Патент USA US2406041код для вставки
2,406,041 ‘UNITED STATES PATENT OFFICE Patented Aug. 20,1946 2,408,041 CHEMICAL PROCESS _ Helmuth G. Schneider, Roselle, and James E. J. Kane, Elizabeth, N. J. assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application April 20, 1944, Serial No. 531,993 9 Claims. (Cl. 252-423) 1 2 ticularly in heavy duty oils used for lubricating high speed Diesel and gasoline engines, for the ?de. Barium tertiary octyl phenol monosul?de may. be represented by the general formula Ba[O(CaHn)CaI-Isla$ or, if the tertiary octyl stock in about 25 to 50%, usually about 40%. This invention relates to an improved process concentration, with or without incorporation of of preparing or improving metal derivatives of lesser amounts of other additives such as higher alkyl phenols or their derivatives, as well as to the aliphatic alcohols, e. g, stearyl alcohol, or all products thus prepared and to uses thereof. As a speci?c instance, the invention relates to the 5 phatic nitrlles, etc. used as defoamers, plasticiz ers, mutual solvents or as detergency promoters, improvement of chemical compounds such as the and ?nally this solution is neutralized with the barium salt of diisobutyl (i. e. tertiary isooctyl) desired basic metal compound such as barium phenol or of the corresponding sul?de or. other hydroxide octahydrate or monohydrate. The re derivative thereof. 7 ' Chemical compounds of the class just referred 10 sulting product, after ?ltration, is a mineral oil concentrate of barium tertiary octyl phenol sul to have been used as lubricating oil additives, par reason that these additives have excellent deter gent properties and improve the performance of 15 group is assumed to be in a position para to the phenolic oxygen, and the sulfur linkage in a meta the lubricant. -They do, however, possess to some position, by the following graphic formula: extent the undesirable property of being water sensitive, that is when contacted with a small amount of water, they form a sludge which may remain emulsi?ed in the oil or settle out as a 20 ?occulent precipitate. This characteristic of the additive, while not affecting the performance of the oil, is nevertheless undesirable in certain re sHn sHn spects such as in storage or handling where the If the sulfur linkage is in‘ an ortho position the oil is apt to become contaminated with water. 25 graphic formula would be: The primary object of the present invention is therefore to treat such additives during the proc ess of manufacture in order to render them water-insensitive so that lubricating oils, or other products in which they may be used, will not tend 30 to emulsify or form sludge when contacted with water. Before discussing the particular improvements of this invention, the general manufacture of The exact location of the various radicals and such products will be explained as applied, for 35 linkages in such compounds has not been deter example, to the treatment of alkylated hydroxy mined with certainty, but it is probable that the aromatic compounds, such as a tertiary octyl product resulting from the commercial operation phenol with a sulfurizing agent, e. g, sulfur di chloride or sulfur monochloride, to form an alkyl of the described process is a mixture of com pounds having the radicals and linkages in sev hydroxy aryl sul?de which is then converted into 40 eral different positions, there being for instance a corresponding metal derivative by neutraliza some tertiary octyl groups in an ortho position tion, preferably in oil solution, with a basic metal or even in 9. meta position unless the original neutralizing agent such as barium hydroxide, thus tertiary octyl phenol‘used was an absolutely pure forming a metal salt of an alkyl hydroxy aryl para compound. Also it is more than likely that sul?de. Throughout this speci?cation and the 45 the commercial product which may be given the claims the word “sul?de” is used in a generic general formula Ba[O(CaHn)CaHa]z_Sn where n sense to include monosul?de, disul?de or polysul has an average value of at least 1.0 and less than ?de or mixtures of these. Such a process may be 2.0, contains at least small amounts of disul?de and polysul?de compounds as well as some poly illustrated by the reaction of about 2 mols of ter tiary octyl phenol with 1 mol, or a slight excess, 50 meric material. In any event corresponding of sulfur dichloride to produce tertiary octyl compounds may readily be made by starting with phenol sul?de. When preparing the alkyl phenol ortho or meta alkyl phenols and mixed alkyl phenols may be used with alkyl groups in any two ‘sul?des on a commercial scale, using technical or more positions. If desired, dialkyl phenols grades of sulfur dichloride, ratios of 1.5 or so mols ' of S012 to 2 mols of alkylated phenol will often 55 may also be used such as 2,4-ditertiary butyl phenol, 2,4-diamyl phenol, 2,6-diamyl phenol, di be found desirable. (The tertiary octyl phenol is tertiary octyl phenol, etc. For some purposes it readily prepared by alkylating phenol with di may even be desirable to use alkyl hydroxy aryl isobutylene in the presence of suitable catalysts.) compounds having more than two alkyl groups, In practice the phenol sul?de is then usually dis solved in a suitable mineral lubricating oil base 60 but the monoalkylated products are preferred, 2,408,041 4 particularly when the ?nal product is desired to Corresponding metal derivatives of the follow ing illustrative types of substituted phenolic have greatest corrosion inhibiting properties. The invention is considered to apply broadly to compounds are among those that can be used, in which R represents an alkyl group, preferably substituted metal phenolates or compounds con taining at least one grouping having the general 5 having at least 4 carbon atoms: formula M-Y,—-Ar(X)n where M is a metal, Y is an element in the righthand side, of group VI of the Periodic Table (Mendeleeif), Ar is an arc matic nucleus which contains like or unlike sub stituents, X, n. in number, replacing nuclear hy 10 drogen, n being at least one. M may be any metal such as barium, calcium, aluminum, cobalt, chromium, magnesium, man ganese, sodium, nickel, lead, tin, zinc, copper, iron, cadmium, potassium, lithium and the like, 15 polyvalent metal being preferred. The substitutents, X, may be organic, inorganic, or both. For example, they may be alkyl radi cals or groups containing one or more of the non metallic elements belonging to groups V, VI, and 20 All these'compounds when employed in high VII of the Periodic System (Mendeleeff): nitro gen, phosphorus, oxygen, sulfur, and halogens, temperature lubrication service tend to corrode such sensitive engine parts as copper-lead and as in amino, nitro, phosphite, phosphate, hydroxy, —alkoxy, sul?de, thioether, mercapto, chloro cadmium-silver bearings. This characteristic can usually be corrected by including, in the lu groups, and the like, or they may be organic radi 26 bricating composition, suitable anti-oxidants or other anti-corrosion agents, e. g. benzyl para cals containing one or more of the inorganic groups. amino phenol, alpha naphthol, tertiary amyl phenol ‘sulfide, triphenyl phosphite, dibutyl In the phenolate salts, it only one of the amine, etc. —It may be mentioned that metallic tuted phenolic radical, such as —O—-A1‘(X)n, the 30 soaps of carboxylic acids are considerably more valences of a polyvalent is connected to a substi other should be connected to other organic groups or to inorganic constituents, For convenience, corrosive than the phenolic salts and that their corrosiveness is less amenable to correction by non-phenolic radicals or groups, as well as phe the use of antioxidants, etc. However, this corrosion problem can also be at nolic groups, attached to the metal are indicated broadly by R in the following types of composi 35 least partially and in most cases completely taken care of by chemically incorporating an element tional formulae, which broadly represent metal derivatives of substituted phenolic compounds of the sulfur family (i. e. S, Se, and Te), sulfur containing the characteristic compositional itself being very effective, ‘into the structure of the substituted phenolate metal salts, thus mak _ R O-Ar(X). o-imx). 40 ing unnecessary the addition of any separate anti-corrosion agent. Thus the metal derivatives M/ , M/ ‘ M/ (x'o-w of the following illustrative types of substituted phenolic compounds are preferred over those list \o-imx), \0-Ar(x')..¢ 0-A1-(x')..' ed in Group A above. Where oxygen is shown in these formulae it may be replaced by sulfur, selenium or tellurium, as in 45 Group B the case‘ of thiophenolic compounds. grouping described: More specifically, some of the structures which substituted divalent metal phenolates may have are indicated in the following list of formulae containing benzene nuclei of compositions 50 —CsH4—-, —CcHa—-, etc., with X, as before, stand ing for nuclear substituents, e. g., —caHzn-l-l, ‘ —NOz, —Cl, -S—, —Sa——, —NI-Ia, etc.) : 65 H0(R) Can-s-mnnm-on Corresponding monovalent metal derivatives would be: s 70 Similarly trivalent or other polyvalent metal derivatives may be used such as: M(O—CcHa-X)a or more M:[(O—(X)CtI-Ia—):X']:, etc. ' ‘2,400,041 .5 e. g. Barium salts of 2 chloro, 4 octadecyl phenol, 2,6-dichloro, 4 diisobutyl phenol, and 8 chloro, These preferred phenolates may also contain sulfur. in other positions or groups .at the same 2,4-ditertiary amyl phenol time as in the places shown in the formulae in - Group B. Furthermore, the formulae in Group III. Alkyl amino phenolates A may have sulfur incorporated therein. More Ba} OCcHa [CHaN (CrHy) :] (01.82am) }: broadly it maybe stated that inorganic substit uents, particularly negative inorganic groups con e. g. barium salts of dicyclohexyl amino methyl taining non-metallic elements of groups V, VI. cliisobutyl phenol and VII of the Mendelee? Periodic System, bene ?cially in?uence the phenolates by increasinz 10 IV. Thioethers of alkyl phenolates their potency for stabilizing the lubricatinz oils and by making the phenolates, in themselves, more stable, as for instance, against hydrolysis. Especially preferred, because they are both very . e. g. barium tertiary’octyl phenol sul?de, barium tertiary amyl cresol sul?de, and barium 2,4-di efficient and also lend themselves to easy and eco 15 tertiary amyl phenol sul?de nomical manufacture, are compounds containing at least One grouping having the general for ' V. Disul?des of alkyl phenolates mula: Ba[O-CaHa—C»Hm+il:B: M 20 e. g. salts of tertiary amyl phenol disul?de t v1. Phosphorus acid esters of alkyl ph'enol sul - ?des ' 5 ' Where Ar is an aromatic nucleus, R is an or; ganic group, Z is a member of the sulfur family, 26 e. g. salts of tertiary amyl phenol sul?de mono and n is an integer of l to 5. Z is preferably sul phosphite fur, and nsis preferably 1 or 2. R represents an organic group which may be either aryl, alkyl, alkaryl, aralkyl or cycloalkyl, and which may contain substituent groups such as halogen, par Other examples of metal alkyl phenol sul?de which may be treated in accordance with the pres 30 ent invention include: calcium tertiary amyl ticularly chlorine, nitro, nitroso, amino, hydroxy, phenol sul?de, tin salts of wax alkylated salicylic carboxy, alkoxy, aroxy, mercapto, land the like, acid sulfide, magnesium tertiary octyl phenol sul but R preferably is or contains an alkyl or al ?de, and barium salts of Clo-C20 branched chain kylenyl group, and preferably contains at least 4 alkyl phenol sul?des prepared from phenols alkyl carbon atoms but may contian many more, such 35 ated with re?nery butene polymers, etc. An ex ample of a trivalent metal alkyl phenol ‘sul?de is as 8, 10, 16, 18, 24, etc. The con?gurations of the compounds are not aluminum tertiary amyl phenol sul?de which may be represented in a general way by the formula , limited to certain positions for the substituent groups, for these may be in ortho, para, or meta relations to one another. Also, the substituents, 40 X, in broader formulae discussed previously in any aromatic nucleus may be alike or different. The aromatic nucleus may be polycyclic as in naphthalene, phenanthrene, diphenyl, etc. Where oxygen occurs, it may be replaced by sul fur, selenium, or tellurium, as in the case of thio phenolic compounds. The alkyl hydroxy aryl compound should have 45 more than three aliphatic carbon atoms and pref erably more than 6, such as 8, 10, 12, etc., up to 24 or more as in the case of para?inlc radicals derived from paraffin wax or olefinic polymers, An important feature of this invention issues such as dimers, trimers, tetramers, etc., of iso from the observation that metal phenolates are 50 butylene. Branched, especially highly branched. alkyl radicals are preferred. bene?ted in solubility and effectiveness as hy _ The aromatic nucleus of the alkyl hydroxy aryl drocarbon lubricating oil blending agents when compound may be mononuclear as in the case of they contain a total of at least 8 and preferably 10 or more carbon atoms per molecule in ali a benzene nucleus or polynuclear as in the case phatic groupings, when sulfur is present in the 55 of a naphthalene nucleus. Instead of using pure individual phenolic materials, one may use crude molecule, and at least 16 carbon atoms and pref commercial products which may be mixtures of erably 18 or more, if no sulfur is present. two or more alkyl hydroxy aryl compounds, such Speci?c examples of preferred substituted as crude petroleum phenols which have an aver-‘ phenolates falling into the classses mentioned, having at least one alkyl radical as a substituent, 60 age chemical composition indicating the presence of four aliphatic carbon atoms and an amount of and using barium as example of a suitable oxygen slightly in excess of that called for by metal, are formulated as follows: I. Alkyl phenolates the formula C4HaCsH4OH. Similarly crude phe nolic materials of coal tar origin may be used 65 such as the so-called tri-cresol which is a mix ture of isomeric ortho, meta and paracresols, which should, of course, be further alkylated with e. g. barium salts of diisobutyl phenol, (p-tert. a higher alkyl group, for best results from an oil solubility point of view. octyl phenol), octadecyl phenol, and 2,4,diter In case of reaction of the alkyl hydroxy aro tiary amyl phenol 70 matic compound with a sulfurizing agent which is II. Alkyl chlorphenolates preferably a sulfur halide, e. g. $012 or $2012, a small amount of halogen may be found to com bine with the aromatic compound in some un 75 known manner, but the proportion of such com 2,400,041 bined halogen is very small‘ and is not objection able. Before carrying out the neutralization of the the reaction by treating with 00: prior to the finishing operation. Although the exact amount or proportion of treating agents such as carbon alkyl hydroxy aromatic compound for convert ing the latter into the corresponding metal de dioxide and steam undoubtedly must be varied to some extent according to the particular type rivative or salt, the alkylated phenol or sul?de or of metal salt being treated and the way in which it was prepared, ordinarily the amount of carbon dioxide, or other weakly acid gas used, should be less than about 25%, and preferably less than other derivative thereof is preferably dissolved in alubricating oil base stock having a viscosity within the approximate limits of 35 to 70 seconds Saybolt at 210° F., and the oil derived from any 10 5%, by weight based on the amount of metal salt in the oil solution being treated. If the pro suitable petroleum crude and having any desired _ viscosity index. The basic metal neutralizing agent is preferably portion of carbon dioxide is calculated on the weight of the entire oil solution being treated then'it should be preferably about 0.5%-to 2% a ?nely divided oxide or hydroxide of the desired metal such as an alkaline earth metal, e. g. cal 15 by weight. Similarly the amount of H20 should be in the same general range, i. e.. less than cium, barium, magnesium, etc., or other polyval ent metals such as nickel, cobalt, tin, lead, zinc, copper, cadmium, manganese, iron, chromium. about 20%, preferably less than 5%, based .on the weight of metal salt being treated, and preferably about 0.1 to 2 or 3% by weight based on the total aluminum, etc., or even monovalent metals such as sodium, potassium, lithium, etc. Although 20 oil solution being treated. the invention is intended to apply particularly to metal salts resulting directly-from a basic metal neutralizing agent, it maybe used to some advan tage in the case of corresponding metal salts‘ made by double decomposition from other corre The use of controlled amounts of water or steam provides better control of the product and more uniform results than if the blowing with carbon dioxide is carried out in the absence of any H2O. The amount of water or steam used is important. It has been found that there is a slight loss of ' sponding metal salts. For instance, one may ?rst metal content of the metal salt during the treat prepare a sodium salt of an alkyl hydroxy aryl ment with CO2 and H20 if used simultaneously sulfide such as tertiary amyl phenol sul?de and and that this loss increases with the amount of then treat the latter with anhydrous barium bro -mide to form the corresponding barium salt of 30 H20 used. After the treatment with carbon dioxide and tertiary amyl phenol sul?de. In such a case the COa-HaO treatment may be applied eitherto the ?rst-formed salt (1. e. the sodium salt) or to the one formed by double decomposition (i. e. the barium salt) or to both‘. when using a basic metal neutralizing agent, steam, or equivalent treating agents, the entire mixture is ?ltered, preferably with the use of a ?lter aid such as Hy?o, Dicalite or other inert di-' atomaceous earths or active clays such as, Super Filtrol, attapulgus, etc. Usually about 0.05 to 0.25 lb. of ?lter aid per gallonwill give satisfactory improvement in the ?ltration. The improved process of this invention, namely the reaction is preferably carried out at a tem perature between the approximate limits of 20° C. (or room temperature) and about 200° 0., pref erably about 90° C. to 175° C. The mixture is 40 the treatment with carbon dioxide and steam, or preferably stirred during this neutralization reac- . tion, for a sufficient length of time to insure com plete reaction, and ordinarily an excess of the basic metal neutralizing agent is used so as to insure incorporation of the metal atom in each molecule of the alkyl hvdroxy aromatic compound or sul?de thereof, to produce for example a metal alkyl phenolate or a metal alkyl phenol sul?de, etc. . Now according to the present invention the resultant solution of metal salt in lubricating oil, with or without minor amounts of stearyl alcohol or other additives such as mentioned above, is treated with a weakly acid substance, preferably equivalent materials, may be carried out by batch operation or continuously, depending upon equip ment available and quantity of material being processed. For batch operation the oil solution of the metal salt can be placed in any suitable con tainer such as an open or closed tank, drum or kettle, etc. provided with heating or cooling coils or exchanger and a pipe or other suitable means of passing the carbon dioxide and steam (or wa ter) into the oil-salt solution preferably near the bottom thereof so that the gas bubbling up through the solution will effect suitable agitation. A mechanical agitator may, of course, be provid ed. After the reaction has been completed the solution should then be discharged from the bot by blowing the solution with a weakly acid gas tom of the container by gravity or by pressure such as carbon dioxide, hydrogen sul?de,‘ etc., blowing. or conveyed by any other suitable means preferably one whose alkali or alkalineearth salts such as by pumping, to a ?lter. On the other are insoluble in oil, to reduce the water-sensitivity hand, for continuous operation several alternative of the metal salt in the oil. Although such blow ing with carbon dioxide, for instance, may effect 60 types of equipment may be used, one being an open vertical drum in which the fresh oil-salt so a substantial bene?t when used alone, it is pref lution is fed in at one side either at the surface erable to carry out this treatment in the presence of, or subsequent to a treatment with, a controlled or at the bottom or at some intermediate height, and the carbon dioxide and steam are blown amount of H20 either in the form of water or steam which is believed to effect a partial hy 65 into the solution near the bottom of the tank either through a pipe ?tted to the bottom of the drolysis of some of the metal salts present. It tank or else through a removable pipe which ex is to be noted that water itself below its boiling tends from the top of the tank down through the point substantially hydrolyzes the metal salts, but liquid near to the bottom, and the treated solu during subsequent drying and ?nishing opera tions the hydrolyzed fractions recombine to form 70 tion is then drawn oil through a suitable over ?ow outlet or by a syphon or otherwise. For water-sensitive material. It is the function of the larger scale continuous operation'it is probably C0: to render the metal inactive during ?nishing best to use a vertical tower which may be of any operations. Accordingly if the hydrolysis is car desired dimensions of height and diameter and ried out with water alone at temperatures below the boiling point _of water, it is necessary to stop may contain packing materials such as rings, eta, 2,406,041 or may be equipped with bubble trays and the stock or an S. A. E. 20 grade having a viscosityv like or not, in any case the oil-salt solution be- index oiabout 100. ‘ - Table 1 Time of treat 15 111-. 1 111-. 134 hrs. ' " 2 hrs. 214-1111 3 hrs. Per cent H10 Per cent H1O Per cent H10 Per cent H10 Per cent H|O Per cent H10 Ba Per cent water added: 0 9. 49 ass 9. 41 9. l7 sens. Ba 412 so 8 l0 sens. 9 1 5 5 9.00 9. 49 7. 99 9. 47 10 7. 83 9. so as s. 44 Ba sens. Ba ' sens. 7 10 l 6 9. 54 9.00 9. 32 7. 34 7 11 2 3 9. 50 o. 12 9.36 7. 56 7 11 2 2 9. 50 9.011 9.25 7. 61 7 11 6 2 7 6. 16 2 6. 31 1 6. 33 l 5 a. as 1 o. as 1 5. 01 1 9. 54 ass 9.44 7. 74 7 ........ .. 11 1. so Ba sens. Ba sens.~ Blank sample (no treat): 9.66% Barium, 65 c. c. water-sensitivity. The data in the above Table 1 indicate that the greatest or at least the most practical reduc tion of water-sensitivity is effected with the use ing fed into the top of the tower and the car bon dioxide and steam or water being fed into the bottom of the tower so that the solution and treating agents will ?ow countercurrently and the 25 of 1% or less of added water and a carbon diox ide blowing treatment of about 2 to 21/2 hours. treated solution will be discharged continuously If much more water is used or a much longer at the bottom of the tower by gravity and residual treating time is used, the loss of barium from the gases released at the top of the tower. Or the ?nished product is substantially increased, with treatment with CO1 and water (or steam) can be conducted either batch or continuous while main 30 out any compensating advantage by further de crease in water-sensitivity. taining a slight pressure of CO1 or steam on the In another set of experiments a. similar oil system. Such pressure will improve the solubility solution of the same type of metal salt, namely of the CO1 and water (or steam) in the oil, re barium tertiary octyl phenol sul?de, was heated sulting in better contact of the liquid and gas and . thereby e?ecting better utilization of the treat 35 to 150° C. with constant CO2 treatment, and ing agents. traces of water (steam) were used. By trace is meant less than 0.15% based on the charge. The data in the following table show the e?‘ect The results were as follows: of various amounts of water in a series of tests Table 2 95 hour Per- Percent 00. 11,0 cent 5 5 0 Ti‘. \ 1 hour 2 hours PerPer- Per- PerPer- Per‘ cent Ba “5 Hl’g- cent 00, mo cent cent Ba g5?- cent 001 H1O cent 9.54 9.29 8 12 10 10 ______________________ _- 0.25 ______________________ ._ 0.26 0 Ti‘. 9.58 9.61 Ti‘. 0.13 9.69 __-_.- 0.50 9 66 9 0.50 9 7 20 20 8 hours Percent Ba - Percent 00. PerB10 cent Percent Ba 4 hours g5?- 0 Tr. 9.56 9.64 10 10 30 80 0 Tl‘. 9.65 9.50 5 5 Tr. 0.26 9.6 9.77 10 2 0.75 0.75 Ti‘. 0.39 9.69 9.68 8 1 Percent 001 PerH1O cent Per cent Ba - .......................... ._ .......................... __ 1.06 <.l5 9.64 10 1.06 0.54 .._.-.. 2 Blank sample (no treat): 9.66% Ba, 65 c. c. H10-sensitivity. The data in the above Table 2 indicate that in which a solution of 40% of barium tertiary 55 when the barium salt solution was treated at 150° octyl phenol sul?de in oil was treated with a C., 3 hours treatment with carbon dioxide was constant amount (10% by weight/hour based on su?icient to produce a very substantial reduction the total solution) of carbon dioxide at 85-90° C. in water-sensitivity, from 65 cc. to 8 or 5 cc. when for various periods of time ranging from 1A.; hour to 3 hours. The barium salt used in this series 60 no water was used and from 65 cc. to 12 or 5 cc. of tests was made by neutralizing tertiary octyl when a trace of water (steam) was used disre garding the amount of carbon dioxide. It is fur phenol sul?de in oil solution with barium hy ther noted that with small percentages of car droxide octahydrate at about 120° C. The percent bon dioxide from 0.5 to 1.0% (by weight on the of barium in the treated product, and the water sensitivity thereof are shown for each concentra 65 total solution) as the water (or steam) increases the water-sensitivity improves from the blank of tion of water used and each duration of carbon dioxide blowing. The term “water-sensitivity” is 65 cc. to 1-2 cc. As to Table 2 per se it is evident that larger amounts of steam with relatively small the amount of sediment that settles out from 500 cc. emulsion after 24 hours standing at room amounts of carbon dioxide are e?ective in reduc temperature when 600 gms. of a (1.0%) solution 70 ing the water-sensitivity to a minimum. Another series of tests was made using as the of the metal salt in oil is contacted with 1% by metal salt one made by neutralizing tertiary octyl weight of water and stirred for 15 minutes with pheno1 sul?de at 85° C. with barium hydroxide a motor-driven egg-beater type of mixer at octahydrate, and then treating a 40% solution Bil-90° F.; the oil used in these tests was a sol vent extracted Midcontinent lubricating oil base 75 thereof in oil with carbon dioxide and steam at ll 150° C. (as in Table 2).. The results were as follows: Table 5 - Table}! Time of treatment Per cent H|O sensi B8 “WW Time of treat. ' 35 hr. Per 1 hr. ' HID Per 18 9.03 2 hrs. H|O Per 13 9.11) 3 hrs. H10 Per 10 8.94 H30 10 egg‘ sens. “1;? sens. 0%? sens. 0%? sens. Per cent wa ter added: trace ______ _. 8.91 10 C’ c. 9. B8 9. 08 9. 04 8. 99 65 65 40 46 9. 24 ll 9. l4 9. 26 9 ii It is not intended that this invention be limited to any of the speci?c examples which have been 15 given solely for the purpose of illustration nor un necessarily by any theory suggested as to the The data in the above Table 3 show that here again the carbon dioxide treatment with a trace of steam was successful in reducing the water sensitivity from 18 down to 10 in 2 to 3 hours. 20 . nechanism of the operation of the invention, but only by the appended claims in which it is in tended to claim all novelty inherent in the inven tion as well as all modi?cations coming within the Some plant performance data showing the scope and spirit of the invention. effect of steam and carbon dioxide treatment of It is claimed: 1. The process of improving the water-sensi barium tertiary octyl phenol sul?de are given tivity of a metal salt containing at least one herebelow: Table 4 25 grouping having the general formula Water sensitivity Percent Ba where M is a metal connected through oxygen to llcfmc (‘Oi-Hi0 After treat- Before treat- trcatmont ment mcnt After treat mcnt v (7:. 32 45 Ge. 5 7 9. 0i 9.68 8. 90 9. 67 46 3 8. 97 8. 91 The above Table 4 shows that in commercial operation which was carried out by injecting the steam-C02 mixture into the discharge line of a system which consisted of a vertical drum equipped with a stirrer and a centrifugal circu lating pump taking suction at bottom of drum discharging through a heat exchanger into the top side of the drum, the water-sensitivity was successfully reduced from relatively high figures an aromatic nucleus Ar containing one or more 80 alkyl substituents R, 11. indicates the number of such substituents, Z is a member of the sulfur family, and 11' indicates the number of Z radicals, which comprises blowing a solution of the said salt in an inert solvent with a weakly acid gas in the presence of H20. 2. Process according to claim 1 in which the salt treated contains at least one grouping having the general formula M—O-Ar(R)--S where M is a polyvalent metal connected at least through 40 one oxygen linkage to an aromatic nucleus Ar containing an alkyl substituent R. 3. The process of improving the water-sensi tivity of a polyvalent metal salt of a higher mono alkyl phenol sul?de which comprises blowing an oil solution of said salt with a weakly acid gas in the presence of H20, and ?ltering to remove un such as 32-45 down to relatively low ?gures such as 3-7, without effecting more than a trace loss of desirable precipitate. 4. The process for improving the water-sensi percent barium. The metal salt used during the accumulation of the data reported in Table 4 was 50 tivity of a crude polyvalent metal salt of a higher monoalkyl phenol sul?de which comprises blow made by neutralizing tertiary octyl phenol sul?de ing an oil solution of said salt with carbon diox at about 120° C. with barium hydroxide octahy ide in the presence of H20 and ?ltering to remove drate, using about 0.7 to 0.75 lbs. of the hydrate undesirable precipitate. per pound of the sulfide, thus being a, 11-15% ex 5. Process according to claim 4 in which an cess of hydrate over the theoretical amount re 55 amount ranging from a trace to about 5% is used quired for neutralization. The subsequent CO2 of the C02 and of the H20, and the treatment is steam treatment was carried out at a tempera carried out at about 20-200° C. for about 1 to 10 ture of about 140-150° 0., using about 1.0% CO: hours. . and about 1.0 to 2.0% steam, based on the weight 6. The process of improving the water-sensitiv of the barium salt being treated. 60 ity of a crude barium salt of tertiary octyl phenol An alternate method of carrying out the water sul?de which comprises blowing a 20-60% solu proo?ng reaction is to treat the metal salt solu tion of said salt‘ in mineral oil with about 1% of tion with water alone at temperatures below about carbon dioxide and about 1% of steam (based on 100° C. to eifect partial hydrolysis of the salt, then the weight of solution treated) at a temperature follow this treatment with CO: prior to drying 65 of about '75 to 150° C. for about 2 to 6 hours, and and ?nishing. This type‘ of operation is illus ?ltering to remove undesirable precipitate. trated in the following example summarized in 7. The process of reducing the water-sensitiv Table 5. ‘ ity of'a metal salt of an alkyl hydroxy aromatic This experiment was conducted by reacting a sul?de having at least 8 aliphatic carbon atoms 40% metal solution in oil with 15% by weight 70 which comprises treating a mineral oil solution of said salt with a weakly acid gas in the presence of water on total solution at 80-90° C. for vary- ing periods of time. In each case the wet solu of H20. 8. The process of reducing the water-sensitivity tion was quenched with C02 prior to heating to of a metal salt of an alkyl hydroxy aromatic sul 140° C. and ?ltering. The water-sensitivity data 75 ?de having at least 8 aliphatic carbon atoms ' and analyses are as follows: 13 2,400,041 which comprises blowing a mineral oil solution of 14 amount or each ranging from a trace to about said salt with carbon dioxide in the presence oi! a 5% based on the solution treated, said treatment small amount of moisture. being carried out at a temperature of about 20 9. The process of reducing the water-sensitivity 200° C. for about 1 to 10 hours, and-?ltering the of barium tertiary octyl phenol sul?de which 5 treated mixture to remove undesired precipitate. comprises blowing a mineral oil solution of the HELMUTH G. SCHNEIDER. same with carbon dioxide and steam, using an JAMES E. J. KANE.