US2794829A - Preparation of basic polyvalent metal salts of organic sulfonic acids - Google Patents
Preparation of basic polyvalent metal salts of organic sulfonic acids Download PDFInfo
- Publication number
- US2794829A US2794829A US407178A US40717854A US2794829A US 2794829 A US2794829 A US 2794829A US 407178 A US407178 A US 407178A US 40717854 A US40717854 A US 40717854A US 2794829 A US2794829 A US 2794829A
- Authority
- US
- United States
- Prior art keywords
- alkaline earth
- sulfonate
- earth metal
- alkylated aromatic
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000003839 salts Chemical class 0.000 title claims description 24
- 229910052751 metal Inorganic materials 0.000 title description 60
- 239000002184 metal Substances 0.000 title description 60
- 150000003460 sulfonic acids Chemical class 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 91
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 58
- 239000002904 solvent Substances 0.000 claims description 51
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 40
- 229930195733 hydrocarbon Natural products 0.000 claims description 39
- 150000002430 hydrocarbons Chemical class 0.000 claims description 39
- 239000004215 Carbon black (E152) Substances 0.000 claims description 30
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 28
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 25
- 239000007790 solid phase Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- 239000000284 extract Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- 125000003118 aryl group Chemical group 0.000 description 29
- -1 alkaline earth metal salts Chemical class 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 239000007858 starting material Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 150000003871 sulfonates Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000010687 lubricating oil Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 239000003502 gasoline Substances 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical class CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- RSZXXBTXZJGELH-UHFFFAOYSA-N 2,3,4-tri(propan-2-yl)naphthalene-1-sulfonic acid Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=C(C(C)C)C(S(O)(=O)=O)=C21 RSZXXBTXZJGELH-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 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
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 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
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical class C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
- C07G99/002—Compounds of unknown constitution containing sulfur
- C07G99/0024—Overbased compounds
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
-
- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbased sulfonic acid salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- This invention relates to a method for preparing basic polyvalent metal salts of organic sulfonic acids. More specifically, it relates to the preparation of highly basic alkaline earth metal salts of alkylated aromatic sulfonic acids.
- a more specific object is to provide an improved process for the preparation of basic divalent metal salts, especially alkaline earth metal salts, of alkylated aromatic sulfonic acids.
- a polyvalent metal, particularly a divalent metal, organic sulfonate of relatively higher basicity can be prepared by reacting a polyvalent metal organic sulfonate of relatively lower basicity with an inorganic polyvalent metal salt apd with an alkali metal hydroxide in the presence of an aliphatic alcohol of from about 1 to about 3 carbon atoms.
- the present process comprises gradually adding an alkali metal hydroxide in solution in water and/ or an aliphatic alcohol of from about 1 to about 3 carbon atoms to a solution of an alkaline earth metal 'alkylated aromatic sultonate of relatively lower basicity and an inorganic salt, preferably a water-soluble salt such as the chloride or bromide, of the corresponding alkaline earth metal in a solvent which comprises at least 25% by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby the basicity of the alkaline earth metal alkylated aromatic sulfonate starting material is substantially increased, and recovering the alkaline earth metal alkylated aromatic sulfonate of relatively higher basicity from the reaction mixture.
- an alkali metal hydroxide in solution in water and/ or an aliphatic alcohol of from about 1 to about 3 carbon atoms to a solution of an alkaline earth metal 'alkylated aromatic sultonate of relatively lower basicity and an inorganic salt,
- Neutral polyvalent metal organic sulfonates are particularly suitable starting materials.
- the present invention is also of utility for increasing the basicity of slightly basic polyvalent metal organic sulfonates.
- the sulfonate starting material can be derived from organic sulfonic acids of various types.
- the sulfonic acids can be aliphatic, cycloaliphatic, hydroaromatic, aromatic, heterocyclic or of a mixed type.
- suitable sulfonic acids are alkyl sulfonic acids, such as amyl, octyl, lauryl and dodecyl sulfonic acids; the sulfonic acids of alkylated or non-alkylated aromatic hydrocarbons, such as benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, polyamylnaphthalenesulfonic acids, diphenylsulfonic acids and sulfonic acids of aromatic hydrocarbons substituted by higher alkyl groups, that is, alkyl groups of from about 8 to about 18 carbon atoms;
- organic polysulfonic acids such as benzene disulfonic acid which may or may.
- the preferred sulfonate starting materials for use in the present invention are those derived from alkylated aromatic sulfonic acids in which the alkyl radical contains at least about 8 carbon atoms, for example, from about 8 to about 22 carbon atoms. These sulfonic acids are particularly suitable for the preparation of additives for lubricating oils.
- the polyvalent metal organic sulfonate starting material, together with an inorganic salt of the corresponding polyvalent metal, is dissolved in a solvent which comprises at least 25%, and preferably at least by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms.
- a solvent which comprises at least 25%, and preferably at least by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms.
- Isopropanol is a particularly suitable alcohol.
- Methanol or ethanol can also be employed, or mixtures of the foregoing alcohols can be employed.
- Water or a liquid hydrocarbon can be used in conjunction with the aliphatic alcohol solvent. Suitable liquid hydrocarbons are the lighter hydrocarbon oils, particularly hydrocarbons of 10 or less carbon atoms or mixtures thereof.
- the hydrocarbons can be paratiinic, naphthenic or aromatic or they can be of a mixed type.
- suitable hydrocarbons are benzene, toluene, xylene, gasoline fractions, such as a gasoline fraction having a boiling range between about C. and about 80 C., and the like.
- Mixtures of such hydrocarbons with alcohols containing up to by weight of the hydrocarbon are suitable solvent media for use in the process of the present invention.
- the inorganic polyvalent metal salt employed is preferably the chloride or the bromide. However, the nitrate is also suitable.
- the polyvalent metal organic sulfonate starting material is generally present in the alcoholic solutionin a concentration of from about 1% to about 10% by weight.
- the inorganic polyvalent metal salt and the alkali metal hydroxide which is subsequently added are preferably employed in amounts in excess of that theoretically required to form a compound having the formula: [(RSO3)nM][M(OII)n], in which M represents the polyvalent metal, n represents its valency, and R represents an organic radical.
- M represents the polyvalent metal
- n represents its valency
- R represents an organic radical.
- an excess of from about 25% to about 250%, particularly from about 25% to about 150%, calculated on this theoretically required quantity is suitable. If-desired, larger quantities can be used.
- the type of the solvent and of the inorganic salt of the polyvalent metal, as well as the quantities of the various components of the starting mixture to which the alkali metal hydroxide solution is gradually added, is selected in such a manner that the starting mixture forms a homogeneous solution.
- a solution of an alkali metal hydroxide in water and/ or an aliphatic alcohol of from about 1 to about 3 carbon atoms is then gradually added to the alcoholic solution of the polyvalent metal organic sulfonate starting material and inorganic polyvalent metal salt.
- the alkali metal hydroxide can be dissolved in the same alcohol as is present in the solution of the polyvalent metal organic sulfonate starting material, or a difierent aliphatic alcohol of 1 to 3 carbon atoms can be employed.
- the alkali metal hydroxide can also be dissolved in water or in a mixture of water and a suitable aliphatic alcohol.
- the alkali metal hydroxide solution is employedin aqueous solution, it is advisable to dissolve the sulfonate starting material and the inorganic polyvalent metaljs'alt in a solvent phase containing suflicient of the aliphatic alcohol of 1 to 3 carbon atoms that, after theaddition of the aqueous alkali metal hydroxidesolution, the reaction mixture contains at least about 25% by weight of the aliphatic alcohol, calculated on the solvent phase.
- a solution of sodium or potassium hydroxide in methanol or ethanol, either alone or in admixture with water is very suitable.
- the concentration of the alkali metal hydroxide solution is preferably from about 0.5 to about 5 normal.
- the alkali metal hydroxide solution should be added very gradually to thesolution of the sulfonate starting material and inorganic polyvalent metal salt in order to prevent a local excess of the free hydroxide of the polyvalent metal from being formed and separating out from the solution as such instead of combining with the sulfonate to form the desired basic sulfonate.
- a satisfactory yield of basic sulfonate can be obtained by adding the alkali metal hydroxide solution over a period of from about 1 minute to about 1 hour. It is further advisable to mix the alkali metal hydroxide as quickly as possible uniformly with the solution of the sulfonate starting material.
- the hydroxide of the polyvalent metal is formed by the reaction of the alkali metal hydroxide with the inorganic polyvalent metal salt, and the resulting polyvalent metal hydroxide combines with the sulfonate starting material to form the desired basic sulfonate.
- the required conversion is promoted if the type and the quantity of the various components of the mixture to be converted are so selected that the alkali metal salt formed during conversion, such as an alkali metal chloride, precipitates from the solution.
- the basic sulfonate formed during the conversion is considerably 'less soluble in the solvents used than the starting sulfonate and, therefore, separates out from the solution. That quantity of the polyvalent metal hydroxide which is formed during the conversion and which does not combine with the starting sulfonate and the alkali metal salt which. is also formed during the conversion also separates out from the solution.
- the unconverted sulfonate starting material remains in solution.
- the insoluble components are first separated from the reaction mixture, for example, by filtering or centrifuging.
- the basic sulfonate product is then extracted from the insoluble components by means of a suitable solvent.
- a suitable solvent In general, light hydrocarbon oils are suitable for the extraction, particularly hydrocarbon oils with a final boiling point of not higher than about 300 C.
- the hydrocarbon oil can be aliphatic, naphthenic, aromatic or mixed base type. Hydrocarbons having 10 or less carbon atoms or mixtures of such hydrocarbons are especially suitable. Examples of suitable hydrocarbons are benzene, heptane, and gasoline fractions, such as a gasoline fraction having a boiling range of from about 60 C. to about C. If desired, the resulting extract can be concentrated by removing all or a portion of the solvent.
- the solution containing the unconverted sulfo-nate starting material can be again subjected to the process of the present invention in order to produce further quantities of basic sulfonates.
- the products obtained contain at least as many hydroxyl groups as R503 groups.
- the basicity of the product will be expressed as the ratio, in per cent, of hydroxyl groups to R803 group s.
- the entire reaction mixture obtained by the process of the present invention can be worked to ob min as product a mixture of the relatively more basic polyvalent metal sulfonate produced in accordance with the present invention and the unconverted relatively less basic polyvalent metal sulfonate starting material.
- a mixture has very valuable properties, especially as a lubricating oil additive.
- the resulting mixture does not have as high a basicity as the relatively more highly basic sulfonate component alone, its basicity is still considerable, generally amounting to or more.
- the solvent is first removed from the entire reaction mixture, for example, by distillation, and the polyvalent metal sulfonates, that is the relatively more basic sulfonate produced by the reaction and the unconverted relatively less basic sulfonate, are extracted from the residue.
- Suitable solvents are the hydrocarbon oils described above with reference to the extraction of the relatively more basic polyvalent metal sulfonate alone.
- liquid concentrates can be prepared which can be added in minor amounts to the same or different lubricating oil fraction than that present in the concentrate.
- Conversion of the polyvalent metal sulfonate starting material of relatively low basicity into a polyvalent metal sulfonate of relatively high basicity in accordance with the present process can be effected at room temperatures or somewhat elevated temperatures. Elevated temperatures are especially suitable when using concentrated solutions of sulfonate starting material since concentrated solutions are often very viscous and an increase in temperature results in a decrease in the viscosity of the solution. The temperatures employed will generally not be higher than the initial boiling point of the solvent at normal pressure.
- the present process can be carried out either continuously or batchwise. When carrying out the process continuously, it is advisable to recycle a portion of the solu-.
- the process of the present invention can also be carried out utilizingas starting material a free sulfonic acid or an, alkali metal or ammonium salt :of a sulfonic acid.
- the freesulfonic acid or alkali metal or ammonium salt. thereof is converted to the corresponding polyvalent metal lsulfonate by reaction with an excess amount of an inorganic polyvalent :metal salt in the presenceof asolvent comprising at least about 25% by weight of an aliphatic alcohol of about 1 to about 3 carbon atoms as described above.
- the resulting solution containing polyvalent metal sulfonate and inorganic polyvalent metal salt is then reacted with a solution of 'suflicient alkali metal hydroxide to react with the inorganic polyvalent metalsalt to form a :polyvalent metal hydroxide which in turn combines with the polyvalent metalsulfonate present to form the desired basic sulfonate.
- suflicient alkali metal hydroxide must be added also to neutralize the free inorganic acid formed in the conversion of the free sulfonic acid to its polyvalent metal salt.
- the exact mechanism of the present process is not fully understood. Although the present invention does not depend on a theoretical explanation of the mechanism of the formation of the basic sulfonate, it is possible that the following occurs.
- the freehydroxide of the polyvalent metal is insoluble or only slightly soluble in the solvent used for the conversion. Extremely fine agglomerates are formed from'th molecules of the resultant free hydroxide of the ,polyvalent metal, and on their formation these agglomerates adsorb the sul-fonate start iug material. In this way, adsorption complexes are formed which are again compietely dispersible in hydrocarbnn oil and, consequently are very efiective lubricating oil additives.
- organic sulfonic acid is represented by the formula RSOzH (:wherein'Ri represents an organic radical) and calcium is usedr-as;'a polyvalent metal, so that the. neutral sulfonate. is represented by (RSOahCa', while CaCla is used asaninorganic salt and NaOH as an alkali metal hydroxide," thetfonnafionfiof the basic sulfonate from theneut'ral sulfonate can be represented by the following equation:
- the present invention is of particular utility for the preparation of highly basic sulfonates of divalent metals, particularly zinc and the alkaline earth metals, including magnesium.
- basic sulfonates of metals of higher valency for example,'iron or chromium, can also be-prepared in accordance with the present process.
- Example I The mixture obtained was then centrifuged, a ;soht-. tion of the neutral calcium sulfonate being separated as the liquid phase. .From the solid components consist ing-of a mixture of basic calcium sulfonate, calcium lay-.- droxide and sodium chloride, the basic sulfonatewa'sextracted by means of 50 :parts by weight of gasoline hav ing-aboiling range of60 C.- C.
- Example 11 H A technical mixture of synthetic sulfoniciacids was prepared by alkylating and sul'fonating an aromatic extract having a boiling range of'180 C.275 C. (obtained by extracting a kerosene richfin aromatics W ith SOa).
- the alkylation was canied'out by reacting '1 part by weight of the extract for minutes at 80 C. with 1' part by weight of a mixture otolefin's having 9-45 "carbon atoms (obtained by cracking paraftlin wax in the vapor phase) using 1.5% by weight of Al'Cl; (calculated on the whole mixture) as catalyst.
- the catalyst sludge was removed from the reaction mixture obtained.. during alkylation.
- the mixture was then treated with a 20% aqueous sodium hydroxide solution in order to neutralize the acid components present and then distilled to a boiling point of 300 C. in order to remove thelighter components which did not take part in the a'lkylag tion reaction.
- the residue thus obtained consisting of alkylation products with an average molecular weight of 470 was suifonate'd with 20%"by weight of oleum ata: temperature of 45 C.
- the highly basic polyvalent metal sulfonates preparedin accordance with the present process' are extremely suitable as lubricating oil additivesbecause. of their detergent properties andtheir anti-corrosive effect. They can be employed in lubricating oils in widely varying. concentrations, generally being employed in concentrations between about 0.1% and about 15% by weight.
- the sulfonates can also be combined with other lubricating oil additives, for example, antioxidants and extreme pressure dopes.
- the present highly basic sulfonates may also advan tageously be used in other hydrocarbons.
- the present highly basic sulfonates may also advan tageously be used in other hydrocarbons.
- sulfonates may also advan tageously be used in other hydrocarbons.
- the present sulfonates can also be incorporated in light hydrocarbon mixtures such as those used as anticorrosives. Because of their surface-active properties, the sulfonates can also be used invpreparing emulsions of water and oil. The sulfonates can also be used in preparing lubricating greases.
- a method for preparing a highly basic alkaline earth metal alkylated aromatic sulfonate which comprises reacting an alkaline earth metal alkylated aromatic sulfonate with a hydrohalic acid salt of the corresponding alkaline earth metal and with an alkali metal hydroxide in the presence of a solvent comprising at least 25 by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted alkaline earth metal alkylated aromatic sulfonate and a solid phase containing a highly basic alkaline earth metal alkylated aromatic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic alkaline earth metal alkylated aromatic sulfonate, and separating the resulting hydrocarbon extract containing said highly basic alkaline earthmetal alkylated aromatic sulfonate from the extracted solid phase.
- a method for preparing a highly basic alkaline earth metal organic sulfonate which comprises reacting an alkaline earth metal organic sulfonate with an alkaline earth metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted alkaline earth metal organic sulfonate and a solid phase containing a highly basic alkaline earth metal organic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic alkaline earth metal organic sulfonate, and separating the resulting hydrocarbon extract containing said highly basic alkaline earth metal organic sulfonate from the extracted solid phase.
- alkaline earth metal organic sulfonate is an alkaline earth metal alkylated aromatic sulfonate and the said solvent for the reaction mixture comprises at least about 25 by weight of said aliphatic alcohol.
- a method for preparing a highly basic divalent metal organic sulfonate which comprises reacting a divalent metal organic sulfonate with a divalent metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted divalent metal organic sulfonate and a solid phase containing a highly basic divalent metal organic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic divalent metal organic sultonate, and separating the resulting hydrocarbon extract containing said highly basic divalent metal organic sulfonate from the extracted solid phase.
- a method for preparing a highly basic polyvalent metal organic sulfonate which comprises reacting a poly valent metal organic sulfonate with a polyvalent metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted polyvalent metal organic sulfonate and a solid phase containing a highly basic polyvalent metal organic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic polyvalent metal organic sulfonate, and separating the resulting hydrocarbon extract containing said highly basic polyvalent metal organic sulfonate from the extracted solid phase.
- a method for preparing basic alkaline earth metal alkylated aromatic sulfonates which comprises reacting an alkaline earth metal alkylated aromatic sulfonate with an alkaline earth metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising an aliphatic alcohol containing from 1 to about 3 carbon atoms, removing said solvent from the said reaction mixture, extracting the residue with a hydrocarbon solvent for alkaline earth metal alkylated aromatic sulfonates, and separating the resulting hydrocarbon extract containing said alkaline earth metal alkylated aromatic sulfonates from the extracted solid residue.
- a method according to claim 11, wherein the said solvent for the reaction mixture comprises at least 25 by weight of said aliphatic alcohol.
- A' method according to claim 11 wherein the said solvent comprises a mixture of liquid hydrocarbon and said alcohol, the weight of the alcohol in said mixture being at least 25% by weight thereof.
- a method for preparing basic alkaline earth metal alkylated aromatic sulfonates which comprises reacting an alkali metal alkylated aromatic sulfonate with an alkaline earth metal slat of hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising at least 25% by weight of an aliphatic alcohol containing from 1 to about 3 carbon atoms, removing said solvent from the said reaction mixture, extracting the residue with a hydrocarbon solvent for alkaline earth metal alkylated aromatic sulfonates, and separating the resulting hydrocarbon extract containing said alkaline earth metal alkylated aromatic sulfonates from the extracted solid residue.
- a method for preparing basic alkaline earth metal alkylated aromatic sulfonates which comprises reacting an alkylated aromatic sulfonic acid with an alkaline earth metal salt of a hydrohalic acid and with an alkali metal hydroxide inthe presence of a solvent comprising at least 25 by weight of an aliphatic alcohol containing from 1 to about 3 carbon atoms, removing said solvent from the said reaction mixture, extracting the residue with a hydrocarbon solvent for alkaline earth metal alkylated aromatic sulfonates, and separating the resulting hydrocarbon extract containing said alkaline earth metal alkylated aromatic sulfonates from the extracted solid residue.
- a method for preparing a highly basic alkaline earth metal alkylated aromatic sulfonat'e which comprises reacting an alkali metal alkylated aromatic sulfonate with an alkaline earth metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising at least 25 by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted alkaline earth metal alkylated aromatic sulfonate and a solid phase containing a highly basic alkaline earth metal alkylated aromatic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic alkaline earth metal alkylated aromatic sulfonate, and separating the resulting hydrocarbon extract containing said highly basic alkaline earth metal alkylated aromatic sulfonate from the extracted solid phase.
- a method for preparing a highly basic alkaline earth metal alkylated aromatic sulfonate which comprises reacting an alkylated aromatic sulfonic acid with an alkaline earth metal salt of a hydrohalic acid and with an alkali metal hydroxide in the presence of a solvent comprising at least 25% by weight of an aliphatic alcohol of from about 1 to about 3 carbon atoms, whereby there is formed a liquid phase comprising said solvent and unconverted alkaline earth metal alkylated aromatic sulfonate and a solid phase containing a highly basic alkaline earth metal alkylated aromatic sulfonate, separating said phases, extracting the separated solid phase with a hydrocarbon solvent for said highly basic alkaline earth metal alkylated aromatic sulfonate, and separating the resulting hydrocarbon extract containing said highly basic alkaline earth metal alkylated aromatic sulfonate from the extracted solid phase.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL176123A NL81935C (es) | 1953-02-17 | 1953-02-17 |
Publications (1)
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US2794829A true US2794829A (en) | 1957-06-04 |
Family
ID=19750595
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US407178A Expired - Lifetime US2794829A (en) | 1953-02-17 | 1954-01-29 | Preparation of basic polyvalent metal salts of organic sulfonic acids |
Country Status (6)
Country | Link |
---|---|
US (1) | US2794829A (es) |
BE (1) | BE526487A (es) |
DE (1) | DE1167334B (es) |
FR (1) | FR1096346A (es) |
GB (1) | GB739434A (es) |
NL (1) | NL81935C (es) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2902511A (en) * | 1956-09-17 | 1959-09-01 | Hall Stewart | Oil additive and process for its preparation |
US2958660A (en) * | 1955-09-26 | 1960-11-01 | Shell Oil Co | Detergent and wear inhibiting mineral lubricating oil compositions |
US3015320A (en) * | 1956-01-05 | 1962-01-02 | Pure Oil Co | Multi-graded lubricant for 2-cycle engines |
US3031498A (en) * | 1958-02-04 | 1962-04-24 | Procter & Gamble | Preparation of detergent compositions |
US3088956A (en) * | 1961-03-20 | 1963-05-07 | Union Carbide Corp | Acyloxymetallosulfophthalates |
US3152991A (en) * | 1961-01-23 | 1964-10-13 | Phillips Petroleum Co | Increasing the base number of metal petroleum sulfonate |
US3247234A (en) * | 1961-10-03 | 1966-04-19 | Dow Chemical Co | Cupric catalyst |
US4104293A (en) * | 1976-05-05 | 1978-08-01 | Petrolite Corporation | Oil-soluble chromium compositions |
US4219540A (en) * | 1977-12-01 | 1980-08-26 | Jass Herman E | Method for inhibiting perspiration |
US4263151A (en) * | 1979-08-03 | 1981-04-21 | Petrolite Corporation | Oil solutions and/or dispersions of hydrated chromium oxides |
US5858208A (en) * | 1994-08-04 | 1999-01-12 | Baker Hughes Incorporated | Methods for improving conversion in fluidized catalytic cracking units |
FR2783824A1 (fr) * | 1998-09-25 | 2000-03-31 | Chevron Chem Sa | Sulfonates d'alkylaryle faibles surbases et huile de lubrification les contenant |
WO2016210051A1 (en) * | 2015-06-24 | 2016-12-29 | Greene Lyon Group, Inc. | Selective removal of noble metals using acidic fluids, including fluids containing nitrate ions |
US11193214B2 (en) | 2013-12-20 | 2021-12-07 | Greene Lyon Group, Inc. | Method and apparatus for recovery of noble metals, including recovery of noble metals from plated and/or filled scrap |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1243676B (de) * | 1956-04-09 | 1967-07-06 | Ulric Bannister Bray | Verfahren zur Herstellung von oelloeslichen Metallsulfonaten |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23082E (en) * | 1949-01-25 | Grease compositions | ||
US2585520A (en) * | 1948-12-03 | 1952-02-12 | Shell Dev | Lubricating compositions containing highly basic metal sulfonates |
US2610946A (en) * | 1951-02-08 | 1952-09-16 | Texas Co | Lithium soap grease containing basic alkaline earth metal sulfonate |
US2671758A (en) * | 1949-09-27 | 1954-03-09 | Shell Dev | Colloidal compositions and derivatives thereof |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2414773A (en) * | 1944-12-18 | 1947-01-21 | Standard Oil Dev Co | Production of divalent metal sulfonates |
US2501731A (en) * | 1946-10-14 | 1950-03-28 | Union Oil Co | Modified lubricating oil |
-
0
- BE BE526487D patent/BE526487A/xx unknown
-
1953
- 1953-02-17 NL NL176123A patent/NL81935C/xx active
-
1954
- 1954-01-29 US US407178A patent/US2794829A/en not_active Expired - Lifetime
- 1954-02-15 DE DEN8474A patent/DE1167334B/de active Pending
- 1954-02-15 GB GB4424/54A patent/GB739434A/en not_active Expired
- 1954-02-17 FR FR1096346D patent/FR1096346A/fr not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE23082E (en) * | 1949-01-25 | Grease compositions | ||
US2585520A (en) * | 1948-12-03 | 1952-02-12 | Shell Dev | Lubricating compositions containing highly basic metal sulfonates |
US2671758A (en) * | 1949-09-27 | 1954-03-09 | Shell Dev | Colloidal compositions and derivatives thereof |
US2610946A (en) * | 1951-02-08 | 1952-09-16 | Texas Co | Lithium soap grease containing basic alkaline earth metal sulfonate |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2958660A (en) * | 1955-09-26 | 1960-11-01 | Shell Oil Co | Detergent and wear inhibiting mineral lubricating oil compositions |
US3015320A (en) * | 1956-01-05 | 1962-01-02 | Pure Oil Co | Multi-graded lubricant for 2-cycle engines |
US2902511A (en) * | 1956-09-17 | 1959-09-01 | Hall Stewart | Oil additive and process for its preparation |
US3031498A (en) * | 1958-02-04 | 1962-04-24 | Procter & Gamble | Preparation of detergent compositions |
US3152991A (en) * | 1961-01-23 | 1964-10-13 | Phillips Petroleum Co | Increasing the base number of metal petroleum sulfonate |
US3088956A (en) * | 1961-03-20 | 1963-05-07 | Union Carbide Corp | Acyloxymetallosulfophthalates |
US3247234A (en) * | 1961-10-03 | 1966-04-19 | Dow Chemical Co | Cupric catalyst |
US4104293A (en) * | 1976-05-05 | 1978-08-01 | Petrolite Corporation | Oil-soluble chromium compositions |
US4219540A (en) * | 1977-12-01 | 1980-08-26 | Jass Herman E | Method for inhibiting perspiration |
US4263151A (en) * | 1979-08-03 | 1981-04-21 | Petrolite Corporation | Oil solutions and/or dispersions of hydrated chromium oxides |
US5858208A (en) * | 1994-08-04 | 1999-01-12 | Baker Hughes Incorporated | Methods for improving conversion in fluidized catalytic cracking units |
FR2783824A1 (fr) * | 1998-09-25 | 2000-03-31 | Chevron Chem Sa | Sulfonates d'alkylaryle faibles surbases et huile de lubrification les contenant |
EP0997518A1 (en) * | 1998-09-25 | 2000-05-03 | Chevron Chemical S.A. | Low overbased alkylaryl sulfonates |
US6551967B2 (en) | 1998-09-25 | 2003-04-22 | Chevron Chemical S.A. | Low overbased alkylaryl sulfonates |
US11193214B2 (en) | 2013-12-20 | 2021-12-07 | Greene Lyon Group, Inc. | Method and apparatus for recovery of noble metals, including recovery of noble metals from plated and/or filled scrap |
WO2016210051A1 (en) * | 2015-06-24 | 2016-12-29 | Greene Lyon Group, Inc. | Selective removal of noble metals using acidic fluids, including fluids containing nitrate ions |
US11136681B2 (en) | 2015-06-24 | 2021-10-05 | Greene Lyon Group, Inc. | Selective removal of noble metals using acidic fluids, including fluids containing nitrate ions |
US11566334B2 (en) | 2015-06-24 | 2023-01-31 | Greene Lyon Group, Inc. | Selective removal of noble metals using acidic fluids, including fluids containing nitrate ions |
Also Published As
Publication number | Publication date |
---|---|
DE1167334B (de) | 1964-04-09 |
NL81935C (es) | 1955-09-15 |
GB739434A (en) | 1955-10-26 |
BE526487A (es) | |
FR1096346A (fr) | 1955-06-17 |
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