US2427272A

US2427272A - Mineral oil composition

Info

Publication number: US2427272A
Application number: US536196A
Authority: US
Inventors: Everett W Fuller; Horace E Redman; Henry G Berger
Original assignee: Socony Vacuum Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1944-05-18
Filing date: 1944-05-18
Publication date: 1947-09-09
Anticipated expiration: 1964-09-09

Description

Patented Sept. 9, 1947 MINERAL OIL COMPOSITION Everett W. Fuller, Woodbury, N. J., Horace E. Redman, Wyandctte, MichL, and Henry G. Berger, Glen Rock, N. J assignors to Socony- Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application May- 18, 1944,

Serial No. 536,196

13 Claims. (01. 252-3237) This invention has to do with the stabilization of petroleum products against the harmful effects of oxidation and deterioration with use. More specifically, it has to do with the improvement or stabilization of mineral oil fractions, particularly viscous mineral oils, by the use of novel reaction products, or a novel class of reaction products, which when admixed with amineral oil in minor proportions will prevent or delay undesirable changes taking place in the oil.

- To those familiar with the art it is well known unstable constituents which may act as oxidation catalysts have been removed by refining operations and also upon the conditions of use.

A large number of characterizing ingredients have been proposed for use as improving agents for petroleum products. For example, various materials containing sulfur or phosphorus, or combinations of these elements, have been suggested as stabilizing agents for viscous petroleum oils. Phosphorusand sulfur-containing reaction products of numerous hydrocarbons and P235 are typical examples of such agents. Although some of these reaction products are fairly effective as mineral oil stabilizing agents, many of them are not entirely satisfactory for various reasons. Some considerably darken the oils in which they are incorporated, thereby militating against their use. Others suffer also from the disadvantage of limited oil solubility and sludgelike character. Still others are undesirable in the relatively small amounts of sulfur and. phosphorus present therein. All of the foregoing undesirable characteristics seriously reduce the saleability of such products in the oil industry. The present invention is predicated upon the discovery of a novel class of oil-soluble, acidic, phosphorusand sulfur-containing reaction products, and the ammonium and metal salts thereof, which are capable of effectin improve- .ment of petroleum fractions, particularly viscous mineral oil fractions; These reaction products, and the said salts thereof, prevent the formation of acidic oxidation products and sludge in anoil, as Well as inhibit the corrosion of metal use herein are unlike the oxidation products of engine parts such as alloy-metal bearings which come in contact with the oil. The said improving agents are particularly desirable in View of the following features: they do not impair the color of the oil fraction in which they are incorporated; they contain substantial quantities of phosphorus and sulfur; they do not contain,

sludge-like constituents, and they are readily soluble in oil fractions.

The improving agents contemplated herein are oil -soluble, acidic, phosphorusand sulfur-containing reaction products obtained by reaction of: phosphorus pentasulfide and an oxidized parafiin wax at an elevated temperature between about 50 C. and about 125 C., and particularly at about C. As indicated hereinabove, the

ammonium and metal salts of the aforesaid reaction products are also contemplated.

The oxidized paraffin wax reactants used in preparing the aforesaid improving agents are obtained by the oxidation of'paraffin wax, or paraffin slackwax which contains a predominant proportion of paraffin wax, in combination with an oil fraction. The paraffin slackwaxes contemplated he'reinshould contain at least about 75 per cent of paraflin wax, in order to obtain effective and desirable reaction products of the type defined above. The paraflin waxes generally contain at least about 18 carbon atoms, although a paraffin wax containing on the average of about 24 carbon'atoms and having a melting point of about 126F. is preferred. As used herein, and in the appended claims, the term"parafiin wax is inclusive of the slackwaxes described above. To oxidize these-waxes, air or oxygen is introduced into a quantity of wax at an'elevated temperature of the order of from about C.'l'.0 about 180 C., and preferably at about C. Temperatures below 120 C. may also be used in the oxidation procedure, but extremely long reaction times are required to effect substantial oxidation; for practical purposes, then, temperaturesabove about 120 C. are used. While the composition of the'oxidized petroleum waxes so obtained is not fully understood, it is known that they are complex products containing several such oxygenated hydrocarbon materials as acids, =hydroxy acids, alcohols, aldehydes, ke

amples provided hereinafter.

The oxidized wax reactants contemplated for many hydrocarbon fractions closely related to those of paraffin waxes and parahin slackwaxes and, as such, are superior thereto. This superiority carries over in turn to the reaction products of this invention- Forexamp'le, equal quantities of a paraffin wax, a paraflin slackwax and of -hydrocarbon fractions identified in Table 1 below were oxidized by blowing air therethrough at 160170 C. for approximately the sameperiod of time. The starting materials and oxidation products are described in Table'l by their neutralization number (N. N.), hydroxylnumber and'saponification number, each of "which is determined by standard procedure known in the art.

4. the filtrate therefrom had an N. N. of 71 and con tained 5.06 per cent sulfur and 2.06 per cent phosphorus. This reaction product is identified hereinafter as product A.

- Exam/{P n II A quantity of a parafiin slackwax containing about 80 per cent paraffin wax and obtained from a petroleum distillate having a Saybolt Universal "Viscosity (S. U. V.) of 120 seconds at 130 F.,

was oxidized by blowing air therethrough at 160 ber' (NJNJ orae saponification number of 36,

Table 1 Reaction No. of Hy- Saponi- Starting Material Time Prod Color N. N. droxyl fica'cion (Hrs) duct No. No.

Paraflin wax (A. S. T. M. melting point 126 F.) 31 .1 Light orange. 44 36 174 Paraffin-slackwax =31. 5 Y 2 Dark red..' 8 69 Hydrocarbonioil (saybolt Universal Viscosity 32 3 Black 2 1 (S. U. V.) of 66 seconds at 210 F.).. Hydrocarbon oil (Saybolt Universal -V'isc0sity 33 4 do 0. 4 1 -2 '(S:'U.V.) of 55 seconds at 210 F.).

It will be apparent from'theforegoing tabulation that'parafiin waxand paraffin slackwax oxidize muchmore readilythando other typical hydrocarbon fractions, and that the oxidation products of th 'said waxes are more suitablefor the purposes of thepresent invention in view of their-colorand oxidation characteristics. In-gem eral,'it-;;is-desirab1e to carry the oxidation-to a point where the hydroxyl and saponification numbers are-at leastabout-20 and the neutralization number is Within the range '5 to 60.

As contemplate d herein, the amount of PzSs reacted witlran oxidizedpetroleum wax reactant is in-theneighborhood of from about 5 per cent to-aboutper cent-by Weight, with about 10 per cent-byweight beingpreferred.

The reaction temperature used in the-preparation of the acidic reaction products defined above is an important consideration. It has been found that elevated temperatures from about 50 C; to about-125 C. are required in order to obtain the desired products, a and elevated temperatures of about-100 C. are.particularlydesirable. If the temperature is too low, as-below about 50 0., little or no reaction occurs and-if too high, as above about'125 C., undesirable-reaction-products containing appreciable quantities of oil-insoluble, sludge-like materials are obtained. For

example, the reaction product of an oxidized paraffin wax and P285 at 150 C. is predominantly a black, tar-like, oil-insoluble material.

Illustrativeof the reaction products contemplated-by-the present invention'are' those shown below in Examples I-through IV,

EEXIXMPLE- I "A'- quantity of a 'parafiln' wax having an A.'S. T.

,..M."inelting point of 126 C. and containing an reaction mixture thus obtained was filtered and cent-by weight of P235 at 100- error 3 hours. The

an iodine number-0f 5 and ahydroxylnumberof 69.

(a) A portion of the oxidized-paraffin slackwax parts'by weight) was reacted wi thl sss (IOpa'rts weight) atl00 C. for 2 hours. The reactionproduct obtained thereby contained 4.9 per cent sulfur and 1.97 per cent phosphorus-and had an N. N. value of 36. This product is'referred to'hereinas product B.

(b) Barium hydroxide octahydrate (Ba (0H) 2.81320) (10. parts by'weight) was reacted with a quantity ofProduct B (100 parts by weight)" at about 0., thereby forming the barium salt of product B. The salt thus obtainedproduct C'c'ontained 4.36per cent barium, 4.58 per cent sulfur arid 1.44 per cent phosphorus and had an N.'N. value of- 11.

' EXAMPLE III 'Aboutone'per cent (by weight) of the Y oxidized parafiin'wax "formed as described in Example I above and having a neutralization number (N. "N.) 'of 40, was added to a 'parafiin "slack'wax (identifiedin Example II) and the resulting mixture was thenfurther oxidized 'withair at C. for '49 hours. The reaction product thus formed had a neutralization number (N. N.) of '16, a'saponification nu'mber of 63 and-a hydroxyl number of 24.

One hundred parts by weight of the oxygenated pa'raffi-n wax so formed was" treated 'w'ithlO parts by weight of P285 'at'l00" 'C. for 5 hours. The reaction. product (product D) contained 4.3 per c'ent"sulfur and 2.06 per cent phosphorus and had 'aneutralization number (N. N.) or-28.

EXAMPLE IV (a) A quantity (100 parts by weight) of a highly oxidized parafiirr wax having a neutralization number '(N. N.) of 51, a saponifica tio'n --r'iumber of 109 'and' a'hydroxyl numberef '56, 'wasreacted With'PzSs (10 parts by weight) at 100C. for. 3 hours. The reaction product (product E) containe'd 5.1'per centsul'furand' 1.12' per 'cerit'ipliosphorus and had a neutralization-number ("N. N.)'of'88. l

(b), Ammonia gas was bubbledthrough a quantity or product E at room temperature (about 20- C.); whereupon thetemperature increased several degrees and the product became more viscous-H The ammonium salt thus formed con. tained 2.95 per centnitrogen, and is referred to hereinas product F. d While the acidic reaction products of this inventio'n, such as products A, BjD and-Eshown above'in Examples I through IV, are particularly desirable for use in petroleum fractions (as are the salts of such products), related'reaction products prepared in a similar. manner from other related hydrocarbonreact'ants are undesirable for such use-1,Th i s is demonstrated by the results shown in 'Table 2 below for products 3 and 4. The oxidized materials shown. therein arecomparative in that all were'prepared in the. same manner, as-described in connection with Table 1 above; The'reaction products shown in Table 2 were prepared by reacting a quantity of an oxidized material (1, 2, 3, and 4, respectively, of Table 1) with P285 per cent by weight); at 100C. forv the same period of time, about 2 6 with the loss of the section in the uninhibited oil. The results are set forth in Table 3 below.

LAUSON ENGINE TEST To further demonstrate the effectiveness of the reaction products-of this invention aspetroleum stabilizing agents a blank oil and blends of the oil and typical reaction products,- product C and product D, were subjected to a Lauson engine test. In this test a single cylinder Lauson engine was run with an oil temperature of 290 F. and a jacket temperature of 212 F. The oil was S. 11.13.

hours. v 10 motor oil, solvent refined. The acidity as Table 2 Hy- Saponi Q J t No. of Product 7 Reaction Per cent Per cent (Table 1) Color I vN. N. dggyl tillcgg on Product (dolor N. P S

Light orange; e 44 36 174 A Light brown 71 2.06 5.06 Dark red 8 69 36 B 36 1.97 4.9 Black 2 l 0 X 12 0. 38 0.97 do 0.4 l 2 7 0.27 0.86

To demonstrate the effectiveness of the reaction products of this invention as mineral, oil improvingagents,v oil blends were prepared containing small quantities of representative reaction products and the blends and the blank oils were subjected to the various tests hereinafter described. It will readily be seen from inspection of the results of these tests that our reaction products are extremely. effective in stabilizing mne lcils. 1

CORROSION INHIBITION f' Motor oils, especially thoserefined by certain solvent extraction methods tend to oxidize when submitted to high temperatures and to, form products that are corrosive to metal bearings. This corrosive action may bequite severe upon said bearings such as those having the corrosion susceptibility of Cd-Ag alloys and may cause their failure within a comparatively short time. The rollowing testis used to determine the corrosive action of motor oil on an automobile connecting rod bearing. 7

The oil used consisted of Pennsylvania neutral and residuum stocks separately refined by means of Chlorex and then blended to give an S. A. E. 2 0 motor oil with a specific gravity of 0.872,.a flash-point of 435 F. and a Saybolt Universal Viscosity of 318 seconds at 100 F. The oil was tested by adding a section of a bearing containing a Cd-Ag alloy surface, weighing about 6 measured by the neutralization number (N. N.)

and the viscosity in centistokes at 210F. 0f the oil :blank and oil blend were determined after 36 OXIDATION TEST highly refined oil, suitable for use in trans-- formers, had been prepared by treating a coastal distillate with 40pounds of 98 per cent sulfuric grams, and heating it to 175 C. for 22 hours andzthe'lossin .weight of the bearing section in therinhibited voilican thus be compared directly? acid and108 pounds of 103 per cent oleum per barrel; followed by washing and clay percolation. It'had a specific gravity of 0.871, a fiash point of 310 F. and a Saybolt Universal viscosity of 69 seconds at F. This type of oil tends to form acidic products on oxidation. It was tested by heating samples to C, and bubbling oxygen therethrough for '70 hours. The acids thus formed were determined by treating with alcoholic potash. Results of the oil alone and for the oil plus a reaction product of the type contemplated herein are presented in Table 5 below.

Table 5 Concf N. N. Per cent Value Oil alone .Q 25v 0 Oi1+0.1 Product C 0.1 0. 10 Oil-l-OJ Product D 0.1 O. 05

RING. SIICKING AND SLUDGE INHIBITION That the reaction products contemplated herein are particularly effective in decreasing the tendency of petroleum lubricatin oils to cause ring sticking and sludge deposition during the operation of an internal combustion engine is denoted by the results given below in Table 6. This is shown by results of the following test which involves the operation of a single cylinder C. F. R. engine at a speed of 1200 R. P. M. over a time interval of 28 hours. The temperature of the cooling medium of the engine was held at approximately 370 F. and the oil temperature was held at 175 F. during the test. The oil used was a lubricating oil stock of 120 seconds Saybolt Universal viscosityat 210 F, and the conditions observed'at the end of the test were: (a) the extent to which the piston rings were stuck, (b) the extent to which the slots in the oil rihgswere filled with carbonaceous deposits in the oil, and (c) the acidity or neutralization number (N. N.) of the oil, The results; obtained from the blank oil and representative blends of, the, oil and typical reaction products are Set; forthin 'I-ablefi below.

l 8 group consisting of an acidic reaction product, anainmonium saltthereof and a metal salt-thereof; said acidic reaction product being obtained by reaction at a temperature between about 50 C. and about 125 C. of phosphorus pentasulfide and an oxidized paraffin wax characterized by a neutralization number from about 5 to. about 60 and hydroxyl and saponification numbers of at least about 20,, said oxidized paraffin wax being obtained by oxidizing a. parafl'ln wax having about ntyo r ar n. atoms and an A. 8.. T.

e n point o 126 F;

Table 6 Ring Conditions, Degrees Slots, Percent Stuck l Filled Deposl H V '7 its N. N.

Oil alone 180 0 360 360 360 70 90 14.0 1. 7 Oi1+1% Product 0. 180 0 0 0 0 0 Trace 0 5. 9 1. 2 Oil alone 360 O 360 360. 180 60 80 40 13. 8 1.6 Oil+1% Product D. 0 0 0 0 0 0 0 0 6.4 1.0

The results set forth in Tables '3 through 6 above. demonstrate that the reaction products contemplated, herein prevent the corrosion of hard metal bearings, and inhibit the development of acids and carbonaceous deposits in engines during use. They further indicate that the said reaction products prevent a substantial increase in viscosity of the oil from taking place during such use.

Concentrations of the reaction products contemplated herein from 0.1 per cent to 5 per cent may be used to efiect a substantial stabilization of the oil fractions in which they are incorporated. In general, however, from 0.1, per cent to 2.0 per cent will be sufiicient. Our reaction products may be used either in straight petroleum fractions, or in fractions containing other additives used. for other, purposes such as detergents, pour point depressants, V. I. improving agents, etc., in which case-they serve to stabilize theresulting blend without detracting from the effectiveness of the other additive or additives that. may be presen It is to be understoodthat while we have hereinabove described typical procedures. for making the oil addition agents contemplated herein and havereferred to certain specific reaction products and specific mineral oils, the invention is not limited thereto but includes variations of the procedures, and other typical reaction products and petroleum fractions coming within the scope of the appended claims.

We claim:

.1. An improved mineral oil composition com prising a major proportion of a viscous mineral oil fraction having in admixture therewith small amount, sufficient to enhance the stability of said oil fraction, of an oil-soluble, phosphorusand sulfurcontaining material selected fromthe neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20 3. An improved mineral oil composition comprising a major proportionof a viscous mineral oil fraction having in admixture therewith a small amount, sufficient to enhance the stability or said. oil fraction, ofv an oil-soluble, phosphorusand sulfurcontaining material selected from the group consisting of an acidic. reaction product, an ammonium salt thereof and a metal salt thereof, said acidic reaction product being obtained by reaction at a temperature between about 50 C. and about C. of phosphorus pentasulfide and an oxidized parafiin wax characterized by aneutralization number from about 5 to about 60 and hydroxyland saponification numbers of at least about 20.

4. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, suflicient to enhance the stability of said oil fraction, of an oil-soluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at a temperature between about 50 C. and about 125 C. of phosphorus pentasulfide and an oxidized parafiin wax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20.

5.. An improved mineral oil composition comprising a. major proportion of a viscou mineral oil fraction having in admixture therewith a small :amount,.sufficient to enhance the stability of;saidoihfraction, of an oil-soluble, acidic, phosphorus-and Sulfurcontaining reaction product obtained by reaction at a temperature between about .9 and. about. 125 C. of phosphorus pentasulfide and an oxidized paraffin wax characterized by a neutralization number from about to about 60 and hydroxyl and saponification numbers of at least about 20, said phosphorus pentasulfide representing from about 5 per cent to about per cent by weight of the said oxi= dized parafiin wax.

6. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, suflicient to enhance the stability of said oil fraction, of an oil-soluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at about 100 C. of phosphorus pentasulfide and an oxidized paraflin wax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20.

'7. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, sufiicient to enhance the stability of said oil fraction, of an oil-so1ub1e, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at about 100 C. of phosphorus pentasulfide and an oxidized parafiin wax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20, said phosphoru pentasulfide representing about 10 per cent by weight of the said oxidized paraflin wax, and the latter being obtained by oxidizing a paraffin wax having about twenty-four carbon atoms and an A. S. T. M. melting point of 126 F.

8. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, sufficient to enhance the stability of said oil fraction, of an oil-soluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at about 100 C. of phosphorus pentasulfide and an oxidized paraffin slackwax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20, said phosphorus pentasulfide representing about 10 per cent by weight of the said oxidized parafiin slackwax, and the latter being obtained by oxidizing a paraffin slackwax containing not less than about 75 per cent of paraffin wax.

9. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, sufiicient to enhance the stability of said oil fraction, of an oil-soluble, acidic, phos phorusand sulfurcontaining reaction product obtained by reaction at about 100 C, of phosphorus pentasulfide and an oxidized parafiin slackwax characterized by a neutralization number from about 5 to about 60 and hydroxy and saponification numbers of at least about 20, said phosphorus pentasulfide representing about 10 per cent by weight of the said oxidized parafiin slackwax and the said oxidized paraiiin slackwax being obtained by oxidizing a paraifin slackwax containing about 80 per cent of paraffin wax.

10. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, sufiicient to enhance the stability of said oil fraction, of a salt of an oil-soluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction' at a temperature between about 50 C. and about 125 C. of phosphorus pentasulfide and an oxidized paraflin wax characterized by a neutralization numher from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20.

11. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, suflicient to enhance the stability of said oil fraction, of an ammonium salt of an oil-soluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at about C. of phosphorus pentasulfide and an oxidized paraflin wax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20, said phosphorus pentasulfide representing about 10 per cent by weight of said oxidized paraffin wax.

12. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a small amount, sufficient to enhance the stability of said oil fraction, of a metal salt of an oilsoluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at a temperature between about 50 C. and about C. of phosphorus pentasulfide and an oxidized paraffin wax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20.

13. An improved mineral oil composition comprising a major proportion of a viscous mineral oil fraction, having in admixture therewith a mall amount, sufficient to enhance the stability of said oil fraction, of a barium salt of an oilsoluble, acidic, phosphorusand sulfurcontaining reaction product obtained by reaction at about 100 C. of phosphorus pentasulfide and an oxidized paraffin slackwax characterized by a neutralization number from about 5 to about 60 and hydroxyl and saponification numbers of at least about 20, said phosphorus pentasulfide representing about 10 per cent by weight of said oxidized paraflin slackwax and the said oxidized parafin slackwax being obtained by oxidizing a parafiin slackwax containing about 80 per cent of parafiin wax.

EVERETT W. FULLER. HORACE E. REDMAN. HENRY G. BERGER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,375,061 Williams et a1 May 1, 1945 2,331,923 Musselman Oct. 19, 1943 2,316,088 Loane Apr. 6, 1943 2,281,824 Bray May 5, 1942 2,242,260 Prutton May 20, 1941