GAS HYDRATE INHIBITORS AND METHODS FOR MAKING AND USING SAME
Nitrate brine compositions reduce hydrate formation in flowlines under conditions conducive for hydrate formation in the absence of the nitrate brines, where the nitrate brines include compatible anti-corrosion system.
1 . A downhole fluid composition comprising:
a base fluid comprising a nitrate brine, and an inhibiting amount of a corrosion system including:
at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,
where the downhole fluid comprises a drilling fluid, a completion fluid, or a production fluid,
where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the downhole fluid, and
where the additives reduce or prevent corrosion by the base fluid.
2 . The composition of claim 1 , wherein the downhole fluid further include:
an effective amount of a foaming system and a gas to form a foamed downhole fluid having desired foam properties,
where the foamed downhole fluid comprises a foamed drilling fluid, a foamed completion fluid, or a foamed production fluid.
3 . The composition of claim 1 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.
4 . The composition of claim 3 , wherein:
the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,
the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and
the transition metal nitrate brines are zinc nitrate brines.
5 . The composition of claim 1 , wherein:
the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and
the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.
6 . The composition of claim 1 , wherein the corrosion system further includes:
a quaternary salt selected from the group consisting of quaternary ammonium salts (R 1 R 2 R 3 R 4 N + A − ), quaternary phosphonium salts (R 1 R 2 R 3 R 4 P + A − ), amines (R 1 R 2 R 3 N), phosphines (R 1 R 2 R 3 P), and mixtures or combinations thereof, where the R 1 , R 2 , R 3 and R 4 are the same or different and are carbyl groups having between 1 and about 20 carbon atoms selected from the group consisting of saturated, unsaturated, cyclic, acyclic, aromatic, or mixed carbyl groups and sufficient hydrogen atoms to satisfy the valence, where one or more carbon atoms may be replaced by a hetero atom or group selected from oxygen, sulfur, amido, boron, or mixtures thereof, and one or more of the hydrogen atoms can be replace by halogens, alkoxides, or mixtures thereof, where A − is a counterion selected from the group consisting of hydroxide ion (OH − ), a halogen ion including F − , Cl − , Br—, and I—, a sulfate ion (SO 4 2− ), a nitrate ion (NO 3 − ), or mixtures thereof.
7 . A drilling fluid composition comprising:
a base fluid comprising a nitrate brine, and
an inhibiting amount of a corrosion system including:
at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,
where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the base fluid, and
where the additives reduce or prevent corrosion by the base fluid.
8 . The composition of claim 7 , wherein the drilling fluid further include:
an effective amount of a foaming system and a gas to form a foamed drilling fluid having desired foam properties,
where the foamed downhole fluid comprises a foamed drilling fluid, a foamed completion fluid, or a foamed production fluid.
9 . The composition of claim 7 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.
10 . The composition of claim 9 , wherein:
the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,
the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and
the transition metal nitrate brines are zinc nitrate brines.
11 . The composition of claim 7 , wherein:
the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and
the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms
12 . The composition of claim 7 , wherein the corrosion system further includes:
a quaternary salt selected from the group consisting of quaternary ammonium salts (R 1 R 2 R 3 R 4 N + A − ), quaternary phosphonium salts (R 1 R 2 R 3 R 4 P + A − ), amines (R 1 R 2 R 3 N), phosphines (R 1 R 2 R 3 P), and mixtures or combinations thereof, where the R 1 , R 2 , R 3 and R 4 are the same or different and are carbyl groups having between 1 and about 20 carbon atoms selected from the group consisting of saturated, unsaturated, cyclic, acyclic, aromatic, or mixed carbyl groups and sufficient hydrogen atoms to satisfy the valence, where one or more carbon atoms may be replaced by a hetero atom or group selected from oxygen, sulfur, amido, boron, or mixtures thereof, and one or more of the hydrogen atoms can be replace by halogens, alkoxides, or mixtures thereof, where A − is a counterion selected from the group consisting of hydroxide ion (OH), a halogen ion including F − , Cl − , Br—, and I—, a sulfate ion (SO 4 2− ), a nitrate ion (NO 3 − ), or mixtures thereof.
13 . A completion fluid composition comprising:
a base fluid comprising a nitrate brine, and
an inhibiting amount of a corrosion system including:
at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,
where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the completion fluid, and
where the additives reduce or prevent corrosion by the base fluid.
14 . The composition of claim 13 , wherein the completion fluid further include:
an effective amount of a foaming system and a gas to form a foamed completion fluid having desired foam properties,
where the foamed downhole fluid comprises a foamed drilling fluid, a foamed completion fluid, or a foamed production fluid.
15 . The composition of claim 13 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.
16 . The composition of claim 15 , wherein:
the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,
the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and
the transition metal nitrate brines are zinc nitrate brines.
17 . The composition of claim 13 , wherein:
the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof, and
the sulfonic acids include, without limitation, alkyl sulfonic acids, alkenyl sulfonic acids, aryl sulfonic acids, where the alkyl groups include 1 to about 20 carbon atoms, the alkenyl groups include 2 to about 20 carbon atoms and the aryl groups include 5 to about 30 carbon atoms.
18 . The composition of claim 13 , wherein the corrosion system further includes:
a quaternary salt selected from the group consisting of quaternary ammonium salts (R 1 R 2 R 3 R 4 N + A − ), quaternary phosphonium salts (R 1 R 2 R 3 R 4 P + A − ), amines (R 1 R 2 R 3 N), phosphines (R 1 R 2 R 3 P), and mixtures or combinations thereof, where the R 1 , R 2 , R 3 and R 4 are the same or different and are carbyl groups having between 1 and about 20 carbon atoms selected from the group consisting of saturated, unsaturated, cyclic, acyclic, aromatic, or mixed carbyl groups and sufficient hydrogen atoms to satisfy the valence, where one or more carbon atoms may be replaced by a hetero atom or group selected from oxygen, sulfur, amido, boron, or mixtures thereof, and one or more of the hydrogen atoms can be replace by halogens, alkoxides, or mixtures thereof, where A − is a counterion selected from the group consisting of hydroxide ion (OH), a halogen ion including F − , Cl − , Br—, and I—, a sulfate ion (SO 4 2− ), a nitrate ion (NO 3 − ), or mixtures thereof.
19 . A production fluid composition comprising:
a base fluid comprising a nitrate brine, and
an inhibiting amount of a corrosion system including:
at least one compatible anti-corrosion and/or neutralization additive is selected from the group consisting of mono carboxylic acids, dicarboxylic acids, poly carboxylic acids, hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, sulfonic acids, sulfinyl acids, phosphoric acid, polyphosphoric acid, and mixtures or combinations thereof,
where the base fluid reduces or inhibits hydrocarbon gas hydrate formation under conditions conducive to hydrocarbon gas hydrate formation in the production fluid, and
where the additives reduce or prevent corrosion by the base fluid.
20 . The composition of claim 19 , wherein the production fluid further include:
an effective amount of a foaming system and a gas to form a foamed production fluid having desired foam properties,
where the foamed downhole fluid comprises a foamed drilling fluid, a foamed completion fluid, or a foamed production fluid.
21 . The composition of claim 19 , wherein the nitrate brines are selected from the group consisting of alkali metal nitrate brines, alkaline earth metal nitrate brines, transition metal nitrate brines, and mixtures or combinations thereof.
22 . The composition of claim 21 , wherein:
the alkali metal nitrate brines are selected from the group consisting of lithium nitrate brines, sodium nitrate brines, potassium nitrate brines, rubidium nitrate brines, cesium nitrate brines, and mixture or combinations thereof,
the alkaline earth metal nitrate brines are selected from the group consisting of magnesium nitrate brines, calcium nitrate brines, and mixture or combinations thereof, and
the transition metal nitrate brines are zinc nitrate brines.
23 . The composition of claim 19 , wherein:
the mono-, di- and polycarboxylic acids are selected from the group consisting of saturated carboxy acids having from 1 to about 20 carbon atoms, unsaturated carboxy acids having from about 2 to about 20 carbon atoms, aromatic acids having from about 5 to about 30 carbon atoms, saturated dicarboxy acids having from 1 to about 20 carbon atoms, unsaturated dicarboxy acids having from about 2 to about 20 carbon atoms, aromatic diacids having from about 5 to about 30 carbon atoms, saturated polycarboxy acids having from 1 to about 20 carbon atoms, unsaturated polycarboxy acids having from about 2 to about 20 carbon atoms, aromatic polyacids having from about 5 to about 30 carbon atoms, or mixtures and combinations thereof.
24 . The composition of claim 19 , wherein the corrosion system further includes:
a quaternary salt selected from the group consisting of quaternary ammonium salts (R 1 R 2 R 3 R 4 N + A − ), quaternary phosphonium salts (R 1 R 2 R 3 R 4 P + A − ), amines (R 1 R 2 R 3 N), phosphines (R 1 R 2 R 3 P), and mixtures or combinations thereof, where the R 1 , R 2 , R 3 and R 4 are the same or different and are carbyl groups having between 1 and about 20 carbon atoms selected from the group consisting of saturated, unsaturated, cyclic, acyclic, aromatic, or mixed carbyl groups and sufficient hydrogen atoms to satisfy the valence, where one or more carbon atoms may be replaced by a hetero atom or group selected from oxygen, sulfur, amido, boron, or mixtures thereof, and one or more of the hydrogen atoms can be replace by halogens, alkoxides, or mixtures thereof, where A − is a counterion selected from the group consisting of hydroxide ion (OM, a halogen ion including F − , Cl − , Br—, and I—, a sulfate ion (SO 4 2− ), a nitrate ion (NO 3 − ), or mixtures thereof.