US2822330A - Weighted corrosion inhibitor - Google Patents

Weighted corrosion inhibitor Download PDF

Info

Publication number
US2822330A
US2822330A US494226A US49422655A US2822330A US 2822330 A US2822330 A US 2822330A US 494226 A US494226 A US 494226A US 49422655 A US49422655 A US 49422655A US 2822330 A US2822330 A US 2822330A
Authority
US
United States
Prior art keywords
oil
inhibitor
corrosion
corrosion inhibitor
composition
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
Application number
US494226A
Inventor
Jr Olen L Riggs
D Arcy A Shock
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.)
ConocoPhillips Co
Original Assignee
Continental Oil Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Continental Oil Co filed Critical Continental Oil Co
Priority to US494226A priority Critical patent/US2822330A/en
Application granted granted Critical
Publication of US2822330A publication Critical patent/US2822330A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/143Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/188Carboxylic acids; metal salts thereof
    • C10L1/1881Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/192Macromolecular compounds
    • C10L1/198Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/232Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/234Macromolecular compounds
    • C10L1/238Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
    • C10L1/2387Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/24Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2462Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
    • C10L1/2475Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
    • C10L1/2487Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds polyoxyalkylene thioethers (O + S 3=)
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/939Corrosion inhibitor

Definitions

  • This invention relates to the prevention of corrosion of metal equipment in producing oil wells. More particularly, the invention relates to the protection of steel casings, steel tubing, and other metal well equipmentfrom the deleterious effects of corrosive formation liquids.
  • Corrosive sulfide brines include alkali and alkaline earth metal sulfides and hydrogen sulfide. Hydrogen sulfide and carbon dioxide are very soluble in water and brines and in addition hydrogen sulfide is soluble in petroleum oil thus forming corrosive solutions which cause deterioration of Welland surface equipment. This corrosion takes place in brines having a .pH' below about 8, which includes practically all natural well brines.
  • ER is common practice to introduce an inhibitor at the wellhead into the annular space between the casing and the tubing in a well extending into a producing formation.
  • the liquid inhibitors which have been used are expected to flow to a producing zone in the well .to mix with the corrosive liquids flowing therefrom and then will flow up through the tubing to the surface.
  • a further object of "the invention isto render oil-soluble inhibitors 'sufliciently limited in solubility so as to pass readily through the oil layer floating upon 'a column of brine without appreciable dissolution by providing a liquid solubility-limiting agent and a Weighting agent in combination with the corrosion inhibitor.
  • Astill further objectof this invention is to provide improved weighted corrosion inhibiting compositions for use in producing -oil wells.
  • aprocess which broadly .stated comprises a method of inhibiting corrosi on "inoil wells which comprises the addition to the annular space between "the casing and the tubing of a producing oil well a 'liquid 'c'orrosion inhibiting compositio'n icomprising' an oil soluble corrosion inhibitor, an immiscibilizing agent for the corrosion inhibitor and a mutual solvent for the inhibitor and the immiscibillzing 2 agent.
  • the mutual solvent must have a specific gravity so that the final composition has a specific gravity greater than 1.01. Based on the weight of the composition, the inhibitor, immiscibilizing agent, and solvent may vary from 20 to 70, 5 to 25, and 5 to percent respectively.
  • the oil soluble corrosion inhibitors which are useful for the practice of this invention are iron corrosion inhibitors and in general they may be of the nitrogen chain or ring type, high molecular weight carboxylic acid, sulfonic acids and various salts of these acids with alkali metals, alkaline earth metals, ammonia, amines, and alkanolarnines.
  • Various alk'yl pyrimidines are also suitable in the process of this invention.
  • Nitrogen ring type inhibitors may be used also.
  • Specific nitrogen ring type inhibitors are the N-aliphatic pyrrolinediones represented by the formula:
  • X and. Y are members from the class consisting of hydrogen, halogen, and simple hydrocarbon groups and R is an aliphatic group, such as disclosed in U. S. Patent No. 2,466,530 issued to C. M. Blair and W. F. Gross, and are available under. the brand name Kontol- 118 which has a density of 0.957 at 60 F.
  • the aliphatic radical contains at least 7 and not more than 32 carbon atoms.
  • the flash point, fire point, pour point, and viscosity are 165" F., .225" F., 20 F, and 477 S. S. U. at 100 F. respectively. It is soluble in oil but insoluble in water.
  • high molecular Weight carboxylic acids suitable in the process of this invention are high molecular weight polycarboxylic acids.
  • polycarboxylic acids obtained by polymerization of unsaturated acids in accordance with a method such as is described in the Journal of the American Oil Chemists Society, 24, 65 (1947).
  • raw materials containing linoleic acid on treatment by this method yield mixtures of dimers, trimers, and higher polymers of linoleic acid.
  • Such a polymer mixture that may be utilized in the process of this invention is available commercially under the trade designation M46lR, dimer acids. It has the following properties:
  • D-85 dimer acid Anothersuitable polymerized unsaturated acid is available commercially under the trade designation D-85 dimer acid. It has the following properties:
  • Suitable sulfonic acids for the process of this invention include various petroleum sulfonic acids known as mahogany sulfonic acids obtained by the sulfonation of high molecular, weight petroleum fractions.
  • Other satisfactory sulfonic acids are those obtained by the sulfonation of alkyl aromatic hydrocarbons obtained by the alkylation of aromatic hydrocarbons with alkyl alkylating agents having more than nine carbon atoms, as, for example, haloparaffing olefins as from dehydrohalogenated haloparafiins, polyolefins such polypropylene, alkylsulfates,
  • Neolene 400 aliphatic alcohols, and others.
  • Specific suitable sulfonic acids are those obtained by sulfon'ating alkyl aromatic hydrocarbons known in the art as dodecylbenzene, postdodecylbenzene, and diwaxbenzene.
  • Dodecylbenzene is obtainable under the trade name of Neolene 400. Physical properties of Neolene 400 are as follows:
  • Postdodecylbenzene is a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3. Its typical physical properties are as follows:
  • the sulfonic acids may be used, the salts formed by neutralizing these acids with alkaline materials are preferred. As stated above, about 20 to 70 percent or even less corrosion inhibitor may be present in the liquid corrosion inhibiting composition for use in oil wells and inhibition of corrosion be obtained, it is desirable that the concentration be about 50 to 70 percent in order for maximum inhibition of corrosion.
  • Suitable solvents for use in the process of this invention are inert solvents which have a boiling point sufficiently high that they will not boil at the temperature and pressure encountered in the well bore. As mentioned above, they should have a specific gravity sutficiently high that when they are added to the inhibitor composition the resultant specific gravity of the mixture will be greater than 1.01 preferably greater than 1.05. In general the solvent will have a specific gravity greater than 1.1.
  • halogenated hydrocarbons including, for example, the following: Monochlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, the dichloroethanes, the trichloroethanes, trichloroethylenes, the chloro and polychloropropanes, the chloro and polychlorobutanes, and the chloro and p'olychloro derivatives of higher members of this homologous series.
  • suitable solvents include cyclohexyl chloride and methyl chloroacetate.
  • the amount of solvent used in the liquid corrosion inhibiting composition for use in oil wells may be varied from 5 percent or less to about 75 percent.
  • the minimum amount of solvent that may be used is that amount which will bring the specific gravity of the composition to at least 1.01.
  • a greater amount of solvent would be used to reduce viscosity of the composition where viscous inhibitors and/ or immiscibilizing agents are used to that viscosity at which the composition will flow to the 4 bottom of the well.
  • more solvent would be used in the composition where the atmospheric temperatures are low in order that the composition may be readily transferred by pouring.
  • the immiscibilizing agent is a nonionic surface active compound soluble in the mixture of corrosion inhibiting compound and solvent and which agent by reason of its hydrophylic nature reduces the solubility of the liquid corrosion inhibiting composition in petroleum oil and which agent assists in the dispersion of the corrosion inhibiting compound under the turbulent conditions at the bottom of the well.
  • Nonionics that may be used are those having certain definite balance between the hydrophylic and lipophylic portion of the molecule. This balance may be expressed by the HLB value of the molecule which may be determined in accordance with the methods taught by W. C. Griffin in Journal of Cosmetic Chemists, vol. II, No. 4, 1954. Thus:
  • HLB hydrophilelipophile balance
  • S susponification number of the nonionic
  • A acid number of the fatty acid portion of the nonionic
  • E weight percentage of the hydrophilic portion of the nonionic.
  • Noni-onics that may be used in the process of this invention have HLB values of from 10 to 17, however, the preferred range is from 13.5 to 15.5. To obtain this range of HLB values the hydrophilic portion of the nonionic molecule may be from 50 to percent of the nonionic molecule.
  • nonionic surface active compounds that may be used are as follows:
  • Polyoxyalkylene ethers ofalkyl 'gg g schoeuet et June above list and having HLB values in the preferred range for use in the process of this invention are known 'by their trade names as Atlas G-1441, Atlas G-2079, Atlas G-2144, Atlas G-3720, Atlas G-3915, Atlas G3920, Tweens 60, 65, 80, and 85.
  • aheaeeo Atlas 6-1441 is a pelyoxyethylene soi-bit'ol lanolin eerivative having an HLB value of 14.
  • Atlas G-2079 is .a.polyoxyethylehe monop'almitatehaving an HLB value of 15.5 and ta general formula:
  • Atlas G--2144 is a polyoxyethylene mono-oleate having anyI-ILB value of 15.1 and a general formula:
  • Atlas 6-5720 is a polyqxyethylene monostearyl ether having an HLB value of 15.3 and a general formula:
  • Atlas 6-3915 and Atlas 6-3920 are polyoxyethylene monooleyl ethers having HLB values of 1553 and 15.4, respectively, and the general formula;
  • Tween 65 is a polyoxyethylene sorbitan tnstearate'having an HLB value of 10.5 .and a general formula:
  • Wb Final weight of coupon subjected to test in the ab sence of inhibitor. 7 v
  • Wc lnitial weight of coupon subjected to test in the presence of inhibitor.
  • Corrosion inhibitor Parts Per 100 Parts of Composition Parts Per 100 Parts of Percent Prote'etion Immiscibilizing Agent Solvent Tween 80.
  • EXAMPLE 1 The efficiencies of the various corrosion inhibitors were compared by determining the percent protection given a EXAMPLE 2 Example 1 was repeated with the exception a hydrogen sulfide environment was maintained for hours rather than a carbon dioxide environment. The results obtained were very similar to those obtained in Example 1.
  • a method of treating oil wells containing a column of corrosive formation liquids which comprises the addition thereto of a weighted corrosion inhibiting composition, said composition comprising an oil soluble iron 7 corrosion inhibitor, an oil immiscibilizing agent for said corrosion inhibitor said immiscibilizing agent is a nonionic surface active compound having a hydrophile-lipophile balance (HLB) value of from 10 to 17 as determined by the following formula:
  • S saponification number of the nonionic
  • A acid number of the fatty acid portion of the nonionic and a mutual solvent having a specific gravity of more than 1.1 for said inhibitor and said immiscibilizing agent in an amount suflicient to increase the specific gravity of the inhibitor composition above that of the corrosive liquids to enable the inhibitor composition to fall readily through the liquid column to the producing zone and diffuse at least partially throughout said liquid column.
  • said immiscibilizing agent is a nonionic surface active compound having a hydrophile-lipophile balance within the range of 13.5 to
  • the immiscibilizing agent is a polyoxyethylene sorbitan mono-oleate.
  • oil soluble iron corrosion inhibitor is a polymerized unsaturated acid having the following properties: acid value 94-116, iodine value 44-50, and molecular Weight ca. 750.
  • oil soluble iron corrosion inhibitor is a polymerized unsaturated acid having the following properties: neutral equivalent 290-310, iodine value -95, dimer content ca. and trimer and higher content ca. 12%.
  • the oil soluble iron corrosion inhibitor is sodium postdodecylbenzene sulfonate wherein said sodium postdodecylbenzene sulfonate is the sodium salt of the sulfonic acid produced by sulnating a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3 having the following physical properties:
  • the oil soluble iron corrosion inhibitor is calcium postdodecylbenzene sulfonate wherein said calcium postdodecylbenzene sulfonate is the calcium salt of the sulfonic acid produced by sulfonating a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3 having the following physical properties:

Description

United States Paten 2,822,330 WEIGHTED CORROSION INHIBITOR Olen L. Riggs, In, and DArcy Shock, Ponca City, :Okla., ;assignors to Continental Oil Company, Ponca City, Okla, a corporation of Delaware N0 Drawing. Application March 14, 1955 Serial No. 494,226
Claims. (Cl. 252-855) This invention relates to the prevention of corrosion of metal equipment in producing oil wells. More particularly, the invention relates to the protection of steel casings, steel tubing, and other metal well equipmentfrom the deleterious effects of corrosive formation liquids.
In the production of oil, corrosion of steel and other metal well equipment is caused by .the action of certain types of sulfur-bearing waters, aqueous carbonic acid, and natural brines. Corrosive sulfide brines include alkali and alkaline earth metal sulfides and hydrogen sulfide. Hydrogen sulfide and carbon dioxide are very soluble in water and brines and in addition hydrogen sulfide is soluble in petroleum oil thus forming corrosive solutions which cause deterioration of Welland surface equipment. This corrosion takes place in brines having a .pH' below about 8, which includes practically all natural well brines.
ER is common practice to introduce an inhibitor at the wellhead into the annular space between the casing and the tubing in a well extending into a producing formation. The liquid inhibitors which have been used are expected to flow to a producing zone in the well .to mix with the corrosive liquids flowing therefrom and then will flow up through the tubing to the surface.
In gas lift Wells in particular and in some pumping and flowing wells, however, a considerable column of oil and water or brine may stand in the annular space between casing and production tubing. In such wells the conventional inhibitors will be rather inelfective in extending protection from "corrosion throughout the well. We have *found that two additional requirements must be metto insure effective placement of the inhibitor. First, the density of .the inhibitor must be greater than that of the liquids contained in the annular space, and second it mustnot be appreciably soluble in oil.
It is a principal object of this invention, therefore, to
provide a method of inhibiting corrosion in producing oil wells in which the corrosion inhibitor is weighted with aliquid to make it fall more readily through any liquid column to a producing zone in a well.
A further object of "the invention isto render oil-soluble inhibitors 'sufliciently limited in solubility so as to pass readily through the oil layer floating upon 'a column of brine without appreciable dissolution by providing a liquid solubility-limiting agent and a Weighting agent in combination with the corrosion inhibitor.
Astill further objectof this invention is to provide improved weighted corrosion inhibiting compositions for use in producing -oil wells.
Other objects of the invention will appear as the descri'ptio'n proceeds.
The foregoing objects are attained by aprocess which broadly .stated comprises a method of inhibiting corrosi on "inoil wells which comprises the addition to the annular space between "the casing and the tubing of a producing oil well a 'liquid 'c'orrosion inhibiting compositio'n icomprising' an oil soluble corrosion inhibitor, an immiscibilizing agent for the corrosion inhibitor and a mutual solvent for the inhibitor and the immiscibillzing 2 agent. The mutual solvent must have a specific gravity so that the final composition has a specific gravity greater than 1.01. Based on the weight of the composition, the inhibitor, immiscibilizing agent, and solvent may vary from 20 to 70, 5 to 25, and 5 to percent respectively.
- Before proceeding with specific examples illustrating our invention it may be well to indicate in general the nature of the materials required in the process.
The oil soluble corrosion inhibitors which are useful for the practice of this invention are iron corrosion inhibitors and in general they may be of the nitrogen chain or ring type, high molecular weight carboxylic acid, sulfonic acids and various salts of these acids with alkali metals, alkaline earth metals, ammonia, amines, and alkanolarnines. Various alk'yl pyrimidines are also suitable in the process of this invention. Nitrogen ring type inhibitors may be used also. Specific nitrogen ring type inhibitors are the N-aliphatic pyrrolinediones represented by the formula:
0 where X and. Y are members from the class consisting of hydrogen, halogen, and simple hydrocarbon groups and R is an aliphatic group, such as disclosed in U. S. Patent No. 2,466,530 issued to C. M. Blair and W. F. Gross, and are available under. the brand name Kontol- 118 which has a density of 0.957 at 60 F. The aliphatic radical contains at least 7 and not more than 32 carbon atoms. The flash point, fire point, pour point, and viscosity are 165" F., .225" F., 20 F, and 477 S. S. U. at 100 F. respectively. It is soluble in oil but insoluble in water. Among the high molecular Weight carboxylic acids suitable in the process of this invention are high molecular weight polycarboxylic acids. Especially suited are polycarboxylic acids obtained by polymerization of unsaturated acids in accordance with a method such as is described in the Journal of the American Oil Chemists Society, 24, 65 (1947). Thus, raw materials containing linoleic acid on treatment by this method yield mixtures of dimers, trimers, and higher polymers of linoleic acid. Such a polymer mixture that may be utilized in the process of this invention is available commercially under the trade designation M46lR, dimer acids. It has the following properties:
Neutralequivalent 290-310 Iodine value -95 Dimer content p'ercent ca. Trimer and higher do ca. 12
Anothersuitable polymerized unsaturated acid is available commercially under the trade designation D-85 dimer acid. It has the following properties:
Acid value 94-116 Iodine value 44-50 Molecular weight ca. 750
Suitable sulfonic acids for the process of this invention include various petroleum sulfonic acids known as mahogany sulfonic acids obtained by the sulfonation of high molecular, weight petroleum fractions. Other satisfactory sulfonic acids are those obtained by the sulfonation of alkyl aromatic hydrocarbons obtained by the alkylation of aromatic hydrocarbons with alkyl alkylating agents having more than nine carbon atoms, as, for example, haloparaffing olefins as from dehydrohalogenated haloparafiins, polyolefins such polypropylene, alkylsulfates,
. aliphatic alcohols, and others. :Spec'ific suitable sulfonic acids are those obtained by sulfon'ating alkyl aromatic hydrocarbons known in the art as dodecylbenzene, postdodecylbenzene, and diwaxbenzene. Dodecylbenzene is obtainable under the trade name of Neolene 400. Physical properties of Neolene 400 are as follows:
Specific gravity at 16 C 0.8742
Average molecular Weight 232 A. S. T. M., .D-158 Engler:
I. B. P F 535 5 F 545 F 550 50 F 560 90 F 580 97 F 592 F. B. P F 603 Refractive index at C 1.4885 Viscosity at 20 C 14 Bromine number 0.16
Postdodecylbenzene is a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3. Its typical physical properties are as follows:
Specific gravity at 38 C 0.8649
Although the sulfonic acids may be used, the salts formed by neutralizing these acids with alkaline materials are preferred. As stated above, about 20 to 70 percent or even less corrosion inhibitor may be present in the liquid corrosion inhibiting composition for use in oil wells and inhibition of corrosion be obtained, it is desirable that the concentration be about 50 to 70 percent in order for maximum inhibition of corrosion.
Suitable solvents for use in the process of this invention are inert solvents which have a boiling point sufficiently high that they will not boil at the temperature and pressure encountered in the well bore. As mentioned above, they should have a specific gravity sutficiently high that when they are added to the inhibitor composition the resultant specific gravity of the mixture will be greater than 1.01 preferably greater than 1.05. In general the solvent will have a specific gravity greater than 1.1. Although unhalogenated compounds satisfying the above requirements may be used, preferred solvents are halogenated hydrocarbons including, for example, the following: Monochlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, the dichloroethanes, the trichloroethanes, trichloroethylenes, the chloro and polychloropropanes, the chloro and polychlorobutanes, and the chloro and p'olychloro derivatives of higher members of this homologous series. Other suitable solvents include cyclohexyl chloride and methyl chloroacetate. The amount of solvent used in the liquid corrosion inhibiting composition for use in oil wells may be varied from 5 percent or less to about 75 percent. The minimum amount of solvent that may be used is that amount which will bring the specific gravity of the composition to at least 1.01. A greater amount of solvent would be used to reduce viscosity of the composition where viscous inhibitors and/ or immiscibilizing agents are used to that viscosity at which the composition will flow to the 4 bottom of the well. Also, more solvent would be used in the composition where the atmospheric temperatures are low in order that the composition may be readily transferred by pouring.
The immiscibilizing agent is a nonionic surface active compound soluble in the mixture of corrosion inhibiting compound and solvent and which agent by reason of its hydrophylic nature reduces the solubility of the liquid corrosion inhibiting composition in petroleum oil and which agent assists in the dispersion of the corrosion inhibiting compound under the turbulent conditions at the bottom of the well. Nonionics that may be used are those having certain definite balance between the hydrophylic and lipophylic portion of the molecule. This balance may be expressed by the HLB value of the molecule which may be determined in accordance with the methods taught by W. C. Griffin in Journal of Cosmetic Chemists, vol. II, No. 4, 1954. Thus:
where HLB=hydrophilelipophile balance S=saponification number of the nonionic A=acid number of the fatty acid portion of the nonionic,
E H LB Where:
E=weight percentage of the hydrophilic portion of the nonionic.
Noni-onics that may be used in the process of this invention have HLB values of from 10 to 17, however, the preferred range is from 13.5 to 15.5. To obtain this range of HLB values the hydrophilic portion of the nonionic molecule may be from 50 to percent of the nonionic molecule.
Different types of nonionic surface active compounds that may be used are as follows:
Prepared in Accordance with U. S. Patent Type of N onionic Compound:
1. Polyoxyalkylene ethers of fatty alcohols. 21 1934 2,425,755, Roberts, August 19, 1947.
2,41%?8139, Fife et al., December 28,
2,542,697, Nevison et al., February 2,559,583, Barker, July 10, 1951. 2,422,486, Johnston, June 17, 1947.
{1,970,578, Schoeller at 211., August 2. Polyoxyalkylene esters of fatty acids.
3. Polyoxyalkylene ethers of polyhygrsoxy alkyl esters of fatty acl Phemls' 2,522,417, Harris, September 12,
1,970,573. 4. Polyoxyalkylene ethers ofalkyl 'gg g schoeuet et June above list and having HLB values in the preferred range for use in the process of this invention are known 'by their trade names as Atlas G-1441, Atlas G-2079, Atlas G-2144, Atlas G-3720, Atlas G-3915, Atlas G3920, Tweens 60, 65, 80, and 85.
aheaeeo Atlas 6-1441 is a pelyoxyethylene soi-bit'ol lanolin eerivative having an HLB value of 14.
Atlas G-2079 is .a.polyoxyethylehe monop'almitatehaving an HLB value of 15.5 and ta general formula:
' 3T 2) t where x=about 20. i l v Atlas G--2144 is a polyoxyethylene mono-oleate having anyI-ILB value of 15.1 and a general formula:
Atlas 6-5720 is a polyqxyethylene monostearyl ether having an HLB value of 15.3 and a general formula:
Atlas 6-3915 and Atlas 6-3920 are polyoxyethylene monooleyl ethers having HLB values of 1553 and 15.4, respectively, and the general formula;
Tween 60 is a elyexyethylene sorbitan moiio'stearate having an value of 14.9 and the general formula: CH3 (CH COO=C H O ==(CH CH O) 5H where x=about 15.5. I
Tween 65 is a polyoxyethylene sorbitan tnstearate'having an HLB value of 10.5 .and a general formula:
(CH (CH CO'O) C H1O (CHCH D) H where x=about 18.
6 mild carbon steel test coupon subject to eorresiencon di'tio'ns in the presence of p. p. m. of inhibitor composition by comparing the Weight loss of a similar test coupon when subject to corrosion conditions in thefabsence of the inhibitor composition. A large mouthed:- tle of about 250 ml. capacity was charged with 150 ml. of Arbuckle brine and 50 m1. of Arbuckle oil containing the corrosion inhibitor composition being tested. The bottle was agitated to distribute the corrosion inhibitor between the two phases, a weighed 1-inch by 3-inch 10-20 mild carbon steel coupon inserted, and the bottle stopper fitted on. Carbon dioxide was bubbled through the solution at a rate of about 12 ml. per second. After about 160 hours, the coupon was removed from the bottle, d'escaled by scrubbing with a nylon bristle brush and a cleaning powder, Weighed and its loss inweight determined. The same technique was followed to obtain "a blank in the absence of corrosion inhibitor. The percent protection was calculated as follows:
P. C. P.- (Wb Wb]) x100 where:
P. C. P.=Percent protection aflorded by inhibitor.
Wbr lnitial weight of coupon subjected to test in the absence of inhibitor.
Wb =Final weight of coupon subjected to test in the ab sence of inhibitor. 7 v
Wc =lnitial weight of coupon subjected to test in the presence of inhibitor.
Wc Final weight of coupon subjected to test in the presence of inhibitor.
Protection zzfiorded by various inhibitor compositions [50 p. p. m. corrosion inhibiting composition in 3 parts of Arbuckle brine and 1 part of Arbuckle oil and a carbon dioxide environment for 160 hours] Corrosion Inhibiting Composition Experiment No.
Corrosion inhibitor Parts Per 100 Parts of Composition Parts Per 100 Parts of Percent Prote'etion Immiscibilizing Agent Solvent Tween 80.
Tween Tween Tween 60- 1 Sodium postdodecylbenzene sulfonate. 1 Postdodeeylbenzene sultonie acid.
EXAMPLE 1 The efficiencies of the various corrosion inhibitors were compared by determining the percent protection given a EXAMPLE 2 Example 1 was repeated with the exception a hydrogen sulfide environment was maintained for hours rather than a carbon dioxide environment. The results obtained were very similar to those obtained in Example 1.
While particular embodiments of the invention have been described, it will be understood, of course, that the invention is not limited thereto since many modifications may be made, and it is, therefore, contemplated to cover by the appended claims any such modifications as fall within the true spirit and scope of the invention.
The invention having thus been described, what is claimed and desired to be secured by Letters Patent is:
1. A method of treating oil wells containing a column of corrosive formation liquids which comprises the addition thereto of a weighted corrosion inhibiting composition, said composition comprising an oil soluble iron 7 corrosion inhibitor, an oil immiscibilizing agent for said corrosion inhibitor said immiscibilizing agent is a nonionic surface active compound having a hydrophile-lipophile balance (HLB) value of from 10 to 17 as determined by the following formula:
wherein S=saponification number of the nonionic A=acid number of the fatty acid portion of the nonionic and a mutual solvent having a specific gravity of more than 1.1 for said inhibitor and said immiscibilizing agent in an amount suflicient to increase the specific gravity of the inhibitor composition above that of the corrosive liquids to enable the inhibitor composition to fall readily through the liquid column to the producing zone and diffuse at least partially throughout said liquid column.
2. The method of claim 1 wherein the amount of said iron corrosion inhibitor, said oil immiscibilizing agent and said mutual solvent based upon the total weight of the corrosion inhibiting composition varies from 20 to 70 percent, 5 to percent, and 5 to 75 percent respectively.
3. The method of claim 1 wherein the amount of said iron corrosion inhibitor, said oil immiscibilizing agent and said mutual solvent based upon the total Weight of the corrosion inhibiting composition varies from to percent, 5 to 25 percent, and 5 to percent respectively.
4. The method of claim 1 wherein said immiscibilizing agent is a nonionic surface active compound having a hydrophile-lipophile balance within the range of 13.5 to
5. The method of claim 1 wherein the immiscibilizing agent is a polyoxyethylene sorbitan mono-oleate.
6. The method of claim 1 wherein the immiscibilizing agent is a polyoxyethylene sorbitan monostearate.
7. The method of claim 1 wherein the oil soluble iron corrosion inhibitor is a polymerized unsaturated acid having the following properties: acid value 94-116, iodine value 44-50, and molecular Weight ca. 750.
8. The method of claim 1 wherein the oil soluble iron corrosion inhibitor is a polymerized unsaturated acid having the following properties: neutral equivalent 290-310, iodine value -95, dimer content ca. and trimer and higher content ca. 12%.
9. The method of claim 1 wherein the oil soluble iron corrosion inhibitor is sodium postdodecylbenzene sulfonate wherein said sodium postdodecylbenzene sulfonate is the sodium salt of the sulfonic acid produced by sulnating a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3 having the following physical properties:
Specific gravity at 38 C 0.8649 Average molecular Weight 365 Percent sulfonamhle 88 A. S. T. M., .D158 Engler:
I. B. P F 647 5 F 682 50 F..- 715 90 F 760 F 775 F. B. P F 779 Refractive index at 23 C 1.4900 Viscosity at:
10" C centipoises 2800 20 C do 280 40 C do 78 80 C do 18 Aniline p int C 69 Pour point F 25 10. The method of claim 1 wherein the oil soluble iron corrosion inhibitor is calcium postdodecylbenzene sulfonate wherein said calcium postdodecylbenzene sulfonate is the calcium salt of the sulfonic acid produced by sulfonating a mixture of monoalkylbenzene and dialkylbenzenes in the approximate ratio of 2:3 having the following physical properties:
References Cited in the file of this patent UNITED STATES PATENTS 2,466,530 Blair et a1 Apr. 5, 1949 2,649,415 Sundberg et a1. Aug. 18, 1953 2,671,757 Wisherd Mar. 9, 1954

Claims (1)

1. A METHOD OF TREATING OIL WELLS CONTAINING A COLUMN OF CORROSIVE FORMATION LIQUIDS WHICH COMPRISES THE ADDITION THERETO OF A WEIGHTED CORROSION INHIBITING COMPOSITION, SAID COMPOSITION COMPRISING AN OIL SOLUBLE IRON CORROSION INHIBITOR, AN OIL IMMISCIBILIZING AGENT FOR SAID CORROSION INHIBITOR SAID IMMISCIBILIZING AGENT IS A NONIONIC SURFACE ACTIVE COMPOUND HAVING A HYDROPHILE-LIPOPHILE BALANCE (HLB) ALUE OF FROM 10 TO 17 AS DETERMINED BY THE FOLLOWING FORMULA:
US494226A 1955-03-14 1955-03-14 Weighted corrosion inhibitor Expired - Lifetime US2822330A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US494226A US2822330A (en) 1955-03-14 1955-03-14 Weighted corrosion inhibitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US494226A US2822330A (en) 1955-03-14 1955-03-14 Weighted corrosion inhibitor

Publications (1)

Publication Number Publication Date
US2822330A true US2822330A (en) 1958-02-04

Family

ID=23963591

Family Applications (1)

Application Number Title Priority Date Filing Date
US494226A Expired - Lifetime US2822330A (en) 1955-03-14 1955-03-14 Weighted corrosion inhibitor

Country Status (1)

Country Link
US (1) US2822330A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3033784A (en) * 1959-05-13 1962-05-08 Pan American Petroleum Corp Water soluble corrosion inhibitor and bactericide
US3300669A (en) * 1963-09-16 1967-01-24 Machlett Lab Inc X-ray vidicon having a target and window assembly with improved thermal conductivity
US3412024A (en) * 1964-04-07 1968-11-19 Nalco Chemical Co Inhibition of corrosion of metals
US3424681A (en) * 1965-11-03 1969-01-28 Nalco Chemical Co Corrosion inhibition
US3623979A (en) * 1967-06-29 1971-11-30 Texaco Inc Composition and process for inhibiting corrosion in oil wells
US4028117A (en) * 1974-05-30 1977-06-07 Edwin Cooper & Company Limited Corrosion inhibitors
US4177768A (en) * 1979-01-19 1979-12-11 Ethyl Corporation Fuel compositions
US4185594A (en) * 1978-12-18 1980-01-29 Ethyl Corporation Diesel fuel compositions having anti-wear properties
US4227889A (en) * 1978-12-26 1980-10-14 Ethyl Corporation Compression ignition fuels for use in diesel engine having anti-wear properties
WO1998016602A1 (en) * 1996-08-06 1998-04-23 Infineum Holdings Bv Fuel compositions
US20130112416A1 (en) * 2010-07-29 2013-05-09 Ramesh Varadaraj Compositions and Methods for Protecting Metal Surfaces from Corrosion

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466530A (en) * 1947-05-07 1949-04-05 Petrolite Corp Process for preventing corrosion and corrosion inhibitor
US2649415A (en) * 1949-12-30 1953-08-18 Gen Aniline & Film Corp Corrosion inhibitor composition
US2671757A (en) * 1951-03-31 1954-03-09 Sinclair Oil & Gas Co Prevention of corrosion

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2466530A (en) * 1947-05-07 1949-04-05 Petrolite Corp Process for preventing corrosion and corrosion inhibitor
US2649415A (en) * 1949-12-30 1953-08-18 Gen Aniline & Film Corp Corrosion inhibitor composition
US2671757A (en) * 1951-03-31 1954-03-09 Sinclair Oil & Gas Co Prevention of corrosion

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3033784A (en) * 1959-05-13 1962-05-08 Pan American Petroleum Corp Water soluble corrosion inhibitor and bactericide
US3300669A (en) * 1963-09-16 1967-01-24 Machlett Lab Inc X-ray vidicon having a target and window assembly with improved thermal conductivity
US3412024A (en) * 1964-04-07 1968-11-19 Nalco Chemical Co Inhibition of corrosion of metals
US3424681A (en) * 1965-11-03 1969-01-28 Nalco Chemical Co Corrosion inhibition
US3623979A (en) * 1967-06-29 1971-11-30 Texaco Inc Composition and process for inhibiting corrosion in oil wells
US4028117A (en) * 1974-05-30 1977-06-07 Edwin Cooper & Company Limited Corrosion inhibitors
US4185594A (en) * 1978-12-18 1980-01-29 Ethyl Corporation Diesel fuel compositions having anti-wear properties
US4227889A (en) * 1978-12-26 1980-10-14 Ethyl Corporation Compression ignition fuels for use in diesel engine having anti-wear properties
US4177768A (en) * 1979-01-19 1979-12-11 Ethyl Corporation Fuel compositions
WO1998016602A1 (en) * 1996-08-06 1998-04-23 Infineum Holdings Bv Fuel compositions
US20130112416A1 (en) * 2010-07-29 2013-05-09 Ramesh Varadaraj Compositions and Methods for Protecting Metal Surfaces from Corrosion

Similar Documents

Publication Publication Date Title
US2822330A (en) Weighted corrosion inhibitor
US2356254A (en) Process for preventing and/or removing accumulation of solid matter in oil wells, pipelines, and flow lines
US4964468A (en) Method of inhibiting corrosion
IE63532B1 (en) Esters of carboxylic acids of medium chain-length as a component of the oil phase in invert drillingmuds
US2643977A (en) Method of inhibiting corrosion of metals
US2217926A (en) Nonaqueous drilling fluid
US2614980A (en) Process for inhibiting corrosion in oil wells
US2659693A (en) Process for preventing corrosion of ferrous metals
US4743385A (en) Oil recovery agent
AU2013265411A1 (en) Surfactant composition
US2568992A (en) Treatment for drilling fluids
US2671757A (en) Prevention of corrosion
US3699118A (en) Reaction products of substituted imidazolines and amino tri(lower alkylidenephosphonic acids)
US2605223A (en) Chemical treatment of wells for the prevention of corrosion
US2978416A (en) Concentrated aqueous detergent composition
US2217927A (en) Nonaqueous drilling fluid
US2785127A (en) Oil well inhibitor
US3127343A (en) Invert emulsion well fluid
US3481869A (en) Inhibiting scale
US3959158A (en) High temperature corrosion inhibitor for gas and oil wells
US2698295A (en) Combating ferrous metal corrosion
US3111998A (en) Foam or mist drilling process
US3260669A (en) Corrosion inhibiting composition for use in oil well fluids
US4511001A (en) Composition and method for corrosion inhibition
US2675355A (en) Method for inhibiting corrosion