US3703475A - Preparation of oil soluble sulfonic acids useful as dispersant additives - Google Patents

Preparation of oil soluble sulfonic acids useful as dispersant additives Download PDF

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US3703475A
US3703475A US155081A US3703475DA US3703475A US 3703475 A US3703475 A US 3703475A US 155081 A US155081 A US 155081A US 3703475D A US3703475D A US 3703475DA US 3703475 A US3703475 A US 3703475A
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alkylate
weight percent
sludge
sulfonation
hexane
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Roy C Sias
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ConocoPhillips Co
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Continental Oil Co
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    • 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
    • C07C303/04—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/12—Sulfonates of aromatic or alkylated aromatic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/909—The agent contains organic compound containing sulfoxy*

Definitions

  • a sulfonic acid composition is prepared by separately sulfonating (a) an alkylate composition consisting essentially of one or more monoalkaryl compounds in which the alkyl substituent contains from about 20 to about 40 carbon atoms, and (b) an alkylate composition containing from about weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about 75 weight percent dialkylbenzenes, and having an average molecular weight of from about 300 to about 500.
  • the sulfonic acid reaction mixtures derived from the two alkylates are then separately gravity settled and a primary acid-sludge split is taken to remove the sludge from each reaction mixture.
  • the de-sludged crude sulfonic acids from the two alkylates are then mixed and dissolved in hexane.
  • the hexane solution of the mixed sulfonic acids is then permitted to settle and another acid-sludge split is made to remove the sludge.
  • the first alkylate starting material may be a so-called dimer alkylate prepared by alkylating benzene with a dimerized tetramer of propylene
  • the second alkylate starting material may be a bottoms fraction yielded in the fractionation of an alkylate mixture produced by alkylating benzene with normal chloroparaffins containing 8 to 18 carbon atoms.
  • This invention relates to the preparation of oil soluble sulfonic acids suitable for use as dispersant additives to lubricating oils, and more particularly, to such sulfonic acids as are particularly suited for neutralization and overbasing in-situ in a non-volatile carrier material.
  • the oil soluble sulfonates described are prepared by sulfonating various types of alkylate starting materials.
  • alkylate starting material which is an excellent sulfonation feedstock is a so-called dimer alkylate which is a mixture of monoalkaryl compounds in which monoalkylbenzene compounds containing from 20 to 40 carbon atoms in highly branched alkyl substituents predominate.
  • Dimer alkylates of this type are prepared by alkylating benzene with a dimerized tetramer of propylene. The method of preparing the dimer used in alkylation is well understood in the art.
  • a sulfonation feedstock is a bottoms fraction yielded in the fractionation of an alkylate mixture produced by alkylating benzene with normal chloroparafiin compounds containing from 8 to 18 carbon atoms.
  • the overhead derived from the fractionation is sulfonated to yield valuable biodegradable detergents.
  • the bottoms fraction can be sulfonated to prepare oil soluble sulfonic acids of the type under discussion.
  • This bottoms fraction in general, contains from about 5 weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent dialkylbenzenes.
  • the alkyl substituents of the alkylated compounds in the bottoms fraction contain from about 10 to 18 carbon atoms, and the average molecular weight of the bottoms fraction is from about 300 to about 500.
  • the bottoms alkylates which contain a relatively high proportion of dialkylbenzenes have been normally preferred, and frequently the raw bottoms alkylate remaining after removal of the lighter detergent grade alkylate is topped or further treated to increase the concentration of dialkylbenzenes therein, and to lower the quantity of diphenylalkanes contained therein.
  • the latter materials do not sulfonate well and tend to decrease the overall quality of the sulfonate product.
  • the raw bottoms alkylate may contain residual small amounts of the higher boiling portion of the biodegradable detergent alkylate stock. This material is thus included in the described ranges of amounts of dialkylbenzenes and alkylated tetralins.
  • the process of this invention is particularly useful in employing bottoms alkylate material containing relatively high concentrations of diphenylalkanes.
  • the process of the present invention provides a method by which improved sulfonates for use as lubricating oil dispersant additives, can be prepared from dimer alkylate and bottoms alkylate starting materials.
  • the procedure constitutes an improvement with respect to co-sulfonation procedures heretofore in use in which the two alkylates described are initially mixed or blended, and then sulfonation is carried out on such mixture, followed by sludge removal and purification.
  • the process of the present invention results in an upgrading of the sulfonic acids yielded in that a higher ratio of actual sulfonic acid to other acidic products is present, the sulfonic acids produced have a higher combining weight, and no significant sacrifice in yield of sulfonic acids per unit of alkylate charged is sufiered.
  • the sulfonic acids produced by the process of the invention can be neutralized and overbased to produce an overbased sulfonate additive which is improved over those prepared by the co-sulfonation process previously employed in that the overbased sulfonates are characterized in having a lower viscosity and improved color.
  • the process of the present invention comprises initially carrying out separate sulfonations of (a) an alkylate composition which consists predominantly of one or more monoalkaryl compounds in which the alkyl substituent contains from about 20 to about 40 carbon atoms, and (b) a second alkylate composition which contains from about weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about 75 weight percent dialkylbenzenes.
  • the second alkylate subjected to the process of the invention contains between about 40 weight percent and 75 weight percent dialkylbenzenes and less than about 20 weight percent diphenylalkanes.
  • a primary sludge split is taken on each of the two reaction products.
  • the sludge split is obtained by permitting the reaction mixture to gravity settle over an extended period of time, and then removing the spent acid sludge from the crude sulfonic acid.
  • the desludged crude sulfonic acids are then mixed and are dissolved in a light organic solvent boiling below about 150 C. and preferably between about 40 C. and 120 C.
  • Suitable materials include petroleum naphtha and light paraffins, such as hexane, heptane and octane.
  • the solution of the mixed sulfonic acids is then permitted to settle, and another acid-sludge split is made to remove the sludge which has settled out.
  • the final solution of mixed sulfonic acids is then preferably purified by techniques well understood in the art.
  • a more specific object of the invention is to improve the sulfonic acid and sulfonate products derived from dimer alkylate, and from alkylates analagous to the bottoms alkylate produced in the manufacture of detergent grade alkylate by alkylating aromatic materials with chlorinated paraffin compounds.
  • FIG. 1 is a block diagram illustrating the manner in which the process of the present invention is practiced.
  • FIG. 2 is a bar graph comparison of the properties of various sulfonic acid and overbased sulfonate products derived from the process of the present invention with the same products as prepared by co-sulfonation of mixed alkylates as heretofore practiced.
  • FIG. 1 of the drawings may be referred to as an aid in understanding the process of the present invention as it is hereinafter described. Since the two types of alkylates which are separately sulfonated in the process are typified by the dimer alkylate and bottoms alkylate to be hereinafter more specifically described, these are indicated in the FIG. 1 diagram.
  • the process of the present invention is commenced by separately sulfonating two types of alkylate materials.
  • One of these contains at least 70 weight percent, and preferably at least 80 weight percent, monoalkaryl compounds in which an aryl compound is substituted by a single alkyl substituent containing from about 20 to about 40 carbon atoms.
  • a typical alkylate of this type is sometimes referred to in the art as dimer alkylate, and is made by alkylating benzene with a highly branched dimerized propylene tetramer containing from about 20 to about 40 carbon atoms.
  • the lakylate is derived from the propylene refinery stream by processes will understood and widely practiced in the art, and is characterized in having an average molecular weight of from about 350 to about 600.
  • the dimer alkylate may contain up to 25 weight percent of dialkylbenzenes which constitute the major constituent other than the described monoalkaryl compounds.
  • An alkylate, other than dimer alkylate, fitting the general definition of the first of the two alkylates sulfonated in the process of this invention is an alkylate in which the monoalkaryl compounds are alkyl substituted benzene compounds in which the alkyl substituents are substantially straight chain in character and contain from about 20 to about 40 carbon atoms.
  • Such alkyl benzenes can be prepared by alkylating benzene with a substantially straight chain olefin, such as an a-olefin.
  • the alkylate is usually initially diluted with a light mineral oil, such as 100 S.S.U. viscosity pale oil, and is then sulfonated by conventional sulfonation procedures. Although $0 or mixtures of S0 and 80;, may be used to sulfonate the alkylate, 20% oleum is preferably employed to sulfonate the alkylates, whereby sulfonic acids substantially free of sulfur dioxide and sulfuric acid are yielded. The oleum is added slowly to the oil-diluted alkylate to a weight ratio of from about 1.0:1 to about 1.6:1 oleum to alkylate, while holding the temperature below about 80 C.
  • a light mineral oil such as 100 S.S.U. viscosity pale oil
  • reaction mass is post-stirred for a period of from about 20 minutes to about 40 minutes at a temperature of from about 40 C. to about 80 C. and preferably from about 55 C. to about '60" C.
  • the reaction mixture is then transferred to a separatory device, such as a separatory funnel, and is settled for from about 8 to about 16 hours at a temperature of about 50 C.
  • the sludge phase is then removed.
  • the second alkylate which is subjected to separate sulfo nation contains from about 5 weight percent to about 35 weight percent diphenylalkanes, and preferably from about 5 weight percent to about 20 weight percent.
  • the alkylate further contains from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent di-n-alkylbenzenes.
  • the average molecular weight of this alkylate is from about 300 to about 500.
  • a typical alkylate of this type is that which is derived by a fractionation process in which the total alkylate prepared by reacting long chain chlorinated n-paratfin hydrocarbons with aromatic compounds, and particularly benzene, is subjected to fractional distillation.
  • the bottoms portion (as contrasted with the overhead) which is yielded by such fractionation is an alkylate coming within the definition and description of the second alkylate subjected to sulfonation in the process of the present invention.
  • This bottoms alkylate will typically contain from about 40 weight percent to about 75 weight percent di-n-alkylbenzenes in which the alkyl substituents contain from about 8 to 18 carbon atoms and are bonded to the benzene group through a secondary carbon atom of the alkyl chain, from about 10 to about 25 percent diphenylalkanes, from about 5 weight percent to about 18 weight percent tetralins, of which the majority are alkylated tetralins, and from about 4 weight percent to about 12 weight percent naphthalenes and indanes.
  • the bottoms alkylate is separated from the overhead, which overhead constitutes an alkylate valuable for the production of biodegradable detergents, by fractionating the alkylate mixture to a cut point of 160 C. at mm. Hg. If it is desired to reduce the diphenylalkane content of the bottoms alkylate thus recovered to the preferred level of from about 5 weight percent to about 20 weight percent, further distillation can be carried out.
  • the average molecular weight of the bottoms alkylate may range from about 300 to about 500.
  • the second alkylate As contrasted with the sulfonation of the first alkylate material as hereinbefore described, the second alkylate, of which the bottoms alkylate specifically identified is an example, is preferably sulfonated neat; that is, it is preferred that no dilution with a light mineral oil be effected prior to sulfonation.
  • the alkylate In carrying out the sulfonation, the alkylate is stirred, and 20% oleum is slowly added to the alkylate in a weight ratio of from about 1.3:1 to about 1.9:1 while maintaining the temperature of the reaction mixture below about 80 C. and preferably below about 60 C.
  • a light hydrocarbon solvent boiling between about 40 and 150' C., and preferably below about 120 C. is added in an amount suflicient to provide about 0.5 to 3.0 weight parts of the solvent per weight part of the alkylate charged.
  • Suitable solvents include light petroleum naphthas, hexane, heptane, octane, and mixtures thereof.
  • up to 30 weight percent of the light hydrocarbon solvent can be replaced by a diluent oil such as pale oil.
  • the mixture is then stirred for an additional period of from about to about 30 minutes at reflux temperature, which is generally from about 55 C. to 60 C.
  • the crude sulfonation mass is transferred to a separatory device, such as a separatory funnel, and is permitted to settle for a period of from about 8 hours to about 16 hours at ambient temperature.
  • a primary sludge split to remove the spent sulfuric acid sludge is then taken, and the hexane-sulfonic acid phase is recovered.
  • the mixed sulfonic acids produced upon co-sulfonation tend, due to the solubilizing effect of the tetralins in the mixed alkylate starting material, to include certain undesirable materials which detract from the quality of the final mixed sulfonic acid product.
  • the crude sulfonic acids are mixed, diluted with a paraffinic hydrocarbon, such as hexane, and placed in a secondary settling device, such as a separatory funnel.
  • the dilution with light hydrocarbon solvent is carried out to adjust the sulfonic acid concentration to about 0.4 to about 0.8 milli-equivalent of acid per gram of the diluted mixture.
  • a paraffinic hydrocarbon such as hexane
  • the diluted mixed sulfonic acids are permitted to gravity settle for a period of from about 8 to about 16 hours, and the sludge is then removed.
  • de-sludging of the two separately sulfonated alkyates to achieve the primary sludge split can be accomplished by centrifugation, as can the secondary sludge split accomplished after the crude sulfonic acids from the two alkylates have been combined. Centrifugation is particularly amenable to usage in desludging the sulfonic acid product resulting from sulfonation of the bottoms alkylate material.
  • the acids are purified by initially de-gassing the acids by blowing an inert gas, such as nitrogen, through the acids for about 15 minutes.
  • an inert gas such as nitrogen
  • Calcium hydroxide in an amount equivalent to about 1.5 times the amount needed to neutralize the sulfuric acid, is then added to the crude acids, and the mixture is again degassed using an inert gas to blow the mixture for a period of about 45 minutes while heating the mixture to a temperature of from about 30 C. to 35 C.
  • the solution is then filtered, and the sulfonic acids thus prepared and purified can be used in the preparation of overbased sulfonate compositions suitable for use as additives to lubricating oils.
  • EXAMPLE 1 575 grams of a dimer alkylate which contained 81.8 mole percent monoalkylbenzenes (each containing from about 22 to about 38 carbon atoms in the highly branched alkyl substitutents), 13.6 mole percent para-dialkylbenzenc compounds, and 4.6 mole percent meta-dialkylbenzene compounds, and having a molecular weight, as determined by osmometer, of 362, were charged, along with 345 grams of pale oil having a viscosity of S.S.U. at 210 C. to a creased flask, and mechanical agitation was commenced. 20% oleum was charged to the flask over a period of 20 minutes.
  • the exothermic reaction was maintained at a temperature of between 55 C. and 60 C. during the addition of the oleum. After addition of the oleum, the reaction mass was post-stirred for a period of 30 minutes, and was then charged to a separatary funnel and permitted to gravity settle overnight at 50 C. On the following day, sludge split was taken to remove sludge from the crude sulfonic acid-oil mixture. 1,070 grams of the crude acid-oil product were recovered, and 624.4 grams of sludge were removed.
  • alkylate bottoms recovered from a detergent alkylate process of the type hereinbefore described was the sulfonation charge stock.
  • This alkylate was characterized in containing, as determined by mass spectrometer, 40.7 volume percent alkylbenzene compounds containing from 8 to 18 carbon atoms in the alkyl substituents, 24.9 volume percent diphenylalkanes, and 23.3% tetralins.
  • the average molecular weight of the alkylate was 350. 1,500 grams of the alkylate were charged to a creased reaction flask and were mechanical agitated as 20% oleum was added to the flask over a period of minutes.
  • the temperature of the reaction mixture was maintained below 60 C.
  • the mixture was post-stirred for a period of minutes.
  • 2,250 ml. of hexane was added to the reaction mixture, and mechanical mixing was then continued for a period of 15 minutes at a temperature of between 55 C. and 60 C.
  • the mixture was then charged to a separatory funnel and permitted to settle at ambient temperature overnight.
  • a sludge split was taken. 2,768 grams of crude acidhexane solution were recovered, and 2,923 grams of sludge were removed.
  • EXAMPLE 2 A dimer alkylate of the type described in Example 1 was diluted with a pale oil having a viscosity of 100 S.S.U. at 210 C. in a weight ratio of 0.54:1 diluent oil to alkylate. 20% oleum was then slowly added to the mixture in an amount suflicient to give a weight ratio of oleum to alkylate of 1.2: 1.
  • the sulfonation conditions were similar to those described in Example 1 in the part thereof which refers to the sulfonation of the dimer alkylate. Following sulfonation, a primary sludge split was taken after permitting the reaction mixture to settle overnight in a separatory funnel.
  • a bottoms alkylate having a molecular weight as determined by osmometer of 344 and containing, by mass spectrometer analysis, 40.6 volume percent alkyl benzene, 35.7 volume percent diphenylalkanes, and 16.7 volume percent tetralins was sulfonated with 20% oleum in a weight ratio of oleum to alkylate of 1.9: l.
  • the alkylate was sulfonated neat, and the temperature and time conditions were similar to those used in the sulfonation of bottoms alkylate as described in Example 1.
  • hexane was added to the reaction mixture in an amount equal to the amount of alkylate used in the sulfonation.
  • the reaction mixture was then charged to a separatory funnel and permitted to gravity settle overnight. After gravity settling, a primary sludge split was taken to recover the crude acid-hexane solution from the spent acid sludge.
  • the acid-hexane solution thus produced was then combined with the crude acid-oil product produced by the akylation of the dimer alkylate as described earlier in this example.
  • the sulfonic acids were mixed in a 1:1 weight ratio.
  • hexane was added to the combined crude acids in a volume ratio of 1.2:1 hexane to crude 8 acid (the term crude acid here referring to the crude acid, hexane and oil present in the combined crude acid products of the two sulfonations).
  • the hexane-acid mixture was then permitted to gravity settle for a period of about 15 hours, and a secondary sludge split was taken to remove sludge from the acid-hexane mixture.
  • EXAMPLE 3 Dimer alkylate of the type utilized in Example 1 was sulfonated neat, using a weight ratio of 20% oleum to alkylate of 12:]. Upon completion of the post-stirring period of the sulfonation, a volume of hexane was added to the reaction mixture in a weight ratio of 1:1 hexane to starting alkylate. The crude sulfonic acid product was recovered by a primary sludge split after settling overnight.
  • Example 2 2,000 grams of the bottoms alkylate utilized in Example 2 were charged to a creased sulfonation flask equipped with a mechanical stirrer, thermometer and dropping funnel. 20% oleum in a weight ratio of 1.9:1 oleum to alkylate was added to the alkylate and sulfonation of the bottoms alkylate carried out as described in Example 2. Hexane was then added to the reaction mixture in an amount equal to the amount of alkylate sulfonated. After overnight settling, a primary sludge split was then taken to recover the crude hexane-acid solution.
  • the crude sulfonic acid-hexane product produced from the bottoms alkylate was then combined with the crude sulfonic acid-hexane product produced by alkylation of the dimer alkylate described earlier in this example in a sulfonic acids weight ratio of 1:1.
  • the mixed acids were then diluted with about 1.2 volumes of hexane, and a secondary sludge split was taken after permitting the mixture to stand overnight.
  • EXAMPLE 4 500 grams of the dimer alkylate described in Example 1 were mixed with 655 grams of pale oil and 500 grams of the bottoms alkylate described in that example, and the mixture was then charged to a creased flask and sulfonated with 1,900 grams of 20% oleum in the manner described in Example 1 as being utilized for the sulfonation of dimer alkylate. After completion of the post-stirring period, the sulfonation mass was charged to a separatory funnel and gravity settled at 50 C. overnight. On the following day, a sludge split was taken and 1,758 grams of sludge were removed to leave 1,731 grams of the crude acid-oil product.
  • EXAMPLE 5 A mixed alkylate charge stock which contained 60 weight percent of the bottoms alkylate and 40 weight percent of the dimer alkylate described in Example 2 was employed in a cosulfonation run. 100 S.S.U. viscosity pale oil was used as a diluent in a weight ratio of 0.5 :1 diluent to total alkylate charge stock. The oil diluted alkylate was then subjected to sulfonation using 25% oleum in a weight ratio of 1.9:1 oleum to total alkylate charge.
  • the crude sulfonic acid-oil mixture was transferred to a separatory funnel, and after a suitable period of gravity settling, a primary sludge split was taken. Hexane was then added to the crude acid-oil raffinate recovered from the sludge split in a volumetric ratio of 1.5:1 hexane to acid-oil product. A secondary sludge split was then taken.
  • a primary sludge split was taken on the following day to remove the sludge from the mixture. There was then charged to the crude acid-hexane mixture, an additional volume of hexane equivalent to the volume of the crude acid-hexane mixture remaining after the primary sludge split. This mixture was then permitted to gravity settle overnight, and a secondary sludge split was taken to isolate the crude acid-hexane mixture from the spent acid sludge materials.
  • EXAMPLE 7 For the purpose of evaluating the crude hexane-sulfonic acid products produced by co-sulfonation and by separate sulfonations as described in Examples 1-6, certain analyses and tests of the several products were made, and the results compared. The results obtained are tabumixture was again de-gassed with nitrogen for an additional period of 45 minutes while heating the mixture to a temperature of from C. to C. The solutions were then filtered, and the flask and funnel used in filtering rinsed with hexane to recover all of the sulfonic acid.
  • the purified sulfonic acid products were then utilized to prepare overbased barium and calcium sulfonate dispersions.
  • the sulfonic acid charge was calculated so as to yield an overbased product having an acetic acid base number of approximately 70, and to contain about 46.5 weight percent neutral barium sulfonate.
  • 200 grams of the purified sulfonic acid-hexane solution were charged to a l-liter creased flask equipped with a mechanical stirrer, thermometer and heating mantle.
  • a neutral mineral oil having a viscosity of 100 S.S.U. at 210 C. was then added to adjust the activity of the sulfonic acid solution as necessary to make the 46.5 percent active product.
  • Methanolic barium oxide solution was then added slowly from a dropping funnel over a period of about 10 minutes to neutralize the sulfonic acid and to provide excess barium oxide.
  • Carbon dioxide was then blown through the mixture from a sintered glass tube at a rate of about 250 ml./min. until the reaction mass became acidic to anaphthol benzene indicator (the time required was from about 15 to about 20 minutes).
  • the solvents were then distilled overhead to a pot temperature of 150 C., and the product stripped with carbon dioxide for a period of lated in Table I. 30 15 minutes.
  • EXAMPLE 8 The crude sulfonic acid products produced in Examples 1-6 were purified by placing the product to be purified TABLE II Example Number Type sulionation Sep- Sep- Sep- Co-sulfo- Co-sulfo- Clo-sulfoarete arate arate nation nation nation b r 76 68 71 69 70 71 l g r e d geti ve a- 47- 2 46- 5 46- 5 46. 4 46.3 46. 5 Viscosit 210 F., SSU. 302. 2 219. 3 293. 7 332.0 237. 8 335. 0 ASTM din. color 1 3. 5 a0 3. 0 5. 0 3. 5 a. 5
  • Example 2 the processing conditions were similar in that in Example 2, the dimer alkylate was sulfonated in oil, and in Example 5, the alklate mixture was sulfonated in oil. Moreover, the bottoms alkylate and dimer alkylate used in both these runs were identical, although the bottoms alkylate differed from that used in Examples 1 and 4. In Examples 3 and 6, the sulfonation of all alkylates was carried out neat, with post-hexane addition in each case.
  • the sulfonic acid products produced by the runs described in Examples 1 and 4 were overbased using a calcium alkoxide-carbonate complex in accordance with the teachings of Hunt US. Pat. No. 3,150,088.
  • the viscosities of overbased calcium sulfonate dispersions produced by this technique from these two sulfonic acid products were compared.
  • the overbased calcium sulfonate disper sion derived from the separate sulfonation procedure described in Example 1 had a base number of 290 and had a viscosity (S.S.U. 210) of 409.3.
  • the overbased calcium sulfonate dispersion derived from the co-sulfonation procedure set forth in Example 4 had a base number of 280 and had a viscosity of 879.3.
  • a very significant improvement in viscosity was achieved through the use of the separate sulfonation technique, as compared to the co-sulfonation procedure previously in use.
  • the process of the invention provides a method by which mixed sulfonic acids derived from two alkylates of the general type described can be upgraded, and their utility as charge materials for the purpose of producing overbased sulfonate dispersions suitable for use as lubricating oils can be improved.
  • certain preferred embodiments of the invention have been herein described in order to provide examples sufficient to enable those skilled in the art to practice the invention, it will be understood that other materials and variations in the described process conditions can be employed without departure from the basic principles of the invention. Changes and innovations of this type are therefore deemed to be circumscribed by the spirit and scope of the invention except as the same may be necessarily limited by the appended claims or reasonable equivalents thereof.
  • sulfonating a first alkylate composition comprising at least weight percent monoalkaryl compounds in which an aryl group is substituted by an alkyl substituent containing from about 20 to about 40 carbon atoms;
  • a second alkylate containing from 5 weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent di-n-alkylbenzenes, and having an average molecular weight of from about 300 to about 500, the alkyl substituents of said di-n-alkylbenzenes containing from about 8 to about 18 carbon atoms;
  • said first alkylate is a dimer alkylate prepared by alkylating benzene with a dimer of a propylene tetramer, and wherein the substituents of the benzene after alkylation are highly branched alkyl groups containing from about 20 to about 40 carbon atoms, said dimer alkylate having a molecular weight of from about 350 to about 600.
  • reaction mixture produced upon sulfonation of said second alkylate is diluted with a parafiinic hydrocarbon solvent in an amount of from about 0.5 gram to about 3 grams of solvent per gram of the second alkylate charged to the sulfonation reaction.
  • said first alkylate is a dimer alkylate prepared by alkylating benzene with a dimer of a propylene tetramer, and wherein the substituents of the benzene after alkylation with said tetramer are highly branched alkyl groups containing from about 20 to about 40 carbon atoms, said dimer alkylate having a molecular weight of from about 350 to about 600.
  • reaction mixture produced upon sulfonation of said second alkylate is diluted with a parafiinic hydrocarbon solvent in an amount of from about 0.5 gram to about 3 grams of hexane per gram of the second alkylate charged to the sulfonation reaction.

Abstract

A SULFONIC ACID COMPOSITION IS PREPARED BY SEPARATELY SULFONATING (A) AN ALKYLATE COMPOSITION CONSISTING ESSENTIALLY OF ONE OR MORE MONOALKARYL COMPOUNDS IN WHICH THE ALKYL SUBSTITUENT CONTAINS FROM ABOUT 20 TO 40 CARBON ATOMS, AND (B) AN ALKYLATE COMPOSITON CONTAINING FROM ABOUT 5 WEIGHT PERCENT TO ABOUT 35 WEIGHT PERCENT DIPHENYLALKANES, FROM ABOUT 5 WEIGHT PERCENT TO ABOUT 50 WEIGHT PERCENT ALKYLATED TETRALINS, AND FROM ABOUT 25 WEIGHT PERCENT TO ABOUT 75 WEIGHT PERCENT DIALKYHLBENZENES, AND HAVING AN AVERAGE MOLECULAR WEIGHT OF FROM ABOUT 300 TO ABOUT 500. THE SULFONIC ACID REACTION MIXTURES DERIVED FROM THE TWO ALKYLATES ARE THEN SEPARATELY GRAVITY SETTLED AND A PRIMARY ACID-SLUDGE SPLIT IS TAKEN TO REMOVE THE SLUDGE FROM EACH REACTION MIXTURE. THE DE-SLUDGED CRUDE SULFONIC ACIDS FROM THE TWO ALKYLATES ARE THEN MIXED AND DISSOLVED IN HEXANE. THE HEXANE SOLUTION OF THE MIXED SULFONIC ACIDS IS THEN PERMITTED TO SETTLE AND ANOTHER ACID-SLUDGE SPLIT IS MADE TO REMOVE THE SLUDGE. THE FIRST ALKYLATE STARTING MATERIAL MAY BE A SO-CALLED DIMER ALKYLATE PREPARED BY ALKYLATING BENZENE WITH A DIMERIZED TETRAMER OF PROPYLENE, AND THE SECOND ALKYLATE STARTING MATERIAL MAY BE A BOTTOMS FRACTION YIELDED IN THE FRACTIONATION OF AN ALKYLATE MIXTURE PRODUCED BY ALKYLATING BENZENE WITH NORMAL CHLOROPARAFFINS CONTAINING 8 TO 18 CARBON ATOMS.

Description

United States Patent US. Cl. 252353 20 Claims ABSTRACT OF THE DISCLOSURE A sulfonic acid composition is prepared by separately sulfonating (a) an alkylate composition consisting essentially of one or more monoalkaryl compounds in which the alkyl substituent contains from about 20 to about 40 carbon atoms, and (b) an alkylate composition containing from about weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about 75 weight percent dialkylbenzenes, and having an average molecular weight of from about 300 to about 500. The sulfonic acid reaction mixtures derived from the two alkylates are then separately gravity settled and a primary acid-sludge split is taken to remove the sludge from each reaction mixture. The de-sludged crude sulfonic acids from the two alkylates are then mixed and dissolved in hexane. The hexane solution of the mixed sulfonic acids is then permitted to settle and another acid-sludge split is made to remove the sludge. The first alkylate starting material may be a so-called dimer alkylate prepared by alkylating benzene with a dimerized tetramer of propylene, and the second alkylate starting material may be a bottoms fraction yielded in the fractionation of an alkylate mixture produced by alkylating benzene with normal chloroparaffins containing 8 to 18 carbon atoms.
BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to the preparation of oil soluble sulfonic acids suitable for use as dispersant additives to lubricating oils, and more particularly, to such sulfonic acids as are particularly suited for neutralization and overbasing in-situ in a non-volatile carrier material.
(2) Brief description of the prior art It is Well known that certain relatively high molecular weight sulfonates constitute valuable dispersants when added to lubricating oils. These sulfonates are often used to suspend or peptize small particles of basic metal compounds in the lubricating oil to which the sulfonates having the metal compounds dispersed therein are added, and in this manner, function to permit an alkaline reserve to be imparted to the lubricating oil so that harmful acidic products of fuel combustion and lubricating oil oxidation can be neutralized.
The oil soluble sulfonates described are prepared by sulfonating various types of alkylate starting materials. One widely used type of alkylate starting material which is an excellent sulfonation feedstock is a so-called dimer alkylate which is a mixture of monoalkaryl compounds in which monoalkylbenzene compounds containing from 20 to 40 carbon atoms in highly branched alkyl substituents predominate. Dimer alkylates of this type are prepared by alkylating benzene with a dimerized tetramer of propylene. The method of preparing the dimer used in alkylation is well understood in the art.
Another alkylate material which has been employed as Patented Nov. 21, 1972 a sulfonation feedstock is a bottoms fraction yielded in the fractionation of an alkylate mixture produced by alkylating benzene with normal chloroparafiin compounds containing from 8 to 18 carbon atoms. The overhead derived from the fractionation is sulfonated to yield valuable biodegradable detergents. The bottoms fraction can be sulfonated to prepare oil soluble sulfonic acids of the type under discussion. This bottoms fraction, in general, contains from about 5 weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent dialkylbenzenes. The alkyl substituents of the alkylated compounds in the bottoms fraction contain from about 10 to 18 carbon atoms, and the average molecular weight of the bottoms fraction is from about 300 to about 500. For use as a sulfonation feedstock, the bottoms alkylates which contain a relatively high proportion of dialkylbenzenes have been normally preferred, and frequently the raw bottoms alkylate remaining after removal of the lighter detergent grade alkylate is topped or further treated to increase the concentration of dialkylbenzenes therein, and to lower the quantity of diphenylalkanes contained therein. The latter materials do not sulfonate well and tend to decrease the overall quality of the sulfonate product.
In cases where the raw bottoms alkylate is not further topped to remove the diphenylalkanes to increase the concentration of the dialkylbenzenes, the raw bottoms alkylate may contain residual small amounts of the higher boiling portion of the biodegradable detergent alkylate stock. This material is thus included in the described ranges of amounts of dialkylbenzenes and alkylated tetralins. The process of this invention is particularly useful in employing bottoms alkylate material containing relatively high concentrations of diphenylalkanes.
For economic reasons, as well as to improve certain properties in the final sulfonic acid compositions, it has become a practice in the lubricating oil additive art to prepare a blend or mixture of the described dimer alkylate and bottoms alkylate, then co-sulfonate the mixture, followed by removal of spent acid sludge, and finally purification of the final sulfonic acid product. Certain product specifications for sulfonate type lubricating oils have been easily met by sulfonate mixtures prepared in this way, but others have been marginally met, and it has been recently found that certain variances in the processes of producing the two alkylates and co-sulfonating the mixed alkylates yield sulfonate products which do not meet all specifications; particularly a color specification imposed by the industry.
BRIEF DESCRIPTION OF THE PRESENT INVENTION The process of the present invention provides a method by which improved sulfonates for use as lubricating oil dispersant additives, can be prepared from dimer alkylate and bottoms alkylate starting materials. The procedure constitutes an improvement with respect to co-sulfonation procedures heretofore in use in which the two alkylates described are initially mixed or blended, and then sulfonation is carried out on such mixture, followed by sludge removal and purification. The process of the present invention results in an upgrading of the sulfonic acids yielded in that a higher ratio of actual sulfonic acid to other acidic products is present, the sulfonic acids produced have a higher combining weight, and no significant sacrifice in yield of sulfonic acids per unit of alkylate charged is sufiered. Moreover, the sulfonic acids produced by the process of the invention can be neutralized and overbased to produce an overbased sulfonate additive which is improved over those prepared by the co-sulfonation process previously employed in that the overbased sulfonates are characterized in having a lower viscosity and improved color.
Broadly described, the process of the present invention comprises initially carrying out separate sulfonations of (a) an alkylate composition which consists predominantly of one or more monoalkaryl compounds in which the alkyl substituent contains from about 20 to about 40 carbon atoms, and (b) a second alkylate composition which contains from about weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about 75 weight percent dialkylbenzenes. Preferably, the second alkylate subjected to the process of the invention contains between about 40 weight percent and 75 weight percent dialkylbenzenes and less than about 20 weight percent diphenylalkanes. After carrying out the separate sulfonations of the two described alkylates, a primary sludge split is taken on each of the two reaction products. The sludge split is obtained by permitting the reaction mixture to gravity settle over an extended period of time, and then removing the spent acid sludge from the crude sulfonic acid. After removing the sludge from each of the sulfonation mixtures, the desludged crude sulfonic acids are then mixed and are dissolved in a light organic solvent boiling below about 150 C. and preferably between about 40 C. and 120 C. Suitable materials include petroleum naphtha and light paraffins, such as hexane, heptane and octane. The solution of the mixed sulfonic acids is then permitted to settle, and another acid-sludge split is made to remove the sludge which has settled out. The final solution of mixed sulfonic acids is then preferably purified by techniques well understood in the art.
It is an important object of the present invention to provide a process for preparing a mixture of sulfonic acids which is suitable for preparing overbased sulfonate additives which may be used to impart reserve alkalinity and high dispersancy to lubricating oils.
A more specific object of the invention is to improve the sulfonic acid and sulfonate products derived from dimer alkylate, and from alkylates analagous to the bottoms alkylate produced in the manufacture of detergent grade alkylate by alkylating aromatic materials with chlorinated paraffin compounds.
Other objects and advantages of the invention will become apparent as the following detailed description of certain preferred embodiments of the invention are considered in conjunction with the accompanying drawings which illustrate certain aspects of the invention and certain benefits derived therefrom.
BRIEF RESCRIPTION OF THE DRAWINGS FIG. 1 is a block diagram illustrating the manner in which the process of the present invention is practiced.
FIG. 2 is a bar graph comparison of the properties of various sulfonic acid and overbased sulfonate products derived from the process of the present invention with the same products as prepared by co-sulfonation of mixed alkylates as heretofore practiced.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE PRESENT INVENTION FIG. 1 of the drawings may be referred to as an aid in understanding the process of the present invention as it is hereinafter described. Since the two types of alkylates which are separately sulfonated in the process are typified by the dimer alkylate and bottoms alkylate to be hereinafter more specifically described, these are indicated in the FIG. 1 diagram.
As previously indicated, the process of the present invention is commenced by separately sulfonating two types of alkylate materials. One of these contains at least 70 weight percent, and preferably at least 80 weight percent, monoalkaryl compounds in which an aryl compound is substituted by a single alkyl substituent containing from about 20 to about 40 carbon atoms. A typical alkylate of this type is sometimes referred to in the art as dimer alkylate, and is made by alkylating benzene with a highly branched dimerized propylene tetramer containing from about 20 to about 40 carbon atoms. The lakylate is derived from the propylene refinery stream by processes will understood and widely practiced in the art, and is characterized in having an average molecular weight of from about 350 to about 600. The dimer alkylate may contain up to 25 weight percent of dialkylbenzenes which constitute the major constituent other than the described monoalkaryl compounds.
An alkylate, other than dimer alkylate, fitting the general definition of the first of the two alkylates sulfonated in the process of this invention is an alkylate in which the monoalkaryl compounds are alkyl substituted benzene compounds in which the alkyl substituents are substantially straight chain in character and contain from about 20 to about 40 carbon atoms. Such alkyl benzenes can be prepared by alkylating benzene with a substantially straight chain olefin, such as an a-olefin.
In sulfonating the first alkylate of the type described, the alkylate is usually initially diluted with a light mineral oil, such as 100 S.S.U. viscosity pale oil, and is then sulfonated by conventional sulfonation procedures. Although $0 or mixtures of S0 and 80;, may be used to sulfonate the alkylate, 20% oleum is preferably employed to sulfonate the alkylates, whereby sulfonic acids substantially free of sulfur dioxide and sulfuric acid are yielded. The oleum is added slowly to the oil-diluted alkylate to a weight ratio of from about 1.0:1 to about 1.6:1 oleum to alkylate, while holding the temperature below about 80 C. and preferably below about 60 C. After addition of the oleum, the reaction mass is post-stirred for a period of from about 20 minutes to about 40 minutes at a temperature of from about 40 C. to about 80 C. and preferably from about 55 C. to about '60" C. The reaction mixture is then transferred to a separatory device, such as a separatory funnel, and is settled for from about 8 to about 16 hours at a temperature of about 50 C. The sludge phase is then removed.
The second alkylate which is subjected to separate sulfo nation contains from about 5 weight percent to about 35 weight percent diphenylalkanes, and preferably from about 5 weight percent to about 20 weight percent. The alkylate further contains from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent di-n-alkylbenzenes. The average molecular weight of this alkylate is from about 300 to about 500. As has been indicated, a typical alkylate of this type is that which is derived by a fractionation process in which the total alkylate prepared by reacting long chain chlorinated n-paratfin hydrocarbons with aromatic compounds, and particularly benzene, is subjected to fractional distillation. The bottoms portion (as contrasted with the overhead) which is yielded by such fractionation is an alkylate coming within the definition and description of the second alkylate subjected to sulfonation in the process of the present invention. This bottoms alkylate will typically contain from about 40 weight percent to about 75 weight percent di-n-alkylbenzenes in which the alkyl substituents contain from about 8 to 18 carbon atoms and are bonded to the benzene group through a secondary carbon atom of the alkyl chain, from about 10 to about 25 percent diphenylalkanes, from about 5 weight percent to about 18 weight percent tetralins, of which the majority are alkylated tetralins, and from about 4 weight percent to about 12 weight percent naphthalenes and indanes. Of the di-n-alkylbenzenes constituting the major constituent of the bottoms alkylate, from about 50 weight percent to about weight percent of these are para-disubstituted alkylbenzenes, and the balance are meta-disubstituted alkylbenzenes. Typically, the bottoms alkylate is separated from the overhead, which overhead constitutes an alkylate valuable for the production of biodegradable detergents, by fractionating the alkylate mixture to a cut point of 160 C. at mm. Hg. If it is desired to reduce the diphenylalkane content of the bottoms alkylate thus recovered to the preferred level of from about 5 weight percent to about 20 weight percent, further distillation can be carried out. The average molecular weight of the bottoms alkylate may range from about 300 to about 500.
As contrasted with the sulfonation of the first alkylate material as hereinbefore described, the second alkylate, of which the bottoms alkylate specifically identified is an example, is preferably sulfonated neat; that is, it is preferred that no dilution with a light mineral oil be effected prior to sulfonation. In carrying out the sulfonation, the alkylate is stirred, and 20% oleum is slowly added to the alkylate in a weight ratio of from about 1.3:1 to about 1.9:1 while maintaining the temperature of the reaction mixture below about 80 C. and preferably below about 60 C. After the oleum has been added, stirring is continued for a period of from about 20 minutes to about 40 minutes thereafter while maintaining the temperature at from about 40 C. to about 80 C., and preferably from about 55 C. to about 60 C. After this time a light hydrocarbon solvent boiling between about 40 and 150' C., and preferably below about 120 C., is added in an amount suflicient to provide about 0.5 to 3.0 weight parts of the solvent per weight part of the alkylate charged. Suitable solvents include light petroleum naphthas, hexane, heptane, octane, and mixtures thereof. As an alternative, up to 30 weight percent of the light hydrocarbon solvent can be replaced by a diluent oil such as pale oil. The mixture is then stirred for an additional period of from about to about 30 minutes at reflux temperature, which is generally from about 55 C. to 60 C.
After this time, the crude sulfonation mass is transferred to a separatory device, such as a separatory funnel, and is permitted to settle for a period of from about 8 hours to about 16 hours at ambient temperature. A primary sludge split to remove the spent sulfuric acid sludge is then taken, and the hexane-sulfonic acid phase is recovered.
As has been previously indicated herein, a practice in use prior to the present invention has been to initially mix or blend the two alkylates of the types described, and then perform a co-sulfonation of the mixed alkylates, followed by sludge separation. The mixed sulfonic acid product yielded by such co-sulfonation procedure has, however, occasionally failed to meet certain specifications, particularly the color specification, when certain slight variations in the alkylate production process which are diflicult to control are encountered. We have determined that separate sulfonation, followed by separate sludge removal from the sulfonic acid products produced by the separate sulfonations, then followed by combining of the sulfonic acids, followed finally by a secondary sludge split, results in the production of an improved mixed sulfonic acid product. This procedure is schematically illustrated in FIG. 1. Although the reason for the improvement in results is not thoroughly understood, it is believed that the tetralins in the second alkylate, of which bottoms alkylate of the type described is typical, tend to solubilize certain undesirable sulfonatable materials, specifically the diphenylalkanes in this alkylate, when the co-sulfonation procedure is followed. In other words, the mixed sulfonic acids produced upon co-sulfonation tend, due to the solubilizing effect of the tetralins in the mixed alkylate starting material, to include certain undesirable materials which detract from the quality of the final mixed sulfonic acid product. Where the sulfonations are carried out separately, it is believed that the primary sludge split taken upon the crude sulfonic acid product of the bottoms alkylate sulfonation efiectively removes certain undesirable by-products from the sulfonic acid product at this point (these being removed in the sludge), and the result is that these materials which cause the final product to be off specification when co-sulfonation is utilized, have been removed, and the final mixed sulfonic acid product is of higher quality.
As indicated in FIG. 1, after the primary sludge split has been accomplished in the primary settlers to remove spent sulfuric acid sludge from the crude sulfonic acids, the crude sulfonic acids are mixed, diluted with a paraffinic hydrocarbon, such as hexane, and placed in a secondary settling device, such as a separatory funnel. The dilution with light hydrocarbon solvent is carried out to adjust the sulfonic acid concentration to about 0.4 to about 0.8 milli-equivalent of acid per gram of the diluted mixture. In general, from about 0.20 to about 2.0 volume of hexane is utilized per volume of crude acids. The diluted mixed sulfonic acids are permitted to gravity settle for a period of from about 8 to about 16 hours, and the sludge is then removed.
It should be here pointed out that, in lieu of gravity settling as hereinbefore described, de-sludging of the two separately sulfonated alkyates to achieve the primary sludge split can be accomplished by centrifugation, as can the secondary sludge split accomplished after the crude sulfonic acids from the two alkylates have been combined. Centrifugation is particularly amenable to usage in desludging the sulfonic acid product resulting from sulfonation of the bottoms alkylate material.
After the crude sulfonic acids have been recovered from the final sludge removal step, the acids are purified by initially de-gassing the acids by blowing an inert gas, such as nitrogen, through the acids for about 15 minutes. Calcium hydroxide, in an amount equivalent to about 1.5 times the amount needed to neutralize the sulfuric acid, is then added to the crude acids, and the mixture is again degassed using an inert gas to blow the mixture for a period of about 45 minutes while heating the mixture to a temperature of from about 30 C. to 35 C. The solution is then filtered, and the sulfonic acids thus prepared and purified can be used in the preparation of overbased sulfonate compositions suitable for use as additives to lubricating oils.
The following examples typify the practice of the invention, and also provide illustrations of the manner in which mixed alkylate co-sulfonation has been previously utilized in the production of oil soluble sulfonic acids. It will be understood that other alkylates differing to some extent in constitution from those specifically cited in the examples may be used as starting materials, and some variation in process conditions may be tolerated without diffculty.
EXAMPLE 1 575 grams of a dimer alkylate which contained 81.8 mole percent monoalkylbenzenes (each containing from about 22 to about 38 carbon atoms in the highly branched alkyl substitutents), 13.6 mole percent para-dialkylbenzenc compounds, and 4.6 mole percent meta-dialkylbenzene compounds, and having a molecular weight, as determined by osmometer, of 362, were charged, along with 345 grams of pale oil having a viscosity of S.S.U. at 210 C. to a creased flask, and mechanical agitation was commenced. 20% oleum was charged to the flask over a period of 20 minutes. The exothermic reaction was maintained at a temperature of between 55 C. and 60 C. during the addition of the oleum. After addition of the oleum, the reaction mass was post-stirred for a period of 30 minutes, and was then charged to a separatary funnel and permitted to gravity settle overnight at 50 C. On the following day, sludge split was taken to remove sludge from the crude sulfonic acid-oil mixture. 1,070 grams of the crude acid-oil product were recovered, and 624.4 grams of sludge were removed.
In another sulfonation run, alkylate bottoms recovered from a detergent alkylate process of the type hereinbefore described was the sulfonation charge stock. This alkylate was characterized in containing, as determined by mass spectrometer, 40.7 volume percent alkylbenzene compounds containing from 8 to 18 carbon atoms in the alkyl substituents, 24.9 volume percent diphenylalkanes, and 23.3% tetralins. The average molecular weight of the alkylate was 350. 1,500 grams of the alkylate were charged to a creased reaction flask and were mechanical agitated as 20% oleum was added to the flask over a period of minutes. During this time, the temperature of the reaction mixture was maintained below 60 C. After addition of the oleum, the mixture was post-stirred for a period of minutes. Following the post-stirring, 2,250 ml. of hexane was added to the reaction mixture, and mechanical mixing was then continued for a period of 15 minutes at a temperature of between 55 C. and 60 C. The mixture was then charged to a separatory funnel and permitted to settle at ambient temperature overnight. On the following day, a sludge split was taken. 2,768 grams of crude acidhexane solution were recovered, and 2,923 grams of sludge were removed.
All of the crude acid-oil product from the described sulfonation of the dimer alkylate was combined and mixed with 1,100 grams of the crude acid-hexane solution derived from the described bottoms alkylene sulfonation. The combined sulfonic acid products were mechanically mixed, and 2,790 ml. of additional hexane were added during the mixing. The hexane-acid mixture was then charged to a separatory funnel and permitted to gravity settle at ambient temperature overnight. On the following day, a secondary sludge split was taken, and there were isolated 3,833 grams of sulfonic acid solution. 166.3 grams of sludge were separated.
EXAMPLE 2 A dimer alkylate of the type described in Example 1 was diluted with a pale oil having a viscosity of 100 S.S.U. at 210 C. in a weight ratio of 0.54:1 diluent oil to alkylate. 20% oleum was then slowly added to the mixture in an amount suflicient to give a weight ratio of oleum to alkylate of 1.2: 1. The sulfonation conditions were similar to those described in Example 1 in the part thereof which refers to the sulfonation of the dimer alkylate. Following sulfonation, a primary sludge split was taken after permitting the reaction mixture to settle overnight in a separatory funnel.
In another sulfonation, a bottoms alkylate having a molecular weight as determined by osmometer of 344 and containing, by mass spectrometer analysis, 40.6 volume percent alkyl benzene, 35.7 volume percent diphenylalkanes, and 16.7 volume percent tetralins was sulfonated with 20% oleum in a weight ratio of oleum to alkylate of 1.9: l. The alkylate was sulfonated neat, and the temperature and time conditions were similar to those used in the sulfonation of bottoms alkylate as described in Example 1. Upon completion of the post-stirring utilized in the sulfonation, hexane was added to the reaction mixture in an amount equal to the amount of alkylate used in the sulfonation. The reaction mixture was then charged to a separatory funnel and permitted to gravity settle overnight. After gravity settling, a primary sludge split was taken to recover the crude acid-hexane solution from the spent acid sludge.
The acid-hexane solution thus produced was then combined with the crude acid-oil product produced by the akylation of the dimer alkylate as described earlier in this example. The sulfonic acids were mixed in a 1:1 weight ratio. After combining the acid products in the manner described, hexane was added to the combined crude acids in a volume ratio of 1.2:1 hexane to crude 8 acid (the term crude acid here referring to the crude acid, hexane and oil present in the combined crude acid products of the two sulfonations). The hexane-acid mixture was then permitted to gravity settle for a period of about 15 hours, and a secondary sludge split was taken to remove sludge from the acid-hexane mixture.
EXAMPLE 3 Dimer alkylate of the type utilized in Example 1 was sulfonated neat, using a weight ratio of 20% oleum to alkylate of 12:]. Upon completion of the post-stirring period of the sulfonation, a volume of hexane was added to the reaction mixture in a weight ratio of 1:1 hexane to starting alkylate. The crude sulfonic acid product was recovered by a primary sludge split after settling overnight.
2,000 grams of the bottoms alkylate utilized in Example 2 were charged to a creased sulfonation flask equipped with a mechanical stirrer, thermometer and dropping funnel. 20% oleum in a weight ratio of 1.9:1 oleum to alkylate was added to the alkylate and sulfonation of the bottoms alkylate carried out as described in Example 2. Hexane was then added to the reaction mixture in an amount equal to the amount of alkylate sulfonated. After overnight settling, a primary sludge split was then taken to recover the crude hexane-acid solution.
The crude sulfonic acid-hexane product produced from the bottoms alkylate was then combined with the crude sulfonic acid-hexane product produced by alkylation of the dimer alkylate described earlier in this example in a sulfonic acids weight ratio of 1:1. The mixed acids were then diluted with about 1.2 volumes of hexane, and a secondary sludge split was taken after permitting the mixture to stand overnight.
EXAMPLE 4 500 grams of the dimer alkylate described in Example 1 were mixed with 655 grams of pale oil and 500 grams of the bottoms alkylate described in that example, and the mixture was then charged to a creased flask and sulfonated with 1,900 grams of 20% oleum in the manner described in Example 1 as being utilized for the sulfonation of dimer alkylate. After completion of the post-stirring period, the sulfonation mass was charged to a separatory funnel and gravity settled at 50 C. overnight. On the following day, a sludge split was taken and 1,758 grams of sludge were removed to leave 1,731 grams of the crude acid-oil product. To 1,196 grams of crude acid-oil produced in the manner described were added 1,880 m]. of hexane. After homogenization by hand mixing in a separatory funnel, the mixture was permitted to gravity settle overnight at ambient temperature. On the following day, a secondary sludge split was taken, and there were isolated 2,357 grams of hexane-sulfonic acid solution. 98.2 grams of secondary sludge was removed.
EXAMPLE 5 A mixed alkylate charge stock which contained 60 weight percent of the bottoms alkylate and 40 weight percent of the dimer alkylate described in Example 2 was employed in a cosulfonation run. 100 S.S.U. viscosity pale oil was used as a diluent in a weight ratio of 0.5 :1 diluent to total alkylate charge stock. The oil diluted alkylate was then subjected to sulfonation using 25% oleum in a weight ratio of 1.9:1 oleum to total alkylate charge. At the end of the post-stirring period, the crude sulfonic acid-oil mixture was transferred to a separatory funnel, and after a suitable period of gravity settling, a primary sludge split was taken. Hexane was then added to the crude acid-oil raffinate recovered from the sludge split in a volumetric ratio of 1.5:1 hexane to acid-oil product. A secondary sludge split was then taken.
9 EXAMPLE 6 For the purpose of further examining the co-sulfonation of mixed alkylates, the bottoms alkylate and dimer alkylate described in Example 3 were mixed in a 60:40 weight ratio. The mixed alkylates were then sulfonated in the manner described in Example 1 for the sulfonation of the dimer alkylate, but utilizing a weight ratio of 20% oleum to alkylate charge of 1.6:1 and without pale oil dilution. Upon completion of the alkylation, a weight of normal hexane equivalent to the weight of alkylate charge was added to the reaction mixture, and the hexane diluted mixture was then permitted to stand overnight at 50 C. A primary sludge split was taken on the following day to remove the sludge from the mixture. There was then charged to the crude acid-hexane mixture, an additional volume of hexane equivalent to the volume of the crude acid-hexane mixture remaining after the primary sludge split. This mixture was then permitted to gravity settle overnight, and a secondary sludge split was taken to isolate the crude acid-hexane mixture from the spent acid sludge materials.
EXAMPLE 7 For the purpose of evaluating the crude hexane-sulfonic acid products produced by co-sulfonation and by separate sulfonations as described in Examples 1-6, certain analyses and tests of the several products were made, and the results compared. The results obtained are tabumixture was again de-gassed with nitrogen for an additional period of 45 minutes while heating the mixture to a temperature of from C. to C. The solutions were then filtered, and the flask and funnel used in filtering rinsed with hexane to recover all of the sulfonic acid.
The purified sulfonic acid products were then utilized to prepare overbased barium and calcium sulfonate dispersions. For the purpose of preparing the overbased barium sulfonate dispersions, the sulfonic acid charge was calculated so as to yield an overbased product having an acetic acid base number of approximately 70, and to contain about 46.5 weight percent neutral barium sulfonate. Thus, in each instance, 200 grams of the purified sulfonic acid-hexane solution were charged to a l-liter creased flask equipped with a mechanical stirrer, thermometer and heating mantle. A neutral mineral oil having a viscosity of 100 S.S.U. at 210 C. was then added to adjust the activity of the sulfonic acid solution as necessary to make the 46.5 percent active product.
Methanolic barium oxide solution was then added slowly from a dropping funnel over a period of about 10 minutes to neutralize the sulfonic acid and to provide excess barium oxide. Carbon dioxide was then blown through the mixture from a sintered glass tube at a rate of about 250 ml./min. until the reaction mass became acidic to anaphthol benzene indicator (the time required was from about 15 to about 20 minutes). The solvents were then distilled overhead to a pot temperature of 150 C., and the product stripped with carbon dioxide for a period of lated in Table I. 30 15 minutes.
TABLE I Example Number Co- Co- Co- Sep- Sep- Sepsuliosultosuito- Type suliouatlonarate arate crate nation nation nation Crude hexane sultonic acid:
Total acid, meqJg. 0. 802 1. 183 0. 78B 1. 034 1. 170 Sulionic acid, meq./ 0. 582 0. 638 0. 573 0. 623 0. 669 Acid ratio 1 3 9-3 4. 2 7. 6 8. 6 Na sulfonatlon ASTM (D color 2. 6 1. 6 4. 0 2. 5 2. 5 Yield data.-
Cornbining Wei ht, (RSOH) 5B 39 444 450 429 Grams RSO H g., alkylate charge 0- 8B 0- 82 0. 81 0. 87 0. 83 0. 8s
1 Expressed as weight percent sulfuric acid based on total Weight of sulfonic acid present. I Determined by ASIM D1500-67T modified by dissolvin 7.0 grams of sodium sulfonate in ml. of hexane. Determined by column analysis of the corresponding so ium sulfonate prepared from the final hexane diluted sulfonic acid.
It will be noted in referring to Table I that the crude hexane-sulfonic acid products produced by separately sulfonating the two alkylate types described were characterized in having higher combining weights and better A.S.T.M. sodium sulfonate color than the products derived from the co-sulfonation processes. Two of the sulfonic acid products had lower acid ratio values than their counterpart products produced by co-sulfonation.
EXAMPLE 8 The crude sulfonic acid products produced in Examples 1-6 were purified by placing the product to be purified TABLE II Example Number Type sulionation Sep- Sep- Sep- Co-sulfo- Co-sulfo- Clo-sulfoarete arate arate nation nation nation b r 76 68 71 69 70 71 l g r e d geti ve a- 47- 2 46- 5 46- 5 46. 4 46.3 46. 5 Viscosit 210 F., SSU. 302. 2 219. 3 293. 7 332.0 237. 8 335. 0 ASTM din. color 1 3. 5 a0 3. 0 5. 0 3. 5 a. 5
1 Determined by ABTM Dl500-57T modified by dissolving 7.6 grams of the overbased barium sulfonate dispersion in 50 ml. hexane.
in a creased three-necked flask equipped with a mechanical stirrer, thermometer and heating mantle. The crude sulfonic acid was then de-gassed for a period of 15 minutes by blowing with nitrogen through a sintered glass tube at ambient temperature. Calcium hydroxide in an amount 1.5 times the weight needed to neutralize the sulfuric acid was then added, and after the addition, the 75 tion in many cases, was reduced significantly in compari- 11 son to the color rating characteristic of the dispersions derived from the cosulfonation procedure.
In order for the data reproduced in Tables I and II to be more meaningfully compared, runs carried out with related starting materials and in substantially the same manner, except for the difference of co-sulfonation, as contrasted with separate sulfonation, are compared in side-by-side relation in bar graph form in FIG. 2 of the drawings. Thus, in Example 1, the dimer alkylate was sulfonated in 100 pale oil and in Example 4, the mixed alkylates were co-sulfonated in such oil. Moreover, in these two runs, the bottoms alkylate and dimer alkylates used were the same materials. In Examples 2 and 5, the processing conditions were similar in that in Example 2, the dimer alkylate was sulfonated in oil, and in Example 5, the alklate mixture was sulfonated in oil. Moreover, the bottoms alkylate and dimer alkylate used in both these runs were identical, although the bottoms alkylate differed from that used in Examples 1 and 4. In Examples 3 and 6, the sulfonation of all alkylates was carried out neat, with post-hexane addition in each case.
In referring to FIG. 2 it will be perceived that, in addition to the clearly established advantages of carrying out separate sulfonations of the two alkylates, the procedure of sulfonating the dimer alkylate while this alkylate is diluted with oil, and sulfonating the bottoms alkylate neat, followed by the addition of hexane after sulfonation, is the superior technique to be followed. Thus, in Examples 1 and 2, each involving separate sulfonations of the two alkylates, with only the bottoms alkylate being sulfonated neat followed by hexane addition, both runs produced sulfonic acids having substantially higher combining weights than in the case of the separate sulfonation carried out in Example 3 where both alkylates were sulfonated neat. It will also be noted that the runs of Examples 1 and 2 yielded products with much lower acid ratios than the product made in Example 3. The yield is also better in the two former runs. Only in the case of the color test does the procedure of separately sulfonating each of the alkylates neat, followed by hexane addition, appear to give comparable results to those obtained where the dimer alkylate is sulfonated in oil.
The sulfonic acid products produced by the runs described in Examples 1 and 4 were overbased using a calcium alkoxide-carbonate complex in accordance with the teachings of Hunt US. Pat. No. 3,150,088. The viscosities of overbased calcium sulfonate dispersions produced by this technique from these two sulfonic acid products were compared. The overbased calcium sulfonate disper sion derived from the separate sulfonation procedure described in Example 1 had a base number of 290 and had a viscosity (S.S.U. 210) of 409.3. As contrasted with this, the overbased calcium sulfonate dispersion derived from the co-sulfonation procedure set forth in Example 4 had a base number of 280 and had a viscosity of 879.3. Thus, a very significant improvement in viscosity was achieved through the use of the separate sulfonation technique, as compared to the co-sulfonation procedure previously in use.
From the foregoing description of the invention, it will be perceived that the process of the invention provides a method by which mixed sulfonic acids derived from two alkylates of the general type described can be upgraded, and their utility as charge materials for the purpose of producing overbased sulfonate dispersions suitable for use as lubricating oils can be improved. Although certain preferred embodiments of the invention have been herein described in order to provide examples sufficient to enable those skilled in the art to practice the invention, it will be understood that other materials and variations in the described process conditions can be employed without departure from the basic principles of the invention. Changes and innovations of this type are therefore deemed to be circumscribed by the spirit and scope of the invention except as the same may be necessarily limited by the appended claims or reasonable equivalents thereof.
What is claimed is:
1. The process of preparing a mixture of oil-soluble sulfonic acids comprising:
sulfonating a first alkylate composition comprising at least weight percent monoalkaryl compounds in which an aryl group is substituted by an alkyl substituent containing from about 20 to about 40 carbon atoms;
separately sulfonating a second alkylate containing from 5 weight percent to about 35 weight percent diphenylalkanes, from about 5 weight percent to about 50 weight percent alkylated tetralins, and from about 25 weight percent to about weight percent di-n-alkylbenzenes, and having an average molecular weight of from about 300 to about 500, the alkyl substituents of said di-n-alkylbenzenes containing from about 8 to about 18 carbon atoms;
separating sludge formed in the sulfonation of said first alkylate from the crude sulfonic acid produced upon sulfonation;
separating sludge formed in the sulfonation of said second alkylate from the crude sulfonic acid produced upon sulfonation;
combining the de-sludged crude sulfonic acid yielded from the sulfonation of said first alkylate with the desludged crude sulfonic acid yielded from the sulfonation of said second alkylate;
adding a hydrocarbon solvent diluent to the combined crude sulfonic acids; and
separating sludge from the hydrocarbon diluted-crude sulfonic acids.
2. The process defined in claim 1 wherein a light mineral oil diluent is mixed with said first alkylate prior to sulfonating said first alkylate.
3. The process defined in claim 1 wherein the sulfonations of said first and second alkylates are carried out using oleum as the sulfonating agent.
4. The process defined in claim 1 wherein said first alkylate is a dimer alkylate prepared by alkylating benzene with a dimer of a propylene tetramer, and wherein the substituents of the benzene after alkylation are highly branched alkyl groups containing from about 20 to about 40 carbon atoms, said dimer alkylate having a molecular weight of from about 350 to about 600.
5. The process defined in claim 1 wherein said second alkylate boils above about C. at 5 mm. Hg and contains from about 40 weight percent to about 75 weight percent di-n-alkylbenzenes in which the alkyl substituents contain from 8 to 18 carbon atoms and are bonded to the benzene group through a secondary carbon atom of the alkyl chain.
6. The process defined in claim 1 wherein said sludge is removed from said crude sulfonic acids before combin ing said sulfonic acids by gravity settling said crude sulfonic acids for a period of from about 8 hours to about 16 hours.
7. The process defined in claim 1 wherein, prior to separating sludge from crude alkylate formed in the sulfonation of said second alkylate, the reaction mixture produced upon sulfonation of said second alkylate is diluted with a parafiinic hydrocarbon solvent in an amount of from about 0.5 gram to about 3 grams of solvent per gram of the second alkylate charged to the sulfonation reaction.
8. The process defined in claim 1 wherein said crude sulfonic acids are combined in a 1:1 weight ratio of the sulfonic acids present in the two crude sulfonic acids.
9. The process defined in claim 1 wherein the monoalkaryl compounds in said first alkylate are alkyl substituted benzene compounds in which the alkyl substituents are substantially straight chain in character and contain from about 20 to about 40 carbon atoms.
10. The process defined in claim 2 wherein said second alkylate is sulfonated neat, and wherein, prior to separating sludge from the crude alkylate formed in the sulfonation of said second alkylate, the reaction mixture produced upon sulfonation of said second alkylate is diluted with a parafiinic hydrocarbon solvent in an amount of from about 0.5 gram to about 3 grams of solvent per gram of the second alkylate charged to the sulfonation reaction.
11. The process defined in claim 3 wherein during the sulfonation of said first and second alkylates with oleum, the temperature of each reaction mixture is maintained below about 80 C. during addition of the oleum to the alkylate.
12. The process defined in claim 2 wherein the hydrocarbon solvent diluent added to the combined crude sulfonic acids is a C -C paraflinic hydrocarbon.
13. The process defined in claim 2 wherein said first alkylate is a dimer alkylate prepared by alkylating benzene with a dimer of a propylene tetramer, and wherein the substituents of the benzene after alkylation with said tetramer are highly branched alkyl groups containing from about 20 to about 40 carbon atoms, said dimer alkylate having a molecular weight of from about 350 to about 600.
14. The process defined in claim 2 wherein said mineral oil diluent is pale oil having a viscosity of about 100 SSU at 210 C.
15. The process defined in claim 2 wherein the sulfonation of said first and second alkylates are carried out using oleum as the sulfonation agent and adding oleum to the alkylates while the temperature of each alkylate is maintained below about 80 C.
16. The process defined in claim 13 wherein said second alkylate boils above about 160 C. at mm. Hg and contains from about 40 weight percent to about 75 weight percent di-n-alkylbenzenes in which the alkyl substituents contain from about 8 to about 18 carbon atoms and are bonded to the benzene group through a secondary carbon atom of the alkyl chain.
17. The process defined in claim 16 wherein the sulfonations of said first and second alkylates are carried out using oleum as the sulfonating agent and adding oleum to the alkylates while the temperature of each alkylate is maintained below about C.
18. The process defined in claim 17 wherein the hydrocarbon solvent diluent added to the combined crude sulfonic acids is normal hexane and is added in the ratio of from about 0.20 to about 1.5 volumes of hexane per volume of the combined crude sulfonic acids.
19. The process defined in claim 18 wherein said crude sulfonic acid are combined in a 1:1 weight ratio of the sulfonic acids present in the two crude sulfonic acids.
20. The process defined in claim 16 wherein, prior to separating sludge from crude alkylate formed in the sulfonation of said second alkylate, the reaction mixture produced upon sulfonation of said second alkylate is diluted with a parafiinic hydrocarbon solvent in an amount of from about 0.5 gram to about 3 grams of hexane per gram of the second alkylate charged to the sulfonation reaction.
References Cited UNITED STATES PATENTS 2,161,174 6/1939 Kyrides 252-353 X 2,463,497 3/1949 Smith et al 252353 X 3,150,088 9/1964 Hunt et al. 25232.7 R
RICHARD D. LOVERING, Primary Examiner US. Cl. X.R. 252--33
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US20030069243A1 (en) * 1997-07-02 2003-04-10 Smithkline Beecham Corporation Novel substituted imidazole compounds
US20030100756A1 (en) * 2000-03-02 2003-05-29 Adams Jerry L 1,5- disubstituted-3,4-dihydro-1h-pyrimido[4,5-d]pyrimidin-2-one compounds and their use in treating csbp/p38 kinase mediated diseases
US20050075352A1 (en) * 1999-11-23 2005-04-07 Smithkline Beecham Corporation 3,4-Dihydro-(1H)-quinazolin-2-ones and their use as CSBP/p38 kinase inhibitors
US7053098B1 (en) 1999-11-23 2006-05-30 Smithkline Beecham Corporation 3,4-Dihydro-(1H) quinazolin-2-one compounds as CSBP/P38 kinase inhibitors
US20070004600A1 (en) * 2005-07-01 2007-01-04 Stoneman Kyle D Sulfonate compositions
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US20030069243A1 (en) * 1997-07-02 2003-04-10 Smithkline Beecham Corporation Novel substituted imidazole compounds
US20050075352A1 (en) * 1999-11-23 2005-04-07 Smithkline Beecham Corporation 3,4-Dihydro-(1H)-quinazolin-2-ones and their use as CSBP/p38 kinase inhibitors
US7053098B1 (en) 1999-11-23 2006-05-30 Smithkline Beecham Corporation 3,4-Dihydro-(1H) quinazolin-2-one compounds as CSBP/P38 kinase inhibitors
US20030100756A1 (en) * 2000-03-02 2003-05-29 Adams Jerry L 1,5- disubstituted-3,4-dihydro-1h-pyrimido[4,5-d]pyrimidin-2-one compounds and their use in treating csbp/p38 kinase mediated diseases
US20070004600A1 (en) * 2005-07-01 2007-01-04 Stoneman Kyle D Sulfonate compositions
US7601676B2 (en) * 2005-07-01 2009-10-13 Afton Chemical Corporation Sulfonate compositions
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