US2170665A - Voltolized oils and products - Google Patents
Voltolized oils and products Download PDFInfo
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- US2170665A US2170665A US2170665DA US2170665A US 2170665 A US2170665 A US 2170665A US 2170665D A US2170665D A US 2170665DA US 2170665 A US2170665 A US 2170665A
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- oils
- oil
- products
- voltolized
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- Expired - Lifetime
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- 239000003921 oil Substances 0.000 title description 104
- 235000019198 oils Nutrition 0.000 description 102
- 239000000203 mixture Substances 0.000 description 52
- 239000000047 product Substances 0.000 description 32
- 239000007788 liquid Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 28
- 239000004164 Wax ester Substances 0.000 description 22
- 235000019386 wax ester Nutrition 0.000 description 22
- 239000010687 lubricating oil Substances 0.000 description 16
- 239000001993 wax Substances 0.000 description 16
- 239000004215 Carbon black (E152) Substances 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- -1 aliphatic alcohols Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 235000019484 Rapeseed oil Nutrition 0.000 description 8
- 239000010775 animal oil Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 6
- 235000015110 jellies Nutrition 0.000 description 6
- 239000008274 jelly Substances 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 230000001050 lubricating Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K Aluminium chloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N Carbon tetrachloride Chemical group ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000010700 blended lubricating oil Substances 0.000 description 4
- 125000004432 carbon atoms Chemical group C* 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229910052570 clay Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 241000283153 Cetacea Species 0.000 description 2
- 230000037250 Clearance Effects 0.000 description 2
- 241001481833 Coryphaena hippurus Species 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- CCGKOQOJPYTBIH-UHFFFAOYSA-N Ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 2
- 229940013317 Fish Oils Drugs 0.000 description 2
- 210000001847 Jaw Anatomy 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- 239000004264 Petrolatum Substances 0.000 description 2
- 229940066842 Petrolatum Drugs 0.000 description 2
- 210000000681 Sperm Head Anatomy 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 230000000274 adsorptive Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 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
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229940074979 cetyl palmitate Drugs 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000035512 clearance Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010908 decantation Methods 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
- 230000001627 detrimental Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010685 fatty oil Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003027 oil sand Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- PXDJXZJSCPSGGI-UHFFFAOYSA-N palmityl palmitate Chemical compound CCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC PXDJXZJSCPSGGI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003415 peat Substances 0.000 description 2
- 235000019271 petrolatum Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000003079 shale oil Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229940084106 spermaceti Drugs 0.000 description 2
- 239000012177 spermaceti Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
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
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- 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
- C10M101/04—Fatty oil fractions
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/401—Fatty vegetable or animal oils used as base material
-
- 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
- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
-
- 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
- This invention relates to the production of valuable materials by subjecting unsaturated oils and liquid waxes, especially from marine animal oils, such as sperm oil, tothe action of silent 5 electric discharge, and to improved lubricating compositions containing such materials.
- the materials which it is preferred to use according to the present invention comprise the normally liquid waxes, and oils, such as cerv tain marine animal oils, which contain substantial amounts thereof, and other oils of similar characteristics.
- oils such as cerv tain marine animal oils, which contain substantial amounts thereof, and other oils of similar characteristics.
- Unsaturated and saturated esters in which either the acid or the alcohol group or preferably both contain more than 8 and up to 20 carbon atoms per molecule thus constitute preferred liquid wax esters to be polymerized by the action of silent electric discharge.
- oils 25 and liquid wax esters may be obtained naturally or may be prepared synthetically by any suitable means.
- they may be prepared by a limited oxidation of high molecular weight parafllnic oils and waxes such as highly parafllnic 3o viscous petroleum oils, petrolatum and parafline wax.
- Some unsaturated esters are formed directly by such oxidation and others may be formed by suitably esterifylng the acids and alcohols in the reaction product or after separation therefrom.
- the preferred oils for use'according to the present invention are the sperm oils.
- the crude sperm oil may be used directly as obtained or after separation into any desirable fractions by fractional distillation, solvent extraction, precipitation or other methods adapted to separate the oil into fractions of relatively highly and lower melting point or volatility or degree of saturation'or molecular weight or other specified characteristics.
- the'sperm head, oil and sperm body oil may be treated according to the present invention either separately or mixed in any desired proportions.
- Spermacetic which consist largely of cetyl palmitate and closely related esters of higher fatty saturated and unsatm atedalcohols such as octadecyl and eicosyl alcohols' and of lower fatty acids, such as capric, lauric, *palmitolelc, myristic, oleic, and stearlc acids, in smaller amounts, may be separated from the oil to any desired extent and the completely Such oils include some unsatuor partially dewaxed oil and the wax fractions may be treated according to the present invention.
- Other marine animal oils of this general class are dolphin oil and porpoise jaw oil which are mentioned merely. by way of example and 5 not in limitation of this invention.
- the process of voltolization consists in subjecting the material to the action of high tension silent electric discharges, preferably of an alternating current.
- the treatment is generally carried out under vacuum.
- the pressure may be varied from .001 mm. to .01 atmosphere, .1 atmosphere, .5 atmosphere, or even as high as .8 atmosphere.
- the voltage used is preferably in the range of 4,000 to 10,000 volts, although higher voltages such as 20,000 or even 50,000 volts may be used, especially when good dielectrics are available.
- the frequency of the alternating current may be as low as 60 cycles and as high as 1200, 3000, 10,000 or more cycles.
- the temperature during the treatment with silent electric discharges is maintained at about roomtemperature or substantially thereabove.
- the heat liberated in thereaction zone is frequently sufflcient to raise the temperature of the mixture to 100, 200 or even 300 C., so that it is necessary to use some cooling means when high temperatures are undesirable or detrimental. It is usual to provide some external means for either heating or cooling the reaction chamber in which the voltolization is carried out.
- the apparatus used in the present process may be of the usual type of tube or trommel design.
- the tube type of apparatus comprises a vertical tube preferably constructed of a di- I electric material such as glass coated on the outside with a conductor electrode, a central electrode disposed in the center of this tube, provision being made for a high tension silent discharge between the electrodes.
- the trommel type of apparatus comprises a series of insulated plates placed a few millimeters apart and mounted on a rotatable shaft, the entire shaft with its plates being disposed within a horizontal drum maintained approximately half full of the material to be voltolized.
- the bottom portions of the plates dip into the material to be voltoliz'ed, and as the shaft rotates the material drips down over the surface of the plates forming a thin film thereon.
- the high tension silent discharge occurs between the plates.
- it is generally preferred to operate at a pressure below about 20 cm. of mercury and preferably at about 2 to 10 cm., and an electrode potential of about 1000 to 10,000 volts or more at a frequency of about 500 to 10,000 cycles or more per second.
- oils and waxes may be voltolized according to the present invention in the pure, commercial or crude state or after being purified by treatment with adsorptive clay or other refining agents, solvent extraction, refrigeration in sol- 'vent solution followed by decantation or filtration, or in combination with other materials of the types mentioned above or in combination with petroleum, mineral oils, waxes, shale oils, fish oils, animal oils, vegetable oils, or derivatives thereof.
- the materials may also be first partially voltolized and then blended with the other materials indicated above.
- the voltolization treatment may also be carried out in the presence of gases such as hydrogen, nitrogen, carbon monoxide, carbon dioxide, oxygen, air, and the like. It may also be conducted in the presence of sulfur, halogens, selenium, hydrogen sulfide, oxygen, phosphorus, boron fiuoride, ketene, and the like.
- the products obtained by voltolization of these materials according to the method described will be found to contain materials having molecular weights ranging from 400 to 1500, 5000, 10,000 or higher. These products may be subjected to hydrogenation, heat treatment with reagents such as aluminum chloride, boron fluoride, sulfuric acid, alkali, and the like. They may also be treated or refined with clay, charcoal, acid, and the like. If desired, any free acidic or hydroxyl groups may be esterified or otherwise neutralized.
- Products of extremely high molecular weight may be precipitated or extracted from the voltolized product by dilution with solvents such as propane, secondary butyl alcohol, methanol, acetone, carbon tetrachloride, and the like, with or without refrigeration and/or filtration.
- solvents such as propane, secondary butyl alcohol, methanol, acetone, carbon tetrachloride, and the like, with or without refrigeration and/or filtration.
- the products obtained according to this process may be adapted to a wide variety of different uses. For example, they may be used directly as lubricants, coating compositions, plastics, resins, plasticizersand impregnating agents or they may be used as blending agents in other materials of these types.
- the amount used may vary from .01% to 1%, to 50% or even more:
- the products of this process are valuable addition agents to crude petroleum oils, partially or highly treated petroleum oils, white oils, solventextracted oils, hydrogenated oils, synthetic oils, as well as to distillation products of tars, lignites, shale, peat, and the like. They are also valuable addition agents to fatty oils, greases, lubricating oils, cable oils, insulating oils, textile oils, industrial lubricants, emulsions, naphthas, Diesel fuels and kerosenes.
- the products or this process may be employed in conjunction with materials such as oxidation inhibitors, pour inhibitors, dyes. resins, solvents, thickeners, sludge dispersers, oiliness agents, extreme pressure lubricants, soaps, glycerin, sulfur compounds and the like.
- Example 1 Sperm oil having a Saybolt viscosity of 44.5 seconds at 210 F. was subjected to treatment by silent electric discharge in a trommel type voltolizer at an absolute pressure of 2 to 4 cm. of mercury and an electric potential of 2,000 to 3,000 volts at a frequency of 10,000 cycles per second, until a product having a viscosity of 600 seconds Saybolt at 210 F. was obtained.
- Mid-Continent crude with acid was gradually added with continuing treatment in the trommel voltolizer until a volume equal to the volume of sperm oil had been added and a voltolized mixture having a viscosity of 1017 seconds at 210 F. was obtained.
- Example 2- Sperm oil was subjected-to the action of silent electric discharge in a glass tube apparatus at a pressure of two cm. of mercury and an electric potential of 7,000 volts at a frequency or 1,200 cycles per second until a product having a viscosity of 540 seconds at 210 F. was obtained. There was then added gradually, with continuing voltolization of the mixture, a petroleum lubricating oil having a viscosity of 65 seconds and obtained from Pan-handle and deep-sand Reagan crudes, until a volume equal to that of the sperm oil had been added and the voltolized mixture had a viscosity of 2087 seconds Saybolt at 210 F.
- the unsaturated liquid waxes such as sperm oil may be thickened to much higher vlscosities by voltolization without formation of jelly-like insoluble products than is possible even with the glycerides previously preferred as raw materials for voltolizetion.
- sperm oil was thickened alone by voltolization to a viscosity above 1500 seconds Saybolt at 210 F. without formation of any insoluble products or jelly, while rapeseed oil, voltolized under the same conditions, developed a content of insoluble jelly-like particles at a viscosity of only 300 seconds.
- Example 3 10 parts by volume 01 the voltolized product obtained in Example 1 was mixed with 90 parts of a petroleum lubricating oil.
- the viscosity and viscosity indices of the original lubricating oil and of the resulting blend are indicated in the following table:
- Example 3 The lubricating oil composition shown in Example 3 was subjected to test in the lubrication of a four-cycle internal combustion test engine operating at 390 F., jacket temperature, and
- a composition of matter consisting essentially of a polymerized liquid wax ester, said poly merized liquid wax ester being soluble in hydrocarbon oils and having a viscosity of at least 540 Saybolt seconds at 210 F. obtained by silent electric discharge polymerization of a liquid wax ester which occurs as an ingredient of spermaceti.
- composition of matter consisting essentially of polymerized spermacetic soluble in hydrocarbon oils and which has a viscosity of at least 540 Saybolt seconds at 210 F. obtained by a silent electric discharge polymerization of spermacetic.
- a composition of matter consisting essentially of thickened sperm oil, said thickened sperm oil being soluble in hydrocarbon oils and having a viscosity of at least 540 Saybolt seconds at 210 F. obtained by a. silent electric discharge polymerization of sperm oil.
- a composition of matter for use in an improved lubricating composition consisting essentially of polymerized liquid wax esters, said polymerized liquid wax esters being soluble in hydrocarbon oils and having viscosities in the range of 540 to 2,000 seconds Saybolt at 210 F. obtained by the action of silent electric discharges on a mixture of hydrocarbon lubricating oil and liquid wax ester components of spermacetic.
- a composition of matter consisting essentially of a polymerized liquid wax ester, said polymerized liquid wax ester being soluble in hydrocarbon oilsand having a. viscosity of at least 540 Saybolt seconds at 210 F. obtained by silent electric discharge polymerization of a liquid wax ester of a monohydric aliphatic alcohol and a monocarboxylic acid, both of which contain more than 8 and up to about 20 carbon atoms per molecule.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
Description
Patented Aug. 22, 1939 UNITED STATES OILS AND rmonuc'rs THEREOF Robert P. Russell, ShortHllls, N. 1., assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application January 31, 1936,
Serial No. 61,749
5 Claims.
This invention relates to the production of valuable materials by subjecting unsaturated oils and liquid waxes, especially from marine animal oils, such as sperm oil, tothe action of silent 5 electric discharge, and to improved lubricating compositions containing such materials.-
The materials which it is preferred to use according to the present invention comprise the normally liquid waxes, and oils, such as cerv tain marine animal oils, which contain substantial amounts thereof, and other oils of similar characteristics. rated esters of monocarboxylic acids and monohydric aliphatic alcohols in which either the acid or the alcohol group contains unsaturated ethylenic linkages. This includes oils having an iodine value between about 50 and 200, but those having iodine values between about 70 and 100 are preferred. Unsaturated and saturated esters in which either the acid or the alcohol group or preferably both contain more than 8 and up to 20 carbon atoms per molecule thus constitute preferred liquid wax esters to be polymerized by the action of silent electric discharge. Such oils 25 and liquid wax esters may be obtained naturally or may be prepared synthetically by any suitable means. For example, they may be prepared by a limited oxidation of high molecular weight parafllnic oils and waxes such as highly parafllnic 3o viscous petroleum oils, petrolatum and parafline wax. Some unsaturated esters are formed directly by such oxidation and others may be formed by suitably esterifylng the acids and alcohols in the reaction product or after separation therefrom.
The preferred oils for use'according to the present invention are the sperm oils. The crude sperm oil may be used directly as obtained or after separation into any desirable fractions by fractional distillation, solvent extraction, precipitation or other methods adapted to separate the oil into fractions of relatively highly and lower melting point or volatility or degree of saturation'or molecular weight or other specified characteristics. For example, the'sperm head, oil and sperm body oil may be treated according to the present invention either separately or mixed in any desired proportions. Spermacetic, which consist largely of cetyl palmitate and closely related esters of higher fatty saturated and unsatm atedalcohols such as octadecyl and eicosyl alcohols' and of lower fatty acids, such as capric, lauric, *palmitolelc, myristic, oleic, and stearlc acids, in smaller amounts, may be separated from the oil to any desired extent and the completely Such oils include some unsatuor partially dewaxed oil and the wax fractions may be treated according to the present invention. Other marine animal oils of this general class are dolphin oil and porpoise jaw oil which are mentioned merely. by way of example and 5 not in limitation of this invention.
The process of voltolization consists in subjecting the material to the action of high tension silent electric discharges, preferably of an alternating current. The treatment is generally carried out under vacuum. The pressure may be varied from .001 mm. to .01 atmosphere, .1 atmosphere, .5 atmosphere, or even as high as .8 atmosphere. The voltage used is preferably in the range of 4,000 to 10,000 volts, although higher voltages such as 20,000 or even 50,000 volts may be used, especially when good dielectrics are available. The frequency of the alternating current may be as low as 60 cycles and as high as 1200, 3000, 10,000 or more cycles.
In the usual voltolization processes, the temperature during the treatment with silent electric discharges is maintained at about roomtemperature or substantially thereabove. The heat liberated in thereaction zone is frequently sufflcient to raise the temperature of the mixture to 100, 200 or even 300 C., so that it is necessary to use some cooling means when high temperatures are undesirable or detrimental. It is usual to provide some external means for either heating or cooling the reaction chamber in which the voltolization is carried out.
The apparatus used in the present process may be of the usual type of tube or trommel design. The tube type of apparatus comprises a vertical tube preferably constructed of a di- I electric material such as glass coated on the outside with a conductor electrode, a central electrode disposed in the center of this tube, provision being made for a high tension silent discharge between the electrodes. The trommel type of apparatus comprises a series of insulated plates placed a few millimeters apart and mounted on a rotatable shaft, the entire shaft with its plates being disposed within a horizontal drum maintained approximately half full of the material to be voltolized. The bottom portions of the plates dip into the material to be voltoliz'ed, and as the shaft rotates the material drips down over the surface of the plates forming a thin film thereon. The high tension silent discharge occurs between the plates. In apparatus of this type, it is generally preferred to operate at a pressure below about 20 cm. of mercury and preferably at about 2 to 10 cm., and an electrode potential of about 1000 to 10,000 volts or more at a frequency of about 500 to 10,000 cycles or more per second.
The oils and waxes may be voltolized according to the present invention in the pure, commercial or crude state or after being purified by treatment with adsorptive clay or other refining agents, solvent extraction, refrigeration in sol- 'vent solution followed by decantation or filtration, or in combination with other materials of the types mentioned above or in combination with petroleum, mineral oils, waxes, shale oils, fish oils, animal oils, vegetable oils, or derivatives thereof. The materials may also be first partially voltolized and then blended with the other materials indicated above. The voltolization treatment may also be carried out in the presence of gases such as hydrogen, nitrogen, carbon monoxide, carbon dioxide, oxygen, air, and the like. It may also be conducted in the presence of sulfur, halogens, selenium, hydrogen sulfide, oxygen, phosphorus, boron fiuoride, ketene, and the like.
The products obtained by voltolization of these materials according to the method described will be found to contain materials having molecular weights ranging from 400 to 1500, 5000, 10,000 or higher. These products may be subjected to hydrogenation, heat treatment with reagents such as aluminum chloride, boron fluoride, sulfuric acid, alkali, and the like. They may also be treated or refined with clay, charcoal, acid, and the like. If desired, any free acidic or hydroxyl groups may be esterified or otherwise neutralized.
Products of extremely high molecular weight may be precipitated or extracted from the voltolized product by dilution with solvents such as propane, secondary butyl alcohol, methanol, acetone, carbon tetrachloride, and the like, with or without refrigeration and/or filtration.
The products obtained according to this process may be adapted to a wide variety of different uses. For example, they may be used directly as lubricants, coating compositions, plastics, resins, plasticizersand impregnating agents or they may be used as blending agents in other materials of these types. The amount used may vary from .01% to 1%, to 50% or even more:
The products of this process are valuable addition agents to crude petroleum oils, partially or highly treated petroleum oils, white oils, solventextracted oils, hydrogenated oils, synthetic oils, as well as to distillation products of tars, lignites, shale, peat, and the like. They are also valuable addition agents to fatty oils, greases, lubricating oils, cable oils, insulating oils, textile oils, industrial lubricants, emulsions, naphthas, Diesel fuels and kerosenes.
The products or this process may be employed in conjunction with materials such as oxidation inhibitors, pour inhibitors, dyes. resins, solvents, thickeners, sludge dispersers, oiliness agents, extreme pressure lubricants, soaps, glycerin, sulfur compounds and the like.
The following examples are presented to illustrate suitable methods for preparing improved products according to the present invention and are not to be construed as limiting this invention in any way.
Example 1 Sperm oil having a Saybolt viscosity of 44.5 seconds at 210 F. was subjected to treatment by silent electric discharge in a trommel type voltolizer at an absolute pressure of 2 to 4 cm. of mercury and an electric potential of 2,000 to 3,000 volts at a frequency of 10,000 cycles per second, until a product having a viscosity of 600 seconds Saybolt at 210 F. was obtained. A viscous petroleum lubricating oil, having a viscosity of 85 seconds Saybolt at 210 F. and prepared by refining a distillate of a. Mid-Continent crude with acid, was gradually added with continuing treatment in the trommel voltolizer until a volume equal to the volume of sperm oil had been added and a voltolized mixture having a viscosity of 1017 seconds at 210 F. was obtained.
Example 2- Sperm oil was subjected-to the action of silent electric discharge in a glass tube apparatus at a pressure of two cm. of mercury and an electric potential of 7,000 volts at a frequency or 1,200 cycles per second until a product having a viscosity of 540 seconds at 210 F. was obtained. There was then added gradually, with continuing voltolization of the mixture, a petroleum lubricating oil having a viscosity of 65 seconds and obtained from Pan-handle and deep-sand Reagan crudes, until a volume equal to that of the sperm oil had been added and the voltolized mixture had a viscosity of 2087 seconds Saybolt at 210 F.
It has been found that the unsaturated liquid waxes such as sperm oil may be thickened to much higher vlscosities by voltolization without formation of jelly-like insoluble products than is possible even with the glycerides previously preferred as raw materials for voltolizetion. For example, sperm oil was thickened alone by voltolization to a viscosity above 1500 seconds Saybolt at 210 F. without formation of any insoluble products or jelly, while rapeseed oil, voltolized under the same conditions, developed a content of insoluble jelly-like particles at a viscosity of only 300 seconds. Also, when voltolizing a mixture of sperm oil and mineral oil, no jelly was apparent in products having a viscosity above 2000 seconds, while in treating a similar mixture of rapeseed oil and mineral oil under the same conditions, jelly appeared when the mixture was thickened only to 1000 seconds. The following examples illustrate the use of the voltolized products of this invention in the preparation of blended lubricating oils.
Example 3 10 parts by volume 01 the voltolized product obtained in Example 1 was mixed with 90 parts of a petroleum lubricating oil. The viscosity and viscosity indices of the original lubricating oil and of the resulting blend are indicated in the following table:
The lubricating oil composition shown in Example 3 was subjected to test in the lubrication of a four-cycle internal combustion test engine operating at 390 F., jacket temperature, and
' with tight clearances, tor the purpose of accelerating any decomposition oi the oil and of making the lubrication of the parts more diflicult than in ordinary service. Comparative rims under carefully controlled and reproducible conditions were made with the lubricating oil-voltolized sperm oil composition shown in Example 3 and with a composition of the same lubricat- 8 oil with 10% of a voltolized rapeseed oil. A blank run was made on a hydrocarbon oil composition consisting of the same base lubricating oil used in the above compositions and thickened by the addition of 1.5% of a polymerized olefin in order to produce a blended lubricating oil having the same viscosity as that of the other two blends. At the end of each run, the engine was dismantled and the parts carefully inspected for condition, wear and carbon deposition, using a decimal system to indicate the extent of degradation. The results of the three runs are indicated in the following table, in which it will be seen that the voltolized sperm oil composition was far superior to the mineral oil in every respect. It was also superior to the voltolized rapeseed oil blend in that the condition of the pistons was substantially better and that no rings were stuck in the run with sperm oil, while two rings were stuck for a total range of The present invention is not to be limited by any explanations or examples all of which have been presented above solely for purpose of illustration, but is limited only by the following claims in which it is desired to claim all novelty insofar as the prior art permits.
I claim:
1. A composition of matter consisting essentially of a polymerized liquid wax ester, said poly merized liquid wax ester being soluble in hydrocarbon oils and having a viscosity of at least 540 Saybolt seconds at 210 F. obtained by silent electric discharge polymerization of a liquid wax ester which occurs as an ingredient of spermaceti.
2. A composition of matter consisting essentially of polymerized spermacetic soluble in hydrocarbon oils and which has a viscosity of at least 540 Saybolt seconds at 210 F. obtained by a silent electric discharge polymerization of spermacetic.
3. A composition of matter consisting essentially of thickened sperm oil, said thickened sperm oil being soluble in hydrocarbon oils and having a viscosity of at least 540 Saybolt seconds at 210 F. obtained by a. silent electric discharge polymerization of sperm oil.
4. A composition of matter for use in an improved lubricating composition consisting essentially of polymerized liquid wax esters, said polymerized liquid wax esters being soluble in hydrocarbon oils and having viscosities in the range of 540 to 2,000 seconds Saybolt at 210 F. obtained by the action of silent electric discharges on a mixture of hydrocarbon lubricating oil and liquid wax ester components of spermacetic.
5. A composition of matter consisting essentially of a polymerized liquid wax ester, said polymerized liquid wax ester being soluble in hydrocarbon oilsand having a. viscosity of at least 540 Saybolt seconds at 210 F. obtained by silent electric discharge polymerization of a liquid wax ester of a monohydric aliphatic alcohol and a monocarboxylic acid, both of which contain more than 8 and up to about 20 carbon atoms per molecule.
ROBERT P. RUSSELL.
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US2170665A true US2170665A (en) | 1939-08-22 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417850A (en) * | 1942-04-14 | 1947-03-25 | Willis M Winslow | Method and means for translating electrical impulses into mechanical force |
US2516733A (en) * | 1947-12-05 | 1950-07-25 | Henry M Unschuld | Soybean oil refining process |
US3100185A (en) * | 1959-12-28 | 1963-08-06 | Gulf Research Development Co | Process of improving the wear properties of a mineral and fatty oil lubricant mixture by radiation |
US3356602A (en) * | 1965-03-26 | 1967-12-05 | Gen Electric | Process of dimerizing carboxylic acids in a corona discharge |
-
0
- US US2170665D patent/US2170665A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417850A (en) * | 1942-04-14 | 1947-03-25 | Willis M Winslow | Method and means for translating electrical impulses into mechanical force |
US2516733A (en) * | 1947-12-05 | 1950-07-25 | Henry M Unschuld | Soybean oil refining process |
US3100185A (en) * | 1959-12-28 | 1963-08-06 | Gulf Research Development Co | Process of improving the wear properties of a mineral and fatty oil lubricant mixture by radiation |
US3356602A (en) * | 1965-03-26 | 1967-12-05 | Gen Electric | Process of dimerizing carboxylic acids in a corona discharge |
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