US2363331A

US2363331A - Method of making motor fuel

Info

Publication number: US2363331A
Application number: US356833A
Authority: US
Inventors: James Joseph Hidy
Original assignee: CLARENCE P BYRNES
Current assignee: CLARENCE P BYRNES
Priority date: 1940-09-14
Filing date: 1940-09-14
Publication date: 1944-11-21
Anticipated expiration: 1961-11-21

Description

. amphoteric oxides.

Patented Nov. 21, 1944 UNITED STATES;

METHOD OFMAKING MOTORYFUEL i Joseph m y James, Pittsburgh,'Pa assignor to Clarencel. Byrn'es, Pittsburgh; Pa.-, as--trus-- No Drawing Application September 14, 194%.

,. SerialNo. 356,833

9 Claims... (01. 136 511); l

-In..,a.-.number of patentssuch as United States- Patent Nos. 1,697,653..of.Jan. 1, 1929 (Reissue 18,522), 1,859,587, 1,948,817, 2,01'0,085,.2,010,086,

2,036,215, 2,054,571; 2,085,221, and. 2,085,499, I 1

have described processes for makingpartial oxidationproducts from aliphatic and naphthenic hydrocarbons, such as petroleum fractions, shale. oil, and oils from the low temperature distillation: of,.coal. In. such process, the vaporized. or finely dividedhyclrolcarbonis mixed with oxygen or an oxygen containinggas andpassed througha re-. action zone, preferably in contact witha catalyst, at atemperature below that of continuous self-:- sustained complete, combustion, and preferably below a red heat.

Th product when condensed. or absorbed and; recovered contains partialoxidationproducts in; a range from alcohols to oxygenated organic acids, including aldehydes, ketones, esters, ethers, lac. tones, etc. Many or all of these bodies are pres: ent in different molecular Weights.

.In thisstep of oxidation I prefer to proportion thevariable factors so that a large percentage of I alcohols is formed as disclosed in my US. Patents 1,7 9 0 @Qlfiiilii'l w th're t ely s a id; though this is not essential, In the oxidation step someacids are formedand there are some incisuch as chlorides, nitrates, and sulfates;- while with strong bases-they form; salts inwhich the aluminum functions as an acid forming with sodium and potassium their aluminates. I have also? found-that zinc chloride (especially when anhydrous) also" functions similarly as a dehyv and the fraction Within the gasoline or motor fuel;

'- range is separatedfrom other andheavier frac-,

dental reactions such as cracking, forming of un- I saturated hydrocarbonsor derivatives, aromatics,

ring body hydrocarbons to, some extent, ,de,-,

pending upon the ratios of the Variable factors inthe partial oxidation stepr I The. present, invention is based uponmy dis coye ies relative to formation of aromatics and I nap henes which I can obtain during cracking onlthelrmal v decomposition of V the product mixture [resulting from the oxidation step. These dis-.

, ies are that if certain dehydrating catalysts areemployedin the crackingstep; they act to eliminate the elements of Water (0H1 and H),

from remote pointsin the hydrocarbon chains,;

resulting, in the formation of material or large.

percentages. of ring compounds such as aromatics or,,naphthenes.in. the product. This changeis especially desirable in making motor fuels and is. enhanced by properly" adjustingthe thermal conditions .of -;catalytic cracking with catalysts of such a grouplor class. The preferable type-of oxide catalysts in such a class is that of inorganic 'In this type I have. found. thataluminumoxides are of high value, though oxidesof. zinc. or tin (or of some rare elements suchasigallium). may be used. Such amphotericl oxideshave thepropertiesof both acidic and basic oxides, since ;.with strong: acid they formisalts tions. This containshydrocarbons, some oxygen. corn-pounds, unsaturateds, and aromatic, and, naphthenic bodies. In carryin out my improved process for making motor fuels. of good or high octane rating, I preferably neutralize or saponify and absorb any acids present in the oxidation product, before cracking. However, thisis not essential and'may be omitted especially where vpartial oxidation of petroleum fractions in the vapor phase is. used and where the vapor exit stream from the oxidation chamber'ispassed on through the cracking unit or units. Catalytic cracking as herein disclosed may be carried out either in the liquid phase where the vapors from oxidation ,are con densed, or in the vapor phase orboth. In each case sufficient ring orv cyclic compounds ofthe naphthenic or aromatic types may be formed to impart material anti-detonating characteristics to the resulting motor fuels.

I will now: give some specific examples:

Example 1.--A portion of ordinary commercial cracked gasoline, oxidized by my Well known' vapor phase catalytic method ,disclosed in my United States patents before recited herein and containing different oxygen derivatives in. the

' range from alcohols through aldehydes to and including organic acids with similar derivatives of different molecular weights, was subjected to my vapor phase catalytic cracking step as follows:-

A smooth steel. tube 2 inches in diameterby 14.: inches long was mounted in a hot airbathwith:

i a thermocouplezin. a .we'll'in the tubeicentel. fort:

giving the vapor temperature. The tub was filled with catalyst balls about the size of grapes or about 1 centimeter in diameter made of 90% by weight of Bakers C. P. aluminum oxide ce- .mented by about by weight of bentonite Per cent by volume Olefines and oxidized bodies 31.4 Aromatic hydrocarbons 49 Naphthenic hydrocarbons 19.6 Saturated aliphatic hydrocarbons 0 Example 2.--A run similar to (1) above, was made with anhydrous zinc chloride as the catalyst and a temperature of 325 C. The yield of liquid product was 91% by volume, and its analysis showed:

Percent by volume Olefines and oxidized bodies 32.2 Aromatic hydrocarbons 24.8 Naphthenic hydrocarbons 23.8 Saturated aliphatic hydrocarbons 19.2

This again shows violent changes in this complex mixture with a different catalyst and with reactions like the above taking place at a relatively low temperature.

In both cases there was a great increase in the percentage of aromatic and naphthenes, due to the peculiar dehydrating effect of the catalyst, carrying such percentage beyond and preferably beyond and thus giving material anti-detonating characteristics thereto.

The desired reactions to give the result are probably of two kinds: the hydrogen on carbon atom remote from a carbon atom holding a hydroxyl group reacted with the hydroxyl group; and/or a similar reaction occurred between two remote hydroxyl groups. These are illustrated in the following equations:

in either or both cases ring compounds form to a sufficient extent to give the desired anti-knocking and high octane rating. The non-condensible vapors and gases from both oxidizing and cracking steps may be polymerized into gasoline, the gases from cracking may be recirculated through the cracking still to give nucleating" or alkylation as set forth in other of my copending applications, and many other changes may be made without departing from my invention. The catalytic cracking with my improved catalysts may be carried out in the vapor or liquid phase or both. The oxidation may be carried out in the liquid phase, though I prefer my vapor phase process.

I claim:

1. In the method of making motor fuel, the

steps comprising partially oxidizing a petroleum fraction in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, thereafter thermally decomposing at a temperature of at least about 325 C. a portion of the product containing hydrocarbons of greater carbon content than gasoline under superatmospheric pressure in the presence of a dehydrating catalyst capable of dehydrating the hydrocarbons under said thermal decomposing conditions to produce a fuel of lower average carbon content than said product and which contains cyclic bodies to a material amount, and then fractionating the cracked product to produce motor fuel.

2. In the method of making motor fuel, the steps comprising partially oxidizing a petroleum fraction containing a mixture of normally liquid hydrocarbons of different molecular weight from the group of aliphatic and naphthenic hydrocarbons in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, thereafter thermally decomposing at a temperature of at least about 325 C. a portion of the product containing hydrocarbons of greater carbon content than gasoline in the presence of a dehydrating catalyst capable of dehydrating the hydrocarbons under said thermal decomposing conditions to produce a fuel of lower average carbon content than said product and which contains cyclic bodies to a material amount, and then fractionating the cracked product to produce a motor fuel.

3. In the method of making motor fuel, the steps comprising partially oxidizing a petroleum fraction in the vapor phase at an elevated temperature in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, thereafter thermally decomposing at a temperature of at least about 325 C. a portion of the product containing hydrocarbons of greater carbon content than gasoline in the presence of a dehydrating catalyst capable of dehydrating the hydrocarbons under said thermal decomposin conditions to produce a fuel of lower average carbon content than said product and which contains cyclic bodies to a material amount, and then'fractionating the cracked product to produce a motor fuel.

4. In the method of making a motor fuel, the steps comprising partially oxidizing a petroleum fraction in the vapor phase 'at an elevated temperature inv the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, thereafter thermally decomposing at a temperature of at least about 325 C. a portion of the product containing hydrocarbons of greater carbon content than gasoline in the vapor phase in the presence of a dehydrating catalyst capable of dehydrating the hydrocarbons under said thermal decomposing conditions to produce a fuel of lower average carbon content than said product and which contains cyclic bodies to a material amount, and then fractionating the cracked product to produce motor fuel.

5. In the method of making motor fuel, the steps comprising partially oxidizing a petroleum fraction in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, thereafter thermally decomposing at a temperature of at least about 325 C. a portion of the product containing hydrocarbons of greater carbon content than gasoline under higher pressure in the presence of a dehydrating catalyst capable of dehydrating the hydro-carbons under said thermal decomposing conditions to produce a fuel of lower average carbon content than said product and which contains cyclic bodies to a material amount, and then fractionating the cracked product to produce motor fuel.

6. In the method of making a motor fuel, the

steps comprising partially oxidizing a petroleum fraction in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, and thereafter thermally decomposing the product at a temperature -a product containing a mixture of oxygen derivatives of' hydrocarbons of different molecular weights in the range from aliphatic alcohols to oxygenated organic acids, and thereafter 'thermally decomposing the product at a temperature of at least about 325 C. inthe presence of, a dehydrating catalyst from the group consisting of aluminum oxide and zinc chloride capable of dehydrating thehydrocarbons under the said thermal decomposing conditions.

8. In the method of making motor fuel, the steps comprising partially oxidizing apetroleum fraction in the presence of free oxygen to produce a product containing a mixture of oxygen derivativesof hydrocarbons of difierent molecular weights in the range from aliphatic alcohols to oxygenated organic acids, and thereafter thermally decomposing the product at a temperature of at least about 325 C. in the presence of a dehydrating catalyst capable of eliminating hydroxyl elements of water from remote points in the hydrocarbon chains to form ring compounds.

9.,In the method of making motor fuel, the steps comprising partially oxidizing a petroleum fraction in the presence of free oxygen to produce a product containing a mixture of oxygen derivatives of hydrocarbons of different molecular weights in the range from alcohols to oxygenated oxidation product and which contains a material proportion of cyclic bodies.

JOSEPH I-IIDY JAMES.