US2948669A - Production of superior neutral oils - Google Patents
Production of superior neutral oils Download PDFInfo
- Publication number
- US2948669A US2948669A US2948669DA US2948669A US 2948669 A US2948669 A US 2948669A US 2948669D A US2948669D A US 2948669DA US 2948669 A US2948669 A US 2948669A
- Authority
- US
- United States
- Prior art keywords
- oil
- neutral
- epoxides
- lubricating oil
- fractions
- 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
Links
- 239000003921 oil Substances 0.000 title claims description 192
- 230000001264 neutralization Effects 0.000 title claims description 154
- 238000004519 manufacturing process Methods 0.000 title description 14
- 238000000034 method Methods 0.000 claims description 88
- 150000002118 epoxides Chemical class 0.000 claims description 84
- 239000010687 lubricating oil Substances 0.000 claims description 62
- 238000005336 cracking Methods 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 230000000875 corresponding Effects 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 30
- 239000000654 additive Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 26
- 150000001336 alkenes Chemical class 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 238000006735 epoxidation reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 239000010779 crude oil Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 238000011065 in-situ storage Methods 0.000 description 16
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 16
- 150000001412 amines Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- -1 hydrocarbon radicals Chemical class 0.000 description 14
- RMVRSNDYEFQCLF-UHFFFAOYSA-N Thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 12
- 230000000996 additive Effects 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 150000004965 peroxy acids Chemical class 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 241000282890 Sus Species 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 230000000670 limiting Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005292 vacuum distillation Methods 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000003247 decreasing Effects 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- UENWRTRMUIOCKN-UHFFFAOYSA-N Benzyl mercaptan Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 229910052570 clay Inorganic materials 0.000 description 6
- 230000002708 enhancing Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 239000008079 hexane Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N 2-mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- 229960000583 Acetic Acid Drugs 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N Benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N Catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- XCRBXWCUXJNEFX-UHFFFAOYSA-N Peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N Phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N Pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating Effects 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000003064 anti-oxidating Effects 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 125000002587 enol group Chemical group 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 230000001050 lubricating Effects 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N stearylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-Ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MVZVDAGWAAZJPE-UHFFFAOYSA-N 1,2-xylene;1,3-xylene;1,4-xylene Chemical compound CC1=CC=C(C)C=C1.CC1=CC=CC(C)=C1.CC1=CC=CC=C1C MVZVDAGWAAZJPE-UHFFFAOYSA-N 0.000 description 2
- IMPKVMRTXBRHRB-MBMOQRBOSA-N 5-Deoxyinositol Chemical compound O[C@@H]1C[C@@H](O)[C@H](O)C(O)[C@H]1O IMPKVMRTXBRHRB-MBMOQRBOSA-N 0.000 description 2
- 229940069428 ANTACIDS Drugs 0.000 description 2
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N Barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 2
- 241000212384 Bifora Species 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N DECANE-1-THIOL Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N Ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N Hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- CDAISMWEOUEBRE-GPIVLXJGSA-N Inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 2
- 229960000367 Inositol Drugs 0.000 description 2
- JORQDGTZGKHEEO-UHFFFAOYSA-N Lithium cyanide Chemical compound [Li+].N#[C-] JORQDGTZGKHEEO-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229960001553 Phloroglucinol Drugs 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N Potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N Propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229940079877 Pyrogallol Drugs 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N Sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 230000001458 anti-acid Effects 0.000 description 2
- 230000000111 anti-oxidant Effects 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 230000003078 antioxidant Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000001691 aryl alkyl amino group Chemical group 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002596 correlated Effects 0.000 description 2
- 231100000078 corrosive Toxicity 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000004059 degradation Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007033 dehydrochlorination reaction Methods 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 230000002939 deleterious Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000003292 diminished Effects 0.000 description 2
- ZUNYMXPJGBXUCI-UHFFFAOYSA-N dioctoxy-sulfanyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(S)(=S)OCCCCCCCC ZUNYMXPJGBXUCI-UHFFFAOYSA-N 0.000 description 2
- 150000004662 dithiols Chemical class 0.000 description 2
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010685 fatty oil Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N hexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- 150000004680 hydrogen peroxides Chemical class 0.000 description 2
- 229960004337 hydroquinone Drugs 0.000 description 2
- DQCOURVTDJUHQM-UHFFFAOYSA-N hydroxy-dioctoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCCOP(O)(=S)OCCCCCCCC DQCOURVTDJUHQM-UHFFFAOYSA-N 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl radical Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000000873 masking Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- 125000005609 naphthenate group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002829 reduced Effects 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 2
- 239000001187 sodium carbonate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- RVEZZJVBDQCTEF-UHFFFAOYSA-N sulfenic acid Chemical class SO RVEZZJVBDQCTEF-UHFFFAOYSA-N 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000004450 types of analysis Methods 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/06—Gaseous phase, at least during working conditions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to .the production of neutral oils possessing superior qualities. More particularly, our invention relates to the production of neutral oils from heavier lubricating oil fractions and to the in situ production of epoxides and epoxide derivatives therein.
- the additives are quite different in chemical structure from the component molecules making up the body of the lubricating oils. Such differences in chemical properties as well as physical properties between the additive and thelubricating oil fraction may create difficulties such as poor compatibility of the additive with the oil, or a shorter period of usefulness of theflblend .in the .motor than would be expected.
- the additive alsomayact to depress or decrease a desired characteristic present in the oil before addition of the additive. Such a circumstance may require a second additive to restore the lost or diminished desirable property.
- additive components of dissimilar structure from the lubricating oil frequently may be easily removed from solution, that is, they may precipitate and form sludge at high temperatures or on long continued use at normal temperatures.
- Neutral oils have recently become more extensively utilized I in motor oil formulations, with consequently decreased'application of vbright stock fractions. Therefore, an oversupply of bright stock fractions is to be expected in the future unlesslotherjuses for such jfrac tions can befound.
- our invention lies in the con a primary or secondary amine, an alkanol amine, an'
- organic acid such as a thio-acid, a dithio-acid, a sulfonic or polysulfonic acid, or a mono-, di-' ior 'polyhydric phenol, thiophenol, or enol, among other reactive compounds.
- a particular pointof novelty in our invention lies in the unique utilization of olefins formed during the cracking step of our process as basic material for the preparation of desirable lubricating oil agents, thus eliminating the tedious and expensive procedure of separating the olefins from the solution before utilizing the oil pro prised during the cracking operation.
- the olefins themselves are generally recognized as deleterious to the performance of lubricating oil fractions, since they tend to promote corrosion and sludge formation, and therefore shouldberemoved from neutrals prepared by cracking heavier oil fractions. Since neutrals prepared from residua are more expensive than those initially obtained by vacuum distillation due to the olefin separation step, this method of preparing neutrals is not commercially utilized.
- vNeutral oil is ordinarily obtained from crude oil by subjecting topped crude to the steps of vacuum distillation,'followed by solvent refining, solvent dewaxing and clay contacting.
- the vacuum distillation divides the oil pane or other suitable solvent, and to solvent refining with phenol, followed by solvent dewaxing and a subse- V invention to vide a process for the preparation of superior neutral quent clay contacting operation. Residuum before the solvent refining step may be utilized as the feed 011 In our process.
- finished bright stock used for blending various oil fractions and consisting of a heavy viscous residual oil with a reddish color, or unfinished bright stock not subjected to solvent dewaxing to remove microcrystalline wax fractions, and/or clay treating may be utilized as the feed in our process.
- the solvent dewaxing step may employ any one or more of a number of suitable solvents, or solvent mixtures, or solvent and anti-solvent mixtures, e.g., a mixture of methyl ethyl ketone and toluene in a ratio of solvent mixture to oil of 1:1 to 4:1, depending on the nature and viscosity of the charge material.
- the bright stock obtained varies in viscosity and other properties according to the type of crude oil and the number, type and sequence of refining steps to which it has been subjected.
- the oil fraction utilized as the starting material in the process of our invention is residuum or cylinder stock such as vacuum residuum from the initial treating step of the crude oil, since it has a lower initial cost than finished bright stock.
- Any crude oil may be utilized as the starting material for the vacuum distillation, or any other type of distillation which separates the neutral oil fractions and other fractions from the heavier, less volatile, residual lubricating oil fraction.
- the crude oil for example, may be Mid-Continent, Pacific Coast, Gulf Coast, Pennsylvania or other type of crude oil which has been subjected to the necessary separation of neutral oils from residuum by appropriate distillation or other methods.
- the bright stock or heavy lubricating oil fraction such as vacuum residuum
- a mild cracking operation and simultaneous distillation under moderately elevated temperature and decreased pressure A cracked product is obtained comprising a neutral oil having as much as 50% olefins.
- Neutral oils may be defined as distillate lubricating oils with viscosities usually not above 200 sec. at 100 F.
- the degree of unsaturation in the neutral oil produced in our process depends upon the specific conditions of cracking and the characteristics of the feed oil.
- the cracking is carried out at a relatively low temperature to reduce the severity of degradation of the oil components. Thus, conditions. are milder than utilized for the preparation of, for example, gasoline from heavy residuum.
- the temperature is correlated with the reduced pressure of the system.
- temperatures of approximately 300 to 600 F. may be utilized with pressures of 2 mm. Hg to 25 mm. Hg
- bright stocks of average viscosity of 150-160 are utilized as the feedoils.
- a bright stock obtained from the processing of a Van Zandt crude oil and having a viscosity of 150 SUS at 210 F. was slowly distilled at 1-4 mm. of mercury pressure and 350 F. to give a 50% yield of an unsaturated neutral oil having a bromine number of 25, an average molecular wt. of 390 and a viscosity of 45.2 SUS at 210 F.
- This step may also be carried out by careful steam distillation in the manner set forth in Wagner 'et a1.
- Patent No. 2,155,745. The neutral type of oil prepared by this step exhibits a viscosity of about 65 to 350 SUS at 100 F. j
- the unsaturated hydrocarbons in the neutral oil are converted to epoxides in the second step of our process.
- the unsaturated hydrocarbons may be low or high molecular weight olefins, diolefins or other-compounds of petroleum origin containing one or more unsaturated bonds. These are compatiblewith the neutral oil so produced, since they are de- ,4, rived from the components initially present in the feed oil.
- R- CHi-l-[0l- Ha I'l R wherein R and R denote the hydrocarbon radicals normally found in the oil.
- the epoxidation procedure may be carried out by any known method.
- epoxidation may be carried out with peroxyacids such as peracetic or perbenzoic acids, with inorganic peroxides such as hydrogen peroxides or barium peroxide, by air oxidation with or without a suitable catalyst, or by hypohalogenation followed by dehydrohalogenation.
- peroxyacids such as peracetic or perbenzoic acids
- inorganic peroxides such as hydrogen peroxides or barium peroxide
- hypohalogenation followed by dehydrohalogenation.
- the epoxidation reaction may be carried out batchwise in the presence of a suitable buflfering agent at temperatures ranging from room temperature to 40 0., according to the method disclosed in US. Patent 2,411,762, November 26, 1946.
- reaction is determined either by titration of aliquots of the solution for epoxy oxygen according to the method of Sworn et a1. (Anal. Chem. 19, 414 (1947)), or from analyses for residual peroxyacid (DAns and Frey, Ber. 45, 1845 (1912); Z. anorg. Chem. 84, 145 (1913)).
- the epoxidation may be carried out either batchwise or as a continuous process by first generating the peroxyacid in situ from a mixture of hydrogen peroxide and acetic acid in the presence of an acid ionexchange resin, then proceeding as above.
- the amount of peracetic acid or other peracid or peroxide utilized may vary widely, depending upon the extent of epoxidation desired and upon the quantity of unsaturated hydrocarbons present per unit volume of the neutral oil.
- the epoxidation ordinarily may be accomplished without resort to greatly increased temperature and/or pressure.
- a typical epoxidation reaction involves the epoxidation of the unsaturated neutral with a mixture of sodium acetate and peracetic acid at room temperature and ordinary pressure.
- the oil layer after the reaction, contains a considerable proportion of epoxides.
- epoxide may be concentrated by extraction. Yields of 40% epoxides or more, based on the amount of unsaturated compounds present in the cracked neutral oil charged to this epoxidation step, can be obtained.
- step one alternate but equally suitable method for the production of the epoxides in situ in the cracked neutral lubricating oil fraction obtained by step one comprises hypochlorination of the unsaturates in the oil followed by dehydrochlorination.
- the unsaturated neutral oil may be stirred with an aqueous solution of hypochlorous acid and the product then treated with strong aqueous caustic alkali solution or other strong base.
- the quantities of reactants may vary widely.
- a further method of treatment to produce epoxides is the reaction of the neutral oil containing the unsaturates with a stream of air or oxygen under atmospheric or superatmospherie pressures, while keeping the reaction mixture in a neutral or slightly alkaline condition.
- a nonlimiting example of this method comprises reacting the neutral oil at 10-20 atm., 100-150 C., and a pH of 8.0 with air.
- Magnesium oxide or sodium carbonate, etc. may be present as base catalyst.
- Other methods of preparing epoxides from olefins as are known in the prior art and which will operate successfully in a neutral oil medium without'deleteriously affecting the medium may be utilized in the second step of this process of our invention.
- the particular operating conditions of each epoxidation procedure vary with the characteristics of the charge material, the reactants and other factors, including the yield of epoxides desired.
- the epoxidized neutral oil components so prepared from the compatible olefins present in the neutral oil have desirable oiliness and acidity reduction characteristics which enhance the quality of the neutral oil.
- neutral oil of substantially improved lubricating and acid-reduction properties may be produced by the combined procedure of steps 1 and 2 of our process;
- the epoxidized neutral oils are of particular importance in crankcase formulations for modern vehicles, due to the ability of the epoxide materials to react with acidic bodies formed by oxidation of the neutral oil during normal and severe use and to neutralize them.
- epoxide groups in the epoxidized oils are not only more compatible than externally produced epoxides and less likely to precipitate from the neutral base oil, while producing no untoward reactions in the oil nor masking valuable characteristics of the base oil, but saidepoxides also are in themselves oiliness agents and antacids, tending to keep the oil non-corrosive and thereby prolonging the service life of the oil and the engines. Engines in contact with the epoxidized neutrals are kept free from rust over longer periods of time.”
- the neutral oil containing the epoxidized unsaturated lubricating oil components maybe subjected to further treatment designed to react the epoxides in a manner well-known in the prior art, that is, by conventional reaction of an epoxide with one or more selected substances containing chemically active hydrogen atoms, such as a mercaptan, a primary or secondary amine, an alkylolamine, an organic acid or anhydride, particularly a dithiophosphoric acid such as dioctylthiophosphoric acid, a mono-, dior polyhydric phenol or thiophenol or'enol.
- chemically active hydrogen atoms such as a mercaptan, a primary or secondary amine, an alkylolamine, an organic acid or anhydride, particularly a dithiophosphoric acid such as dioctylthiophosphoric acid, a mono-, dior polyhydric phenol or thiophenol or'enol.
- the neutral oil containing the epoxides may be reacted with a suflicientamount of mercaptan to convert all or some of the epoxides present into mercaptan-epoxide derivatives, suchas substituted hydroxy sulfides.
- Mercaptans are organic compounds containing the radical SH.
- Suitable non-limiting examples of mercaptans efiective in our process are alkanethiols such as ethane-, methane, or decanethiol and benzyl mercaptan, dithiols such as 1,2-ethanedithiol, hydroxy thiols such as 2-mercapto-ethanol, and various other substituted thiols such as Z-dibutylamino ethanethiol.
- the reactionbetweenthe epoxides and the mercaptans results in'the formation of oxidation-resistant materials, which in turn impart this desirable characteristic to the neutral oil in which they are dissolved.
- a 150 vis., SUS at 100 F., neutral oil containing 5% by wt. of epoxides may be treated with a theoretical excess of benzyl mercaptan in the presence of alkali, such as an aqueous sodium hydroxide solution to yield an anti-oxidant type of neutral oil.
- alkali such as an aqueous sodium hydroxide solution
- the reaction takes place at low temperature with the alkali serving as a promoter or catalyst.
- the temperature may be, for example 125-200 C. or
- reaction may be carried out at normal pressure, preferably, however, at increased pressure and temperatures higher than 200 C. if no catalyst is present.
- speed of reaction and the proportion of-components necessarily depend upon the mercaptans used and the amount and typ'of epoxides to be reacted.
- aryl alkyl amino compounds containing an hydroxyl radical are formed from epoxides and amines.
- Aliphatic amines such as fatty amines, for example, octadecylamine, octadecenylamine and hexadecylamine; lower molecular weight amines, such as propylamine, butylamine, etc.; aromatic amines, such as benzylamine; and indeed, any amine soluble in neutral oils may be utilized in our process.
- diamines such as pphenylene diamine, and ethylenediamine
- hydroxyamines such as ethanoland di-ethanolamine.
- Hydrogen cyanide or alkali cyanides such as sodium cyanide, potassium cyanide or lithium cyanide, may also be reacted with our epoxides of neutral oils to produce agents having increased lubricity.
- a suitable non-limiting example is as follows. Gaseous hydrogen cyanide is bubbled through 10 liters of an epoxidized neutral oil of 150 vis., SUS at 100 F., containing 6% epoxides, at room temperature (65 F.) and for a period sufficient to convert all epoxide groups.
- --Mono-, dior polyhydric phenols such as phenol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, quercitol and inositol among others, may be used as the reagent to produce epoxide derivatives exhibiting detergency.
- Thiophenols may also be used in place of the phenols in the reaction with the epoxides of the neutral oil;
- a suitable non-limiting example is the reaction of thiophenol in the presence of sodium or potassium hydroxide at temperatures from 150 C. to 250 C.'for 4-15 hours, with epoxides to produce a sulfurcontaining derivative in the neutral oil.
- a neutral oil formulation On completion of-the above step of conversion of epoxides to derivatives, a neutral oil formulation has been obtained which is ready for use without further necessity of refinement.
- the fortified neutral oil may be used as .a lubricant alone or be added to other mineral oil fractions; alternatively, it may have one or more property-modifying agents added to it.
- the neutral oil obtained by step two of the above process may likewise be utilized directly as a lubricating oil, or with added ingredients, or be added to other mineral oil fractions or -The following examples further illustrate formulations.
- ExampleI A bright stock obtained from the processing of Van Zandt crude oil by the steps of vacuum distillation, prob pane deasphalting, solvent extraction with phenol, and
- dewaxing with methyl ethyl ketone is utilized as the to keep the reaction at the indicated temperature.
- oil layer is then washed several times with an excessof 50% of the'initial charge of material is obtained in-theform of highly unsaturated neutral oil.
- a 20 gram sample of the oil. is reserved for testing as indicated below.
- the free organic acid developed during the aging test is negligible compared to that of 21 sample of ordinary neutral tested under the. same conditions but containing no epoxides.
- Example II tral oil obtained by the first step ofExample I.
- the neutral oil exhibits no incompatibility with the epoxides and/or epoxide derivatives formed in situ and may possess increased detergency, oxidation stability, anti-corrosion, anti-wear, lubricity, and other properties or combinations of properties, depending upon the particular epoxy compounds or derivatives thereof formed and upon the number and particular conditions involved in the steps of the process.
- neutral oil which has not been derived from step 1 of our process is treated, that is, when neutral oil not containing substantial amounts of unsaturated constituents is used, as in Example II, the desired results are not obtained.
Description
2,948,669 Patented Aug. 95196.0
rnouUcrroN or SUPERIOR NEUTRAL ons Nathaniel L. Remes, Elgin, and George W. Ayers, Chicago, Ill., assignors to The Pure Oil Company, Chicago, 11]., a corporation of Ohio No Drawin Filed Nov. 17, 1955, Ser. No. 547,547
' 16 Claims 01. 208-7 The present invention relates to .the production of neutral oils possessing superior qualities. More particularly, our invention relates to the production of neutral oils from heavier lubricating oil fractions and to the in situ production of epoxides and epoxide derivatives therein.
It has been found that. requirements of motors, whetherautomotive, such as trucks, automobiles and the like, or of the fixed-machine'type, such as factory machinery, etc., are such that unfortified lubricating oil fractions are generally unsatisfactory for use. It is known that certain desirable properties, such as antioxidation, anti-corrosion, anti-wear and detergency characteristics may be imparted to lubricating oil fractions by the addition thereto of selected additives. Thus, for example, sulfonates or naphthenates may be added for detergency, and sulfurized, phosphorized or sufurizedphosphorized fatty oils may be added for increased wear and load-bearing characteristics. In many cases, the additives are quite different in chemical structure from the component molecules making up the body of the lubricating oils. Such differences in chemical properties as well as physical properties between the additive and thelubricating oil fraction may create difficulties such as poor compatibility of the additive with the oil, or a shorter period of usefulness of theflblend .in the .motor than would be expected. The additive ,alsomayact to depress or decrease a desired characteristic present in the oil before addition of the additive. Such a circumstance may require a second additive to restore the lost or diminished desirable property. Moreover, additive components of dissimilar structure from the lubricating oil frequently may be easily removed from solution, that is, they may precipitate and form sludge at high temperatures or on long continued use at normal temperatures. Moreover, such additives not infrequently have been found to undergo decomposition more rapidly than the natural components of the lubricating oil and to break down into engine-fouling, degradation products. These degradation products may seriously interfere with the oiliness or anti-wear characteristics of the lubricating oil, and also may promote or catalyze deterioration, break-down and polymerization of other components of the formulation. If the functional group responsibe for the special properties were part of a naturally occurring lubricating oil molecule, breakdown of the agent would be decreased. Moreover,-many more functional groups would be available for use than'are presently available in additives due to difliculties with instability and/ or insolubility in lubricating oil fractions. Thus, enhanced compatibility and longer service life would result if the functional groups were attached to lubricatingoil molecules rather than to a separately prepared agent. 4
Neutral oils have recently become more extensively utilized I in motor oil formulations, with consequently decreased'application of vbright stock fractions. Therefore, an oversupply of bright stock fractions is to be expected in the future unlesslotherjuses for such jfrac tions can befound.
We have unexpectedly discovered ahproces sffofthe,
utilization of heavier lubricating oil fractions, especially bright stocks or other heavy residua, such as the vacuum residuum obtained in the manufacture of lubricating oil fractions, for the production of neutral oils possessinginsitu-formed additives which enhance the anti-oxidation, anti-corrosion, anti-wear, lubricity, orgdetergency char acteristics of the neutral oil fractions.
Accordingly, it is an object of our oil fractions. m
It is another object of our invention to provide a process for'the preparation in situ of lubricating oil additives of increased compatibility with lubricating oil fractions. 7
It is another object of this invention to provide superior neutral oils fortified with in-situ-prepared lubricating oil additives in a simple, inexpensive process.
It is still another object of our invention to provide for the conversion of heavy lubricating oil fractions into neutral oils of superior properties without removal of olefins so produced. e p
It is still another object of our invention to provide for the preparation of superior neutrol oils having epoxides and/or epoxide reaction products formed in situ in aninexpensive, simple manner from lubricating oil component molecules.
In general, therefore, our invention lies in the con a primary or secondary amine, an alkanol amine, an'
organic acid (or acid anhydride) such as a thio-acid, a dithio-acid, a sulfonic or polysulfonic acid, or a mono-, di-' ior 'polyhydric phenol, thiophenol, or enol, among other reactive compounds. I
A particular pointof novelty in our invention lies in the unique utilization of olefins formed during the cracking step of our process as basic material for the preparation of desirable lubricating oil agents, thus eliminating the tedious and expensive procedure of separating the olefins from the solution before utilizing the oil pro duced during the cracking operation. The olefins themselves are generally recognized as deleterious to the performance of lubricating oil fractions, since they tend to promote corrosion and sludge formation, and therefore shouldberemoved from neutrals prepared by cracking heavier oil fractions. Since neutrals prepared from residua are more expensive than those initially obtained by vacuum distillation due to the olefin separation step, this method of preparing neutrals is not commercially utilized. r
vNeutral oil is ordinarily obtained from crude oil by subjecting topped crude to the steps of vacuum distillation,'followed by solvent refining, solvent dewaxing and clay contacting. The vacuum distillation divides the oil pane or other suitable solvent, and to solvent refining with phenol, followed by solvent dewaxing and a subse- V invention to vide a process for the preparation of superior neutral quent clay contacting operation. Residuum before the solvent refining step may be utilized as the feed 011 In our process. Alternatively, finished bright stock used for blending various oil fractions and consisting of a heavy viscous residual oil with a reddish color, or unfinished bright stock not subjected to solvent dewaxing to remove microcrystalline wax fractions, and/or clay treating, may be utilized as the feed in our process. The solvent dewaxing step may employ any one or more of a number of suitable solvents, or solvent mixtures, or solvent and anti-solvent mixtures, e.g., a mixture of methyl ethyl ketone and toluene in a ratio of solvent mixture to oil of 1:1 to 4:1, depending on the nature and viscosity of the charge material. The bright stock obtained varies in viscosity and other properties according to the type of crude oil and the number, type and sequence of refining steps to which it has been subjected. Preferably, the oil fraction utilized as the starting material in the process of our invention is residuum or cylinder stock such as vacuum residuum from the initial treating step of the crude oil, since it has a lower initial cost than finished bright stock. Any crude oil may be utilized as the starting material for the vacuum distillation, or any other type of distillation which separates the neutral oil fractions and other fractions from the heavier, less volatile, residual lubricating oil fraction. The crude oil, for example, may be Mid-Continent, Pacific Coast, Gulf Coast, Pennsylvania or other type of crude oil which has been subjected to the necessary separation of neutral oils from residuum by appropriate distillation or other methods.
As the first step in the process of our invention, the bright stock or heavy lubricating oil fraction, such as vacuum residuum, is subjected to a mild cracking operation and simultaneous distillation under moderately elevated temperature and decreased pressure. A cracked product is obtained comprising a neutral oil having as much as 50% olefins. Neutral oils may be defined as distillate lubricating oils with viscosities usually not above 200 sec. at 100 F. The degree of unsaturation in the neutral oil produced in our process depends upon the specific conditions of cracking and the characteristics of the feed oil. The cracking is carried out at a relatively low temperature to reduce the severity of degradation of the oil components. Thus, conditions. are milder than utilized for the preparation of, for example, gasoline from heavy residuum. The temperature is correlated with the reduced pressure of the system. Thus, temperatures of approximately 300 to 600 F. may be utilized with pressures of 2 mm. Hg to 25 mm. Hg Where bright stocks of average viscosity of 150-160 are utilized as the feedoils. Thus, as a non-limiting example of this step of our invention, a bright stock obtained from the processing of a Van Zandt crude oil and having a viscosity of 150 SUS at 210 F. was slowly distilled at 1-4 mm. of mercury pressure and 350 F. to give a 50% yield of an unsaturated neutral oil having a bromine number of 25, an average molecular wt. of 390 and a viscosity of 45.2 SUS at 210 F. Sometimes it may be desirable to dewax the product.
This step may also be carried out by careful steam distillation in the manner set forth in Wagner 'et a1. Patent No. 2,155,745. The neutral type of oil prepared by this step exhibits a viscosity of about 65 to 350 SUS at 100 F. j
After the neutral oil has been prepared in accordance with the procedure above, and olefins are present in substantial amount in the oil fraction, the unsaturated hydrocarbons in the neutral oil are converted to epoxides in the second step of our process. The unsaturated hydrocarbons .may be low or high molecular weight olefins, diolefins or other-compounds of petroleum origin containing one or more unsaturated bonds. These are compatiblewith the neutral oil so produced, since they are de- ,4, rived from the components initially present in the feed oil.
The epoxide structure 0.. is introduced into the oil according to the following generic equation:
R- =CHi-l-[0l- Ha I'l R wherein R and R denote the hydrocarbon radicals normally found in the oil.
The epoxidation procedure may be carried out by any known method. Thus, epoxidation may be carried out with peroxyacids such as peracetic or perbenzoic acids, with inorganic peroxides such as hydrogen peroxides or barium peroxide, by air oxidation with or without a suitable catalyst, or by hypohalogenation followed by dehydrohalogenation. With peracids such as peracetic or perbenzoic acids, the epoxidation reaction may be carried out batchwise in the presence of a suitable buflfering agent at temperatures ranging from room temperature to 40 0., according to the method disclosed in US. Patent 2,411,762, November 26, 1946. The extent of reaction is determined either by titration of aliquots of the solution for epoxy oxygen according to the method of Sworn et a1. (Anal. Chem. 19, 414 (1947)), or from analyses for residual peroxyacid (DAns and Frey, Ber. 45, 1845 (1912); Z. anorg. Chem. 84, 145 (1913)).
Alternately, the epoxidation may be carried out either batchwise or as a continuous process by first generating the peroxyacid in situ from a mixture of hydrogen peroxide and acetic acid in the presence of an acid ionexchange resin, then proceeding as above.
Thus, a mixture of the unsaturated neutral oil obtained from the cracking operation, hydrogen peroxide in concentrations ranging from 50% to and glacial acetic acid is passed through an ion-exchange resin of the sulfonated type, and recirculated until the desired epoxide content (as determined by titration) is obtained.
The amount of peracetic acid or other peracid or peroxide utilized may vary widely, depending upon the extent of epoxidation desired and upon the quantity of unsaturated hydrocarbons present per unit volume of the neutral oil. The epoxidation ordinarily may be accomplished without resort to greatly increased temperature and/or pressure. A typical epoxidation reaction involves the epoxidation of the unsaturated neutral with a mixture of sodium acetate and peracetic acid at room temperature and ordinary pressure. The oil layer, after the reaction, contains a considerable proportion of epoxides. Optionally, it may be subjected to washing with water and dilution with hexane, washing with sodium bicarbonate solution to a neutral reaction with litmus paper, followed by washing with sodium chloride solution, drying, and removal of the hexane by distillation. The epoxide may be concentrated by extraction. Yields of 40% epoxides or more, based on the amount of unsaturated compounds present in the cracked neutral oil charged to this epoxidation step, can be obtained.
'An alternate but equally suitable method for the production of the epoxides in situ in the cracked neutral lubricating oil fraction obtained by step one comprises hypochlorination of the unsaturates in the oil followed by dehydrochlorination. Thus, for example, the unsaturated neutral oil may be stirred with an aqueous solution of hypochlorous acid and the product then treated with strong aqueous caustic alkali solution or other strong base. The quantities of reactants may vary widely.
A further method of treatment to produce epoxides is the reaction of the neutral oil containing the unsaturates with a stream of air or oxygen under atmospheric or superatmospherie pressures, while keeping the reaction mixture in a neutral or slightly alkaline condition. Thus, a nonlimiting example of this method comprises reacting the neutral oil at 10-20 atm., 100-150 C., and a pH of 8.0 with air. Magnesium oxide or sodium carbonate, etc. may be present as base catalyst. Other methods of preparing epoxides from olefins as are known in the prior art and which will operate successfully in a neutral oil medium without'deleteriously affecting the medium may be utilized in the second step of this process of our invention. The particular operating conditions of each epoxidation procedure vary with the characteristics of the charge material, the reactants and other factors, including the yield of epoxides desired.
The epoxidized neutral oil components so prepared from the compatible olefins present in the neutral oil have desirable oiliness and acidity reduction characteristics which enhance the quality of the neutral oil. Thus, even if the third step of the process, namely conversion of the epoxides to selected highly effective derivatives is not practiced, neutral oil of substantially improved lubricating and acid-reduction properties may be produced by the combined procedure of steps 1 and 2 of our process; The epoxidized neutral oils are of particular importance in crankcase formulations for modern vehicles, due to the ability of the epoxide materials to react with acidic bodies formed by oxidation of the neutral oil during normal and severe use and to neutralize them. Thus, epoxide groups in the epoxidized oils are not only more compatible than externally produced epoxides and less likely to precipitate from the neutral base oil, while producing no untoward reactions in the oil nor masking valuable characteristics of the base oil, but saidepoxides also are in themselves oiliness agents and antacids, tending to keep the oil non-corrosive and thereby prolonging the service life of the oil and the engines. Engines in contact with the epoxidized neutrals are kept free from rust over longer periods of time."
As a third step in our invention, the neutral oil containing the epoxidized unsaturated lubricating oil components maybe subjected to further treatment designed to react the epoxides in a manner well-known in the prior art, that is, by conventional reaction of an epoxide with one or more selected substances containing chemically active hydrogen atoms, such as a mercaptan, a primary or secondary amine, an alkylolamine, an organic acid or anhydride, particularly a dithiophosphoric acid such as dioctylthiophosphoric acid, a mono-, dior polyhydric phenol or thiophenol or'enol. Ordinarily, greatly increased temperatures and/or pressures are unnecessary in order to bring about the desired in situ prep aration of the epoxide derivatives. Thus, for example, the neutral oil containing the epoxides may be reacted with a suflicientamount of mercaptan to convert all or some of the epoxides present into mercaptan-epoxide derivatives, suchas substituted hydroxy sulfides.
Mercaptans are organic compounds containing the radical SH. Suitable non-limiting examples of mercaptans efiective in our process are alkanethiols such as ethane-, methane, or decanethiol and benzyl mercaptan, dithiols such as 1,2-ethanedithiol, hydroxy thiols such as 2-mercapto-ethanol, and various other substituted thiols such as Z-dibutylamino ethanethiol. The reactionbetweenthe epoxides and the mercaptans results in'the formation of oxidation-resistant materials, which in turn impart this desirable characteristic to the neutral oil in which they are dissolved. As a non-limiting example of the third step of our process, a 150 vis., SUS at 100 F., neutral oil containing 5% by wt. of epoxides may be treated with a theoretical excess of benzyl mercaptan in the presence of alkali, such as an aqueous sodium hydroxide solution to yield an anti-oxidant type of neutral oil. The reaction takes place at low temperature with the alkali serving as a promoter or catalyst. Thus, the temperature may be, for example 125-200 C. or
lower. Other catalyst and promoter compounds are also available, and the reaction may be carried out at normal pressure, preferably, however, at increased pressure and temperatures higher than 200 C. if no catalyst is present. The speed of reaction and the proportion of-components necessarily depend upon the mercaptans used and the amount and typ'of epoxides to be reacted.
Reaction of amines with the epoxidized neutral under known reaction conditions as a third step in our process produces neutral oil which possesses detergency, anti-rust properties and reserve alkalinity to combat acidic bodies formed during the use of the oil in internal combustion engines under normal and severe operating conditions. Corrosion and wear are thereby materially decreased. Thus, for example, aromatic diamines and epoxy compounds may be reacted to produce anti-oxidants -in a manner set forth in U.S. 2,576,448 (E. F. Hill and H. Baldwin, November 27, 1951). Another method for the preparation of amines is set forth in U.S. 2,325,533 (I. B. Montgomery et al., July 27, 1943), in which aryl alkyl amino compounds containing an hydroxyl radical are formed from epoxides and amines. Aliphatic amines, such as fatty amines, for example, octadecylamine, octadecenylamine and hexadecylamine; lower molecular weight amines, such as propylamine, butylamine, etc.; aromatic amines, such as benzylamine; and indeed, any amine soluble in neutral oils may be utilized in our process. Other suitable examples are diamines, such as pphenylene diamine, and ethylenediamine; and hydroxyamines, such as ethanoland di-ethanolamine.
Hydrogen cyanide or alkali cyanides, such as sodium cyanide, potassium cyanide or lithium cyanide, may also be reacted with our epoxides of neutral oils to produce agents having increased lubricity. A suitable non-limiting example is as follows. Gaseous hydrogen cyanide is bubbled through 10 liters of an epoxidized neutral oil of 150 vis., SUS at 100 F., containing 6% epoxides, at room temperature (65 F.) and for a period sufficient to convert all epoxide groups.
--Mono-, dior polyhydric phenols, such as phenol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, quercitol and inositol among others, may be used as the reagent to produce epoxide derivatives exhibiting detergency. Thiophenols may also be used in place of the phenols in the reaction with the epoxides of the neutral oil; A suitable non-limiting example is the reaction of thiophenol in the presence of sodium or potassium hydroxide at temperatures from 150 C. to 250 C.'for 4-15 hours, with epoxides to produce a sulfurcontaining derivative in the neutral oil.
On completion of-the above step of conversion of epoxides to derivatives, a neutral oil formulation has been obtained which is ready for use without further necessity of refinement. The fortified neutral oil may be used as .a lubricant alone or be added to other mineral oil fractions; alternatively, it may have one or more property-modifying agents added to it. The neutral oil obtained by step two of the above process may likewise be utilized directly as a lubricating oil, or with added ingredients, or be added to other mineral oil fractions or -The following examples further illustrate formulations.
our invention:
" ExampleI A bright stock obtained from the processing of Van Zandt crude oil by the steps of vacuum distillation, prob pane deasphalting, solvent extraction with phenol, and
dewaxing with methyl ethyl ketone, is utilized as the to keep the reaction at the indicated temperature. oil layer is then washed several times with an excessof 50% of the'initial charge of material is obtained in-theform of highly unsaturated neutral oil. A 20 gram sample of the oil. is reserved for testing as indicated below.
The remainden'approximately 100 grams, of the unsaturated neutral oil is then subjected to admixture in an open kettle with 1.5-grams of commercial grade of sodium acetate and 38 grams of 40% peracetic acid in water. The mixture is stirred mechanically for a period of 7.6
versed in the art are contemplated as within the purview of our invention.- I
.We claim and particularly point out. as ourinvention:
l The process of preparing neutral lubricating oil comprising lightly cracking residual petroleum oil having. a viscosity higher than that of neutral oil under conditions I toconvert it to distillate oil having a viscosity correhrs. at 87 F., external cooling being applied in order The water, diluted with an equal amount of hexane, washed with an excess of sodium bicarbonate solution until new tral to litmus paper, washed with saturated sodium chloride solution, and dried. The hexaneis removed by distillation and. the yield'of epoxides in the neutral oil,
based on the oxirane number and the bromine number of the unsaturated neutral, is 40%.
The epoxidized oil-is agedat 250-F. for 60 hours in the presence of air. The free organic acid developed during the aging test is negligible compared to that of 21 sample of ordinary neutral tested under the. same conditions but containing no epoxides.
' Example II tral oil obtained by the first step ofExample I.
to the process as defined in the second step of Example I;
. It is found that the neutral oil contains no epoxide. This result is obtained since no appreciable amount ofunsaturates, principally olefins, are present in the feed neutral oil. Therefore, the treatment according to the second step does not yield epoxides unless the first step has been carried out. I I I It is seen from the above that the process of our invention results in the" preparation of .a superior neutral oil of any desired viscosity from heavier lubricating oil fractions, including residuum or cylinder stock or bright stock. The finished oil may be used alone as a lubricating oil or may have various additives added thereto, or may in turn be added to lubricating oil formulations. The neutral oil exhibits no incompatibility with the epoxides and/or epoxide derivatives formed in situ and may possess increased detergency, oxidation stability, anti-corrosion, anti-wear, lubricity, and other properties or combinations of properties, depending upon the particular epoxy compounds or derivatives thereof formed and upon the number and particular conditions involved in the steps of the process. As seen from the example above, when neutral oil which has not been derived from step 1 of our process is treated, that is, when neutral oil not containing substantial amounts of unsaturated constituents is used, as in Example II, the desired results are not obtained. Our process is not only adaptable to the preparation of a Wide range of fortified neutral oils of various enhanced propcrties, but also has the advantages of simplicity and the utilization of a plentiful feed, that is, heavy Such modifications of our process, manipulative procedures and equipment as are within the skill of those amount of epoxides in situ.
sponding to that of neutral oil containing a substantial amount of unsaturated hydrocarbonaand epoxidizing said converted oil under conditions to form a substantial 2. Process in accordance with claim 1 in which. said unsaturated hydrocarbonsare epoxidized by means of a peroxy acid in the presence of a bufferingagent at a temperature between room temperature and 40 C.
3.. Process in accordance with claim 2 in which the, 'peroxy acidis peracetic acid and the buffering agent is sodium acetate.
4. Process in accordance with claim, 1 in which the resulting product isreacted with a mercaptan.
5. The process of claim 1 in which said, residual petro leum oil is selected from thegroup consisting of bright stock, cylinder stock and residua remaining on separation of neutral lubricating oil fractions and lighter hydrow carbon fractions from crude oil.
I .6, The process of claiml in which the epoxy groups of said epoxidized neutral oil are further reacted'withav compound containing a chemicallyactive hydrogen atom to'form a product which further enhances the lubricating qualities of said epoxidized oil. I 7.. The process of. claim 6 in which said compound is arnercaptan.
8. The process of claim 7 in which said mercaptan is benzyl mercaptan.
1 9. The process of claim 7 in which said. mercaptan is methanethiol. e
selected from the group consisting of primary amines, 1 secondary amines and alkylolamines.
12. The process of a claim 11 in which said compound is stearylamine.
13. The process of claim 11 in which said compound is benzylamine.
14. Process in accordance with claim 6 in which said compound is from the group consisting of mercaptans, alkyl-, aryland alkanolamines, phenols, hydrogen cyanide, alkali metal cyanides, thiophenols and organic dithiophosphoric acids. I
- 15. The process of claim 14 in which said compound is phenol.
l6. Theprocess of claim 14 in which said compound is dioctyldithiophosphoric acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,265,948 Loder Dec. 9, 1941 2,496,508 Watson et al Feb. 7, 1950 2,552,084 Bishop et al May 8, 1951 2,660,563 Banes et al. Nov. 24, 1953 FOREIGN PATENTS 660,110 Great Britain Oct. 31, 1951 735,974 Great Britain Aug. 31, 1955
Claims (1)
1. THE PROCESS OF PREPARING NEUTRAL LUBRICATING OIL COMPRISING LIGHTLY CRACKING RESIDUAL PETROLEUM OIL HAING A VISCOSITY HIGHER THAN THAT OF NEUTRAL OIL UNDER CONDITIONS TO CONVERT IT TO DISTILLATE OIL HAVING A VISCOSITY CORRESPONDING TO THAT OF NEUTRAL OIL CONTAINING A SUBSTANTIAL AMOUNT OF UNSATURATED HYDROCARBONS, AND EPOXIDIZING SAID CONVERTED OIL UNDER CONDITIONS TO FORM A SUBSTANTIAL AMOUNT OF EPOXIDES IN SITU.
Publications (1)
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US2948669A true US2948669A (en) | 1960-08-09 |
Family
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US2948669D Expired - Lifetime US2948669A (en) | Production of superior neutral oils |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3425814A (en) * | 1963-05-03 | 1969-02-04 | Exxon Research Engineering Co | Stabilized oil |
US20080293913A1 (en) * | 2007-05-22 | 2008-11-27 | Malaysian Palm Oil Board | Process to produce polyols |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2265948A (en) * | 1939-08-02 | 1941-12-09 | Du Pont | Catalytic oxidation of lower aliphatic hydrocarbons |
US2496508A (en) * | 1946-06-26 | 1950-02-07 | Standard Oil Co | Stabilized organic sulfur-containing compounds |
US2552084A (en) * | 1946-09-21 | 1951-05-08 | Gen Motors Corp | Working fluid for a compression refrigeration system |
GB660110A (en) * | 1947-10-24 | 1951-10-31 | James George Fife | Improvements in or relating to the preparation of lubricants and compositions containing the same |
US2660563A (en) * | 1949-07-28 | 1953-11-24 | Standard Oil Dev Co | Mineral oil containing substituted polyolefins |
GB735974A (en) * | 1952-08-07 | 1955-08-31 | Union Carbide & Carbon Corp | Improvements in the epoxidation of ethylenically unsaturated organic compounds |
-
0
- US US2948669D patent/US2948669A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2265948A (en) * | 1939-08-02 | 1941-12-09 | Du Pont | Catalytic oxidation of lower aliphatic hydrocarbons |
US2496508A (en) * | 1946-06-26 | 1950-02-07 | Standard Oil Co | Stabilized organic sulfur-containing compounds |
US2552084A (en) * | 1946-09-21 | 1951-05-08 | Gen Motors Corp | Working fluid for a compression refrigeration system |
GB660110A (en) * | 1947-10-24 | 1951-10-31 | James George Fife | Improvements in or relating to the preparation of lubricants and compositions containing the same |
US2660563A (en) * | 1949-07-28 | 1953-11-24 | Standard Oil Dev Co | Mineral oil containing substituted polyolefins |
GB735974A (en) * | 1952-08-07 | 1955-08-31 | Union Carbide & Carbon Corp | Improvements in the epoxidation of ethylenically unsaturated organic compounds |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3425814A (en) * | 1963-05-03 | 1969-02-04 | Exxon Research Engineering Co | Stabilized oil |
US20080293913A1 (en) * | 2007-05-22 | 2008-11-27 | Malaysian Palm Oil Board | Process to produce polyols |
US7932409B2 (en) * | 2007-05-22 | 2011-04-26 | Malaysian Palm Oil Board | Process to produce polyols |
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