EP0007260B1 - Procédé perfectionné de préparation d'additifs détergents dispersants métalliques de haute alcalinité notamment pour huiles lubrifiantes et produit obtenu - Google Patents
Procédé perfectionné de préparation d'additifs détergents dispersants métalliques de haute alcalinité notamment pour huiles lubrifiantes et produit obtenu Download PDFInfo
- Publication number
- EP0007260B1 EP0007260B1 EP79400390A EP79400390A EP0007260B1 EP 0007260 B1 EP0007260 B1 EP 0007260B1 EP 79400390 A EP79400390 A EP 79400390A EP 79400390 A EP79400390 A EP 79400390A EP 0007260 B1 EP0007260 B1 EP 0007260B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- parts
- calcium
- magnesium
- weight
- alkylphenol
- 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
Links
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 10
- 239000000654 additive Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims description 8
- 239000003513 alkali Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 75
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 70
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 alkaline-earth metal alkylbenzene sulfonates Chemical class 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 10
- 238000010790 dilution Methods 0.000 claims abstract description 10
- 239000012895 dilution Substances 0.000 claims abstract description 10
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 7
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract 13
- 239000011575 calcium Substances 0.000 claims description 126
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 125
- 229910052791 calcium Inorganic materials 0.000 claims description 124
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 114
- 239000011777 magnesium Substances 0.000 claims description 84
- 229910052749 magnesium Inorganic materials 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000347 magnesium hydroxide Substances 0.000 claims description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 57
- 150000004996 alkyl benzenes Chemical class 0.000 abstract description 28
- 239000011593 sulfur Substances 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 239000002585 base Substances 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 13
- 238000005987 sulfurization reaction Methods 0.000 description 13
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical class CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 description 1
- JTZKEVHEBCTHLN-UHFFFAOYSA-N 3-(2-methylprop-1-enyl)pyrrolidine-2,5-dione Chemical compound CC(C)=CC1CC(=O)NC1=O JTZKEVHEBCTHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 241001080024 Telles Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000010710 diesel engine oil Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010711 gasoline engine oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 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
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
Definitions
- the present invention relates to an improved process for the preparation of detergent-dispersant metal additives of high alkalinity, in particular for lubricating oils.
- the Applicant has found an improved process for obtaining metallic detergent-dispersant additives with TBN (Total Basic Number Standard ASTM D 2896) greater than 200, in a simple and rapid manner, in the absence of excess sulfur. and without the essential presence of heavy monoalcohol.
- TBN Total Basic Number Standard ASTM D 2896
- the sulfurization step is preferably carried out at a temperature between 120 and 180 ° C; it can optionally be completed at a higher temperature between 130 and 185 ° C., preferably at a pressure less than or equal to atmospheric pressure.
- the carbonation operation is preferably carried out at a temperature between 100 and 185 ° C using an amount of C0 2 substantially equal to that which can be completely absorbed.
- alkylphenols which can be used to carry out the process which is the subject of the invention, mention may preferably be made of those carrying one or more C 9 -C 15 alkyl substituents, and very particularly nonyl, decyl, dodecyl or tetradecylphenols.
- alkylbenzene sulfonate any solution containing 40 to 95% by weight, preferably 55 to 85% by weight of an alkylbenzene sulfonate in a dilution oil, which may or may not be the same as that used to carry out the process subject of the invention.
- alkylbenzene sulfonates which can be used, there may be mentioned the salts of sulfonic acids (of molecular weight preferably greater than 400) obtained by sulfonation of petroleum or synthetic fractions obtained by sulfonation of alkylbenzenes derived from olefins or polymers C 1 -C 3 olefins and alkaline earth metals such as calcium or magnesium.
- the alkaline earth compound used consists of lime and / or magnesium hydroxide or oxide.
- magnesium oxide any type of magnesium oxide can be used, however, "active" magnesium oxide is preferred.
- active magnesium oxide denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m 2 / g, for example between 100 and 170 m 2 / g.
- magnesium oxide MgO with a specific surface greater than or equal to 80 m 2 / g, for example between 100 and 170 m 2 / g.
- Maglite DE with a specific surface area close to 140 m 2 / g sold by Merck
- the "Ferumag” with a specific surface area close to 160 m 2 / g and marketed by RHONE-POULENC INDUSTRIES.
- the metal from which the alkaline earth alkylbenzene sulfonate is derived may or may not be the same as that or those contained in the alkaline earth compound.
- alkali metal hydroxides which can be used, mention may be made of sodium, lithium and potassium hydroxides.
- the amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting alkylbenzene sulfonate) represents from 20 to 60% by weight of said product and of preferably 25 to 55% of said product.
- a variant of the process which is the subject of the invention consists in preparing "in situ" before the sulfurization-neutralization step, the alkaline earth metal alkyl benzene sulfonate by the action of an oxide or hydroxide of said alkali metal. earthy on an alkylbenzene sulfonic acid as defined above in the presence of oil and optionally alkylene glycol, at a temperature between 40 and 110 ° C, the amount of oxide or hydroxide of alkaline earth metal and of oil to be used being such that the alkylbenzene sulfonate obtained has a TBN less than or equal to 150, preferably less than or equal to 50.
- the process which is the subject of the invention is very particularly advantageous for preparing detergent-dispersants with a TBN greater than or equal to 250 and having a large percentage by weight of calcium (at least 10%).
- the process which is the subject of the invention is also advantageous for preparing detergent-dispersants with a TBN greater than 200 and containing at least 2% by weight of magnesium and optionally at least 0.5% by weight of. calcium.
- the present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above. These have the advantage of good compatibility with viscous oils and a very low rate of sediment. They can be added to lubricating oils in amounts depending on the TBN of said detergent-dispersants, and depending on the future use of said oils; thus for a gasoline engine oil, the amount of detergent-dispersants of TBN between 200 and 300 for example to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5%; for marine engine oil this can be up to 25%.
- the lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as lubricating oils of naphthenic base, of paraffinic base, and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from coal products, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide in the presence of water or alcohols, for example ethyl alcohol, the esters of dicarboxylic acids of the liquid esters of phosphorus acids, of alkylbenzenes and of dialkylbenzenes of polyphenyls, of alkyl biphenyl ethers, of polymers of silicon.
- lubricating oils such as lubricating oils of naphthenic base, of paraffinic base, and of mixed base, of other hydrocarbon lubricants, for example lubricating oils derived from coal products, and synthetic oils, for example
- Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.
- a carbonation operation is carried out using carbon dioxide at 165-170 ° C at atmospheric pressure until the absorption of CO 2 has ended; this hard phase about 1 hour 30 minutes; the viscosity of the medium drops rapidly at the start of this phase and then stabilizes.
- the medium is brought to a temperature of 184 ° C. under 20 mm of mercury for one hour.
- the medium is filtered to remove the sediments and a solution is recovered in 100 N oil of over-alkalized detergent-dispersant, which is degassed and the characteristics of which appear in Table 1.
- the operation lasted a total of 10 hours.
- Example 1 to 4 The operations described in Examples 1 to 4 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.4 % calcium and having a TBN of around 45.
- Examples 1 to 4 are carried out under the same conditions from an 80% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.37 % of calcium with a TBN of 33.
- Example 2 The operation described in Example 2 is carried out by replacing the calcium sulfonate solution with a solution of approximately 60% in 1 100 N oil of a magnesium alkylbenzene sulfonate (Mg sulfonate for short) with a molecular mass of 470 approximately, solution containing 1.5% magnesium and having a TBN of approximately 20, in order to obtain a detergent-dispersant containing calcium and magnesium.
- Mg sulfonate magnesium alkylbenzene sulfonate
- the base stock used consists of one of the products prepared in Examples 2, 6, 10 or 14.
- Example 6 The operation described in Example 6 is carried out by carrying out the sulfurization step at 170 ° C. at atmospheric pressure for one hour; the subsequent stage of dehydration is then superfluous.
- Example 6 The operation described in Example 6 is carried out using 40 g of base stock, at instead of 160 g; there is a slightly higher viscosity of the medium after sulfurization and a slightly lower filtration speed.
- Example 6 The operation described in Example 6 is carried out using 203 g of base stock instead of 160 g.
- Example 6 The operation described in Example 6 is carried out using 152 g of glycol instead of 174 g.
- Example 6 The operation described in Example 6 is carried out using 230 g of glycol instead of 174 g.
- Example 6 The operation similar to that described in Example 6 is carried out by using 160 g of a base stock consisting of sulfurized and overbased calcium dodecylphenate of TBN 200 instead of a mixture of sulfurized dodecylphenate and alkylbenzene TBN 260 sulfonate.
- Example 6 The operation described in Example 6 is carried out using a base stock consisting of calcium alkylbenzene sulfonate of TBN 260 instead of a mixture of sulfurized dodecylphenate and alkylbenzene sulfonate of TBN 260.
- the amount of glycol is readjusted to its initial value and a carbonation operation is carried out using carbon dioxide at 165 ° C. for 7 hours. Cool to 110 ° C for 1 hour 30 minutes.
- the 3rd phase and the 4th phase are carried out as in the previous examples.
- Example 28 The operation described in Example 28 is repeated, carrying out the sulfurization step at 180 ° C.
- Example 28 The operation described in Example 28 is repeated, carrying out the carbonation step at 145 ° C.
- Example 28 The operation described in Example 28 is carried out using a magnesium alkylbenzene sulfonate in 60% solution having a TBN of 45 and a magnesium level of 2.2%.
- Example 29 The operation described in Example 29 is repeated, carrying out the sulfurization operation in the presence of glycol and tridecyl alcohol.
- Example 28 The operation described in Example 28 is repeated by carrying out the sulfurization step by using a base stock consisting of an overbased magnesium alkylbenzene sulfonate of TBN 200.
- Example 28 The operation described in Example 28 is repeated, using an overbased calcium dodecylphenate of TBN 200 as the base of the curve.
- Example 32 The operation described in Example 32 is carried out, replacing the 20 g of lime with 10 g of soda; the characteristics of the product obtained are equivalent to those of that of Example 32.
- Example 28 The operation described in Example 28 is carried out without introducing water during the carbonation operation. The characteristics of the product obtained are equivalent to those of that of Example 28.
- Example 33 The product of Example 33 is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium.
- the solution is stored for 15 days at 20 ° C; we see that the solution remains clear.
- mixture (A) is brought for 25 days to 80 ° C. and is then added to an SAE 30 oil so as to have a concentration of 6.6% by weight of mixture (A).
- the solution is stored for 5 days at 80 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT79400390T ATE243T1 (de) | 1978-06-26 | 1979-06-14 | Verfahren zur herstellung von metall enthaltenden reinigenden dispergierenden zusatzstoffen hoher alkalitaet, besonders fuer schmieroel, und daraus hergestelltes produkt. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7818946 | 1978-06-26 | ||
| FR7818946A FR2429832A1 (fr) | 1978-06-26 | 1978-06-26 | Procede perfectionne de preparation d'additifs detergents-dispersants, metalliques de haute alcalinite notamment pour huiles lubrifiantes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0007260A1 EP0007260A1 (fr) | 1980-01-23 |
| EP0007260B1 true EP0007260B1 (fr) | 1981-09-23 |
Family
ID=9209959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79400390A Expired EP0007260B1 (fr) | 1978-06-26 | 1979-06-14 | Procédé perfectionné de préparation d'additifs détergents dispersants métalliques de haute alcalinité notamment pour huiles lubrifiantes et produit obtenu |
Country Status (11)
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2063250B (en) * | 1979-10-02 | 1984-05-31 | Bdh Chemicals Ltd | Liquid crystal esters |
| FR2529224B1 (fr) * | 1982-06-24 | 1986-02-07 | Orogil | Nouvel additif detergent-dispersant suralcalinise pour huiles lubrifiantes |
| FR2529225B1 (fr) * | 1982-06-24 | 1986-04-25 | Orogil | Nouvel additif detergent-dispersant metallique de haute alcalinite pour huiles lubrifiantes |
| US5024773A (en) * | 1986-10-21 | 1991-06-18 | Chevron Research Company | Methods for preparing, group II metal overbased sulfurized alkylphenols |
| US4744921A (en) * | 1986-10-21 | 1988-05-17 | Chevron Research Company | Methods for preparing, group II metal overbased sulfurized alkylphenols |
| US4971710A (en) * | 1986-10-21 | 1990-11-20 | Chevron Research Company | Methods for preparing, Group II metal overbased sulfurized alkylphenols |
| US4832857A (en) * | 1988-08-18 | 1989-05-23 | Amoco Corporation | Process for the preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions |
| US4973411A (en) * | 1989-09-15 | 1990-11-27 | Texaco Inc. | Process for the preparation of sulfurized overbased phenate detergents |
| US5370803A (en) * | 1993-09-03 | 1994-12-06 | Texaco Inc. | Efficient method of producing lubricant detergent additives |
| US9029304B2 (en) * | 2008-09-30 | 2015-05-12 | Chevron Oronite Company Llc | Lubricating oil additive composition and method of making the same |
| CN113186015B (zh) * | 2021-02-02 | 2024-02-06 | 安徽澳润新材料有限公司 | 一种高碱值磺酸镁清净剂及其制备方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1080531A (fr) * | 1952-02-01 | 1954-12-09 | Standard Oil Dev Co | Préparation de produits composés contenant des sulfonates métalliques et des selsmétalliques de sulfures aromatiques |
| US3178368A (en) * | 1962-05-15 | 1965-04-13 | California Research Corp | Process for basic sulfurized metal phenates |
| USB194963I5 (enrdf_load_stackoverflow) * | 1962-05-15 | |||
| US3493516A (en) * | 1966-05-04 | 1970-02-03 | Chevron Res | Carboxylate modified phenates |
| US3629109A (en) * | 1968-12-19 | 1971-12-21 | Lubrizol Corp | Basic magnesium salts processes and lubricants and fuels containing the same |
| GB1429243A (en) * | 1973-02-22 | 1976-03-24 | Orobis Ltd | Overbased phenates |
| GB1469289A (en) * | 1974-07-05 | 1977-04-06 | Exxon Research Engineering Co | Detergent additives |
| JPS5272707A (en) * | 1975-12-15 | 1977-06-17 | Karonaito Kagaku Kk | Preparation of additive for perbasic lubricating oil |
-
1978
- 1978-06-26 FR FR7818946A patent/FR2429832A1/fr active Granted
-
1979
- 1979-06-14 EP EP79400390A patent/EP0007260B1/fr not_active Expired
- 1979-06-14 AT AT79400390T patent/ATE243T1/de not_active IP Right Cessation
- 1979-06-14 DE DE7979400390T patent/DE2960884D1/de not_active Expired
- 1979-06-19 US US06/049,959 patent/US4293431A/en not_active Expired - Lifetime
- 1979-06-21 MX MX798107U patent/MX5560E/es unknown
- 1979-06-22 CA CA330,659A patent/CA1129842A/fr not_active Expired
- 1979-06-25 BR BR7903979A patent/BR7903979A/pt not_active IP Right Cessation
- 1979-06-25 ES ES481864A patent/ES481864A1/es not_active Expired
- 1979-06-26 ZA ZA793196A patent/ZA793196B/xx unknown
- 1979-06-26 JP JP54079792A patent/JPS6056199B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| BR7903979A (pt) | 1980-03-25 |
| ES481864A1 (es) | 1980-02-16 |
| EP0007260A1 (fr) | 1980-01-23 |
| CA1129842A (fr) | 1982-08-17 |
| ZA793196B (en) | 1980-06-25 |
| MX5560E (es) | 1983-10-11 |
| JPS5540765A (en) | 1980-03-22 |
| ATE243T1 (de) | 1981-10-15 |
| FR2429832A1 (fr) | 1980-01-25 |
| JPS6056199B2 (ja) | 1985-12-09 |
| DE2960884D1 (en) | 1981-12-10 |
| FR2429832B1 (enrdf_load_stackoverflow) | 1982-04-02 |
| US4293431A (en) | 1981-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0133088B1 (fr) | Procédé de préparation d'additifs détergents-dispersants de très haute alcalinité à base de calcium et produits ainsi obtenus | |
| EP0007257B1 (fr) | Procédé de préparation de détergents-dispersants de haute alcalinité pour huiles lubrifiantes et produit obtenu | |
| EP0164286B1 (fr) | Procédé de préparation d'additifs détergents-dispersants pour huiles lubrifiantes à base d'alkylarylsulfonates de métaux alcalino-terreux ne moussant pas | |
| EP0003694B1 (fr) | Procédé de préparation de détergents-dispersants de haute alcalinité pour huiles lubrifiantes et produit obtenu | |
| EP0404650B1 (fr) | Additifs surbasés pour huiles lubrifiantes renfermant un complexe du molybdène, leur procédé de préparation et compositions renfermant lesdits additifs | |
| EP0007260B1 (fr) | Procédé perfectionné de préparation d'additifs détergents dispersants métalliques de haute alcalinité notamment pour huiles lubrifiantes et produit obtenu | |
| FR2917421A1 (fr) | Additifs et formulations de lubrifiants pour ameliorer les proprietes antiusure. | |
| EP0102255B1 (fr) | Procédé de préparation d'alkylphénates sulfurisés de métaux alcalino-terreux utilisables comme additifs pour huiles lubrifiantes | |
| EP0102254B1 (fr) | Nouvel additif détergent-dispersant suralcalinisé pour huiles lubrifiantes | |
| EP0101334B1 (fr) | Nouvel additif détergent-dispersant métallique de haute alcalinité pour huiles lubrifiantes | |
| EP0016676B1 (fr) | Procédé de préparation d'alkylphénates de magnésium | |
| EP0308445B1 (fr) | Procede de preparation d'un additif suralcanilise renfermant un derive inorganique du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif | |
| EP0006796B1 (fr) | Procédé de préparation de détergents-dispersants métalliques suralcalinisés pour huiles lubrifiantes et produits obtenus | |
| FR2625219A1 (fr) | Additifs detergents-dispersants a base de sels de metaux alcalino-terreux et alcalins pour huiles lubrifiantes | |
| FR2909684A1 (fr) | Additifs et formulations de lubrifiants utilises pour obtenir des proprietes antiusure ameliorees | |
| EP0211722B1 (fr) | Nouveaux additifs détergents-dispersants sulfones et sulfurisés pour huiles lubrifiantes | |
| EP0219382B1 (fr) | Nouveaux additifs détergents-dispersants suralcalinisés stables à l'hydrolyse pour huiles lubrifiantes et leur procécé de préparation | |
| EP0598645A1 (fr) | Produits colloidaux contenant du calcium, et/ou du magnésium ainsi que du bore et/ou du phosphore, et/ou du soufre, leur préparation et leur utilisation comme additifs pour lubrifiants | |
| EP0383359A2 (fr) | Procédé de préparation d'un additif suralcanisé renfermant un dérivé inorganique du bore, l'additif ainsi obtenu et compositions lubrifiantes renfermant ledit additif |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
| 17P | Request for examination filed | ||
| ITF | It: translation for a ep patent filed | ||
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LU NL SE |
|
| REF | Corresponds to: |
Ref document number: 243 Country of ref document: AT Date of ref document: 19811015 Kind code of ref document: T |
|
| REF | Corresponds to: |
Ref document number: 2960884 Country of ref document: DE Date of ref document: 19811210 |
|
| KL | Correction list |
Free format text: 82/03 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19920515 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19920520 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19920521 Year of fee payment: 14 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19920603 Year of fee payment: 14 |
|
| ITTA | It: last paid annual fee | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19920630 Year of fee payment: 14 |
|
| EPTA | Lu: last paid annual fee | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19930614 Ref country code: AT Effective date: 19930614 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930615 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Effective date: 19930630 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19940101 |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19940630 Year of fee payment: 16 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19940809 Year of fee payment: 16 |
|
| EUG | Se: european patent has lapsed |
Ref document number: 79400390.5 Effective date: 19940110 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19950630 |
|
| BERE | Be: lapsed |
Owner name: OROGIL Effective date: 19950630 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19960301 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19980505 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980603 Year of fee payment: 20 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990613 |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Effective date: 19990613 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |