US2865850A - Desulfurization process - Google Patents

Desulfurization process Download PDF

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Publication number
US2865850A
US2865850A US532706A US53270655A US2865850A US 2865850 A US2865850 A US 2865850A US 532706 A US532706 A US 532706A US 53270655 A US53270655 A US 53270655A US 2865850 A US2865850 A US 2865850A
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hydrogen
feed
range
hydrogen sulfide
desulfurization
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US532706A
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Inventor
Henry A Holcomb
Morris R Morrow
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US532706A priority Critical patent/US2865850A/en
Priority to GB23579/56A priority patent/GB797637A/en
Priority to FR1168911D priority patent/FR1168911A/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/007—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment

Definitions

  • the process of the present invention may be briefly described as contacting a petroleum hydrocarbon feed stock boiling within the range of about 275 to 430 F. with a desulfurization catalyst in the presence of about 250 to 2,000 cubic feet of hydrogen per barrel of feed stock and about 0.1 to 10 mol percent ofadded'hydrogen sulfide (H 8), based on the total amount of feed material, under reaction conditions including a temperature Within the range of about 500 to about 750 F.
  • the feed stock-tobe employed in accordance with the present invention may be derived from a petroleum crude oil or from a thermally or catalytically treated portion thereof.
  • thefeed stock may bea 'virgin naphtha, a naphtha fraction derived from the thermal or catalytic cracking of a petroleum crude oil or a fraction thereof, a naphtha derived from the polymerization of-lower boiling unsaturated hydrocarbons such as ethylene,- propylene, butylenes, butene, etc. Mixtures of two or more such materials may also be used'if desired.
  • Hydrogen for. the process may be provided by charging a hydrogen-containing gas. to the catalyst along'with the mixture of hydrogen and inertgas, a mixture of hydrogen and light hydrocarbons e. g., a hydrogen-containing oifgas from a catalytic reforming. process),.etc. Hydrogen which. is not consumed during the .desulfurization reaction may, if desired,be recycled.
  • the amount of hydrogen sulfide to be added should preferably be within the range of about 0.1 to about 10 mol percent of hydrogen sulfide, based on the total amount of feed material and preferably in the range of about 0.1 to about 5 mol percent.
  • feed material includes the feed stock, the hydrogen, the added hydrogen sulfide and such other inert gaseous materials as may be charged to the reactor.
  • the reaction conditions to be employed include a temperature Within the range of about 500 to about 750 F., a space velocity within the range of about 1 to about 16 volumes of feed per volume of catalyst per hour, and a reactor pressure within the range of about 50 to about 300 pounds per square inch gauge.
  • a temperature of about550 to about 700 F., a space Velocity of about 2 to about 6 v./v./hr. and a pressure of about 150 to about 250 p. s. i. g. are employed.
  • the reactor pressure and hydrogen charge rate should be correlated to provide a hydrogen partial pressure in the reactor within the range of about 50 to about 150 pounds per square inch absolute.
  • Fig. 1 is a schematic diagram illustrating one preferred manner in which the process of the present invention may be accomplished.
  • Figs. 2 to 5 are graphs illustrating the effect of reaction conditions on the percent desulfurization, Saybolt color and gum content.
  • the line 16 passes to a suitable cooling means 18 wherein the reaction products are cooled to an extent sufficient to liquefy the products boiling in about the naphtha boiling range and the thuscooled mixture is fed by way of a line 20 to a suitable separator 22 wherein phase separation occurs between the liquefied and gaseous or vaporous components of the reaction products.
  • the liquefied material is discharged from the separator 22 through a line 24 and the gaseous and/or vaporous material, comprising hydrogen, hydrogen sulfide and normally gaseous hydrocarbons is discharged overhead through a line 26 controlled by a valve 34.
  • the liquefied material discharged through the line 24 comprises the desulfurized product and may be recovered as such.
  • higher boiling components are formed which tend to increase the final boiling point of the product.
  • the desulfurized product is to be utilized in the preparation of commercial grades of gasoline, and when the final boiling point of the feed stock is up to a limiting final boiling point for gasoline products, as is normally the case, it is desirable that the above-mentioned higher boiling components be removed from the liquefied product.
  • the liquid material in the line 24 is charged to a suitable fractionation zone,such as a distillation column 28 wherein the liquid material is distilled to provide an overhead product boiling in the gasoline range and delivered through a line 30 and to provide a bottoms fraction delivered through the line 32 comprising the undesirable higher boiling components.
  • a suitable fractionation zone such as a distillation column 28 wherein the liquid material is distilled to provide an overhead product boiling in the gasoline range and delivered through a line 30 and to provide a bottoms fraction delivered through the line 32 comprising the undesirable higher boiling components.
  • the gaseous material discharged from the separator 22 through the overhead line 26 may be discarded from the system if it is desired to supply all of the hydrogen and hydrogen sulfide required for desulfurization from extraneous sources or, if desired, all or part of the gaseous materials may be recycled to the desulfurization zone 10. Even when the gaseous material is to be recycled, however, it will generally be necessary to supply extraneous hydrogen in that the desulfurization reaction normally consumes at least a portion of the hydrogen charged to the desulfurization Zone 10.
  • the gaseous material is to be recycled, care should be taken to compensate for the hydrogen sulfide contained therein which was formed in the desulfurization reactions. If the gaseous material is substantially freed from hydrogen sulfide or contains up to the maximum amount of hydrogen sulfide to be used, the gaseous material may be directly recycled. In this instance, any addi tion hydrogen sulfide that is required may be supplied from an extraneous source.
  • the gaseous material When the gaseous material contains an excessive amount of hydrogen sulfide, it may be treated to remove all or an appropriate amount of the hydro-gen sulfide or, as an alternative, part of the gaseous material may be admixed with a hydrogen-containing gas from an extraneous source which does not contain excessive hydrogen sulfide in an amount sufficient to provide a mixture having the desired hydrogen sulfide and hydrogen content.
  • reaction conditions to be employed in the desulfurization zone and therates of charge of the feed stock, hydrogen and hydrogen sulfide should be regulated in order to satisfy the hydrogen partial pressure requirements and themercaptan number control equation given above, whereby there is obtained a desulfurized product having improved Saybolt color characteristics and containing reduced amounts of gum and mercaptans.
  • the percent of desulfurization may be regulated by control of the H 5 level as shown below for the The effect of added hydrogen sulfide on the degree of desulfurization obtained is graphically set forth in Fig. 2, From Fig. 2 it will be noted that for otherwise constant operating conditions the percent desulfurization increases as the added hydrogen sulfide content increases.
  • Example II Portions of blends of 275 to 430 F. boiling range cracked naphthas were desulfurized by contact with a TABLE III.MOLYBDENUM OXIDE CATALYST Mol Percent H28 in Reactants Entering Product Saybolt Color Minus Feed Saybolt Color Temp, F.
  • gum content is reduced in accordance with the present invention by conducting the desulfurization reaction in the presence .of hydrogen while maintaining a hydrogen partial pressure within the range of about 50 to p. s. i. a., as shown by the following examples- Example 111 With a molybdena catalyst, a plurality of runs were made at operating conditions of 500 to 700 F., 2 to 12 liquid hourly space velocities, 50 to 250 p. s. i. g. total pressures, 250 to 2000 s. c. f. H /bbl. oil and with blends of nominal 275 to 430 F.
  • the naphthas contained about 13 to 33 mg. of gum/1 ml. (General Motors Gum.) In these trials it wasfound that the gum contents of the treated naphthas were essentially determined by the partial pressure of the hydrogen in the reactor as shown by the datain the following table.
  • reaction conditions can be changed in order, for example, to permit the utilization of larger amounts of hydrogen sulfide without increasing the mercaptan number of the product as is shown by the following example.
  • Example V The naphtha blend of Example IV was desulfurized over a cobalt molybdate catalyst in the presence of hydrogen and various amounts ofadded hydrogen sulfide under the reaction conditions of Example IV with but one exception, namely, the use of a reaction temperature of about 650 F.
  • the amount of hydrogen sulfide added, the hydrogen partial pressure within the reaction zone and the mercaptan number, Saybolt color and gum content of the products are set forth in Table TABLE VIIL-RESULTS OBTAINED BY DESU'LFU'RIZA'IION OF NAPHTHA FEEDSTOGK OVER COBALT IVIOLYBDATE AT 650 F.; 8 V. Hz/BBL. OF FEED STOCK /V./HR.;200 P. S. I. G. AND 1,000 CU'.FT..OF
  • Example VI The hydrogen charge rate does not materially affect product mercaptan number as is shown by the results obtained through the desulfurization of a blend of catalytic and thermal naphthas having a feed mercaptan number of about 0.6 over a cobalt molybdate catalyst.
  • the reaction conditions employed and the results obtained are set forth in Table X.
  • T a space velocity in the range of about 1 to about 16 volumes of feed per volume of catalyst per hour (v./v./hr.), a reactor pressure within the range of about 50 to about 300 pounds per square inch gauge and a hydrogen partial pressure within the range of about 50 to about 150 pounds per square inch d ing a petroleum hydrocarbon naphtha boiling in the range of about 275 F. to about 430 F. in contact with a desulfurization catalyst in the presence of about 250 to about 2,000 cubic feet of hydrogen per barrel of feed stock and about 1.0 to about 10 mol percent of added hydrogen sulfide (H 8), based on the total amount of feed material, under reaction conditions including a temperature Within the range of about 500 to about 750 F.
  • H 8 added hydrogen sulfide

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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)
  • Catalysts (AREA)
US532706A 1955-09-06 1955-09-06 Desulfurization process Expired - Lifetime US2865850A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US532706A US2865850A (en) 1955-09-06 1955-09-06 Desulfurization process
GB23579/56A GB797637A (en) 1955-09-06 1956-07-31 Desulfurizing petroleum hydrocarbons
FR1168911D FR1168911A (fr) 1955-09-06 1956-08-27 Procédé de désulfuration d'hydrocarbures du pétrole

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GB (1) GB797637A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2985586A (en) * 1958-11-26 1961-05-23 Exxon Research Engineering Co Hydrofining of lubricating oil fractions
US3052625A (en) * 1959-10-06 1962-09-04 Exxon Research Engineering Co Production of color-stable kerosene by hydrofining followed by hypochlorite treatment
US3907667A (en) * 1973-08-22 1975-09-23 Gulf Research Development Co Process for producing a lubricating oil from a residue feed

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2273299A (en) * 1938-10-08 1942-02-17 Albert C Travis Treatment of hydrocarbons
US2370707A (en) * 1942-11-02 1945-03-06 Shell Dev Treatment of hydrocarbons
US2604438A (en) * 1949-05-23 1952-07-22 Shell Dev Catalytic dehydrogenation of hydrocarbon oils
US2687983A (en) * 1953-02-11 1954-08-31 Socony Vacuum Oil Co Inc Catalytic desulfurization of hydrocarbons
US2761816A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process using a cobalt molybdate catalyst presulfided with the feed under specific conditions
US2799661A (en) * 1953-07-15 1957-07-16 Universal Oil Prod Co Manufacture of molybdenumcontaining catalysts

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2273299A (en) * 1938-10-08 1942-02-17 Albert C Travis Treatment of hydrocarbons
US2370707A (en) * 1942-11-02 1945-03-06 Shell Dev Treatment of hydrocarbons
US2604438A (en) * 1949-05-23 1952-07-22 Shell Dev Catalytic dehydrogenation of hydrocarbon oils
US2687983A (en) * 1953-02-11 1954-08-31 Socony Vacuum Oil Co Inc Catalytic desulfurization of hydrocarbons
US2799661A (en) * 1953-07-15 1957-07-16 Universal Oil Prod Co Manufacture of molybdenumcontaining catalysts
US2761816A (en) * 1954-06-21 1956-09-04 Exxon Research Engineering Co Hydrodesulfurization process using a cobalt molybdate catalyst presulfided with the feed under specific conditions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2985586A (en) * 1958-11-26 1961-05-23 Exxon Research Engineering Co Hydrofining of lubricating oil fractions
US3052625A (en) * 1959-10-06 1962-09-04 Exxon Research Engineering Co Production of color-stable kerosene by hydrofining followed by hypochlorite treatment
US3907667A (en) * 1973-08-22 1975-09-23 Gulf Research Development Co Process for producing a lubricating oil from a residue feed

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Publication number Publication date
GB797637A (en) 1958-07-02
FR1168911A (fr) 1958-12-18

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