US3376216A - Reclamation of used lubricating oils by sulfuric acid treatment - Google Patents
Reclamation of used lubricating oils by sulfuric acid treatment Download PDFInfo
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- US3376216A US3376216A US573461A US57346166A US3376216A US 3376216 A US3376216 A US 3376216A US 573461 A US573461 A US 573461A US 57346166 A US57346166 A US 57346166A US 3376216 A US3376216 A US 3376216A
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- sulfuric acid
- oil
- lubricating oils
- lubricating
- acid treatment
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title description 46
- 239000010687 lubricating oil Substances 0.000 title description 16
- 238000010306 acid treatment Methods 0.000 title description 5
- 239000002270 dispersing agent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000002480 mineral oil Substances 0.000 description 16
- 235000010446 mineral oil Nutrition 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 239000012535 impurity Substances 0.000 description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 12
- 239000010802 sludge Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- -1 for instance Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000010688 mineral lubricating oil Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- MVMRYSSNWDNQEZ-UHFFFAOYSA-N 1,1-diethyl-2-pentylhydrazine Chemical compound CCCCCNN(CC)CC MVMRYSSNWDNQEZ-UHFFFAOYSA-N 0.000 description 1
- WGFYKSNMQJBURX-UHFFFAOYSA-N 1-methyl-1-pentyl-2-propylhydrazine Chemical compound CCCCCN(C)NCCC WGFYKSNMQJBURX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- GZUCMODGDIGMBI-UHFFFAOYSA-N n',n'-dipropylpropane-1,3-diamine Chemical compound CCCN(CCC)CCCN GZUCMODGDIGMBI-UHFFFAOYSA-N 0.000 description 1
- UVSDKMISWYGPIQ-UHFFFAOYSA-N n'-butyl-n-propylethane-1,2-diamine Chemical compound CCCCNCCNCCC UVSDKMISWYGPIQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical group O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
Definitions
- This invention relates to an improved process for the removal of carbonaceous impurities and sludge from mineral lubricating oils having present therein acylated nitrogen-containing, polymeric ashless dispersants. More particularly this invention concerns the use of sulfuric acids for removing carbonaceous impurities and sludge from petroleum lubricants containing amide, imide or amidinetype ashless dispersants.
- mineral oils of lubricating viscosity containing acylated nitrogen-containing ashless dispersants, carbonaceous impurities and sludge when treated with an aqueous sulfuric acid solution having a sulfuric acid concentration of about 80 to 95% by volume, preferably about 85 to 95%, and allowed to settle, provide lubricating oils possessing excellent color and viscosity.
- the sulfuric acid solution can be added in a dosage of at least about 20 pounds per barrel of lubricatin oil, preferably about 25 to 40 pounds per barrel.
- the lubricating oil can be treated with the sulfuric acid solution at room temperature up to about 500 F., preferably about 100 to 140 F.
- the contact time will vary but is a time sufficient to effect removal of carbonaceous impurities and sludge and provide upon settling a lubricating oil of improved viscosity and good color, for instance an ASTM color of less than 5, preferably less than 2. Ordinarily, the contact time is at least about 0.5 hour up to about 5 hours.
- the settling time after the acid treatment can vary anywhere from about 18 to greater than about 40 hours, to 22 hours.
- the used lubricating oils treated by the process of the present invention can be any mineral oil of lubricating viscosity, for instance, a solvent-extracted or solventrefined oil obtained in accordance with conventional methods of solvent refining lubricating oils.
- lubricating oils have viscosities from about 20 to 250 SUS at 210 F.
- the base oil may be derived from parafiinic, naphthenic, asphaltic or mixed base crude, and if desired, a blend of solvent-treated Mid-Continent neutral and Mid-Continent bright stocks may be employed.
- acylated nitrogen-containing, polymeric dispersants present in the lubricating oils to be treated by the process of the present invention, known as acylated nitrogen-containing, polymeric dispersants, their use and manner of preparation are well known in the lubricating oil art.
- acylated nitrogen is meant a nitrogen atom which is directly attached to a carboxylic acid or anhydride radical so as to form an amide, imide or amidine linkage, i.e.
- o H I preferably about 18
- the carboxyl carbon atom is, in turn, attached either directly or indirectly to a substantially aliphatic polymer of sufiicient molecular weight to render the dispersant mineral oil-soluble. Examples of these compounds, their method of preparation, and use are found throughout the patent literature, for instance, in U.S. Patent Nos. 2,800,- 452; 3,018,250; 3,018,291; 3,024,195; 3,024,237; 3,048,- 544; and 3,087,936.
- oil-soluble, acylated nitrogen-containing, polymeric dispersants often preferred for use in mineral lubricating oils are the amidic and imidic reaction products of (A) a monohydrocarbylsuccinic anhydride corresponding to the general formula:
- R is a hydrocarbon radical, preferably aliphatic, having a molecular weight of about 400 to 4000, preferably about 750 to 2000, and (B) a polyamine corresponding to the general formula:
- R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to about 30 carbon atoms, R is a divalent alkylene radical of 2 to about 14 carbon atoms, and n is 1 to about 10.
- the hydrocarbyl substituent on the succinic anhydride group can advantageously be supplied by a polymerized olefin, preferably an alpha-olefin and preferably of 2 to about 30 carbon atoms.
- a polymerized olefin such as, for instance, ethylene, propylene, l-butene, 2-butene, isobutene or their higher homologues or mixtures thereof can be polymerized to a molecular weight of about 400 to 4000.
- polymerized olefin there may also be present in the substantially aliphatic hydrocarbyl radical coploymerized ethylenically unsaturated aromatic monomers such as styrene and its homologues, e.g., vinyl toluene, alpha methyl styrene, etc., and/or diolefins such as butadiene and isoprene.
- the polymer can then be reacted in the absence of coplymerization catalysts with maleic anhydride in approximately equimolar quantities to form an addition product of maleic anhydride and the polyolefin, i.e., to form a monohydrocarbylsuccinic anhydride.
- Suitable polyamines for reaction with the monohydrocarbylsucciuic anhydride include monoalkylene diarnines, dialkylaminoalkylamines and the polyalkylenepolyamines.
- suitable monoalkylene diamincs are ethylene diamine, propylene butylene diamine, octylene diamine, etc.
- dialkylaminoalkylamines examples include dimetbylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamylamine, propylbutylaminoethylamine, etc.
- Non-limiting examples of the polyalkylenepolyamine reactants are diethylenetriamine; triethylenetetramine; tetraethylenepentamine; polyethyleneirnine; di-(methylethylene)triamine; hexapropyleneheptamine; tri(ethylethylene) tetrarnine; penta (1 methylpropylene hexamine, tetrabutylenepentamines; etc.
- acylated nitrogen-containing ashless dispersants are often present in lubricating oils in amounts of about 0.5% to 3% by Weight and may even be as high as about 6 to 10% by weight.
- a method for removing carbonaceous impurities and sludge from a mineral oil of lubricating viscosity containing the same and an acylated nitrogen-containing, polymeric ashlessdispersant which comprises contacting said mineral oil with at least about 20 lbs. per barrel of mineral oil of aqueous sulfuric acid having a concentration of about to 90% by volume, settling the contacted mix ture and separating a mineral oil of lubricating viscosity, improved viscosity and good color.
- a method for removing carbonaceous impurities and sludge from a mineral oil of lubricating viscosity containing the same and an acylated nitrogen-containing, polymeric ashless dispersant which comprises contacting said mineral oil with about 25 to 40 lbs. per barrclof mineral oil of aqueous sulfuric acid having a concentration of about 85 to 90% by volume, settling the contacted mixture and separating a mineral oil of lubricating viscosity, improved viscosity and good color.
- the method of claim has a concentration of about 85%.
- a method for removing carbonaceous impurities and containing same, said mineral 1 wherein the sulfuric acid meric ashless dispersant which comprises contacting said mineral oil at about 100 to 140 F. with about to lbs. per barrel of mineral oil of aqueous sulfuric acid having a concentration of about to 90% by volume, settling the contacted mixture and separating a mineral oil of improved viscosity and color.
- the ashless dispersant is a reaction product of (A) a Inonohydrocarbylsuccinic anhydride corresponding to the general formula:
- R is a hydrocarbon radical of about 400 to 4000 molecular weight
- B a polyamine corresponding 'to wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to about 30 carbon atoms
- R" is a divalent alkylene radical of 2 to about 14 carbon atoms
- n is 1 to about 10.
- the method of claim 11 wherein the sulfuric acid has a concentration of about 13.
- the method of claim 12 wherein the sulfuric acid has a concentration of about References Cited Nelson: Petroleum Refinery Engineering, third ed., 1949, pub. McGraW-Hill Book CO. Inc., N.Y., 1949, pp. 252 to 2574 HERBERT LEVINE, Primary Examiner.
- the ashless dispersant is a reaction product of (A) a monohydrocarbylsuccinic anhydride corresponding to the general formula:
- R-CH c CH c wherein R is a hydrocarbon radical of about 400 to 4000 molecular weight, and (B) a polyamine corresponding to the general formula:
- R is selected from the group consisting of hydrogen and hydrocarbon radicals of l to about 30 carbon atoms
- R is a divalent alkylene radical of 2 to about 14 carbon atoms
- n l to about 10.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Description
3,3 76,2 l Patented Apr. 2, 1 968 than 3,376,216 RECLAMATION OF USED LUBRICA'HNG OILS BY SULFURIC ACID TREATMENT Donald D. Carlos, Crown Point, and Joseph M. Divijak, Jr., Griffith, Ind, assignors to Sinclair Research, Inc, New York, N.Y., a corporation of Delaware No Drawing. Filed Aug. 19, 1966, Ser. No. 573,461 13 Claims. (Cl. 208-179) ABSTRACT OF THE DISCLOSURE Carbonaceous impurities and sludge are removed from mineral lubricating oils which contain acylated nitrogencontaining, polymeric ashless dispersants by contacting the oil with at least about lbs, often about to 40 lbs., per barrel of oil, of aqueous sulfuric acid having a concentration of about 80 to 90 volume percent, allowing the resultant mixture to settle and then separating a lubricating oil of improved viscosity and color.
This invention relates to an improved process for the removal of carbonaceous impurities and sludge from mineral lubricating oils having present therein acylated nitrogen-containing, polymeric ashless dispersants. More particularly this invention concerns the use of sulfuric acids for removing carbonaceous impurities and sludge from petroleum lubricants containing amide, imide or amidinetype ashless dispersants.
Removal of carbonaceous impurities and sludge from lubricating and industrial oils has generally been achieved by using high concentrations of sulfuric acids, that is concentrations of 98% and preferably even higher. In fact, fuming sulfuric acid has been considered even more desirable. Although sulfuric acids of these concentrations have been effective for removal of carbonaceous impurities and sludge from certain lubricants, they have been totally ineffective for this purpose in reclaiming lubricating oils provided with acylated nitrogen-containing ashless dispersants. The presence of such ashless dispersants in the lubricant appears to interfere with the settling of the acid sludge after the sulfuric acid treatment. Thus, highly concentrated sulfuric acid, for example, greater than about 98%, rather than refine the oil tends to hinder removal of the carbonaceous impurities and sludge. The net result is an increased amount of time required for settling and a poor recovery of oil possessing the desired color and viscosity. Thus, all attempts to purify lubricating oils provided with acylated nitrogencontaining ashless dispersants by chemical and physical means have met with little or no success.
It has now been found that mineral oils of lubricating viscosity containing acylated nitrogen-containing ashless dispersants, carbonaceous impurities and sludge when treated with an aqueous sulfuric acid solution having a sulfuric acid concentration of about 80 to 95% by volume, preferably about 85 to 95%, and allowed to settle, provide lubricating oils possessing excellent color and viscosity. The sulfuric acid solution can be added in a dosage of at least about 20 pounds per barrel of lubricatin oil, preferably about 25 to 40 pounds per barrel. The lubricating oil can be treated with the sulfuric acid solution at room temperature up to about 500 F., preferably about 100 to 140 F. The contact time will vary but is a time sufficient to effect removal of carbonaceous impurities and sludge and provide upon settling a lubricating oil of improved viscosity and good color, for instance an ASTM color of less than 5, preferably less than 2. Ordinarily, the contact time is at least about 0.5 hour up to about 5 hours. The settling time after the acid treatment can vary anywhere from about 18 to greater than about 40 hours, to 22 hours.
The used lubricating oils treated by the process of the present invention can be any mineral oil of lubricating viscosity, for instance, a solvent-extracted or solventrefined oil obtained in accordance with conventional methods of solvent refining lubricating oils. Generally, lubricating oils have viscosities from about 20 to 250 SUS at 210 F. The base oil may be derived from parafiinic, naphthenic, asphaltic or mixed base crude, and if desired, a blend of solvent-treated Mid-Continent neutral and Mid-Continent bright stocks may be employed.
The ashless dispersants present in the lubricating oils to be treated by the process of the present invention, known as acylated nitrogen-containing, polymeric dispersants, their use and manner of preparation are well known in the lubricating oil art. By acylated nitrogen is meant a nitrogen atom which is directly attached to a carboxylic acid or anhydride radical so as to form an amide, imide or amidine linkage, i.e.
o H I preferably about 18 The carboxyl carbon atom is, in turn, attached either directly or indirectly to a substantially aliphatic polymer of sufiicient molecular weight to render the dispersant mineral oil-soluble. Examples of these compounds, their method of preparation, and use are found throughout the patent literature, for instance, in U.S. Patent Nos. 2,800,- 452; 3,018,250; 3,018,291; 3,024,195; 3,024,237; 3,048,- 544; and 3,087,936.
Among the oil-soluble, acylated nitrogen-containing, polymeric dispersants often preferred for use in mineral lubricating oils are the amidic and imidic reaction products of (A) a monohydrocarbylsuccinic anhydride corresponding to the general formula:
0 wherein R is a hydrocarbon radical, preferably aliphatic, having a molecular weight of about 400 to 4000, preferably about 750 to 2000, and (B) a polyamine corresponding to the general formula:
wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to about 30 carbon atoms, R is a divalent alkylene radical of 2 to about 14 carbon atoms, and n is 1 to about 10.
The hydrocarbyl substituent on the succinic anhydride group can advantageously be supplied by a polymerized olefin, preferably an alpha-olefin and preferably of 2 to about 30 carbon atoms. Thus, an olefin such as, for instance, ethylene, propylene, l-butene, 2-butene, isobutene or their higher homologues or mixtures thereof can be polymerized to a molecular weight of about 400 to 4000. In addition to the polymerized olefin, there may also be present in the substantially aliphatic hydrocarbyl radical coploymerized ethylenically unsaturated aromatic monomers such as styrene and its homologues, e.g., vinyl toluene, alpha methyl styrene, etc., and/or diolefins such as butadiene and isoprene. The polymer can then be reacted in the absence of coplymerization catalysts with maleic anhydride in approximately equimolar quantities to form an addition product of maleic anhydride and the polyolefin, i.e., to form a monohydrocarbylsuccinic anhydride.
Acid Strength, percent Dosage, lbs./Bbl Settling Time, Hr Oil Losses, Wt., Percc Overhead. Final Yield, Wt., Reclaimed Oil Inspect; 4
API Gravity KV/100 F., cs. KV/210 F., cs ASTM Colon... Acylated nitroge 1 Layer separation poor. 2 No layer separation. 3 Acid oil would not filter.
4 Clay treated with lbs. Clay/B Suitable polyamines for reaction with the monohydrocarbylsucciuic anhydride include monoalkylene diarnines, dialkylaminoalkylamines and the polyalkylenepolyamines. Illustrative of suitable monoalkylene diamincs are ethylene diamine, propylene butylene diamine, octylene diamine, etc. Examples of suitable dialkylaminoalkylamines are dimetbylaminomethylamine, dimethylaminoethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminoamylamine, dipropylaminopropylamine, methylpropylaminoamylamine, propylbutylaminoethylamine, etc. Non-limiting examples of the polyalkylenepolyamine reactants are diethylenetriamine; triethylenetetramine; tetraethylenepentamine; polyethyleneirnine; di-(methylethylene)triamine; hexapropyleneheptamine; tri(ethylethylene) tetrarnine; penta (1 methylpropylene hexamine, tetrabutylenepentamines; etc.
The acylated nitrogen-containing ashless dispersants are often present in lubricating oils in amounts of about 0.5% to 3% by Weight and may even be as high as about 6 to 10% by weight.
EXAMPLE A railroad diesel engine lubricating oil containing an acylated nitrogen-containing as'hless dispersant and contaminated with carbonaceous impurities and sludge had the following composition:
Base oil (89.3 volume percent):
56% 600 SUS at 180 F. Mid-Continent Neutral Oil; 16% 1200 SUS at 100 F. Naphthenic Base Oil; 28% 2000 SUS at 100 F. Naphthenic Base Oil.
Additives (10.7 volume percent):
3.6% Basic calcium mahogany sulfonate 4.9% Calcium salt of condensation product of octylphenol, formaldehyde and diethylene triamine; 2.2% acylated nitrogen-conta ning ashless dispersant 0.001% Dow Corning fluid (a defo-aming agent). 1 A 45% concentrate in mineral oil solution which analyzes: 3% calcium; base No. 28.0.
An approximately 48% concentrate in mineral oil of the reaction product prepared by reacting polyisobutylene having a molecular weight of approximately 1000 with maleic anhydride and then reacting the resulting polyisobutenyl succinic auhydrlde with tetraethylenepentaamlne.
The above-identified contaminated lubricant was contacted with an aqueous solution of sulfuric acid in varying concentrations for about 1 hour at about 120 F., and
ontaining ashless dispersant None None bl. of oil at 550 F. for 30 minutes.
As can be seen from the data listed above, acid treatment with a sulfuric acid concentration less than 98% was very efiective. For example, a 90% sulfuric acid concentration treatment of the railroad diesel engine lubricant containing 2.2% of the acylated nitrogen-containing ashless dispersantiresulted in high recovery of oil possessing excellent color and viscosity. However, for acid concentrations of 98% or greater, layer separation was very poor. The data also demonstrate the importance of using a sufiicient dosage in the treatment.
It is claimed:
1. A method for removing carbonaceous impurities and sludge from a mineral oil of lubricating viscosity containing the same and an acylated nitrogen-containing, polymeric ashlessdispersant, which comprises contacting said mineral oil with at least about 20 lbs. per barrel of mineral oil of aqueous sulfuric acid having a concentration of about to 90% by volume, settling the contacted mix ture and separating a mineral oil of lubricating viscosity, improved viscosity and good color.
2. The method of claim 1 wherein the ashless dispersant is present in the mineral oil in an amount of about 0.5 to 10% by weight.
3. The method of claim 1 wherein the lubricating oil has a viscosity in the range of about 20 to 250 SUS at 4. The method of claim 1 wherein the sulfuric acid has a concentration of about to 5. A method for removing carbonaceous impurities and sludge from a mineral oil of lubricating viscosity containing the same and an acylated nitrogen-containing, polymeric ashless dispersant, which comprises contacting said mineral oil with about 25 to 40 lbs. per barrclof mineral oil of aqueous sulfuric acid having a concentration of about 85 to 90% by volume, settling the contacted mixture and separating a mineral oil of lubricating viscosity, improved viscosity and good color.
6. The method of claim 1 wherein the a concentration of about 80%.
7. The method of claim has a concentration of about 85%.
sulfuric acid has.
8. The method of claim 1 wherein the sulfuric acid 3 has a concentration of about 90% 9. A method for removing carbonaceous impurities and containing same, said mineral 1 wherein the sulfuric acid meric ashless dispersant, which comprises contacting said mineral oil at about 100 to 140 F. with about to lbs. per barrel of mineral oil of aqueous sulfuric acid having a concentration of about to 90% by volume, settling the contacted mixture and separating a mineral oil of improved viscosity and color.
10. The method of claim 9 wherein the ashless dispersant is a reaction product of (A) a Inonohydrocarbylsuccinic anhydride corresponding to the general formula:
CHz-C wherein R is a hydrocarbon radical of about 400 to 4000 molecular weight, and (B) a polyamine corresponding 'to wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals of 1 to about 30 carbon atoms, R" is a divalent alkylene radical of 2 to about 14 carbon atoms, and n is 1 to about 10.
11. The method of claim 10 wherein the sulfuric acid has a concentration of about 80%.
12. The method of claim 11 wherein the sulfuric acid has a concentration of about 13. The method of claim 12 wherein the sulfuric acid has a concentration of about References Cited Nelson: Petroleum Refinery Engineering, third ed., 1949, pub. McGraW-Hill Book CO. Inc., N.Y., 1949, pp. 252 to 2574 HERBERT LEVINE, Primary Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,376,216 April 2, 1968 Donald D. Carlos et al.
It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 3, line 43, (l-methylpropylene" should read (l-methylpropylene) Column 5, line 7, beginning with "10. The method" cancel all to and including "1 to about 10." in line 10, column 6, and insert the following:
10. The method of claim 9 wherein the ashless dispersant is a reaction product of (A) a monohydrocarbylsuccinic anhydride corresponding to the general formula:
R-CH c CH c wherein R is a hydrocarbon radical of about 400 to 4000 molecular weight, and (B) a polyamine corresponding to the general formula:
wherein R is selected from the group consisting of hydrogen and hydrocarbon radicals of l to about 30 carbon atoms R is a divalent alkylene radical of 2 to about 14 carbon atoms, and
n is l to about 10.
Signed and sealed this 13th day of January 1970.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. WILLIAM E. I SCHUYLER, JR. Attesting Officer Commissioner of Patents
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US573461A US3376216A (en) | 1966-08-19 | 1966-08-19 | Reclamation of used lubricating oils by sulfuric acid treatment |
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US573461A US3376216A (en) | 1966-08-19 | 1966-08-19 | Reclamation of used lubricating oils by sulfuric acid treatment |
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US3376216A true US3376216A (en) | 1968-04-02 |
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US573461A Expired - Lifetime US3376216A (en) | 1966-08-19 | 1966-08-19 | Reclamation of used lubricating oils by sulfuric acid treatment |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4948829A (en) * | 1988-05-13 | 1990-08-14 | Kansai Paint Co., Ltd. | Aqueous coating composition and coating method using same |
WO1998010045A1 (en) * | 1996-09-09 | 1998-03-12 | Destiny Oil Anstalt | Method of refining waste oils (petroleum products) |
US20110024259A1 (en) * | 2009-07-31 | 2011-02-03 | Vertex Energy, Lp | System for making a usable hydrocarbon product from used oil |
-
1966
- 1966-08-19 US US573461A patent/US3376216A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
None * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4948829A (en) * | 1988-05-13 | 1990-08-14 | Kansai Paint Co., Ltd. | Aqueous coating composition and coating method using same |
WO1998010045A1 (en) * | 1996-09-09 | 1998-03-12 | Destiny Oil Anstalt | Method of refining waste oils (petroleum products) |
US20110024259A1 (en) * | 2009-07-31 | 2011-02-03 | Vertex Energy, Lp | System for making a usable hydrocarbon product from used oil |
US8613838B2 (en) * | 2009-07-31 | 2013-12-24 | Vertex Energy, Lp | System for making a usable hydrocarbon product from used oil |
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