US2717857A - Method for manufacturing heating oil - Google Patents

Method for manufacturing heating oil Download PDF

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Publication number
US2717857A
US2717857A US271556A US27155652A US2717857A US 2717857 A US2717857 A US 2717857A US 271556 A US271556 A US 271556A US 27155652 A US27155652 A US 27155652A US 2717857 A US2717857 A US 2717857A
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US
United States
Prior art keywords
heating oil
catalyst
range
virgin
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US271556A
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English (en)
Inventor
Ii Stanley O Bronson
Robert C Morbeck
Sumner B Sweetser
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
Priority to BE545907D priority Critical patent/BE545907A/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US271556A priority patent/US2717857A/en
Priority to GB29690/52A priority patent/GB732387A/en
Application granted granted Critical
Publication of US2717857A publication Critical patent/US2717857A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil

Definitions

  • heating oil blends comprised a relatively large oils tend to cause clogging of filters, perennials, or conduits associated with the burning systems in which they are employed.
  • this fraction is treated as for example sodium hydroxfor example, a thermal or a catalytic cracking process.
  • the present invention is particularly directed toward the production of a high quality virgin-cracked heating oil blend wherein the cracking process comprises a catalytic cracking operation, as for example a fluid catalytic cracking operation.
  • a fluid catalytic cracking plant is composed of three sections: cracking, regeneration, and fractionation.
  • the cracking reaction takes place continuously in one reactor at a temperature in the range from about 800 F. to l050 F.
  • the spent catalyst is removed continuously for regeneration in a separate vessel, from which it is returned to the cracking vessel, which is at a pressure below about 200 lbs. usually below about 50 lbs. per sq. in.
  • Continuity of flow of catalyst as well as of oil is thus accomplished, and the characteristic features of fixed-bed designs involving the intermittent shifting of reactors through cracking, purging, and regeneration cycles are eliminated.
  • Regenerated catalyst is withdrawn from the regenerator and ows by gravity down a standpipe, wherein a sufficiently high pressure head is built up on the catalyst to allow its injection into the fresh liquid oil stream.
  • the cracking that takes place results in carbon deposition on the cracked product oil vapors are withdrawn from the top of the reactor after passing through cyclone separators to free them of any entrained catalyst particles, while the spent catalyst is withdrawn from the bottom of the reactor and is iniected into a stream of undiluted air which carries the catalyst into the regeneration vessel.
  • the products of combustion resulting from the regeneration of the catalyst leave the top of this vessel and pass through a series of cyclones where the bulk of the entrained catalyst is recovered.
  • the regenerated catalyst is withdrawn from the bottom of the vessel to complete its cycle.
  • the cracked products are removed from cracking zone 30 (overhead from the reactor) by means of line 'Z8 and introduced into a distillation zone 16.
  • Temperature and pressure conditions in zone 16 are adjusted to remove overhead by means of line 17 normally gaseous constituents and to remove by means of line 18 hydrocarbon constituents boiling in the motor fuel boiling range.
  • a fraction boiling above the heating oil boiling range is removed as a bottoms fraction by means of line 19.
  • a fraction boiling in the heating oil boiling range is removed by means of line 20 and in accordance with the present invention may be caustic washed in zone 21.
  • the fresh caustic or other treating agent is introduced by means of line 22 while the spent treating agent is removed by means of line 23.
  • the caustic washed cracked heating oil is blended with the mild hydroned virgin heating oil.
  • the virgin heating oil removed by means of line 5 is, mildly hydrofined in hydrofining zone 8. It is essential in practicing the present invention that the hydrofming operation conducted on the virgin heating oil be a mild hydrofming operation, This is to be distinguished from conventional hydroning operations heretofore practiced in the art. Such hydroining operations have been employed at pressures from 200 to 500 lbs. per sq. in., at feed rates of .5 to 2.0 volumes of feed per volume of catalyst per hour. Relatively high rates of hydrogen recycle have been employed as for example, 2,000 to 4,000 standard cu. ft. per barrel in order to prevent carbonization of the catalyst. Likewise, very active catalysts have been used which are effective for P desulfurization.
  • the catalyst heretofore employed has been a cobalt molybdate supported on a carrier, as for example alumina.
  • The, mild hydroiining, conditions of the present invention may be secured by lowering the temperature, increasing the feed rate per volume of catalyst or by using a less active catalyst.
  • the temperatures used are in the range from about 400 to 700 F., preferably in the range from about 500 to 650 F.
  • Pressures employed are in the range from 50 to 250 lbs. per sq. in., preferably in the range from about 100 to 200 lbs. per sq. in.
  • the feed rates, in accordance with the present process are in the range from about l-l6 volumes of liquid per volume of catalyst per hour. Preferred feed rates are in the range from 4l0 v./v./hr.
  • the hydrogen in the gas to the hydroning unit may vary from 50 to 100%.
  • a particularly desirable method of hydroning in accordance with the present process is to recycle appreciable quantities of hydrogen to the hydroning unit in order to completely prevent carbonization of the catalyst.
  • the catalyst utilized in the present operation may comprise known hydroning catalyst, as for example cobalt molybdate on a carrier as for example alumina, providing other operating conditions are adjusted to secure a mild hydroning process.
  • the preferred catalyst, however, of the present invention comprises molybdenum oxide on a carrier preferably alumina.
  • the amount of molybdenum oxide employed is about 5 to 13% by weight based upon the weight of the alumina.
  • the catalyst is prepared by known methods, such as by impregnation of the alumina with a water-soluble molybdenum salt, followed by heating to convert this salt to molybdenum oxide, or by coprecipitation of aluminum and molybdenum hydroxides by addition of an ammoniacal solution of ammonium molybdate to an acid solution of an aluminum salt followed by water washing and by heating to convert to the oxides.
  • the mild hydrofming conditions of the present invention are secured by the adjustment of the above named operating conditions. For instance, if a relatively high liquid feed rate is used as compared to the amount of catalyst present, the higher ternperature range may be employed. On the other hand, if a very active catalyst is used, it is desirable to use a relatively high feed rate or to use a relatively low ternperature.
  • the mild hydrofining conditions of the present invention are measured by the amount of hydrogen consumption per barrel of oil feed.
  • conventional hydrofining operations utilized for the desulfurization of certain stocks are conducted under conditions whereby the hydrogen consumption ranges from 150 to 600 standard cu. ft. of hydrogen per barrel of oil. These operations used heretofore in the art secured a substantial sulfur reduction (50 to 90%
  • operating conditions are adjusted so that the hydrogen consumption in standard cu. ft. per barrel does not exceed 60 and is wir?
  • the extent of the sulfur reduction when utilizing the mild hydroning conditons of the present invention does not exceed about 35% and preferably does not exceed about ⁇ 20%. ⁇
  • Cracked heating oil was a blend of th 1 West Texas virgin heating oil had a boiling range of B30-660 F. and a sulfur content of 0.65 wt. percent.
  • the preferred operating conditions include the use of the M003 on Al catalyst at 600 F. with a feed rate of 4 to 16 v./v./hr. Satisfactory o'perlation can also be obtained at 500i F. with either catalyst at lower feed rates.
  • Light virgin heating oil had a boiling range of B25-530 F.
  • the catalytically cracked heating oil had a boiling range of 42o/650 F. It was treated only by caustic washing before use and had a carbon residue of 0.08% and sulfur content of about 1.3 wt. percent.
  • hydroiined virgin constituents after removal from the hydroiining zone may be further rened or treated as desired.
  • HzS dissolved HzS
  • constituents may be removed either by steam stripping or by caustic washing. If caustic washing is utilized, a caustic solution having a strength from 2-l0% sodium hydroxide may be ernployed.
  • a virgin heating oil is sweetened by hydroning under relatively mild conditions whereby mercaptan sulfur in the oil is converted to hydrogen sulde, which is separated from the oil by conventional means.
  • the virgin heating oil is then blended with cracked heating oil components which have been treated only by caustic washing to obtain a heating oil blend which is satisfactory with respect to requirements for carbon residue, as well as other inspections for heating oil. This is to be contrasted with other sweetening methods where considerably more severe conditions would of necessity have to be utilized on the cracked stock than if the virgin oil were not hydroned as described in accordance with the present operation.
  • a process for improving the quality of virgin heating oil which comprises subjecting virgin heating oil constituents to a temperature in the range of 400 to 700'F., and pressure in the range of 50 to 250 pounds per square inch in the presence of extraneously generated hydrogen and a hydroning catalyst comprising molybdenum oxide on a carrier at feed rates in the range of l to 16 v./v./hr. so that there is a consumption of hydrogen not in excess of about 60 standard cubic feet per barrel and so that the sulfur reduction does not exceed about 2.
  • the process dened by claim 1 in which the said hydrogen consumption does not exceed about standard cubic feet of hydrogen per barrel, and the said sulfur reduction does not exceed about 20%.
  • a process for the preparation of a high quality heating oil blend comprising virgin fractions and cracked fractions, which comprises segregating virgin hydrocarbon constituents boiling in the heating oil boiling range and cracked hydrocarbon constituents boiling in the heating oil boiling range, subjecting said virgin constituents to a temperature in the range of 400" to 700 F., and pressure in the range of to 250 pounds per square inch in the presence of extraneously generated hydrogen and a catalyst consisting of cobalt molybdate on a carrier at feed rates in the range of l to 16 v./v.hr. so that there is a consumption of hydrogen not in excess of about standard cubic feet per barrel and so that the sulfur reduction does not exceed about 35%, and thereafter blending said treated virgin constituents with said cracked constituents to produce a high quality heating oil blend.

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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)
US271556A 1952-02-14 1952-02-14 Method for manufacturing heating oil Expired - Lifetime US2717857A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BE545907D BE545907A (fr) 1952-02-14
US271556A US2717857A (en) 1952-02-14 1952-02-14 Method for manufacturing heating oil
GB29690/52A GB732387A (en) 1952-02-14 1952-11-24 Improved method for manufacturing heating oil

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US271556A US2717857A (en) 1952-02-14 1952-02-14 Method for manufacturing heating oil

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BE (1) BE545907A (fr)
GB (1) GB732387A (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2840512A (en) * 1955-09-29 1958-06-24 Kellogg M W Co Stabilization of furnace oil by hydrotreating to remove sulfur and gum
US2891006A (en) * 1954-08-26 1959-06-16 Hydrocarbon Research Inc Method of stabilizing olefinic gasoline by hydrofining with a chromium iron oxide catalyst
US2936281A (en) * 1956-06-26 1960-05-10 Pure Oil Co Refining process
US2951033A (en) * 1958-03-28 1960-08-30 Atlantic Refining Co Process for preparing stable heating oil
US3424673A (en) * 1966-03-07 1969-01-28 Sun Oil Co Process for hydrodesulfurizing the lower boiling fraction of a cracked gas oil blend
US3850744A (en) * 1973-02-27 1974-11-26 Gulf Research Development Co Method for utilizing a fixed catalyst bed in separate hydrogenation processes
US3870626A (en) * 1973-02-27 1975-03-11 Gulf Research Development Co Method for reducing the mercaptan content of a middle distillate oil
US3876532A (en) * 1973-02-27 1975-04-08 Gulf Research Development Co Method for reducing the total acid number of a middle distillate oil

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2347515A (en) * 1940-04-11 1944-04-25 Standard Oil Dev Co Refining mineral oils
US2547380A (en) * 1945-10-01 1951-04-03 Union Oil Co Catalyst for hydrocarbon conversion
FR989481A (fr) * 1948-06-24 1951-09-10 Anglo Iranian Oil Co Ltd Procédé de désulfuration catalytique de distillats de pétrole
US2574447A (en) * 1948-06-01 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2574448A (en) * 1948-06-24 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oil
US2577823A (en) * 1948-02-06 1951-12-11 Standard Oil Co Hydrodesulfurization of sulfurcontaining hydrocarbon fractions
US2592383A (en) * 1949-06-28 1952-04-08 Standard Oil Dev Co Process for preparing heating oil

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2347515A (en) * 1940-04-11 1944-04-25 Standard Oil Dev Co Refining mineral oils
US2547380A (en) * 1945-10-01 1951-04-03 Union Oil Co Catalyst for hydrocarbon conversion
US2577823A (en) * 1948-02-06 1951-12-11 Standard Oil Co Hydrodesulfurization of sulfurcontaining hydrocarbon fractions
US2574447A (en) * 1948-06-01 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
FR989481A (fr) * 1948-06-24 1951-09-10 Anglo Iranian Oil Co Ltd Procédé de désulfuration catalytique de distillats de pétrole
US2574448A (en) * 1948-06-24 1951-11-06 Anglo Iranian Oil Co Ltd Catalytic desulfurization of gas oil
US2592383A (en) * 1949-06-28 1952-04-08 Standard Oil Dev Co Process for preparing heating oil

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891006A (en) * 1954-08-26 1959-06-16 Hydrocarbon Research Inc Method of stabilizing olefinic gasoline by hydrofining with a chromium iron oxide catalyst
US2840512A (en) * 1955-09-29 1958-06-24 Kellogg M W Co Stabilization of furnace oil by hydrotreating to remove sulfur and gum
US2936281A (en) * 1956-06-26 1960-05-10 Pure Oil Co Refining process
US2951033A (en) * 1958-03-28 1960-08-30 Atlantic Refining Co Process for preparing stable heating oil
US3424673A (en) * 1966-03-07 1969-01-28 Sun Oil Co Process for hydrodesulfurizing the lower boiling fraction of a cracked gas oil blend
US3850744A (en) * 1973-02-27 1974-11-26 Gulf Research Development Co Method for utilizing a fixed catalyst bed in separate hydrogenation processes
US3870626A (en) * 1973-02-27 1975-03-11 Gulf Research Development Co Method for reducing the mercaptan content of a middle distillate oil
US3876532A (en) * 1973-02-27 1975-04-08 Gulf Research Development Co Method for reducing the total acid number of a middle distillate oil

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Publication number Publication date
BE545907A (fr)
GB732387A (en) 1955-06-22

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