US3598725A - Hydrocarbon desulfurization with a rhenium catalyst on siliceous carrier material - Google Patents
Hydrocarbon desulfurization with a rhenium catalyst on siliceous carrier material Download PDFInfo
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- US3598725A US3598725A US809050A US3598725DA US3598725A US 3598725 A US3598725 A US 3598725A US 809050 A US809050 A US 809050A US 3598725D A US3598725D A US 3598725DA US 3598725 A US3598725 A US 3598725A
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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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/36—Rhenium
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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
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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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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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
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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
- 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
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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
- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
Definitions
- the present invention involves the purification of hydrocarbon mixtures containing olefinic hydrocarbons and further contaminated with sulfurous compounds.
- the catalytic composite employed comprises a siliceous carrier material combined with rhenium sulfide.
- Other catalytically active components those from Groups VI-B and particularly the Iron-group are combined therewith, the selection being principally dependent ,upon the character of the charge stock, especially with respect to contaminant level and boiling range, and the desired end result.
- the catalytically active metallic components exist in a sulfided state prior to contact with the particular hydrocarbon, or hydrocarbon mixture.
- the catalytic composites of my invention may be utilized to great advantage, as a direct result of inherent increased hydrogenation activity, in the preparation of substantially saturated charge stocks.
- the charge stocks suitable for processing in accordance with the present invention will be readily recognized by those possessing expertise in the field of petroleum processing; however, a brief discussion of applicable charge stocks is believed warranted.
- hydrocarbonaceous fractions and/ or distillates are divided into various categories determined by the overall boiling range. Depending upon various refinery demands, as well as the particular locale in which the final product is to be utilized, the boiling ranges of the various distillates will vary individually, and may even overlap in some instances.
- the gasoline, or naphtha boiling range is generally considered to include pentanes and heavier hydrocarbons boiling up to an end boiling point of about 400 F. to about 425 F., with intermediate fractions being designated as light naphtha, or heavy naphtha.
- the kerosene boiling range commonly has an initial boiling point of from 300 F. to 425 F., and an end boiling point of from 500 F. to about 600 F.
- Light gas oils therefore, generally have an initial boiling point of from 500 F. to about 600 F. and an end boiling point of about 750 F. to about 800F., while heavy gas oils boil from about 750 F. to an end boiling point of about 1050 F.
- a principal object of my invention is to provide a desulfurization catalytic composite of a siliceous carrier material combined with rhenium sulfide.
- a corollary objective resides in a desulfurization catalyst which comprises a sulfided composite of a siliceous carrier material combined with rhenium and Iron-group metallic component.
- an object of the present invention is to effect the desulfurization of a sulfurous, hydrocarbonaceous charge stock, utilizing the novel catalyst of the present invention. Therefore, in one embodiment, the present invention is directed toward a desulfurization catalytic composite of a siliceous carrier material combined with rhenium sulfide and the sulfide of at least one metal component from Group VI-B and the Iron-group.
- the present invention provides a process for the desulfurization of a sulfur-containing hydrocarbonaceous charge stock, which process comprises reacting said charge stock with hydrogen, at desulfurization conditions, in contact with a desulfurization catalyst comprising a siliceous carrier material combined with rhenium sulfide, and the sulfide of at least one metal selected from the group consisting of the metals from Group VI-B and the Iron-group, separating the resulting product efiluent to provide a hydrogen-rich vaporous phase and to recover a desulfurized normally liquid hydrocarbon product.
- a desulfurization catalyst comprising a siliceous carrier material combined with rhenium sulfide, and the sulfide of at least one metal selected from the group consisting of the metals from Group VI-B and the Iron-group
- the siliceous carrier material may be an amorphous composite of alumina and silica, or a zeolitic composite of alumina and silica, the latter commonly referred to in the art as a crystalline aluminosilicate, or a molecular sieve.
- the various process variables, or operating conditions are a pressure of from about 300 to about 5000 p.s.i.g. and a catalyst bed inlet temperature in the range of from about 200 F. to about 800 F.
- the catalytic composite is formulated from two principal categories of ingredients; one ingredient constitutes one or more catalytically active metallic components, selected from the group consisting of the metals hereinafter specifically set forth, while the second ingredient is a carrier material therefor, being selected from one or more refractory inorganic oxides.
- the carrier material be siliceous in nature, and that the catalytically active metallic component be sulfided rhenium, and/or technetium, in combination with at least one metallic component selected from Group VIB and the Iron-group of the Periodic Table.
- suitable metallic components are selected from the group consisting of rhenium, technetium, chromium, molybdenum, tungsten, iron, cobalt, nickel and mixtures thereof.
- the rhenium, or technetium component will be present within the catalytic composite, in a sulfided form, in concentrations within the range of from about 0.01% to about 2.0% by weight, and preferably from about 0.05% to about 1.0% by Weight, calculated as the element.
- a metallic component from Group VIB for example molybdenum
- it is present in an amount of from about 4.0% to about 40.0% by weight, and preferably from about 10.0% to about 30.0% by weight, calculated as the element.
- iron-group metals these are employed in amounts of from about 1.0% to about 6.0% by weight.
- the overall method for preparing the catalytic composite is not considered an essential feature of my invention, it is necessary that the metallic components be sulfided prior to being placed in service for the desulfurization of hydrocarbonaceous feed stocks. It must be acknowledged that a wide variety of sulfiding techniques are well-known and Well-described in the literature; however, one sulfiding technique is particularly preferred in order to obtain all the beneficial results of the rhenium component in admixture with the other components.
- the composite is dried at a temperature in the range of from about 200 F. to about 400 F. for a period of from about 2 to about 24 hours.
- the dried composite is then subjected to a calcination technique, in an atmosphere of air or other free oxygen containing gaseous mixture, at an elevated temperature of about 500 F. to about 1200 F., and for a period ranging from about 0.5 to about hours.
- the sulfiding technique is effected when the composite is in a substantially reduced state; therefore, following the calcination treatment, an inert gas is utilized to sweep the composite free from excess oxygen, and the composite reduced in an atmosphere of substantially dry hydrogen.
- Substantially dry hydrogen is intended to connote a hydrogen stream containing less than about 5.0 ppm. of water, by volume.
- the reduction operation may be effected at the same temperature level as the calcination technique, it is preferred to reduce the catalytic composite while cooling the same to a lower temperature within the range of from about 400 F. to about 700 F.
- the time for the reduction technique is generally short, ranging from about 0.5 to about 5.0 hours.
- the substantially reduced composite is initially contacted at the lower temperature level with a stream of hydrogen and hydrogen sulfide in which the hydrogen/hydrogen sulfide mol ratio is at least about 1.5: 1, with an upper limit of about 4: 1.
- the temperature of the composite, during the sulfiding procedure is increased to a level in the range of from about 750 F. to about 850 F., and the sulfiding continued at this temperature for a period of about one hour.
- the overall sulfiding technique should be effected for a period of at least about 2 hours.
- hydrogen sulfide is introduced intermittently, as is necessary to maintain a positive pressure of at least about 15.0 p.s.i.g., on the sulfided catalyst, while the latter is being cooled to a temperature below about 400 F.
- a stream of suitable inert gaseous material such as nitrogen, may be employed to cool the sulfided catalyst further in order to facilitate handling and ultimate storage.
- the catalytically active components are combined with a siliceous carrier material.
- a siliceous carrier material Regardless of the use of other refractory inorganic oxides, whether alumina, zirconia, magnesia, titania, boria, hafnia, etc., or mixtures thereof, it is preferred that the carrier material have a silica content of from about 10.0% by weight to about 90.0% by weight.
- a relatively low-silica carrier material is preferred.
- the carrier material when desulfurizing a heavy vacuum gas oil in order to produce an ultimate product suitable for hydrocracking into lower-boiling gasoline components, a relatively high-silica composite is preferred.
- the carrier material may be prepared by any of the co-precipitative, or successive precipitation methods known to the art.
- the carrier material is zeolitic in nature
- the crystalline aluminosilicate including Type X, Type Y, mordenite, or mordenite dispersed in an alumina, silica, or aluminasilica matrix, may also be prepared by any method known to the art.
- the incorporation of the catalytically active metallic components may be effected by co-precipitation with the siliceous material, impregnation of a dried and/ or calcined carrier material, or ion-exchange as is the case with zeolitic material.
- the catalytic composite may contain a halogen component, the precise form of the association thereof with the carrier material not being accurately known.
- a halogen component the precise form of the association thereof with the carrier material not being accurately known.
- the halogen may be either fluorine, chlorine, iodine, bromine or mixtures thereof, with fluorine being particularly preferred.
- the halogen component may be added to the carrier material in any suitable manner, either during the preparation thereof, or before or after the addition of the other catalytically active components. When utilized, halogen component will be composited in such a manner as results in a final composite containing about 0.1% to about 1.5% by weight, and preferably from about 0.4% to about 0.9% by weight, calculated on an elemental basis.
- Suitable desulfurization conditions of operation include a quantity of catalyst, preferably disposed in one or more fixed-bed reaction zones, such that the liquid hourly space velocity (defined as volumes of fresh feed charge per hour per volume of catalyst disposed Within the zone) is within the range of from about 0.4 to about 10.0.
- the liquid hourly space velocity defined as volumes of fresh feed charge per hour per volume of catalyst disposed Within the zone
- Hydrogen circulation, through the catalyst bed, during processing is a preferred technique from the standpoint of maintaining a clean" catalytic composite, or one in which the deactivation rate due to the deposition of carbonaceous material is inhibited.
- Hydrogen circulation rates ranging from about 500 to about 15,000 standard cubic feet per barrel are utilized, again depending primarily on the character of the charge and the desired result.
- Operating pressures will generally range from about 500 to about 5000 p.s.i.g., while the catalyst bed inlet temperature is generally maintained in the range of from about 200 F. to about 800 F. Since the reactions being effected are exothermic in nature, a temperature increase will be experienced as the charge stock flows through the catalyst bed, resulting in a higher catalyst bed outlet temperature.
- a preferred technique limits the temperature increase to F., and quized at intermediate loci of the catalyst bed, may be very often to 50 F conventional quench streams, intro- CATALYST PREPARATION METHOD
- the entire method of manufacturing the catalytic composite is not essential to my invention. However, for the sake of being complete, one such preferred method is herein set forth.
- Water glass containing 28.0% by weight of silica and having a specific gravity of 1.38, is commingled with water to make a 50/50 diluted solution.
- hydrochloric acid 32.0% HCl by weight
- having a specific gravity of about 1.16 is commingled with water to provide a 50/50 by weight, diluted solution.
- the hydrochloric acid and water glass solutions are intimately commingled.
- An aqueous solution of 7.65% by weight of aluminum oxide and 26.0% of aluminum sulfate, having a specific gravity of 1.31, is added to the previously prepared water glass-hydrochloric acid mixture.
- the resulting finely-divided slurry is filtered and water- Washed to remove excessive ammonium hydroxide, sodium and sulfate ions.
- the final filter cake is dried to a volatile matter content of about 17.0% by weight, and subsequently ground to a talc-like powder.
- a suitable lubricating and binding agent, polyvinyl alcohol, is added thereto, and the powder is formed into /a;" x /s" cylindical pills having a nominal crushing strength of about 12.0 pounds.
- the pills are calcined in an atmosphere of air for 2 hours at a temperature of about 1150 F.
- Molybdic acid, 85.0% by Weight of molybdenum oxide, and hydrated nickel nitrate are separately commingled with the 28.0% solution of ammonium hydroxide, the individual solutions being commingled and utilized as an impregnating solution for the previously prepared aluminasilica pills.
- the impregnated pills are dried for three hours at 300 F., and calcined in air for one hour at 1100 F.
- the unimpregnated carrier material is 88.0% by weight of aluminaand 12.0% by weight of silica.
- the impregnating solution is utilized in an amount to yield a final catalyst containing 2.0% by weight of nickel and 6.0% by weight of molybdenum, calculated on the basis of the elements.
- the calcined alumina/silica composite is swept with nitrogen at the elevated tempenature for about one-half hour, and the temperature is reduced to 500 F. in a flowing hydrogen stream.
- a gaseous stream of hydrogen sulfide and hydrogen in which the H /H S mol ratio is 3:1 is introduced into contact with the catalyst.
- the temperature is raised to 700 F., and the component concentration changed to 2:1 H /H S.
- the sulfiding stream is discontinued and the catalyst cooled to 300 F., during which time 100.0% hydrogen sulfide is intermittently introduced to maintain a positive pressure of about 15.0 p.s.i.g.
- the introduction of hydrogen sulfide is ceased at a temperature of 300 F., and a stream of nitrogen employed to cool the catalyst to a temperature suitable for handling.
- Example I The charge stock utilized in this example is a blend of straight-run and coker distillates boiling within the gasoline boiling range.
- the charge stock has a gravity of about 55.9 API, an initial boiling point of about 194 R, an end boiling point of about 409 F, a bromine number of 7.2, and contains about 10.0 p.p.m. of nitrogen and about 0.052% by weight of sulfur (520 p.p.m.).
- the standard hydrodesulfurization catalyst, with which the catalyst of the present invention is compared, is a composite of an alumina carrier material combined with about 6.0% by weight of molybdenum and about 2.2% by weight of cobalt.
- the catalytic components are combined by way of impregnation, and this technique is followed by drying and calcination in an atmosphere of air.
- the composite is reduced in a stream of hydrogen, after which it is placed in a bench-scale reaction zone fabricated from l-inch, Schedule 80, Type 316 stainless steel.
- the catalyst bed is in an amount of about 50.0 cubic centimeters, and is maintained at an operating pressure of about 800 p.s.i.g.
- the hydrogen circulation rate is 3000 standard cubic feet per barrel of liquid charge, and the inlet temperature to the catalyst bed is 700 F. Sulfiding of the catalyst is effected in situ during the processing of the sulfurous charge stock.
- the normally liquid product eflluent indicates a gnavity of 56.2 AP I, an initial boiling point of about 207 R, an end boiling point of about 411 F., a nitrogen content of about 0.5 p.p.m., a bromine number of about 0.4 and a sulfur concentration of about 19 p.p.m. by weight.
- a sulfided catalytic composite encompassed by the present invention is prepared in the manner hereinbefore set forth.
- the carrier material is an amorphous composite of 90.0% by weight of alumina and 10.0% by weight of silica. Since the intended object is to prepare a charge stock suitable for use in a catalytic reforming unit, an excessive degree of hydrocracking to lower-boiling components is not desired.
- the catalytic composite is substantially halogen-free, containing 6.0% by weight of molybdenum and 1.0% by weight of rhenium, calculated as the elements, notwithstanding a presulfiding technique in an atmosphere of hydrogen and hydrogen sulfide, with hydrogen in a molar excess of about 2:1.
- the operating conditions are maintained at a pressure of 800 p.s.i.g., a catalyst bed inlet temperature of 700 F., a hydrogen circulation rate of 3000 standard cubic feet per barrel and a liquid hourly space velocity of about 6.0. Inspection of the normally liquid product effluent indicates a gravity of 562 ARI, an initial boiling point of about F., an end boiling point of about 410 F., a bromine number of about 0.1, the presence of nitrogen in an amount of about 0.10 p.p.m. and a sulfur concentration less than about 1.0 p.p.m.
- the charge stock is a light cycle oil having a gravity of about 25.9 API, an initial boiling point of 324 R, an end boiling point of about 670 F., a bromine number of 15.6, and contains 322 p.p.m. of nitrogen and 3400 p.p.m. of sulfur.
- a single change is effected in the composition of the catalytic composite.
- the catalytic composite considered as the standard hydro-desulfurization catalyst is also sulfided prior to contact with the charge stock.
- the pressure is about 1000 p.s.i.g., the catalyst bed inlet temperature is about 720 F., the hydrogen circulation rate is about 2500 standard cubic feet per barrel and the liquid hourly space velocity is 3.0.
- the catalytic composite without the rhenium component produces a normally liquid product having a nitrogen concentration of about 60.0 p.p.m., a bromine
- This example is presented to illustrate the benefits of the desulfurization catalyst of my invention when processing a kerosene boiling range feed stock for the purpose of improving its jet fuel characteristics.
- the kerosene fraction has a gravity of about 409 API, an initial boiling point of about 361 R, an end boiling point of about 518 F., and is further characterized by an IPT Smoke Point of about 20.8 mm., a sulfur concentration of about 1480 p.p.m. and an aromatic hydrocarbon content of about 19.0 vol. percent.
- the kerosene fraction is initially processed with about 650 standard cubic feet per barrel of hydrogen, in contact with a catalytic composite of about 0.75% by weight of rhenium and 5.7% by weight of molybdenum, combined with a carrier material of 90.0% by weight of alumina and 10.0% by weight of silica.
- a catalytic composite Prior to contacting the kerosene fraction, as the last step in the manufacturing procedure, the catalytic composite is subjected to the presulfiding technique hereinbefore set forth.
- the pressure imposed upon the reaction zone is about 550 p.s.i.g., and the catalyst bed inlet temperature is at a level necessary to control the outlet temperature at about 725 F.
- the liquid hourly space velocity through the reaction zone is 4.8, and the operation is effected for a period of about 50 hours.
- Analyses of the product effluent indicate a gravity of 41.1 API, an initial boiling point of 340 F. and an end boiling point of 512 F.
- the .IPT Smoke Point is slightly increased to a level of about 21.9 mm., the aromatic concentration is about 17.0 vol. percent and the sulfur concentration is reduced to about 30 p.p.m.
- the normally liquid product effluent from the first catalytic reaction zone, following the removal of hydrogen sulfide, is processed in contact with a catalytic composite of 1.0% by weight of nickel and 0.75% by weight of rhenium, combined with a carrier material of 90.0% by weight of alumina and 10.0% by weight of silica.
- the catalytic composite is presulfided in accordance with the previously-described procedure, and utilized in an amount such that the liquid hourly space velocity therethrough is about 1.0.
- the reaction zone is maintained under an imposed pressure of 810 p.s.i.g., and the hydrogen circulation rate is about 4000 standard cubic feet per barrel.
- a process for the desulfurization of a sulfurous, hydrocarbonaceous charge stock which comprises reacting the sulfur content of said charge stock with hydrogen in contact with a desulfurization catalyst comprising an alumina-silica carrier material containing at least 10% by weight of silica combined with rhenium sulfide and the sulfide of at least one metal selected from the group consisting of the metals from Group VI-B and the Iron-group, and separating the resulting efiiuent to recover a desulfurized normally liquid hydrocarbon product.
- a proces for the desulfurization of a sulfurous, hydrocarbon-aceous charge stock which comprises reacting the sulfur content of said charge stock with hydrogen in contact with a sulfided catalytic composite of an alumina-silica carrier material containing at least 10% by weight of silica combined with 0.01% to 2.0% by weight of a rhenium component and 4.0% to about 40.0% by weight of a Group VI-B metal component, and separating the resulting product efiluent to recover a desulfurized normally liquid hydrocarbon product.
- catalytic composite contains 1.0% to about 6.0% by weight of an Iron-group metal component.
Abstract
Description
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US80905069A | 1969-03-20 | 1969-03-20 |
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US3598725A true US3598725A (en) | 1971-08-10 |
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US809050A Expired - Lifetime US3598725A (en) | 1969-03-20 | 1969-03-20 | Hydrocarbon desulfurization with a rhenium catalyst on siliceous carrier material |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915848A (en) * | 1973-12-07 | 1975-10-28 | Texaco Inc | Hydrodesulfurization of heavy petroleum oil at higher temperatures and space velocities |
US4368115A (en) * | 1977-05-16 | 1983-01-11 | Exxon Research And Engineering Co. | Catalysts comprising layered chalcogenides of group IVb-group VIIb prepared by a low temperature nonaqueous precipitate technique |
US4390514A (en) * | 1977-05-16 | 1983-06-28 | Exxon Research And Engineering Co. | Method of preparing chalocogenides of group VIII by low temperature precipitation from nonaqueous solution, the products produced by said method and their use as catalysts |
US10329220B2 (en) * | 2013-04-03 | 2019-06-25 | Scg Chemicals Company Limited | Process for converting paraffin to olefin and catalyst for use therein |
-
1969
- 1969-03-20 US US809050A patent/US3598725A/en not_active Expired - Lifetime
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3915848A (en) * | 1973-12-07 | 1975-10-28 | Texaco Inc | Hydrodesulfurization of heavy petroleum oil at higher temperatures and space velocities |
US4368115A (en) * | 1977-05-16 | 1983-01-11 | Exxon Research And Engineering Co. | Catalysts comprising layered chalcogenides of group IVb-group VIIb prepared by a low temperature nonaqueous precipitate technique |
US4390514A (en) * | 1977-05-16 | 1983-06-28 | Exxon Research And Engineering Co. | Method of preparing chalocogenides of group VIII by low temperature precipitation from nonaqueous solution, the products produced by said method and their use as catalysts |
US10329220B2 (en) * | 2013-04-03 | 2019-06-25 | Scg Chemicals Company Limited | Process for converting paraffin to olefin and catalyst for use therein |
US10329219B2 (en) | 2013-04-03 | 2019-06-25 | Scg Chemicals Company Limited | Process for converting paraffin to olefin and catalyst for use therein |
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