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3,031,497 United States Patent "ice 2 1 , Patented Apr. 241, 1962 several possible explanations of this phenomenon the 3,031,497 following is one of the simplest Ways‘ of representing it. . PREPARATION OF BARIUM SULFONATES Loren A. Bryan, Railway, and Charles Burke Miles, West (1) ’ H2O AeOH + Ba(OH)z —> AcO‘—Ba—OH + H20 ?eld, N.J., assignors to FMC Corporatioma corpora tion of Delaware (2) . H2O AcO~Ba-—OH + BMOH); -——> AcOBaOBaOH -l- H1O Filed Apr. 23, 1959, Ser. No. 808,368 10 Claims. (Cl. 260—5ll4) ’ Basic salts may be prepared in a number of ways. This invention relates to an improved process for the One well known method is to use a weakly acid promoter preparation of barium sulfonates by a reaction of organ 1.0 such as a phenol. In this case the Reaction 2 would be ic sulfonic acids or sulfonates with barium silicates. The represented as follows: barium silicates are prepared by the decomposition of (25,) insoluble barium compounds with a ‘source of silicon ~ _. ' 7 H2O Ac0—Ba-OE + BMOHM + HA ——-» A‘cOBaOBaOA + 221,0 dioxide, and the residual silicon dioxide containing mate rials from the reaction of Organic sulfonic acids and 15 '_In the above fonnulas AcOI-I is an oil-soluble organic sulfonates with barium silicates is recycled as this source acid and HA is a weakly acidic material such as a phenol. of silicon dioxide. Barium salts of organic sulfonic acids have found wide . The above ‘products can be ‘treated with an acid gas, such as CO2. This is a stronger acid than HA in the application as‘articles of commerce in ‘substantial torn presence or" water and causes the release (of HA’. or The barium saltsof organic sulfonic acids are 20 neutralization of the free hydroxyl group: nagles. ‘' useful as paint additives, insecticides, rust preventa tives and detergents. in motor oils. The oil-soluble barium salts of organic sulfonic acids have been found to be especially useful as additives for the improvement of lubricating oils. These oil-soluble barium salts of organic (3) . ¢ . ~ I ZAoO BaOBaOH + coir-e» (A00 m0 B8)2CO3 + 1110 I sulfonic acids have dispersant properties and prevent ring sticking and deposition of lacquer on pistons and other functional parts in gasoline and diesel engines. The preparation of sulfonic acids in the opt-grading of petroleum oils by treatment of the oil with strong 30 sulfuric acid or oleum has been common practice in the oil re?ning industry for several years.~ The resulting petroleum sulfonic acids of molecular weight lower than (4a) AcOBaOBaOAl-H2O+CO2~>HA+ AcOBaOBaOCO2l-I (4b) 2AcOBaOBaOA+HzO+CO2+ 2HA+ (AcOB aOBa) 2CO3 The ?nal neutral product as shown in Equations 3, 4a and 4b would contain ‘four equivalents of metal for an about 350 are water-soluble and are called “green acids.” ' equivalent of the'organic acid radical, AcO. ' The per The sulfonic acids’ of higher molecular weight are "called 35 formance of these salts when added to lubricating oils as “mahogany acids,” and upon neutralization form oil dispersants (detergents) improves as their metalcontent increases,-and the chemical ‘combination of several equiv soluble salts. ‘ ' The barium petroleum sul-fonates may be classi?ed as alents of metal for each equivalent of organic acid to give “neutral salts” or “basic salts.” The latter class contains an oil-soluble product makes it possible to obtain a con an fexcess of barium over that required for the‘neutral 40 centrate which can be added in much smaller vproportions . to a lubricant and still obtain the same metal content and The “neutral” salts have heretofore been produced by performance as would be present if larger amounts of a neutralization of sulfonic acids or by a metathesis reac normal'or neutral salt of the acid were added. tion with a sodium "sulfonate. In general, the barium All of these processes require the use "of barium hy . compounds used for neutralization of the sulfonic acids 45 droxide 0r barium‘ oxide as a source of barium and, by are barium oxide or barium hydroxide. Forthe prepara present commercial methods, ‘these compounds are fairly tion of a barium sulfonate from a salt of an organicysul expensive. Barium occurs naturally in‘such insoluble salt and has some titratable alkalinity. fonic acid two methods are known. A barium halide such asBaClz‘is'reacted with sodium sulfonateinjthe presence of water in a metathesis that yields barium sul 50 ores as barite (BaSOQ and Wither-ite (BaCOa). Barite ore is commercially available in large. amounts. The present commercial process for producingbarium ‘hy fonate and sodium-halide. Another reaction involves the ~ droxide or barium oxide from barite involves many displacement of ammonia from anammonium 'sulfonate operations and ‘results in substantial production costs. It involves decomposing the barium sulfate by heating by a basic bariurn'compound. ' In general, the barium compounds used in any of these reactions are barium with coke in a rotary kiln furnace to produce barium sul';_ ’ oxide or barium hydroxide. ‘v; Barium oxide hydrates 55 ?de according to the following reaction: vreadily and ‘is lower in unit cost than the hydroxide. This is one reason why it is used. Barium oxide can be (5) BaSO4+‘2C—> BaS+2CO2 " slurried in oil and then reacted with sulfonic acid in the The barium sul?de is leached from the kiln product and presence of water. Barium oxide can also be dissolved in methanol and reacted with sulfonic acid to produce 60 converted to BaCOs by reaction with soda ash or carbon dioxide. The barium carbonate is decomposed with barium snlfonates. Water or alcohol is necessary .‘for practically all of these reactions. Water may be added‘as . . water or as water of crystallization in'bariurn ‘hydroxide. The “basic” salts are saltsof barium and an organic carbon to give barium oxide in an electric~arc or. fuel ?red furnace as follows: ‘ ' ' acid in which the amount of barium combined is sub 65 stantially in excess of the stoichiom'etric amount required ' The barium oxidev is hydrated to obtain barium hydroxide. to prepare the neutralsalt' of the acid. While there ‘are 3,031,497 3 An object of our invention is the production of barium salts of sulfonic acids by reaction with barium silicates. which contains most of the excess reacted barium in a form that is water-soluble. The theoretical equation for this reaction with BaSO; as a starting material is as A further object of our invention is a new and im proved process for the production of neutral barium sulfonates from the neutralization of sulfonic acids with follows: - ‘ water-insoluble barium silicates or barium silicates con (7) taining water-soluble barium values. This polybarium silicate so produced reacts with an organic sulfonic ‘acid as follows: (8) Another object of our invention is a new and improved process for the production of neutral barium sulfonates by a metathesis reaction of sodium sulfonates with bari um silicates containing water-soluble barium values. Another object of our invention is a new and im proved process for the production of basic barium sul The BaOSiOz residue is water-insoluble, but it likewise fonates by the reaction of neutral barium sulfonates ‘ reacts with an organic sulfonic acid as follows: with barium silicates containing water-soluble barium 15 (9) values. A still further object ‘of our invention is a new and economical process for the continuous production of The polybarium silicate also undergoes metathesis barium salts of sulfonic acids by the decomposition of with organic sulfonates as follows: an insoluble barium-containing mineral with a source of 20 silicon dioxide to give a barium silicate, reacting the (me) barium silicate with a sulfonic acid or a sulfonate to give a barium salt of a sulfonic acid and a silicon di- 1 2B?0.si02 + 2ArSO3Na + 21101 —> H20 (ArSOa)2Ba + BaO.SiO2 + ZNaCl + 1110 oxide-containing residue and recycling this residue as a source of silicon dioxide. 25 Various other objects and advantages of our inven or (10b) tion will appear as this description proceeds. H20 aBaosioi + 2ArSOrNH4 ———> Y We have discovered that in a simple two-step reac (ArSOalzBa + BaO.SiOz + 2NH3 + H1O tion, in step one an insoluble barium-containing mineral such as barite can be decomposed by heating with a 30 The organic sulfonates will react further with the bari source of silicon ‘dioxide to "give a barium'silicate con um silicate residue in the presence of mineral acid to taining water-soluble barium values. This barium sili form neutral barium sulfonates as follows: . cate containing water-soluble barium values is for con venience hereinafter sometimes called polybarium sili (11) cate. This polybarium silicate in step two can be re 35 acted with an organic sulfonic acid directly to give, a neutral barium sulfonate and either a silicon dioxide residue or a barium silicate residue. The barium silicate The polybarium silicate also reacts with neutral barium residues differ from polybarium silicate in that a portion sulfonates in the presence of phenolic promoters as‘ fol of the available barium has been removed by a prior reaction. The barium silicate residue can be likewise reacted with an organic sulfonic acid to give a neutral (12) barium sulfonate and a silicon dioxide residue. The polybarium silicate can also be reacted with a salt of a sulfonic acid by a metathesis reaction to give a neutral 45 barium sulfonate and a barium silicate residue. Also, neutral barium sulfonate prepared in any manner can be Upon treatment of the above product with an acid gas reacted with polybarium silicate, in the presence of a such as CO2 the promoter‘ is released similar tov Equa promoter, if desired, to 7 give basic barium sulfonates tions 4a and 4!) according to the following: lows: ‘ . " - - ' and barium silicate residues. The barium silicate residues can be further reacted with organic sulfonic acids as noted above or with other strong acids or they can be recycled along with the silicon dioxide residues as the source of silicon dioxide‘ in the original decomposition reaction. ‘‘ The promoter may be recovered and reused. 55 FIGURE 1 is a diagrammatic ?ow sheet of the cyclic process for preparing barium salts of organic sulfonic ' The B'aO.'SiO2 and the SiO;,, residues may be recycled as a source of silicon dioxide as follows: acids according to our invention. As therein illustrated, polybarium silicate containing soluble barium values is prepared by heating a barium 60 containing mineral with a source of silicon dioxide at a temperature between 1300 and 1500“ C. This poly barium silicate is reacted with various sulfonic acids or Varying amounts of BaSO; may be used in excess of the sulfonates according to processes A, B, C, D or E to produce neutral or basic barium sulfonates and the un 65 2 to 1 ratio of barium to silicon shown, with increasing yields of water-soluble barium values. However, if reactedv barium values and silicon dioxide are recycled and reused in the process. , , amounts in excess of a 2.7 to 1 ratio are used di?iculties are encountered in that the barium silicate produced The polybariumv silicate containing water-soluble bari undergoes sintering or fusion which results in a product um values is prepared by decomposing insoluble barium ; which is di?lcult to react. Inasmuch as the insoluble _ containing compounds such, as barium sulfate, barium 70 barium silicate can be recycled, high yields of water carbonate, barium sul?te, 'etc., with a source of silicon soluble barium values can be obtained without the use dioxide by heating at temperatures of between 1300 and of a high. barium tosilicong'ratio. 1500” C. for the required period of time. If an excess The reaction to produce barium silicate containing of barium over a barium to silicon ratio of 1 to 1 ‘ is . utlized in the feed material, a barium silicate will result 75 water-soluble barium values from other barium com pounds is similar as shown in the following. equations 3,031,497 . 5 phenol, alkylated phenols such as, for example, cresol, utlizing barium carbonate and barium sul?te as start ing materials: " (16)’ 6 . xylenol, p-ethyl phenol, diethylphenols, n-propylphenols, ' di-isopropylphenols, p-t-butylphenol, p-t-amylphenol, p cyclopentylphenol, sec-:hexylphenols, n-heptylphenols, di 2BaCO3 +:SiO2-> 2BaO.SiO2+2COz isobutylphenols, 3,5,5-trimethyl-n-hexylphenols, octyl phenols, n-decylphenols, cetylphenols, etc.; ary1~substi tuted phenols, ve.g.,phenylphenol, diphenylphenol, etc.; polyhydroxy ‘aromatic compounds such as alizarin, quin izarin,‘ or polyhydroxbenzenes, e.g., hydroquinone, cate In the ?ow sheet, Reaction 7 or i4 and/or 15 takes place in the kiln. Process A is that of Reaction 8 or 8 10 chol, pyrogallol, etc.; monohydroxynaphthalenes, e.g. al pha-naphthol, beta-naphthol; polyhydroxynaphthalenes, and 9, Process B is that of Reactions 10a and 10b, Proc ess C is that of ReactionslZ and 13, Process D is that of ‘ ve.g. naphthohydroquinone, naphthoresorcinol, etc.; the alkylated polyhydroxy aromatic compounds such as octyl Reaction 9, and Process E is that of Reaction 11. Op catechols, mono>(t_ri-isobutyl)-pyrogallols, etc.; substi tionally Processes A and C can be combined in one operation. The recycling steps are those of Reactions 15 tuted phenols such as p-nitrophenol, picric acid, o-chloro— >14 and '15. phenol, t-butylchlorophenols, p-nitro-o-chlorophenol, p > aminophenol, etc.; lower molecular weight hydroxy aro matic carboxylic acids such as salicylic acid, chlorosali As organic sulfonic acids, we may use any sulfonic acid having an organic radical attached thereto. This radical ‘can be either aliphatic or cyclic. We prefer to use oil cylic acids, di-isopropyl salicylic acids, gallic acid, 4-hy soluble sulfonic acids derived from hydrocarbons having 20 droxy-l-naphthoic acid, etc.; lower molecular weight aro matic sulfonic acids such as p-cresol sulfonic acid, p-t at least 18 carbon atoms. I ' butylphenol sulfonic acid, beta~naphthol alpha-sulfonic The following are speci?c examples of oil-soluble sul acid, etc.; and lower molecular weight aromatic acids. vtonic acids which may be used. For every "sulfonic acid We prefer octyl " phenol and barium octylphenoxide'as enumerated it is intended that the barium salt thereof is also illustrated. 25 Such sulfonic acids are mahogany sul promoters. The acidic material used for treating the organic barium ‘toni'c acids; petrolatum sulfonic acids; mono- and poly ‘wax-substituted sulfonic and polysulfonic acids; sulfonic complex to liberate part or all of the promoter and re duce the alkalinity of the complex may be a, liquid or a and polysulfonic acids of aromatic compounds, for ex ample, naphthalene, benzene, diphenyl ether, ‘naphthalene - gas. The liquids can include hydrochloric, sulfuric, nitric, carbonic,v etc, acids; the gases, hydrogen chloride, ‘sulfur disul?de, diphenyl amine, thiophene, 'alpha-chloronaph dioxide, carbon dioxide, air (because of its carbon dioxide . thalene, etc.; substituted sulfonic acids suchas cetylchloro content), nitrogen dioxide, hydrogen sul?de, nitrogen tri oxide, sulfonyl chloride, chlorine dioxide, hydrogen selen benzene sulfonic acids, cetylphenyl monosul?de sulfonic acids, cetoxycaprylbenzene sulfonic-acids, dicethylthian threne disulfonic acid, Vdilauryl beta-naphthol sulfonic acids, dicapryl nitronaphthalene sulfonic acids, aliphatic ide, boron trifluoride, carbon disul?de, and carbon oxy 35 sul?de. urated para?'in wax sulfonic acids, hydroxy-substituted para?in wax sulionic acids, tetraisobutylene sulfonic acids, tetra-amylene sulfonic acids, chloro-substituted para?in ‘wax sulfonic acids, nitroso parai‘?n wax sulfonic acids, etc.; cycloaliphatic sulfonic acids such as petroleum naph We prefer gaseous carbon dioxide as a readily available acidic blowing agent. sulfonic acids such as para?‘in wax sulfonic acids, unsat 4:0 Barite can be decomposed with silicon dioxide-contain ing materials without fusion and in high yields in batch or continuous furnaces, such as rotary kilns, by the use of a critically ‘controlled slightly reducing atmosphere in the kiln, so that only small amounts, up to 2% of BaS, are formed in thekiln reaction product and by the use of a ‘thene' sulfonic acids, cetyl~cyclopentyl sulfonic acids, barium to silicon ratio of the kiln feed material of from lauryl cyclohexyl sulfonic acids, bis-(diisobutyl) cyclo 2.2 to 1 to 2.7 ml. .Conversions can be increased fur hexyl sulfonic acids, mono- or poly-wax substituted cyclo- ' 45 ther, with a decrease in occurrence of fusion by pelletiz hexyl sulfonic acids, etc. ing the kiln charge’ and by recycling barium silicate or From the above oil-soluble sulfonic acids, the so-called silicon dioxide produced by the sulfonating steps, with petroleum sulfonic acids are both readily available and provisions for a bleed to avoid'build-up of contaminants. ‘admirably adapted to our process. A variety of sulfonic The barium silicate process can utilize barite feeds of acids are produced in the upgrading of lubricating oil various qualities, but best barium e?iciency is obtained and their speci?c chemical structures will vary according when a relatively high-grade barite is used. The desirable to the type‘of oil being treated .and the extent of treat kiln feed composition is a Ba/Si molar ratio of 2.5, or ment with‘the sulfonating agent. In this process, we are "about 10% Si02 by weight. A high-grade barite (93% dealing with sulfonic acids having suf?ciently high molec ular weight to be classi?ed as mahogany acids. These ' 55 or more BaSOQ requires addition of a substantial amount of SiO2, which can be obtained 'by recycling monobarium acids range in molecular weight from about 350 upwards. silicate or SiOz residue, thus permitting also recovery of While it is not possible to de?ne rigidly these waterin most of the barium values in the residue. . ' Y ' soluble acids on the basis of ionization constants, their Theoretically the reactions .for the barium silicate proc effective acidity is at least greater than that of oil-soluble monoalkyl phenols, such as octylphenol. While we have 60 ess, utilizing recycled monobarium silicate,~can be written as follows: ' ' limited our examples to the higher molecular weight “mahogany acids,” described as “oil-soluble” and as hav ing “oil-soluble salts,” there is no intent to exclude the so calledt‘green acids” of molecular weight below 350 which If it is desired to produce a barium 65 sulfonate or": one of these “green acids,” this is within the In practice, however, complete decomposition of barite scope of our invention. In addition, any of the other is not obtained, so that the polybarium silicate contains enumerated sulfonic acids are likewise operable in our‘ some BaSOg which remains unreacted and is recycled V are water-soluble. process. I . In the metathesis reaction, the various alkali metal or 70 ammonium salts of the above acids can be used as start ing materials. ' i ‘ The phenolic compounds‘ or their barium salts serving with the residue. ' The reaction ‘conditions for the production of the vari ous barium salts of sulionic acids varyfsomewhat and will bev discussed individually as Processes A and‘ D (Equations 8. and 9), Processes B and E (Equations 10a, as promoters in the production of “basic” barium )sul- '‘ 10b and Ill) and Process C (Equations 12 and 13) are fonates are illustrated by the following speci?c examples: 75 described. a 3,031,497 7 8 REACTION, CONDITIONS FOR PROCESSES form neutral barium sulfonates and a residue of silica. A AND D In general, the reaction medium will consist of a non aqueous phase comprising a hydrocarbon mixture boiling from about 70° C. upwards to hydrocarbon oils exempli ?ed by SAE 30 motor oil or mixtures thereof containing the dissolved sulfonic acid, and an aqueous phase in in timate contact with the polybarium silicate and the oil phase. Other polar solvents capable of dissolving barium values may be used to replace all or part of the water. The quantity of barium used is'based on the available barium in the polybarium silicate or barium silicate residue REACTION CONDITIONS FOR PROCESS C The reaction can be carried out in mineral spirits or other solvents such as petroleum naphtha, xylene, toluene, ethylbenzene, propylbenzene, butylbenzene, etc. The time required for the preparation of the metal complex will range from about 2 to 5 hr. or more depend— ing upon the batch size and dehydration time. In addi tion the product may be blown for 1-5 hr. with an acid gas to neutralize the excess alkalinity of the complex that is‘ leachable from the barium silicate with hydro chloric acid. About one equivalent of available barium 15 and liberate all or at least most of the promoter, if such is desired. The time required is dependent upon batch is used for each equivalent of sulfonic acid to form the size, rate of input of the gas and temperature. It has neutral salt. When more than one equivalent of available been found that 3 hr. are, generally sufficient to complete barium is used, the product may be basic unless the the reaction and dehydration, with an additional 3 hr. reaction time is suitably controlled. If less than one equivalent of available barium per equivalent of sulfonic 20 of mild blowing at elevated temperature with moist car bon dioxide su?icient to neutralize the product. acid is used, the product will be more acidic than the The temperature for cooking of the ingredients is ap neutral salt because of the barium de?ciency. It is prefer proximately 100° C. and is controlled by the re?ux of the able to use a slight excess of available barium, perhaps 5 ‘Water. During the dehydration step the temperature to 10% so that the total charge corresponds to 105 to 1>10% of the theoretical amount required, to produce the 25 ranges from about 100° C. to about 165° C. or higher, Reaction periods ranging from 1.25 to 4.5 hours for depending upon the boiling range of the solvent. Three basic procedures have been used for the prepara > neutralization and removal of the water represent the tion of basic salts and will be listed as Methods 1,. 2 and neutral salt. > range used, The preferred time is not over two hours with up to about, one hour for neutralization and the ‘remainder for dehydration of the reaction mixture. 'It is convenient to work at the re?ux temperature of the reaction mixture. Lower temperatures could .be used with additional time expenditures. Dehydration tempera tures range from about 100° C. to about 165° C., the higher temperature being su?‘icient to remove substantially all of the water, although temperatures of up to 180° C. 3, respectively. ~ Method 1.—The organic sulfonic acid (50% in oil) or its barium salt, the promoter, and solvent, i.e. mineral spirits, are placed in a reaction vessel equipped with stirrer, thermometer, re?ux condenser ‘and heating means and warmed where necessary to provide a homogeneous solu tion. The polybarium silicate and water are added and the mixture is re?uxed for about 2 hours at about 100° C. A water trap is inserted between the reaction vessel and condenser and the mixture dehydrated by increasing the are permissible, provided the hydrocarbon solvent is suf heat gradually to about 160° C. When the dehydration ?ciently high boiling to remain Within the reaction vessel. A solution of the organic sulfonic. acid in a hydrocar 40 is complete the material is removed and ?ltered or option ally blown with carbon dioxide for about three hours bon solvent is placed in a reaction vessel ?tted with heat with the temperature maintained in the range of 135—l50° ing means, stirrer, thermometer and re?ux condenser. C. and then ?ltered. The promoter liberated when the Water and polybarium silicate (or barium silicate residue) blowing with carbon dioxide step is used, may be re containing su?‘icient. available barium to neutralize the sulfonic acid are added. The stirred mixture is heated 45 covered. Method 2.—The organic sulfonic acid, promoter and under re?ux for 0.5 to 3.0 hours. A water trap is then inserted between the reaction vessel and the re?ux con denser and the temperature gradually increased to eifect removal of the water. When the dehydration is complet solvent such as mineral spirits are placed in the reactor and warmed to provide a homogeneous solution. Then water and enough polybarium silicate are- added to neu ed, the hot mixture is ?ltered to remove residual inert 50 tralize the sulfonic acid, assuming that the total available barium (water-soluble plus acid-soluble) will react with material. the sulfonic acid. The mixture is re?uxed for 1‘ hr., REACTION CONDITIONS FOR PROCESSES cooled to about '80" C., the remainder of the polybarium B AND E silicate added, and heating continued at the re?ux tem Polybarium silicate is reacted with an alkali metal 55 perature for 1 hr. The temperature is then increased to effect dehydration. After dehydration heating is con saltof an organic sulfonic acid in the presence of water tinued for 1 hr. at ISO-160° C., and the processing com and one equivalent of a mineral acid, such as hydro pleted ‘as described under Method 1. chloric acid or nitric acid, under the same conditions of Method 3.—This operation involves the use of barium solvents and temperatures-as outlined above. When a sodium sulfonate is utilized as the alkali metal sulfona-te, 60 silicate residues left over from a previous preparation of a basic or neutral salt to prepare neutral barium sul the sodium sulfonate in a hydrocarbon or other solvent fonate by Process D which is then processed according is reacted with the barium silicate in the presence of a to Method 1. mineral acid and water at elevated temperatures until The following examples illustrate our invention. It substantially all of the sodium in the sulfonate molecule has been displaced by the barium from the barium silicate. 65 is understood, however, that these examples are illustra tive only and to enable one skilled in the art to practice The barium silicate should contain a BaOzSiO2 ratio our invention. They are not to be considered as limiting ranging from 0.l:l.0 to about 3.0:l.0 or greater and preferably from about l.0:1.0 to 3.0:1.0. When an am in any fashion the scope of our invention. . The speci?c organic sulfonic acid used in our examples monium sulfonate is substituted for the alkali metal sul tonate, the mineral acid can be omitted if the BaOzSiOZ 70 is “Petronic Acid” produced by L. Sonneborn Sons, Inc. ratio is above ‘1.0:1.0, and the reaction proceeds with ' This acid consists of 50% of a mahogany petroleum sul simultaneous dehydration and evolution of ‘ammonia, and the formation of a barium silicate residue. > . Alkali metal sulfonates also react with barium silicate residues and mineral acid under the same conditions to fonic acid (a primarily-aliphatic,v saturated-hydrocarbon sultonic acid mix with an average of approximately 25 carbon atoms), 48.5% mineral oil, 1% water and up to i 0.5% sulfuric acid. This acid has an acid number of‘79 3,031,497 . 9’ 10 general conditions as outlined above under the heading mg. KOH/ gram and a molecular weight of 440 to 460. All weights are calculated on the active acid content. Examples According to Processes A and D , “Reaction Conditions for Process C.” Examples of processing according to Method 1 are‘ given in Tables III and IV. In this series various com binations of starting ingredients are shown together with the best combinations of materials to get efficient utiliza— tion of the barium. On the‘ basis of the results, Examples 12and 13, in' which barium “Petronate” with octylphenol esses A and D” are tabulated. ' . -' ' as promoter reacted with 'polybarium silicate, gave the Table I gives the reactant variations for Examples 1-5; M10 highest metal ratio and ranked second in barium, e?i Table II gives the results. ' . 5 In the following tables the results of examples of the process conducted according to the methods outlined above under the teaching “Reaction Conditions for Proc TABLE r Quantities of Reactants Used in ‘the Preparation of Barium Sulfonates Polybarium‘Silicate (Process A) Available Ba Example No. “Petronic Acid” Percent EquivJ Weight of BaO gm. in 2 gms. .4 . 010a .4, . 0103 Equiv. — _ weigh Barium silicate ‘Weight Equiv'. Mineral weight ' spirits in gms. 0. 030 0; 100 19. 65. 1 Added solvents in girls. Water > 39 20 20 50 0. 159 0. 091 15.4 8. 76 Mineral oil Barium Silicate Resid ues (Process D)! 5. 42 33. 6 20. 2 . 0100 . 0090 . 0096 0. 054 0. 303 0. 194 1 Residues from the preparation of basic salts. 2 Product as received, 50% active in mineral oil. TABLE II Barium "Petr0nates” REACTION CONDITIONS AND RESULTS Fresh Polybarium Silicate Barium'usage Product Example No. Time in - hrs. Weight in g‘ms. Percent ‘ Ba “Petronic Acid”v ' Available, ‘'Reacted, equiv. I equiv. Percent ’ Added equiv. 7 ~ 53 neutral rzed 0. 039 > 25 130' 09 102 93 100 ciency. Examples 6 and 7, in which “Petronic Acid” As shown by Table II, the polybarium silicate reacted, with barium octylphenate as promoter reacted with poly readily with va slight excess of “Petronic Acid” to give barium silicate, gave the second highest metal ratio and up all of the available barium (Example 2‘). > A similar the highest barium e?iciency. The amount of water result was obtained (Example 3) in which the barium silicate residue released all of its available barium to 60 soluble barium in these cases was less than in the'pre vious examples and may have had a direct bearing on form a nearly neutral barium‘ “Petronate.” The removal the metal ratio and barium ef?ciency. In Examples 8 of the barium from barium silicate residues was slightly and 9, when barium “Petronate” with barium oc‘tylphe less e?'icient in two other examples (Examples 4 and 5) mate as promoter was allowed to react with the poly due to the use of larger batches with shorter time for the reaction to go to completion. When a substantial excess 65 barium silicate, the results were inconsistent with fair to poor metal ratio and mediocre barium e?icicncy. In of barium was available (Example 1), as basic barium Examples 10 and 11, when “Petronic Acid” with octyl ‘_‘Petronate” was formed readily and a barium silicate . phenol as promoter was reacted with polybarium silicate, residue resulted. This barium silicate residue was reused the metal ratios were poor although in Example 10 this ' as the barium silicate source in Example 3. was probably due to the small excess of barium present. .Even under these adverse‘conditions, however, a sub Examples According to Process C stantial reaction occurred. Example 14 represents the preparation of a basic barium sulfonate by reacting poly Methods 1, 2 and 3 The following examples were performed under the 75 barium silicate with a sulfonic acid without the use of a promoter. ' l 3,031,497 TABLE HI Basic Salts Prepared by Method 1. Reactants _ Reactant quantities Added solvents Example Acid or salt ((3.)1 Polybarium . 6 ....... .- “Petronic Acid” __________________ _; 7 _____d0_- 8 _______ _. 9 Barium “Petronate” ______________ __ _-___do_- 10 ______ __ 11 __.__d0__ 12 ______ __ 13 Barium “Petronate” ______________ __ ___--d0__ 14 ______ __ 9.95 15. 4 9.95 15. 4 9. 27 7.02 39. 8 “Petronic Acid” __________________ __ Dialkyl benzene sulfonic acid _____ __ Promoter ‘ v silicate (g.) ' ((3.) . Barium octylphenoxide?n; 5. 34 d 5.34 4. 68 76. 7 9.90 17. 9 8. 68 ' Water Mineral (g.) spirits (g.) 39 20 39 20 20 16 60 22 . 12 10 60 33.6 65.8 .1 60 20 39.0 90. 7 .1 60 .......... -_ 39.4 82. 7 .1 60 __________ __ 80.1 216. 76 2 46 1 Material was used in solution of oil or lighter hydrocarbon solvent; values given for barium “Petronate” were found by analysis. 9 Mineral 011. TABLE IV Basic Salts Prepared by Method 1. Conditions and Results Equivalents of reactants Example Reaction type sulfonate promoter Time (hr.) Sulfonate uble poly- Percent of water sol uble Ba Metal ratio 1 Water-sol- Promoter Cook CO3 blow reacted barium silicate Acid- D1118 salt ............. -_ . 030 . 063 .7018 2. 1 0 2. 55 94 ---_d0 ...... __ .' 030 . 063 . 018 4. 5 0 2. 54 94 Salt plus salt- . 025 .0287 .015 4.0 0 2. 03 - .10 .330 .059 3. 2 3.0 .030 . 0356 .020 11.0 . 10 .400 . 059 2.8 . 10 .329 .059 2.8 3.0 3. 31 77 .10 .20 .300 1.18 .059 3.0 5.0 3.0 0 > 3. 25 2. 23 80 38 ___._do _____ __ Acid plus acid" _____do _____ __ Salt plus acid__ .--__do_.-._______ __ Acid____-_______.____-______ 0 2. 8 65 ' 2. 94 36 1. 50 127 1. 89 47 1 Ratio of barium equivalents to sulfonlc acid equivalents in the product. TABLE V Basic Salts Prepared by Method 2, Conditions and Results Equivalents of reactants Solvents (g) Reaction time (hr.) ' Example . - Water- Octyl- “Petronic soluble phenol Acid” polybarium promoter - Water Mineral spirits Mineral oil 1 ‘ Percent Metal > of water ratio 1 Cook GOzblOW soluble Ba reacted silicate 0.10 0. 10 0. 1O 0. 396 0. 396 0. 50 0.10 0.40 0. 10 0. 10 0. 10 0. 10 0. 40 0. 30 0. 30 0.50 0.059 0. 059 0.059 60. 0 60.0 60.0 0 0 20.0 94 94 94 2. 8 3. 8 3. 5 2. 8 2. 7 2. 8 2. 66 3. 53 2. 93 67 89 59 0.059 60.0 20.0 94 3.0 2. 8 - 2.90 72 0.059 0.059 0. 059 0. 059 34.0 60. 0 26. O 42. 5 20. 0 20.0 20. 0 20.0 94 94 94 94 3. 5 4. 0 4. 2 3.8 3. 0 2.8 2. 6 2. 8 2. 47 2. 33 2. 84 2. 70 61 78 95 54 r 1 Comprises solvent for .“Petronic Acid” plus 61 g. light mineral oil. _ 2 Ratio of barium equivalents to sulfonic acid equivalents in thcgproduct. mols H2O per equivalent of Water-soluble barium) were Examples of the use of Method 2 are given in Table used with 0.30, 0.40 and 0.50 equivalents of water-soluble V. By the use of Method 2, no independent preparation of barium salts as starting materials is necessary. The 60 barium. vUnder these conditions, Example 18 was best with a metal ratio of 2.90 and 72% e?iciency of the bar “Petronic Acid,” and, optionally, the phenol as promoter, ium. In Example 17 the metal ratio was approximately are placed in the reaction vessel with sufficient polybarium the same as in Example 18 but the barium e?iciency was silicate to neutralize all of the “Petronic Acid.” The lower. In Example 20 the barium efficiency was a little “Petronic Acid” is strong enough to react with both the acid- and water-soluble barium present in the polybarium 65 higher but the metal ratio was substantially lower. In Examples 21, 19 and 22, 0.3, 0.4‘ and 0.5 equivalents of silicate. After about 1 hr. of re?ux the remainder of the water-soluble barium, respectively, were used with about poly‘oarium silicate is added to provide the additional 4.7 mols of water per equivalent of water-soluble barium. barium for increasing the metal ratio. Examples 15 and Example 21 was the best with the highest metal ratio and 16 represent identical runs except that in 16 heating was continued for 1 hr. after the dehydration step prior to 70 barium e?iciency. The larger excesses of barium in Ex amples 19 and 22 yielded slightly lower metal ratios and blowing with carbon dioxide. The 1 hr. of heating after the e?iciencies were relatively low. dehydration was used in all the succeeding examples. In Examples 17 through 22 the effects of varying the amounts 1 EXAMPLE 23 of polybariumrsilicate and Water added are shown. In Examples 20, 18 and 17, 60 grams of water (6.7 to 11.0 75 This example illustrates the practice of the invention ac 3,031,497 14 , cording to Method 3 of, Proce'ssC. A barium silicate’ silicon ratio to 2.5 ‘to 1. This feed composition was at residue was used whichhad resulted from the reaction of a tained as follows: polybarium silicate with sultonic ‘acid in the preparation . of a basic sulfonate. It contained 69.1% available barium calculated as BaO. 33.6 grams of this residue containing ., Mols of barium m . I . present From fresh barite _____ __»_ __________________ __ 2.24 From recycled BaSO4 residue _____________ __-_->_ 0.26 0.303 equivalent of available barium was reacted with 202 grams (0.300equivalent.) of a sulfonic acid (“-Petronic” ' ' Mols of silicon acid) in mineral oil in the presence'of 175 grams of min eral spirits and 60 grams of water. The nearly neutral barium sullfonate produced‘was separated from the sili 10 From SiOB content of fresh barite ________ ________ 0.13’ From recycled residue _____ -i. ______________ __ 0.87 ceous residue. It contained 0.259 equivalent of combined Total ._...... _ ‘1.00 barium corresponding to an 86% recovery of the available barium values in the original barium silicate residue. An The polybarium silicate produced was reacted with or aliquot of the barium sulfonate solution containing 0.100 ganic 'sulfonic acid derivatives as in any of the preceding equivalent of sulfonate and 0.086 equivalent of combined Total ~ »- ~ I -- - ‘ ___ > 2.50 present examples with comparable results. ' The above examples are illustrative, but are not to be considered as limitations of our invention, the scope of barium was then reacted in the presence of 0.059 equiva lent of octyl-phenol promoter with polybarium silicate containing 0.329 equivalent of water soluble barium ac which is to be determined by the appended claims. cording to Example 12. The basic barium sulfonate ob tained from this reaction contained 0.331 equivalent of 20 We claim: I l. The process of producing barium salts of organic, combined barium corresponding to a metal ratio of 3.31. sulfonic acids from organic sulfonic acid derivatives The recovery of water soluble barium from the poly selected from the group consisting of oil-soluble'organic barium silicate was 75% ‘and the barium’ silicate residue ~ sulfonic acids derived'from hydrocarbons'having at least was reacted with sulfonic acid to make additional neutral '18 carbon atoms and ammonium and alkali metal salts thereof‘ and‘ insoluble barium compounds selected from the group consisting of barium sulfate, barium sul?te and barium sulfonate as in the ?rst step of this example. EXAMPLE 24 barium carbonate, which comprises decomposing said . insoluble barium compounds by heating with a source of silicon dioxide at a temperature between 1300” and 1500° Barite ore obtained from Missouri and analyzing C., said insoluble barium compounds and the source of silicon dioxide being present in a barium to silicon ratio of from 1.1 to l, to 3 to 1 to produce a polybarium sili 96.5% 'BaSO4, 2.5% SiO-Z' and 0.5% Fe203 was ground to —100 mesh in a hammer-mill and mixed with silica ?our (—200 mesh, 96.2% SiO2). 2% of a 50% calcium lignosulfate slurry in the form of a 12.5% solution was cate, reacting said polybarium silicate with said sulfonic sprayed on the dry powder to act as a binder and the 35 acid derivative in the presence of water and a hydro carbon solvent at re?uxing temperatures, recovering said whole mixed in a pug mill.. The amounts of barite and ‘ .barium salts of organic sulfonic acids and a silicon di silica ?our were adjusted so that the mixture contained ' oxide-containing residue and recycling said residue as a a barium to silicon ratio of 2.5 to 1 by molecular equiva source of silicon dioxide. lents. 2. The process of claim 1 wherein said organic sulfonic This mixture was fed into va rotary kiln 35’ long with 21 40 acid derivatives are mahogany petroleum sulfonic acid 1A2" pitch per foot and a 30” shell diameter lined with a _70% alumina refractory brick 41/2” thick. The kiln was derivatives. I ' v _ “ . I ‘ > ?tted with means to control the rate of admission of air 3. The process of claim, 1 wherein said polybarium so that the proper atmospheric control within the kiln silicate is reacted with a petroleum sulfonic acid in the could be maintained vand a gas burner burning natural gas 45 presence of water and a’ hydrocarbon solvent and the was used to ?re the kiln. The material exit of the rotary barium salt of the petroleum sulfonic acid is further re kiln was a spill gate adjustable to allow only product to acted with said polybarium silicate and a promoter flow through. The exhaust gases from the kiln were con_ selected from the group consisting of phenols and barium phenolates. tinuously analyzed, and the gas and air adjusted to main tain an exhaust gas concentration of hydrogen of 2% to 50 4. The process of claim 1 wherein said silicon dioxide 2.5% and a temperature in the hottest zone of 14000 C. to containing residue recovered contains residual barium 1450“ C. values and is further reacted with a petroleum sulfonic The mixture was fed into the kiln at a rate of 150 acid in the presence of water and a hydrocarbon solvent, ~ lbs./hr., allowing pelletization to occur in the back end to recover further barium salts of petroleum sulfonic of the kiln. The decomposition of barite averaged about 55 acids and a silicon dioxide-containing residue. 80%. The polybarium silicate product produced con 5. The process of claim 1 wherein said silicon dioxide tained water-soluble barium values and some undecome containing residue recovered contains residual‘ barium values and is further reacted with a mineral acid in the vposed B21804. The polybarium silicate produced was reacted with “Petronic Acid” in the same manneras described in Ex‘ ample 3. Upon ?ltration of the hot- neutral barium sul-‘ 60 presence of vwater to recover ‘the residual barium values as water soluble barium salts of said mineral acid and , a silicon dioxide-containing residue. fonate solution a residue was obtained which consisted ' 6. The process’ of claim 1‘ wherein said polybarium sili primarily of SiO2 and BaSO4 in a ratio of approximately cate is reacted with an alkali metal petroleum sulfonate 1.1 mol of SiOz to 0.3 mol of undecomposed BaSO4. in the presence of a mineral acid, water and a hydro This residue can be recycled to replace the silica ?our in 65 carbon solvent. whole or in part. 7. The process of claim 6 wherein said silicon dioxide containing residue contains residual barium values and EYAMPLE 25 The same procedures as in Example 24 were followed, 70 except that the kiln feed was a mixture of silicon dioxide containing residue as obtained from Example 24 and barite. A continuous operation was e?ected by recycling the silicon dioxide-containing residue and adding su?i cient barite containing 96.5% BaSO4 to bring the bariur‘n/ 75 is further reacted with an alkali metal petroleum sul fonate in the presence of a mineral acid, water and a hydrocarbon solvent. 8. The process of claim 1 wherein said polybarium silicate is reacted with an ammonium petroleum sul _ fonate in the presence of water and a hydrocarbon sol vent. ' 9. The process of claim 8 wherein said silicon dioxide- 0 3,031,497 15 16 containing residue contains residual barium values and - carbon solvent at re?uxing temperatures, recovering said is further reacted with an alkali metal petroleum sul fonate in the presence of a mineral acid, water and a barium salts of mahogany petroleum sulfonic acids and a silicon dioxide-containing residue, and recycling said hydrocarbon solvent. residue as a source of silicon dioxide. 10. The process of producing barium salts of mahog any petroleum sulfonic acids from (1) mahogany petro leium sulfonic acid derivatives selected from the group consisting of the free acids, and ammonium and alkali metal salts thereof, and (2) insoluble Kbarite, which com prises decomposing said barite by heating with a source 10 of silicon dioxide at a temperature between 1300° and 15000 C., said barite and said source of silicon dioxide being present in a barium to silicon ratio of from 2.2 to 1 to 2.7 to 1 to produce a polybarium silicate, reacting said polybarium silicate with said mahogany petroleum sul 15 fonic acid derivative in the presence of Water and a hydro References Cited in the ?le of this patent UNITED STATES PATENTS . 2,483,800 2,846,466 Zimmer et a1 ___________ __ Oct. 4, 1949 Crosby _______________ __ Aug, 5, 1958 2,856,360 Schlicht ______________ __ Oct. 14, 1958 797,409 Great Britain __________ .._ July 2, 1958 FOREIGN PATENTS OTHER REFERENCES Mellor: “Comp. Treat. on Inorg. and Theor. Chem,” vol. 6, pages 353, 371 (1925).