US3184405A - Desulfurizing petroleum with alkali and di-alkyl sulfoxide - Google Patents

Desulfurizing petroleum with alkali and di-alkyl sulfoxide Download PDF

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Publication number
US3184405A
US3184405A US351832A US35183264A US3184405A US 3184405 A US3184405 A US 3184405A US 351832 A US351832 A US 351832A US 35183264 A US35183264 A US 35183264A US 3184405 A US3184405 A US 3184405A
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United States
Prior art keywords
alkali
oil
mercaptan
dmso
sulfoxide
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Expired - Lifetime
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US351832A
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English (en)
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Charles O Hoover
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Individual
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Priority to US351832A priority Critical patent/US3184405A/en
Priority to GB30921/64A priority patent/GB1025375A/en
Priority to BE651950D priority patent/BE651950A/xx
Priority to NL6410858A priority patent/NL6410858A/xx
Priority to DEH55290A priority patent/DE1301411B/de
Priority to FR7883A priority patent/FR1425936A/fr
Priority to ES0310456A priority patent/ES310456A1/es
Priority to NO157179A priority patent/NO115085B/no
Application granted granted Critical
Publication of US3184405A publication Critical patent/US3184405A/en
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Classifications

    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • C10G19/04—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions containing solubilisers, e.g. solutisers
    • 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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/22—Compounds containing sulfur, selenium, or tellurium
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier

Definitions

  • the present invention therefore, has for its primary object, the provision of a chemical treating process which will effectively and easily remove substantially all of the mercaptan-type sulfur compounds from petroleum stocks and particularly from the lighter distillates obtained by the conventional processes for refining crude oils.
  • the process in accordance with this invention comprises admixing with a petroleum stock in the liquid phase, first, an alkali hydroxide, and second, a sulfoxide compound having the general formula:
  • R and R either or both, is a methyl-, ethyl-, or propyh, group.
  • the preferred sulfoxide is dimethyl sulfoxide (herein designated DMSO) because of its ready availability and its high efficiency in the process.
  • My invention is based upon the discovery that sulfoxides of the character defined have exceptionally high solvent capacity for the alkali salts of the mercaptans,
  • the mercaptans namely, the mercaptides.
  • the alkali hydroxide by first reacting the mercaptans with the alkali hydroxide, and thereafter, before removal of alkali reaction products, admixing with the oil-alkali mixture at suitable proportion of the sulfoxide, substantially complete removal of the mercaptan sulfur compounds can be readily effected.
  • the treatment may be conducted entirely under ambient atmospheric conditions of temperature and pressure, thereby minimizing the complexity and expense of the required apparatus.
  • the quantity of alkali hydroxide employed is stoichiometrically related to the quantity of sulfur present as mercaptan sulfur.
  • the alkali hydroxide will be added in the proportion of at least one mol of the alkali per mol of mercaptan sulfur present in the oil.
  • an excess of alkali will be employed to assure effective mixing and completeness of the reaction both with the mercaptans and with other acidic constituents which may be present.
  • the molal quantities required are quite small, even for very sour oils, a substantial molal excess of the alkali will represent only a very small quantity on a volumetric or weight basis relative to the oil being treated.
  • the preferred alkali hydroxide is sodium hydroxide but potassium hydroxide may also be used, although it is more expensive and less easily handled.
  • the alkali hydroxide may be used in solid form, in which case, the powdered or granulated form is preferred. It may also be employed in aqueous solution in any concentration ranging from about 5% by weight of the solution to the maximum concentration at which it may be maintained in liquid form. Where aqueous solutions are employed, concentrations from about 30% to 50% are found most use ful with a 50% concentration preferred in most instances in order to minimize the quantity of sulfoxide required, as the solvent efiiciency of the latter for the alkali mercaptides decreases generally in proportion to the amount of water present.
  • Example 1 A super sour naphtha having an initial mercaptan sulfur content of 0.91% by weight was treated with various concentrations of NaOH and differing proportions of dimethyl sulfoxide (DMSO) in accordance with the following table.
  • DMSO dimethyl sulfoxide
  • Example 3 A kerosene initially containing 0.012% sulfur as mercaptans was treated successively with 10 mols 50% NaOH 3 7 solution and 20% by volume of DMSO. The mercaptan sulfur was reduced to 0.00'06% by weight, a reduction of 95%. v i
  • the final 'mercap'tan sulfur content was 0.0009% by weight, a reduction of 96.7%. a r
  • Example 7- Thefinal mercaptan sulfur content was 0.0002%, a re- 7 Asour haphtha 'havingan initial 'mercapta'n sulfur content or" 0.81% by weightwas treated with 1.1 mols of 98% (solid) 'Na'OH followed by 10% by volume of.
  • Example 8 v Asample'of the 'supe'rsour naphtha initially containing 0.91 "by'weiglitof sulfur as 'mercaptan was treated with 1.1 mol'sjof 9 8% '(solidylqaOH followed by 1"5%[-by' volume ofdithyl 'sul foxide.
  • Thetreated oil contained 0005870 by Weight'of mercaptan sulfur, a reduction of V Example 9 65% by volumeof dipropyl sulfoxide was substituted for the diethyl sulfoxide of Example 8.
  • the DMSO mayf'be reclaimed fofr -re-use, iif'desired, bya number of relatively simple procedures.
  • the soluwhereiri R and R either from the resultingzadmixture.
  • sulfoxide is dimethyl sulfoxide.
  • a process. for desulifur-izin'gfa mercaptan con'taining petroleum oil stock comprising, successively admixing with said stockin the liquid phase in the following order (a) a strongalkali and ('b) a di-alkyl sulfoxide having the general-forrnu'la I v R's-R1 f or both, is methyl-, ethyl-, or .propyl-group, the'additionof the di-alkyl 'sulfoxide being made Without separation of 'reactionproducts' :from the oil stock-alkali admiXtureQand separating the treated oil '2.".
  • A process according toiclaim 1 wherein the die'alkyl '3.
  • a processaccordingato claim *1 alkaliis'sodiumhydroxide. 7 v p '4; A process, according to claim 1 wherein thestrong whereinthe strong alkali is admixed in the proportion of at least one 'mol per mol 'of mercaptan.sulfur'inxthebilstock. 5. A pro'cess in accordance'with . clai1n 1 wherein the -strong2alkali-is an aqueous solution containing from. about '30.% to about 50%:by weight of'sodium hydroxide.
  • a iprocess for desulfurizin'g a *m'ercaptan-containing petroleum oil stoCkQcomprising, successivelyadmixing tion s'epafatin'g-frornthe oil layer-after'treatmentinaccordance with any of the foregoing examples, will "comprise a DMsO-wat'er sodium (potassium) trierca'ptide hy- -dro'carbon solution. Ino'ne-procedure the separated'solution may b'e'neutrali'zed Withasuitable acid.
  • The'DMSO-water was distilled overhead, leaving a bottom product containing the sodium mercaptides.”
  • the overhead material- may be further purified -to reducethe water content of the with 'said 's'tock'in'the liquid vphase in the following-order: (-c'l.) "sodium hydroxide in the proportion of.

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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)
  • Generation Of Surge Voltage And Current (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US351832A 1964-03-13 1964-03-13 Desulfurizing petroleum with alkali and di-alkyl sulfoxide Expired - Lifetime US3184405A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US351832A US3184405A (en) 1964-03-13 1964-03-13 Desulfurizing petroleum with alkali and di-alkyl sulfoxide
GB30921/64A GB1025375A (en) 1964-03-13 1964-08-04 Process for desulfurizing petroleum
BE651950D BE651950A (en)) 1964-03-13 1964-08-18
NL6410858A NL6410858A (en)) 1964-03-13 1964-09-17
DEH55290A DE1301411B (de) 1964-03-13 1965-02-24 Verfahren zur Entschwefelung Mercaptan enthaltender Erdoelfraktionen
FR7883A FR1425936A (fr) 1964-03-13 1965-03-04 Procédé de désulfuration d'une charge dérivée des pétroles
ES0310456A ES310456A1 (es) 1964-03-13 1965-03-12 Un proceso para el desazufrado de una materia prima de petroleo que contiene mercaptanos.
NO157179A NO115085B (en)) 1964-03-13 1965-03-12

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US351832A US3184405A (en) 1964-03-13 1964-03-13 Desulfurizing petroleum with alkali and di-alkyl sulfoxide

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US3184405A true US3184405A (en) 1965-05-18

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US (1) US3184405A (en))
BE (1) BE651950A (en))
DE (1) DE1301411B (en))
ES (1) ES310456A1 (en))
FR (1) FR1425936A (en))
GB (1) GB1025375A (en))
NL (1) NL6410858A (en))
NO (1) NO115085B (en))

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3409543A (en) * 1966-04-20 1968-11-05 Universal Oil Prod Co Treatment of sour organic streams

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2365898A (en) * 1943-10-19 1944-12-26 Shell Dev Solvent extraction process
US2927076A (en) * 1957-09-16 1960-03-01 Sun Oil Co Stabilizing sulfonated petroleum with organic sulfoxides
US3052626A (en) * 1960-07-08 1962-09-04 Nalco Chemical Co Treatment of petroleum products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2365898A (en) * 1943-10-19 1944-12-26 Shell Dev Solvent extraction process
US2927076A (en) * 1957-09-16 1960-03-01 Sun Oil Co Stabilizing sulfonated petroleum with organic sulfoxides
US3052626A (en) * 1960-07-08 1962-09-04 Nalco Chemical Co Treatment of petroleum products

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3409543A (en) * 1966-04-20 1968-11-05 Universal Oil Prod Co Treatment of sour organic streams

Also Published As

Publication number Publication date
ES310456A1 (es) 1966-01-01
DE1301411B (de) 1969-08-21
GB1025375A (en) 1966-04-06
NL6410858A (en)) 1965-09-14
BE651950A (en)) 1965-02-18
FR1425936A (fr) 1966-01-24
NO115085B (en)) 1968-07-22

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