GB958567A - Improved process for refining hydrocarbon oils to obtain refined oil and oil soluble sulphonates - Google Patents

Improved process for refining hydrocarbon oils to obtain refined oil and oil soluble sulphonates

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Publication number
GB958567A
GB958567A GB2222060A GB2222060A GB958567A GB 958567 A GB958567 A GB 958567A GB 2222060 A GB2222060 A GB 2222060A GB 2222060 A GB2222060 A GB 2222060A GB 958567 A GB958567 A GB 958567A
Authority
GB
United Kingdom
Prior art keywords
oil
sulphonates
sulphonation
phase
acid
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
Application number
GB2222060A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from FR799618A external-priority patent/FR1287319A/en
Priority claimed from FR819661A external-priority patent/FR90801E/en
Application filed by Individual filed Critical Individual
Publication of GB958567A publication Critical patent/GB958567A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G17/00Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/62Sulfonated fats, oils or waxes of undetermined constitution

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Oil soluble sulphonates are prepared by sulphonating a hydrocarbon oil containing hydrocarbon sulphonatable at below 35 DEG C. to yield oil soluble sulphonates, with not more than 15% by weight of the weakest sulphonating agent selected from 66 DEG Baum<\>ae sulphuric acid, 98-100% sulphuric acid, an oleum, chlorosulphonic acid, fluoro sulphonic acid and SO3, able to sulphonate some of the hydrocarbon at below 35 DEG C., the sulphonation being affected at below 35 DEG C. while maintaining the reactants in intimate admixture and allowing a contact time sufficient only for mono-sulphonation to occur, thereafter neutralizing the resulting sulphonic acids before any secondary reactions occur, treating the sulphonated oil, separated or not from an acid fraction containing sulphonic acids in excess acid reagent, before, during or after the neutralization step with an alcohol having less than 4 carbon atoms in the presence of sufficient water to form at least an oil phase and a hydro-alcoholic phase containing dissolved sulphonated hydrocarbons, separating and if necessary neutralizing the hydro-alcoholic phase, then adding to the separated neutralized alcoholic solution sufficient of the said alcohol containing at most 10% by weight of water to form three phases: oil, an alcoholic solution of the sulphonates and an aqueous solution of metal salts, then recovering the oil, separating the sulphonate phase and distilling it to recover the solvent, removing any last residue of precipitated inorganic salts and obtaining purified sulphonates containing minor proportions of oil. The recovered oil may be repeatedly treated by the above series of steps using the appropriate sulphonating agent able to react with the sulphonatable hydrocarbon remaining in the oil. The hydrocarbon oils treated may be petroleum oils which may be solvent extracted, shale oil, coal oils and synthetic oils. In one embodiment, the sulphonation product is separated into an oil solution of sulphonic acids and an acid phase comprising sulphonic acids in excess sulphonating agent. The oil solution is then either neutralized, separated from an aqueous salt phase, and mixed with a 50:50 water-ethanol or -isopropanol mixture or the oil solution is mixed with the alcohol containing not more than 10% water during or after neutralization before any separation of metal salts; in each case three phases: oil, hydroalcoholic solution of sulphonates and aqueous salt solution are formed and separated and the sulphonate phase is mixed with alcohol containing not more than 10% water whereby the three phases are again formed and separated and the alcoholic phase is distilled to obtain the sulphonates. The aforesaid acid phase of sulphonic acids and excess acid reagent may be worked up in the same manner to recover oil and sulphonates, or be neutralized, separated from aqueous salts and then extracted with 90% alcohol to recover the sulphonates. In another embodiment, the whole sulphonation mixture is worked up by either of these methods. A further embodiment comprises treating the acid sulphonation mixture with the 50:50 aqueous alcohol to form three phases of oil, hydroalcoholic solution of sulphonic acids and a layer of excess acid reagent, separating and neutralizing the alcoholic phase and extracting the sulphonates therefrom with alcohol as above. The sulphonation mixture may be clarified, before further treatment, by means of powdered aluminium or sodium aluminate or an absorptive earth. The neutralization may be effected with sodium hydroxide or carbonate, ammonia, lime wash or aqueous baryta. The 50:50 aqueous alcohol extractant may include an alkanolamine or soap thereof to improve phase separation. Ammonium sulphonates obtained according to the process may be converted into lithium, calcium, aluminium, molybdenum or other sulphonates by reaction with bases or salts. Examples describe inter alia (1) the repeated sulphonation with oleum, with intermediate neutralization and alcoholic extraction of the sulphonates, of a solvent extracted sulphuric acid washed Coastal oil to give a variety of oil soluble sulphonates and purified oil; (5) the repeated sulphonation of a spindle oil with 66 DEG Baum<\>ae sulphuric acid, 98-100% sulphuric acid and oleum with neutralization and recovery of sulphonates after each sulphonation yielding white oil and oil soluble sulphonates; when oleum only is used in the sulphonation it is stated that large amounts of water soluble sulphonates are also formed; and (7) the sulphonation of a high boiling fraction obtained in the alkylation of benzene and comprising fully alkylated hydrocarbons and sulphonable hydrocarbons. Specification 823,237 is referred to.ALSO:Refined hydrocarbon oils are prepared by sulphonating a hydrocarbon oil containing hydrocarbon sulphonatable at below 35 DEG C. to yield oil-soluble sulphonates, with not more than 15% by weight of the weakest sulphonating agent selected from 66 DEG Baume<\>ae sulphuric acid, 98-100% sulphuric acid, an oleum, chlorosulphonic acid, fluoro sulphonic acid and SO3, able to sulphonate some of the hydrocarbon at below 35 DEG C., the sulphonation being effected at below 35 DEG C. while maintaining the reactants in intimate admixture and allowing a contact time sufficient ohly for mono-sulphonation to occur, thereafter neutralizing the resulting sulphonic acids before any secondary reactions occur, treating the sulphonated oil, separated or not from an acid fraction containing sulphonic acids in excess acid reagent, before, during or after the neutralization step with an alcohol having less than 4 carbon atoms in the presence of sufficient water to form at least an oil phase and a hydro-alcoholic phase containing dissolved sulphonated hydrocarbons, separating and if necessary neutralizing the hydro-alcoholic phase, then adding to the separated neutralized alcoholic solution sufficient of the said alcohol containing at most 10% by weight of water to form three phases: oil, an alcoholic solution of the sulphonates and an aqueous solution of metal salts, then recovering the oil, separating the sulphonate phase and distilling it to recover the solvent, removing any last residue of precipitated inorganic salts and obtaining purified sulphonates containing a minor proportion of oil. The recovered oil may be repeatedly refined by the above series of steps using the appropriate sulphonating agent able to react with the sulphonatable hydrocarbon remaining in the oil. The hydrocarbon oils treated may be petroleum oils which may be solvent extracted, shale oil, coal oils and synthetic oils. In one embodiment, the sulphonation product is separated into an oil solution of sulphonic acids and an acid phase comprising sulphonic acids in excess sulphonating agent. The oil solution is then either neutralized, separated from an aqueous salt phase, and mixed with a 50 : 50 waterethanol or isopropanol mixture or the oil solution is mixed with the alcohol containing not more than 10% water during or after neutralization before any separation of metal salts; in each case three phases: oil, hydro-alcoholic solution of sulphonates and aqueous salt solution are formed and separated and the sulphonate phase is mixed with alcohol containing not more than 10% water whereby the three phases are again formed and separated and the alcoholic phase is distilled to obtain the sulphonates. The aforesaid acid phase of sulphonic acids and excess acid reagent may be worked up in the same manner to recover oil and sulphonates therefrom. In another embodiment, the whole sulphonation mixture is worked up by either of these methods. A further embodiment comprises treating the acid sulphonation mixture with the 50 : 50 aqueous alcohol to form three phases of oil, hydro-alcoholic solution of sulphonic acids and a layer of excess acid reagent, separating and neutralizing the alcoholic phase and extracting the sulphonates therefrom with alcohol as above. The sulphonation mixture may be clarified, before further treatment, by means of powdered aluminium or sodium aluminate or an absorptive earth. The neutralization may be effected with sodium hydroxide or carbonate, ammonia, lime wash or aqueous baryta. The 50 : 50 aqueous alcohol extractant may include an alkanolamine or soap thereof to improve phase separation. Ammonium sulphates obtained according to the process may be converted into lithium, calcium, aluminium, molybdenum or other sulphonates by reaction with bases or salts. Examples describe inter alia (1) the repeated sulphonation with oleum, with intermediate neutralization and alcoholic extraction of the sulphonates, of a solvent extracted sulphuric acid washed Coastal oil to give a variety of oil soluble sulphonate and purified oil; (5) the repeated sulphonation of a spindle oil with 66 DEG Baume<\>ae sulphuric acid, 98-100% sulphuric acid and oleum with neutralization and recovery of sulphonates after each sulphonation yielding white oil and oil soluble sulphonates; when oleum only is used in the sulphonation it is stated that large amounts of water soluble sulphonates are also formed; and (7) the treatment of a high boiling fraction obtained in the alkylation of benzene and comprising fully alkylated hydrocarbons and sulphonatable hydrocarbons. Specification 823,237 is referred to.
GB2222060A 1959-07-08 1960-06-24 Improved process for refining hydrocarbon oils to obtain refined oil and oil soluble sulphonates Expired GB958567A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR799618A FR1287319A (en) 1959-07-08 1959-07-08 Production, integral extraction and simultaneous purification of sulfonates in the refining of mineral oils
FR819661A FR90801E (en) 1959-07-08 1960-02-26 Production, integral extraction and simultaneous purification of sulfonates in the refining of mineral oils
FR820938A FR91103E (en) 1959-07-08 1960-03-06 Production, integral extraction and simultaneous purification of sulfonates in the refining of mineral oils

Publications (1)

Publication Number Publication Date
GB958567A true GB958567A (en) 1964-05-21

Family

ID=27245288

Family Applications (1)

Application Number Title Priority Date Filing Date
GB2222060A Expired GB958567A (en) 1959-07-08 1960-06-24 Improved process for refining hydrocarbon oils to obtain refined oil and oil soluble sulphonates

Country Status (1)

Country Link
GB (1) GB958567A (en)

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