US3782911A - High octane gasoline components - Google Patents

Abstract

ADDITIVES FOR INCREASING THE OCTANE RATING OF GASOLINE MAY BE OBTAINED FRON C1-6 ALDEHYDES OR C3-6 KETONES BY CONVERTING THEM INTO HIGHER MOLECULAR WEIGHT UNSATURATED CORBOYYL COMPOUNDS FOLOWED BY PARTIAL ISOMERIZATION OF THE DOUBLE BOND AND OR PARTIAL ISOMZATION OF FROM A FURAN RING. THESE STEPS PROVIDE A MIXTURE OF COMPOUNDS WHICH NEED NOT BE SEPARATED INTO THEIR PURE COMPONENTS AMD WHICH POSSESS A HIGHER BVON THAN THE STARTING MATERIAL.

Description

United States Patent M 3,782,911 HIGH OCTANE GASOLINE COMPONENTS David M. Hoiiman, Wilmington, Del., assignor to Sun Research and Development Co., Philadelphia, Pat. No Drawing. Filed Oct. 26, 1971, Ser. No. 192,328 Int. Cl. Cl N22 US. Cl. 44-63 3 Claims ABSTRACT OF THE DISCLOSURE Additives for increasing the octane rating of gasoline may be obtained from C aldehydes or C ketones by converting them into higher molecular weight unsaturated carbonyl compounds followed by partial isomerization of the double bond and/or partial dehydrocyclization to form a furan ring. These steps provide a mixture of compounds which need not be separated into their pure components and which possess a higher BVON than the starting material.

BACKGROUND OF THE INVENTION This invention relates to the preparation of additives for gasoline which increase its octane rating and fuel compositions containing the same. More particularly, this invention relates to the condensation of C aldehydes or C ketones with aldehydes or ketones followed by catalytic isomerization of the resulting double bond and/ or dehydrocyclization to form furan structures which have a higher BVON than the corresponding starting materials. The gasoline composition to which this invention is likewise directed is comprised of known hydrocarbon components to which the reaction products of this process have been added.

In addition to the known hydrocarbon components of gasoline, many materials containing atoms other than carbon and hydrogen can be useful as automotive fuel components. A large variety of compounds have sufficiently high blending value octane numbers (BVON) that their presence in gasoline is desirable provided the cost of production or some property of the compounds did not prohibit their use.

Although blending values are most often determined on pure components, particularly when considering nonhydrocarbon compounds, it has been determined that it is not necessary that additives of high purity be introduced into gasoline in order to improve its performance. A process which converts one high octane component either wholly or partially into one or more components of even higher blending value can thus be of value even though isolation of the higher octane component may not be economical.

SUMMARY OF THE INVENTION It has now been found, in accordance with the present invention, that when C aldehyde or C ketones are converted to their corresponding unsaturated carbonyl condensation derivatives, and thereafter isomerizcd and/ or dehydrocyclized, there is provided a gasoline additive composition having a higher BVON than do the corresponding starting aldehydes or ketones. The gasoline into which these additives are incorporated is thus provided with a higher octane rating. By gasoline is meant known hydrocarbon fuels used chiefly in internal combustion engines and which are in the general boiling range of from to 400 F.

DESCRIPTION OF THE INVENTION The process of this invention will now be described w1th part1cular reference to acetone as a typical ketone starting material. It will be understood by those skilled 3,782,91 1 Patented Jan. 1, 1974 in the art, however, that this process is similarly applicable to other ketones or aldehydes such as 2-butanone, 3- pentanone, propionaldehyde, butyraldehyde or the like.

Acetone may be dimerized in a known manner by contacting the acetone with an alkaline catalyst.

The resulting mesityl oxide, after recovery from the reaction mixture, may then conveniently be partially isomerizcd and oxydehydrocyclized to form a mixture comprising mesityl oxide, 4-rnethylpent-4-en-2-one, and the furan 2,4-dimethylfuran, which mixture has a higher BVON (blending value octane number) than does mesityl oxide alone. This mixture is advantageous not only in having a higher BVON, but also in that it may be added directly to the gasoline fuel as a mixture without the necessity of first separating and recovering any of the individual components thereof. Moreover, in the case of e.g. acetone, the product mixture desirably is much less water soluble than the acetone starting material.

The isomerization and oxydehydrocyclization of the mesityl oxide is conveniently achieved by passing it in the vapor phase with oxygen or air over an appropriate acidic oxydehydrocyclization catalyst, as for example, bismuth phosphomolybdate, or an acid-treated alumina, at temperatures of from about 400 to 600 C., and preferably 475 to 560 C. When bismuth phosphomolybdate is employed, it is desirable but not critical that the ratio of BizMo be in the range of about 1:1.

In a further embodiment of this process it has been found that when the mesityl oxide is contacted in the vapor phase with the catalyst and oxygen or air in the presence of water, the composition of the resulting mixture may be varied considerably by varying the temperature, the GHSV, and the amount of oxide, oxygen, and water employed (i.e. by varying the partial pressure of the feedstream components) in accordance with the parameters illustrated in Example II below. Thus, for example, the composition of the components of the mixture may be varied widely e.g. the amount of furan may range anywhere from about 3 to 50 weight percent depending upon the conditions used.

The resulting mixture of mesityl oxide, methylpentenone and dimethylfuran described above, when added to a typical gasoline blend in amounts of about 0.1 to 15 percent by volume of the gasoline, provides a significantly higher octane gasoline than that obtainable from mesityl oxide alone. Thus, for example, a composition comprising about percent mesityl oxide, 24 percent 4-methylpent-4-en-2-one, and 5 percent 2,4-dimethylfuran has, at a 5 percent level, a BVON of 115, measured by the Motor Method, as compared with a BVON of 108 for mesityl oxide alone.

The invention described herein will now be illustrated by the following examples.

Example 1 Mesityl oxide, combined with nitrogen (1:14 mole ratio) was passed over a bismuth phosphomolybdate catalyst contained in a 20 mm. diameter quartz tube at 475 C. and a total gas hourly space velocity (GHSV) of 13,000 (GHSV=volume of gas at STP/volume of cata lyst/hour). The effluent was condensed in a Dry Ice trap and analyzed 'by VPC. The liquid product contained 70% mesityl oxide, 24% 4-methylpent-4-en-2-one, 5% 2,4dimethylfuran and 1% unidentified material. This reaction material had a blending value octane number (BVON) by the Motor Method at a 5% level in a typical gasoline of 115, whereas the BVON of the starting mesityl oxide was 108 under the same condition.

Example II The composition of the reactor efiiuent is subject to various reaction conditions. The following examples illus- 3 trate how the inclusion of oxygen and Water in the reactant stream influences the product distribution and thus the composition of the gasoline additive. The catalyst is again bismuth phosphomolybdate.

TABLE I Product composition 1 (wt. percent) 02 E20 GHSV A B 0 I A=Mesity1 oxide; B=4-methy1pent-4-en-2-one; C=2,4-dimethy1 man.

2. An octane improving additive mixture for hydrocarbon fuels boiling in the gasoline range comprising mesityl oxide, 4-methylpent-4-en-2-one, and 2,4-dimethy1- furan.

3. A process of preparing an octane-improving additive mixture for hydrocarbon fuels boiling in the gasoline range which comprises dimerizing acetone in the presence of an alkaline catalyst, and thereafter contacting the resulting mesityl oxide with bismuth phosphomolybdate to form an additive mixture comprising mesityl oxide, 4-methylpent-4-en-2-one, and 2,4-dimethylfuran.

References Cited UNITED STATES PATENTS 2,321,311 6/1943 Mottlau et a1. 44-63 2,210,942 8/1940 Lipkin 44-77 2,599,089 6/1952 Castle et a1. 260346.1 R

DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner U.S. Cl. X.R. 4477; 252386