US3509044A - Hydrodesulfurization of petroleum residuum - Google Patents

Hydrodesulfurization of petroleum residuum Download PDF

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US3509044A
US3509044A US3509044DA US3509044A US 3509044 A US3509044 A US 3509044A US 3509044D A US3509044D A US 3509044DA US 3509044 A US3509044 A US 3509044A
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catalyst
hydrodesulfurization
percent
activity
silica
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Clark E Adams
William T House
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • 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 a process for the hydrodesulfurization of petroleum residuum. More particularly the invention relates to the hydrodesulfurization of petroleum residuum in the presence of a catalyst having a support material characterized by a critical silica content and pore size distribution.
  • the process of the invention is applied to a petroleum residuum feedstock.
  • residua contains l) asphaltenes and other high molecular weight, aromatic structures which severely inhibit the rate of hydrodesulfurization, and cause catalyst deactivation, (2) ash forming constituents such as metallo-organic compounds which result in catalyst contamination and interfere with catalyst regeneration, and (3) a relatively large quantity of sulfur which gives rise to objectionable quantities of S0 and 80;, upon combustion in industrial furnaces.
  • Hydrodesulfurization has long been recognized as a means of removing sulfur from residual oils and asphalts.
  • hydrodesulfurization processes generally result in improvement in other properties of residual fuels by nitrogen removal and metals removal.
  • the commercial application of hydrodesulfurization to residua to produce improved residual fuels has been minimal.
  • Low economic incentives for improved fuel oil properties and high operating costs associated with the relatively high pressure required, the high hydrogen consumption and short catalyst life have hindered the utilization of such processes.
  • the principal object of the present invention is to reduce the sulfur content of petroleum residuum without significantly changing the properties of the oil.
  • the process is centered on nondestructive hydrodesulfurization as distinguished from destructive hydrogenation or hydrocracking. Thus, conversion to gas and light ends is minimized.
  • Another object of this invention is to provide a process specifically designed to treat a feed consisting entirely of petroleum residuum as distinguished from naphthas, gas oils or residua containing added diluents. In most cases satisfactory processes and catalysts have been developed for the lighter materials and diluted feedstocks.
  • Another object of this invention is to provide a hydrodesulfurization process for petroleum residua which is economically feasible in view of the low return available from the marketing of the treated residuum as residual fuel oil. Cost studies have shown that the key factors are catalyst activity and catalyst activity maintenance. Therefore the specific object of the invention is to provide a process 3,509,044 Patented Apr. 28, 1970 which is carried out at moderate pressure, temperature and other conditions with a catalyst which features low cost and high activity maintenance. Further objects and advantages of the invention will be apparent from the following description which discloses certain nonlimiting embodiments.
  • the objects of the invention are attained by hydrodesulfurizing petroleum residua at moderate conditions in the presence of a catalyst comprising an oxide or sulfide of nickel or cobalt and an oxide or sulfide of molybdenum or tungsten deposited upon a support material consisting essentially of 1 to 6 wt. percent silica and 94 to 99 'Wt. percent alumina.
  • the catalyst has a maximum pore volume and surface area in pores 30 to 70 A. in diameter.
  • FIGURE 1 is a graph comparing the temperature increase requirement of one of the catalysts of the invention compared to that of a typical prior art catalyst and
  • FIGURE 2 is a graph relating relative catalyst activity to the quantity of silica in the catalyst.
  • the process feedstock is a petroleum residuum obtained from distillation or other treating or separation process. From 30 to 100% of the feed boils have 900 F.
  • the process is designed to treat a residuum without any preprocessing; however, when the metal content of the oil is greater than about 500 to 1000 p.p.m. it may be necessary to employ a metals removal step such as HF treatment or solvent precipitation with propane, butane, mixtures of propane and butane, pentane, hexane or naphtha.
  • the petroleum residuum can be a blend of high boiling materials such as atmospheric bottoms, vacuum bottoms, deasphalted oil, visbreaker products, heat soaked materials, gas oil cuts, etc.
  • the feedstocks of the invention contain relatively large amounts of sulfur, asphaltenes, metals and ash. Some of these materials or conversion products thereof deposit on the hydrodesulfurization catalyst when hot oil is brought in contact with the catalyst surface.
  • the feedstocks treated have the following properties and inspections:
  • the support can be prepared by precipitating the oxides or hydrated oxides of aluminum and silicon from aqueous solutions of water salts of these metals.
  • suitable proportions of the water soluble salts of aluminum such as the sulfate, chloride or nitrate and suitable proportions of water soluble silicon salts such as sodium silicate are precipitated from solution by adjusting the pH of the solution with acidic or basic material.
  • the precipitate is washed and otherwise treated to remove impurities as necessary.
  • the support can be impregnated with the metals while it is wet or after drying and calcining.
  • a preferred method of preparing the catalysts is to treat alkaline aqueous aluminate solutions which contain predetermined amounts of silica with acidic reagents to precipitate an aluminosilicate in the hydrous form.
  • a slurry produced by this technique is then dried by known methods to furnish a preferred catalyst support of this invention.
  • the supports of the types prepared above are then impregnated with metals which promote a hydrodesulfurization reaction.
  • the catalyst containing all the active ingredients is then (1) dried and extruded, or (2) dried to remove excess moisture, impregnated and extruded, or (3) dried to remove excess moisture, extruded, dried and then impregnated.
  • the preferred alkaline aqueous aluminate solution is a solution of sodium aluminate. It is understood that other alkali metal aluminates can be used except they are not preferred from an economic standpoint.
  • the acidic reagents which can be used are the mineral acid salts of aluminum, e.g., aluminum halides, nitrates, and sulfates. Also useful are the well-known mineral acids themselves, e.g., hydrochloric, nitric, sulfuric acids, and the like.
  • the conditions for preparing the support are so controlled that the finished support has an apparent bulk density of less than 0.70 g./cc. It is further characterized as being opaque as distinguished from glassy in appearance (indicating that a large quantity of the alumina is in a crystalline form).
  • the catalyst is extrudable.
  • the support resulting from the reaction is in the form of a dilute slurry.
  • This slurry may then be concentrated and subjected to spray-drying operations at temperatures ranging between 200-2000 F., preferably 200-500" F.
  • the spray-dried material may be subjected to Water washing to remove excess alkali metal ions and sulfate ions.
  • the support can then be impregnated with the catalytic metals and extruded or pilled or otherwise formed into any desired physical form.
  • the aforementioned silica-alumina hydrogels can b composited with other synthetic and/or semi-synthetic aluminas, silica gels, and/or other silica-alumina-clay hydrogel compositions for the purpose of adjusting the alumina and/or silica present during impregnation. It is essential that the silica content of the catalyst be maintained in the range of 1-6 Weight percent, preferably 1.5-5 Weight percent.
  • the resulting catalyst, when calcined, should have a total surface area greater than 150 m. /g. and the pore volume is preferably greater than 0.25 cc./g. as measured by the BET procedure with nitrogen.
  • the active metallic components in the finished catalyst are a Group VI-B salt, specifically a molybdenum salt or tungsten salt selected from the group consisting of molybdenum oxide, molybdenum sulfide, tungsten oxide, tungsten sulfide, and mixtures of these and" a Group VIII-B salt, specifically a nickel or cobalt salt selected TABLE III.CATALYST COMPOSITION Broad Preferred range range (wt. percent) (wt. percent) Nickel or cobalt (as oxide) 1-15 2-10 Tungsten or molybdenum (as oxide) 5-25 10-20 Silica 1-6 1. 5-5 Alumina 93-52 86-64 The structure of the catalyst is also an important aspect of the invention.
  • EXAMPLE 1 The following illustrates a typical catalyst preparation.
  • EXAMPLE 2 A silica-alumina support is prepared in the manner set forth in Example 1 and is composited with suitable quantities of molybdenum oxide and cobalt carbonate by impregnation. The slurry is filtered and dried to provide a catalyst (dry weight basis containing 3.5% cobalt oxide, 12.0% molybdenum oxide, 1.7% SiO and the balance alumina). This catalyst is hereinafter referred to as Catalyst B.
  • the support can be impregnated with the other hydrogenation metals of the invention, i.e., nickel and tungsten in the same manner.
  • Catalyst A A commercial catalyst was selected for the purpose of obtaining comparative data. It contained 3.5 weight per cent cobalt oxide, 12.5 weight percent molybdenum oxide, 0.2 weight percent SiO and the balance alumina. This catalyst is designated hereinafter as Catalyst A.
  • the hydrodesulfurization reaction is carried out in a conventional reactor of the fixed bed, moving bed or fluidized bed type. A slurry or ebbulating bed can also be used. Considering the nature of the feedstock, the reaction conditions are relatively mild. The oil is contacted in the liquid phase. Typical conditions are as follows:
  • FIGURE 1 sets forth the temperature increase requirement (TIR) for runs with Catalyst A and Catalyst B.
  • TIR temperature increase requirement
  • the TIR for Catalyst B is 017 F./day, showing a very low activity decline.
  • Catalyst A exhibited the usual initial high activity decline then lined out at a TIR of 1.7 F./day.
  • Catalyst B has an activity maintenance ten times better than that of Catalyst A. This result was completely unexpected because the two catalysts demonstrated no such difference in the hydrodesulfurization of distillates.
  • Runs with Catalyst B demonstrate the following improvements: (1) greatly improved catalyst life, (2) lower pressure operation (1500 vs. 2200 p.s.i.g. which was previously considered necessary for good catalyst life), and (3) lower gas rates (1500 vs. 3000 s.c.f./bbl. also previously considered necessary for good catalyst life).
  • the new catalyst shows about half the metals laydown usually experienced with petroleum residuum feeds.
  • Table V shows the relative activity of a number of hydrodesulfurization catalysts. All runs were carried out on Safaniya atmospheric residuum (4.0% S) at the following conditions: 1500 p.s.i.g., 725 F., 3000 s.c.f. Hg/ bbl., 1 v./v./hr., cc. catalyst.
  • EXAMPLE 3 A pilot plant'unit containing 200 cc. of catalyst was used in this example. The oil was passed down through the catalyst bed.
  • the catalyst was calcined overnight at 1200 F. and then sulfided using 5 wt. percent carbon disulfide in a light petroleum distillate. Sulfiding was carried out at 1 v./v./hr., 1500 p.s.i.g., and 1500 s.c.f./b.
  • the reactor was held at 500 F. for two hours and then raised to 750 F. and held there for 16 hours.
  • the temperature was lowered to near 700 F. and feed was cut in.
  • the feedstock was a Safaniya residuum having the properties set forth in Table I. Side-by-side comparative runs were made to give a direct comparison to measure the activity decline of the catalysts.
  • the pressure was 1500 p.s.i.g., the space velocity was 1 v./v./hr., and the hydrogen rate was 1500 s.c.f./bbl.
  • the reactor temperature was increased as necessary to obtain 55% desulfurization of the residuum.
  • Catalyst A was selected for comparison because it was effective in hydrodesulfurization of distillate stocks. It contained 3.5 wt. percent C00 and 12.5 wt. percent M00 on a support containing 0.2 wt. percent SiO and the balance alumina.
  • Catalyst B is prepared in The relative volume activity of the catalysts employed in the process of the invention, i.e., catalysts B, C, D, E, F, and G is far superior to the activity of the prior art catalysts, i.e., A, H, I, and I. It can be seen that silica content is critical.
  • FIGURE 2 shows the criticality of silica in the range of 1 to 6 in the catalyst base in attaining high activity and activity maintenance. Since catalyst are sold by the pound, we prefer the catalysts having the lowest metals content and bulk density which will give superior activity maintenance, i.e., catalysts like Catalyst B.
  • the catalysts employed in the process of the invention have excellent surface area stability and they are effectively regenerated by conventional techniques at temperatures ranging from 6001000 F.
  • Catalysts A and B of the first two examples have some similar properties as shown by lines 1-5 of Table VI, below. For example, the overall surface areas are nearly equivalent. However, the nature of the surface areas are considerably different. Catalyst A has a surface area in 30 to 70 A. pores of 86 square meters per gram. Catalyst B has a surface area in 30 to 70 A. pores of 174 square meters per gram. The relatively large number of pores in the 30 to 70 A. range of Catalyst B seems to be one of the reasons for its extended life in processing residua.
  • Weight activity is determined by Relative Vol. Activity Bulk Density of Reference Catalyst Bulk Density of Test Catalyst
  • Catalyst B proved to have at least five times as much catalyst life as Catalyst A.
  • Catalysts C and E which are nickel-molybdenum type catalysts had a high relative weight activity.
  • a surface area in 30-70 A. pores of at least 100 m. /g., preferably 100-300 m. g. provides excellent activity and activity maintenance.
  • hydrodesulfurization of residua can be improved by subjecting the feed to such pretreating steps as deasphalting, deasphaltening, dilution, metals removal, etc.; however, usually the cost of the multistep processes cannot be justified.
  • the process of this invention provides adequate sulfur removal without any other major treating steps unless the feed has a very high metals content.
  • the catalysts of this invention are sufiiciently active so that hydrodesulfurization reaction pressures in the range of 800 to 1500 p.s.i.g. are satisfactory depending upon feedstock.
  • Prior art processes require pressures of 2500 to 3000 p.s.i.g. and a high treat gas recycle because of the low activity of the catalyst. Furthermore, they require 25 more investment and higher operating costs to achieve the same throughput.
  • hydrodesulfurization above 825 F. is not practical because of excessive gas make and hydrogen consumption.
  • the process of the invention operates well at lower temperatures. Conversion to light ends, gasoline and other light stocks is less than about 15 wt. percent based on the feedstock.
  • a process for the hydrodesulfurization of petroleum residuum containing -100 wt. percent of materials boiling above 900 F., 1-8 Wt. percent sulfur, 210-1000 p.p.m. metals and 1-20 Wt. percent asphaltenes comprising contacting said residuum in the liquid phase at a temperature of 650-800 F. and a pressure of 500-2500 p.s.i.g. in the presence of 500-7500 s.c.f./b.
  • hydrodesulfurization catalyst consisting essentially of a molybdcnum salt selected from the group consisting of molybdenum oxide and molybdenum sulfide and a nickel or cobalt salt selected from the group consisting of nickel oxide, cobalt oxide, nickel sulfide, cobalt sulfide and mixtures thereof deposited on a support material comprising silica stabilized alumina, said catalyst being characterized by having a maximum of its surface area in pores having pore diameters in the 30 to A. range.
  • a process for the nondestructive hydrodesulfurization of a feedstock consisting essentially of petroleum residuum containing 3-6 wt. percent sulfur comprising contacting said residuum in essentially the liquid phase at a temperature of 650 to 800 F., and a pressure of 1000 to 1800 p.s.i.g. in the presence of 1000 to 5000 s.c.f./b.
  • hydrodesulfurization catalyst consisting essentially of a molybdenum salt selected from the group consisting of molybdenum oxide and molybdenum sulfide and a Group VIII-B salt selected from the group consisting of nickel oxide, cobalt oxide, nickel sulfide, cobalt sulfide and mixtures thereof deposited on a support material comprising silica stabilized alumina, said catalyst being characterized by a maximum of pores having diameters in the range of 30-70 A.

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DE (1) DE1770704C3 (enrdf_load_stackoverflow)
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Cited By (29)

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US3658681A (en) * 1970-02-24 1972-04-25 Texaco Inc Production of low sulfur fuel oil
US3668116A (en) * 1970-10-16 1972-06-06 Exxon Research Engineering Co Slurry hydrodesulfurization of a heavy petroleum oil
US3691152A (en) * 1971-03-10 1972-09-12 Texaco Inc Hydrodesulfurization and blending of residue-containing petroleum oil
JPS4810364B1 (enrdf_load_stackoverflow) * 1967-06-26 1973-04-03
US3732155A (en) * 1971-03-31 1973-05-08 Exxon Research Engineering Co Two-stage hydrodesulfurization process with hydrogen addition in the first stage
DE2252332A1 (de) * 1971-12-07 1973-06-14 Shell Int Research Katalysator aus einem oder mehreren hydrierungsaktiven metallen auf einem traegermaterial, verfahren zu seiner herstellung und seine verwendung
US3770618A (en) * 1967-06-26 1973-11-06 Exxon Research Engineering Co Hydrodesulfurization of residua
DE2354330A1 (de) * 1973-10-12 1975-05-07 American Cyanamid Co Verfahren zur behandlung von erdoeldestillaten mit wasserstoff in gegenwart von geformten katalysatorteilchen
DE2354558A1 (de) 1973-10-12 1975-05-07 American Cyanamid Co Katalysatorformteilchen und verfahren zu ihrer verwendung
JPS5067787A (enrdf_load_stackoverflow) * 1973-10-20 1975-06-06
US3905916A (en) * 1971-07-14 1975-09-16 Exxon Research Engineering Co Process for preparing a hydrotreating catalyst
US3933623A (en) * 1974-08-09 1976-01-20 Texaco Inc. Desulfurization process
US3960712A (en) * 1973-04-30 1976-06-01 Universal Oil Products Company Hydrodesulfurization of asphaltene-containing black oil with a gamma-alumina composite catalyst of specified particle density
US4028227A (en) * 1974-09-24 1977-06-07 American Cyanamid Company Hydrotreating of petroleum residuum using shaped catalyst particles of small diameter pores
DE2730698A1 (de) * 1977-07-07 1979-01-18 Exxon Research Engineering Co Katalysator und verfahren zur wasserstoffbehandlung von mineraloelen
US4341625A (en) * 1973-08-09 1982-07-27 Chevron Research Company Method for preparing a catalyst carrier, a catalyst containing the carrier, and a hydrocarbon hydrodesulfurization process using the catalyst
US4366047A (en) * 1981-06-02 1982-12-28 Exxon Research And Engineering Co. Combination hydrorefining, heat-treating and hydrocracking process
US4368113A (en) * 1981-08-31 1983-01-11 Exxon Research And Engineering Co. Hydrocarbon hydrocracking process
EP0070125A3 (en) * 1981-07-09 1983-07-20 Exxon Research And Engineering Company Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst
DE3322884A1 (de) * 1983-01-24 1984-07-26 Intevep, S.A., Los Teques, Estado Miranda Verfahren zur herstellung eines katalysators zur entmetallisierung und gleichzeitigen entschwefelung von schwerem rohoel
US4634515A (en) * 1985-10-25 1987-01-06 Exxon Research And Engineering Company Nickel adsorbent for sulfur removal from hydrocarbon feeds
US4652545A (en) * 1985-05-06 1987-03-24 American Cyanamid Company Catalyst for hydroconversion of heavy oils and method of making the catalyst
US4686030A (en) * 1986-04-28 1987-08-11 Union Oil Company Of California Mild hydrocracking with a catalyst having a narrow pore size distribution
DE2366459C2 (enrdf_load_stackoverflow) * 1973-10-31 1989-09-28 American Cyanamid Co., Wayne, N.J., Us
US5210061A (en) * 1991-09-24 1993-05-11 Union Oil Company Of California Resid hydroprocessing catalyst
US5851381A (en) * 1990-12-07 1998-12-22 Idemitsu Kosan Co., Ltd. Method of refining crude oil
US6218333B1 (en) 1999-02-15 2001-04-17 Shell Oil Company Preparation of a hydrotreating catalyst
US6281158B1 (en) 1999-02-15 2001-08-28 Shell Oil Company Preparation of a co-containing hydrotreating catalyst precursor and catalyst
US20110229396A1 (en) * 2008-09-18 2011-09-22 Johnson Matthey Plc Catalyst and process

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RU2301703C1 (ru) * 2006-03-15 2007-06-27 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" Катализатор и способ гидропереработки нефтяного сырья с его использованием

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US3770618A (en) * 1967-06-26 1973-11-06 Exxon Research Engineering Co Hydrodesulfurization of residua
JPS4810364B1 (enrdf_load_stackoverflow) * 1967-06-26 1973-04-03
US3658681A (en) * 1970-02-24 1972-04-25 Texaco Inc Production of low sulfur fuel oil
US3668116A (en) * 1970-10-16 1972-06-06 Exxon Research Engineering Co Slurry hydrodesulfurization of a heavy petroleum oil
US3691152A (en) * 1971-03-10 1972-09-12 Texaco Inc Hydrodesulfurization and blending of residue-containing petroleum oil
US3732155A (en) * 1971-03-31 1973-05-08 Exxon Research Engineering Co Two-stage hydrodesulfurization process with hydrogen addition in the first stage
US3905916A (en) * 1971-07-14 1975-09-16 Exxon Research Engineering Co Process for preparing a hydrotreating catalyst
DE2252332A1 (de) * 1971-12-07 1973-06-14 Shell Int Research Katalysator aus einem oder mehreren hydrierungsaktiven metallen auf einem traegermaterial, verfahren zu seiner herstellung und seine verwendung
US3960712A (en) * 1973-04-30 1976-06-01 Universal Oil Products Company Hydrodesulfurization of asphaltene-containing black oil with a gamma-alumina composite catalyst of specified particle density
US4341625A (en) * 1973-08-09 1982-07-27 Chevron Research Company Method for preparing a catalyst carrier, a catalyst containing the carrier, and a hydrocarbon hydrodesulfurization process using the catalyst
DE2354330A1 (de) * 1973-10-12 1975-05-07 American Cyanamid Co Verfahren zur behandlung von erdoeldestillaten mit wasserstoff in gegenwart von geformten katalysatorteilchen
DE2354558A1 (de) 1973-10-12 1975-05-07 American Cyanamid Co Katalysatorformteilchen und verfahren zu ihrer verwendung
JPS5067787A (enrdf_load_stackoverflow) * 1973-10-20 1975-06-06
DE2366459C2 (enrdf_load_stackoverflow) * 1973-10-31 1989-09-28 American Cyanamid Co., Wayne, N.J., Us
US3933623A (en) * 1974-08-09 1976-01-20 Texaco Inc. Desulfurization process
US4028227A (en) * 1974-09-24 1977-06-07 American Cyanamid Company Hydrotreating of petroleum residuum using shaped catalyst particles of small diameter pores
DE2730698A1 (de) * 1977-07-07 1979-01-18 Exxon Research Engineering Co Katalysator und verfahren zur wasserstoffbehandlung von mineraloelen
US4366047A (en) * 1981-06-02 1982-12-28 Exxon Research And Engineering Co. Combination hydrorefining, heat-treating and hydrocracking process
EP0070125A3 (en) * 1981-07-09 1983-07-20 Exxon Research And Engineering Company Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocess utilizing the catalyst
US4513090A (en) * 1981-07-09 1985-04-23 Exxon Research And Engineering Co. Crystalline silica zeolite-containing catalyst
US4368113A (en) * 1981-08-31 1983-01-11 Exxon Research And Engineering Co. Hydrocarbon hydrocracking process
DE3322884A1 (de) * 1983-01-24 1984-07-26 Intevep, S.A., Los Teques, Estado Miranda Verfahren zur herstellung eines katalysators zur entmetallisierung und gleichzeitigen entschwefelung von schwerem rohoel
US4652545A (en) * 1985-05-06 1987-03-24 American Cyanamid Company Catalyst for hydroconversion of heavy oils and method of making the catalyst
US4634515A (en) * 1985-10-25 1987-01-06 Exxon Research And Engineering Company Nickel adsorbent for sulfur removal from hydrocarbon feeds
US4686030A (en) * 1986-04-28 1987-08-11 Union Oil Company Of California Mild hydrocracking with a catalyst having a narrow pore size distribution
US5851381A (en) * 1990-12-07 1998-12-22 Idemitsu Kosan Co., Ltd. Method of refining crude oil
US5210061A (en) * 1991-09-24 1993-05-11 Union Oil Company Of California Resid hydroprocessing catalyst
US5334307A (en) * 1991-09-24 1994-08-02 Union Oil Company Of California Resid hydroprocessing catalyst
US6218333B1 (en) 1999-02-15 2001-04-17 Shell Oil Company Preparation of a hydrotreating catalyst
US6281158B1 (en) 1999-02-15 2001-08-28 Shell Oil Company Preparation of a co-containing hydrotreating catalyst precursor and catalyst
US6290841B1 (en) 1999-02-15 2001-09-18 Shell Oil Company Hydrotreating process using sulfur activated non-calcined catalyst
US20110229396A1 (en) * 2008-09-18 2011-09-22 Johnson Matthey Plc Catalyst and process
US8945497B2 (en) * 2008-09-18 2015-02-03 Johnson Matthey Plc Catalyst and process

Also Published As

Publication number Publication date
JPS4810364B1 (enrdf_load_stackoverflow) 1973-04-03
DE1770704B2 (de) 1980-10-09
DE1770704C3 (de) 1981-07-30
FR1569510A (enrdf_load_stackoverflow) 1969-05-30
DE1770704A1 (de) 1971-12-09
NL6808924A (enrdf_load_stackoverflow) 1968-12-27
NL158837B (nl) 1978-12-15
GB1230142A (enrdf_load_stackoverflow) 1971-04-28
BE717161A (enrdf_load_stackoverflow) 1968-12-27

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