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US1873084A - Method of preventing corrosion in oil wells - Google Patents

Method of preventing corrosion in oil wells Download PDF

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Publication number
US1873084A
US1873084A US294067A US29406728A US1873084A US 1873084 A US1873084 A US 1873084A US 294067 A US294067 A US 294067A US 29406728 A US29406728 A US 29406728A US 1873084 A US1873084 A US 1873084A
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United States
Prior art keywords
well
liquids
oil
solution
corrosion
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Expired - Lifetime
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US294067A
Inventor
Walker John Charles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMPIRE OIL AND REFINING Co
EMPIRE OIL AND REFINING COMPAN
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EMPIRE OIL AND REFINING COMPAN
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Priority to US294067A priority Critical patent/US1873084A/en
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Expired - Lifetime legal-status Critical Current

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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
    • C23F11/08—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
    • C23F11/185—Refractory metal-containing 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
    • Y10S507/939—Corrosion inhibitor

Definitions

  • acidic salts such as ferrous and ferric chlorides and sulphates, and magnesium chlorides and sulphates. These acidic salts hydrolize to some extent to form the metal oxide or hydroxide and mineral acid. Any oxygen present in the well liquids causes accelerated corrosion of metal parts in contacttherewith. Sometimes very corrosive well waters give an alkaline reaction to methyl orange indicator, showing the absence .in such liquids of free strong mineral acids. Most of these corrosion promoting compounds are acidic in char-- acter and many of them are very active in destroying iron and steel parts.
  • the present invention contemplates the prevention of corrosion of metal parts in contact with oil well liquids (particularly the brines or natural waters produced with the oil) containing one or more of such com-,
  • chromium com introduced into the oil well in such a manner as to be brought into intimate contact with the liquids in the well. These compounds act to neutralize acidic or corrosive components of the well liquids and to render the.
  • the invention also contemplates the prevention of scale formation on metal arts in oil wells by holding any precipitate matter which normally forms the scalein a form such that it will be carried out of the well with the water and oil pumped from the well.
  • iron oxide hydrated is formed upon contact of such brine with metal parts in the well; such oxide being deposited on the iron parts of the well as scale (rust).
  • strontium chloride or other soluble strontium salt which is contained in the top waters of wells in many localities.
  • strontium chloride or other soluble strontium salt which is contained in the top waters of wells in many localities.
  • strontium sulfate Upon admixture of strontium containing top waters with bottom waters containing sodium or calcium sulfate in solution, forexam le, strontium sulfate is formed.
  • Normally t e strontium sulfate is formed slowly because of the high concentration of the chloride ions, and accordingly deposits as a very hard compact scale. While strontium sulfate does not itself have any extensive corrosive efl'ect, its deposition as a hard scale causes serious mechanical troubles.
  • caustic soda has a very strong neutralizing effect on the acidic components of oil well brines, but-that its use is generally disadvantageous for the reason that it reacts .quickly and apparently selectively with calcium and magnesium salts contained in the brines, thus rapidly depleting the neutralizing strength of the. caustic and forming undesirable precipitates of calcium-and magnesium water insoluble salts. Accordingly if sodium hydroxide is used alone as a corrosion inhibiting treating agent for the well liquids, it usually takes an undesirably large amount of the caust1c soda to accomplish the desired corrosion inhibiting.
  • the chromium as it is added to the oil well liquids has been found to be very effective for reducing the corrosive action of, the well liquids (as well as for preventing or retarding rust scale formation).
  • the sodium chromate solution reacts slowly with any calcium and magnesium salts in the well liquids. No insoluble calcium or magnesium salts are usually formed for the reason that the sodium chromate is used in such small quantities that the solubility of the alkaline earth chromates in the large excess of brine is not exceeded.
  • the caustic sodium chromate solution normally has sufiiciently active neutralizing properties to pacify the acidic or corrosive properties of the oil well brines and to render inactive any oxygen present in the well liquids.
  • the sodium chromate solution acts to keep the metal surfaces in contact with the well liquids clean and its use therefore materially aids the pumping of the well in that the pump iston and packing operate much more ef- Eciently in the working barrel, and the friction losses are held at a minimum. The action in turn aids in lessening the amount of power which is used in pumping and in lessening the strain on the pumping rods and associated parts.
  • Treatment of the well liquids with an alkaline solution of sodium chromate prevents the formation of rust or hydrated ferric oxide scale on the metal parts.
  • an organic or inorganic colloid or colloidal forming material such as tannic acid, glue or sodium silicate
  • the treating agent may be made effective for inhibiting the formation of adherent hardscales of strontium sulfate and the like.
  • colloidal or gelatinous component of the treating agent causes the scale forming materials to remain in suspension in the-well liquids until they are carried to the surface by the action of the well pump. Potassium and sodium dichromates are sometimes used to advantage, either alone or in alkaline solution.
  • the chromate or chromium compound in alkaline solution is particularly effective for treating well liquids the corrosive action of which is chiefly due to mineral acids or acid salts with or without the presence of oxygen or carbon dioxide or both oxygen and carbon dioxide in the brine.
  • the di-chromate, chromate, chromous acid, or chromic acid may generally be employed alone to advantage because such reagents render the iron parts in contact with the well liquids passive without causing precipitation of insoluble calcium or magnesium carbonate.
  • the chemical or neutralizing agent may be added to the well in various ways.
  • One satisfactory schedule of operation is to introduce 50% or more of the reagent solution between the casing and the pump delivery pipe as rapidly as possible just after the pump is started. The remainder of the reagent is added in the same way but about fifteen minutes before the well is pumped off. However, when the well pumps continuously and with such metal parts.
  • a method of preventing corrosion of metal parts in contact with oil well liquids comprising treating such liquors prior to removal thereof from the well with a caustic solution of sodium chromate in amounts sufficient to inhibit corrosion of the oxidation type without causing substantial'precipitation of insoluble alkaline earth salts.
  • a method of preventing corrosion of metal parts by oil well liquids comprising mixing with the Well liquids a solution of a chromium salt having a specific gravity substantially equal to that of the well water.
  • a method of preventing corrosion of metal parts in contact with liquids from oil wells comprising mixing with said liquids an alkaline solution of an oil soluble chromium compound.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Lubricants (AREA)

Description

Patented Aug. 23, 1932 UNITED STATES PATENT OFFICE JOHN CHARLES WALKER,- OF TALLANT, OKLAHOMA, ASSIGNOR 'I'O OIL AND REFINING GOMPANY,-OF DOV ER, DELAWARE, A CORPORATION OF DELAWARE mnrnon or ranvnnmmo connosloiv m on. WELLS No Drawing.
part.
It is the particular object of the present invention to provide a process for treating oil well liquids whereby the serious losses of material and time which are normally caused by the corrosive attacks by such liquids on casings, pumps, and other metal parts installed in the well are prevented or avoided.
Among the compounds present in oil well liquids which have been found to be responsible for the corrosion of metal parts in contact with such liquids are acidic salts such as ferrous and ferric chlorides and sulphates, and magnesium chlorides and sulphates. These acidic salts hydrolize to some extent to form the metal oxide or hydroxide and mineral acid. Any oxygen present in the well liquids causes accelerated corrosion of metal parts in contacttherewith. Sometimes very corrosive well waters give an alkaline reaction to methyl orange indicator, showing the absence .in such liquids of free strong mineral acids. Most of these corrosion promoting compounds are acidic in char-- acter and many of them are very active in destroying iron and steel parts.
The present invention contemplates the prevention of corrosion of metal parts in contact with oil well liquids (particularly the brines or natural waters produced with the oil) containing one or more of such com-,
. pounds. pounds, preferably in alkaline solution, are
To accomplish this, chromium com introduced into the oil well in such a manner as to be brought into intimate contact with the liquids in the well. These compounds act to neutralize acidic or corrosive components of the well liquids and to render the.
Application filed July 19, 1 928. Serial No. 294,067.
metal parts passive or resistant to corrosive attack by the well liquids.
The invention also contemplates the prevention of scale formation on metal arts in oil wells by holding any precipitate matter which normally forms the scalein a form such that it will be carried out of the well with the water and oil pumped from the well.
If oil well waters or brines come in contact with carbonic acid or oxygen, or contain either one and come incontact with the other, .or contain .both carbonic acid and oxygen, iron oxide (hydrated) is formed upon contact of such brine with metal parts in the well; such oxide being deposited on the iron parts of the well as scale (rust). A
further source of troublesome scale is strontium chloride or other soluble strontium salt which is contained in the top waters of wells in many localities. Upon admixture of strontium containing top waters with bottom waters containing sodium or calcium sulfate in solution, forexam le, strontium sulfate is formed. Normally t e strontium sulfate is formed slowly because of the high concentration of the chloride ions, and accordingly deposits as a very hard compact scale. While strontium sulfate does not itself have any extensive corrosive efl'ect, its deposition as a hard scale causes serious mechanical troubles. In general the scales encountered or formed during oil well operation, a few of which are referred to above, promote rather than inhibit the corrosion of metal parts in contact with the oil well liquids, as well as interfering with the proper operation of the pumping apparatus which may be installed at the bottom of the well.
It has been found that caustic soda has a very strong neutralizing effect on the acidic components of oil well brines, but-that its use is generally disadvantageous for the reason that it reacts .quickly and apparently selectively with calcium and magnesium salts contained in the brines, thus rapidly depleting the neutralizing strength of the. caustic and forming undesirable precipitates of calcium-and magnesium water insoluble salts. Accordingly if sodium hydroxide is used alone as a corrosion inhibiting treating agent for the well liquids, it usually takes an undesirably large amount of the caust1c soda to accomplish the desired corrosion inhibiting.
. results, and furthermore undesirable preci itates are formed which add to the difliculties of pumping or otherwise operating the well.
ably formed by mixing salts of chromous or chromic acid with a slight excess of caustic soda. The amount of excess of caustic soda employed in making up the sodlum chromate solution is governed by the composition of the well liquids to be treated, and is normally so adjusted that the well liquids are rendered substantially neutral or preferably slightly alkaline by the treatment wlthout, however, carrying the neutralization far enough to precipitate appreciable quantities of calcium or magnesium carbonates 1n cases where the well liquids contain such alkaline earths in the form of bicarbonates. V
In place of sodium chroma-te other salts of chromous or chromic acid may in many cases be used to advantage, such for example as other alkali metal or ammonium chromates and dichromates. In employing an excess of alkali as above described, any d1- chromates used will be converted to chromates. If for any reason it is not desired to use an alkali solution of the treating agent, the dichromates may in general be used to advantage. In treating certain types of well liquids oil-soluble chromium compounds such as chromium resinate are in some cases advantageously employed. The invention therefore contemplates the addition to the' well liquids of chromium either in the form of an acid radical as in the chromate or in the form of a basic metal ion asin chromium resinate.
The chromium as it is added to the oil well liquids, for example in the form ofa caustic solution of sodium chromate, has been found to be very effective for reducing the corrosive action of, the well liquids (as well as for preventing or retarding rust scale formation). The sodium chromate solution reacts slowly with any calcium and magnesium salts in the well liquids. No insoluble calcium or magnesium salts are usually formed for the reason that the sodium chromate is used in such small quantities that the solubility of the alkaline earth chromates in the large excess of brine is not exceeded. The caustic sodium chromate solution normally has sufiiciently active neutralizing properties to pacify the acidic or corrosive properties of the oil well brines and to render inactive any oxygen present in the well liquids.
The sodium chromate solution acts to keep the metal surfaces in contact with the well liquids clean and its use therefore materially aids the pumping of the well in that the pump iston and packing operate much more ef- Eciently in the working barrel, and the friction losses are held at a minimum. The action in turn aids in lessening the amount of power which is used in pumping and in lessening the strain on the pumping rods and associated parts.
Treatment of the well liquids with an alkaline solution of sodium chromate prevents the formation of rust or hydrated ferric oxide scale on the metal parts. By adding to the treating agent a small amount of an organic or inorganic colloid or colloidal forming material such as tannic acid, glue or sodium silicate, the treating agent may be made effective for inhibiting the formation of adherent hardscales of strontium sulfate and the like. Such colloidal or gelatinous component of the treating agent causes the scale forming materials to remain in suspension in the-well liquids until they are carried to the surface by the action of the well pump. Potassium and sodium dichromates are sometimes used to advantage, either alone or in alkaline solution. In general the chromate or chromium compound in alkaline solution is particularly effective for treating well liquids the corrosive action of which is chiefly due to mineral acids or acid salts with or without the presence of oxygen or carbon dioxide or both oxygen and carbon dioxide in the brine. In cases where the corrosive action of well liquidsis essentially of the oxidation type and there is substantially no free acid present in the brine, the di-chromate, chromate, chromous acid, or chromic acid may generally be employed alone to advantage because such reagents render the iron parts in contact with the well liquids passive without causing precipitation of insoluble calcium or magnesium carbonate.
When treating the liquids in the well ac cording to the present invention, it has been found that it is necessary for best results and for the best protection of all the metal parts of or in the well that the corrosion inhibiting compound'difluses rapidly through the well liquids on being added thereto. This result is accomplished according to the present invention by making up the treating agent in a brine or salt water solution having a specific gravity substantially the same as the specific gravity of the water in the well to be treated. In making up the treating agent latter case a calculated excess of caustic or other neutralizingcompound is added to compensate for the calcium salts precipitated from the brine component of the solution.
The chemical or neutralizing agent may be added to the well in various ways. One satisfactory schedule of operation is to introduce 50% or more of the reagent solution between the casing and the pump delivery pipe as rapidly as possible just after the pump is started. The remainder of the reagent is added in the same way but about fifteen minutes before the well is pumped off. However, when the well pumps continuously and with such metal parts.
2. A method of preventing corrosion of metal parts in contact with oil well liquids,
comprising adding to the well liquids a solu- ,tion of a chromium compound in amounts sufficient to inhibit corrosion of the oxidation type Without causing precipitation of insoluble alkaline earth salts.
3. A method of preventing corrosion of metal parts in contact with oil well liquids comprising treating such liquors prior to removal thereof from the well with a caustic solution of sodium chromate in amounts sufficient to inhibit corrosion of the oxidation type without causing substantial'precipitation of insoluble alkaline earth salts.
4. A method of preventing corrosion of metal parts by oil well liquids comprising mixing with the Well liquids a solution of a chromium salt having a specific gravity substantially equal to that of the well water.
5. A method of preventing corrosion of metal parts in contact with oil well liquids comprlsing mixing with the well liquids an' aqueous. solution of sodium chromate having substantially the same specific gravity as the well water.
6. A method of preventing corrosion of metal parts in contact with liquids from oil wells comprising mixing with said liquids an alkaline solution of an oil soluble chromium compound.
In testimony whereof I atfix my signature.
JOHN CHARLES WALKER.
US294067A 1928-07-19 1928-07-19 Method of preventing corrosion in oil wells Expired - Lifetime US1873084A (en)

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426317A (en) * 1944-12-30 1947-08-26 Stanolind Oil & Gas Co Inhibiting well corrosion
US2426318A (en) * 1945-11-15 1947-08-26 Stanolind Oil & Gas Co Inhibiting corrosion
US2429593A (en) * 1946-01-02 1947-10-28 Gulf Oil Corp Chemical treatment of oil wells for the prevention of corrosion and scale
US2429594A (en) * 1946-01-02 1947-10-28 Gulf Oil Corp Chemical treatment of oil well liquids for preventing scale formation
US2437475A (en) * 1945-12-05 1948-03-09 Sun Oil Co Method of mitigating corrosion in wells
US2453881A (en) * 1946-01-24 1948-11-16 Standard Oil Dev Co Inhibition of corrosion in wells
US2453882A (en) * 1946-01-24 1948-11-16 Standard Oil Dev Co Inhibiting corrosion in wells
US2461359A (en) * 1946-01-26 1949-02-08 Standard Oil Dev Co Inhibiting acidic corrosion in wells
US2466517A (en) * 1948-01-10 1949-04-05 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2468163A (en) * 1948-01-10 1949-04-26 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2493462A (en) * 1946-12-28 1950-01-03 Stanolind Oil & Gas Co Inhibiting corrosion in wells
US2510771A (en) * 1946-11-01 1950-06-06 Pure Oil Co Method of protecting metal surfaces against hydrogen sulfide corrosion
US2523898A (en) * 1947-01-27 1950-09-26 Phillips Petroleum Co Corrosion inhibition
US2531829A (en) * 1948-01-31 1950-11-28 John L Seymour Inhibition of oil well corrosion
US2546586A (en) * 1946-01-28 1951-03-27 Kansas City Testing Lab Corrosion prevention
US2588369A (en) * 1947-05-14 1952-03-11 Us Interior Apparatus for use in the treatment of oil, gas, and gas-condensate wells
US2717651A (en) * 1952-07-22 1955-09-13 California Research Corp Apparatus for preventing corrosion in oil wells
US2728400A (en) * 1952-07-22 1955-12-27 California Research Corp Apparatus for preventing corrosion in oil wells
US2760584A (en) * 1952-07-22 1956-08-28 California Research Corp Method and apparatus for preventing corrosion in oil wells
US2913420A (en) * 1956-10-18 1959-11-17 Dow Chemical Co Corrosion inhibition of brine
US4967838A (en) * 1989-09-14 1990-11-06 Occidental Chemical Corporation Oil well and method using completion fluid

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2426317A (en) * 1944-12-30 1947-08-26 Stanolind Oil & Gas Co Inhibiting well corrosion
US2426318A (en) * 1945-11-15 1947-08-26 Stanolind Oil & Gas Co Inhibiting corrosion
US2437475A (en) * 1945-12-05 1948-03-09 Sun Oil Co Method of mitigating corrosion in wells
US2429593A (en) * 1946-01-02 1947-10-28 Gulf Oil Corp Chemical treatment of oil wells for the prevention of corrosion and scale
US2429594A (en) * 1946-01-02 1947-10-28 Gulf Oil Corp Chemical treatment of oil well liquids for preventing scale formation
US2453881A (en) * 1946-01-24 1948-11-16 Standard Oil Dev Co Inhibition of corrosion in wells
US2453882A (en) * 1946-01-24 1948-11-16 Standard Oil Dev Co Inhibiting corrosion in wells
US2461359A (en) * 1946-01-26 1949-02-08 Standard Oil Dev Co Inhibiting acidic corrosion in wells
US2546586A (en) * 1946-01-28 1951-03-27 Kansas City Testing Lab Corrosion prevention
US2510771A (en) * 1946-11-01 1950-06-06 Pure Oil Co Method of protecting metal surfaces against hydrogen sulfide corrosion
US2493462A (en) * 1946-12-28 1950-01-03 Stanolind Oil & Gas Co Inhibiting corrosion in wells
US2523898A (en) * 1947-01-27 1950-09-26 Phillips Petroleum Co Corrosion inhibition
US2588369A (en) * 1947-05-14 1952-03-11 Us Interior Apparatus for use in the treatment of oil, gas, and gas-condensate wells
US2468163A (en) * 1948-01-10 1949-04-26 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2466517A (en) * 1948-01-10 1949-04-05 Petrolite Corp Processes for preventing corrosion and corrosion inhibitors
US2531829A (en) * 1948-01-31 1950-11-28 John L Seymour Inhibition of oil well corrosion
US2717651A (en) * 1952-07-22 1955-09-13 California Research Corp Apparatus for preventing corrosion in oil wells
US2728400A (en) * 1952-07-22 1955-12-27 California Research Corp Apparatus for preventing corrosion in oil wells
US2760584A (en) * 1952-07-22 1956-08-28 California Research Corp Method and apparatus for preventing corrosion in oil wells
US2913420A (en) * 1956-10-18 1959-11-17 Dow Chemical Co Corrosion inhibition of brine
US4967838A (en) * 1989-09-14 1990-11-06 Occidental Chemical Corporation Oil well and method using completion fluid

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