WO1993003117A1 - Procede d'hydroconversion utilisant un concentre de catalyseur a base de molybdene sulfure - Google Patents

Procede d'hydroconversion utilisant un concentre de catalyseur a base de molybdene sulfure Download PDF

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Publication number
WO1993003117A1
WO1993003117A1 PCT/US1991/005686 US9105686W WO9303117A1 WO 1993003117 A1 WO1993003117 A1 WO 1993003117A1 US 9105686 W US9105686 W US 9105686W WO 9303117 A1 WO9303117 A1 WO 9303117A1
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Prior art keywords
concentrate
catalyst
oil
hydrocarbonaceous
sulfur
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PCT/US1991/005686
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English (en)
Inventor
Roby Bearden, Jr.
Clyde Lee Aldridge
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Exxon Research And Engineering Company
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Application filed by Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to JP04501232A priority Critical patent/JP3058344B2/ja
Priority to CA002115048A priority patent/CA2115048C/fr
Priority to PCT/US1991/005686 priority patent/WO1993003117A1/fr
Priority to EP92900361A priority patent/EP0639219A4/fr
Publication of WO1993003117A1 publication Critical patent/WO1993003117A1/fr

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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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
    • C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding

Definitions

  • This invention relates to a hydroconversion process for converting a heavy hydrocarbonaceous feedstock to lower boiling products, which process involves the use of a sulfided catalyst concentrate which is prepared by use of elemental sulfur as the sulf ⁇ ding source.
  • One type of process suitable for hydroconversion of heavy feedstocks is a slurry process using a catalyst prepared in a hydrocarbon oil from a thermally-decomposable, metal compound catalyst precursor.
  • the catalyst is formed in situ in the hydroconversion zone.
  • hydroconversion with reference to a hydrocarbo ⁇ naceous oil, is used herein to designate a catalytic process conducted in the presence of hydrogen in which at least a portion of the heavy constituents of the oil is converted to lower boiling products.
  • the simultaneous reduction of the concentration of nitrogenous compounds, sulfur compounds and metallic constituents of the oil may also result.
  • introducing a catalyst precursor as a concentrate in a hydrocarbonaceous oil into a hydroconversion zone containing a heavy hydrocarbonaceous chargestock has certain advantages when compared with a process wherein the catalyst precursor is introduced into the hydrocon ⁇ version zone without first forming a concentrate; that is, by introducing the catalyst precursor directly into the feed in the reactor.
  • the advantages include: (i) ease of mixing the precursor with a small stream instead of the whole feed; (ii) the ability to store the precursor concentrate for future use and/or activity certification; and (iii) the ability to use a hydrocarbonaceous oil, other than the feedstock, as dispersing medium for the catalyst precursor, which hydrocarbonaceous oil other than the feedstock can be more optimum for developing catalyst activity-
  • converting a catalyst precursor concentrate to a catalyst concentrate comprised of solid catalyst particles dispersed in the hydrocarbonaceous oil and subsequently introducing a portion of this catalyst concentrate into the hydrocarbonaceous chargestock to be hydroconverted, with or without coal will provide certain additional advantages, such as greater flexibility of conditions.
  • Such advantages include: (i) use of higher concentrations of sulfiding agent than those concentrations that could practically be used to treat the total chargestock; (ii) flexibility of heat balance; and (iii) economy of energy.
  • Treatment of only the catalyst precursor concentrate to produce the catalyst instead of treating the entire feedstock containing the catalyst precursor permits reduction of equipment size.
  • preparing a catalyst concentrate permits storage of the catalyst concentrate for use as needed on-site or to send to another site.
  • a process for hydroconverting a heavy hydrocarbonaceous chargestock to lower boiling products comprises reacting the hydrocarbonaceous chargestock with a catalyst in the presence of hydrogen at hydroconversion conditions, said catalyst having been prepared by a method which comprises:
  • a catalyst precursor concentrate by mixing together: (i) a hydrocarbonaceous oil comprising constituents boiling above about 1050°F; (ii) a metal compound, said metal being selected from the group consisting of Groups IVB, VB, VIB, VHB and VIII of the Periodic Table of the Elements, in an amount to provide from about 0.2 to 2 wt% metal, based on said hydrocarbonaceous oil;
  • the metal compound is an aqueous solution of phosphomolybdic acid and a drying step is performed before the catalyst precursor is introduced into the heating zone.
  • the hydrocarbonaceous oil of step (i)(a) is a blend of a lighter oil with at least 10 wt% heavier oil, said lighter oil boiling below about 570°C and said heavier oil boiling above about 570°C.
  • the elemental sulfur is added as a concentrate in hydrocarbonaceous oil and is added to the precursor concentrate: (i) prior to the introduction of the precursor into the heating zone of step (b) or (ii) in the heating zone.
  • Figure 1 is a schematic flow plan of one embodiment of the present invention.
  • Figure 2 is a plot of toluene insoluble coke yield on 520 +o C feed and 520 +o C conversion versus S/Mo atomic ratios in the catalyst concentrate for the catalyst materials of this invention when tested as hydroconversion catalysts.
  • Figure 3 is a plot of toluene insoluble solid yield versus performing temperature (heating) used in forming the catalyst concentrates of this invention when tested under hydroconversion conditions.
  • Figure 1 hereof represents one of the preferred embodiments for carrying out the instant invention wherein an aqueous solution of phosphomolybdic acid is used as the metal compound.
  • phosphomolybdic acid is used herein to designate aqueous solutions of the reaction product of Mo0 3 with dilute phosphoric acid in which the phosphorus to molybdenum atomic ratio ranges from 0.083 to 2, preferably from 0.083 to 1 and most preferably from 0.083 to 0.5.
  • Said solutions can contain one or more phosphomolybdic acid species such as the 12-molybdophosphoric acid and the dimeric 18-molybdophosphoric acid.
  • the crystalline 12 and 18 acids can be used to prepare the water solutions of phosphomolybdic acid used in the process of this invention. If such crystalline phosphomolybdic acids are used, additional H 3 P0 4 or other phosphorus compounds may be added to the solution to provide the desired P/Mo ratio. Phosphomolybdic acids are described in Topics In Current Chemistry No. 76. published by Springer- Verlag of New York, pp. 1-64. 1978; which is incorporated herein by reference.
  • a heavy hydrocarbonaceous oil is introduced by line 10 into mixing zone 1.
  • Suitable hydrocarbonaceous oils for introduction into mixing zone 1 include hydrocarbonaceous oils comprising constituents boiling above 570°C, preferably having at least 10 wt% constituents boiling above 570°C, such as crude oils, atmospheric residua boiling above 330°C, and vacuum residua boiling above 570°C.
  • the hydrocarbonaceous oil has an initial boiling point above at least 330°C and comprises asphaltenes and/or resins.
  • the hydrocarbonaceous oils comprise a lighter boiling oil boiling below about 570°C and a heavier oil boiling above about 570°C in a blend comprising at least about 22 wt% materials boiling above 570°C.
  • Preferred concentrations of the 570 +o C fraction in the blend include from about 22 to 85 wt% heavier oil, more preferably from about 30 to 85 wt% heavier oil, still more preferably about 40 to 85 wt% heavier oil and, most preferably about 45 to 75 wt% heavier oil, based on the total weight of the blend (mixture of oils).
  • the light oil may be a gas oil and heavier oil may be a vacuum residuum. Alternatively, an atmospheric residuum having the appropriate amount of desired constituents may be used as the oil of line 10.
  • the hydrocarbonaceous oil carried by line 10 may be derived from any source, such as petroleum, tar sand oil, shale oil, liquids derived from coal liquefaction processes and mixtures thereof. Generally, these oils have a
  • Conradson carbon content ranging from about 5 to about 50 wt% (as to
  • Elemental sulfur either as the sublimed powder or as a concen ⁇ trated dispersion of sublimed powder, such as commercial Flowers of sulfur, in heavy hydrocarbonaceous oil, is introduced into mixing zone 1 by line 12. Allotropic forms of elemental sulfur, such as orthorhombic and monoclinic sulfur are also suitable for use herein.
  • the preferred physical form of sulfur is the sublimed powder (flowers of sulfur), although sulfur may also be introduced as molten sulfur and as sulfur vapor.
  • the amount of sulfur added into mixing zone 1 is such that the atomic ratio of sulfur to molybdenum is from about 1/1 to 8/1, preferably from about 2/1 to 7/1 and, more preferably from about 3/1 to 6/1.
  • sulfur can be added at any point in the catalyst concentration preparation procedure as long as it is not contacted with an aqueous solution prior to being introduced into oil.
  • it can be added as a concentrate in a hydrocarbonaceous oil after the precursor concentrate has been dried. It can also be introduced into the heating zone during formation of the catalyst concentrate.
  • the elemental sulfur is added as a concentrate in oil, the amount of sulfur in the concentrate is such that it still meets the aforementioned requirements pertaining to atomic ratio of sulfur to metal. That is,, the atomic ratio of sulfur to metal of the metal compound will remain 1/1 to 8/1.
  • the mixture from mixing zone ' 1 is passed to mixing zone 2 via line 14 where an appropriate metal compound, such as an aqueous solution of phosphomolybdic acid (catalyst precursor) is also introduced via line 16.
  • an appropriate metal compound such as an aqueous solution of phosphomolybdic acid (catalyst precursor) is also introduced via line 16.
  • a sufficient amount of the aqueous phosphomolybdic acid solution is introduced into mixing zone 2 to provide from about 0.2 to 2 wt%, preferably from about 0.2 to 1 wt%, more preferably 0.3 to 1 wt% molybdenum from the phosphomolybdic acid, calculated as elemental molybdenum based on the hydrocarbonaceous oil.
  • the resulting mixture is a water-containing catalyst precursor concentrate (i.e., wet catalyst precursor concentrate).
  • the wet catalyst precursor concentrate is removed from mixing zone 2 by line 18 and passed to drying zone 3 in which water is removed from the wet catalyst precursor concentrate by any suitable manner.
  • a suitable manner includes heating the water-containing catalyst precursor concentrate to a temperature sufficient to vaporize the water, for example, at a temperature ranging from 100 to 150°C.
  • the water is removed from drying zone 3 by line 20.
  • the dried catalyst precursor concentrate is removed from drying zone 3 and is passed via line 22 to heating zone 4.
  • the dried catalyst precursor concentrate is heated, in the absence of added hydrogen, to a temperature of at least about 275°C, preferably at a temperature ranging from about 275°C to about 425°C, more preferably from about 315°C to about 410°C and, most preferably from 330°C to about 400°C.
  • the total pressure in heating zone 4 will range from about 0 psig to about 500 psig, preferably from about 0 psig to about 100 psig.
  • the precursor concentrate is heated for an effective amount of time.
  • By "effective amount of time” we mean that amount of time needed to convert the catalyst precursor to the corresponding catalyst concentrate.
  • Zone 4 may be considered a catalyst formation zone in which the sulfur-containing catalyst precursor concentrate of phosphomolybdic acid is converted to the solid molybdenum-containing catalyst concentrate.
  • the catalyst concentrate is removed from heating zone 4 by line 24. At least a portion of the catalyst concentrate is introduced, via line 25, into line 26 which carries a carbonaceous chargestock comprising a hydro ⁇ carbon which may have the same boiling point range as the hydrocarbonaceous oil of line 10.
  • the hydrocarbon may also comprise a single hydrocarbon (e.g., tetralin) or a mixture of hydrocarbons having the same, or different, boiling point range as the hydrocarbonaceous oil of line 10 or a different boiling point range from the hydrocarbonaceous oil of line 10.
  • the carbonaceous chargestock may be a hydrocarbonaceous oil or coal in a hydrocarbon diluent.
  • Suitable hydrocarbonaceous oil chargestocks include crude oils; mixtures of hydrocarbons boiling above 220°C, preferably above 340°C; for example, gas oils, vacuum residua, atmospheric residua, once-through coker bottoms and asphalt.
  • the hydrocarbonaceous oil chargestock may be derived from any source, such as petroleum, shale oil, tar sand oil, oils derived from coal liquefaction processes, including coal liquefaction bottoms and mixtures thereof.
  • the hydrocarbonaceous oils have at least 10 wt% materials boiling above 570°C. More preferably, the hydrocarbonaceous oils have a Conradson carbon content ranging from about 5 to about 50 wt%. Coal may be added to any of these oils.
  • slurries of coal in a hydrocarbon diluent may be used as chargestock to convert the coal (i.e., coal liquefaction).
  • the diluent may be a single type of hydrocarbon or a mixture of hydrocarbons and may be a light hydrocarbon or a heavy hydrocarbon, as described in U.S. Patent No. 4,094,765, column 1, lines 54 to column 2, line 43, the teaching of which is hereby incorporated herein by reference.
  • the concentrate When the chargestock, into which at least a portion of the catalyst concentrate is introduced, is an oil, the concentrate disperses in the oil. If the chargestock comprises coal in a diluent, the concentrate may be added to the diluent before, after, or simultaneously with the addition of coal to the diluent.
  • a hydrogen-containing gas is introduced by line 27 into line 26. The mixture of carbonaceous chargestock, catalyst concentrate and hydrogen is passed into slurry hydroconversion zone 5.
  • the catalyst concentrate of line 25 is added to the carbonaceous chargestock in an amount sufficient to provide from about 10 to about 2000 wppm, preferably from about 50 to 1000 wppm, more preferably from about 50 to 800 wppm molybdenum and, most preferably from about 50 to 300 wppm metal, calculated as the elemental metal, preferably molybdenum, based on the total hydroconversion zone chargestock, i.e., concentrate plus carbonaceous chargestock.
  • the hydroconversion zone effluent is removed by line 28 and passed to a gas-liquid separation zone 6 wherein the normally gaseous phase is separated from a normally liquid phase.
  • the gaseous phase is removed from separation zone 6 by line 30.
  • the gaseous phase, which comprises hydrogen may be recycled by line 32, preferably after removal of undesired constituents, to slurry hydroconversion zone 5 via line 27.
  • the normally liquid phase which comprises the molybdenum-containing catalytic solids and a hydroconverted hydrocarbonaceous oil product, is passed by line 34 to separation zone 7 for fractionation by conventional means, such as distillation into various fractions; such as light, medium boiling, and heavy bottoms fractions.
  • the light fraction is removed by line 36.
  • the medium boiling fraction is removed by line 38.
  • the heavy bottoms fraction is removed by line 40 and, if desired, at least a portion of the bottoms fraction may be recycled to the hydroconversion zone.
  • the catalytic solids may be separated from the hydroconverted oil product and the separated solids may be recycled to the hydroconversion zone.
  • a metal compound other than an aqueous solution of phosphomolybdic acid, is introduced into one or both of the mixing zones.
  • the metal compound may be a compound or mixture of compounds as finely divided solids, or a compound or mixture of compounds as finely divided solids mixed with an organic liquid that is soluble in said hydrocarbonaceous oil, a compound or mixture of compounds that is soluble in the hydrocarbonaceous oil or a compound that is soluble in an organic compound (liquid medium) that can be dispersed in the hydrocarbonaceous oil.
  • metal compound can also be a compound that is water soluble and the resulting aqueous solution dispersed in the hydrocarbonaceous material.
  • the metal compound may be in a phenolic medium, in water, in alcohol, etc.
  • Suitable metal compounds convertible (under preparation conditions) to solid, metal- containing catalysts include: (1) inorganic metal compounds such as carbonyls, halides, oxyhalides; polyacids such as isopolyacids and heteropolyacids (e.g., phosphomolybdic acid, and molybdosilicic acid); (2) metal salts of organic acids such as acyclic and cyclic aliphatic carboxylic acids and thiocarboxylic acids containing two or more carbon atoms (e.g., naphthenic acids); aromatic carboxylic acids (e.g., toluic acid); sulfonic acids (e.g., toluenesulfonic acid); sulfinic acids; mercaptans; x
  • the metal constituent of the metal compound that is convertible to a solid, non-colloidal, metal-containing catalyst is selected from the group consisting of Groups IVB, VB, VIB, V B and VHI and mixtures thereof of the Periodic Table of the Elements.
  • the Periodic Table of the Elements referred to herein is published by Sergeant-Welsh Scientific Company being copyrighted in 1979 and available from them as Catalog Number S- 18806.
  • Non-limiting examples include zinc, antimony, bismuth, titanium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel and the noble metals including platinum, iridium, palladium, osmium, ruthenium and rhodium.
  • the preferred metal constituent of the metal compound is selected from the group consisting of molybdenum, tungsten, vanadium, chromium, cobalt, titanium, iron, nickel and mixtures thereof.
  • Preferred compounds of the given metals include the salts of acyclic (straight or branched chain) aliphatic carboxylic acids, salts of cyclic aliphatic carboxylic acids, polyacids, carbonyls, phenolates and organoamine salts.
  • the preferred metal compounds are inorganic polyacids of metals selected from Groups VB, VIB and mixtures thereof, that is, vanadium, niobium, chromium, molybdenum, tungsten and mixtures thereof.
  • Suitable inorganic polyacids include phosphomolybdic acid, phosphotungstic acid, phosphovanadic acid, silicomolybdic acid, silicotungstic acid, silicovanadic acid and mixtures thereof.
  • the preferred polyacid is a phosphomolybdic acid.
  • heteropolyacids and “isopolyacids” are used herein in accordance with the definitions given in Advanced Inorganic Chemistry. 4th Edition, by S.A. Cotton and Gerissay Wilkinson, Interscience Publishers, New York, pages 852-861.
  • a 500-ml stainless steel beaker was charged with 99.23 g of Cold Lake Crude oil that contained 50 wt% components boiling above 520 +o C, 12.9 wt% Conradson Carbon and which exhibited an initial boiling point of 471°F.
  • the beaker was then heated to 80-90°C and 0.77 g of colloidal sulfur (a sublimed, pharmaceutical grade product supplied by Battelle-Renwick Company, lot 2195) was stirred into the oil and the mixture was held _at 80-90°C for a period of 15 minutes.
  • the autoclave Upon completion of the 10-minute stirred period at 80°C, the autoclave was heated to 150°C and held at this temperature with stirring and with nitrogen flow-through at atmospheric pressure to remove water.
  • the dry catalyst precursor concentrate obtained in Step C was converted to catalyst concentrate by increasing the autoclave temperature to 385°C and maintaining this temperature for a stirred contact period of 30 minutes. After venting autoclave pressure (some light hydrocarbon removed) and cooling to room temperature, there was obtained 78 g of catalyst concentrate that contained 0.51 wt Mo.
  • This concentrate was assayed to determine formation of a solid molybdenum-containing catalyst by the following procedure: a sample of 30 g of this concentrate was diluted with 150 g of toluene and filtered over a Number 2 Whatman paper. Recovered solids, after toluene washing and drying under vacuum at 100°C, amounted to 1.04 g (3.47 wt% catalyst solids in catalyst concentrate). The Mo content of the recovered solids was 14.7 wt%.
  • Example 1 The procedures of Example 1 were repeated except that the blend used in Step A comprised 99.61 g Cold Lake Crude and 0.39 g colloidal sulfur, an amount of sulfur that provided a S/Mo atomic ratio of 2.6/1 in Step B. There was obtained 76 g of catalyst concentrate that contained 0.53 wt% Mo and 2.9 wt% toluene-insoluble catalyst solids. The Mo content of the solids was 18.5 wt%.
  • Example 1 The procedures of Example 1 were repeated except that the blend used in Step A comprised 98.85 g Cold Lake Crude and 1.15 g colloidal sulfur, an amount of sulfur that provided a S/Mo atomic ratio of 7.6/1 in Step B.
  • catalyst concentrate that contained 0.54 wt% Mo and 3.1 wt% toluene-insoluble catalyst solids.
  • the Mo content of the solids was 17.4 wt%.
  • Example 1 The procedures of Example 1 were repeated except that the blend used in Step A comprised 98.6 g Cold Lake Crude and 1.40 g colloidal sulfur, an amount of sulfur that provided a S/Mo atomic ratio of 9.5/1 in Step B.
  • Example 1 The procedures of Example 1 were repeated except that colloidal sulfur was not added to Cold Lake Crude in Step A.
  • catalyst concentrate that contained 0.49 wt Mo and 2.7 wt% catalyst solids.
  • the Mo content of the solids was 18.1 wt .
  • a solution of phosphomolybdic acid was prepared by dissolving 2 g of crystalline phosphomolybdic acid in 18 g of de-ionized water. This solution was mixed with 0.68 g of colloidal sulfur with stirring. Next, 9 g of this solution, which contained 4 wt% Mo, was injected into a 300-cc stirred Autoclave Engineer's Autoclave. The autoclave was heated to 80°C while stirring and was held at that temperature, with stirring, for 10 minutes. The S/Mo atomic ratio of the blend was 4.5/1.
  • the autoclave Upon completion of the 10-minute stirred period at 80°C, the autoclave was heated to 150°C and held at this temperature, with stirring and with nitrogen flow-through at atmospheric pressure to remove water. The autoclave was then pressured to 100 psig with H 2 S and was held, with stirring, at 150°C for 30 minutes. At this point, the autoclave was vented, flushed with nitrogen, sealed and heated to 365°C.
  • catalyst concentrate that contained 0.52 wt% Mo and 4 wt% of catalyst solids.
  • the Mo content of the solids was 11.8 wt%.
  • the autoclave Upon cooling to room temperature, the autoclave was charged to 1350 psig with hydrogen and, with stirring, the autoclave was heated to 385°C and held at that temperature for a period of 20 minutes.
  • Liquid and solid products in the autoclave reactor still at about 90°C, were filtered over a Number 2 Whatman filter paper to determine the yield of hot, oil insoluble solids (composite of catalyst, demetallization products and carbonaceous material). Filtered oil, after removal of 6.0 g for analytical tests, was set aside for determination of toluene-insoluble solids content. Liquid and solids remaining in the reactor after pouring out the hot oil contents were washed out with hot toluene and this wash was filtered by passing over the paper + solids from the hot oil filtration step. Filtered toluene wash liquid was then added to the oil from hot filtration and additional toluene was added so that the total weight of toluene was about 360 g.
  • Example 2 The catalyst concentrate of Example 2 was tested according to the procedure given in Example 6.
  • the reactor charge consisted of 109.5 g of vacuum Cold Lake Bottoms, 5.75 g of Cold Lake Crude and 4.75 g of the catalyst concentrate of Example 2. This amount of catalyst provided a Mo concentration of 208 wppm on the total reactor charge of feed and catalyst.
  • Example 3 The catalyst concentrate of Example 3 was tested according to the procedure given in Example 6.
  • the reactor charge consisted of 109.5 g of Cold Lake vacuum bottoms, 5.87 g of Cold Lake Crude and 4.63 g of the catalyst concentrate of Example 3. This amount of concentrate was sufficient to provide a Mo concentration of 208 wppm on total feed.
  • Example 4 The catalyst concentrate of Example 4 was tested according to the procedure given in Example 6.
  • the reactor charge consisted of 109.5 g of Cold lake vacuum bottoms, 5.50 g of Cold Lake Crude and 5.00 g of the catalyst concentrate of Example 4. This amount of concentrate provided 208 wppm Mo on total feed.
  • Example 5 The catalyst concentrate' of Example 5 was tested according to the procedure given in Example 6.
  • the reactor charge consisted of 109.5 g- of Cold lake vacuum bottoms, 5.60 g Cold Lake Crude and 4.90 g of the catalyst concentrate of Example 5. This amount of concentrate provided 208 wppm Mo on total feed.
  • the catalyst concentrate of Comparative Example I was tested according to the procedure of Example 6.
  • the reactor charge consisted of 109.5 g of Cold Lake vacuum bottoms, 4.63 g of Cold Lake crude and 5.87 g of the catalyst concentrate of Example 13. This amount of concentrate provided 250 wppm Mo on total reactor feed.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Procédé de conversion d'une charge hydrocarbonée lourde en produits à point d'bullition bas qui consiste à faire réagir ladite charge avec un concentré de catalyseur en présence d'hydrogène, dans des conditions d'hydroconversion, ledit concentré de catalyseur ayant été préparé (a) en formant un précurseur de concentré de catalyseur en mélangeant ensemble (i) une huile hydrocarbonée comprenant des constituants qui bouillent au-dessus de 570 °C environ et (ii) un composé métallique, ledit métal étant sélectionné dans le groupe constitué des groupes II, III, IV, V, VIB, VIIB et VIII du tableau périodique des éléments, dans une quantité équivalente à environ 0,2 à 2 % en poids de métal, par rapport à ladite huile hydrocarbonée; et (b) en chauffant le précurseur de concentré de catalyseur, du soufre élémentaire utilisé comme agent de sulfuration dans une quantité telle que le rapport atomique du soufre au métal est d'environ 1/1 à 8/1.
PCT/US1991/005686 1991-08-09 1991-08-09 Procede d'hydroconversion utilisant un concentre de catalyseur a base de molybdene sulfure WO1993003117A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP04501232A JP3058344B2 (ja) 1991-08-09 1991-08-09 硫化モリブデン触媒濃縮物を用いる水素化転化方法
CA002115048A CA2115048C (fr) 1991-08-09 1991-08-09 Procede d'hydroconversion avec un concentre de molybdene sulfure catalyseur
PCT/US1991/005686 WO1993003117A1 (fr) 1991-08-09 1991-08-09 Procede d'hydroconversion utilisant un concentre de catalyseur a base de molybdene sulfure
EP92900361A EP0639219A4 (fr) 1991-08-09 1991-08-09 Procede d'hydroconversion utilisant un concentre de catalyseur a base de molybdene sulfure.

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EP0712703A2 (fr) 1994-11-21 1996-05-22 Sinco Engineering S.P.A. Procédé pour la cristallisation de résines polyesters
WO2001044408A1 (fr) * 1999-12-16 2001-06-21 Chevron U.S.A. Inc. Cuvees de remplacement d'hydrotraitement de presulfuration d'un catalyseur
EP1754770A1 (fr) 2005-08-16 2007-02-21 Research Institute of Petroleum Procédé pour la hydro-conversion de courants hydrocarbonés lourds
US7947623B2 (en) 2004-09-10 2011-05-24 Oleg Mironov Hydroprocessing bulk catalyst and uses thereof
DE19928672B4 (de) * 1998-06-25 2013-02-28 IFP Energies Nouvelles Katalysatorschwefelungsverfahren in Gegenwart von Kohlenstoff und Elementarschwefel
RU2652122C1 (ru) * 2017-09-08 2018-04-25 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Способ получения суспензии катализатора гидроконверсии тяжелого нефтяного сырья
RU2672254C1 (ru) * 2018-05-25 2018-11-13 Публичное акционерное общество "Газпром" Способ комплексной переработки остатка атмосферной дистилляции газового конденсата и установка для его осуществления
RU2674160C1 (ru) * 2018-05-25 2018-12-05 Публичное акционерное общество "Газпром" Способ гидроконверсии остатка атмосферной дистилляции газового конденсата

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
EP0712703A2 (fr) 1994-11-21 1996-05-22 Sinco Engineering S.P.A. Procédé pour la cristallisation de résines polyesters
DE19928672B4 (de) * 1998-06-25 2013-02-28 IFP Energies Nouvelles Katalysatorschwefelungsverfahren in Gegenwart von Kohlenstoff und Elementarschwefel
WO2001044408A1 (fr) * 1999-12-16 2001-06-21 Chevron U.S.A. Inc. Cuvees de remplacement d'hydrotraitement de presulfuration d'un catalyseur
US7947623B2 (en) 2004-09-10 2011-05-24 Oleg Mironov Hydroprocessing bulk catalyst and uses thereof
EP1754770A1 (fr) 2005-08-16 2007-02-21 Research Institute of Petroleum Procédé pour la hydro-conversion de courants hydrocarbonés lourds
US7585406B2 (en) 2005-08-16 2009-09-08 Research Institute Of Petroleum Industry (Ripi) Process for hydroconverting of a heavy hydrocarbonaceous feedstock
RU2652122C1 (ru) * 2017-09-08 2018-04-25 Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт нефтехимического синтеза им. А.В. Топчиева Российской академии наук (ИНХС РАН) Способ получения суспензии катализатора гидроконверсии тяжелого нефтяного сырья
RU2672254C1 (ru) * 2018-05-25 2018-11-13 Публичное акционерное общество "Газпром" Способ комплексной переработки остатка атмосферной дистилляции газового конденсата и установка для его осуществления
RU2674160C1 (ru) * 2018-05-25 2018-12-05 Публичное акционерное общество "Газпром" Способ гидроконверсии остатка атмосферной дистилляции газового конденсата

Also Published As

Publication number Publication date
EP0639219A4 (fr) 1995-05-10
CA2115048C (fr) 2001-09-18
JPH06509365A (ja) 1994-10-20
JP3058344B2 (ja) 2000-07-04
EP0639219A1 (fr) 1995-02-22
CA2115048A1 (fr) 1993-02-18

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