US2792336A - Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking - Google Patents

Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking Download PDF

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Publication number
US2792336A
US2792336A US398031A US39803153A US2792336A US 2792336 A US2792336 A US 2792336A US 398031 A US398031 A US 398031A US 39803153 A US39803153 A US 39803153A US 2792336 A US2792336 A US 2792336A
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Prior art keywords
hydrogen
catalytic cracking
oil
gasoline
petroleum
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US398031A
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English (en)
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Naci F Kubicek
Raymond C Archibald
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Shell Development Co
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Shell Development Co
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Priority to BE534075D priority Critical patent/BE534075A/xx
Application filed by Shell Development Co filed Critical Shell Development Co
Priority to US398031A priority patent/US2792336A/en
Priority to DEN9896A priority patent/DE1004756B/de
Priority to GB35977/54A priority patent/GB766404A/en
Priority to FR1121932D priority patent/FR1121932A/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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen

Definitions

  • This invention relates to the conversion of petroleum oils heavier than gasoline into gasoline and related lighter products by a process involving hydrogenation and catalytic cracking.
  • catalytic gasoline and related lighter products designate light liquid hydrocarbon fractions boiling below about 430 F. obtained by catalytically cracking petroleum oils heavier than gasoline and the normally gaseous products including C1C4 hydrocarbons normally obtained in minor amounts by such cracking.
  • petroleum oils heavier than gasoline we use the expression petroleum oils heavier than gasoline to designate fractions of virgin petroleum boiling essentially above 430 F. including so-called reduced crude obtained by topping petroleum.
  • gas oil is used to designate distillate oils boiling above 430 F. but devoid of any appreciable amounts of tars or other extremely high boiling materials which cannot be distilled in commercial practice without decomposition.
  • thermal gas oil is used to designate distillate oils boiling in the gas oil range but containing hydrocarbons produced by non-catalytic cracking of higher boiling oils; such oils are obtained upon heating virgin oils to decomposition temperatures and have a different composition and character than virgin petroleum oils of the same boiling range.
  • catalytic cracking is used to designate the process of converting higher boiling hydrocarbon oils into lower boiling hydrocarbon oils by treating them in the vapor phase with a solid catalyst which promotes cracking.
  • catalytic cracking is one of the most important processes used in the refining of petroleum, and its importance is steadily increasing. This importance is due to the fact that by catalytic cracking, the higher boiling part of the petroleum may be converted in good yields to gasoline and related lighter by-products of better quality than possible by the previously used processes. The situation is such that it is to the advantage of refiners to process as much as possible of the higher boiling petroleum constituents by catalytic cracking. The most desirable practice on this basis would, therefore, be to subject to catalytic cracking the total reduced crude remaining after removing the straight-run gasoline from the petroleum by conventional topping operations. Certain prior patents have suggested the catalytic cracking of such reduced crudes and such operation has, in fact, been tried.
  • feed stocks such as reduced crude which contain considerable amounts of asphaltic constituents and a certain amount of ash constituents produce inordinate amounts of carbonaceous deposits (coke) on the cracking catalyst and ruin the 2,792,336 Patented May 14, 1957 cracking catalyst by contamination with ash constituents.
  • feed stock is generally obtained from the reduced crude by flashing, viscosity breaking, and/ or deasphaltizing.
  • catalytic cracking feed stocks may be improved by subjecting them to a suitable hydrogenation treatment.
  • the uptake of hydrogen in such treatment depends upon the severity of the hydrogenation conditions.
  • relatively small amounts of hydrogen e. g., less than s. c. f./bbl.
  • the hydrogen uptake increases until the oil is completely hydrogenated. This requires a hydrogen uptake of the order of 700 s. c. f./bbl.
  • the improvement as a catalytic cracking feed stock increases as the depth of hydrogenation is increased.
  • the present invention is based on the discovery that the total product values produced by catalytically cracking hydrogenated feed stocks is much improved if the limited supply of hydrogen (usually by-product hydrogen) is used to hydrogenate certain portions of the feed quite deeply rather than in hydrogenating a broader range fraction less deeply. This is contrary to the previously supposed situation.
  • a refinery receives a crude petroleum or mixture of petroleums from different fields. These petroleums contain in a favorable case, at most about 25% straight-run gasoline which is removed in the so-called topping columns leaving a remainder of 75% as a socalled reduced crude.
  • the refiner is able by flashing, viscosity breaking, and further vacuum flashing or deasphaltizing, to obtain about 70% of the reduced crude as a catalytic cracking feed stock, leaving an asphaltic residue of approximately 30%.
  • the naphtha portion of the straight-run gasoline separated in the topping operation (ca. 50%) has a poor octane number and is hydroformed (which is essentially a dehydrogenation process) with the production of at most about 500 to 700 cubic feet of hydrogen per barrel.
  • This hydrogen, 1 based on the-"catalytic cracking feed stock corresponds-to approximatelyaround 150 cubic feet per barrel. In practice, all of this hydrogen cannot be reacted with the flashed distillate. However, assuming 100% utilizationof the available hydrogen, the catalytic cracking feed stock would be tip-graded by the hydrogenation and the value of he products obtained upon catalytically cracking t... hydrogenated feed would be improved.
  • Figure I of the attached drawing is a flow diagram illustrating the'process. The process of the invention will be described in more detail with reference to a specific example. This example, which is typical of the situation confronted by refineries, is for the case of a refinery in Southernv California processing California petroleum. For ease of consideration, the quantities given are those per 1000barrels of crudeintake. Referring to Figure I, 1000'barrels of desalted crude is charged to the topping section wherein' it is topped to produce 240 barrels of straight-run gasolineand 760 barrels of straight-run residue.
  • the straight-runv gasoline isfractionated in the fractionation section to "produce 105'barrels of light straight-run gasoline which requires no further treating other than a caustic wash, and 135 barrels ofstraight-run naphtha (ASTM boiling range ZOO-400 F.) which has an F-l clear octane number of 57.
  • This straight-run naphtha is passed into the reforming section wherein it is platformed to an octane'number of 89 with the production of 730 s. c. f. of hydrogen per barrel ofoil.
  • the platforming operation is carried out underthe following conditions:
  • the lower boiling flashed distillate fraction is passed to the hydrogenation unit wherein it is hydrogenated with the product gas from the platforming unit.
  • the available hydrogen is 179 s. c. f. per barrel of total flashed distillate.
  • the hydrogenation is etfected under the conditions given in Table IV whereby the hydrogen uptake is 284 cubic feet per barrel of the light flashed distillate.
  • the unhydrogenated heavy flashed distillate and the hydrogenated light flashed distillate are combined and passed to the catalytic cracking unit wherein they are cracked in the conventional manner with a synthetic silica alumina composite catalyst under the following conditions:
  • our invention is based upon the application of the unexpected finding that, in the utilization of by-product hydrogen to improve clean'feed stock for catalytic'cracking, it-is 'advantageous to react the available hydrogen with a part of the flashed distillate under relatively severe conditions and with a high hydrogen uptake per barrel of feed hydrogenated than to use the available hydrogen to treat the total feed at the same hydrogen consumption. While some improvement over hydrogenating the whole feed may be obtained by reacting the available hydrogen with a portion of the whole feed, or in the alternative, reacting the available hydrogen with only the higher boiling portion of the feed, an unexpected larger improvement in the product values is obtained if the available hydrogen is reacted with the lower boiling part of the total feed.
  • An alternative application of the principle of the invention is to utilize the available hydrogen from the dehydrogenation of the straight-run naphtha in the hydrogenation of the lowest and part of the highest boiling portion of the catalytic cracking feed stock, leaving the middle portion unhydrogenated.
  • This alternative although more complicated from the feed preparation standpoint, has the additional advantage of allowing the desired increased product values to be obtained with a somewhat greater reduction in the coke make.
  • the lower and higher boiling portions of the total teed may be separated by fractional distillation, but other methods may be used. For instance, it is possible and practicable to effect the separation by flash distilling the residue in two operations under difierent flashing conditions, in which case the material obtained from the first flashing operation is lower boiling than the material obtained by the second or subsequent flashing operation.
  • the lighter fraction may be obtained by a conventional flashing operation and the residue from this flashing operation may be subjected to a conventional deasphaltizing treatment to produce a clean, substantially ash rree heavier fraction.
  • the hydro genated portion of the feed is the lighter boiling part, the hydrogenated portion and the unhydrogenated portion are combined and catalytically cracked together, although they may be introduced into the catalytic cracking unit at the same or difierent feed points.
  • the hydrogen uptake per barrel of material hydrogenated is preterably between about 200 and 400 s. c. f. per barrel but hydrogen uptakes as low as 100 s. c. f. and up to about 700 s. c. f. per barrel can be used to some advantage.
  • the split between the portion of the feed to be hydrogenated and the portion not to be hydrogenated therefore is preferably not arbitrarily set at 50:50 but is preferably adjusted such that the amount of material to be hydrogenated will consume the available hydrogen from the naphtha with hydrogen uptakes in the stated range.
  • the process of the invention provides a better and more profitable way of utilizing the by-product hydrogen from such reforming, since the available hydrogen in such cases is only sufficient to provide a relatively small hydrogen uptake based on the gas oil used as catalytic cracking feed stock.
  • the improvement which comprises splitting said virgin oil destined for catalytic cracking into two portions A and B, the split being made such that portion A is between 1 and 7 barrels per 700 s. c. f. of the available hydrogen and comprises the lower boiling constituents of said oil, portion B being the remainder, catalytically and, non-destructively hydrogenating said portion A to a hydrogen uptake within 100-700 s. c. per barrel with an available supply of hydrogen which is insuificient to completely non-destructively hydrogenate the total amount of said oil and is limited in amount to a value in s. e. f.
  • the improvement which comprises fractionating petroleum to separate a straight-run gasoline fraction, 21 straight-run nahtha fraction and straight-run residue, catalytically reforming the straight-run naphtha fraction to produce a reformed naphtha and a product gas rich in hydrogen, separating from the straight-run residue a clean virgin oil boiling above gasoline as catalytic cracking feed stock, said oil being incapable of being completely non-destructively hydrogenated by said hydrogen, splitting said virgin oil destined for catalytic cracking into two portions A and B, the split being made so that portion A is between one and two barrels per 400 s. c. f.
  • portion B being the remainder, catalytically and nondestructively hydrogenating said portion A with said hydrogen to a hydrogen uptake within 200 and 400 s. c. f. per barrel, and catalytically cracking the thus hydro genated portion A simultaneously with the remaining unhydrogenated portion B to produce gasoline and related by-products.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US398031A 1953-12-14 1953-12-14 Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking Expired - Lifetime US2792336A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE534075D BE534075A (enrdf_load_stackoverflow) 1953-12-14
US398031A US2792336A (en) 1953-12-14 1953-12-14 Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking
DEN9896A DE1004756B (de) 1953-12-14 1954-12-13 Verfahren zur Herstellung von Benzin und verwandten Produkten aus hoehersiedenden Erdoelfraktionen durch Hydrierung und katalytische Spaltung
GB35977/54A GB766404A (en) 1953-12-14 1954-12-13 A process for the production of gasoline and related lighter products by means of hydrogenation and catalytic cracking
FR1121932D FR1121932A (fr) 1953-12-14 1954-12-13 Procédé de préparation d'hydrocarbures légers à partir d'huiles de pétrole par hydrogénation et cracking catalytique

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US398031A US2792336A (en) 1953-12-14 1953-12-14 Production of lighter hydrocarbons from petroleum oils involving hydrogenation and catalytic cracking

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BE (1) BE534075A (enrdf_load_stackoverflow)
DE (1) DE1004756B (enrdf_load_stackoverflow)
FR (1) FR1121932A (enrdf_load_stackoverflow)
GB (1) GB766404A (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2895897A (en) * 1956-08-28 1959-07-21 Shell Dev Production of gasoline from petroleum residues
US2914457A (en) * 1957-06-28 1959-11-24 Texaco Inc Petroleum refining process
US2915457A (en) * 1957-06-14 1959-12-01 Shell Dev Process for the conversion of heavy residual oils
US2925374A (en) * 1958-05-19 1960-02-16 Exxon Research Engineering Co Hydrocarbon treating process
US2939832A (en) * 1955-11-22 1960-06-07 Shell Oil Co Blended gasolines
US2944003A (en) * 1954-10-29 1960-07-05 Shell Oil Co Production of aviation gasoline
US2964463A (en) * 1956-12-10 1960-12-13 Pure Oil Co Upgrading hydrocarbon oils in the presence of hydrogen with a tungsten oxide, molybdenum oxide on silica-alumina catalyst composite
US2998380A (en) * 1959-02-27 1961-08-29 Standard Oil Co Catalytic cracking of reduced crudes
US4462894A (en) * 1981-08-18 1984-07-31 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
US4565620A (en) * 1984-05-25 1986-01-21 Phillips Petroleum Company Crude oil refining
US4713221A (en) * 1984-05-25 1987-12-15 Phillips Petroleum Company Crude oil refining apparatus

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD267770S (en) 1977-12-14 1983-02-01 Karl Fischer Cooking appliance

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205434A (en) * 1937-11-30 1940-06-25 Process Management Co Inc Treatment of hydrocarbon oils
US2360622A (en) * 1943-04-30 1944-10-17 Standard Oil Dev Co Method of producing aviation gasoline
US2663676A (en) * 1951-03-16 1953-12-22 Standard Oil Dev Co Catalyst recovery
US2671754A (en) * 1951-07-21 1954-03-09 Universal Oil Prod Co Hydrocarbon conversion process providing for the two-stage hydrogenation of sulfur containing oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2205434A (en) * 1937-11-30 1940-06-25 Process Management Co Inc Treatment of hydrocarbon oils
US2360622A (en) * 1943-04-30 1944-10-17 Standard Oil Dev Co Method of producing aviation gasoline
US2663676A (en) * 1951-03-16 1953-12-22 Standard Oil Dev Co Catalyst recovery
US2671754A (en) * 1951-07-21 1954-03-09 Universal Oil Prod Co Hydrocarbon conversion process providing for the two-stage hydrogenation of sulfur containing oils

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2944003A (en) * 1954-10-29 1960-07-05 Shell Oil Co Production of aviation gasoline
US2939832A (en) * 1955-11-22 1960-06-07 Shell Oil Co Blended gasolines
US2895897A (en) * 1956-08-28 1959-07-21 Shell Dev Production of gasoline from petroleum residues
US2964463A (en) * 1956-12-10 1960-12-13 Pure Oil Co Upgrading hydrocarbon oils in the presence of hydrogen with a tungsten oxide, molybdenum oxide on silica-alumina catalyst composite
US2915457A (en) * 1957-06-14 1959-12-01 Shell Dev Process for the conversion of heavy residual oils
US2914457A (en) * 1957-06-28 1959-11-24 Texaco Inc Petroleum refining process
US2925374A (en) * 1958-05-19 1960-02-16 Exxon Research Engineering Co Hydrocarbon treating process
US2998380A (en) * 1959-02-27 1961-08-29 Standard Oil Co Catalytic cracking of reduced crudes
US4462894A (en) * 1981-08-18 1984-07-31 Mitsubishi Oil Co., Ltd. Process for producing pitch for using as raw material for carbon fibers
US4565620A (en) * 1984-05-25 1986-01-21 Phillips Petroleum Company Crude oil refining
US4713221A (en) * 1984-05-25 1987-12-15 Phillips Petroleum Company Crude oil refining apparatus

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DE1004756B (de) 1957-03-21
BE534075A (enrdf_load_stackoverflow)
GB766404A (en) 1957-01-23
FR1121932A (fr) 1956-08-28

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