US2740747A - Catalytically sweetening of naphtha - Google Patents

Catalytically sweetening of naphtha Download PDF

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Publication number
US2740747A
US2740747A US321653A US32165352A US2740747A US 2740747 A US2740747 A US 2740747A US 321653 A US321653 A US 321653A US 32165352 A US32165352 A US 32165352A US 2740747 A US2740747 A US 2740747A
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US
United States
Prior art keywords
caustic
sweetening
alumina
range
oil
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Expired - Lifetime
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US321653A
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English (en)
Inventor
Sumner B Sweetser
Ii Stanley O Bronson
Robert C Morbeck
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US321653A priority Critical patent/US2740747A/en
Priority to GB29709/53A priority patent/GB767592A/en
Priority to FR1089667D priority patent/FR1089667A/fr
Priority to NL182670A priority patent/NL96832C/xx
Priority to BE524240D priority patent/BE524240A/xx
Priority to DEST7320A priority patent/DE1027352B/de
Application granted granted Critical
Publication of US2740747A publication Critical patent/US2740747A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen

Definitions

  • the present invention is concerned with an improved process for the manufacture of high quality hydrocarbon products boiling in the motor fuel boiling range.
  • the invention is more particularly concerned with the production of a low sulfur, mercaptan-free, high octane number motor fuel having a good odor.
  • a hydrocarbon feed boiling in the motor fuel boiling range is treated in an initial zone with a catalyst selected from a particular class.
  • Suitable catalysts are molybdenum oxide on alumina, cobalt molybdate on alumina, and mixtures of nickel and tungsten suldes.
  • the treated product is passed to a secondary zone to remove hydrogen sulfide and nally processed in a tertiary zone utilizing caustic and air in order to remove the nal traces of mercaptan sulfur.
  • the present invention is broadly concerned with the production of a high quality improved motor fuel which boils below about 430 F. It is more particularly con cerned with the sweetening of sour naphthas by an improved combination process comprising a catalytic sweetening step and an air sweetening step.
  • a catalytic sweetening step the oil is contacted with a catalyst selected from the class consisting of cobalt molybdate on alumina, molybdenum oxide on alumina, and a mixture of nickel and tungsten sulfide.
  • a hydrocarbon oil boiling in the range from about 100 to 430 F. is introduced into treating z'one 1 by means of line 2.
  • zone 1 the oil is contacted with a catalyst comprising about 5 to 15% molybdenum oxide on alumina.
  • Temperatures are preferably in the range from about 400 F. to 700 F., while pressures are in the range from about 0 to 500 p. s. i. g.
  • a preferred temperature is in the range from about 550 F. to 650 F., while the preferred pressure is in the range from about 50 to 250 p. s. i. g.
  • the feed rates may vary appreciably, but desirable feed rates are from l to 16 volumes of feed per volume of catalyst per hour.
  • the segregated oil is removed from zone 6 by means of line 8 and mixed with from 5 to 15% by volume, preferably with about 10% by volume of an 8 to 15 B. strength caustic solutionwhich is introduced lby means of line 9, and an inhibitor, as for example, of the phenylene-diamine type may be added by means of line 10.
  • Air is introduced by means of line 11 and the entire mixture passed through a mixing zone 12.
  • the mixture is passed to settling zone 13, wherein spent caustic may be removed by means of line 14.
  • the treated oil is separated by means of line 15 and passed to a storage zone 16 Where it is preferred the same remain in storage for a period from about 1 to 7 days.
  • the treated oil substantially free of mercaptans and of a high quality sufficient to pass the doctor test is removed from zone 16 by means of line 17 and handled or further refined as desired.
  • the amount of caustic utilized in the air sweetening may vary appreciably, as for example, from 5 to 25% of caustic by volume based upon the oil.
  • the strength of the caustic may also vary appreciably, as for example,y
  • the doctor test a small sample of the oil is shaken vigorously with a small amount of the doctor solution which consists of 15 B. caustic saturated with litharg'e. After shaking the sample with the doctor sclution a small amount of powdered sulfur is added to the mixture and shaking repeated. It no discoloration of the sulfur at the interface between the hydrocarbon and aqueous layers develops, the sample passes the doctor test.
  • the doctor test is an indication of Whether or not the oil i-s completely free of mercaptans.
  • air caustic sweetening is thus shown to be elective for removing small amounts of mercaptans from catalytically sweetened products
  • the air caustic sweetening process isv not suitable for treating the raw virgin feed with a mercaptan number as high as 4l since excessively severe treats and long periods of contact with air would be required inorder to obtain even a partial removal of rnercaptans.
  • Examplel The feed utilized in Examplel has also been catalytically sweetened with a cobalt molybdate catalyst.
  • the results in the above table show that with a cobalt molybdate catalyst the extent of sweetening obtained was at least as good as with the catalyst which was used in Example 1.
  • the present invention is concerned with the catalytic sweetening of petroleum oils boiling in the motor fuel boiling range. No hydrogen or other extraneous gas is added to the catalytic sweetening zone.
  • the catalysts are selected from the class consisting of cobalt molybdate on alumina, molybdenum oxide on alumina and a mixture of nickel and tungsten sulfide. The amount of cobalt molybdate and molybdenum oxide utilized is in the range from about 5 to 15% by weight based upon the alumina.
  • Preferred temperatures are'in the rangefrom about 550 F. to 650' F., while preferred pressures are in the range from about 50 to 250 p. s. i. g.
  • Improved process for the complete removal of mercaptan compounds from petroleum oils boiling in the motor fuel boiling range which comprises contacting these oils with a catalyst selected from the class consisting of cobalt molybdate on alumina, molybdenum oxide on aluminaand a mixture of tungsten sulfide and nickel suliide at a pressure belowv about 500 p. s. i. g., a tempera tureY in the range from about 400 to 700 F., and in the absence of added hydrogen, removing the treated oil and separating hydrogen sulfide therefrom, thereafter contacting the oil with caustic in the presence of added air, whereby a doctor pass product is secured.
  • a catalyst selected from the class consisting of cobalt molybdate on alumina, molybdenum oxide on aluminaand a mixture of tungsten sulfide and nickel suliide at a pressure belowv about 500 p. s. i. g., a tempera ture

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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)
US321653A 1952-11-20 1952-11-20 Catalytically sweetening of naphtha Expired - Lifetime US2740747A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US321653A US2740747A (en) 1952-11-20 1952-11-20 Catalytically sweetening of naphtha
GB29709/53A GB767592A (en) 1952-11-20 1953-10-27 Improvements in or relating to the refining of hydrocarbon oils
FR1089667D FR1089667A (fr) 1952-11-20 1953-10-28 Procédé de raffinage des huiles de pétrole
NL182670A NL96832C (en(2012)) 1952-11-20 1953-11-09
BE524240D BE524240A (en(2012)) 1952-11-20 1953-11-13
DEST7320A DE1027352B (de) 1952-11-20 1953-11-18 Verfahren zur Entschwefelung von Kohlenwasserstoffen vom Siedebereich der Motortreibstoffe und des Destillatheizoels

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US321653A US2740747A (en) 1952-11-20 1952-11-20 Catalytically sweetening of naphtha

Publications (1)

Publication Number Publication Date
US2740747A true US2740747A (en) 1956-04-03

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Family Applications (1)

Application Number Title Priority Date Filing Date
US321653A Expired - Lifetime US2740747A (en) 1952-11-20 1952-11-20 Catalytically sweetening of naphtha

Country Status (6)

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US (1) US2740747A (en(2012))
BE (1) BE524240A (en(2012))
DE (1) DE1027352B (en(2012))
FR (1) FR1089667A (en(2012))
GB (1) GB767592A (en(2012))
NL (1) NL96832C (en(2012))

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3141842A (en) * 1961-02-21 1964-07-21 Exxon Research Engineering Co Sweetening of sour hydrocarbons with transition metal compounds
US3531399A (en) * 1968-03-06 1970-09-29 Gulf Research Development Co Annular flow contacting system
US4336130A (en) * 1980-11-28 1982-06-22 Union Oil Company Of California Desulfurization of hydrocarbons
US4419224A (en) * 1980-11-28 1983-12-06 Union Oil Company Of California Desulfurization of hydrocarbons
US4775462A (en) * 1987-06-22 1988-10-04 Uop Inc. Non-oxidative method of sweetening a sour hydrocarbon fraction
US4906354A (en) * 1987-09-10 1990-03-06 Mobil Oil Corporation Process for improving the thermal stability of jet fuels sweetened by oxidation
US5064525A (en) * 1991-02-19 1991-11-12 Uop Combined hydrogenolysis plus oxidation process for sweetening a sour hydrocarbon fraction
WO2001079391A1 (en) * 2000-04-18 2001-10-25 Exxonmobil Research And Engineering Company Selective hydroprocessing and mercaptan removal

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB852868A (en) * 1958-09-22 1960-11-02 Exxon Research Engineering Co Hydrofining of middle distillate feed stock
US8398848B2 (en) 2008-10-02 2013-03-19 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing copper metal
US8696889B2 (en) 2008-10-02 2014-04-15 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing a transition metal oxide
US8968555B2 (en) 2008-10-02 2015-03-03 Exxonmobil Research And Engineering Company Desulfurization of heavy hydrocarbons and conversion of resulting hydrosulfides utilizing copper sulfide
MX375006B (es) 2015-08-06 2025-03-06 Mexicano Inst Petrol Uso de polímeros como donadores de hidrógeno heterogéneos en el mejoramiento de crudos pesados y extrapesados.
MX2017009054A (es) 2017-07-10 2019-02-08 Mexicano Inst Petrol Procedimiento de preparacion de agentes de transferencia de hidrogeno solidos mejorados para el procesamieno de crudos pesados, extrapesados y residuos, y producto resultante.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1257829A (en) * 1915-10-25 1918-02-26 Edward Victor Evans Eliminating sulfur from oils.
US2392579A (en) * 1945-02-10 1946-01-08 Shell Dev Process for the treatment of olefinic sulphur-bearing gasoline to effect substantialdesulphurization and refining
US2393288A (en) * 1943-07-06 1946-01-22 Union Oil Co Process for the catalytic reforming of hydrocarbon mixtures
US2413312A (en) * 1945-01-26 1946-12-31 Shell Dev Catalytic finishing of gasolines
US2413945A (en) * 1944-03-09 1947-01-07 Standard Oil Co Treating petroleum distillates

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB543968A (en) * 1939-03-31 1942-03-23 Standard Oil Dev Co An improved catalytic treatment of hydrocarbon oils and the manufacture of motor fuels by such treatment
FR968479A (fr) * 1947-06-30 1950-11-28 Anglo Iranian Oil Co Ltd Procédé de désulfuration de naphtes naphténiques
DE883626C (de) * 1947-08-26 1953-07-20 Anglo Iranian Oil Co Ltd Verfahren zur katalytischen Entschwefelung naphthenhaltiger Erdoelfraktionen
GB667368A (en) * 1947-09-17 1952-02-27 Standard Oil Dev Co Process for the removal of aromatic mercaptans from catalytically cracked gasoline
GB663038A (en) * 1947-12-16 1951-12-12 Anglo Iranian Oil Co Ltd Improvements relating to the catalytic desulphurisation of petroleum distillates
NL70360C (en(2012)) * 1948-04-19
GB669552A (en) * 1948-06-01 1952-04-02 Anglo Iranian Oil Co Ltd Improvements relating to the catalytic desulphurisation of petroleum hydrocarbons
GB669553A (en) * 1948-06-24 1952-04-02 Anglo Iranian Oil Co Ltd Catalytic desulphurisation of gas oils
US2565349A (en) * 1949-09-12 1951-08-21 Standard Oil Dev Co Method for sweetening petroleum distillates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1257829A (en) * 1915-10-25 1918-02-26 Edward Victor Evans Eliminating sulfur from oils.
US2393288A (en) * 1943-07-06 1946-01-22 Union Oil Co Process for the catalytic reforming of hydrocarbon mixtures
US2413945A (en) * 1944-03-09 1947-01-07 Standard Oil Co Treating petroleum distillates
US2413312A (en) * 1945-01-26 1946-12-31 Shell Dev Catalytic finishing of gasolines
US2392579A (en) * 1945-02-10 1946-01-08 Shell Dev Process for the treatment of olefinic sulphur-bearing gasoline to effect substantialdesulphurization and refining

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3141842A (en) * 1961-02-21 1964-07-21 Exxon Research Engineering Co Sweetening of sour hydrocarbons with transition metal compounds
US3531399A (en) * 1968-03-06 1970-09-29 Gulf Research Development Co Annular flow contacting system
US4336130A (en) * 1980-11-28 1982-06-22 Union Oil Company Of California Desulfurization of hydrocarbons
US4419224A (en) * 1980-11-28 1983-12-06 Union Oil Company Of California Desulfurization of hydrocarbons
US4775462A (en) * 1987-06-22 1988-10-04 Uop Inc. Non-oxidative method of sweetening a sour hydrocarbon fraction
US4906354A (en) * 1987-09-10 1990-03-06 Mobil Oil Corporation Process for improving the thermal stability of jet fuels sweetened by oxidation
US5064525A (en) * 1991-02-19 1991-11-12 Uop Combined hydrogenolysis plus oxidation process for sweetening a sour hydrocarbon fraction
WO2001079391A1 (en) * 2000-04-18 2001-10-25 Exxonmobil Research And Engineering Company Selective hydroprocessing and mercaptan removal
US20030127362A1 (en) * 2000-04-18 2003-07-10 Halbert Thomas R. Selective hydroprocessing and mercaptan removal
US20030188992A1 (en) * 2000-04-18 2003-10-09 Halbert Thomas R. Selective hydroprocessing and mercaptan removal
US7244352B2 (en) 2000-04-18 2007-07-17 Exxonmobil Research And Engineering Company Selective hydroprocessing and mercaptan removal

Also Published As

Publication number Publication date
BE524240A (en(2012)) 1953-11-30
DE1027352B (de) 1958-04-03
FR1089667A (fr) 1955-03-21
NL96832C (en(2012)) 1961-02-15
GB767592A (en) 1957-02-06

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