EP0007260A1 - Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained - Google Patents
Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained Download PDFInfo
- Publication number
- EP0007260A1 EP0007260A1 EP79400390A EP79400390A EP0007260A1 EP 0007260 A1 EP0007260 A1 EP 0007260A1 EP 79400390 A EP79400390 A EP 79400390A EP 79400390 A EP79400390 A EP 79400390A EP 0007260 A1 EP0007260 A1 EP 0007260A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- parts
- weight
- calcium
- alkylphenol
- alkylbenzene sulfonate
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 claims abstract description 116
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 83
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 71
- -1 alkaline-earth metal alkylbenzene sulfonates Chemical class 0.000 claims abstract description 51
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002270 dispersing agent Substances 0.000 claims abstract description 32
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000003921 oil Substances 0.000 claims abstract description 26
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 238000010790 dilution Methods 0.000 claims abstract description 11
- 239000012895 dilution Substances 0.000 claims abstract description 11
- 239000010687 lubricating oil Substances 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 110
- 229910052791 calcium Inorganic materials 0.000 claims description 108
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 104
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 67
- 239000011777 magnesium Substances 0.000 claims description 52
- 229910052749 magnesium Inorganic materials 0.000 claims description 48
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 37
- 229910052788 barium Inorganic materials 0.000 claims description 31
- 239000002585 base Substances 0.000 claims description 31
- 238000005987 sulfurization reaction Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 13
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 239000000470 constituent Substances 0.000 claims 2
- 150000004692 metal hydroxides Chemical class 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 150000001669 calcium Chemical class 0.000 claims 1
- 150000002680 magnesium Chemical class 0.000 claims 1
- 159000000003 magnesium salts Chemical class 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229960002317 succinimide Drugs 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 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
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 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
- 150000001991 dicarboxylic acids Chemical class 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Chemical class 0.000 description 1
- 239000000314 lubricant Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 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
- 150000003839 salts Chemical class 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 subject of the present invention is an improved process for the preparation of high alkalinity detergent-dispersant metal additives, in particular for lubricating oils.
- the Applicant has found an improved process making it possible to obtain metal detergent-dispersant additives with TBN (Total Basic Number Standard ASTM D 2896) greater than 200, and this in a simple and rapid manner in the presence of low alkylene glycol. quantity and without the presence of a monoalcohol is essential.
- TBN Total Basic Number Standard ASTM D 2896
- alkylbenzene sulfonate denotes any solution containing from 40 to 95% by weight, preferably from 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 which is the subject of the invention.
- 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 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 cuts obtained by sulfonation of alkylbenzenes derived from olefins or polymers C 15 - C 30 olefins, and alkaline earth metals such as calcium, barium, magnesium ...
- the alkaline-earth compound to be used can consist of oxides or hydroxides of calcium, barium, magnesium ... taken alone or as a mixture; 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.
- the 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" prior to the sulfurization-neutralization step, the alkaline earth metal alkyl benzene sulfcnate by the action of an oxide or hydroxide of said alkaline earth metal on an alkylbenzene sulfonic acid as defined above in the presence of oil and of alkylene glycol optionally, at a temperature between 40 and 110 ° C, the amount of metal oxide or hydroxide alkaline earth metal and 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 T B N greater than or equal to 250 and having a large percentage by weight of calcium or barium (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.
- magnesium oxide any type can be used, "active" magnesium oxide is preferred.
- active magnesium oxide denotes magnesium oxide Mg 0 with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g.
- magnesium oxide Mg 0 with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g.
- Maglite DE with a specific surface area close to 140 m2 / g marketed by Merck
- the "Ferumag” with a specific surface area close to 160 m2 / g and marketed by Rhône-Poulenc Industries.
- 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-dispersant of TBN between 200 and 300 for example to be added is generally between 1 and 3.5%; for an oil. for diesel engine 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 naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkyl benzenes and. dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers of silicon.
- lubricating oils such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives
- Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; we can cite for example antioxidant additives, anti-corrosion, ashless dispersant additives ...
- a carbonation operation is carried out using carbon dioxide at 165-170 ° C at atmospheric pressure until the absorption of C0 2 has ended; this phase lasts approximately 1 hour 30 minutes; the viscosity of the medium drops rapidly at the start of this phase and then stabilizes.
- the medium is filtered to remove the sediments and a solution is recovered in oil 100 N of detergent-, over-alkalized dispersant, which is degassed and whose characteristics are shown in Table I '.
- 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 solution of calcium sulfonate with a solution of approximately 60% in 1 oil 100 N of an alkylbenzene sulfonate of magnesium (sulfonate Mg for short) of 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.
- sulfonate Mg for short an alkylbenzene sulfonate of magnesium (sulfonate Mg for short) of 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.
- the base of the tank 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, instead of 160 g; there is a higher pew 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 alkylbenzene calcium sulfonate of TBN 260 instead of a mixture of sulfurized dodecylphenate and alkylbenzene sulfonate of TBN 260.
- 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, 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 stock.
- 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 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 that of Example 28.
- Example 33 The product of Example 33 is added to an S AE 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.
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- 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)
Abstract
Description
La présente invention a pour objet un procédé perfectionné de préparation d'additifs détergents-dispersants métalliques de haute alcalinité notamment pour les huiles lubrifiantes.The subject of the present invention is an improved process for the preparation of high alkalinity detergent-dispersant metal additives, in particular for lubricating oils.
Il est connu d'après le brevet français n° 1 356 763 de préparer des alkylphénates sulfurisés basiques par sulfurisation d'un alkylphénol en présence d'un sulfonate métallique, d'un monoalcool en C8-C18, d'une base alcalino- terreuse et d'éthylène glycol suivie d'une carbonatation à l'aide de gaz carbonique. Un tel procédé présente l'inconvénient de nécessiter des quantités relativement importantes d'éthylène glycol et en outre la présence d'un monoalcool.It is known from French Patent No. 1,356,763 to prepare basic sulfurized alkylphenates by sulfurization of an alkylphenol in the presence of a metal sulfonate, a C 8 -C 18 monoalcohol, an alkaline base - earthy and ethylene glycol followed by carbonation using carbon dioxide. Such a process has the disadvantage of requiring relatively large amounts of ethylene glycol and in addition the presence of a monoalcohol.
La demanderesse a trouvé un procédé perfectionné permettant d'obtenir.des additifs détergents-dispersants métalliques de TBN (Total Basic Number Norme ASTM D 2896) supérieur à 200, et ce d'une manière simple et rapide en présence d'alkylène glycol en faible quantité et sans que la présence d'un monoalcool soit indispensable.The Applicant has found an improved process making it possible to obtain metal detergent-dispersant additives with TBN (Total Basic Number Standard ASTM D 2896) greater than 200, and this in a simple and rapid manner in the presence of low alkylene glycol. quantity and without the presence of a monoalcohol is essential.
Le procédé perfectionné de préparation de détergents-dispersants métalliques à partir d'alkylbenzène sulfonates de métaux alcalino-terreux, d'alkylphénols, d'un composé de base alcalino-terreux, d'un alkylène glycol et de gaz carbonique est caractérisé :
- 1) en ce que l'on fait réagir du soufre sur un alkylphénol portant un ou plusieurs substituants alkyles en CS-C60, en présence d'une huile de dilution, d'un alkylbenzène sulfonate de métal alcalino-terreux de masse moléculaire supérieure à 300 et de TBN inférieur ou égal à 150, d'un composé alcalino-terreux, éventuellement d'hydroxyde de métal alcalin, d'un pied de cuve à base d'un détergent-dispersant métallique de TBN supérieur ou égal à 200 choisi parmi les alkylphénates suralcalinisés et sulfurisés de métaux alcalino-terreux et les mélanges d'alkylphénates suralcalinisés et sulfurisés de métaux alcalino-terreux et d'alkylbenzène sulfonates de métaux alcalino-terreux, et d'un alkylène glycol, à une température comprise entre 100 et 190°C, selon les quantités de réactifs suivantes :
- - au moins 5 parties en poids d'alkylphénol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - jusqu'à 95 parties en poids d'alkylbenzène sulfonate pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - de 1 à 18 parties en poids de soufre pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - de 4 à 45 parties en poids de composé alcalino-terreux pour 100 parties en poids de mélange alkylphénol- alkylbenzéne sulfonate.
- - jusqu'à 10 parties en poids d'hydroxyde de métal alcalin pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- de 2 à 35 parties en poids de pied de cuve pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - et de 8 à 200 parties en poids d'alkylène glycol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- 2) éventuellement, en ce que l'on poursuit l'opération de sulfurisation par chauffage à une température supérieure comprise entre 100 et 190°C.
- 3) en ce que l'on carbonate le mélange obtenu à l'aide de gaz carbonique à une température comprise entre 100 et 200°C, la quantité de CO2 étant comprise entre celle pouvant être complètement absorbée et un excès de 30 % de cette quantité.
- 4) en ce qu'on élimine l'akylène glycol.
- 5) en ce que l'on sépare le détergent-dispérsant métallique de haute alcalinité ainsi obtenu.
- 1) in that sulfur is reacted on an alkylphenol carrying one or more alkyl substituents in CS-C 60 , in the presence of a dilution oil, of an alkaline earth metal alkylbenzene sulfonate of higher molecular mass at 300 and a TBN less than or equal to 150, of an alkaline-earth compound, optionally of alkali metal hydroxide, of a base stock based on a metallic detergent-dispersant of TBN greater than or equal to 200 chosen among alkalinized and sulfurized alkylphenates of alkaline earth metals and mixtures of alkylphenates overbased and sulfurized with alkaline earth metals and alkylbenzene sulfonates with alkaline earth metals and an alkylene glycol, at a temperature between 100 and 190 ° C, according to the following amounts of reactants:
- - At least 5 parts by weight of alkylphenol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - Up to 95 parts by weight of alkylbenzene sulfonate per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - from 1 to 18 parts by weight of sulfur per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - from 4 to 45 parts by weight of alkaline-earth compound per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - Up to 10 parts by weight of alkali metal hydroxide per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- from 2 to 35 parts by weight of the base stock per 100 parts by weight of the alkylphenol-alkylbenzene sulfonate mixture.
- - And from 8 to 200 parts by weight of alkylene glycol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- 2) optionally, in that the sulfurization operation is continued by heating to a higher temperature between 100 and 190 ° C.
- 3) in that the mixture obtained is carbonated using carbon dioxide at a temperature between 100 and 200 ° C, the amount of CO 2 being between that which can be completely absorbed and an excess of 30% of that amount.
- 4) in that the akylene glycol is eliminated.
- 5) in that the metal detergent-dispersant of high alkalinity thus obtained is separated.
On désigne par "alkylbenzène sulfonate" toute solution contenant de 40,à 95 % en poids, de préférence de 55 à 85 % en poids d'un alkylbenzène sulfonate dans une huile de dilution, qui peut être ou peut ne pas être la même que celle mise en oeuvre pour-réaliser le procédé objet de l'invention.The term “alkylbenzene sulfonate” denotes any solution containing from 40 to 95% by weight, preferably from 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 which is the subject of the invention.
D'une manière préférentielle, on réalisera :
- 1) l'étape de sulfurisation à partir d'un alkylbenzène sulfonate de TBN inférieur ou égal à 50, à une température comprise entre 120 et 180°C, à une pression inférieure ou égale à la pression atmosphérique, avec les quantités de réactifs suivantes :
- - de 10 à 60 parties en poids d'alkylphénol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - de 40 à 90 parties en poids d'alkylbenzène sulfonate pour 100 parties en poids de mélange alkylphénol-alkyl-' benzène sulfonate.
- - de 2 à 12 parties en poids de soufre pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - de 6 à 40 parties en poids décomposé alcalino-terreux pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate..
- - jusqu'à 8 parties en poids d'hydroxyde de métal alcalin pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - de 3 à 20 parties en poids de pied de cuve pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- - et de 10 à 50 parties en poids d'alkylène glycol pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate.
- 2) l'étape éventuelle de sulfurisation complémentaire à une température supérieure comprise entre 130'et 185°C, à une pression inférieure ou égale à la pression atmosphérique.
- 3) l'étape de carbonatation à une température comprie se entre 100 et 185°C, à l'aide d'une quantité de CO2 sensiblement égale à celle àouvant être complètement absorbée,
- 1) the sulfurization step from an alkylbenzene sulfonate with a TBN less than or equal to 50, at a temperature between 120 and 180 ° C., at a pressure less than or equal to atmospheric pressure, with the following amounts of reactants :
- - from 10 to 60 parts by weight of alkylphenol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - from 40 to 90 parts by weight of alkylbenzene sulfonate per 100 parts by weight of alkylphenol-alkyl- 'benzene sulfonate mixture.
- - from 2 to 12 parts by weight of sulfur per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - from 6 to 40 parts by weight of alkaline-earth decomposed per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture. .
- - up to 8 parts by weight of alkali metal hydroxide per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- - from 3 to 20 parts by weight of the base stock per 100 parts by weight of the alkylphenol-alkylbenzene sulfonate mixture.
- - And from 10 to 50 parts by weight of alkylene glycol per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture.
- 2) the optional step of additional sulfurization at a higher temperature between 130 ° and 185 ° C., at a pressure less than or equal to atmospheric pressure.
- 3) the carbonation stage at a temperature between 100 and 185 ° C, using an amount of CO 2 substantially equal to that to be able to be completely absorbed,
Parmi les alkylphénols pouvant être mis en oeuvre pour réaliser le procédé objet de l'invention, on peut citer de préférence ceux portant un ou plusieurs substituants alkyles en C9 - C15, et tout particulièrement les nonyl, décyl, dodécyl ou tétradécylphénols.Among the 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.
Parmi les alkylbenzène sulfonates pouvant être mis en oeuvre on peut citer les sels d'acides sulfoniques (de poids moléculaire de préférence supérieur à 400) naturels obtenus par sulfonation de coupes pétrolières ou synthétiques obtenus par sulfonation d'alkylbenzènes dérivant d'oléfines ou de polymères d'oléfines en C15 - C30, et de métaux alcalino-terreux tels que calcium, baryum, magnésium ...Among the 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 cuts obtained by sulfonation of alkylbenzenes derived from olefins or polymers C 15 - C 30 olefins, and alkaline earth metals such as calcium, barium, magnesium ...
Le composé alcalino-terreux à mettre en oeuvre peut être constitué d'oxydes ou d'hydroxydes de calcium, baryum, magnésium ... pris seul ou en mélange ; le métal dont dérive l'alkylbenzène sulfonate alcalino-terreux mis en oeuvre peut-être ou peut ne pas être le même que celui ou ceux contenus dans le composé alcalino-terreux. Parmi les hydroxydes de métaux alcalins pouvant être mis en oeuvre on peut citer les hydroxydes de sodium, lithium, potassium.The alkaline-earth compound to be used can consist of oxides or hydroxides of calcium, barium, magnesium ... taken alone or as a mixture; 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. Among the alkali metal hydroxides which can be used, mention may be made of sodium, lithium and potassium hydroxides.
Parmi les huiles de dilution pouvant être mises en oeuvre on peut citer de préférence les huiles paraffiniques telles que l'huile 100 Neutral ... ; les huiles naphténiques ou mixtes peuvent également convenir. La quantité d'huile de dilution pouvant être mise en oeuvre est telle que la quantité d'huile contenue dans le produit final (y compris celle provenant de l'alkylbenzène sulfonate de départ) représente de 20 à 60 % en poids dudit produit et de préférence de 25 à 55 % dudit produit.Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil, etc .; naphthenic or mixed oils may also be suitable. 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.
Une variante du procédé faisant l'objet de l'invention consiste à préparer "in situ" préalablement à l'étape de sulfurisation-neutralisation, l'alkylbenzène sulfcnate de métal alcalino-terreux par action d'un oxyde ou hydroxyde dudit métal alcalino-terreux sur un acide alkylbenzène sulfonique tel que défini ci-dessus en présence d'huile et d'alkylène glycol éventuellement, à une température comprise entre 40 et 110°C, la quantité d'oxyde ou d'hydroxyde de métal alcalino-terreux et d'huile à mettre en oeuvre étant telle que l'alkylbenzène sulfonate obtenu présente un T B N inférieur ou égal à 150, de préférence inférieur ou égal à 50.A variant of the process which is the subject of the invention consists in preparing "in situ" prior to the sulfurization-neutralization step, the alkaline earth metal alkyl benzene sulfcnate by the action of an oxide or hydroxide of said alkaline earth metal on an alkylbenzene sulfonic acid as defined above in the presence of oil and of alkylene glycol optionally, at a temperature between 40 and 110 ° C, the amount of metal oxide or hydroxide alkaline earth metal and 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.
Le procédé faisant l'objet de l'invention est tout particulièrement intéressant pour préparer des détergents dispersants de T B N supérieur ou égal à 250 et présentant un pourcentage en poids important de calcium ou de baryum (au moins 10 %).The process which is the subject of the invention is very particularly advantageous for preparing detergent dispersants with T B N greater than or equal to 250 and having a large percentage by weight of calcium or barium (at least 10%).
Ledit procédé pourra être réalisé à partir d'un alkylbenzène sulfonate de calcium et/ou de baryum avec les quantités particulières des réactifs suivants :
- - de 15 à 45 parties en poids, de préférence de 18 à 40 parties en poids d'hydroxyde de calcium ou de baryum comme composé alcalino-terreux pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate de calcium et/ou de baryum.
- - de 2 à 35 parties en poids, de préférence de 3 à 18 parties en poids de pied de cuve de TBN supérieur ou égal à 250 constitué d'un alkylphénate sulfurisé et car-. bonaté de calcium et/ou de baryum et/ou d'un alkylbenzène sulfonate carbonaté de calcium et/ou de baryum pour 100 parties en poids de mélange alkylphénol - alkylbenzène sulfonate de calcium et/ou de baryum.
- - de 6 à 30 parties en poids, de préférence de 10 à 20 parties en poids d'alkylène glycol pour 100 parties en poids de mélange àlkylphénol-alkylbenzène sulfonate de calcium et/ou de baryum.
- - from 15 to 45 parts by weight, preferably from 18 to 40 parts by weight of calcium hydroxide or barium as alkaline-earth compound per 100 parts by weight of calcium alkylphenol-alkylbenzene sulfonate and / or barium mixture.
- - from 2 to 35 parts by weight, preferably from 3 to 18 parts by weight of the base stock of TBN greater than or equal to 250 consisting of a sulfurized alkylphenate and car-. bonate of calcium and / or barium and / or of an alkylbenzene sulfonate calcium carbonate and / or of barium per 100 parts by weight of alkylphenol - calcium alkylbenzene sulfonate and / or barium mixture.
- - from 6 to 30 parts by weight, preferably from 10 to 20 parts by weight of alkylene glycol per 100 parts by weight of mixture of alkylphenol-alkylbenzene sulfonate of calcium and / or barium.
Le procédé faisant l'objet de l'invention est également intéressant pour préparer des détergents-dispersants de TBN supérieur à 200 et contenant au moins 2 % en poids de magnésium et éventuellement au moins 0,5 % en poids de calcium.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.
Le procédé consiste alors à mettre en oeuvre :
- - un alkylbenzène sulfonate de magnésium et/ou de calcium comme alkylbenzène sulfonate de métal alcalion- terreux.
- - un mélange d'oxyde de magnésium et d'hydroxyde de calcium comme composé alcalino-terreux ou de l'oxyde de magnésium comme composé alcalino-terreux, en mélange avec un hydroxyde de métal alcalin.
- - un pied de cuve constitué d'un alkylbenzène sulfonate carbonaté de magnésium et/ou de calcium et/ou d'un alkylphénate sulfurisé et carbonaté de magnésium et/ou de calcium de TBN supérieur ou égal à 200 et éventuellement à traiter à un stade quelconque de l'étape de carbonatation le milieu par O à 10 % en poids, de préférence par 0 à 5 % en poids d'eau par rapport au poids dudit milieu réactionnel.
- - A magnesium and / or calcium alkylbenzene sulfonate as alkali earth metal alkylbenzene sulfonate.
- - a mixture of magnesium oxide and calcium hydroxide as an alkaline earth compound or of magnesium oxide as an alkaline earth compound, in admixture with an alkali metal hydroxide.
- - a base stock consisting of a carbonated alkylbenzene sulfonate of magnesium and / or calcium and / or a sulfurized and carbonated alkylphenate of magnesium and / or calcium of TBN greater than or equal to 200 and optionally to be treated at a stage any of the carbonation step the medium with 0 to 10% by weight, preferably with 0 to 5% by weight of water relative to the weight of said reaction medium.
Bien que n'importe quel type d'oxyde de magnésium puisse être utilisé, on préfère toutefois l'oxyde de magnésium "actif"Although any type of magnesium oxide can be used, "active" magnesium oxide is preferred.
On désigne par oxyde de magnésium "actif" de l'oxyde de magnésium Mg 0 de surface spécifique supérieure ou égale à 80 m2/g, par exemple comprise entre 100 et 170 m2/g. A titre d'exemple on peut citer la "Maglite DE" de surface' spécifique voisine de 140 m2/g commercialisée par Merck et le "Ferumag" de surface spécifique voisine de 160 m2/g et commercialisé par Rhône-Poulenc Industries.The term “active” magnesium oxide denotes magnesium oxide Mg 0 with a specific surface greater than or equal to 80 m2 / g, for example between 100 and 170 m2 / g. By way of example, there may be mentioned the "Maglite DE" with a specific surface area close to 140 m2 / g marketed by Merck and the "Ferumag" with a specific surface area close to 160 m2 / g and marketed by Rhône-Poulenc Industries.
Pour une bonne réalisation de ce procédé, on met en oeuvre les quantités particulières de réactifs suivants :
- - de 4 à 40 parties, de préférence de 5 à 30 parties en poids de composé alcalino-terreux pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate de magnésium et/ou de calcium.
- - de 4 à 25 parties, de préférence de 5 à 20 parties en poids d'ogyde de magnésium pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate de magnésium ét/ou de calcium.
- - jusqu'à 25 parties, de préférence jusqu'à 18 parties en poids d'hydroxyde de calcium pour 100 parties de mélange alkylphénoo-alkylbenzène sulfonate de magnésium et/ou de calcium.
- - jusqu'à 10 parties, de préférence de 0,1 à 8 parties d'hydroxyde de métal alcalin pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate de magnésium et/ou de calcium.
- - de 8 à 200 parties, de préférence de 10 à 50 parties d'alkylène glycol pour 100 parties de mélange alkylpnénol- alkylbenzène sulfonate de magnésium et/ou de calcium.
- - de 2 à 25 parties de préférence de 10 à 20 parties de pied de cuve pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate de magnésium et/ou de calcium.
- - from 4 to 40 parts, preferably from 5 to 30 parts by weight of alkaline-earth compound per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium.
- - from 4 to 25 parts, preferably from 5 to 20 parts by weight of magnesium oxide per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium et / or calcium.
- - up to 25 parts, preferably up to 18 parts by weight of calcium hydroxide per 100 parts of alkylphenoo-alkylbenzene mixture of magnesium and / or calcium.
- - Up to 10 parts, preferably from 0.1 to 8 parts of alkali metal hydroxide per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium.
- - from 8 to 200 parts, preferably from 10 to 50 parts of alkylene glycol per 100 parts of alkylpnenol-alkylbenzene sulfonate mixture of magnesium and / or calcium.
- - from 2 to 25 parts, preferably from 10 to 20 parts of base stock per 100 parts of alkylphenol-alkylbenzene sulfonate mixture of magnesium and / or calcium.
La présente invention a également pour objet les détergents-dispersants de haute alcalinité obtenus par le procédé décrit ci-dessus. Ceux-ci présentent l'avantage d'une bonne compatibilité avec les huiles visqueuses ainsi qu'un très faible taux de sédiments. Ils peuvent être ajoutés à des huiles lubrifiantes selon des quantités fonction du TBN desdits détergents-dispersants, et fonction de l'utilisation future desdites huiles ; ainsi pour une huile pour moteur à essence, la quantité de détergents-dispersant de TBN compris entre 200 et 300 par exemple à ajouter est généralement comprise entre 1 et 3,5 % ; pour une huile . pour moteur diesel elle est généralement comprise entre 1,8 et 5 % ; pour une huile pour moteur marin celle-ci peut aller jusqu'à 25 %.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-dispersant of TBN between 200 and 300 for example to be added is generally between 1 and 3.5%; for an oil. for diesel engine it is generally between 1.8 and 5%; for marine engine oil this can be up to 25%.
Les huiles lubrifiantes que l'on peut ainsi améliorer peuvent être choisies parmi des huiles lubrifiantes très variées, comme les huiles lubrifiantes de base naphténique, de base paraffinique et de base mixte, d'autres lubrifiants hydrocarbonés, par exemple des huiles lubrifiantes dérivées de produits de la houille, et des huiles synthétiques, par exemple des polymères d'alkylène, des polymères du type oxyde d'alkylène et leurs dérivés, y compris les polymères d'oxyde d'alkylène préparés en polymérisant de l'oxyde d'alkylène en présence d'eau ou d'alcools, par exemple d'alcool éthylique, les esters d'acides dicarboxyliques, des esters liquides d'acides du phosphore, des alkylben- zènes et. des dialkylbenzènes,des polyphényles, des alkyl biphényl éthers, des polymères du silicium.The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkyl benzenes and. dialkylbenzenes, polyphenyls, alkyl biphenyl ethers, polymers of silicon.
Des additifs supplémentaires peuvent également être présents dans lesdites huiles lubrifiantes à côté des détergents-dispersants obtenus selon le procédé de l'invention ; on peut citer par exemple des additifs antioxydants, anti-corrosion, des additifs dispersants sans cendres ...Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; we can cite for example antioxidant additives, anti-corrosion, ashless dispersant additives ...
Les exemples suivants sont donnés à titre indicatif et ne peuvent être considérés comme une limite du domaine et de l'esprit de l'invention.The following examples are given for information only and cannot be considered as limiting the scope and spirit of the invention.
On décrit ci-après le mode général de préparation (4 phases) des détergents-dispersants suralcalinisés faisant l'objet des exemples 1 à 4 et dans les tableaux I et I' les quantités de réactifs nécessaires à leur préparation.The general mode of preparation (4 phases) of the overbased detergent-dispersants described in Examples 1 to 4 is described below and in the tables I and I ′ the quantities of reagents necessary for their preparation.
On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage :
- - du dodécylphénol (DDP)
- - de l'huile 100 N
- - une solution à environ 60 % dans de l'huile de dilution 100 N d'un alkylbenzène sulfonate de calcium (sulfonate Ca en abréviation) de masse moléculaire 470 environ (masse du sel de sodium), solution contenant 2,7% de calcium et présentant un TBN de 25 environ ;
- - un antimousse commercialisé par Rhône-Poulenc sous la dénomination SI 200 ;
- - un pied de cuve constitué d'un mélange de détergents suralcalinisés de TBN 260, à base de dodécylphénate de calcium sulfurisé et suralcalinisé et d'alkylbenzène sulfonate de calcium suralcalinisé de masse moléculaire 470 environ.
- - dodecylphenol (DDP)
- - 100 N oil
- - a solution of about 60% in 100 N dilution oil of a calcium alkylbenzene sulfonate (sulfonate Ca for short) of molecular weight about 470 (mass of the sodium salt), solution containing 2.7% of calcium and having a TBN of about 25;
- - an antifoam sold by Rhône-Poulenc under the name SI 200;
- - a base stock consisting of a mixture of overbased detergents of TBN 260, based on sulfurized and overbased calcium dodecylphenate and of overbased calcium alkylbenzene sulfonate of molecular weight 470 approximately.
On introduit alors sous agitation de la chaux et du soufre ; on porte le milieu à 145°C sous légère dépression, puis on ajoute du glycol en 80 minutes en chauffant à 165°C et on maintient cette température pendant 1 heure sous légère dépression pour éliminer complètement l'eau de réaction provenant de la neutralisation de la chaux, et pour prolonger la sulfurisation.Then introduced with stirring lime and sulfur; the medium is brought to 145 ° C. under slight depression, then glycol is added over 80 minutes while heating to 16 5 ° C. and this temperature is maintained for 1 hour under slight depression to completely eliminate the reaction water originating from neutralization lime, and to prolong the sulfurization.
L'eau éliminée entraine toujours avec elle un peu de glycol.The eliminated water always carries with it a little glycol.
Après avoir réajusté la quantité de glycol à sa valeur première, on réalise une opération de carbonatation à l'aide de gaz carbonique à 165-170°C à pression atmosphérique jusqu'à la fin de l'absorption de C02 ; cette phase dure environ 1 h 30 ; la viscosité du milieu chute rapidement au début de cette phase puis se stabilise.After having readjusted the amount of glycol to its initial value, a carbonation operation is carried out using carbon dioxide at 165-170 ° C at atmospheric pressure until the absorption of C0 2 has ended; this phase lasts approximately 1 hour 30 minutes; the viscosity of the medium drops rapidly at the start of this phase and then stabilizes.
De l'eau s'élimine en entraînant avec elle un peu de glycol.Water is eliminated by carrying with it a little glycol.
On porte le milieu à une température de 184°C sous 20 mm de mercure pendant une heure.The medium is brought to a temperature of 184 ° C. under 20 mm of mercury for one hour.
Le milieu est filtré pour éliminer les sédiments et on récupère une solution dans de l'huile 100 N de détergent-, dispersant suralcalinisé, que l'on dégaze et dont les caractéristiques figurent au tableau I'.The medium is filtered to remove the sediments and a solution is recovered in oil 100 N of detergent-, over-alkalized dispersant, which is degassed and whose characteristics are shown in Table I '.
L'opération a duré au total 10 heures.The operation lasted a total of 10 hours.
Les opérations décrites aux exemples 1 à 4 sont réalisées dans les mêmes conditions à partir d'une solution à 60 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium, de masse moléculaire de 470 environ, solution contenant 3,4 % de calcium et présentant un TBN de 45 environ.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.
De plus, les produits obtenus respectivement aux exemples 1 à 4 sont utilisés comme pieds de cuve respectivement dans les exemples 5 à 8.In addition, the products obtained respectively in Examples 1 to 4 are used as base stock respectively in Examples 5 to 8.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux II et II' .The quantities of reagents used and the characteristics of the products obtained are shown in Tables II and II '.
Les opérations décrites aux exemples 1 à 4 sont réalisées dans les mêmes conditions à partir d'une solution à 60 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium neutre de masse moléculaire 470 environ, solution contenant 1,8 % de calcium et présentant un TBN nul.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 neutral calcium alkylbenzene sulfonate of molecular weight approximately 470, solution containing 1.8% calcium and having a zero TBN.
Les produits obtenus respectivement aux exemples 1 à 4 ou 5 à 8 sont utilisés comme pieds de cuve respectivement dans les exemples 9 à 12.The products obtained respectively in Examples 1 to 4 or 5 to 8 are used as base stock respectively in Examples 9 to 12.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux III et III'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables III and III '.
Les opérations décrites aux exemples 1 à 4 sont réalisées dans les mêmes conditions à partir d'une solution à 80 % dans de l'huile 100 N d'un alkylbenzène sulfonate de calcium, de masse moléculaire de 470 environ, solution contenant 3,37 % de calcium présentant un TBN de 33.The operations described in 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.
Les produits obtenus respectivement soit aux exemples 1 à 4, aux exemples 5 à 8 ou aux exemples 9 à 12 sont utilisés comme pieds de cuve dans les exemples 13 à 16.The products obtained respectively in Examples 1 to 4, in Examples 5 to 8 or in Examples 9 to 12 are used as base stock in Examples 13 to 16.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux IV et IV'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IV and IV '.
L'opération décrite à l'exemple 2 est réalisée en remplaçant la solution de sulfonate de calcium par une solution à environ 60 % dans de 1 huile 100 N d'un alkylbenzène sulfona té de magnésium (sulfonate Mg en abréviation) de masse moléculaire de 470 environ, solution contenant 1,5 % de magnésium et présentant un TBN de 20 environ, afin d'obtenir un détergent-dispersant contenant du calcium et du magnésium.The operation described in Example 2 is carried out by replacing the solution of calcium sulfonate with a solution of approximately 60% in 1 oil 100 N of an alkylbenzene sulfonate of magnesium (sulfonate Mg for short) of 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.
Le pied de cuve utilisé est constitué par l'un des produits préparés aux exemples 2, 6, 10 ou 14.The base of the tank used consists of one of the products prepared in Examples 2, 6, 10 or 14.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux V et V' .The quantities of reagents used and the characteristics of the products obtained are shown in Tables V and V '.
On réalise l'opération décrite à l'exemple 6 en modifiant comme suit le mode opératoire :
- - la phase de sulfurisation est réalisée à 155°C à pression atmosphérique en présence de 175 g de glycol et 35 g d'alcool OXO en C10 (soit 20 % du poids de glycol) et suivie d'un stade de déshydratation à 180°C à pression atmosphérique.
- - the sulfurization phase is carried out at 155 ° C at atmospheric pressure in the presence of 175 g of glycol and 35 g of C 10 OXO alcohol (i.e. 20% by weight of glycol) and followed by a dehydration stage at 180 ° C at atmospheric pressure.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en effectuant l'étape de sulfurisation à 170°C à pression atmosphérique pendant une heure ; le stade subséquent de déshydratation est alors superflu.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.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en modifiant comme suit le mode opératoire :
- - la phase de sulfurisation est réalisée à 145°C à pression atmosphérique en présence de 175 g de glycol et 35 g d'hexanol (soit 20 % du poids de glycol) et suivie d'un stade de déshydratation à 150°C à pression atmosphérique.
- - the sulfurization phase is carried out at 145 ° C at atmospheric pressure in the presence of 175 g of glycol and 35 g of hexanol (i.e. 20% by weight of glycol) and followed by a dehydration stage at 150 ° C at pressure atmospheric.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6, en modifiant comme suit le mode opératoire :
- - la phase de sulfurisation est réalisée à 155°C sous 580 mmHg en présence de 200 g de glycol, et suivie d'une phase de déshydratation à 145°C sous 400 mmHg. les caractéristiques du produit sont semblables à celles de celui de l'exemple 6.
- - The sulfurization phase is carried out at 155 ° C under 580 mmHg in the presence of 200 g of glycol, and followed by a dehydration phase at 145 ° C under 400 mmHg. the characters the product is similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en mettant en oeuvre 40 g de pied de cuve, au lieu de 160 g ; on constate une viscosité un pew plus importante du milieu après sulfurisation et une vitesse de filtration légèrement inférieure.The operation described in Example 6 is carried out using 40 g of base stock, instead of 160 g; there is a higher pew viscosity of the medium after sulfurization and a slightly lower filtration speed.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en mettant en oeuvre 203 g de pied de cuve au lieu de 160 g.The operation described in Example 6 is carried out using 203 g of base stock instead of 160 g.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en mettant en oeuvre 152 g de glycol au lieu de 174 g.The operation described in Example 6 is carried out using 152 g of glycol instead of 174 g.
Les caractéristiques du produit obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to that of Example 6.
On réalise l'opération décrite à l'exemple 6 en mettant en oeuvre 230 g de glycol au lieu de 174 g.The operation described in Example 6 is carried out using 230 g of glycol instead of 174 g.
Les caractéristiques du produit-obtenu sont semblables à celles de celui de l'exemple 6.The characteristics of the product obtained are similar to those of Example 6.
On réalise l'opération semblable à celle décrite à l'exemple 6 en mettant en oeuvre 160 g d'un pied de cuve constitué de dodécylphénate de calcium sulfurisé et suralcalinisé de TBN 200 au lieu d'un mélange de dodécylphénate sulfurisé et d'alkylbenzène sulfonate de TBN 260.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.
Les quantités de réactifs mises en oeuvre et les caractéristiques du produit obtenu, figurent aux tableaux VI et VI' .The quantities of reagents used and the characteristics of the product obtained are shown in Tables VI and VI '.
On réalise l'opération décrite à l'exemple 6 en mettant en oeuvre un pied de cuve constitué d'alkylbenzène sulfonate de calcium de TBN 260 au lieu d'un mélange de dodécylphénate sulfurisé et d'alkylbenzène sulfonate de TBN 260.The operation described in Example 6 is carried out using a base stock consisting of alkylbenzene calcium sulfonate of TBN 260 instead of a mixture of sulfurized dodecylphenate and alkylbenzene sulfonate of TBN 260.
Les caractéristiques du produit obtenu sont semblables à celles de l'exemple 6, ainsi que les quantités de réactifs mises en oeuvre.The characteristics of the product obtained are similar to those of Example 6, as well as the quantities of reagents used.
On décrit ci-après le mode général de préparation des détergents-dispersants suralcalinisés contenant au moins 2 % de magnésium faisant l'objet des exemples 28 à 37 et dans les tableaux VII et VIII les quantités de réactifs nécessaires à leur préparation.The general mode of preparation of the overbased detergent-dispersants containing at least 2% magnesium described in Examples 28 to 37 and in Tables VII and VIII are described below the amounts of reagents necessary for their preparation.
On introduit dans un réacteur tétracol de 4 litres muni d'un système d'agitation et d'un dispositif de chauffage :
- - du dodécylphénol
- - de l'huile 100 N
- - une solution à environ 60 % dans dé l'huile de dilution 100 N d'un alkylbenzène sulfonate de magnésium (sulfonate Mg en abréviation) de masse moléculaire 470 environ, solution contenant 1,8 % de magnésium et présentant un TBN de 25 environ.
- - un antimousse commercialisé par RHONE-POULENC sous la dénomination SI 200.
- - un pied de cuve constitué d'un mélange de détergents-dispersants suralcalinisés à base d'un dodécylphénate de calcium sulfurisé et suralcalinisé et d'un alkylbenzène- sulfonate de magnésium suralcalinisé de masse moléculaire 470 environ.
- - dodecylphenol
- - 100 N oil
- - a solution of about 60% in 100 N dilution oil of a magnesium alkylbenzene sulfonate (sulfonate Mg for short) of molecular weight about 470, solution containing 1.8% of magnesium and having a TBN of about 25 .
- - an antifoam sold by RHONE-POULENC under the name SI 200.
- - a base stock consisting of a mixture of overbased detergent-dispersants based on a sulfurized and overbased calcium dodecylphenate and an overbased magnesium alkylbenzene sulfonate of molecular weight 470 approximately.
. On introduit sous agitation de la "Maglite DE", de la chaux et du soufre ; on porte le milieu à 145°C sous légère dépression, puis on ajoute du glycol en 1 heure en chauffant à 165°C ; on maintient cette température pendant 1 heure sous légère dépression.. Are introduced with stirring "Maglite DE", lime and sulfur; the medium is brought to 145 ° C under slight depression, then glycol is added over 1 hour while heating to 165 ° C; this temperature is maintained for 1 hour under slight depression.
2ème phase (carbonatation)2nd phase (carbonation)
On réajuste la quantité de glycol à sa valeur première et on réalise une opération de carbonatation à l'aide de gaz carbonique à 165°C pendant 7 heures. On re- froidit à 110°C pendant 1 heure 30 minutes.We readjust the amount of glycol to its value first and a carbonation operation is carried out using carbon dioxide at 165 ° C for 7 hours. R is e - froidit at 110 ° C for 1 hour 30 minutes.
La 3ème phase et la 4ème phase sont réalisées comme aux exemples précédents.The 3rd phase and the 4th phase are carried out as in the previous examples.
On répète l'opération décrite à l'exemple 28 en réalisant l'étape de sulfurisation à 180°C.The operation described in Example 28 is repeated, carrying out the sulfurization step at 180 ° C.
Les caractéristiques du produit obtenu sont analogues à celles de celui de l'exemple 28.The characteristics of the product obtained are similar to those of that of Example 28.
On répète l'opération décrite à l'exemple 28 en réalisant l'étape de carbonatation à 145°C.The operation described in Example 28 is repeated, carrying out the carbonation step at 145 ° C.
Les caractéristiques du produit obtenu sont analogues à celles de celui de l'exemple 28.The characteristics of the product obtained are similar to those of that of Example 28.
L'opération décrite à l'exemple 28 est réalisée à partir d'un alkylbenzène sulfonate de magnésium en solution à 60 % présentant un TBN de 45 et un taux de magnésium de 2,2 %.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%.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux IX et IX'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IX and IX '.
On répète l'opération décrite à l'exemple 29 en réalisant l'opération de sulfurisation en présence de glycol et d'alcool.tridécylique.The operation described in Example 29 is repeated, carrying out the sulfurization operation in the presence of glycol and tridecyl alcohol.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux IX et IX'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IX and IX '.
On répète l'opération décrite à l'exemple 28 en réalisant l'étape de sulfurisation en mettant en oeuvre un pied de cuve constitué d'un alkylbenzène sulfonate de magnésium suralcalinisé de TBN 200.The operation described in Example 28 is repeated, carrying out the sulfurization step by using a base stock consisting of an overbased magnesium alkylbenzene sulfonate of TBN 200.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produits obtenus figurent aux tableaux IX et IX'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IX and IX '.
On répète l'opération décrite à l'exemple 28 en mettant en oeuvre un dodécylphénate de calcium suralcalinisé de TBN 200 comme pied de cuve.The operation described in Example 28 is repeated, using an overbased calcium dodecylphenate of TBN 200 as the base stock.
Les quantités de réactifs mises en oeuvre et les caractéristiques des produite obtenus figurent aux tableaux IX et IX'.The quantities of reagents used and the characteristics of the products obtained are shown in Tables IX and IX '.
On réalise l'opération décrite à l'exemple 32, en remplaçant les 20 g de chaux par 10 g de soude ; les caractéristiques du produit obtenu sont équivalents à celles de celui de l'exemple 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 example 32.
On réalise l'opération décrite à l'exemple 28 sans introduire d'eau au cours de 1'opération de carbonatation. Les caractéristiques du produit obtenu sont équivalentes à celles de celui de l'exemple 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 that of Example 28.
Les % de sédiments figurant dans les tableaux ci-dessous ont été mesurés selon la norme ASTMD 2273-67, en apportant toutefois les modifications suivantes : .
- - vitesse de rotation de la centrifugeuse 6 000 t/mn,
- - force centrifuge relative 10 000
- - le produit à analyser est dilué au quart dans de l'essence E (25 cm3 de produit à analyser + 75 cm3 d'essence E) .
- - durée de la centrifugation : 10 minutes.
- - rotation speed of the centrifuge 6,000 rpm,
- - relative centrifugal force 10,000
- - the product to be analyzed is diluted to a quarter in gasoline E (25 cm3 of product to be analyzed + 75 cm3 of gasoline E).
- - duration of centrifugation: 10 minutes.
Les tests de compatibilité figurant dans les tableaux ci-dessous ont été réalisés par addition de 10 % en poids de produit à tester à une huile minérale SAE 30, stockage de la solution obtenue pendant 1 mois à 20°C et étude de l'aspect de la solution en fonction du temps.The compatibility tests appearing in the tables below were carried out by adding 10% by weight of product to be tested to a SAE 30 mineral oil, storage of the solution obtained for 1 month at 20 ° C. and study of the appearance. of the solution as a function of time.
Le produit de l'exemple 33 est ajouté à une huile SAE 50 à tendance paraffinique de façon à obtenir une solution contenant 125 millimolés de calcium + magnésium. La solution est stockée pendant 15 jours à 20°C ; on comstate que la solution reste limpide.The product of Example 33 is added to an S AE 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.
Le même test est réalisé avec un mélange :
- - d'alkylbenzène sulfonate de magnésium de TBN 100
- . - d'alkylbenzène sulfonate de calcium de TBN 25
- - d'alkylphénate de calcium de TBN 150 en quantité telle que la solution obtenue contienne 125 millimoles de calcium + magnésium.
- - TBN 100 magnesium alkylbenzene sulfonate
- . - TBN 25 calcium alkylbenzene sulfonate
- - calcium alkylphenate of TBN 150 in an amount such that the solution obtained contains 125 millimoles of calcium + magnesium.
Après 15 jours de stockage à 20°C, la solution est trouble et floculeuse.After 15 days of storage at 20 ° C, the solution is cloudy and flocculent.
On prépare un mélange (A) d'additifs contenant :
- - 2 % d'un dispersant à base de polyisobutenyl suc- cinimide,
- - 1,6 millimole d'un dithiophosphate de zinc
- - et 2,3 % de produit de l'exemple 33.
- - 2% of a dispersant based on polyisobutenyl succinimide,
- - 1.6 millimole of a zinc dithiophosphate
- - and 2.3% of product from Example 33.
Ce mélange est porté pendant 25 jours à 80°C puis est ajouté à une huile SAE 30 de manière à avoir une concentration de 6,6 % en poids de mélange (A)..This mixture 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).
La solution est stockée pendant 5 jours à 80°C.The solution is stored for 5 days at 80 ° C.
Ce même test est réalisé avec un mélange (B) constitué de :
- - 2 % d'un dispersant à base de polyisobutenyl- succinimide,
- - 1,6 m mole de dithiophosphate de zinc
- - et 2,3 % d'un mélange constitué :
- - d'alkylbenzènè sulfonate de magnésium de TBN 400
- - d'alkylbenzène sulfonate de calcium de TBN 25
- - d'alkylphénate de calcium de TBN 150 présentant un nombre de millimoles de calcium + magnésium équivalent à celui du produit de l'exemple 33.
- - 2% of a dispersant based on polyisobutenyl-succinimide,
- - 1.6 mole of zinc dithiophosphate
- - and 2.3% of a mixture consisting of:
- - of magnesium alkylbenzene sulfonate of TBN 400
- - TBN 25 calcium alkylbenzene sulfonate
- - TBN 150 calcium alkylphenate having a number of millimoles of calcium + magnesium equivalent to that of the product of Example 33.
On constate que la solution contenant le mélange (A) est plus claire et plus brillante que celle contenant le mélange (B).
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT79400390T ATE243T1 (en) | 1978-06-26 | 1979-06-14 | PROCESS FOR THE MANUFACTURE OF HIGH ALKALINE METAL CONTAINING CLEANING DISPERSING ADDITIVES, ESPECIALLY FOR LUBRICATION OIL AND PRODUCT MADE THEREOF. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7818946 | 1978-06-26 | ||
| FR7818946A FR2429832A1 (en) | 1978-06-26 | 1978-06-26 | IMPROVED PROCESS FOR THE PREPARATION OF HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVES, PARTICULARLY FOR LUBRICATING OILS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0007260A1 true EP0007260A1 (en) | 1980-01-23 |
| EP0007260B1 EP0007260B1 (en) | 1981-09-23 |
Family
ID=9209959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP79400390A Expired EP0007260B1 (en) | 1978-06-26 | 1979-06-14 | Process for the preparation of metalliferous detergent-dispersant additives of high alkali content, especially for lubricating oils, and product obtained |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4293431A (en) |
| EP (1) | EP0007260B1 (en) |
| JP (1) | JPS6056199B2 (en) |
| AT (1) | ATE243T1 (en) |
| BR (1) | BR7903979A (en) |
| CA (1) | CA1129842A (en) |
| DE (1) | DE2960884D1 (en) |
| ES (1) | ES481864A1 (en) |
| FR (1) | FR2429832A1 (en) |
| MX (1) | MX5560E (en) |
| ZA (1) | ZA793196B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2063250B (en) * | 1979-10-02 | 1984-05-31 | Bdh Chemicals Ltd | Liquid crystal esters |
| FR2529224B1 (en) * | 1982-06-24 | 1986-02-07 | Orogil | NEW SURALKALINIZED DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS |
| FR2529225B1 (en) * | 1982-06-24 | 1986-04-25 | Orogil | NEW HIGH ALKALINITY METAL DETERGENT-DISPERSANT ADDITIVE FOR LUBRICATING OILS |
| US4971710A (en) * | 1986-10-21 | 1990-11-20 | Chevron Research Company | Methods for preparing, Group II metal overbased sulfurized alkylphenols |
| 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 |
| JPH039917Y2 (en) * | 1987-05-11 | 1991-03-12 | ||
| US4832857A (en) * | 1988-08-18 | 1989-05-23 | Amoco Corporation | Process for the preparation of overbased molybdenum alkaline earth metal and alkali metal dispersions |
| JPH0527277Y2 (en) * | 1989-08-23 | 1993-07-12 | ||
| 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 (en) * | 2021-02-02 | 2024-02-06 | 安徽澳润新材料有限公司 | High-base-number magnesium sulfonate detergent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1080531A (en) * | 1952-02-01 | 1954-12-09 | Standard Oil Dev Co | Preparation of compound products containing metal sulphonates and metal salts of aromatic sulphides |
| GB1015769A (en) * | 1962-05-15 | 1966-01-05 | California Research Corp | Process for overbased sulfurized metal phenates |
| US3923670A (en) * | 1973-02-22 | 1975-12-02 | John Crawford | Overbased phenates |
| FR2335588A1 (en) * | 1975-12-15 | 1977-07-15 | Karonite Chem Co Ltd | PROCESS FOR PREPARING SUPERALKALINIZED ADDITIVES FOR LUBRICATING OILS AND PRODUCTS OBTAINED |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3178368A (en) * | 1962-05-15 | 1965-04-13 | California Research Corp | Process for basic sulfurized metal phenates |
| 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 |
| GB1469289A (en) * | 1974-07-05 | 1977-04-06 | Exxon Research Engineering Co | Detergent additives |
-
1978
- 1978-06-26 FR FR7818946A patent/FR2429832A1/en active Granted
-
1979
- 1979-06-14 AT AT79400390T patent/ATE243T1/en not_active IP Right Cessation
- 1979-06-14 EP EP79400390A patent/EP0007260B1/en not_active Expired
- 1979-06-14 DE DE7979400390T patent/DE2960884D1/en not_active Expired
- 1979-06-19 US US06/049,959 patent/US4293431A/en not_active Expired - Lifetime
- 1979-06-21 MX MX798107U patent/MX5560E/en unknown
- 1979-06-22 CA CA330,659A patent/CA1129842A/en not_active Expired
- 1979-06-25 ES ES481864A patent/ES481864A1/en not_active Expired
- 1979-06-25 BR BR7903979A patent/BR7903979A/en not_active IP Right Cessation
- 1979-06-26 ZA ZA793196A patent/ZA793196B/en unknown
- 1979-06-26 JP JP54079792A patent/JPS6056199B2/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1080531A (en) * | 1952-02-01 | 1954-12-09 | Standard Oil Dev Co | Preparation of compound products containing metal sulphonates and metal salts of aromatic sulphides |
| GB1015769A (en) * | 1962-05-15 | 1966-01-05 | California Research Corp | Process for overbased sulfurized metal phenates |
| US3923670A (en) * | 1973-02-22 | 1975-12-02 | John Crawford | Overbased phenates |
| FR2335588A1 (en) * | 1975-12-15 | 1977-07-15 | Karonite Chem Co Ltd | PROCESS FOR PREPARING SUPERALKALINIZED ADDITIVES FOR LUBRICATING OILS AND PRODUCTS OBTAINED |
| US4057504A (en) * | 1975-12-15 | 1977-11-08 | Karonite Chemical Co., Ltd. | Method of preparing overbased lubricating oil additives |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0007260B1 (en) | 1981-09-23 |
| JPS6056199B2 (en) | 1985-12-09 |
| ES481864A1 (en) | 1980-02-16 |
| CA1129842A (en) | 1982-08-17 |
| JPS5540765A (en) | 1980-03-22 |
| FR2429832A1 (en) | 1980-01-25 |
| BR7903979A (en) | 1980-03-25 |
| ZA793196B (en) | 1980-06-25 |
| ATE243T1 (en) | 1981-10-15 |
| FR2429832B1 (en) | 1982-04-02 |
| MX5560E (en) | 1983-10-11 |
| DE2960884D1 (en) | 1981-12-10 |
| US4293431A (en) | 1981-10-06 |
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