US3250706A - Method of reducing corrosion - Google Patents
Method of reducing corrosion Download PDFInfo
- Publication number
- US3250706A US3250706A US305845A US30584563A US3250706A US 3250706 A US3250706 A US 3250706A US 305845 A US305845 A US 305845A US 30584563 A US30584563 A US 30584563A US 3250706 A US3250706 A US 3250706A
- Authority
- US
- United States
- Prior art keywords
- oil
- acid
- inhibitor
- octahydrophenanthridine
- solution
- 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
Classifications
-
- 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
-
- 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
- C23F11/10—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 organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
- C23G1/063—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors heterocyclic compounds
-
- 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
-
- 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
- Y10S507/939—Corrosion inhibitor
Definitions
- the present invention relates to a method of reducing corrosion of metal.
- One aspect of the invention pertains to the reduction of corrosion of metal apparatus in contact with petroliferous oil and gas well fluids and in contact with acidic compositions utilized in 'acidizing oil and gas wells.
- Another aspect of the invention relates to the reduction of the corrosion of metal subjected to acidizing treatments such as pickling.
- the acidizing solutions increase production by attacking and dissolving portions of the petroliferous fluid bearing rock thereby opening up new channels for the petroliferous fluid to flow through.
- the temperature at which acidizing is conducted is the temperature of the rock formation which may be as high as about 175 C.
- the acid treat-ing compositions normally comprise between about to 30 wt. percent aqueous solutions of strong acid such as sulfuric, hydrochloric, hydrofluoric, orthophosphoric, nitric, monofluorophosphoric, polyfluorophosphoric acid and organic acids such as acetic, abromopropionic acid and trichloroacetic acid.
- Hydrochloric acid and mixtures of, hydrochloric and hydrofluoric acids are usually employed.
- the acidizing solutions are, however, highly corrosive to the oil and gas well metal apparatus, e.g., ferrous metals such as steel and cast iron. In the absence of some method of retarding this corrosive attack the life of the oil and gas well equipment is materially shortened.
- Metal pickling can be defined as the removal of metal oxide from the surface of a metal structure by immersing said structure in a dilute mineral acid at a temperature ranging from ambient to about 90 C.
- the metals normally treated are the ferrous metals, copper, magnesium and the like and alloys thereof.
- the treatment is normally conducted with between about 5 to 80 wt. percent mineral acid such as sulfuric or hydrochloric acid.
- mineral acid such as sulfuric or hydrochloric acid.
- octahydrophenanthridine inhibitors contemplated herein are of the formula:
- R is an alkyl radical of from 5 to 10 carbons and R and R are selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbons.
- octahydrophenanthridine inhibitors of the invention are 6-pentyl-1,2,3,4,7,8,9,10-octahydrophenanthridine; 2,8-dimethyl-6-(3'-methylpentyl)-1,2,3,4,7,'8,9, 10-0ctahydrophenanthridine; 3,9-dimethyl-6-(4-methylpentyl)-l,2,3,4,7,8,9,10-octahydrophenanthridine; 1,7-dimethyl 6 (2'-methylpentyl)-1,2,3,4,7,8,9,IO-Octahydrophenanthridine and 2,8-dipropyl-6-(3' propylpentyl)-1,2, 3,4,7,8,9, 10-0ctahydrophenan
- the octahydrophenanthridine inhibitors of the invention are prepared by contacting cyclohexanone, 2-alkylcyclohexanone, or 4-alkylcyclohexanone with ammonia at between about 300 and 400 C. in the presence of a thoria catalyst in a mole ratio of ammonia/cyclohexanone or alkylated cyclohexanone of between about 2:1 to 8:1.
- the alkyl portion of the alkylated cyclohexanones have from 1 to 5 carbons. cyclohexanone, 2-butylcyclohexanone and 4-propylcyclohexanone.
- alkyl-substituted octahydrophenanthridines employed in the method of this invention, as well as methods for their preparation, are disclosed and claimed in commonly assigned applications, Serial Nos. 356,061 and 356,064, filed March 31, 1964.
- the octahydrophenanthridine inhibitor may be added to the petroliferous corrosive fluids in the ways known to the art.
- the octahydrophenanthridine may be added directly or as a solution in oil or other inert hydrocarbon solvents.
- the inhibitor or solution is normally poured down the annular space between the casing and the tubing string.
- the inhibitor can be injected at various points along the length thereof.
- the octahydrophenanthridine inhibitors need not be diluted. However, to insure a proper mixing solvent solutions containing 1 to 70 wt. percent of the inhibitor are properly employed.
- oils are the most economical diluent for the inhibitor
- other diluents which are themselves oil soluble may be employed, for example, solvents such as kerosene, benzene, methyl alcohol, ethyl alcohol and isopropyl alcohol.
- solvents such as kerosene, benzene, methyl alcohol, ethyl alcohol and isopropyl alcohol.
- the amount of inhibitor combination employed in corrosive oil fluids is dependent on intensity of corrosive conditions and the degree of protection desired, normally between about .05 and 5 wt. percent of the inhibitor based on the corrosive well fluid mixture is utilized.
- the inhibitor is normally incorporated into the acidizing solution prior to the solutions introduction into the well.
- One method of introduction is simultaneously introducing separate streams of inhibitor and acid solution into the tubing in the well bore at the well head.
- inert diluents such as alcohols of the type and quantity described in relation to inhibiting petroliferous fluids may be employed.
- the inhibitor is normally introduced directly into the pickling acid solution without dilution and the acid is agitated to insure inhibitor distribution therein.
- the quantity of inhibitor utilized in the acidizing and pickling solutions is desirably between about .05 and 5 wt. percent.
- EXAMPLE I This example illustrates the preparation of 6-pentyl- 1,2,3,4,7,8,9,10-octahydrophenanthridine.
- EXAMPLE II This example demonstrates the effectiveness of the novel inhibitor in suppressing corrosion of metals in contact with corrosive petroliferous oil and gas well fluids.
- test mixture oil-brine exposure fluid
- Hydrogen sulfide was used as the saturating gas for simulating sour systems.
- the bottle is then stoppered to maintain the carbon dioxide or hydrogen sulfide atmosphere.
- the stoppered bottle was then tumbled on a wheel for a period of 2 days at a temperature of about 155 F.
- the test coupons are brushed, washed with acetone and water. dried and reweighed. For each test run a corresponding blank test run was made in which no inhibitor was employed.
- EXAMPLE III acid or an aqueous mixture containing 6 wt. percent hydrofluoric and 9 wt. percent hydrochloric acid.
- a weighed steel test coupon P-l05 steel. The beaker was covered and maintained at a temperature of 100 C. for a period of 2 to hours. At the end of the test period the test coupon was removed, rinsed successively with water and acetone, dried and reweighed.
- the inhibitor employed was the octahydrophenanthridine of Example I.
- This example further demonstrates the effectiveness of the inhibitor of the invention in reducing corrosion of metals in contact with acid treating solutions such as pickling solutions.
- a method of reducing the corrosion of ferrous metals comprising contacting said metals with a corrosive acidic solution selected from the group consisting of petroliferous oil and gas well fluid, acidizing solution for oil and gas rock bearing formations and metal pickling acid solution, containing a corrosion inhibiting amount of an octahydrophenanthridine of the formula:
- R is an alkyl radical of from 5 to 10 carbons and R and R are selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbons.
- said acidic solution is petroliferous oil and gas well fluid.
- said acidic solution is an acidizing solution comprising aqueous hydrochloric acid.
- said acidic solution is an acidizing solution comprising an aqueous mixture of hydrofluoric acid and hydrochloric acid.
- said acidic solution is a metal pickling solution comprising aqueous sulfuric acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
United States Patent 3,250,706 METHOD OF REDUCING CGRROSION Wayne Kuhn, Fishkill, N.Y., and Charles C. Nathan, Bellalre, Tex., assignors to Texaco Inc., New York, N.Y., a corporation of Delaware No Drawing. Fiied Aug. 30, 1963, Ser. No. 305,845 7 Claims. (Cl. 252-855) The present invention relates toa method of reducing corrosion of metal. One aspect of the invention pertains to the reduction of corrosion of metal apparatus in contact with petroliferous oil and gas well fluids and in contact with acidic compositions utilized in 'acidizing oil and gas wells. Another aspect of the invention relates to the reduction of the corrosion of metal subjected to acidizing treatments such as pickling.
In oil and gas condensate fields the production of petroliferous fluids from subsurface formations is often accompanied by extremely severe corrosion of metal appar-atus contacting the fluid produced. In some instances it is 'found that these fluids contain substantial amounts of organic acid materials such as acetic acid and/or carbon dioxide in the form of carbonic acid. These fluids are classified in the petroleum art as sweet. In other cases the fluids include corrosive sulfides such as alkali metal, and alkaline earth metal sulfides and hydrosulfides, hydrogen sulfide, .and/ or organic sulfides. The sulfide containing fluids are normally designated as sour.
Also in respect to oil and gas wells they are periodically subjected to an acidizing treatment in order to increase oil production. The acidizing solutions increase production by attacking and dissolving portions of the petroliferous fluid bearing rock thereby opening up new channels for the petroliferous fluid to flow through. The temperature at which acidizing is conducted is the temperature of the rock formation which may be as high as about 175 C. The acid treat-ing compositions normally comprise between about to 30 wt. percent aqueous solutions of strong acid such as sulfuric, hydrochloric, hydrofluoric, orthophosphoric, nitric, monofluorophosphoric, polyfluorophosphoric acid and organic acids such as acetic, abromopropionic acid and trichloroacetic acid. Hydrochloric acid and mixtures of, hydrochloric and hydrofluoric acids are usually employed. The acidizing solutions are, however, highly corrosive to the oil and gas well metal apparatus, e.g., ferrous metals such as steel and cast iron. In the absence of some method of retarding this corrosive attack the life of the oil and gas well equipment is materially shortened.
A corrosion problem closely related to that found in the aforedescribed acidizing treatment arises in the pickling of metals. Metal pickling can be defined as the removal of metal oxide from the surface of a metal structure by immersing said structure in a dilute mineral acid at a temperature ranging from ambient to about 90 C.
' The metals normally treated are the ferrous metals, copper, magnesium and the like and alloys thereof. The treatment is normally conducted with between about 5 to 80 wt. percent mineral acid such as sulfuric or hydrochloric acid. One of the problems as in the aoidizing treatment is to permit the acid to attack the oxide scale while inhibiting the acid attack of the metal itself.
We have discovered, and this constitutes the invention, that by incorporating a corrosion inhibiting amount of an alkyl (saturated aliphatic hydrocarbyl) substituted 1,2,3, 4,7,8,9,IO-octahydrophenanthridine in petroliferous oil and gas well fluids, oil and gas well acidizing solutions and acid pickling solutions the corrosion of metals in contact therewith is substantially reduced.
ice
The octahydrophenanthridine inhibitors contemplated herein are of the formula:
where R is an alkyl radical of from 5 to 10 carbons and R and R are selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbons. Specific examples of the octahydrophenanthridine inhibitors of the invention are 6-pentyl-1,2,3,4,7,8,9,10-octahydrophenanthridine; 2,8-dimethyl-6-(3'-methylpentyl)-1,2,3,4,7,'8,9, 10-0ctahydrophenanthridine; 3,9-dimethyl-6-(4-methylpentyl)-l,2,3,4,7,8,9,10-octahydrophenanthridine; 1,7-dimethyl 6 (2'-methylpentyl)-1,2,3,4,7,8,9,IO-Octahydrophenanthridine and 2,8-dipropyl-6-(3' propylpentyl)-1,2, 3,4,7,8,9, 10-0ctahydrophenanthridine.
The octahydrophenanthridine inhibitors of the invention are prepared by contacting cyclohexanone, 2-alkylcyclohexanone, or 4-alkylcyclohexanone with ammonia at between about 300 and 400 C. in the presence of a thoria catalyst in a mole ratio of ammonia/cyclohexanone or alkylated cyclohexanone of between about 2:1 to 8:1. The alkyl portion of the alkylated cyclohexanones have from 1 to 5 carbons. cyclohexanone, 2-butylcyclohexanone and 4-propylcyclohexanone.
The alkyl-substituted octahydrophenanthridines employed in the method of this invention, as well as methods for their preparation, are disclosed and claimed in commonly assigned applications, Serial Nos. 356,061 and 356,064, filed March 31, 1964.
The octahydrophenanthridine inhibitor may be added to the petroliferous corrosive fluids in the ways known to the art. For example, if the inhibitor is to be applied to an oil well, gas well or pipeline, the octahydrophenanthridine may be added directly or as a solution in oil or other inert hydrocarbon solvents. In respect to oil and gas wells the inhibitor or solution is normally poured down the annular space between the casing and the tubing string. As to the pipelines the inhibitor can be injected at various points along the length thereof. The octahydrophenanthridine inhibitors need not be diluted. However, to insure a proper mixing solvent solutions containing 1 to 70 wt. percent of the inhibitor are properly employed. Although petroleum oils are the most economical diluent for the inhibitor, other diluents which are themselves oil soluble may be employed, for example, solvents such as kerosene, benzene, methyl alcohol, ethyl alcohol and isopropyl alcohol. In oil and gas petrolife'rous well fluid corrosion, although the amount of inhibitor combination employed in corrosive oil fluids is dependent on intensity of corrosive conditions and the degree of protection desired, normally between about .05 and 5 wt. percent of the inhibitor based on the corrosive well fluid mixture is utilized.
In respect to the oil and gas well acidizing solutions for producing formations the inhibitor is normally incorporated into the acidizing solution prior to the solutions introduction into the well. One method of introduction is simultaneously introducing separate streams of inhibitor and acid solution into the tubing in the well bore at the well head. To facilitate introduction of the inhibitor into the acid solution, inert diluents such as alcohols of the type and quantity described in relation to inhibiting petroliferous fluids may be employed.
Specific examples are Z-methyl- In regard to the pickling acid solutions the inhibitor is normally introduced directly into the pickling acid solution without dilution and the acid is agitated to insure inhibitor distribution therein.
The quantity of inhibitor utilized in the acidizing and pickling solutions is desirably between about .05 and 5 wt. percent.
The following examples further illustrate the invention but are not to be interpreted as limitations thereof.
EXAMPLE I This example illustrates the preparation of 6-pentyl- 1,2,3,4,7,8,9,10-octahydrophenanthridine.
.A glass reaction tube containing an 80 wt. percent thoria, wt. percent alumina catalyst was preheated to 350 C. while being swept with dry nitrogen. At 350 C. a stream of ammonia and cyclohexanone in a mole ratio of 4.721 was then passed through the tube at a residence time rate of 9.6 seconds. The gaseous product was condensed, collected and distilled. A water white viscous oil distillate fraction was analyzed by chromatography and determined to be 6-pentyl-1,2,3,4,7,8,9,10- octahydrophenanthridine having the following properties: Boiling point 170172 C. at 3 mm. Hg; density, C.=1.0071; refractive index, n =1.5455, n =1.5436
EXAMPLE II This example demonstrates the effectiveness of the novel inhibitor in suppressing corrosion of metals in contact with corrosive petroliferous oil and gas well fluids.
To a 4 ounce glass bottle there was added 100 milliliters (rnls.) of test mixture (oil-brine exposure fluid). The test mixture was prepared by combining 90 rnls. of
synthetic brine aqueous solution containing 10 wt. percent sodium chlorine and 0.5 wt. percent calcium chloride) and 10 mls. of an oil solution containing the octahydrophenanthridine inhibitor of Example I. The inhibitor was present in an amount to give the final 100 mls. mixture an inhibitor content of 1000 ppm. The oil used had a kinematic viscosity at 100 F. of about 4.5 centistrokes and an API Gravity of about 37. One ml. of a 6 wt. percent acetic acid was then added to the test bottle prior to sweetening or souring together with a weighed polished steel coupon. To simulate the sweet systems the fluid in the bottle was saturated with carbon dioxide gas at room temperature. Hydrogen sulfide was used as the saturating gas for simulating sour systems. In either case the bottle is then stoppered to maintain the carbon dioxide or hydrogen sulfide atmosphere. The stoppered bottle was then tumbled on a wheel for a period of 2 days at a temperature of about 155 F. At the end of the test period the test coupons are brushed, washed with acetone and water. dried and reweighed. For each test run a corresponding blank test run was made in which no inhibitor was employed.
In Table I below there is a compilation of corrosion test results:
Table I Test period, days Percent COI 'I'OS10!1 inhibition 1 Test conditions Sweet Sour 1 Bla.nk=0%. 1 Average of 3 test runs.
EXAMPLE III acid or an aqueous mixture containing 6 wt. percent hydrofluoric and 9 wt. percent hydrochloric acid. There was also added a weighed steel test coupon (P-l05 steel). The beaker was covered and maintained at a temperature of 100 C. for a period of 2 to hours. At the end of the test period the test coupon was removed, rinsed successively with water and acetone, dried and reweighed.
The inhibitor employed was the octahydrophenanthridine of Example I.
In the following Table 11 there is found a compilation of the corrosion data and test results:
This example further demonstrates the effectiveness of the inhibitor of the invention in reducing corrosion of metals in contact with acid treating solutions such as pickling solutions.
A weighed 70 mm. pure iron wire, British standard gage No. 24 was immersed for a 3.5 hour period in a stirred 7.5 wt. percent aqueous sulfuric acid solution maintained at 60 C. At the end of the 3.5 hour period the iron Wire was removed, washed with water and reweighed. Test runs were made in which the sulfuric acid pickling solution contained the octahydrophenanthridine of Example I. A blank run was also made in which no inhibitor was included in the pickling solution. The test data and results are reported in Table III:
1 Based on 7.5 wt. percent aqueous H2804 solution.
We claim:
1. A method of reducing the corrosion of ferrous metals comprising contacting said metals with a corrosive acidic solution selected from the group consisting of petroliferous oil and gas well fluid, acidizing solution for oil and gas rock bearing formations and metal pickling acid solution, containing a corrosion inhibiting amount of an octahydrophenanthridine of the formula:
where R is an alkyl radical of from 5 to 10 carbons and R and R are selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbons.
2. A method in accordance with claim 1 wherein said corrosion inhibiting amount is between about 0.05 and 5 wt. percent.
3. A method in accordance with claim 2 wherein said 5 octahydrophenanthridine is 6 .pentyl 1,2,3,4,7,8,9,10- octahydrophenanthridine.
4. A method in accordance with claim 3 wherein said acidic solution is petroliferous oil and gas well fluid.
5. A method in accordance with claim 3 wherein said acidic solution is an acidizing solution comprising aqueous hydrochloric acid.
6. A method in accordance with claim 3 wherein said acidic solution is an acidizing solution comprising an aqueous mixture of hydrofluoric acid and hydrochloric acid.
7. A method in accordance with claim 3 wherein said acidic solution is a metal pickling solution comprising aqueous sulfuric acid.
References Cited by the Examiner UNITED STATES PATENTS 1,746,679 2/1930 Rhodes 252148 2,167,621 7/1939 Beaver 252-448 2,814,593 11/1957 Beiswanger et al. 252-8.55 2,955,083 10/1960 Levin 252-8.55
JULIUS GREENWALD, Primary Examiner.
H. B. GUYNN, Assistant Examiner.
Claims (1)
1. A METHOD OF REDUCING THE CORROSION OF FERROUS METALS COMPRISING CONTACTING SAID METALS WITH A CORROSIVE ACIDIC SOLUTION SELECTED FROM THE GROUP CONSISTING OF PETROLIFEROUS OIL AND GAS WELL FLUID, ACIDIZING SOLUTION FOR OIL AND GAS ROCK BEARING FORMATIONS AND METAL PICKLING ACID SOLUTION, CONTAINING A CORROSION INHIBITING AMOUNT OF AN OCTAHYDROPHENANTHRIDINE OF THE FORMULA:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US305845A US3250706A (en) | 1963-08-30 | 1963-08-30 | Method of reducing corrosion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US305845A US3250706A (en) | 1963-08-30 | 1963-08-30 | Method of reducing corrosion |
Publications (1)
Publication Number | Publication Date |
---|---|
US3250706A true US3250706A (en) | 1966-05-10 |
Family
ID=23182616
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US305845A Expired - Lifetime US3250706A (en) | 1963-08-30 | 1963-08-30 | Method of reducing corrosion |
Country Status (1)
Country | Link |
---|---|
US (1) | US3250706A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3408351A (en) * | 1966-08-25 | 1968-10-29 | Texaco Inc | Method of preparing octahydro-phenanthridines |
US4665180A (en) * | 1984-11-06 | 1987-05-12 | Petrolite Corporation | Substituted tetrahydropyrimidines and octahydrophenanthridines |
EP0275646A1 (en) * | 1987-01-02 | 1988-07-27 | Petrolite Corporation | Carbon dioxide corrosion inhibiting composition and method of use thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1746679A (en) * | 1929-07-18 | 1930-02-11 | Fred H Rhodes | Chemical reagent |
US2167621A (en) * | 1937-09-14 | 1939-08-01 | Monsanto Chemicals | Metal pickling process |
US2814593A (en) * | 1953-12-18 | 1957-11-26 | Gen Aniline & Film Corp | Corrosion inhibition |
US2955083A (en) * | 1956-08-13 | 1960-10-04 | Bj Service Inc | Corrosion inhibitors in well treating compositions |
-
1963
- 1963-08-30 US US305845A patent/US3250706A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1746679A (en) * | 1929-07-18 | 1930-02-11 | Fred H Rhodes | Chemical reagent |
US2167621A (en) * | 1937-09-14 | 1939-08-01 | Monsanto Chemicals | Metal pickling process |
US2814593A (en) * | 1953-12-18 | 1957-11-26 | Gen Aniline & Film Corp | Corrosion inhibition |
US2955083A (en) * | 1956-08-13 | 1960-10-04 | Bj Service Inc | Corrosion inhibitors in well treating compositions |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3408351A (en) * | 1966-08-25 | 1968-10-29 | Texaco Inc | Method of preparing octahydro-phenanthridines |
US4665180A (en) * | 1984-11-06 | 1987-05-12 | Petrolite Corporation | Substituted tetrahydropyrimidines and octahydrophenanthridines |
EP0275646A1 (en) * | 1987-01-02 | 1988-07-27 | Petrolite Corporation | Carbon dioxide corrosion inhibiting composition and method of use thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2889277A (en) | Method of inhibiting corrosion of metals | |
US6192987B1 (en) | Metal corrosion inhibitors, inhibited acid compositions and methods | |
US2496354A (en) | Method of inhibiting hydrogen sulfide corrosion of metals | |
US4522658A (en) | Method and composition for protecting metal surfaces from oxidative environments | |
US5976416A (en) | Corrosion inhibited organic acid compositions and methods | |
US5013483A (en) | Process and composition for inhibiting iron and steel corrosion | |
US2659693A (en) | Process for preventing corrosion of ferrous metals | |
US2643227A (en) | Method of inhibiting corrosion of metals | |
CA2274925C (en) | Corrosion inhibiting compositions and methods | |
US2643977A (en) | Method of inhibiting corrosion of metals | |
MX2010010834A (en) | Organic corrosion inhibitor package for organic acids. | |
US2596273A (en) | Method of inhibiting hydrogen sulfide corrosion of metals | |
US3766053A (en) | Corrosion inhibitors for refining & petrochemical processing equipment | |
US2846440A (en) | Composition for and method of inhibiting corrosion of metals | |
US2643978A (en) | Method of inhibiting corrosion of metals | |
US2596425A (en) | Method of inhibiting hydrogen sulfide corrosion of metals | |
US3250706A (en) | Method of reducing corrosion | |
US2436198A (en) | Chemical removal of an acid-soluble metal part in a deep well | |
US4330419A (en) | Method of and solvent for removing inorganic fluoride deposits | |
US2698295A (en) | Combating ferrous metal corrosion | |
US3038856A (en) | Corrosion inhibition | |
US2799649A (en) | Method for inhibiting corrosion | |
US2675355A (en) | Method for inhibiting corrosion | |
US2950246A (en) | Process for increasing the permeability of oil bearing chalk formations | |
US3260669A (en) | Corrosion inhibiting composition for use in oil well fluids |