Method of limiting chemical degradation due to nitrogen dioxide contamination

A method of limiting the chemical degradation of a hydrocarbonaceous liquid in service at bulk liquid temperatures of between 60 and 180ºC, the degradation being initiated by nitration of the liquid resulting from contamination with nitrogen dioxide in service, comprising:

• preparing, or obtaining a freshly-prepared, hydrocarbonaceous liquid suitable for service at bulk liquid temperatures of between 60 and 180° C. and being free of aged components and nitrogen dioxide contamination;
• adding to said hydrocarbonaceous liquid, prior to service at bulk liquid temperatures of between 60 and 180° ° C., an ionic liquid and a detergent additive, wherein:
• the ionic liquid comprises:
• (i) one or more organic cations each comprising a central atom or ring system bearing the cationic charge and multiple pendant hydrocarbyl substituents, and
• (ii) one or more halogen-, sulfur- and boron-free organic anions each comprising one or more hydrocarbyl groups and one or more heteroatom-containing functional groups bearing a localised or delocalised anionic charge;
• wherein each anion (ii) of the ionic liquid comprises a carboxylate functional group attached to an aliphatic group or an aromatic group;
• wherein the aliphatic carboxylate functional group is a C5 to C17 linear alkyl group, and the aromatic carboxylate functional group is a C6 to C28 linear alkyl substituted salicylate;
• and wherein the detergent additive comprises a 200 to 450 TBN calcium alkyl salicylate;
• wherein the ionic liquid is added at from 0.5 to 5.0 wt. % and the detergent additive is added at from 0.5 to 4.0 wt. % the hydrocarbonaceous liquid in service at bulk liquid temperatures of between 60 and 180° C., in the presence of nitrogen dioxide contamination;
• and
• putting said hydrocarbonaceous liquid into service, wherein the ionic liquid and detergent additive thereby limit the resulting chemical degradation of the liquid.

A method for the co-operative use of an ionic liquid and a detergent additive to limit the chemical degradation of a hydrocarbonaceous liquid in service at bulk liquid temperatures of between 60 and 180° C., the degradation being initiated by nitration of the hydrocarbonaceous liquid resulting from contamination with nitrogen dioxide during service, wherein the ionic liquid comprises:

• (i) one or more organic cations each comprising a central atom or ring system bearing the cationic charge and multiple pendant hydrocarbyl substituents, and
• (ii) one or more halogen-, sulfur- and boron-free organic anions each comprising one or more hydrocarbyl groups and one or more heteroatom-containing functional groups bearing a localised or delocalised anionic charge;
• wherein each anion (ii) of the ionic liquid comprises a carboxylate functional group attached to an aliphatic group or an aromatic group;
• wherein the aliphatic carboxylate functional group is a C5 to C17 linear alkyl group, and the aromatic carboxylate functional group is a C6 to C28 linear alkyl substituted salicylate;
• and wherein the detergent additive comprises a 200 to 450 TBN calcium alkyl salicylate, as the active ingredient,
• wherein the ionic liquid is added at from 0.5 to 5.0 wt. % and detergent additive is added at from 0.5 to 4.0 wt. % to the hydrocarbonaceous liquid free of aged components and nitrogen dioxide prior to service, and wherein the ionic liquid and detergent active ingredient thereafter inhibit the nitration of the hydrocarbonaceous liquid in service at bulk liquid temperatures of between 60 and 180° C. in the presence of nitrogen dioxide contamination.

A method to increase the efficacy of an ionic liquid additive comprising adding 0.5 to 4.0 wt. % detergent additive to a hydrocarbonaceous liquid containing 0.5 to 5.0 wt. % ionic liquid additive prior to service at bulk liquid temperatures of between 60 and 180° C. and exposure to nitrogen dioxide contamination, wherein the detergent additive comprises a 200 to 450 TBN calcium alkyl salicylate, as the active ingredient, and the ionic liquid comprises:

• ionic liquid
• (i) one or more organic cations each comprising a central atom or ring system bearing the cationic charge and multiple pendant hydrocarbyl substituents, and
• (ii) one or more halogen-, sulfur- and boron-free organic anions each comprising one or more hydrocarbyl groups and one or more heteroatom-containing functional groups bearing a localised or delocalised anionic charge;
• wherein each anion (ii) of the ionic liquid comprises a carboxylate functional group attached to an aliphatic group or an aromatic group;
• wherein the aliphatic carboxylate functional group is a C5 to C17 linear alkyl group, and the aromatic carboxylate functional group is a C6 to C28 linear alkyl substituted salicylate;
• wherein the efficacy of the ionic liquid additive for inhibiting the nitration of a hydrocarbonaceous liquid in service at bulk liquid temperatures of between 60 and 180° C. and resulting from contamination with nitrogen dioxide in service is increased.

A hydrocarbonaceous liquid composition comprising a major amount of hydrocarbonaceous liquid an ionic liquid at from 0.5 to 5.0 wt. % and a detergent additive at from 0.5 to 4.0 wt. %, the ionic liquid comprising:

• (i) one or more organic cations each comprising a central atom or ring system bearing the cationic charge and multiple pendant hydrocarbyl substituents, and
• (ii) one or more halogen-, sulfur- and boron-free organic anions each comprising one or more hydrocarbyl groups and one or more heteroatom-containing functional groups bearing a localised or delocalised anionic charge;
• wherein each anion (ii) of the ionic liquid comprises a carboxylate functional group attached to an aliphatic group or an aromatic group;
• wherein the aliphatic carboxylate functional group is a C5 to C17 linear alkyl group, and the aromatic carboxylate functional group is a C6 to C28 linear alkyl substituted salicylate;
• and the detergent additive comprising a 200 to 450 TBN calcium alkyl salicylate, as active ingredient.