, and the reactor was charged with hydrogen to 12 MPa.
  • LHSV liquid hourly space velocity
  • the feed used in all tests was a whole shale oil generated in situ from oil shale and having properties as shown in Table 1. Also shown in the table are properties of samples of product taken on the last day of each test.
  • Catalyst II exhibited superior hydrodenitrogenation activity as measured by both total and basic product nitrogen. Based on first order hydrodenitrogenation kinetics observed for total nitrogen removal, Catalyst II had a hydrodenitrogenation activity about 1.5 times that of control Catalyst I and about 1.7 times that of control Catalyst III. It also can be seen from Table 1 that Catalyst II gave about 95% removal of product sulfur indicating high hydrodesulfurization activity.
  • Example IV A series of catalysts was prepared according to the general procedure of Examples I ⁇ III and tested as in Example IV. Composition of the catalysts and hydrodenitrogenation activity based upon both total and basic nitrogen relative to control Catalyst I (see Example I) are reported in Table 2. For completeness, relative activities of Catalyst II and control Catalyst III also are included in the table. Unless otherwise indicated, Mo03 content of catalysts was 15 wt.% and phosphorus content, calculated as the element, was 1.3 wt.%.
  • Catalysts II, VI and VII according to the invention were significantly more active for hydrodenitrogenation than any of the other catalysts, with Catalysts II and VII, in which molybdenum and phosphorus component precursors were simultaneously impregnated, being superior to Catalyst VI, in which phosphorus and molybdenum component precursors were sequentially impregnated.
  • Direct comparison of results with Catalysts IV and V to results with the other catalysts is difficult because the pore structure of the alumina- and phosphorus oxide-containing support of the former significantly different from that of the small-pore alumina used for the other catalysts.
  • comparison of results with Catalyst IV to those with Catalyst V indicates that the presence of phosphorus in the support was detrimental to attempted promotion of hydrogenating metal with phosphorus component.
  • the calcined alumina has the following surface area distribution: 58.9 m 2 /gm in pores having diameters of 50A to 80A, 137.4 m 2 /gm in pores having diameters of 80A to 130A, 84.9 m 2 /gm in pores having 80A to 100A, 525.5 m 2 /gm pores having diameters of 100A to 130A, and 2.2 m 2 /gm in pores having diameters greater than 130A.
  • the resulting product is designated Catalyst A, and its metals content, pore volume, pore volume distribution, surface area, surface area distribution and average pore diameter are presented in Table 3.
  • Catalysts A, B, C and D were employed in a two-reactor system for the demetallation and desulfurization of a resid feed.
  • the metals content, pore volume, pore volume distribution, surface area, surface area distribution and average pore diameter of each of Catalysts B, C and D are also presented in Table 3, Catalyst D is marketed as Amocat 1A.
  • Each reactor was 81 centimeters long and had an inside diameter of 0.95 centimeter.
  • the feed flowed upwardly through the first or upstream reactor and the effluent from the first reactor then flowed upwardly through the second or downstream reactor.
  • the upstream reactor was loaded with a uniform mixture of 10 cubic centimeters of Catalyst C and 10 cubic centimeters of 10/14 mesh porous alpha-alumina diluent
  • the downstream reactor was loaded with a uniform mixture of 20 cubic centimeters of Catalyst B and 20 cubic centimeters of 10/14 mesh porous alpha-alumina diluent.
  • Example 9 the upstream reactor was loaded with a uniform mixture of 10 cubic centimeters of Catalyst C and 10 cubic centimeters of 10/14 mesh alpha-alumina diluent, and the downstream reactor was loaded with a uniform mixture of 20 cubic centimeters of Catalyst A and 20 cubic centimeters of 10/14 mesh, alpha-alumina diluent.
  • Example 10 the upstream reactor was loaded with a uniform mixture of 10 cubic centimeters of Catalyst D and 20 cubic centimeters of 10/14 mesh vermiculite diluent, and the downstream reactor was loaded with a uniform mixture of 20 cubic centimeters of Catalyst A and 20 cubic centimeters of 10/14 mesh vermiculite diluent.
  • Example 11 the upstream reactor was loaded with a uniform mixture of 10 cubic centimeters of Catalyst D and 20 cubic centimeters of 10/14 mesh alpha-alumina diluent, and the downstream reactor was loaded with a uniform mixture of 20 cubic centimeters of Catalyst A and 20 cubic centimeters of 10/14 mesh alpha-alumina diluent.
  • the feed used in Examples VII-XI was a vacuum resid, an atmospheric resid or a blend of these resids.
  • the feed characteristics are presented in Table 4.
  • both upstream and downstream reactors were filled with gas oil and pressured to 13.8 MPa with hydrogen.
  • the temperature of each reactor was then raised to 149°C for at least one hour and then was raised to the desired reactuon temperature.
  • resid feed was then introduced to the upstream reactor, from which the effluent then passed into the downstream reactor.
  • the feed rate in each reactor was from about 0.2 to about 1.0 volume per hour per volume of catalyst, in terms of space velocity.
  • Each of Examples VII-XI was conducted for 14 to 61 days with daily sampling and analysis of the liquid product recovered using a high pressure separator.
  • Example VII-XI The conditions employed in Examples VII-XI are shown in Table 5.
  • the reaction temperature, space velocity or identity of the feed employed in Examples IX-XI were varied during the course of the run. Consequently, in Table 5, the reaction temperature, space velocity and identity of the feed are listed for each stage of the runs where one of them is changed.
  • the feed rate presented in Table 5 is the overall space velocity based on combined volume of catalysts in the upstream and downstream reactors.
  • the higher metals content of Feed 2 was employed, and generally at higher space velocities, to accelerate the substantial deposition of metal contaminants on the catalyst, under which condition, prior art catalysts are known to deactivate.
  • Example IX the conversion to product boiling below 538°C was at substantially the same level in Example IX at the 9th day of the run and at a reaction temperature of only 405°C as in Example VII at the 23rd day of the run and at the higher reaction temperature of 416°C.

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Claims (17)

1. Une composition de catalyseur d'hydrotraitement comprenant un composant d'hydrogénation constitué essentiellement de (1) un composant métallique dont le métal est choisi dans le groupe VIB et (2) un composant phosphoré, déposé sur la surfaced'un support comprenant un oxyde minéral réfractaire poreux et dépourvu de composant zéolitique, le composant de métal du groupe VIB ayant une concentration dans la gamme de 1 % en poids à 30% en poids calculée en oxyde métallique et relativement au poids du catalyseur, et le composant phosphoré ayant une concentration dans la gamme de 0,1% en poids à 5% en poids calculée en phosphore élémentaire et relativement au poids du catalyseur, et la . composition de catalyseur ayant un volume des pores dans la gamme de 0,4 cm3/g à 0,9 cm'/g, une surface spécifique BET dans la gamme de 130 m2/g à 300 m2/g, un diamètre moyen des pores dans la gamme de 90À à 160À (9-16 nm) et une distribution du volume des pores telle que moins de 40% de son volume total des pores consistent en des pores ayant des diamètres dans la gamme de 50Â à 80Å (5-8 nm), 45% à 90% de son volume des pores consistent en des pores ayant des diamètres dans la gamme de 80Å à 130Â (8-13 nm) et moins de 15% de son volume des pores consistent en des pores ayant des diamètres supérieurs à 130À (13 nm).
2. La composition de catalyseur de la revendication 1 dans laquelle l'oxyde minéral réfractaire poreux comprend de l'alumine.
3. La composition de catalyseur de la revendication 1 dans laquelle le métal du groupe VIB est le molybdène ou une combinaison de molybdène et d'au moins un du chrome et du tungstène.
4. La composition de catalyseur de la revendication 1 ayant la distribution suivant du volume des pores:
Figure imgb0014
5. La composition de catalyseur de la revendication 1 dans laquelle les pores ayant des diamètres dans la gamme de 80Å à 130À (8-13 nm) contiennent de 90 à 180 m2/g de surface spécifique BET.
6. La composition de catalyseur de la revendication 1 dans laquelle le composant à métal du groupe VIB est présent en une concentration de 8% en poids à 22% en poids calculée en oxyde de métal et relativement au poids du catalyseur.
7. La composition de catalyseur de la revendication 1 dans laquelle le composant d'hydrogénation consiste essentiellement en (1) le composant à métal du groupe VIB, (2) le composant phosphoré et (3) un composant à métal du groupe VIII à une concentration dans la gamme de 0% en poids à 15% en poids calculée en oxyde métallique.
8. La composition de catalyseur de la revendication 7 ayant une concentration du composant phosphoré dans la gamme de 0,5% en poids à 3% en poids calculée en phosphore élémentaire et une concentration du composant à métal du groupe VIII dans la gamme de 0,5% en poids à 12% en poids calculée en l'oxyde métallique, toutes les concentrations étant relatives au poids du catalyseur.
9. Un procédé d'hydrotraitement d'une alimentation hydrocarbonée comprenant le contact de l'alimentation hydrocarbonée avec de l'hydrogène dans des conditions d'hydrotraitement et en présence d'un catalyseur comprenant un composant d'hydrogénation constitué essentiellement de (1) un composant métallique dont le métal est choisi dans le groupe VIB et (2) un composant phosphoré, déposé sur la surfaced'un composant support comprenant un oxyde minéral réfractaire poreux et dépourvu de composant zéolitique, le composant de métal du groupe VIB ayant une concentration dans la gamme de 1% en poids à 30% en poids calculée en oxyde métallique et relativement au poids du catalyseur, et le composant phosphoré ayant une concentration dans la gamme de 0,1 % en poids à 5% en poids calculée en phosphore élémentaire et relativement au poids du catalyseur, et la composition de catalyseur ayant un volume des pores dans la gamme de 0,4 cm3/g à 0,9 cm'/g, une surface spécifique BET dans la gamme de 130 m2/g à 300 m2/g, un diamètre moyen des pores dans la gamme de 90Å à 160Â (9-16 nm) et une distribution du volume des pores telle que moins de 40% de son volume total des pores consistent en des pores ayant des diamètres dans la gamme de 50Â à 80A (5-8 nm), 45% à 90% de son volume des pores consistent en des pores ayant des diamètres dans la gamme de 80Å à 130Â (8-13 nm) et moins de 15% de son volume des pores consistent en des pores ayant des diamètres supérieurs à 130Å (13 nm).
10. Le procédé de la revendication 9 dans lequel l'ôxyde minéral réfractaire poreux comprend de l'alumine.
11. Le procédé de la revendication 9 dans lequel le métal du groupe VIB est le molybdène ou une combinaison de molybdène et d'au moins un du chrome et du tungstène.
12. Le procédé de la revendication 9 dans lequel l'alimentation hydrocarbonée contient au moins 0,1% en poids de soufre et les conditions d'hydrotraitement comprennent des conditions d'hydrodésulfuration qui comprennent une température de 399°C à 427°C, une pression de 12,4 MPa à 20,7 MPa, un taux d'addition d'hydrogène d'environ 178 m3/m3 à 1 780 m3/m3 et une vitesse spatiale de 0,1 à 5 volumes d'alimentation par volume de catalyseur par heure.
13. Le procédé de la revendication 9 dans lequel le catalyseur comprend de 8% en poids à 22% en poids du composant à métal du groupe VIB calculée en oxyde métallique et relativement au poids du catalyseur et de 0,5% en poids à 3% en poids du composant phosphoré calculée en phosphore élémentaire et relativement au poids du catalyseur.
14. Procédé selon la revendication 9 dans lequel l'alimentation hydrocarbonée contient au moins 0,1 % en poids d'azote total et les conditions d'hydrotraitement comprennent des conditions d'hydrodénitrogénation qui comprennent une température de 388°C à 427°c, une pression de 8,3 MPa à 17,3 MPa, un taux d'addition d'hydrogène de 178 m3/m3 à 1 780 m3/m3 et une vitesse spatial de 0,3 à 2 volumes d'alimentation par volume de catalyseur par heure, dans lequel le catalyseur a un volume des pores dans la gamme de 0,3 cm3/g à 1,2 cm3/g, une surface spécifique BET dans la gamme de 100 m2/g à 350 m2/g et un diamètre moyen des pores dans la gamme de 70Å (7 nm) à 120Å (12 nm) et dans lequel le catalyseur comprend de 15% en poids à 22% en poids du composant à métal du groupe VIB calculé en oxyde métallique et relativement au poids du catalyseur et de 0,5% en poids à 3% en poids du composant phosphoré calculé en phosphore élémentaire et relativement au poids du catalyseur.
15. Le procédé de la revendication 9 dans lequel l'alimentation hydrocarbonée contient au moins 150 ppm de métaux totaux et les conditions d'hydrotraitement comprennent des conditions d'hydrodémétallation, qui comprennent une température de 371°C à 454°C, une pression de 7 MPa à 21 MPa, un taux d'addition d'hydrogène de 178 m3/m3 à 1 780 m3/m3 et une vitesse spatiale de 0,1 à 5 volumes d'alimentation par volume de catalyseur par heure, dans lequel le catalyseur est constitué essentiellement de (1) de composant à métal du groupe VIB à une concentration de 1 % en poids à 30% en poids calculée en oxyde métallique et relativement au poids du catalyseur, (2) le composant phosphoré à une concentration de 0,5% en poids à 3% en poids calculée en phosphore élémentaire et relativement au poids du catalyseur et (3) un composant à métal du groupe VIII à une concentration de 0% en poids à 15% en poids calculée en oxyde métallique et relativement au poids du catalyseur et dans lequel le catalyseur a un volume des pores dans la gamme de 0,7 cm3/g à 1,7 cm3/g, une surface spécifique BET dans la gamme de 100 m2/g à 400 m2/g et un diamètre moyen des pores dans la gamme de 125Â à 350Å.
16. Le procédé de la revendication 15 dans lequel le métal du groupe VIII a une concentration dans le catalyseur de 0,5% en poids à 12% en poids calculée en oxyde métallique et relativement au poids du catalyseur.
17. Un procédé d'hydrodémétallation et d'hydrodésulfuration d'une alimentation hydrocarbonée contenant des asphaltènes et une quantité notable de métaux, ladite alimentation comprenant au moins un composant choisi dans le groupe constitué par le pétrole brut, le pétrole brut étêté, des résidues hydrocarbonés de pétrole, des huiles obtenues à partir de sables asphaltiques, des résidus dérivés d'huiles de sables asphaltiques, des produits hydrocarbonés dérivés du charbon et des mélanges de quelconques des résidus précités avec des matières à point d'ébullition plus bas, lequel procédé comprend:
(a) le contact de ladite alimentation dans une première zone de réaction avec de l'hydrogène et un catalyseur de premier étage comprenant (1) un composant à métal d'hydrogénation comprenant au moins un métal du groupe VIB et un métal du groupe VIII et (2) un support constitué d'un oxyde minéral poreux, ledit métal d'hydrogénation étant sous au moins une forme choisie dans le groupe constitué par la forme élémentaire, l'oxyde et le sulfure et ledit catalyseur ayant une surface spécifique de 100 m2/g à 400 m2/g, un volume des pores de 0,7 cm3/g à 1,7 cm3/g et un diamètre moyen des pores de 125À à 350Å (12,5-35 nm), sous réserve que lorsqu'un métal du groupe VIB est présent, il est présent à la concentration de 1 à 30% en poids du métal calculée en oxyde et lorsqu'un métal du groupe VIII est présent, il est présent à une concentration de 0,5 à 12% en poids du métal calculée en oxyde; et (b) le contact de l'effluent de la première zone de réaction dans une seconde zone de réaction avec un catalyseur de second étage comprenant un composant d'hydrogénation constitué essentiellement de (1) un composant métallique dont le métal est choisi dans le groupe VIB et (2) un composant phosphoré déposé sur la surface d'un support comprenant un oxyde minéral réfractaire poreux et dépourvu d'un composantzéolitique et ayant une volume des pores dans la gamme de 0,4 cm3/gà 0,9 cm3/g, une surface spécifique dans la gamme de 130 m2/g à 300 mz/g, un diamètre moyen des pores dans la gamme de 90A à 160A (9-16 nm) et une distribution du volume des pores telle que moins de 40% de son volume total des pores consistent en des pores ayant des diamètres dans la gamme de 50À à 80Â (5-8 nm), 45% à 90% de son volume total des pores consistent en des pores ayant des diamètres dans la gamme de 80Â à 130Â (8-13 nm) et moins de 15% de son volume total des pores consistent en des pores ayant des diamètres supérieurs à 130Å (13 nm), le composant à métal du groupe VIB étant à une concentration dans la gamme de 8% en poids à 22% en poids calculée en oxyde métallique et relativement au poids du catalyseur et le composant phosphoré ayant une concentration dans la gamme de 0,5% en poids à 3% en poids calculée en phosphore élémentaire et relativement au poids du catalyseur, les conditions opératoires dans la première et la seconde zones de réaction comprenant une pression dans la gamme de 7 MPa à 21 MPa, une température moyenne du lit de catalyseur dans la gamme de 371°C à 454°C, une VSLH dans la gamme de 0,1 volume d'hydrocarbure par heure par volume de catalyseur à 5 volumes d'hydrocarbure par heure par volume de catalyseur et un taux de recyclage de l'hydrogène ou un taux d'addition de l'hydrogène dans la gamme de 178 m3/m3 à 2 671 m3/m3.
EP19830307379 1982-12-06 1983-12-05 Catalyseur et procédé d'hydrotraitement Expired EP0112667B1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10144882B2 (en) 2010-10-28 2018-12-04 E I Du Pont De Nemours And Company Hydroprocessing of heavy hydrocarbon feeds in liquid-full reactors

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DE3375803D1 (en) 1988-04-07
EP0112667A1 (fr) 1984-07-04
AU2180583A (en) 1984-06-14
CA1243976A (fr) 1988-11-01
AU571189B2 (en) 1988-04-14

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