US2048362A - Acid composition for treatment of deep wells - Google Patents
Acid composition for treatment of deep wells Download PDFInfo
- Publication number
- US2048362A US2048362A US723958A US72395834A US2048362A US 2048362 A US2048362 A US 2048362A US 723958 A US723958 A US 723958A US 72395834 A US72395834 A US 72395834A US 2048362 A US2048362 A US 2048362A
- Authority
- US
- United States
- Prior art keywords
- acid
- treatment
- per cent
- well
- diphenyloxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000002253 acid Substances 0.000 title description 25
- 239000000203 mixture Substances 0.000 title description 3
- 239000000243 solution Substances 0.000 description 26
- 230000001590 oxidative effect Effects 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 9
- 239000012965 benzophenone Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108010080511 serum sodium transport inhibitor Proteins 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
-
- 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
- C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/933—Acidizing or formation destroying
- Y10S507/934—Acidizing or formation destroying with inhibitor
Definitions
- the invention relates to the treatment of deep wells and is more especially concerned with the treatment of wells in which the producing stratimi comprises a silicate rockformation of which serpentine is representative.
- inhibiting agents which 86 are suitable for use at room temperature, and which at such temperatures are capable of sub-v stantially inhibiting the attack of oxidizing acid solutions upon metal, for example, alpha-naphthyl-amine, para-phenylenediamine, benzidine,
- the temperature conditions encountered in a deep well make it imperative that the inhibitor be effective at 100 F.'and slightly higher.
- the temperature in the producing stratum is about 104 F.. and in themain producing stratum of the Texas field it is approximately 150 F.
- the aforesaid inhibitors although eifective at ordinary temperatures, e. g. about 70 60 lose their effectiveness at 100 F., and therefore are'not suitable to inhibit oxidizing acid solutions in thetreatment of deep wells.
- Example 1 15 15 per cent HCl-5 per cent HNOa. Temperatum-100 F.
- Example 2 15 per cent HCl-3 per cent HN03--2 per cent HF. Temperature-100 F. a
- Example 3 15' per cent HCl-5 per cent HNOa. Temperaure-151 F.
- aqueous oxidizing acid solutions containing the diamino derivatives 40 of diphenyloxide and benzophenone have substantially no action upon the metals ordinarily employed in wells and in apparatus for the treatment of wells.
- aqueous oxi- 45 dlzing acid solutions containing the diamino derivatives of diphenyloxide or benzophenone may be accomplished according to the known procedures.
- the acid solution is preferably added in amount calculated to fill the bore of the well to a depth not exceeding the thickness of the fluid producing stratum.
- the acid solution may be followed by a charge of oil, water, or other liquid, or pressure may be applied by other suitable means, e. g. by air pressure'or by means of a pump.
- the acid attacks the rock structure and dissolves or disintcgrates it, thereby enlarging the pores or channels in the rock or opening up new channels.
- the spent solution may be pumped or bailed out. In many cases it may be desirable to repeat the treatment one or more times.
- Another method which may be used in treating 2 a deep'well with our aqueous oxidizing acid solution employing our inhibitors is to introduce into the well in concentrated form, ahead oi the main oxidizing acid charge, a quantity of the diamino derivative of diphenyloxide or benzophenone thereby forming protective surfaces over the metal equipment within the well before said main charge of acid is contacted with such surfaces.
- the diamino derivative may be employed in the form of a solution or emulsion thereof with any vehicle which does not react therewith to destroy its inhibiting properties.
- any vehicle which may be employed we mention particularly ethyl alcohol.
- ethyl alcohol ethyl alcohol.
- Other modes of applying theprinciple of our invention may be-employed instead of the one explained, change beingmade as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed. We therefore particularly point out and distinctly claim as our invention:-
- An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid and a relatively small amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzo- 25 phenone.
- An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid, between about 5.0 and about 20.0 per cent by weight of hydrochloric acid, and a relativelysmall amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone.
- An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight 35 of nitric acid, between about 1.0 and about 10.0 per cent by weight of hydrofluoric acid, and a relatively small amount of a diamino derivative of a compound selected from the group consisting of .diphenyloxide and benzophenone. 40
- An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid. between about 5.0 and about 20.0 per cent by weight of hydrochloric acid, between about 1.0 and about 10.0 per cent by weight of 45 hydrofluoric acid, and between about 0.1 and 1.0 per cent by weight of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented July 21, 1936 PATENT owner:
ACID, COMPOSITION FOR DEEP WELLS TREATMENT OF Sylvia M. Stoesser and William Fry, Midland, Micln, assignors to The Dow Chemical Company, Ml Michigan No Drawing.
dland, Mich, a corporation of Application May 4, 1934,
Serial No. 123,958
a claims. (01. 23-5) The invention relates to the treatment of deep wells and is more especially concerned with the treatment of wells in which the producing stratimi comprises a silicate rockformation of which serpentine is representative.
The treatment of deep wells in a limestone formation with aqueous hydrochloric acid containing various inhibiting agents to prevent the attack of the raw acid upon the metal parts of the 10 Well is disclosed in United States Patent 1,877,504. The use of hydrochloric 'acid in wells drilled into a serpentine formation has not given satisfactory results as to increasing the output of fluid prodnot from the well. We have now found that the l5 use of an aqueous oxidizing acid solution, containing hydrochloric acid and nitric acid, and more particularly, the use of an aqueous solution containing hydrochloric acid, nitric acid, and hydrofluoric acid, gives satisfactory results in the treatment of wells in a serpentine formation, However, such a solution is oxidizing in nature, and the inhibitin agents normally employed in solutions of hydrochloric acid alone are not effective to inhibit'sufiiciently the attack of such oxidizing acid solution upon the metal parts of the well.
It is therefore an object of the present invention to provide materials suitable for use as inhibitlng agents, which will efiectively prevent the 80 attack of a raw oxidizing acid solution upon the metal parts of a deep well, particularly at the elevated temperatures encountered at the base of the bore of such'wells.
There are a number of inhibiting agents which 86 are suitable for use at room temperature, and which at such temperatures are capable of sub-v stantially inhibiting the attack of oxidizing acid solutions upon metal, for example, alpha-naphthyl-amine, para-phenylenediamine, benzidine,
phenyl-hydrazine, pyrrole, and quinoline. However, the temperature conditions encountered in a deep well make it imperative that the inhibitor be effective at 100 F.'and slightly higher. For instance, in the Michigan oil field the temperature in the producing stratum is about 104 F.. and in themain producing stratum of the Texas field it is approximately 150 F. We have deter {mined that the aforesaid inhibitors, although eifective at ordinary temperatures, e. g. about 70 60 lose their effectiveness at 100 F., and therefore are'not suitable to inhibit oxidizing acid solutions in thetreatment of deep wells.
We have now discovered, however, that the diamino derivatives of benzophenone and diphenyl- I oxide, when added to aqueous oxidizing acid solutions, are effective at the temperature encountered in deep wells to inhibit the attack of such acid solutions upon the well tubing, etc.
The following examples show the effectiveness of diamino-diphenyloxide and of diaminobenzo- 5 phenone to inhibit the attack upon mild steel by aqueous oxidizing acid solutions maintained at elevated temperatures. Weighed strips of sandblasted, clean mild steel of like surface area were immersed in solutions of the composition shown, 10 and after 18 hours the strips were removed. rinsed, and weighed. All percentages of acid and inhibitor are by weight based on the total weight of solution.
Example 1 15 15 per cent HCl-5 per cent HNOa. Temperatum-100 F.
Grams loss Blank 10.587 p 0.4% diaminodiphenyloxide 0.509 0.4% diamlnobenzophenone 0.494
Example 2 15 per cent HCl-3 per cent HN03--2 per cent HF. Temperature-100 F. a
Example 3 15' per cent HCl-5 per cent HNOa. Temperaure-151 F.
Grams loss Blank 18.903 1% diaminodiphenyloxide -1- 2.587 1% diaminobenzophenone 2.540
At a temperature of 68 F. aqueous oxidizing acid solutions containing the diamino derivatives 40 of diphenyloxide and benzophenone have substantially no action upon the metals ordinarily employed in wells and in apparatus for the treatment of wells.
The treatment of a deep well with aqueous oxi- 45 dlzing acid solutions containing the diamino derivatives of diphenyloxide or benzophenone may be accomplished according to the known procedures. We incorporatebetween about 0.1 and 1.0 per cent by weight of such a derivative with an aqueous solution containing preferably between about 5 and about 20 per cent of hydrochloric acid, and between about 1 and about 10 per cent of nitric acid, with or without the addition of small amounts of hydrofluoric acid, e. g.
between about 1 and about 10 per cent thereof.
5 drawn prior to the treatment. It is suiflcient merely to pull the pump rod and valves and pour the acid solutionv in through the tube. The acid solution is preferably added in amount calculated to fill the bore of the well to a depth not exceeding the thickness of the fluid producing stratum. In order to force the charge of acid out of the pump tube into the producing stratum it may be followed by a charge of oil, water, or other liquid, or pressure may be applied by other suitable means, e. g. by air pressure'or by means of a pump. When introduced into the bottom of the well the acid attacks the rock structure and dissolves or disintcgrates it, thereby enlarging the pores or channels in the rock or opening up new channels. After the action of the acid has practically ceased, the spent solution may be pumped or bailed out. In many cases it may be desirable to repeat the treatment one or more times.
Another method which may be used in treating 2 a deep'well with our aqueous oxidizing acid solution employing our inhibitors is to introduce into the well in concentrated form, ahead oi the main oxidizing acid charge, a quantity of the diamino derivative of diphenyloxide or benzophenone thereby forming protective surfaces over the metal equipment within the well before said main charge of acid is contacted with such surfaces.
The diamino derivative may be employed in the form of a solution or emulsion thereof with any vehicle which does not react therewith to destroy its inhibiting properties. Among the various vehicles which may be employed we mention particularly ethyl alcohol. Having in this manner substantially immunized the metal surfaces within the well, we may then introduce the acid charge into the well and follow the general procedure outlined above for treatment with inhibited acid. Other modes of applying theprinciple of our invention may be-employed instead of the one explained, change beingmade as regards the materials employed, provided the ingredients stated by any of the following claims or the equivalent of such stated ingredients be employed. We therefore particularly point out and distinctly claim as our invention:-
1. An aqueous oxidizing solution containing nitric acid and a relatively small amount of a diamino derivative of a compound selected from the group consisting of diphenylomde and hen?- phenone. 6
2. An aqueous oxidizing solution containing nitric acid, hydrochloric acid, and a relatively small amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone. 10
3. An aqueous oxidizing solution containing nitric acid, hydrofluoric acid, and a relatively small amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone. l5
4. An aqueous oxidizing solution containing nitric acid, hydrochloric acid, hydrofluoric acid, and a relatively small amount of a diamino derivative of a compound selected from the group. consisting of diphenyloxide and benzophenone. 20
5. An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid and a relatively small amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzo- 25 phenone.
6. An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid, between about 5.0 and about 20.0 per cent by weight of hydrochloric acid, and a relativelysmall amount of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone.
7. An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight 35 of nitric acid, between about 1.0 and about 10.0 per cent by weight of hydrofluoric acid, and a relatively small amount of a diamino derivative of a compound selected from the group consisting of .diphenyloxide and benzophenone. 40
8. An aqueous oxidizing solution containing between about 1.0 and about 10.0 per cent by weight of nitric acid. between about 5.0 and about 20.0 per cent by weight of hydrochloric acid, between about 1.0 and about 10.0 per cent by weight of 45 hydrofluoric acid, and between about 0.1 and 1.0 per cent by weight of a diamino derivative of a compound selected from the group consisting of diphenyloxide and benzophenone.
SYLVIA M. STOESSER. 50 WILLIAM FRY.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US723958A US2048362A (en) | 1934-05-04 | 1934-05-04 | Acid composition for treatment of deep wells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US723958A US2048362A (en) | 1934-05-04 | 1934-05-04 | Acid composition for treatment of deep wells |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2048362A true US2048362A (en) | 1936-07-21 |
Family
ID=24908387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US723958A Expired - Lifetime US2048362A (en) | 1934-05-04 | 1934-05-04 | Acid composition for treatment of deep wells |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2048362A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2760845A (en) * | 1953-05-04 | 1956-08-28 | North American Aviation Inc | Stabilized fuming nitric acid |
| US2910437A (en) * | 1956-03-09 | 1959-10-27 | Universal Oil Prod Co | Stabilization of lubricants |
| US2926093A (en) * | 1957-08-12 | 1960-02-23 | Universal Oil Prod Co | Stabilization of organic substances |
| US2964479A (en) * | 1958-03-07 | 1960-12-13 | Universal Oil Prod Co | Stabilizing mixture of 4, 4'-diaminodiphenyl ether and 2, 4'-diaminodiphenyl ether |
| US3167123A (en) * | 1961-09-07 | 1965-01-26 | Jersey Prod Res Co | Method of acidizing and introducing a corrosion inhibitor into a hydrocarbon producing formation |
-
1934
- 1934-05-04 US US723958A patent/US2048362A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2760845A (en) * | 1953-05-04 | 1956-08-28 | North American Aviation Inc | Stabilized fuming nitric acid |
| US2910437A (en) * | 1956-03-09 | 1959-10-27 | Universal Oil Prod Co | Stabilization of lubricants |
| US2926093A (en) * | 1957-08-12 | 1960-02-23 | Universal Oil Prod Co | Stabilization of organic substances |
| US2964479A (en) * | 1958-03-07 | 1960-12-13 | Universal Oil Prod Co | Stabilizing mixture of 4, 4'-diaminodiphenyl ether and 2, 4'-diaminodiphenyl ether |
| US3167123A (en) * | 1961-09-07 | 1965-01-26 | Jersey Prod Res Co | Method of acidizing and introducing a corrosion inhibitor into a hydrocarbon producing formation |
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