US2023372A - Motor fuel - Google Patents

Description

Patented Dec. 3, 1935 UNITED sTATEs 7 M'o roa FUEL Nicolaas Max, Amsterdam, Netherlands, assignor, by mesne assignments, to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application July 16, 1931, Serial No. I 551,297. In the Netherlands August 8, 1930 4 Claims."

My invention relates to a process for the manufacture of non-knocking fuels for internal combustion engines.

It is known that the so-calledknocking in the 5 motor cylinder can be avoided or reduced by admixing various substances with the motor fuel. By admixing these so-called antiknock agents it is possible to increase'the highest useful compression of the gas mixture obtained from the fuel.

It has now been found that non-knocking fuels can be obtained by adding to a motor fuel, such as benzine, a small quantity of a metal compound of the type cheaper than benzol for increasing the H. U. C. 15

R-;('J=QH X It has been found that the exhaust gases remain I free from poisonous components. in which X represents an OH or NHz group, R. In addition to the above-mentioned metal com-' represents any organic radical, and R represents pounds other substances, such as halogen comeither hydrogen or a member of a cyclic radical pounds, which prevent the segregation of metal 20 of whichR forms-a part.- on the valves of the engine, and/or other anti- The metal compounds in question, of which, knock agents may also be added to the motor fuel for instance, the copper'or the ferri compound at the same time. ofoxymethylene-camphor or the copper com- It is to be observed that the formula of the 5 pound of amino-methylene-acetone may be mencopper compound of oxy-methylenecamphor is tioned, comply with the requirements very imobtained by substitutingthe H of the OH group portant for antiknock agents, of volatility and in two molecules of oxy-methylenecamphor by a solubility in benzine and when added in very Cu, the formula thusbeing: V

CHP CH: H H 0112*- (3H:v HI oo-ou-o- =0 0 1 35 small quantities to the fuel have even an excep- In the case of amino-methyleneacetone tional antiknock effect. CH:OO=0NH:

In addition to being readily volatile and readily l l I 40 soluble in benzinethe metal salts of the oxy or H 7 amino-methylene compounds mentioned have a t e metal co po is deriveddrom e B1101" characteristic colour; for instance, ferrioxyform so that the formula is: methylene camphor, even'in dilute solution, has

a very intensive reddish-violet colour.- I

It is evident from the following examples what (L H high satisfactory results are obtained with the a compounds in question: 1. To a standard benzine having a H. U. C.' i 7' (highest useful compression) of 5.40 sufficient R copper salt of oxymethylene camphor is added to l give the liquid a Cu content of 0.05%. As a result of this admixture the H. U. 0., determined in the Ricardo engine, is increased to 5.72. When I so much is added that the Cu. content of the liq- CHCC=CNH: uid becomes 0.1%, the H. U. C. rises to 6.03. 55

2. To the same benzine as mentioned in Example 1 ferrisalt of oxymethylene camphor is added until the liquid contains 0.025% Fe. It is found that through this admixture the 'H. U. C. can be increased from 5.40 to 5.64. 5

3. To a benzine with a-H. U. C. of 5.40 copper salt of amino-methylene-acetone is added until the liquid contains 0.023% Cu. It is then found that this increases the H. U. C. to 5.69.

From these examples it is clear that the metal compounds mentioned increase the H. U. C. 'considerably.

. An important advantage of the metal compounds in question is that they are considerably In these formulas the dotted lines represent complex valences. Of course, another metal such as iron, nickel, cobalt and the like may be used in place of copper.

It is to be noted that the present invention provides a process for the manufacture of nonknocking motor fuels comprising adding to a motor fuel of a relatively small quantity of r a metal compound of an organic compound of the type RCC=CX t t 1'.

In this formula X represents an OH or NH: group, whilst R represents any organic radical, such as an alkylor aryl-group 'or the rest of a cyclic radical, of which both the carbon atom of the carbonyl group and the carbon atom linked to the oxyor aminomethylene group form a part, thus belonging to the type A satisfactory method of preparing oxymethylene camphor and aminomethylene acetone and metal compound thereof is as follows:

500 grams of alpha camphor are dissolved in 3 litres of toluol. The solution is heated to boiling point in a 5 litre-flask provided with a reflux cooler of large diameter, and then '70 grams of sodium are slowly added. When the sodium has practically totally disappeared the boiling solution is filtered and subsequently cooled with an ice-salt mixture. Then a quantity of amylformiate corresponding to the quantity of camphor, is added within 2 hours while vigorously shaking. The mixture is slowly brought to room temperature and kept at that temperature during one night. An equal volume of iced water is then added and the mixture shaken during minutes. All the Na-salt is thus dissolved in the water layer. The aqueous layer is then separated from the toluol layer, the former layer being washed several times with ether or benzol in order to eliminate all camphor and bomeol. The aqueous solution is filtered, and the filtrate cooled at 0 C.. whereafter an excess of 30% acetic acid is added while vigorously shaking the flask. Oxymethylene-camphor precipitates in white crystalline particles, which can be very easily drained. The crystals 'are washed with water and dried. 158 grams of oxy-methylene-camphor are thus obtained, which corresponds to a yield of 54% based on the quantity of Na-camphor.

The copper compound of oxy-methylene camphor can be produced as follows:

36 grams of oxy-methylene camphor (0.2 mol.) are dissolved in 100 ccs. of 2n KOH while heating.

To this solution an excess of Cu SO4-S01llti0ll is.

added. The granular precipitate is drained, washed with water and dried during 12 hours on a porous dish in vacuo over H2804. The product is powdered and dissolved in benzol, and the solution is filtered in order to eliminate impurities and evaporated on the water bath. The residue, which when powdered has a light green colour, is the Cucompound of oxy-methylene camphor.

The ferric compound is prepared in a similar manner from oxy-methylene camphor and FeCh in the presence of an excess of aqueous sodium acetate solution.

Amino-methylene acetone can be prepared by shaking 29 grams of the Na-compound of oxymethylene acetone with 50 cos. of absolute alcohol and 15 grams of pulverized NH4C1 during 12 hours, filtering the brown solution from the salts, evaporating the alcohol and distilling the residue in vacuo. Amino-methylene acetone passes over as a yellowish, oily liquid, which can be purified by redistillation.

' The copper compound of amino-methylene acetone is prepared in the same manner as indicated above for that of oxy-methylene camphor.

Of course, other methods of preparing the foregoing compounds which are described in the prior art, may be used.

What I claim is:

1. A gasoline type motor fuel containing a small amount sufllcient to impart non-knocking properties to said fuel of a metal compound of an organic compound of the type R-C=O 'CCHX in which the letter X represents an OH or NH: group, the letter R represents an oxygen-substituted hydrocarbon radical, and the letter R represents hydrogen or a member of the organic radical represented by the letter R.

2. A gasoline type motor fuel containing a smaJl amount of a heavy metal compound of an organic compound of the type in which X represents one member of the group consisting of 0H and NH2, R represents a hydrocarbon radical and R1 represents a member of the group consisting of hydrogen atom and a carbon atom of the radical R, said amount being sufficient to improve the anti-knock rating of the fuel.

3. A gasoline type motor fuel containing a small amount of a heavy metal compound of oxymethylene camphor, said amount being sufficient to improve the anti-knock rating of the fuel.

4. A gasoline type motor fuel containing a small amount of a heavy metal compound of aminomethylene acetone, said amount being sufficient to improve the anti-knock rating of the fuel.