Method and composition for acidizing subterranean formations

A method of inhibiting the corrosivity an aqueous corrosive acid comprising hydrochloric acid in contact with a ferrous metal at elevated temperatures which comprise adding to said corrosive acid comprising hydrochloric acid an inhibiting effective amount of a corrosion inhibitor composition consisting essentially of:

• at least one acetylenic alcohol having the general formula ##STR3## wherein R.sub.1, R.sub.2 and R.sub.3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals present in an amount sufficient to comprise at least about 5 percent by volume of said inhibitor composition;
• (a quaternary ammonium compound selected from the group consisting of the N-methyl, N-benzyl and chloromethyl naphthalene quaternaries of alkyl pyridines and quinoline, isoquinoline compounds, benzoquinoline compounds and mixtures thereof;
• an aromatic hydrocarbon compound which exhibits high oil-wetting characteristics present in an amount sufficient to provide a ratio by volume of acetylenic alcohol to aromatic hydrocarbon of at least about 0.05:1;
• and
• an antimony compound capable of activation by the other constituents of said corrosion inhibitor composition whereby the corrosivity of said corrosive acid in contact with said ferrous metal is reduced, said antimony compound being at least one member selected from the group consisting of antimony trioxide, pentoxide, trichloride, sulfide, pentachloride, tartrate, and trifluoride, alkali metal salts of antimony tartrate, alkali metal salts of pyroantimonate, antimony adducts of ethylene glycol and solutions containing ethylene glycol, and the oxidized product of hydrogen peroxide and at least one member selected from the group consisting of trivalent antimony compounds and being present in an amount sufficient to provide an antimony concentration of from about 0.0007 to about 0.04 molar to said corrosive acid.

An acidic composition comprising:

• an aqueous ferrous metal corrosive acid comprising hydrochloric acid;
• and
• a corrosion inhibitor composition consisting essentially of at least one acetylenic alcohol having the
• general formula ##STR4## wherein R.sub.1, R.sub.2 and R.sub.3 are selected from the group consisting of hydrogen, alkyl, phenyl, substituted phenyl and hydroxy-alkyl radicals present in an amount sufficient to comprise at least about 5 percent by volume of said inhibitor composition;
• a quaternary ammonium compound selected from the group consisting of the N-methyl, N-benzyl and chloromethyl naphthalene quaternaries of alkyl pyridines and quinoline, isoquinoline compounds, benzoquinoline compounds and mixtures thereof;
• an aromatic hydrocarbon compound which exhibits high oil-wetting characteristics present in an amount sufficient to provide a ratio by volume of acetylenic alcohol to aromatic hydrocarbon of at least about 0.05:1;
• and
• an antimony compound capable of activation by the other constituents of said corrosion inhibitor composition whereby the corrosivity of said corrosive acid in contact with said ferrous metal is reduced, said antimony compound being at least one member selected from the group consisting of antimony trioxide, pentoxide, trichloride, sulfide, pentachloride, tartrate, and trifluoride, alkali metal salts of antimony tartrate, alkali metal salts of pyroantimonate, antimony adducts of ethylene glycol and solutions containing ethylene glycol, and the oxidized product of hydrogen peroxide and at least one member selected from the group consisting of trivalent antimony compounds and being present in an amount sufficient to provide an antimony concentration of from about 0.0007 to about 0.04 molar to said corrosive acid.