US2798797A - Gasoline fuel additives - Google Patents

Description

about 10 years because of corrosion.

United States Patent oAsoLnsE FUEL ADDITIVES Charles C. Shepherd, Berkley, Mich assignor to Ethyl Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 28, 1953, Serial No. $58,185

13 Claims. (c1. 44-66) This invention relates to a new class of organicmaterial. More particularly, the present invention relates to a novel class of metallic monobasic acid compounds of particular utility as corrosion inhibitors and stabilizers.

The need for corrosion inhibitors in petroleum products particularly in gasoline, has long been known. The storage, handling and transfer operations associated with petroleum products, especially of the gasoline boiling range necessitates the use of iron and steel containers, pipe lines and the like. If it were possible, or at least economically feasible to maintain such hydrocarbon products in an essentially anhydrous condition, corrosion undoubtedly would be almost non-existent. However, during the manufacturing, storage and shipment operations to which fuel is subjected,-considerable quantities of water are encountered, particularly on exposure to air, and as a result such fuel contains substantial quantities of water. Thus, tankers and pipe lines are generally highly susceptible to corrosion resulting from the wet gasoline contained therein. This corrosion is especially deleterious, often resulting in an extremely short period during which the tankers and pipe lines can be utilized. In the case of tankers used for transporting gasoline there have been estimates that the effective life is somewhat less than In the case of pipe lines, it has been stated that the carrying capacity may be reduced by more than 12 percent in one year if no efiort is made to control corrosion. It has been further stated that this effect results from the formation-and growth of rust filrrls which increase the roughness of the pipe causing increased "friction losses and proportionately increased power costs to maintain the original capacity.

Gasoline storage tanks are also subject to corrosion Such tanks are susceptible to corrosion attack of several different types. On the one hand 'there isa tendency to corrode'in the bottoms of the tanks bevcause of the concentration of water b'ottoms 'at these points. Likewise, there is a severe tendency for corrosion to occur at the gasoline level and'also in the vapor phase,

that is, above the surface of the fuel. In thecase of storage tank corrosion the efiect becomes especially significant in that frequent tank cleaning operations are required. Obviously such operations aredifficult, costly, and time consuming.

Another type of fuel corrosion results from the storage of-gasoline in gasoline drums which are often made from hot or cold rolled steel, or galvanized iron. Another 'type of metallic container susceptible to corrosion is the fuel tank of motor vehicles such as automobiles, trucks, and buses.

In each of the aforementioned types of 'fuel containers the corrosion results in premature destruction of utility, and, likewise, results in theformation of rust, scale, and other sludge deposits which cause'discolo'ration of the 2,798,797 Patented July 9, 1957 2 fuel and the clogging of filters, fuel pumps, carburetors, and the like.

As indicated previously such corrosion generally oc} curs at the'solid-liquid-liquid interface, that is, the point 5 of contact between the metallic container, the hydrocarbon phase and the aqueous phase. Such corrosion re sults from the presence of water in both treated and untreated hydrocarbon fuel. That is to say, corrosion is a serious problem Whether or not the fuel contains antiknock agents or other a'djuvants. However, in the case of -fuels containing or-ganolead 'antiknock compositions another problem is encountered. It has been found that the presence of water in fuel containing organic bromine compounds, generally used as lead scavengers, results in a chemical reaction producing halogen acids, particularly hydr'obromic acid. This results in a loss of effective scavenging material as well as a contribution to the overall corrosion problem. As an example of this mechanism, it has been proposed that the reaction between the metal surface, to wit: zinc, iron or both and water and the organic bromine compound results in the formation of a complex mixture of zinc and iron halides or hydroxides. It is evident, therefore, that such corrosion will result in a severe etching of the metallic container particularly at the interface.

It has been proposed heretofore to obviate these corrosion problems by two alternative means. First, attempts have been made to apply diverse coatings of plastics, lacquers, metallic phosphates and the like so as 30 to protect the metallic interface against the corrosive action. Second, attempts have been made't'o utilize corrosion inhibitors such as chromates and numerous and sundry organic and inorganic substances. It 'has been found, however, that neither 'of these methods "has been entirely satisfactory. In the case of the use of "coating materials for the metallic containers -the difficulties result from chipping, peeling and etching of the surfaces which result in the formation of additionalsolids and the concomitant efiects of sediment formation, discoloration and carburetion 'dificulties. In addition to this, a serious drawback is the expense involved in applying and maintaining such coated surfaces. The corrosion inhibitors proposed in the prior art as means for the obviation of this problem have likewise been largely ineifectual since they have not possessed the'proper distribution characteristics. In other words,'the inorganic substances tend to be highly' soluble in the aqueous phase and conversely the organic substances tend to be highly soluble in the hydrocarbon phase and as a result there is 'littlejprotection afforded at thesolid-liquid-liquid interface. This, as indicated hereinbefore, is the point at which the most severe corrosion occurs and consequently the need exists for-a class of materials which have the proper phase distribution characteristics.

It is, therefore, an-objectof the present invention to provide as new compositions of mature class 'of-compounds of particular effectiveness as corrosion inhibitors and as halogen l'oss prevent-attives. Likewise, it is an ob- :ject of this invention to provide processes for thepre'paration of these new compositions of'matter. Among "the additional objects of theipresentinvention' is that of pro- 'viding processes for inhibiting'both corrosion and halo'gen' compositions of matter a class of partially hydroxylated hydrates of metallic monobasic acid compounds. The materials of the present invention are partially hydroxylated polyvalent metallic materials derived from monobasic acids capable of forming hydrates. Thus, the new compositions of matter of the present invention are derived from polyvalent metallic salts of such acids as fatty acids which can be saturated or unsaturated open chain monobasic acids or cyclic monobasic acids. Therefore, the partially hydroxylated hydrates of metallic monobasic acids can be prepared from such acids a lauric, myristic, palmitic, stearic, arachidic, eicosane-carboxylic, behenic, lignoceric, cerotic, melissic, psyllastearic, naphthenic, oleic, erucic, elaidic, ricinoleic, brassidic, tiglic, citronellic, undecylenic, geranic, linoleic, dehydrogeranic, linolenic and like acids.

As indicated previously the compositions of matter of the present invention contain a polyvalent metal. Thus, the materials of the present invention can contain such polyvalent metals as magnesium, zinc, thorium, calcium, aluminum, lead, vanadium as vanadyl and the like.

The preferred materials of the present invention are termed partially hydroxylated hydrates of metallic monobasic straight chain unsaturated acids containing from about to 30 carbon atoms per molecule. Likewise, the preferred metallic constituent of the new compositions of matter of the present invention is magnesium.

To better understand the nature of the present invention an illustrative material, magnesium oleate, is consid' ered in detail.

It has been found that the fatty acid derivatives of metals of the character described hereinbefore are capable of existing in a number of chemical forms. For example, magnesium oleate can exist in at least four states of aggregation as follows:

1. Anhydrous magnesium oleate 2. Magnesium oleate dihydrate 3. Partially hydroxylated hydrate of magnesium oleate 4. Basic hydrate of magnesium oleate The fact that such materials can exist in these diverse states of aggregation is of extreme importance in their effective utilization particularly in the obviation of corrosion as will become still further apparent from the discussion hereinafter.

Again referring to the illustrative example, magnesium oleate, the transformations which occur serve to elucidate, at least in part, the chemical nature of the diverse physical and chemical forms. Anhydrous magnesium oleate has been shown capable of coordinating or otherwise incorporating into its molecular structure two molecules of water of hydration. It has now been found that such hydrated polyvalent derivatives of monobasic acids, for example magnesium oleate dihydrate, can be treated under hydroxylation conditions such that the material is transformed into what is termed a partially hydroxylated hydrate of magnesium oleate. The hydroxylation conditions referred to can be produced in a number of ways. For example, magnesium oleate dihydrate can be subjected to temperatures between about to C. for a period of time in the order of about six months or more in order to bring about a transformation in the characteristics of chemical structure, physical appearance, and corrosion effectiveness.

Another variant in producing the hydroxylation conditions for the preparation of the partially hydroxylated hydrates of metallic monobasic acid compounds of the present invention consists of subjecting a polyvalent metallic compound derived from a monobasic acid to temperatures in the order of about 40 to C., for a period of about three months.

In order to further establish the nature of the new compositions of matter of the present invention the following simplified explanation of the hydroxylation reaction is of help. On subjecting magnesium oleate dihydrate Hydroxylation ii conditions Partially hydroxylated hydrate of magnesium oleate As indicated in the above hypothetical reactions the equilibrium as between the magnesium oleate dihydrate represented as I and the partially hydroxylated hydrate of magnesium oleate, II under hydroxylation conditions favors the formation of the latter. However, it is to be noted that the theoretical end product represented by 111 is apparently not formed in any significant quantity under such conditions.

As indicated hereinbefore the above reactions are believed theoretically possible and are presented to explain as nearly as possible the nature of the new compositions of matter of the present invention. However, it is to be understood that such reactions are probably over simplified. For example, it will be noted that the double bonds present in the magnesium oleate dihydrate are susceptible to oxidation when the compound is treated under the hydroxylation conditions. As a result of this, it is probable that at least minute quantities of epoxides, aldehydes, ketones, acids and peroxides are formed during this process. Likewise, it is conceivable that under certain circumstances the molecule may rupture across the double bond to form a number of individual chemical entities from what appears to be a simple starting material. Furthermore, in the processes of oxidation and cleavage and under the conditions of the hydroxylation process the environment appears favorable for the formation of a number of coordination complexes and the like. In short, it appears that both the nature of the hydroxylation process and the nature of the partially hydroxylated hydrate of magnesium oleate so formed are of an extremely complex nature, and, therefore, defy more precise definition. The

specific examples presenting experimental data which appear hereinafter will further indicate the complexity of the processes and products of the present invention.

The fact that the hydroxylation of polyvalent metallic salts of monobasic acids capable of forming hydrates is of a complex nature is further evidenced by considering in somewhat greater detail the nature of the partially hydroxylated hydrates so formed. For example, referring again to the illustrative material, magnesium oleate, it was found that, in general, the partially hydroxylated hydrate of magnesium oleate exists either as a loosely bonded coordination complex or as a mixture or agglomeration of diverse components formed during the hydroxylation reaction. As an indication of this fact it has been found that the material can be treated with organic solvents such as, for example, ketones, aldehydes and the like with the resulting formation of and/or separation into two distinct phases. That is to say, on extracting the partially hydroxylated hydrate of magnesium oleate with acetone it was found that a portion of the material re- 75 mained insoluble whereas the remainder of the material synapse was readily soluble. On vaporizing the solvent subsequent'to the separation, a yellow liquid was obtained whereas the insoluble portion remained as a free flowing white powder. A further discussion regarding the nature of these materials will be presented hereinafter.

To further understand the nature of the present invention reference is made to the following specific examples wherein all parts and percentages are by weight.

EXAMPLE I Magnesium oleate dihydrate.-To 500 parts of water was added 11 parts of magnesium chloride and to 500'p'arts of water was added 15 parts of sodium oleate. The resulting homogeneous solutions were mixed in a reaction vessel while stirring. It was found that a white crystalline precipitate was formed which, after filtration and air drying, remained as a free flowing powder. Analysis of'the precipitate so formed disclosed the presence of 3.87 percent of magnesium whereas the formula requires 3.90 percent of magnesium. Upon subjecting the material to X-ray diifractio'n studies a sharp line pattern resulted with lines at :3.0, 4.10, 6.10, 10.0, 15.95, 18.10, 19.90, 20.35, and 21.90 degrees. The magnesium oleate dihydrate prepared as described above exhibited a vapor pressure of'8 mm. at 22 C.

EXAMPLE II Anhydrous magnesium oleate;---To 40 parts of the magnesium oleate dihydrate as prepared in Example I was added 270 parts of benzene. The resulting composition was then placed in an all-glass vacuum apparatus and subjected to a'zeo'tropi'c distillation by evaporation under vacuum. In contrast with the crystalline appearance of the magnesium oleate dihydrate the anhydrous material wasa tacky yellow glass. 6n subjecting this'rnaterial to magnesium analysis, it was found that there was 4112 percent of magnesium present. The formula M'g(C1sI I3sO2)z requires 4.14 percent of magnesium. X-ray diffraction studies of the material showed a broad diifuse band between 18 and 22.

EXAMPLE III Partially h ydroxylated hydrate 0 magnesium0leate. Approximately 100 parts of magnesium oleate-dihydrate as prepared in Example I was placed in a glass: container in contact with the atmosphere while maintaining the temperature in the order of between about 20 and C. for a period of sixteen months. Under these conditions it was found that the material had changed from an odorless, free-flowing powder to a waxy material possessing a characteristic odor.

As indicated previously the partially -hydroxylated hydrates formed in accordance-with the present invention appear to be either loosely bonded coordination complexes or are aggregates of materials formed during the hydroxylation reaction. A further study of the materials termed herein as partially 'hydroxylated hydrates was made using the material prepared inExample III. The results of this study are .presented'in Example IV.

EXAMPLE IV Too 500 milliliter Jena funnel was added 30 parts of the material prepared in Example III. The material was then extracted with approximately 100 parts of acetone and the extract separated from the insoluble residue. The liquid extract was then evaporated resulting in the formation of 9.9 parts of a yellow liquid amounting to about 33 percent of theoriginal material. The acetone insoluble portion amounting to 20.4 parts or 68 percent of 'the starting material remained as a free-fiowing'white powder. .X-ray diffraction patterns showed only a broad diifus'e band from about 20:15 to 22. Both portions of the material obtained by the above treatment wefesiib- 6 jected' to analyses, the results of: which are shown in Represents about 1% perperoxide Olliter). xide Magnesium (percent) Acetone-insoluble residue:

Magnesium (percent) Eleetrometrie titration (0H as percent Mg(OH) o 0. 16 Represents 4% magnesium oleate.

Mg oleate dihydrate 3.87.

From the results of the experiments described in Example IV it is evident that the partially, hydroxylated hydrates represent either a complex coordination compound or an aggregation of a number of complex reaction products. Likewise, it'isapparent from the data represented supra that the equilibria of the illustrative hypothetical reactions presented hereinbefore find support in the experimental work. That is, the compound as partially hydroxylated hydrate of magnesium oleate contains at most 5.32 percent of magnesium whereas the dihydrate and the theoretical. end product represented by III re.- quire respectively 3.90 and 7.18' percent of magnesium. Similarly, reference to Table I indicates the presence of about .1 percent of peroxide oxygen which is in conform itwith. the preceding considerations regarding the susceptibility of the double bonds to undergo a number of complex oxidation reactions when the hydrated polyvalent metallic derivatives of monobasic unsaturated acids are, subjected to hydroxylation conditions.

The. hydroxylation reaction described above with reference to the dihydrate of magnesium oleate occurs with other polyvalent metallic materialsderived from mono basic acids. capable of forming hydrates, as well as with otherrnagnesium containing monobasic acid compounds. For example, upon subjecting the hydrate of zinc ricinoleate tohydroxylation conditions, that is, upon subjecting this material to a temperature of between about 20 and about 30 C. fora period of about six months or longer the transformation herein defined as partial hydroxylation occurs. That is to say, the material apparentlyundergoes a complex partial hydroxylation reaction whereby the resulting-material contains asubstantially greater percentage of. .zinc than the starting material,.yetdoes not contain the theoretical amount requiredby the end productwhich. can be represented by the formula Similarly, by subjectingthe"hydratesfofaluminum-linoleateandcalcium undecylenate to temperatures between about 20 C. and 50 C. for extended periods of time of partial hydroxylation reaction occurs with the concomitant effects indicated above.. Furthermore, upon treating the partially hydroxylate'd hydrates of zinc ricinoleate, aluminum linoleate andcalcium undecylenate-witha solvent such as acetone partition products are obtained. That is to. say, ineac'hof the aforementioned cases. treatment with acetone'yields a liquid phase possessing acidic properties which contains only minor proportions of the metals zinc, aluminum andca'lcium respectively. The insoluble products remaining after the acetone treatment, on the other hand, are free-flowing substances having a characteristic crystalline appearance. Similar considerations apply to the other materials within thecontemplation of the present invention.

It has been indicated previously that the existence of the different forms of the polyvalent metallic salts of monobasic acids is of considerable importance in both corrosion and halogen loss prevention. Likewise, this is undoubtedly due to the solubility and phase distribution characteristics of these differing forms. For example, it has been found that, in general, the anhydrous materials, that is, the polyvalent metallic salts of monobasic acids are extremely soluble in hydrocarbons such as gasoline and the like. Likewise, the hydrates of such materials possess the characteristics of being readily soluble in such hydrocarbon material, although in general, the coordination or incorporation of the Water of hydration tends to decrease the solubility to some extent. In contrast with this, it has been found that the partially hydroxylated hydrates derived from the hydrated material by subjecting the same to hydroxylation conditions results in a material which has a rather low solubility in hydrocarbon fuel. This discovery is particularly intercst ing in view of the fact that when this loosely bonded coordination complex or aggregation of individual chemical entities is treated with a material such as, for example, acetone as described hereinbefore one portion of the material so obtained appears readily soluble in fuel whereas the residue is practically insoluble. The generalities just presented regarding the solubility of the differing physical and chemical forms of the polyvalent metallic derivatives of monobasic acids likewise applies in the case of fuel in contact with considerable quantities of water. That is to say, the anhydrous, hydrate and partially bydroxylated hydrate of these polyvalent metallic salts possess respectively high, medium and low solubility in the fuel. Inasmuch as all of these materials are generally only sparingly soluble in water it' is manifest that the partially hydroxylated hydrates therefore tend to collect at the liquid-liquid interface and for this reason are particularly applicable as corrosion inhibitors- By the same token the insoluble residue obtained by the extraction of the partially hydroxylated hydrates possesses the proper phase distribution characteristics such that it too is an effective material for this purpose. To more clearly illustrate the preceding discussion a large number of experiments were run on both the solubility characteristics of the several forms of the polyvalent metallic monobasic acid derivatives and the effect of each upon corrosion and halogen loss prevention.

In order to study the distribution of the illustrative material, magnesium oleate, at low concentration levels in gasoline-water systems, storage tests were carried out in which the samples were stored either in two-liter glass stoppered bottles or in two-litered cans of cold rolled steel made with welded seams. The samples consisted of 1,000 milliliters of a commercially available hydrocarbon fuel with 100 milliliters of water and the desired amounts of the diverse chemical forms of magnesium oleate. The samples were stored at room temperature and at convenient intervals milliliter samples of the gasoline phase were removed and subjected to spectographic analyses. The results of the bottle storage tests are presented in Table II and those of the steel can tests are shown in GASOLINE AND WATER (GLASS) [Magnesium concentrations are shown as lbs. Mg oleate/1000 bbl.]

Table III DISTRIBUTION OF NIAGNESIULM OLEATE BETWEEN GASOLINE AND WATER (STEEL) [ldagncsium concentrations are shown as lbs. Mg oleate i000 bbl.]

1 This sample was shaken daily throughout the test period whereas the other samples were not.

In order to determine the effectiveness of the different forms of magnesium oleate as a corrosion inhibitor recourse was made to the following type of storage tests. A large number of samples was prepared by blending different quantities of the different forms of magnesium oleate with commercially available fuels of diverse compositions. In some instances these fuels had been previously treated with tetraethyllead as an antiknock fluid comprising either tetraethyllead, 0.5 theory of bromine as ethylene dibrornide and 1.0 theory of chlorine as ethylene dichloride, or tetraethyllead, and 1.0 theory of bromine as ethylene dibromide such that the fuel contained respectively 3.0 or 4.6 milliliters of tetraethyllead per gallon. Upon agitating the treated or untreated fuels with the magnesium oleates, in each instance a homogeneous fuel blendwas obtained which was then stored in half filled glass bottles each containing 5 or 10 percent of water by volume and a weighed strip of cold rolled steel, the dimensions of which were 1.6 x 20 cm. Control tests to establish base lines were run with both leaded and unleaded fuel which did not contain any magnesium oleate derivative. The samples so prepared were stored for a period of two months at 110 F. and at the completion of this period the steep strips were cleaned and reweighed to determine the loss of corroded materials. Likewise, representative samples of fuel were analyzed for total bromine content to determine the amount of halogen loss. The results of these tests are shown in Table IV. For convenience the different forms of magnesium oleate are represented in this table as follows: magnesium oleate dihydrate, II, and partially hydroxylated hydrate of magnesium oleate III.

Table IV SIMULATED BULK STORAGE TESTS [Storage conditions: 2 mo. at 110 F., outage, 10 vol. percent water,

steel strips (1.6 x 20 cm.).]

Corrosion Inhibitor TEL Corrosion Br loss, Test No. mL/gal. loss, mg. percent Kind lb./l,000

bbl.

3 III 14 3 III 14 Mg oleate in sample Mg content of gasoline Description Cohen. 1 wk. 3 wk. 7 wk. 18 wk.

Anhydrous 24 12.2 2. 9 2. 5 0. 5 Dihydrate 28 0. 4 1. 8 l. 3 0.8 Partially Hydroxylated Hydrate 31 1. 2 0 6 0. 5 0.7

The data shown in Table IV indicate that, in general, the hydrates of polyvalent metallic salts of monobasic acid compounds are moderately effective as corrosion inhibitors for both treated and untreated fuels, that is, leaded or unleaded fuels. It will be noted, however, that the partially hydroxylated hydrates of polyvalent metallic monobasic acids are especially effective in this regard.

A closer study of the partially hydroxylated hydrate of magnesium oleate was conducted to determine its efiectiveness on corrosion. In addition both the acetone extract and insoluble residue obtained from this material were tested for this activity. The tests utilized were essentially identical with those described in accordance with the data presented in Table IV with the exception that the period of storage was one month at 110 F. The effectiveness of a number of closer related materials was likewise determined for comparative purposes. The data of these tests are shown in Table V.

Table V SIMULATED BULK sronnon 'rns'rs Storage conditions: 1 mo. at 110 F., 50% outage, vol. percent water, steel strips (1.6 x 20 cm.).]

The results of the test Nos. 15, 16, and 17 shown in Table V are particularly interesting. It can be seen that the partially hydroxylated hydrate of magnesium oleate completely eliminated corrosion loss and that the insoluble residue obtained by extracting such material with acetone was also extremely effective. In contrast, however, the acetone soluble extract of the partially hydroxylated magnesium oleate, although utilizable as a corrosion inhibitor, was not as eifective as the other materials. Thus, it would appear that the loosely bonded coordination complex or aggregation of chemical entities termed herein as the partially hydroxylated hydrate of magnesium oleate possesses synergistic corrosion inhibition qualities. That is to say, the eflfectiveness of the acetone extract and the acetone residue would indicate that the sum total of these materials would be an effective corrosion inhibitor, but would not appear to indicate that the partially hydroxylated hydrate would possess the extreme potency as indicated in test No. 15.

From the foregoing it is evident that beneficial effects with regard to both corrosion prevention and halogen loss prevention can be obtained by blending with hydrocarbon fuels especially those containing or likely to contain water, hydrates of polyvalent metallic monobasic acid compounds, partially hydroxylated hydrates derived from such compounds by subjecting them to hydroxylation conditions and the materials obtained from the latter by treatment with an organic solvent such as an aldehyde, a ketone and the like. However, because of their greater effectiveness the partially hydroxylated hydrates and the insoluble residue obtained therefrom by extraction with such solvents are preferred.

Although the major portion of the discussion heretofore has been concerned primarily with the several physical and chemical forms of magnesium oleate it is again to be indicated that this invention is applicable to the corresponding materials derived from polyvalent metallic materials derived from monobasic acids capable of forming hydrates. Thus, similar efiects on both corrosion and halogen loss can be obtained by blending with hydrocarbon fuels the hydrates, partially hydroxylated hydrates and solvent extracts and residues of such materials as magnesium elaidate, magnesium ricinoleate, magnesium stearate, magnesium laurate, magnesium isooleate, magnesium palmitate, magnesium linoleate, zinc naphthenate, thorium naphthenate, lead naphthenate, vanadyl naphthenate, aluminum oleate, lead oleate, vanadyl oleate, aluminum stearate, aluminum ricinoleate,

1O 1 aluminum elaidate, aluminum nervonate, aluminum undecylenate, lead margarate, aluminum elaeastearate; lead erucate, vanadyl elaeomargarate, zinc palmitate, vanadyl capronate, thorium laurate, thorium capronate, thorium caprylate, and the like.

In accordance with the present invention fuels are improved by adding from about one to about fifty pounds per thousand barrels of a hydrated polyvalent monobasic acid derivative, that is, a member selected from the class consisting of hydrates of polyvalent metallic salts of monobasic acids, partially hydroxyla'ted hydrates of polyvalent metallic monobasic acids, organic solvent extracts of partially hydroxylated hydrates of polyvalent metallic mom obasic a'cid materials and organic solvent residues of polyvalent metallic monobasic acid materials. As indicated previously, it is preferred to utilize partially, hy-' droxylated hydrates of polyvalent metallic monobasic acids and organic solvent residues of partially hydroxylated hydrates of polyvalent' metallic monobasic acid ma terials as corrosion inhibitors and halogen loss preventa tives'. Variations in such employment include introducing the requisite quantity of such materials into storage tanks, drums, and the like prior to theintroduction of fuel for storage. Similarly, such'material can be added directly to the fuel, preferably subsequent to conventional refinery operations such as blending. Thus, in general, the materials utilizedas corrosion inhibitors and halogen loss'preventatives in accordance with the present invention can be placed in contact with fuel at any time prior to or during storage or shipment of the fuel.

As indicated from the experimental data presented hereinbefore corrosion and halogen loss are problems attendant with the storage, shipment and usage of both leaded and unleaded fuel. It has thus been demonstrated that the materials used in accordance with the present invention as corrosion and halogen loss preventatives can be utilized with both leaded and unleaded hydrocarbon fuels. Therefore, the stabilizers of the present invention can be successfully utilized in combination with organolead antiknock agents and organolead-containing compositions such as antiknock fluids containing diverse halogen scavengers. Similarly, beneficial results are to be obtained by employing such stabilizers in combination with fuels containing other heavy metal derivatives frequently used as antiknock agents such as iron carbonyl, and the like. Moreover, particular benefits are to be derived by incorporating in the protected compositions of the present invention conventional amounts of organic dyes, antioxidants and, indeed, other fuel adjuvants employed for the obviation of other secondary problems.

Having described the nature of the present invention, the need therefor, and a number of embodiments which can be utilized to eifect especially beneficial results, it is not intended that the present invention be limited except within the spirit and scope of the appended claims.

Iclaim:

1. As a new composition of matter, a partially hydroxylated hydrate of a metallic monobasic acid compound prepared by subjecting a hydrated monobasic acid salt of a polyvalent metal selected from the group consisting of magnesium, zinc, thorium, calcium, aluminum, lead and vanadium, said acid being a monobasic straight chain unsaturated acid containing from about 10 to 30 carbon atoms per molecule, to a temperature between about 25 and about 50 C. for a period sufficient to bring about a change in chemical composition of said salt, said change being an increase in the Weight percent of said metal in said compound over the weight percent of said metal in said salt, said increase being insufiicient to satisfy the weigh-t percentage of said metal theoretically required by the corresponding basic metal salt.

2. As a new composition of matter, a partially hydroxylated hydrate of a magnesium monobasic acid compound prepared by subjecting a hydrated monobasic straight chain unsaturated acid salt of magnesium, said acid containing from about 10 to about 30 carbon atoms per molecule, to a temperature between about 25 and 50 C. for a period sufficient to bring about a change in chemical composition of said salt, said change being an increase in the weight percent of magnesium in said compound over the weight percent of magnesium in salt, said increase being insufficient to satisfy the weight percentage of magnesium theoretically required by the corresponding basic magnesium salt.

3. As a new composition of matter, the acetone extract of the composition of claim 2.

4. As a new composition of matter, the residue remaining after extraction with acetone of the composition of claim 2.

5. As a new composition of matter, a partially bydroxylated hydrate of magnesium oleate prepared by subjecting a magnesium oleate dihydrate to a temperature between about 25 and about 50 C. for a period sufficient to bring about a change in chemical composition of said dihydrate, said change being an increase in the weight percent of magnesium in said partially hydroxylated hydrate over the Weight percent of magnesium in said dihydrate, said increase being insufficient to satisfy the Weight percentage of magnesium theoretically required by the basic hydrate of magnesium oleate.

6. As a new composition of matter, the acetone extract of the composition of claim 5.

7. As a new composition of matter, the residue remaining after extraction with acetone of the composition of claim 5.

8. Gasoline normally in contact with water containing, in amount sufiicient to inhibit corrosion, the composition of Claim 1.

9. Gasoline normally in contact with water containing, in amount sufficient to inhibit corrosion, the composition of claim 2.

10. Leaded gasoline normally in contact with water containing, in amount sufiicient to inhibit corrosion and bromine loss, the composition of claim 1.

11. Leaded gasoline normally in contact with water containing, in amount sufiicient to inhibit corrosion and bromine loss, the composition of claim 2.

12. As a new composition of matter, an acetone extract of the composition of claim 1.

13. As a new composition of matter, the residue remaining after acetone extract of the composition of claim 1.

References Cited in the file of this patent UNITED STATES PATENTS Schiller Nov. 27, 1945 Stewart Dec. 17, 1946 OTHER REFERENCES

Claims (2)

1. AS A NEW COMPOSITION OF MATER, A PARTIALLY HYDROXYLATED HYDRATE OF A METALLIC MONOBASIC ACID COMPPOUND PREPARED BY SUBJECTING A HYDRATED MONOBASIC ACID SALT OF A POLYVALENT METAL SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM, ZINC, THORIUM, CALCIUM, ALUMINUM, LEAD AND VANADIUM, SAID ACID BEING A MONOBASIC STRAIGHT CHAIN UNSATURATED ACID CONTAINING FROM ABOUT 10 TO 30 CARBON ATOMS PER MOLECULSE, TO A TEMPERATURE BETWEEN ABOUT 25 AND ABOUT 50* C. FOR A PERIOD SUFFICIENT TO BRING ABOUT A CHANGE IN CHEMICAL COMPOSITION OF SAID SALT, SAID CHANGE BEING AN INCREASE IN THE WEIGHT PERCENT OF SAID METAL IN SAID COMPOUND OVER THE WEIGHT PERCENT OF SAID METAL IN SAID SALT, SAID INCREASE BEING INSUFFICIENT TO SATISFY THE WEIGHT PRECENTAGE OF SAID METAL THEORETICALLY REQUIRED BY THE CORRESPONDING BASIC METAL SALT.

10. LEADED GASOLINE NORMALLY IN CONTACT WITH WATER CONTAINING, IN AMOUNT SUFFICIENT TO INHIBIT CORROSION AND BROMINE LOSS, THE COMPOSITION OF CLAIM 1.