Composition and methods to prevent corrosion by CO
View Patent ↗Methods and compositions that protect cement compositions from corrosion, particularly from wet carbon dioxide, are provided. A soluble salt additive is provided to react with reaction products generated during the reactions that occur when cement is exposed to wet carbon dioxide. The soluble salt reacts to form an insoluble salt that forms a protective layer on the surface of the cement that protects it from further corrosion from exposure to wet carbon dioxide.
1. A method of reducing corrosion of a hardened cement in a cementing application comprising:
(i) hardening a cement composition comprising Portland cement and an additive;
(ii) exposing the cement composition to wet carbon dioxide after the cement composition has hardened;
(iii) forming an insoluble calcium salt from the additive and calcium cations, the calcium cations having been formed from carbonic acid in wet carbon dioxide; and
(iv) preventing carbon dioxide from penetrating into the set cement by forming a protective barrier from the insoluble calcium salt, wherein the protective barrier protects the cement from corrosion and further prevents loss of integrity to the hardened cement.
2. The method of claim 1 , wherein the additive comprises H 2 NaO 4 P, Na 2 HPO 4 , Na 3 PO 4 , NH 4 .H 2 PO 4 , (NH 4 ) 3 PO 4 , (NH 4 ) 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , tricalcium phosphate or combinations thereof.
3. The method of claim 1 , wherein the additive comprises FeCl 2 , FeSiF 6 .6H 2 O, (Fe(NO 3 ) 2 ), FeSO 4 , Pb(C 2 H 3 O 2 ) 2 , Pb(BrO 3 ) 2 , PbSiF 6 , Pb(NO 3 ) 2 , MnF 2 , MnSiF 6 .6H 2 O, Mn(NO 3 ) 2 , MnSO 4 , Hg 2 (ClO 4 ) 2 , Hg(C 2 H 3 O 2 ) 2 , Hg(ClO 3 ) 2 , HgCl 2 , Hg(CN) 2 , Nd(C 2 H 3 O 2 ) 3 .H 2 O, Nd(BrO 3 ) 3 , NdCl 3 , Nd(NO 3 ) 3 , Nd 2 (SeO 4 ) 3 , Nd 2 (SO 4 ) 3 , AgClO 3 , AgClO 2 , Ag 2 Cr 2 O 7 , AgF, AgNO 3 , AgClO 4 , AgMnO 4 , Ag 2 SO 4 , Sr(C 2 H 3 O 2 ) 2 , Sr(BrO 3 ) 2 .H 2 O, SrBr 2 , SrCl 2 , Sr(HCO 2 ) 2 , Sr(OH) 2 .8H 2 O, SrI 2 , Sr(NO 3 ) 2 , SrS 2 O 3 .5H 2 O, Y(C 2 H 3 O 2 ) 3 .4H 2 O, Y(BrO 3 ) 3 .9H 2 O, YBr 3 , YCl 3 , Y(NO 3 ) 3 , Y 2 (SO 4 ) 3 , Zn(C 2 H 3 O 2 ) 2 , ZnBr 2 , Zn(ClO 3 ) 2 , ZnCl 2 , ZnF 2 , Zn(HCO 2 ) 2 , ZnI 2 , Zn(NO 3 ) 2 , Zn(MnO 4 ) 2 , ZnSO 4 , Zr(SO 4 ) 2 .4H 2 O, ZrF 4 , or combinations thereof and wherein the insoluble salt comprises iron (II) carbonate, lead (II) carbonate, manganese (II) carbonate, mercury (I) carbonate, neodymium carbonate, silver (I) carbonate, strontium carbonate, yttrium carbonate, zinc carbonate, zinc carbonate monohydrate, or combinations thereof.
4. The method of claim 1 , wherein the additive is present in a range of about 1 lb. per 500 lb. cement composition to about 100 lb. per 500 lb. cement composition.
5. The method of claim 1 , wherein the additive is added prior to water being added to the cement composition.
6. The method of claim 1 , wherein the cementing application comprises introducing the cement composition into a well and further wherein the cement composition is hardened in the well.
7. A method of reducing corrosion in a cement composition exposed to wet carbon dioxide by preventing the propagation of carbonic acid within the cement, the method comprising the steps of:
(a) forming a cement composition comprising Portland cement and an additive;
(b) adding water to the cement composition and allowing the cement composition to set into a hard mass;
(c) exposing wet carbon dioxide to the hardened cement to produce an insoluble salt from the calcium cation and additive; and
(d) preventing the propagation of carbonic acid within the cement by forming a protective barrier within the cement from the insoluble salt of step (c).
8. The method of claim 7 , wherein the additive comprises H 2 NaO 4 P, Na 2 HPO 4 , Na 3 PO 4 , NH 4 .H 2 PO 4 , (NH 4 ) 3 PO 4 , (NH 4 ) 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , tricalcium phosphate or combinations thereof
9. The method of claim 7 , wherein the additive comprises FeCl 2 , FeSiF 6 .6H 2 O, (Fe(NO 3 ) 2 ), FeSO 4 , Pb(C 2 H 3 O 2 ) 2 , Pb(BrO 3 ) 2 , PbSiF 6 , Pb(NO 3 ) 2 , MnF 2 , MnSiF 6 .6H 2 O, Mn(NO 3 ) 2 , MnSO 4 , Hg 2 (ClO 4 ) 2 , Hg(C 2 H 3 O 2 ) 2 , Hg(ClO 3 ) 2 , HgCl 2 , Hg(CN) 2 , Nd(C 2 H 3 O 2 ) 3 .H 2 O, Nd(BrO 3 ) 3 , NdCl 3 , Nd(NO 3 ) 3 , Nd 2 (SeO 4 ) 3 , Nd 2 (SO 4 ) 3 , AgClO 3 , AgClO 2 , Ag 2 Cr 2 O 7 , AgF, AgNO 3 , AgClO 4 , AgMnO 4 , Ag 2 SO 4 , Sr(C 2 H 3 O 2 ) 2 , Sr(BrO 3 ) 2 .H 2 O, SrBr 2 , SrCl 2 , Sr(HCO 2 ) 2 , Sr(OH) 2 .8H 2 O, SrI 2 , Sr(NO 3 ) 2 , SrS 2 O 3 .5H 2 O, Y(C 2 H 3 O 2 ) 3 .4H 2 O, Y(BrO 3 ) 3 .9H 2 O, YBr 3 , YCl 3 , Y(NO 3 ) 3 , Y 2 (SO 4 ) 3 , Zn(C 2 H 3 O 2 ) 2 , ZnBr 2 , Zn(ClO 3 ) 2 , ZnCl 2 , ZnF 2 , Zn(HCO 2 ) 2 , ZnI 2 , Zn(NO 3 ) 2 , Zn(MnO 4 ) 2 , ZnSO 4 , Zr(SO 4 ) 2 .4H 2 O, ZrF 4 , or combinations thereof and wherein the insoluble salt comprises iron (II) carbonate, lead (II) carbonate, manganese (II) carbonate, mercury (I) carbonate, neodymium carbonate, silver (I) carbonate, strontium carbonate, yttrium carbonate, zinc carbonate, zinc carbonate monohydrate, or combinations thereof.
10. The method of claim 7 , wherein the additive is present in a range of about 1 lb. per 500 lb. cement composition to about 100 lb. per 500 lb. cement composition.
11. The method of claim 7 , wherein the cementing application comprises introducing the cement composition into a well and further wherein the cement composition is hardened in the well.
12. The method of claim 7 , wherein the additive is added prior to water being added to the cement composition.
13. The method of claim 7 , wherein the cement composition further comprises a member selected from the group consisting of glass, dispersing agents, fluid loss additives, hydrogen foaming agents, and combinations thereof.
14. A method of reducing corrosion during a cementing application comprising the steps of:
(a) forming a cement composition comprising Portland cement and an additive;
(b) adding water to the cement composition;
(c) exposing wet carbon dioxide to cement;
(d) reacting the calcium cation with the additive to produce an insoluble salt as the cement composition sets up and hardens; and
(e) protecting the set cement composition from corrosion by the insoluble salt produced in step (d).
15. The method of claim 14 , wherein the additive comprises H 2 NaO 4 P, Na 2 HPO 4 , Na 3 PO 4 , NH 4 .H 2 PO 4 , (NH 4 ) 3 PO 4 , (NH 4 ) 2 HPO 4 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , tricalcium phosphate or combinations thereof.
16. The method of claim 14 , wherein the additive comprises FeCl 2 , FeSiF 6 .6H 2 O, (Fe(NO 3 ) 2 ), FeSO 4 , Pb(C 2 H 3 O 2 ) 2 , Pb(BrO 3 ) 2 , PbSiF 6 , Pb(NO 3 ) 2 , MnF 2 , MnSiF 6 .6H 2 O, Mn(NO 3 ) 2 , MnSO 4 , Hg 2 (ClO 4 ) 2 , Hg(C 2 H 3 O 2 ) 2 , Hg(ClO 3 ) 2 , HgCl 2 , Hg(CN) 2 , Nd(C 2 H 3 O 2 ) 3 .H 2 O, Nd(BrO 3 ) 3 , NdCl 3 , Nd(NO 3 ) 3 , Nd 2 (SeO 4 ) 3 , Nd 2 (SO 4 ) 3 , AgClO 3 , AgC 1 O 2 , Ag 2 Cr 2 O 7 , AgF, AgNO 3 , AgClO 4 , AgMnO 4 , Ag 2 SO 4 , Sr(C 2 H 3 O 2 ) 2 , Sr(BrO 3 ) 2 .H 2 O, SrBr 2 , SrCl 2 , Sr(HCO 2 ) 2 , Sr(OH) 2 .8H 2 O, SrI 2 , Sr(NO 3 ) 2 , SrS 2 O 3 .5H 2 O, Y(C 2 H 3 O 2 ) 3 .4H 2 O, Y(BrO 3 ) 3 .9H 2 O, YBr 3 , YCl 3 , Y(NO 3 ) 3 , Y 2 (SO 4 ) 3 , Zn(C 2 H 3 O 2 ) 2 , ZnBr 2 , Zn(ClO 3 ) 2 , ZnCl 2 , ZnF 2 , Zn(HCO 2 ) 2 , ZnI 2 , Zn(NO 3 ) 2 , Zn(MnO 4 ) 2 , ZnSO 4 , Zr(SO 4 ) 2 .4H 2 O, ZrF 4 , or combinations thereof and wherein the insoluble salt comprises iron (II) carbonate, lead (II) carbonate, manganese (II) carbonate, mercury (I) carbonate, neodymium carbonate, silver (I) carbonate, strontium carbonate, yttrium carbonate, zinc carbonate, zinc carbonate monohydrate, or combinations thereof.
17. The method of claim 14 , wherein the additive comprises NaF, KF, [NH 4 ][HF 2 ], NH 4 F, LiF, Na 2 B 4 O 7 , Na 2 B 4 O 7 .10H 2 O, B 2 O 3 , B 8 Na 2 O 13 , BBr 3 , BF 3 , B 10 H 14 , B 2 H 6 , BH 3 , K 2 B 4 O 7 .H 2 O, B(OH) 3 , Na 4 B 4 O 7 and its hydrate forms, Na 2 B 8 O 13 and its hydrate forms.
18. The method of claim 14 , wherein the additive is added prior to water being added to the cement composition.
19. The method of claim 14 , wherein the additive is present in a range of about 1 lb. per 500 lb. cement composition to about 100 lb. per 500 lb. cement composition.
20. The method of claim 14 , wherein the cement composition further comprises a member selected from the group consisting of glass, dispersing agents, fluid loss additives, hydrogen foaming agents, and combinations thereof.