US 2436046 A
Description (OCR text may contain errors)
Patented Feb. 17, 1948 UNITED STATESPATENT OFFICE EMULSIFIABLE SOLUBLEOIL coMrosrrroNs Norman E. Lemmon and Frederick W. Schuessler, Hammond, Ind., assignors to Standard Oil Company, Chicago, 111;, a corporation of Indiana v No Drawing. Application December 22, 1944,
Serial No. 569,411 4 Claims. ((11.252-312), I
I This invention relates to improvements i sul- Ionic compounds and moreparticularly to the compounding of sulfonic acids possessing'difier- Tent solubility properties to produce a product having the'desired oil and water solubilities.
.. In the refining of-petroleum oils with sulfuric acid, particularly concentrated orfumin sulfuric acids, two types of sulfonic acids are formed; one type is preferentially water-soluble and is found in the acid sludge layer. These .1 preferentially water-soluble sulfonic acids are of a greenish color and because of this characteristic color are known and referred to in the petroleum refining art as green sulionic acids. The other type of sulfonic acids are preferentially oilsoluble and are found in the sulfuric acid treated oil, These preferentially. oil-soluble sulfonic acids have a characteristic reddish-brown or mahogany color and are commonly referred to and identified as mahogany sulfonic acids; While i these preferentially oil-soluble sulfonic acidsor jsulfonates from different. stocks and by different acid treatments as a class are all soluble in oil, they all do not behavesimilarly in water solubility and/or emulsibility, that is, certain of the preferentially oil-soluble sulfonic compounds form relatively stable emulsions with water while other types of preferentially oil-solublev compounds do not formemulsions with water or are diflicultly emulsifiable with water.
The mahogany sulfonic acids range in molecular weight from about 300 to about 600 and while they all are preferentially oil-soluble as compared to the green acids, their solubility in oil increases withincrease in their molecular weights.- The preferentially oil-soluble mahogany acids and the soaps thereof have found wide use in the preparation of emulsifiable petroleum products, such ,as insoluble cutting oils, drawing compounds, 'emulsifiable insect spray compounds, and in other fields such as in the preparation of anti-rust com-pounds, mineral aggregate coating agents, .etc, For these various uses hydrocarbon sulfonic acidswithin the molecular weight range of from Iabout 350 to about 5 50 ,have been found most molecular weights above, about 425' to render effective. The preferentially oil-soluble hydrocarbon sulfonic compounds having molecular weights above about 425 are of the type which are substantially water-insoluble or which are non-emulsifiable with water. Hereinafter and in the appended .claims preferentially oil-soluble hydrocarbon sulfonic com ounds, which ,term is used generically to include the sulfonic acids as well as the sulfonates which are prefierentially oil-soluble but .substantially nonemulsifiable with, water, will be referred to as preferentially oil-soluble water non-emulsifiable sulionic compounds. By the termfwat'er non-emulsiflable" as used herein and in the appended claims is meant an oil-soluble sulfonic compound which does not pass the emulsion test described by F. M. Archibald in the soluble petroleum sulfonic acids have found little utility and in many cases must be considered as .waste Icy-products or used for inferior products. ,The most effective preferentially oil-soluble sulfonic acids for use in the compounding of emulf siflable, products arefthose having molecular weights within the. range of from about 350'to about 425;. The sulfonic acids having molecular weightsbelow, about 350 possess such low oilsolubility properties that they are unsuited for this use, whilethe sulfonic acids having molecular weights above about 425 yield soaps which are so water-insoluble as to render them unsatisfactory for compounding in emulsifiable prod- ,ucts. A method of modifyingthe water and oil- 'solubility properties of the sulfonic acids having them satisfactory for use in emulslfiable compounds is therefore highly desirable,
It is an object of the present invention to provide a, method of modifying the waterand oilsolubilities of soaps of sulfonic acids having molecular weights above about 425 to render such soaps satisfactory for use in the compounding of emulsifiable products. Another object of the invention is to provide a method for utilizing sulfonic acids having molecular weights above about 425 in emulsifiable products. Still another object of the invention is to prepare satisfactory emulsifiable products containing hydrocarbon sulfonic acids having molecular weights above about 425i Stub-another. object of the invention is to provide a method "of preparing soluble oil products utilizing hydrocarbon sulfonic acids having molecular weights above about 425. An additional object of this invention is to preparesolsuble oil products containing hydrocarbon 'sul ionic acids having molecular weights above about 425. Other objects and advantages of: thisiirvention will become apparent from'thefollowlng;
In accordance with the present invention sulhalf pound increments or dumps.
ion, are water non-emulsiflable and unsatisfactory for use in the compounding of soluble oil products. These hydrocarbon sulfonic acids have molecular weights ranging from about 450 to 560. These hydrocarbon sulfonic acids cannot be satisfactorily used in the formulation of emulsifiable soluble oil products without modifying their properties with a water-soluble, detergent type soap, for example the alkylated aromatic sulfonates of the type hereinafter-described.
A method of obtaining these preferentially oilsoluble water non-emulsifiable sulfonic acid soaps which must be modified to make them suitable for use in soluble oil products is illustrated by the following example :1 I
A petroleum oil distillate having a Saybolt Universal viscosity at 100 F. of about 200 seconds is treated with from about 7 to about 8 pounds ofifumingsulfuric acid per gallon of oil in one- After the acid sludge from each one-half pound acid dump? issettled'and withdrawn, the next onehalf, pound of" fuming sulfuric acid is added to the oil. Thev temperature of the oil before the fuming acid is added thereto is maintained at a temperature below about 60 F. but due to the fonic acids, particularly the hydrocarbon sul fonic acids, such as petroleum sulfonic acids; re
sulting from the treatment of petroleum oils with sulfonating agents, andzhaving molecular weights above about 425 which normally are notsatisfactory for useinth'e preparation off'emulsiffabl'e soluble. oil products are made useful'for this:p11r'-'- pose by employing the soaps of such sulfonic acids. in combination.withwater-soluble, deter"- gent type soaps, such as, forv example, water soluble alkylated aromat'icsulfonates, sulfates; etc. The. quantity ofthe waterasoluble detergent y-pe. soap employed will.vary with the molecularweight. of the preferentially oilksoluble hydro carbon sulfonic acid soap employed. Stated in another way,,, the morewater-insolubl preferentially oil-soluble hydrocarbon sulfonic acidsrequire the addition .of greater amounts of the water-soluble detergent type, soaps. In general for. the preparation of most emulsifiablesolubl'e oil. products employing. preferentially oil-soluble water non-emulsifiable hydrocarbon. sulfonic acid soaps. require from. aboutv 0.5% to about 10% or. more and preferably from about 1% to about 5% of water-soluble, detergent type soaps in order to obtain, the satisfactory emulsifying properties.
In, the refining of petroleum oils it is. thejgenleral practice. to treatthe oils'with concentrated or fuming sulfuric acid. .in increments of. about poundsof acid per gallon offoil. The sludge formedaftereach. dump of acidjis settled and withdrawn and] the oil again. treated with? /2 pound of the acid per gallon of the oil. This treatment, is continueduntil the oil'has been refined to the. desired degree. In the. preparation of. white oils such as thosev knownas technical -wl'iiteoils and medicinal mineral oils, the oil." is
usually treat'edwith a total of from about; 3' to about. 9 pounds of acid per gallon of'oill.
The preferentially OilSOlllbll hydrocarbon sul onic acids produced during each increment of distillate of? l00'to 300 seconds" Saybolt Universal viscosity'at 100-F. with-5or more pounds of acid per'ga-llon or from the treatment of-"a distillate 'of3'00 to-900';ormoreseconds Saybolt Universal viscosity with 3* or "more pounds-of acid pergal heat of reaction upon the addition of the sulfuric acid; the temperature of the oil may rise to from about F. to about F. After the required total amount of fuming sulfuric acid has been added" tothe 'oil and the'oil freed of' acid sludge, the. acid-treated oil containing oil-soluble sulfonic acids dissolved therein; is neutralized with a solution of sodium hydroxide. The. aqueous alkali solution is then separated from the oil solution containing-dissolved therein sodium soap of sulfonic acids and the latter then separated from the'oil by extraction with alcohol of about 60% strength. The alcohol layer containing dissolved sodium sulfonates is then separated from the oil and subsequently'distilled' to recoverthe alcohol and water. The sulfonic soap obtained i'n-this manner contains from about 30% toabout 60% sodium sulfonate, from about 30% to about 60% oil, from about 1% to about 10% water, and up"to"10'% of inorganic salts which may beremoved by the procedure hereinafter described:
' The above procedure may be modified by separating the acid sludge from'the acid'treatedoil. andextractingthe oil'withabout 60% alcohol to remove the sulfonic acids, which may then be neutralized with sodium hydroxide and subsequently freed of the alcohol by distillation.
The crude soaps of these preferentially oilsoluble sulfonic acids obtained by the procedure described above may be freed of inorganic salts by purification. This purification is preferably accomplished by dilution of the crude soap" with from about" V2 to about 10 parts, preferably 1 to 2 parts of 50% or higher-strength alcohol, preferably alcoholof 60' to 70% strength, and allowingthesalts to settle while maintaining the mixt'ure-within the temperature range of'130 to 175 F.',,preferably= to F: When the salts have settledthe supernatant alcohol-soap'layeris separate'd and the alcohol is recovered by conventional distillation procedure.-
, Preferentially oil-soluble water' non-emul'sifi' ablehydi'ocarbon sulfonic acids of'this type are also obtained by treating a'Kittrell distillate having" a- Saybolt Universal viscosity at 100 F; of fromabout 300 seconds to about 600 seconds in dump's'of' pound of fuming sulfuric acid per gallon of distillate oil until'a total of 3-t'o 4 pounds or acid per gallon of oil has been used; After removal of the acid sludge the oil-soluble sulfonic' alcohol required for the extraction being within the range of from about gallons to about 30 gallons of alcohol per .100 gallons of oil. The alcohol solutions ,of the preferentially oil-soluble hydrocarbon sulfonic acids are then treatedsuch as by distillation to remove the alcohol. soaps of the preferentially oil-soluble sulfonic :acids so obtained are substantially as non-emulsifiable with water as are the preferentially oilsoluble sulfonic acid soaps obtained by treating The petroleum distillates with 6 to 9 pounds of acid per gallon of oil, as above described; thatis, these ,soaps are not suited for use in the formulation of oil-soluble products and must be modified by the addition of detergent type, water-soluble soaps before they can be used for this purpose.
.The preferentially oil-soluble water non-emulsifiable sulfonates obtained in the manner herein- .deseribed are typical of those of sulfonic acids having molecular weights aboveabout 450 and which exhibit poor emulsifying properties.
Typical-of the water soluble detergent type soaps-which are suitable as modifying soaps to render the preferentially oil-soluble water non- ,emulsifiable hydrocarbonsulfonic acid soaps of "the type herein-described suitable components forthe formulation of oil-soluble products are the alkylated aromatic sulfonic acid soaps in which the alkylsubstituents contain from about 9 to about 1'7 and preferably from about 12 to about 16 carbon atoms in the alkyl groups. In
.the preparation of these alkylated aromatic sulfonicacid soaps an aromaticcompound isalkylated by any suitable means-and'the alkylate sulfonated with a strong sulfonating agent such as sulfuric acid, S03, etc. The aromatic nucleus can .be a monocyclic or polycyclic aromatic such as, for example, benzene, toluene, xylene, cumene,
' naphthalene, methyl naphthalene,v ethyl naphthalene, isopropyl naphthalene, diphenyl, alkyl diphenyl, anthracene; and alkyl anthracenes. The nucleus may contain in addition to the alkyl substituents halogen,-nitro, hydroxy or other substituents. Suitable alkylating agents are'olefin polymers, particularly those of ethylene, propylene, butylene and the like or mixtures thereof, preferably those having from about 9 to about 16 carbon-atoms. Suitable olefin polymers are those having a distillation range of from about 320 to about 485 F. While it is preferable to alkylate the aromatic with'an olefin polymer boiling within this distillation range, olefin polymershaving awider distillationrange can be used and the alkylated aromatic fractionated to obtain a fraction having the desired distillation characteristics. Thealkylation of the aromatic compound canbe accomplished by reacting the aromatic and the alkylating agent in' the presence of 90% to about 190% sulfuric acid, aluminum chloride, preferably activated with a trace ofhydrogen chloride, hydrogen fluoride, boronfluoride, mixtures of hydrogen fluoride and boron fluoride, or other known alkylation' catalysts. In' addition to,-the olefin-polymers. other suitable alkylating agents are haloparaffins, olefins, alkyl sulfates,
aliphatic alcoholsor aliphatic esters of wide molecular weight range.
Suitable water-soluble, detergent typesulfonates are the alkylated mono-nuclear aromatic Sulfonates suchas alkylated benzene or toluene polymer of from about 9 to about 1''! carbon atoms in the presence of sulfuric acid or aluminum chloride. The alkylated'aromatic compound so obtained which contains from about 9 to about 17 carbon atoms in the alkyl groups is sulfonated with sulfuric acid of from about 88 weight percent to about 98 weight percent sulfuric acid. The reaction mass is then permitted to stratify and three strata are obtained. The lowest stratum comprises essentially spent sulfuric acid and alkylated aromatic sulfonic acids in which the alkyl groups contain less than about 9 carbon atoms andthe upper strata comprises predominantly unsulfonated alkylated aromatics in which the alkyl groups contain more than about 1'? carbon atoms and are of the type which upon sulfonation with suitable sulfonating' agents would result in oil-soluble sulfonates. A middle stratum comprises predominantly the watersoluble, detergent type alkylated aromatic sulfonic acids. These alkylated aromatic sulfonates are suitable materials for modifying the emulsification characteristics of the preferentially oil-Q soluble and water non-emulsifiable hydrocarbon sulfonic acids of the type hereinbefore-described. The preparation of the water-soluble detergent type alkylated aromatic sulfonates suitable for the herein-described purpose is described in U. S. Patent 2,232,118, issued to L. P. Kyrides on' February 18, 1941.
Suitable water-soluble, detergent type sulfonates are those prepared by the method de scribed in U. S. 2,233,408, issued to L. H. Flett on March 4, 1941, and in U. S. Patent 2,218,472, issued to L. P. Kyrides on October 15, 1940. Other suitable water-soluble, detergent type ma.-
terials suitable for the herein-described purpose are the soaps of sulfated or sulfonated fatty acids or alcoholsknown in the trade as surface-active agents.
'The preferentially oil -soluble Water non-emulsiflable hydrocarbon sulfonates of the type described above possess certain desirable properties which if they could be incorporated in soluble oil type products would greatly increase the value of such products. Thus, for example, these sulfonates are very effective rust inhibitors and it would be highly desirable to incorporate them in soluble oil type products. However, because "of their resistance to emulsificati'on they cannot be satisfactorily employed in such products. However, by modifying these preferentially oil-soluble, water 'non-emulsifiable hydrocarbon sulionates in the manner herein-described, they can readily be employed in soluble oil type products; The effect of adding small'amounts of water-soluble, detergenttype "sulfonates to the preferentially oil-soluble, water non-emulsifiable hydrocarbon sulfonates is demonstrated by the following data which show the emulsification and rust inhibiting properties of a soluble oil base employing a preferentially oil-soluble, water non-emulsifiable mahogany sulfonate to which have been added various amounts of a watersoluble, detergent type sulfonate. The soluble oil base used was a mixture'of 22% of a preferentially oil-soluble mahogany sulfonate having-n. molecular weight of about-450 to about 550, 3.5%
inthe side chains. In the table below the followd ing: rating; is used:
=good 4=passing specifications 3=questionab1e 2=not passing 1 =poor Efict of addition of water-soluble detergent type 1 sulfonate and diluent 'oilto soluble oil base formulated with a preferentiallii oil-soluble water non-emulsifiable mahogany su'ljoizdtc Adjuncts Emul'slonandRustRating it? 0 1d '3 t- W v i 0 us mgr. emp. Base, 335%; on Water Rating Emulsion parts. Salim Emulsion 1 Rating Rating nate, .cent per cent Sol 2% 4% 2% 4 7 .891 Sol s01 .soi
100 o 0 4, v5- 2 2 100' 0 l 100 1.0 0 5 5 5 K5 3:5v 100 1.5 0 5 2. 2 4 4. 100 1.5 V 20 5 '5 5 -3.5 3,-5 100 1.5 2- 5- 5 3 3 100 2. 0 20 .5, v 5 5 4- 4 100 2.0 80 3.5 5" 5 4 4 The addition of the hydrocarbon oil inthe above test. was used to show more clearly the 2% of the. water -soluble, detergent type sulfonate.
As-stated above, the present invention is particularly adapted to the formulation of soluble oil products; for example, acomposition comiprising a hydrocarbon oil, from; about 5% to about 11% of a preferentially oil-soluble, water non-emulsifiable petroleumsulfonate, from about 1% to about 5% of, a water-soluble, detergent type soap such as, for example, an alkylated aromatic sulfonate havingfrom. about 9 to about 17 carbon atoms in the-side chains and from; about 1%.to about 4% of a watersoluble-sodal soap of a carboxyl acid. -The following exampleis illustrative. of: a soluble. oil-product formulation employing a preferentially elk-soluble: water nonemulsifiable hydrocarbon. sulfonate and a water:- soluble detergent type soap. A soluble oil base is prepared by mixing 22%;of a-preferentially' oil.- soluble Water non-emulsifiable -mahogany soap soap and 5.0% oil): with 3.5% soda rosin soap. and 74.5% of a hydrocarbon. oil havinga Saybolt. Universal viscosity at 100 F. of about 7.0 to 80 seconds and heating the mixture to a temp rature of about.250;". 1 Thesmixturewis then cooled and.fromabout.-1 tor-about 4% of a water. or alcoholssolutionofa. water-soluble. dc:- tergent type sulfonate added; to the mixture which is again reheated to a temperature of about 250 F. Alternatively thetwo typesof sulfonates may be mixed and-heated. to about 250 F. and
the rosin soap and the hydrocarbon oil then addedto the heated mixture. If desired, from about 1% to about 3% 01' water and alcohol may be added to the-soluble oil base to prevent phase separation'instorage.
Although the present-invention is particularly well adapted to the formulation of soluble oil bases, it is not limited to this. particular use since we have found that the preferentially oil soluble, water non emulsifiablehydrocarbon sul fonates modified by the addition thereto ofsa water-soluble, detergent type sulfonate togive the proper water solubility are. effective mineral aggregate coating agents. They can therefore be effectively used in bituminous materials such as road oils, asphalts-and the like to form water resistant bituminous coatings on mineral aggr'e gates.
While wehave described our inventionby reference to specific embodiments thereof, the invention is not intended to be limited thereto-but includes within its scope such modifications as come within the scope of the appended claims.
1. A readily normally liquid soluble-oil com.
position comprising a major proportion of' a hysodium soap of a preferentially oil-soluble'petroleum sulfonic acid having a molecular weight above about 450, which soap is normallyunsuitable for use in soluble-oil compositions, from about 0 .5% to about 10% of a water-solublealkylated aromatic hydrocarbon suifonate in which the alkyl substituents contain from about 9' to about 17- carbonatoms in the side chain and from about 1 toabout 3%:water.
2."A readily 'emulsifiable normally liquid soluble-oil composition comprising a major proportion of ahydrocarbon oil, from about 5% to about 11% of a sodium soap of a preferentially oil-soluble water non-emulsifiable petroleumsulfonic acid having a molecularweight above about 450, which soap is normally unsuitable for use in soluble-oil compositions, from about 0.5% to about 10% of a sodium salt of an alkylated aromatic hydrocarbon'sulfoni'c acid having from about 12 to about 16 carbon atoms-in; the side chain and:
from about 1% to about 3% water.
. 3. A readily emulsifi'able normally liquid soluble-oil composition comprisinga major proportion of a hydrocarbon oil,- from about 5 to about 11% of a sodium soap'of a preferentially oilsoluble water non-emulsifiable petroleum sulfonic acid having a molecular weight above about450 and which soap is'normall'y unsuitable for use-in soluble-oil compositions, from about 1% to about 5%"of awaters'olubl'e alkylated'aromatic hydro c'arbon sulf'onatehaving from about 9 to about 17' carbon atoms in the side chain from about 1 to about 3% water.
4'. A readily emulsifiabl'e normally liquid solu- 'b'le-oil composition comprising a maj Orpropoltion -matic hydrocarbon sulfonate having from about 9 to about 1'7 carbon atoms in the side chain from Number about 1 to about 3% water. 2,328,727 NORMAN E. LEMMON. 2,205,950 FREDERICK W. SCHUESSLER. 3,3 2,123
REFERENCES CITED The following references are of record in the m Number file of this patent: 523,520
Great Britain July 16, 1940