US3260745A - N-t-alkyl-beta-amino propionic acids - Google Patents

Description

United States Patent O 3,260,745 N-t-ALKYL-BETA-AMINO PROPIONIC ACIDS Harry J. Andress, Jr., Pitman, and Paul Y. C. Gee, Woodbury, Ni, assignors to Socony Mobil Oil Company, Inc., a corporation of New York N Drawing. Original application Apr. 18, 1962, Ser. No. 188,564. Divided and this application June 25, 1964, Ser. No. 378,035

2 Claims. (Cl. 260-534) This application is a division of our copending application Serial No. 188,564 filed April 18, 1962, now abancloned.

This invention relates to the improvement of nonlubricating petroleum fractions such as distillate fuel oils containing additives adapted to inhibit the appearance of sediment during prolonged storage periods, to prevent screen-clogging, to prevent rusting of ferrous metal surfaces and, additionally to inhibit the fuel oils against objectionable emulsification.

It is well known that fuel oils are prone to form sludge or sediment during periods of prolonged storage. This sediment, of course, has an adverse effect on burner operation, because it has a tendency to clog screens and nozzles. In addition to sediment formed during storage, most fuel oils contain other impurities, such as rust, dirt, and entrained water. The sediment and impurities tend to settle out on equipment parts, such as nozzles, screens, filters, etc., thereby clogging them and causing the equipment to fail, Still further, petroleum distillate fuel oils have a tendency to form objectionable emulsions.

A factor, incident to the storage and handling of distillate fuels, i.e., gasoline and fuel oils, is the breathing of storage vessels. This results in the accumulation of considerable amounts of Water in the tanks, which presents a problem of rusting in the tanks. Then, when the fuel is removed for transportation, sufficient water may be carried along to cause rusting of ferrous metal surfaces in pipelines, tankers, and the like.

Generally, in the case of fuel oils, it has been the practice to overcome the aforedescribed difiiculties with a separate additive for each purpose, i.e., with a sediment inhibitor, an antiscreen clogging agent, an antirust agent, and emulsion inhibitor. The use of several additives, however, gives rise to problems of additive compatibility, thus restricting the choice of additive combinations. In addition, of course, the use of a plurality of additives unduly increases the cost of the fuel.

It has now been found that all of the aforesaid problems, i.e., sedimentation, screen clogging, rusting, and emulsification can be solved by the use of a single fuel oil addition agent. It has been discovered that a distillate fuel oil containing minor amounts of certain nitrogencontaining compounds is effectively inhibited, simultaneously, against all of the aforementioned difficulties.

Accordingly, it is a broad object of this invention to provide a distillate fuel oil having improved properties. Another object is to provide a fuel oil having a single additive adapted to inhibit sedimentation, to prevent screen clogging, to prevent rusting of ferrous metal surfaces with which it comes in contact, and to inhibit emulsification. A specific object is to provide a distillate fuel that contains certain nitrogen-containing compounds that achieve these results. Other objects and advantages of this invention will become apparent to those skilled in the art from the following detailed description.

The present invention provides a distillate fuel containing between about 0.5 pound and about 200 pounds per 1000 barrels of fuel of a compound from the group consisting of:

(a) RNHCH CH COOH 3,260,745 Patented July 12, 1966 "ice and

( CHzOHzCOOH wherein R is an alkyl group containing from about four to about thirty carbon atoms and having a tertiary carbon atom attached to the nitrogen atom. Such compounds can be prepared, for example, by reacting one mole of glacial acrylic acid at from about 50 C. to about 200 C. with one mole of a primary alkyl amine containing from about four to about thirty carbon atoms, and having a tertiary carbon atom attached to the nitrogen atom to form compound (a); and by reacting two moles of glacial acrylic acid with one mole of such a primary alkyl amine at the stated temperatures to form compound (b).

Amines utilizable for forming the aforesaid products are alkyl amines having between about 4 to about 30 carbon atoms per molecule, or mixtures of such amines, in which the amino (NH group is attached to a tertiary carbon atom. These amines all contain the terminal p.

Non-limiting examples of such amine reactants are tbutyl primary amine, t-octyl primary amine, t-decyl primary amine, t-dodecyl primary amine, t-tetradecyl primary amine, t-octadecyl primary amine, t-eicosyl primary amine, t-docosyl primary amine, t-tetracosyl primary amine, and t-triacontyl primary amine. The amine reactants can be prepared in several ways well known to those skilled in the art. Specific methods of preparing the t-alkyl primary amines are disclosed in the Journal of Organic Chemistry, vol. 20, page 295 et seq. (1955). Mixtures of such amines can be made from a polyolefin fraction (e.g., polypropylene and polybutylene cuts) by first hydrating with sulfuric acid and water to the corresponding alcohol, converting the alcohol to alkyl chloride with dry hydrogen chloride, and finally condensing the chloride with ammonia, under pressure, to produce a t-alkyl primary amine mixture.

The distillate fuels that are improved in accordance with the present invention are distillate fuel oils that are hydrocarbon fractions having an initial boiling point of at least about F. and an end boiling point no higher than about 750 F., and boiling substantially continuously throughout their distillation range. Such fuel oils are generally known as distillate fuel oils. It is to be understood, however, that this term is not restricted to straightrun distillate fractions. The distillate fuel oils can be straight-run distillate fuel oils, catalytically or thermally cracked (including hydr-ocracked) distillate fuel oils, or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as, acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.

The distillate fuel oils are characterized by their relatively low viscosities, pour points, and the like. The principal property which characterizes the contemplated hydrocarbons, however, is the distillation range. As mentioned hereinbefore, this range will lie between about 100 F. and about 750 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range falling, nevertheless, within the above-specified limits. Likewise, each fuel oil with boil substantially continuously throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2, and 3 fuel oils used in heating and as diesel fuel oils, and the jet combustion fuels. The domestic fuel oils generally conform to the specifications set forth in ASTM Specifications D39648T. Specifications for diesel fuels are defined in ASTM Specifications D97548T. Typical jet fuels are defined in Military Specification MIL-F- 5624B.

The amount of the additive embodied for use herein that is added to the distillate fuel depend, of course, upon the intended purpose and the particular additive selected, as they are not equivalent in their activity. Some may have to be used in greater concentrations than others to be effective. In most cases, in which it is desired to obtain all of the aforesaid beneficial results in fuel oil, namely, to inhibit sedimentation, to reduce screen clogging, to prevent rusting of ferrous metal surfaces, and to inhibit emulsification, additive concentrations varying between pounds per thousand barrels of oil and about 200 pounds per thousand barrels of oil will be employed. It may not always be desired, however, to accomplish all of the aforementioned results. In such cases, where it is desired to effect only one or two of such results lower concentrations can be used. Thus, if it is desired only to prevent rust under dynamic conditions, as in a pipeline, it has been found that concentrations as low as about 2.5 p.p.m., i.e., about 0.5 pound of additive per thousaand barrels of oil, are effective, In general, therefore, the amount of the additive that can be added to the distillate fuel, in order to achive a beneficial result, will vary generally between about 0.5 pound per thousand barrels of oil and about 200 pounds per thousand barrels of oil. Preferably, it will vary between about 10 and about 200 pounds per thousand barrels of oil.

If it is desired, the distillate fuel compositions can contain other additives for the purpose of achieving other results. Thus, for example, there can be present foam inhibitors, ignition and burning quality improvers, and others. Examples of such additives are silicones, dinitro propane, amyl nitrate, metal sulfonates, and the like.

The following specific examples are for the purpose of illustrating the distillate fuel compositions of this invention, and of exemplifying the specific nature thereof. Included in such examples is the preparation of compounds embodied for use in practice of this invention, their use in fuel oils, and, for the purpose of comparison, the use of similar products but devoid of a tertiary-carbon atom group as aforediscussed. At is evident from the data set forth hereinafter, the products embodied for use herein markedly inhibit emulsification whereas similar condensation products devoid of the t-alkyl group provide fuel oils that emulsify severely. It is to be strictly understood, however, that this invention is not to be limted by the particular additives and fuels, or to the operations and manipulations described therein.

The amine reactants used in the following examples for reaction acrylic acid were as follows: Amine A is a mixture of primary amines having a carbon atom of a tertiary butyl group attached to the amino (-NH group and containing principally 18 to 24 carbon atoms, and marketed by Rohm & Haas Co. as Primene JMT; and Amine B is commercial oleyl amine.

EXAMPLE 1 A mixture of 303 grams (one mole) of Amine A and 72 grams (one mole) of glacial acrylic acid were stirred at 105 C. for about 2 hours and at 175 C. for about one hour to produce the N-tertiary .alkyl beta-amino propionic acid; i.e., the compound of Formula a.

EXAMPLE 2.

A mixture of 144 grams (two moles) of glacial acrylic acid and 303 grams (one mole) of Amine A, was stirred at 135 C. for about two hours and at 185 C. for one hour to produce the N-t-alkyl beta-amino dipropionic acid; i.e., the compound of Formula b.

4 EXAMPLE 3 A mixture of 72 grams (one mole) of glacial acrylic acid and 300 grams (1.0 mole) of oleylamine was stirred at 110 C. for about 4 hours to produce N-oleyl beta amine p-ropionic acid.

Sedimentation The test used to determine the sedimentation character istic of fuel oils is the 110 F. Storage Test. In this test, a SOC-milliliter sample of the fuel oil under test is placed in a convected oven maintained at 110 F. for a period of 12 weeks. Then, the sample is removed from the oven and cooled. The cooled sample is filtered through a tared asbestos filter (Gooch crucible) to remove insoluble matter. The Weight of such matter in milligrams is reported as the amount of sediment. A sample of the blank, unihibited oil is run along with a fuel oil blend under test. The effectiveness of a fuel oil containing an inhibitor is determined by comparing the weight of sediment formed in the inhibited oil with that formed in the uninhibited oil.

EXAMPLE 4 TABLE I Conan. of Sediment, Additive Additive, mg./liter lbs/1,000 bbls.

Base Fuel None None 13 Do Example 1 10 4 Example 2 10 9 Screen clogging The anti-screen clogging characteristics of a fuel oil were determined as follows: The test is conducted using a Sundstrand V3 or S1 home fuel oil burner pump with a self-contained -mesh Monel metal screen. About 0.05 percent, by weight, of naturally-formed fuel oil sediment, composed of fuel oil, water, dirt, rust, and organic sludge is mixed with 10 liters of the fuel oil. This mixture is circulated by the pump through the screen for 6 hours. Then, the sludge deposit on the screen is Washed off with normal pentane and filtered through a tared Gooch crucible. After drying, the material in Gooch crucible is washed with a 50-50 (volume) acetone-methanol mixture. The total organic sediment is obtained by evaporating the pentane and the acetone-methanol filtrates. Drying and weighing the Gooch crucible yields the amount of inorganic sediment. The sum of the organic and inorganic deposits on the screen can be reported in milligrams recovered or converted into percent screen clogging.

EXAMPLE 5 Using the test fuel oil described in Example 4, blends of the additives of Examples 1 and 2 in this fuel were prepared. Each blend was subjected to the Screen Clogging Test, as aforedescribed. Test results are set forth in Table II.

TABLE Ill-SCREEN CLO GGING Rust Test in fuel oil The rusting characteristics of fuel oils were determined in the Static Rust Test, which simulates conditions encountered in storage vessels, such as, the home fuel storage tank. In this test, a strip of 16-20 gauge sand blasted steel plate is placed in a clear quart bottle. The length of the strip is sufficient to reach from the bottom of the bottle into the neck of the bottle without interfering with the cap. One hundred cc. of synthetic sea water with pH adjusted to 5 (ASTM D-655) and 750 cc. of test oil are placed in the bottle. The bottle is capped tightly, shaken vigorously for one minute, and permitted to stand quietly at 80 F. for 21 days. At the end of that time the amount of rust that occurs on the surface of the plate immersed in the water is used as a measure of the effectiveness of the fuel to inhibit rusting in storage vessels. It is generally preferred that no more than 5 percent of the surface should be rusted. This test is much more severe than the ASTM Rust Test. Many compositions that pass the ASTM test fail in the Static Test.

pared. Each blend was subjected to the Static Rust Test. Pertinent data are set forth in Table III.

TABLE III.STATIC RUST TEST Inhibitor, Example No. Cone, lbs/1,000 bbls. Rusting, percent l 100 50 0 50 Trace 1 Heavy rust.

In reference to inhibiting emulsification, it has been found that products similar to those embodied for use herein but which do not contain a tertiary carbon atom group as aforedescribed do not inhibit emulsification whereas the products from the defined t-carbon atom containing products (Examples 1 and 2) markedly inhibit emulsification. To illustrate such a function performed by the additives useful for practice of this invention, the products of Examples 1 to 2 were individually blended with a distillate fuel oil in concentrations of 25, 50, and 100 lbs/thousands barrels of the fuel oil and subjected to the following emulsion test, said fuel oil comprising 60% catalytically cracked components and 40% straight run components and boiling in the range of 320-640 F.

Emulsion test The procedure for the fuel oil emulsion test is as follows: a 200 milliliter portion of the fuel to be tested and 20 milliliters of distilled water are placed in a clear glass pint bottle. The bottle is tightly capped and set in an Everbach mechanical shaker in a horizontal position such that the maximum degree of agitation is afforded. The shaker is run at its maximum setting for 5 minutes. The bottle is then removed, and allowed to stand in an upright position in the dark for 24 hours. At the end of the 24 hour settling period, the appearance of the water layer is noted. The fuel layer is siphoned off, care being taken not to disturb the oil-water interface, and is discarded. A fresh portion of the fuel oil being tested is then added. The described sequence of steps is repeated. If no emulsion appears in the water layer after this sequence has been performed ten times, the oil is considered to have passed the test. On the other hand, if, after any 24 hour settling period in the procedure, there is any degree of emulsification in the water layer, the fuel is considered to have failed the test. This test procedure has been found to provide emulsions in inhibited oils similar to emulsions which occur in these same oils only after prolonged periods of normal handling and storage in the field on a commercial basis.

RATING SCALE FOR REPORTING EMULSION TEST RESULTS Description of Emulsion Clean break on the interface of oil and water. No dirt, skin,

or bubbles present.

Very slight skin at the oil-water interface that usually does not break on tilting the bottle.

Skin at oil'water interface, heavier than #1 and usually accompanied with dirt and bubbles on the skin. No evidence of any white emulsion.

First sign of white emulsion. Usually forms at the bottom and in the center of the bottle. It is circular in shape and approximately 34 to 1 inch in diameter.

Approximately the same amount of emulsion on the bottom of the bottle as #3. However, emulsion is also beginning to form at oil-water interface and extends 142 to Me downward into the water layer. Roughly 15% of water layer occupied by emulsion.

Circular emulsion at bottom of bottle extends outward and upward resemblin spokes. Emulsion at the interface a little thicker than More emulsion than #5. Thin film of emulsion forming on sides of bottle surrounding the water layer. Water is still visible looking through the sides and looking up from the bottom of the bottle.

Emulsion on bottom of water layer is almost solid. Emulsion on sides of bottle is broken in a few spots enabling the operator to see the water layer.

Semi-solid emulsion with perforations or bubbles similar to a honeycomb. No water visible except that seen in the bubbles.

Same (inalllSiOll as #8 but with less bubbles. 7590% emulsion Almost completely solid emulsion with only a few air bubbles VlSl e. Completely solid emulsion (mayonnaise type).

The results obtained from the foregoing emulsion test were as follows:

Cone. of Additive lbs/1,000 bbls. Rating Base Fuel plus Example 1 Do Basalt) Fuel plus Example O Base Fuel plus Example It is apparent from the foregoing that the additives (Examples 1 and 2) embodied for use herein are markedly effective as emulsion inhibitors whereas corresponding additives (Example 3) but devoid of a t-carbon atom as aforediscussed resulted in severe emulsification.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

What is claimed is:

1. As a new chemical compound, adapted for use as addition agents for distillate fuel oils, a compound from the group consisting of:

(a) RNHCH CH COOH and C HzC HzC O O H C H20 H20 0 O H wherein R is an alkyl group containing from about 4 to about 30 carbon atoms and having a tertiary carbon atom attached to the nitrogen atom.

2. A compound, as defined in claim 1, wherein R contains from about 18 to about 24 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,787,640 4/ 1957 Strong 260-534 2,851,345 9/1958 Marsh 44-71 3,054,750 9/1962 Jolly 44-71 X LORRAINE A. WEINBERGER, Primary Examiner.

D. P. CLARKE, T. L. GALLOWAY,

Assistant Examiners.

Claims (1)

1. AS A NEW CHEMICAL COMPOUND, ADAPTED FOR USE AS ADDITION AGENTS FOR DISTILLATE FUEL OILS, A COMPOUND FROM THE GROUP CONSISTING OF-