BE552837A - - Google Patents

Description

       

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   The present invention relates to fuels used in internal combustion engines and which contain anti-knock products and to mixtures of anti-knock agents used to produce these fuels.



   It is known that an alkylated lead compound, generally tetraethyl lead, is used in fuels for internal combustion engines in order to increase the octane number.



   To prevent metal or metal oxide deposits from forming in the combustion chamber with the easily predictable consequences that this would entail, to the anti-knock agent, for example tetraethyl lead, halogen compounds such as ethylene dibromide and ethylene dichloride.



  These halogenated hydrocarbons are generally called "scavenging agents" and are intended to form volatile lead halides at the combustion temperature, which halides are in-

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 trailed with the gaseous products of combustion.



   In the compositions of anti-knock mixtures with an alkyl lead base for automobile engines, an amount of these halogenated hydrocarbons is generally used which is one and a half times the amount necessary to form a salt with the metallic lead, in order to be sure that no lead deposit can form in the combustion chamber, preferring to this drawback the possible risk of an excess of halogen.



   Halogenated hydrocarbons which have a vapor pressure not exceeding 100 to 120 mm of mercury at about 50 are suitable for this purpose. Halogenated hydrocarbons other than dibromide and ethylene dichloride can therefore be used.



   It has been observed in practice that, despite the precaution of adding to the anti-knock mixture based on pb alkyl a notable excess of halogen relative to the theoretical amount, the formation of lead oxyhalides and lead oxides (n PbO .PbAl2) in the combustion chamber with deposition of these halides cannot be entirely avoided. The deposit on the spark plugs with their consequence on the ignition, the corrosion of the exhaust valves, the need for a higher octane number for the engine, the formation and chipping of deposits are effects attributable to this default.



   The object of the present invention is to prevent gasoline containing lead from causing these drawbacks by providing other sweeping agents which are not the halides mentioned above and which have the effect of transforming lead into compounds of a pulverulent nature. extremely subdivided, unmelted and therefore easily entrained with the products of combustion.



   The scavenging compounds used according to the present invention are hydrogenated organic compounds of phosphorus, more specifically alkyl and aryl derivatives of phosphine.

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 and diphosphine and their halogenated derivatives. Typical examples of these products are: isoamylphosphine, octylphosphine, triethylphosphine, triisobutylphosphine, dimethylphenylphosphine, triphenylphosphine, triparatolylphosphine, phenylphosphine, dibenzylphosphine, phosphenyl chloride, and. p-chlorophenylphosphine.



   It has been observed that the aryl compounds exert a more advantageous action than the corresponding allcyl compounds.



   Halogenated derivatives are particularly suitable because they contain in their molecule halogens capable of supplying with lead volatile compounds of the type described, suitable for the removal of lead from the combustion chamber, and phosphorus which acts according to the present invention to form infusible compounds. For these reasons, the halogenated derivatives of the esters of oxyacids of phosphorus or of arsenic are particularly suitable.



   Corresponding compounds where the phosphorus atom is replaced by arsenic have been tested with success.



  But their use is reduced by the general toxicity of these derivatives. The new preparations can replace all or part of the halogenated hydrocarbon compounds and have the advantage of being able to be used in substantial excess without causing the risk of corrosion as was the case with the halogenated hydrocarbons.



   The compounds of the present invention can be mixed with the lead-containing gasoline either separately or together with the lead compounds and are not mutually exclusive. the use in gasoline of other adjuvants, antioxidants etc. commonly used. The use of the agents which are the object of the present invention does not cause the engine to require an increase in the octane number to maintain the absence of knocking, a requirement which arises when adopting the anti-knock mixtures. ordinary lead-based alkyls to prevent deposits from forming in the combustion zone.

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   Due to the different physical nature of the new lead compounds that are formed by the addition of these scavenging agents, compounds are obtained which are not fusible at the temperature of the medium in which they are formed and which do not adhere to metal surfaces. of the motor.



   Experiments were carried out by using mixtures containing once the theoretical amount of halide relative to lead (mixture 1 @ and by employing mixtures containing halides in quantity 1.5, T, and completely replacing these halides by the phosphorus coupos mentioned above.



   The tests are carried out on a Fiat 1100 cm3 actor with 4 cylinders with two carburetors, each of which feeds two cylinders.



  The engine runs for 50 hours in each test at a speed of 3000 rpm and under identical conditions with regard to temperature, pressure, air humidity, cooling water temperature, exhaust gas temperature, consolidation fuel, fuel / air ratio, fuel quality.



   In particular, gasoline having the following characteristics is used as fuel:
Density at 15 = 0.702
Negative corrosion
Initial distillation point = 34 C
End point of Distillation = 167 C
Residue 0.8
N.O. (B.M.) t.q. = 60.



  As the ethylation index, 0.8%, or 0.8 cm3 of tetraethyl lead per liter of gasoline, is used, an index which is greater than the normal which is 0.5 cm3 of tetraethyl lead.



  I TEST Cvindres 1 and 2 Ethyl gasoline at 0.8 with 1.5 T of adjuvant with bromide and ethylene chloride

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 deposit weight 4.05 g lead weight 2.22 g Lead / halogen ratio 40 g appearance of hard-melt deposit condition of spark plug tips poor condition of exhaust valves covered with hard, black, stubborn encrustation.



  Cylinders 3 and 4 Ethyl gasoline as for cylinders 1 and 2 with 0.3 times the theoretical quantity of phosphorus agent Weight of the deposit 2.41 g Weight of lead 0.88 g Lead / halogen ratio 32 g Appearance of the powder deposit, easily detachable Condition of spark plug tips good Condition of exhaust valves easily detachable powder II TEST Cylinders 1 and 2 0.8% ethyl gasoline with: active substance with ethylene bromide 1 T Weight of deposit 3.62 g Weight of lead 1.99 g Lead / halogen ratio .44 g Aspect of the hard-molten deposit Condition of the spark plug tips bad Condition of the exhaust valves Hard encrustation difficult to detach.



  Cylinders3 and 4 Ethyl gasoline at 0.8% but without halogen and with 1.20 times the theoretical quantity of phosphorus agent.



  Weight of the deposit 2.78 g Weight of the lead 1.07 g Lead / halogen ratio 21 g Condition of the spark plug tips good Appearance of the powder deposit which can be carried away Condition of the exhaust valves deposit easily detached by
 EMI5.1
 and hal ama 0'0

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In other tests it was noticed that the time necessary for the fouling of the candles with the addition of 0.3 times the theoretical amount of phosphorus compounds is approximately. 3 times longer than in the case where phosphorus is not present.



   Experiments carried out with the addition of agents
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 such as 2,6-di.-tertio-butyl-1 .-: - .; L1 ,, '1} h: 101, = -: oss.al::z.?paraminophenol, N, Na: - at;' :. (1r ir :: - 1:; Qtrl-) arap1: lényl-en0ia.tline, did not give results S? R2.1.i-I'L: ', slow different from the results indicated above .



   The experiences cited relate to mixtures
 EMI6.2
 anti-knock agents containing pioJib-tetraethyl! 'But the results are also good in the case of other antic1? toüQJ1.tr c lead-based agents, such as diethyl-di ::> 5thy "1 lead, t2trathy10 lead, lead tetraohenyl or based on others. ': /': '. 1.11: co' '.' '.. ie 13 fer' and 1-3 nickel carbonyl, C'y :: diethylhexanoate, ". '. [;. ;; 1s triethyl bismuth, tellurium, selenium or eadaiua. '. :: i0t: -:, / J ..:. = :, l'ttai.n tetraethyl etc ..



     The order in which the different agents are added
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 gasoline does not matter. In da'j.tr.3. ::::; ss, the phosphorus C (1) lJose which are the subject of the present invention can be added separately to gasoline or be incorporated into the fluid which. con
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 holds the tetraalkyl lead.



  DREAM: 1 DIGATI 0 II 1.- Own compositions k to be added to hydrocarbon-based carbons for internal combustion engines, characterized in that they include a mixture of agents <1j1 t-LQttO ': Wrl ts, horn lead alkyl or aryl and an organic compound hydra; = r3 phsophorus or arsenic more specifically an alkyl or aryl derivative of phosphine or arsine and their halogenated derivatives or mixtures of these compounds.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

2.- Own compositions. be added to hydrocarbon fuels for internal combustion engines, characterized in that they include a mixture of anti-knock agents suitable for <Desc / Clms Page number 7> lead alkyl or aryl and a halogen derivative of the oxy-acid esters of phosphorus or arsenic or mixtures thereof. compounds. 3. - Compositions according to claim 1, characterized in that the anti-knock agent is a mixture of lead alkyl or aryl or other metal, alkyl or aryl compounds, in which the lead is replaced by another metal such as tin, bismuth, selenium, tellurium etc., or other metallo-organic compounds such as iron and nickel carbonyl, cobalt 2-ethyl-hexanoate, derivatives of other metal salts of acids branched chain aliphatics etc. 4. Compositions according to claim 2, characterized in that the antiknock agent is a mixture of alkyl or aryl lead or other metal, alkyl or aryl compounds, in which another metal such as lead is used. tin, bismuth, selenium, tellurium, etc., or other metallo-organic compounds such as iron and nickel, carbonyl, cobalt 2-ethylhexanoate, derivatives of other metal salts of branched chain aliphatic acids etc. 5. - Composition according to claims 1,, 2, 3 and 4, where the anti-knock agent is tetraethyl lead. 6. - Composition according to either of the claims 1, 2, 3, 4 and 5, characterized in that it also contains an agent of the halogenated hydrocarbon type. 7. - Composition according to claims 1, 2, 3, 4, 5 and 6, characterized in that the agent of the halogenated hydrocarbon type is ethylene dibromide, ethylene dichloride or mixtures of these compounds. 8.- Composition according to claims 1 to 7, including, characterized in that it further contains dyes, stabilizing agents, solvents, oxidation inhibitors, corrosion inhibitors, anti-gum agents. , hydrocarbons and derivatives such as petroleum, benzine, benzol, naphthalene, chloronaphthalene, diphenylamine, 2,6-di- <Desc / Clms Page number 8> tertio-butyl-4-methylphenol, lecithin etc. 9. Fuel for internal combustion engines containing an anti-knock agent according to claims 1, 2, 3 and 4 and an amount of organic phosphorus or arsenic compounds derived from phosphine or alcohol and their halogenated derivatives or mixtures of these compounds. 10. - Fuel for internal combustion engines containing an amount of anti-knock agents according to claims 1, 2, 3 and 4 and an amount of halogenated derivatives of oxyacid esters of phosphorus or arsenic. 11. Fuel according to claims 9 and 10, characterized in that the anti-knock agent is leadtetraethyl. 12. - Fuel according to claims 9, 10 and 11, wherein the active compound is a hydrogen derivative of phosphorus or one of these halogenated derivatives or a halogenated derivative of an ester or an oxyacid of phosphorus. 13. - Fuel according to either of the preceding claims, characterized in that it contains an anti-knock agent with an agent of the halogenated hydrocarbon type. 14. A fuel according to the preceding claims, characterized in that the agent of the halogenated hydrocarbon type is ethylene dibromide, ethylene dichloride or a mixture of these compounds. 15.- Fuel according to either of the preceding claims, containing an anti-knock agent, a hydrogenated organic compound of phosphorus or arsenic, derivatives of phosphine or arsine and their halogen derivatives and chlorinated derivatives oxyacids of phosphorus or arsenic or their mixture, additionally containing dyes, stabilizers, solvents, oxidation inhibitors, corrosion inhibitors, antigum agents, hydrocarbons and derivatives, such as petroleum, benzine, benzol, naphthalene, chloronaphthalene, diphenylamine, 2,6-di-tertio-butyl-4-methylphenol, lecithin, <Desc / Clms Page number 9> 16. - Fuel according to any one of the preceding claims, containing an anti-knock agent, an active halogen compound, a hydrogenated organic compound of phosphorus or arsenic derived from phosphine or arsine and their derivatives EMI9.1 112],)? RJ'1I <; S and chlorinated oxyacid derivatives of phosphorus and arsenic and their mixture and which also contain dyes, stabilizers, solvents, oxidation inhibitors, inhibitors of corrosion, antigums, hydrocarbons and derivatives, such as petroleum, benzine, benzol, naphthalene, EMI9.2 chloronaphthalene, diphenylamine, 1e, 6-di tertio-butyl-.r: ethylphenol lecitin, etc. 17. A composition according to claims 1 to 8, including, characterized in that the compounds of claims 1 to 8 are used as a mixture.