Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J23/889—Manganese, technetium or rhenium
  • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
• • 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
• • 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
  • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • 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
  • C10G45/10—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 containing platinum group metals or compounds thereof
• • 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
  • 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
  • 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
  • B01J35/635—0.5-1.0 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
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm

Definitions

• This invention relates to the desulfurization of petroleum fractions. More particularly, it is concerned with the catalytic hydrodesulfurization of heavy petroleum oils under conditions whereby the throughput and desulfurization of a unit may be increased and the hydrogen consumption in the desulfurization procedure may be reduced with prolonged catalyst life.
• the start-of-run temperature using fresh or freshly regenerated catalyst is preferably between about 625 and 650F. and the end-of-run temperature about. 750F., a gradual increase in temperature being made to compensate for loss of activity of the catalyst throughout the onstream period.
• Pressures range generally between about 500 and 1,000 psig with hydrogen rates of about 500-2,000 scfb.
• the space velocity is controlled to obtain the desired amount of desulfurization with 85-90% desulfurization being considered as the most practical from an efficiency standpoint.
• conventional commercial heavy oil desulfurization units are designed to operate at a space velocity of about I.
• the efficiency of a desulfurization unit is improved by contacting a sulfurcontaining petroleum oil having an initial boiling point of at least about 500F. with added hydrogen at a temperature between 750 and 850F., a pressure between about 300 and 3000 psig and a space velocity between 3 and 10 preferably from 4 to 8 v/v/hr. in the presence of a hydrogenation catalyst comprising a Group V] metal and an iron group metal or compounds thereof supported on a refractory inorganic oxide and containing from about 0.1 to 5% by weight of a Group VI metal such as manganese or rhenium based on the catalyst composite.
• a hydrogenation catalyst comprising a Group V] metal and an iron group metal or compounds thereof supported on a refractory inorganic oxide and containing from about 0.1 to 5% by weight of a Group VI metal such as manganese or rhenium based on the catalyst composite.
• Feeds which may be used in the process of our invention are heavy petroleum oil fractions having an initial boiling point of at least about 500F. and preferably at least 625F.
• feeds are gas oils such as vacuum gas oils, atmospheric residua, vacuum residua, heavy coker distillates, coal tar distillates and gas oils obtained from shale, tar sand and the like. Generally, they contain from 0.5 to 5.0 weight sulfur.
• the hydrogen used in our process may be obtained from any suitable source such as reformer by-product hydrogen, electrolytic hydrogen or hydrogen produced by the partial oxidation of carbonaceous or hydrocarbonaceous materials followed by shift conversion and CO removal.
• the hydrogen should have a purity of at least 50% and preferably at least 65% by volume.
• the catalyst used in the process of our invention v comprises a Group VIII metal such as an iron group metal or compound thereof composited with a group VI metal or compound thereof on a refractory inorganic oxide support.
• Suitable Group VIII metals are particularly nickel and cobalt used in conjunction with tungsten or molybdenum.
• the metals are in the form of the oxide or sulfide.
• the r iron group metal is present in an amount between about l.0 and 10% and the Group VI metal is present in an amount between about 5 and 30% based by weight on the catalyst composite.
• refractory inorganic oxides useful as supports are alumina, magnesia, zirconia and the like or mixtures thereof.
• the support is composed for the most part of alumina stabilized with a minor amount, e.g. up to about 5 wt. silica.
• the catalyst also contains as an agent for reducing the deactivation rate of the catalyst, a small amount e.g., 0.5-5.0 preferably from 0.2-2.0 percent of a Group VII metal e.g. rhenium or manganese based on the weight of the catalyst composite.
• a Group VII metal e.g. rhenium or manganese based on the weight of the catalyst composite.
• These metals or their compounds are particularly effective in reducing the deactivation rate when the catalyst is used at high temperatures such as 800-850F. and high space velocities such as 4-8 v/v/hr.
• the catalyst may be prepared by conventional means such as those disclosed in US. Pat. No. 2,437,533 issued Mar. 9, 1948.
• the catalyst may be prepared by forming the support which, as mentioned above, is, for example, alumina containing a small amount of silica.
• the support may then be impregnated with the desired metals by use of a solution of a water-soluble compound of the metal.
• water solutions of ammonium molybdate, cobalt nitrate, nickel nitrate, ammonium metatungstate, manganous nitrate or perrhenic acid may be used for the impregnation.
• the composite is heated to dry and then calcined for several hours in air at high temperature e.g., 900l000F. thereby converting the metals to the oxide.
• the catalyst may be used as a slurry, a moving bed, a fixed bed or a fluidized bed.
• the catalyst is used as a fixed bed of particles which may be spheroids or cylindroids, the latter being preferred.
• the oil flow may be either upward or downward with concurrent hydrogen flow or the flow of oil may be downward counter to upwardly flowing hydrogen.
• the hydrogen and the oil both pass downwardly through the fixed bed of catalyst particles.
• EXAMPLE I This example shows that the presence of rhenium in the catalyst reduces the deactivation rate of the catalyst.
• the composition of catalyst A is 3 wt. cobalt, 12 wt. molybdenum, 3 wt. silica and the balance alumina. The cobalt and molybdenum are present as the oxides.
• the catalyst has a surface area of 290 m lg, a pore volume of 0.63 cc/g and an average pore diameter of 82.5A.
• Catalyst B is the same as catalyst A except that it additionally contains 0.5 wt. rhenium.
• the charge stock is a West Texas-New Mexico vacuum gas oil having an API Gravity of 22 and a sulfur content of 1.85 wt.
• Example I is repeated with catalyst C containing 3 wt. nickel, 13.6 wt. molybdenum and the balance alumina.
• Catalyst D is similar to catalyst C but in addition contains 1.0 wt. rhenium.
• the reaction conditions are the same as those of Example I.
• EXAMPLE III This is a substantial duplicate of Example II except that Catalyst E contains 1 wt. manganese and the reaction conditions are 800F., 350 psig, 6 v/v/hr. with a hydrogen circulation rate of 1,500 SCFB recycle hydrogen and 500 SCFB fresh hydrogen.
• EXAMPLE IV This example is similar to Example I with respect to charge stock and reaction conditions,.the difference being that Catalyst F contains 2 wt. rhenium. As in the other examples, the time on-stream is reported in terms of barrels of feed per pound of catalyst.
• a comparisonof this example with catalyst A of Example shows the effectiveness of the addition of 2 wt. rhenium to the catalyst in reducing the deactivation rate of the catalyst at high temperature and low pressure specifically a temperature of 800-850F. and a pressure below 500 psig.
• a process for the hydrodesulfurization of a petroleum oil fraction having an initial boiling point of at least about 500F. which comprises contacting said fraction in the presence of added hydrogen under hydrodesulfurization conditions with a catalyst comprising an iron group metal, oxide or sulfide thereof and a Group V! metal, oxide or sulfide thereof on a refractory inorganic oxide support selected from the group consisting of alumina, magnesia and zirconia and mixtures thereof and containing between 0 and 5 wt. silica, said catalyst also containing from 0.1-5% by weight based on the catalyst composite of a Group V" metal or oxide thereof at a temperature between about 800 and 850F. and a space velocity between about 4 and 8 v/v/hr.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

Priority Applications (12)

Applications Claiming Priority (1)

Publications (1)

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Family Applications (1)

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Cited By (4)

Citations (3)

• 1973
  • 1973-12-07 US US422630A patent/US3915848A/en not_active Expired - Lifetime
• 1974
  • 1974-09-26 CA CA210,134A patent/CA1035713A/fr not_active Expired
  • 1974-11-28 BE BE150972A patent/BE822730A/fr unknown

Patent Citations (3)

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