US20130089460A1 - Inhibiting corrosion caused by aqueous aldehyde solutions - Google Patents
Inhibiting corrosion caused by aqueous aldehyde solutions Download PDFInfo
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- US20130089460A1 US20130089460A1 US13/253,706 US201113253706A US2013089460A1 US 20130089460 A1 US20130089460 A1 US 20130089460A1 US 201113253706 A US201113253706 A US 201113253706A US 2013089460 A1 US2013089460 A1 US 2013089460A1
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- phosphate salt
- soluble phosphate
- basic soluble
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- 238000005260 corrosion Methods 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 31
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title 1
- 230000002401 inhibitory effect Effects 0.000 title 1
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 44
- 239000004135 Bone phosphate Substances 0.000 claims abstract description 22
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 35
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 10
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 7
- 229940015043 glyoxal Drugs 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000010779 crude oil Substances 0.000 claims description 6
- 230000000116 mitigating effect Effects 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000007836 KH2PO4 Substances 0.000 claims description 3
- 229910010951 LiH2 Inorganic materials 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 abstract 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005553 drilling Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 241000266847 Mephitidae Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/20—Hydrogen sulfide elimination
Definitions
- the invention relates to the prevention or mitigation of corrosion.
- the invention particularly relates to the prevention or mitigation of corrosion caused by aldehydes.
- H 2 S Sulfide (H 2 S) and/or mercaptans are often encountered in the exploration for and production of oil and natural gas.
- the presence of H 2 S and mercaptans is usually objectionable because they may react with other hydrocarbons or fuel system components.
- Another reason that the H 2 S and mercaptans are objectionable is that they are often highly corrosive.
- Still another reason that H 2 S and mercaptans are undesirable is that they have highly noxious odors.
- the odors resulting from H 2 S and mercaptans are detectable by the human nose at comparatively low concentrations and are well known.
- mercaptans are used to odorize natural gas and used as a repellant by skunks and other animals.
- H 2 S and/or mercaptans Certain aldehydes are known to be useful for these purposes. For example, glyoxal (OHCCHO) has been used at pH neutral as a successful scavenger. Glyoxal and other aldehydes such as acrolein and formaldehyde are known to be useful in a variety of other applications such as biocides, disinfectants, and the like.
- Aldehydes may be corrosive to metals such as aluminum, iron, and steel. It would be desirable to be able to employ such aldehydes at high concentration while minimizing the corrosion caused to metals in contact with the aldehydes.
- the invention is a method for employing an aldehyde in an aqueous solution while mitigating corrosion to metal in contact with the aldehyde solution.
- the method includes employing a corrosion inhibitor prepared using a member selected from the group consisting of a mono-basic soluble phosphate salt, di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
- the invention is, in a process for the exploration for or the production of crude oil and/or natural gas, employing an aldehyde as a H 2 S sulfide scavenger and employing a corrosion inhibitor prepared using a member selected from the group consisting of a mono-basic soluble phosphate salt, di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
- the disclosure is directed to a method for employing an aldehyde in an aqueous solution while mitigating corrosion to metal in contact with the aldehyde solution, the method including employing a corrosion inhibitor prepared using a formulation including a mono-, di- or tri-basic soluble phosphate salt.
- an aldehyde aqueous solution is employed.
- the aldehydes which may be employed in the practice of the method of the disclosure include, but are not limited to glyoxal, acrolein, glutaraldehyde, formaldehyde, and combinations thereof. Any aldehyde that may be employed in an aqueous solution and is effective at scavenging H2S may be employed.
- the aldehydes may be particularly a problem when in a comparatively concentrated form.
- the method of the disclosure is often employed where the aldehydes are present at a concentration of from about 20 to about 95% by weight.
- the aldehydes When the aldehydes are more dilute or concentrated, they often are not sufficiently corrosive to warrant a corrosion inhibitor; however they may be employed anytime that the aldehydes are present at a concentration such that a significant amount of corrosion may occur. This will vary according to the type of metal the aldehydes are contacting and the level of resilience of the system to which they are applied.
- the aldehyde will be present at a concentration of from about 25 to about 80 wt. %. In other embodiments, the concentration may be from about 30 to about 75 wt. %.
- a mono-, di- or tri-basic soluble phosphate salt is used to mitigate corrosion by the aldehydes as discussed about. While any soluble salt may be used, in many embodiments, the phosphate salts employed will be selected from the group consisting of LiH 2 PO 4 NaH 2 PO 4 , Na 2 HPO 4 , Na 3 HPO 4 , KH 2 PO 4 , K 2 HPO 4 ; K 3 HPO 4 ; and combinations thereof.
- the mono-, di- or tri-basic soluble phosphate salt may include more than one cation.
- the mono-, di- or tri-basic soluble phosphate salt may be selected from the group consisting of lithium, potassium, and sodium.
- the phosphate salts may be employed in any concentration effective to prevent or mitigate corrosion caused by the aldehydes.
- the mono-, di- or tri-basic phosphate salts may be present at a concentration of from about 100 ppm to 30% (by wt.). In other embodiments, they may be present at a concentration of from about 1000 ppm to about 20%. In still other embodiments, they are present at a concentration of from about 1 percent to about 10 percent.
- the phosphate salts, aldehyde, and water may be admixes in any way known to be useful to those of ordinary skill in the art of preparing additives. For example these components may be combined in a single container batch and admixed using a static or active mixer.
- the aldehyde and water may be first admixed and then a solution of the mono-, di- or tri-basic phosphate salt introduced.
- the three streams may be introduced simultaneous through a static mixes into a vessel.
- the alkaline phosphate salts useful with the method of the disclosure may be employed at a pH range of from about 4.0 to about 9.0. In some embodiments, the pH range may vary from about 4.5 to about 8.5 while in other embodiments the pH may be from about 5 to about 9.
- the mono-, di- and tr-basic salt employed in the method of disclosure work in two ways to prevent corrosion.
- the phosphates contact and build an inorganic insoluble metal phosphate film on the metal surface.
- an iron phosphate film forms.
- the basic nature of the mono-, di- and tri-basic phosphate salts either partially or perhaps fully removes the acidic H 2 S(s) from the aldehydes. Interfering with the acid H 2 S could affect the ability of the aldehydes to chelate metal thus removing or at least moderating this corrosion mechanism.
- the disclosure includes a process for the exploration for or the production of crude oil and/or natural gas, the process including employing an aldehyde as a H 2 S sulfide scavenger and employing a corrosion inhibitor prepared from a formulation including a mono-, di- or tri-basic soluble phosphate salt.
- the process of the disclosure includes both exploration and production. Exploration includes drilling an oil and gas well, and then completing the well to start production of hydrocarbons. Production includes producing production fluid from the oil and gas well.
- the drilling fluids, formation brines, or the crude oil and/or natural gas encountered in either exploration or production may include undesirable levels of H2S and/or other mercaptans. Employment of an aldehyde scavenger as well as a corrosion may be required in these circumstances.
- the aldehyde scavengers maybe employed in the process of the disclosure in any way known to be useful to those of ordinary skill in the art of producing oil and gas. For example, it may be atomized and introduced into a gas stream or directly admixed, liquid phase to liquid phase, with a crude oil stream. It may be employed as in, for example, the U.S. Provisional Patent Application having the Ser. No. 61/467116, which application is fully incorporated herein by reference.
- Corrosion tests were performed by holding mild steel corrosion coupons at 60° C. for the times shown in the Table. Corrosion was determined as mils per year loss of metal. The concentration of each compound tested was 1% except as noted below. The blank (control) and each sample was 40% by weight aqueous glyoxal. Results are shown below in the table.
- di-basic phosphate salts are effective at mitigation of corrosion by glyoxal.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Aldehydes useful as H2S sulfide scavengers may be corrosive to some metals such as steel, iron and aluminum, but the corrosive effect of the aldehydes may be mitigated by employing a corrosion inhibitor selected from the group consisting of a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
Description
- 1. Field of the Disclosure
- The invention relates to the prevention or mitigation of corrosion. The invention particularly relates to the prevention or mitigation of corrosion caused by aldehydes.
- 2. Background Of The Disclosure
- H2S Sulfide (H2S) and/or mercaptans are often encountered in the exploration for and production of oil and natural gas. The presence of H2S and mercaptans is usually objectionable because they may react with other hydrocarbons or fuel system components. Another reason that the H2S and mercaptans are objectionable is that they are often highly corrosive. Still another reason that H2S and mercaptans are undesirable is that they have highly noxious odors. The odors resulting from H2S and mercaptans are detectable by the human nose at comparatively low concentrations and are well known. For example, mercaptans are used to odorize natural gas and used as a repellant by skunks and other animals.
- One solution to these problems is to “scavenge” H2S and/or mercaptans. Certain aldehydes are known to be useful for these purposes. For example, glyoxal (OHCCHO) has been used at pH neutral as a successful scavenger. Glyoxal and other aldehydes such as acrolein and formaldehyde are known to be useful in a variety of other applications such as biocides, disinfectants, and the like.
- But the use of such aldehydes can of themselves sometimes be a problem. Aldehydes may be corrosive to metals such as aluminum, iron, and steel. It would be desirable to be able to employ such aldehydes at high concentration while minimizing the corrosion caused to metals in contact with the aldehydes.
- In one aspect, the invention is a method for employing an aldehyde in an aqueous solution while mitigating corrosion to metal in contact with the aldehyde solution. The method includes employing a corrosion inhibitor prepared using a member selected from the group consisting of a mono-basic soluble phosphate salt, di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
- In another aspect, the invention is, in a process for the exploration for or the production of crude oil and/or natural gas, employing an aldehyde as a H2S sulfide scavenger and employing a corrosion inhibitor prepared using a member selected from the group consisting of a mono-basic soluble phosphate salt, di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
- In one embodiment, the disclosure is directed to a method for employing an aldehyde in an aqueous solution while mitigating corrosion to metal in contact with the aldehyde solution, the method including employing a corrosion inhibitor prepared using a formulation including a mono-, di- or tri-basic soluble phosphate salt. In practicing the various embodiments of the method of the disclosure, an aldehyde aqueous solution is employed. The aldehydes which may be employed in the practice of the method of the disclosure include, but are not limited to glyoxal, acrolein, glutaraldehyde, formaldehyde, and combinations thereof. Any aldehyde that may be employed in an aqueous solution and is effective at scavenging H2S may be employed.
- The aldehydes may be particularly a problem when in a comparatively concentrated form. For example, in some embodiments, the method of the disclosure is often employed where the aldehydes are present at a concentration of from about 20 to about 95% by weight. When the aldehydes are more dilute or concentrated, they often are not sufficiently corrosive to warrant a corrosion inhibitor; however they may be employed anytime that the aldehydes are present at a concentration such that a significant amount of corrosion may occur. This will vary according to the type of metal the aldehydes are contacting and the level of resilience of the system to which they are applied. For example, in some embodiments, the aldehyde will be present at a concentration of from about 25 to about 80 wt. %. In other embodiments, the concentration may be from about 30 to about 75 wt. %.
- In the practice of the application, a mono-, di- or tri-basic soluble phosphate salt is used to mitigate corrosion by the aldehydes as discussed about. While any soluble salt may be used, in many embodiments, the phosphate salts employed will be selected from the group consisting of LiH2PO4 NaH2PO4, Na2HPO4, Na3HPO4, KH2PO4, K2HPO4; K3HPO4; and combinations thereof.
- In other embodiments, there may be more than a single cation in the salt, for example, Na2KPO4 or NaLiKPO4, and the like. Stated another way, the mono-, di- or tri-basic soluble phosphate salt may include more than one cation. In some embodiments, when the mono-, di- or tri-basic soluble phosphate salt includes two or more cations, they may be selected from the group consisting of lithium, potassium, and sodium.
- The phosphate salts may be employed in any concentration effective to prevent or mitigate corrosion caused by the aldehydes. For example, in some embodiments, the mono-, di- or tri-basic phosphate salts may be present at a concentration of from about 100 ppm to 30% (by wt.). In other embodiments, they may be present at a concentration of from about 1000 ppm to about 20%. In still other embodiments, they are present at a concentration of from about 1 percent to about 10 percent.
- The phosphate salts, aldehyde, and water may be admixes in any way known to be useful to those of ordinary skill in the art of preparing additives. For example these components may be combined in a single container batch and admixed using a static or active mixer. In another embodiment, the aldehyde and water may be first admixed and then a solution of the mono-, di- or tri-basic phosphate salt introduced. In still another embodiment, the three streams may be introduced simultaneous through a static mixes into a vessel.
- The alkaline phosphate salts useful with the method of the disclosure may be employed at a pH range of from about 4.0 to about 9.0. In some embodiments, the pH range may vary from about 4.5 to about 8.5 while in other embodiments the pH may be from about 5 to about 9.
- While not wishing to be bound by any theory, it is nevertheless believed that the mono-, di- and tr-basic salt employed in the method of disclosure work in two ways to prevent corrosion. In a first way, it is believe that the phosphates contact and build an inorganic insoluble metal phosphate film on the metal surface. For example, in the case of iron or steel, an iron phosphate film forms. In the second way, it is believed that the basic nature of the mono-, di- and tri-basic phosphate salts either partially or perhaps fully removes the acidic H2S(s) from the aldehydes. Interfering with the acid H2S could affect the ability of the aldehydes to chelate metal thus removing or at least moderating this corrosion mechanism.
- In another embodiment, the disclosure includes a process for the exploration for or the production of crude oil and/or natural gas, the process including employing an aldehyde as a H2S sulfide scavenger and employing a corrosion inhibitor prepared from a formulation including a mono-, di- or tri-basic soluble phosphate salt. The process of the disclosure includes both exploration and production. Exploration includes drilling an oil and gas well, and then completing the well to start production of hydrocarbons. Production includes producing production fluid from the oil and gas well.
- In some applications, the drilling fluids, formation brines, or the crude oil and/or natural gas encountered in either exploration or production may include undesirable levels of H2S and/or other mercaptans. Employment of an aldehyde scavenger as well as a corrosion may be required in these circumstances.
- The aldehyde scavengers maybe employed in the process of the disclosure in any way known to be useful to those of ordinary skill in the art of producing oil and gas. For example, it may be atomized and introduced into a gas stream or directly admixed, liquid phase to liquid phase, with a crude oil stream. It may be employed as in, for example, the U.S. Provisional Patent Application having the Ser. No. 61/467116, which application is fully incorporated herein by reference.
- The following examples are provided to illustrate the invention. The examples are not intended to limit the scope of the invention and they should not be so interpreted. Amounts are in weight parts or weight percentages unless otherwise indicated.
- Corrosion tests were performed by holding mild steel corrosion coupons at 60° C. for the times shown in the Table. Corrosion was determined as mils per year loss of metal. The concentration of each compound tested was 1% except as noted below. The blank (control) and each sample was 40% by weight aqueous glyoxal. Results are shown below in the table.
-
TABLE Corrosion Rate Corrosion Rate (mpy) (mpy) Sample ID/Inhibitor 2 day test 14 day test Ex. 1: Na2HPO4 15 110 Ex. 2: K2HPO4* — 8 A: Blank 120 750 B: Cinnamaldehyde 80 — C: NaOH 100 — D: Bytyl-2yne-1,4 diol 40 — *2% concentration - The Examples clearly show that di-basic phosphate salts are effective at mitigation of corrosion by glyoxal.
Claims (20)
1. A method for employing an aldehyde in an aqueous solution while mitigating corrosion of metal in contact with the aldehyde solution, the method comprising employing a corrosion inhibitor with the aldehyde wherein the corrosion inhibitor comprises a member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
2. The method of claim 1 wherein the aldehyde is selected from the group consisting of glyoxal, acrolein, glutaraldehyde, formaldehyde, and combinations thereof.
3. The method of claim 1 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof is selected from the group consisting of LiH2PO4, NaH2PO4, Na2HPO4, Na3HPO4, KH2PO4, K2HPO4, K3HPO4 and combinations thereof.
4. The method of claim 1 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof includes more than one cation.
5. The method of claim 4 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof includes two or more cations selected from the group consisting of lithium, potassium, sodium and combinations thereof.
6. The method of claim 1 wherein the aqueous aldehyde solution has an aldehyde concentration of from about 20 to about 90 weight percent.
7. The method of claim 1 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof is present in the aqueous aldehyde solution at a concentration of from about 100 ppm to 30% (by wt.).
8. The method of claim 1 wherein the aldehyde and corrosion inhibitor solution is employed at a pH range of from about 4.0 to about 9.0.
9. The method of claim 8 , wherein the pH range may vary from about 4.5 to about 9.
10. A process for exploring for or producing crude oil and/or natural gas comprising employing a H2S sulfide scavenger solution comprising an aldehyde and employing a corrosion inhibitor in the solution comprising a member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof.
11. The process of claim 10 wherein the aldehyde is selected from the group consisting of glyoxal, acrolein, glutaraldehyde, formaldehyde, and combinations thereof.
12. The process of claim 10 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof is selected from the group consisting of LiH2PO4; NaH2PO4, Na2HPO4; Na3HPO4; KH2PO4, K2HPO4; K3HPO4; and combinations thereof.
13. The process of claim 10 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof includes more than one cation.
14. The process of claim 13 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof includes two or more cations selected from the group consisting of lithium, potassium, sodium, and combinations thereof.
15. The process of claim 10 wherein the H2S sulfide scavenger solution has an aldehyde concentration of from about 20 to about 90 weight percent.
16. The process of claim 10 wherein the member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof is present in the H2S sulfide scavenger solution at a concentration of from about 100 ppm to 30% (by wt.).
17. The process of claim 10 wherein the H2S sulfide scavenger solution comprising aldehyde and member selected from the group consisting of a mono-basic soluble phosphate salt, a di-basic soluble phosphate salt, a tri-basic soluble phosphate salt, and combinations thereof, has a pH range of from about 4.0 to about 9.0.
18. The process of claim 17 , wherein the pH range may vary from about 4.5 to about 9.
19. The process of claim 10 wherein the H2S sulfide scavenger and corrosion inhibitor is atomized and injected into a gas stream.
20. The process of claim 10 wherein the H2S sulfide scavenger and corrosion inhibitor is admixed with crude oil.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/253,706 US20130089460A1 (en) | 2011-10-05 | 2011-10-05 | Inhibiting corrosion caused by aqueous aldehyde solutions |
| US13/540,383 US20130090271A1 (en) | 2011-10-05 | 2012-07-02 | Inhibiting corrosion caused by aqueous aldehyde solutions |
| US13/589,794 US9068269B2 (en) | 2011-10-05 | 2012-08-20 | Inhibiting corrosion caused by aqueous aldehyde solutions |
| GB1217742.4A GB2495399B (en) | 2011-10-05 | 2012-10-04 | Inhibiting corrosion caused by aqueous aldehyde solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/253,706 US20130089460A1 (en) | 2011-10-05 | 2011-10-05 | Inhibiting corrosion caused by aqueous aldehyde solutions |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/540,383 Continuation US20130090271A1 (en) | 2011-10-05 | 2012-07-02 | Inhibiting corrosion caused by aqueous aldehyde solutions |
| US13/540,383 Continuation-In-Part US20130090271A1 (en) | 2011-10-05 | 2012-07-02 | Inhibiting corrosion caused by aqueous aldehyde solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20130089460A1 true US20130089460A1 (en) | 2013-04-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/253,706 Abandoned US20130089460A1 (en) | 2011-10-05 | 2011-10-05 | Inhibiting corrosion caused by aqueous aldehyde solutions |
| US13/540,383 Abandoned US20130090271A1 (en) | 2011-10-05 | 2012-07-02 | Inhibiting corrosion caused by aqueous aldehyde solutions |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/540,383 Abandoned US20130090271A1 (en) | 2011-10-05 | 2012-07-02 | Inhibiting corrosion caused by aqueous aldehyde solutions |
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| Country | Link |
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| US (2) | US20130089460A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068269B2 (en) | 2011-10-05 | 2015-06-30 | Baker Hughes Incorporated | Inhibiting corrosion caused by aqueous aldehyde solutions |
| WO2018062254A1 (en) | 2016-09-27 | 2018-04-05 | 株式会社クラレ | Metal corrosion suppressing method |
| WO2018097108A1 (en) | 2016-11-22 | 2018-05-31 | 株式会社クラレ | Composition for removal of sulfur-containing compound |
| US10119079B2 (en) | 2014-03-17 | 2018-11-06 | Kuraray Co., Ltd. | Composition for removal of sulfur-containing compounds |
| US10294428B2 (en) | 2015-01-29 | 2019-05-21 | Kuraray Co., Ltd. | Composition for removing sulfur-containing compounds |
| CN113343498A (en) * | 2021-07-05 | 2021-09-03 | 西南石油大学 | Containing H2S/CO2Method for calculating corrosion rate of environmental pipeline steel |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021120136A (en) * | 2018-04-27 | 2021-08-19 | 株式会社クラレ | Composition for removing sulfur-containing compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060194700A1 (en) * | 2005-02-25 | 2006-08-31 | Weatherford/Lamb | Corrosion inhibitor systems for low, moderate and high temperature fluids and methods for making and using same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2891909A (en) * | 1955-11-16 | 1959-06-23 | Cities Service Res & Dev Co | Method of inhibiting corrosion of metals |
| US3081146A (en) * | 1959-02-27 | 1963-03-12 | Nalco Chemical Co | Inhibition of corrosion of metal surfaces in contact with corrosive aqueous media |
| US3637341A (en) * | 1969-12-29 | 1972-01-25 | Bethlehem Steel Corp | Method and means for corrosion protection of cables exposed to underground environments |
| GB8711534D0 (en) * | 1987-05-15 | 1987-06-17 | Ciba Geigy Ag | Corrosion inhibiting composition |
| US4554090A (en) * | 1984-03-09 | 1985-11-19 | Jones L W | Combination corrosion/scale inhibitor |
| US5386038A (en) * | 1990-12-18 | 1995-01-31 | Albright & Wilson Limited | Water treatment agent |
| US5556832A (en) * | 1992-09-21 | 1996-09-17 | Union Oil Company Of California | Solids-free, essentially all-oil wellbore fluid |
| US20060264335A1 (en) * | 2005-05-17 | 2006-11-23 | Bj Services Company | Corrosion inhibitor intensifier and method of using the same |
-
2011
- 2011-10-05 US US13/253,706 patent/US20130089460A1/en not_active Abandoned
-
2012
- 2012-07-02 US US13/540,383 patent/US20130090271A1/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060194700A1 (en) * | 2005-02-25 | 2006-08-31 | Weatherford/Lamb | Corrosion inhibitor systems for low, moderate and high temperature fluids and methods for making and using same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9068269B2 (en) | 2011-10-05 | 2015-06-30 | Baker Hughes Incorporated | Inhibiting corrosion caused by aqueous aldehyde solutions |
| US10119079B2 (en) | 2014-03-17 | 2018-11-06 | Kuraray Co., Ltd. | Composition for removal of sulfur-containing compounds |
| US10294428B2 (en) | 2015-01-29 | 2019-05-21 | Kuraray Co., Ltd. | Composition for removing sulfur-containing compounds |
| WO2018062254A1 (en) | 2016-09-27 | 2018-04-05 | 株式会社クラレ | Metal corrosion suppressing method |
| WO2018097108A1 (en) | 2016-11-22 | 2018-05-31 | 株式会社クラレ | Composition for removal of sulfur-containing compound |
| US11434433B2 (en) | 2016-11-22 | 2022-09-06 | Kuraray Co., Ltd. | Composition for removal of sulfur-containing compound |
| CN113343498A (en) * | 2021-07-05 | 2021-09-03 | 西南石油大学 | Containing H2S/CO2Method for calculating corrosion rate of environmental pipeline steel |
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| Publication number | Publication date |
|---|---|
| US20130090271A1 (en) | 2013-04-11 |
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| STCB | Information on status: application discontinuation |
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