[go: up one dir, main page]

USH751H - Method of inhibiting acid corrosion of ferrous metals - Google Patents

Method of inhibiting acid corrosion of ferrous metals Download PDF

Info

Publication number
USH751H
USH751H US07/204,839 US20483988A USH751H US H751 H USH751 H US H751H US 20483988 A US20483988 A US 20483988A US H751 H USH751 H US H751H
Authority
US
United States
Prior art keywords
aryl
acid
halogen
substituted
quaternary compound
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.)
Abandoned
Application number
US07/204,839
Inventor
Daniel S. Sullivan
Stanley J. Brois
Robert C. Portnoy
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to US07/204,839 priority Critical patent/USH751H/en
Application granted granted Critical
Publication of USH751H publication Critical patent/USH751H/en
Abandoned legal-status Critical Current

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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes

Definitions

  • This invention relates generally to acid corrosion inhibitors and in particular to corrosion inhibitors useful in oil field treating operations.
  • the invention relates to a method of using a substituted quaternary compound as an acid corrosion inhibitor.
  • the invention relates to the use of an aqueous acid solution containing a substituted quaternary compound.
  • an aqueous acid solution is injected down the well into the formation to dissolve formation materials and/or other materials deposited in the wellbore thereby improving permeability of the formation and its production.
  • the acid treatment may be carried out under matrix injection rates or fracturing rates.
  • a serious problem associated with acidizing formations is the high corrosivity of the acid solution on surface and subsurface metal equipment.
  • the acid normally HCl or mud acid (HCl-HF mixture)
  • HCl-HF mixture is highly corrosive to ferrous metals. Accordingly, the acid treatment almost always involves the use of corrosion inhibitors.
  • Corrosion inhibitors used in the past in acid treatment of wells include various acetylenic alcohols, fluorinated surfactants, quaternary derivatives of heterocyclic nitrogen bases and halomethylated aromatic compounds, formamides and surface active agents, alone or in combination with other materials. Examples of these prior art corrosion inhibitors are disclosed in U.S. Pat. Nos. 3,658,720 and 4,028,268.
  • the method of the present invention involves the steps of contacting a ferrous metal, which is susceptible to acid corrosion, with an effective amount of a corrosion inhibitor comprising a quaternary compound prepared by reacting a tertiary aromatic heterocyclic amine with a (halo-substituted-aryl) alkyl halide wherein the alkyl group contains from 1 to 3 carbon atoms and the halogen substitution of the (halo-substituted-aryl) group is on the aromatic ring.
  • the preferred halides include halobenzyl halides and (halo-substituted-phenyl) alkyl halides.
  • the preferred method of practicing the present invention is to prepare a corrosion inhibitor formulation package including the corrosion inhibitor quaternary compound with or without other compounds and inhibitors, and to subsequently use this corrosion inhibitor formulation package to prepare an inhibited acid solution in one step.
  • the corrosion inhibitor preferably has the following formula: ##STR1## wherein ARYL is a heterocyclic aromatic ring or rings; N + is a positively charged nitrogen atom and is part of ARYL; ARYL is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N + to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is hydrogen or a halogen substituted on ARYL'.
  • the preferred method for carrying out the present invention involves incorporating a small but effective amount of the quaternary corrosion inhibitor in an aqueous acid solution for treatment of subterranean formations.
  • the aqueous acid solution includes solutions of hydrochloric acid (HCl), mud acid (a mixture of hydrochloric acid and hydrofluoric acid), acetic acid and formic acid.
  • hydrochloric acid HCl
  • mud acid a mixture of hydrochloric acid and hydrofluoric acid
  • acetic acid formic acid.
  • sulfuric acid is not normally used in the petroleum industry, it is used in pickling operations and therefore is included herein. All of these acids are highly corrosive to ferrous metals and therefore require inhibition.
  • the concentration of the corrosion inhibitor should be sufficiently high to inhibit corrosion of the ferrous metals and normally will range from 0.01 to 10 percent (preferably 0.05 to 3.0 %) by volume based on the combined volume of the inhibitor and acid solution.
  • the inhibitor concentration in a particular treatment will depend on several factors including acid type and concentration, temperature, exposure time, and the presence of other additives. It is important that the inhibitor be added to the acid as early as possible to protect storage, pumping and handling equipment, as well as tubular goods in the well.
  • the quaternary compound is the reaction product of a tertiary aromatic heterocyclic amine and a (halo substituted aryl) alkyl halide, having the following formula. ##STR2## wherein ARYL is a heterocyclic aromatic ring or rings; N + is a positively charged nitrogen atom and is part of AHYL; ARYL' is an aromatic ring or rings; and R is an alkyl group containing from 1 to 3 carbon atoms and connects N + to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'.
  • the preferred quaternary compound is selected from the group consisting of: ##STR3## wherein R is an alkyl group containing from 1 to 3 carbon atoms; X and Y are halogens; and Z is a halogen or hydrogen.
  • the preferred tertiary aromatic heterocyclic amines include quinoline, quinaldine, isoquinoline, pyridine, acridine, phenanthridine, and mixtures and substitutions of these.
  • Certain industrially available mixtures of amines are particularly suited for this role including coal tar bases, which contain mixtures of quinoline, isoquinoline, substituted quinolines and isoquinolines, quinaldine and other unreactive materials such as indole.
  • Industrially available mixtures of alkyl pyridines are also quite suitable for this role.
  • the preferred (halo-substituted-aryl) alkyl halides are (halobenzyl) halides or halo substituted halomethyl naphthalenes having the following formulas: ##STR4## where X and Y are halogens and Z is hydrogen H, or a halogen.
  • Chlorine is the most preferred halogen substituent.
  • Z be the same as Y.
  • the preferred (halo-substituted-aryl) alkyl halides are the (halo substituted) or (dihalo substituted) benzyl halides.
  • Specific benzyl halides useable include chlorobenzyl chloride, fluorobenzyl chloride, bromobenzyl chloride, iodobenzyl chloride and the various isomeric dichlorobenzyl chlorides (also known as trichlorotoluene, in which of the chlorine atoms are on the aromatic ring and one of the chlorine atoms is on the methylene carbon), with the halobenzyl chlorides being preferred, in particular, the chlorobenzyl chlorides.
  • the chlorobenzyl chlorides are relatively low in cost and exhibit excellent inhibition properties.
  • the tertiary aromatic amine compound is reacted with the (halo-substituted-aryl) alkyl halide in proper stoichiometric proportions and at the reaction conditions to achieve substantial formation of the quaternary compound wherein the halogen on the aromatic ring of the (halo-substituted-aryl) alkyl halide does not enter into the reaction and remains intact on the aromatic ring. It is believed that the presence of this halogen contributes to the corrosion inhibition properties of the quaternary compound.
  • the reaction of a tertiary heterocyclic amine with a halobenzyl halide may be described as follows.
  • the selected tertiary heterocyclic amine and the selected halobenzyl halide are charged to a reactor on an equal mole to mole basis.
  • a small amount of solvent e.g. 10% of charge
  • the reaction mixture is heated with agitation and the temperature is elevated to between about 120° to 140° C.
  • the reaction is continued for three to seven hours depending on the specific reactants selected.
  • additional solvent may be added to produce a solution of a quaternary compound in liquid form. Sixty percent (60%) in isopropanol has been found to be a convenient concentration.
  • the corrosion inhibitor, dissolved or dispersed in the solvent may be introduced into the aqueous acid at a concentration to provide protection of ferrous metals against acid corrosion.
  • additives which may be included in the aqueous acid package are acetylenic alcohol, surfactants, hydrocarbons, formic acid derivatives (e.g. formamide), other quaternary compounds, etc.
  • additives for well stimulation and workover treatments may be included in the package. These include compounds such as mutual solvents (e.g. ethylene glycol monobutyl ether) and complex surfactant formulations designed to prevent formation of emulsions. These additives as well as many others are routinely used in acid corrosion formulation packages.
  • the preferred corrosion inhibitor additive components for introduction into an aqueous acid include the following:
  • acetylenic alcohols improves effect of quaternary compound
  • surfactant water soluble; dispersant; contributes to pitting control to reduce corrosion rates
  • hydrocarbon liquid oil wet metal surface (e.g. heavy aromatic naphtha, pine oil, mineral oil and C 14 -C 20 fatty acids such as tall oil fatty acid.
  • oil wet metal surface e.g. heavy aromatic naphtha, pine oil, mineral oil and C 14 -C 20 fatty acids such as tall oil fatty acid.
  • the corrosion inhibitor may be used alone but preferably is used in a package (containing one or more of the the above additives), which is especially formulated for optimum performance.
  • the entire package may be added to the acid solution.
  • the preferred corrosion inhibitor packages are as follows:
  • the corrosion inhibitor package may be added to the acid solution and transported to the well site.
  • the aqueous acid solution with the corrosion inhibitor package may then be pumped into the well using conventional techniques and equipment.
  • Samples 1, 18, and 27 represent prior art corrosion inhibitors.
  • Samples 1 through 27 were prepared as a 60% concentrated solution in isopropyl alcohol and tested in an acid corrosion testing autoclave. Certain test samples included corrosion inhibitor and additives and other test samples included only the corrosion inhibitor. The corrosion inhibitor sample and other additives, if used, were added to a 15% HCl acid solution at a concentration as indicated in Table II based on the total weight of the final solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

A method for inhibiting acid corrosion of metal well equipment which comprises introducing into an aqueous acid solution an inhibiting amount of a quaternary compound prepared by reacting a tertiary aromatic heterocyclic amine with a (halo-substituted-aryl) alkyl halide, and contacting the well equipment with the inhibited aqueous acid solution.

Description

FIELD OF THE INVENTION
This invention relates generally to acid corrosion inhibitors and in particular to corrosion inhibitors useful in oil field treating operations. In one aspect the invention relates to a method of using a substituted quaternary compound as an acid corrosion inhibitor. In another aspect the invention relates to the use of an aqueous acid solution containing a substituted quaternary compound.
BACKGROUND OF THE INVENTION
In the acid treatment of subterranean formations penetrated by a wellbore, an aqueous acid solution is injected down the well into the formation to dissolve formation materials and/or other materials deposited in the wellbore thereby improving permeability of the formation and its production. The acid treatment may be carried out under matrix injection rates or fracturing rates.
A serious problem associated with acidizing formations is the high corrosivity of the acid solution on surface and subsurface metal equipment. The acid, normally HCl or mud acid (HCl-HF mixture), is highly corrosive to ferrous metals. Accordingly, the acid treatment almost always involves the use of corrosion inhibitors.
Corrosion inhibitors used in the past in acid treatment of wells include various acetylenic alcohols, fluorinated surfactants, quaternary derivatives of heterocyclic nitrogen bases and halomethylated aromatic compounds, formamides and surface active agents, alone or in combination with other materials. Examples of these prior art corrosion inhibitors are disclosed in U.S. Pat. Nos. 3,658,720 and 4,028,268.
SUMMARY OF THE INVENTION
The method of the present invention involves the steps of contacting a ferrous metal, which is susceptible to acid corrosion, with an effective amount of a corrosion inhibitor comprising a quaternary compound prepared by reacting a tertiary aromatic heterocyclic amine with a (halo-substituted-aryl) alkyl halide wherein the alkyl group contains from 1 to 3 carbon atoms and the halogen substitution of the (halo-substituted-aryl) group is on the aromatic ring. The preferred halides include halobenzyl halides and (halo-substituted-phenyl) alkyl halides.
The preferred method of practicing the present invention is to prepare a corrosion inhibitor formulation package including the corrosion inhibitor quaternary compound with or without other compounds and inhibitors, and to subsequently use this corrosion inhibitor formulation package to prepare an inhibited acid solution in one step.
The corrosion inhibitor preferably has the following formula: ##STR1## wherein ARYL is a heterocyclic aromatic ring or rings; N+ is a positively charged nitrogen atom and is part of ARYL; ARYL is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is hydrogen or a halogen substituted on ARYL'.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred method for carrying out the present invention involves incorporating a small but effective amount of the quaternary corrosion inhibitor in an aqueous acid solution for treatment of subterranean formations. The aqueous acid solution includes solutions of hydrochloric acid (HCl), mud acid (a mixture of hydrochloric acid and hydrofluoric acid), acetic acid and formic acid. Although sulfuric acid is not normally used in the petroleum industry, it is used in pickling operations and therefore is included herein. All of these acids are highly corrosive to ferrous metals and therefore require inhibition. The concentration of the corrosion inhibitor should be sufficiently high to inhibit corrosion of the ferrous metals and normally will range from 0.01 to 10 percent (preferably 0.05 to 3.0 %) by volume based on the combined volume of the inhibitor and acid solution. The inhibitor concentration in a particular treatment will depend on several factors including acid type and concentration, temperature, exposure time, and the presence of other additives. It is important that the inhibitor be added to the acid as early as possible to protect storage, pumping and handling equipment, as well as tubular goods in the well.
The quaternary compound, as mentioned above, is the reaction product of a tertiary aromatic heterocyclic amine and a (halo substituted aryl) alkyl halide, having the following formula. ##STR2## wherein ARYL is a heterocyclic aromatic ring or rings; N+ is a positively charged nitrogen atom and is part of AHYL; ARYL' is an aromatic ring or rings; and R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'.
The preferred quaternary compound is selected from the group consisting of: ##STR3## wherein R is an alkyl group containing from 1 to 3 carbon atoms; X and Y are halogens; and Z is a halogen or hydrogen.
The preferred tertiary aromatic heterocyclic amines include quinoline, quinaldine, isoquinoline, pyridine, acridine, phenanthridine, and mixtures and substitutions of these. Certain industrially available mixtures of amines are particularly suited for this role including coal tar bases, which contain mixtures of quinoline, isoquinoline, substituted quinolines and isoquinolines, quinaldine and other unreactive materials such as indole. Industrially available mixtures of alkyl pyridines are also quite suitable for this role.
The preferred (halo-substituted-aryl) alkyl halides are (halobenzyl) halides or halo substituted halomethyl naphthalenes having the following formulas: ##STR4## where X and Y are halogens and Z is hydrogen H, or a halogen.
Chlorine is the most preferred halogen substituent. In the embodiment which employs di halogen substitution on the aromatic ring, it is preferred that Z be the same as Y.
The preferred (halo-substituted-aryl) alkyl halides are the (halo substituted) or (dihalo substituted) benzyl halides. Specific benzyl halides useable include chlorobenzyl chloride, fluorobenzyl chloride, bromobenzyl chloride, iodobenzyl chloride and the various isomeric dichlorobenzyl chlorides (also known as trichlorotoluene, in which of the chlorine atoms are on the aromatic ring and one of the chlorine atoms is on the methylene carbon), with the halobenzyl chlorides being preferred, in particular, the chlorobenzyl chlorides. The chlorobenzyl chlorides are relatively low in cost and exhibit excellent inhibition properties.
In preparing the corrosion inhibitor, the tertiary aromatic amine compound is reacted with the (halo-substituted-aryl) alkyl halide in proper stoichiometric proportions and at the reaction conditions to achieve substantial formation of the quaternary compound wherein the halogen on the aromatic ring of the (halo-substituted-aryl) alkyl halide does not enter into the reaction and remains intact on the aromatic ring. It is believed that the presence of this halogen contributes to the corrosion inhibition properties of the quaternary compound. While not fully understood, it is believed that the presence of the halogen on the aromatic ring exerts an electron withdrawing influence on the aromatic ring and therefore contributes to formation of a more dense packing of molecules on the metal surface. This dense packing results in improved protection from the acid. The degree of protection is particularly surprising in view of the relatively small size the ring halogen atom in comparison to the quaternary compound. The corrosion inhibitor prepared from the preferred (halo substituted) benzyl chlorides offer advantages over several corrosion inhibitors because they can be prepared from readily available starting materials.
The reaction of a tertiary heterocyclic amine with a halobenzyl halide may be described as follows. The selected tertiary heterocyclic amine and the selected halobenzyl halide are charged to a reactor on an equal mole to mole basis. A small amount of solvent (e.g. 10% of charge) is then added to the reactor. The reaction mixture is heated with agitation and the temperature is elevated to between about 120° to 140° C. The reaction is continued for three to seven hours depending on the specific reactants selected. At the end of the reaction, additional solvent may be added to produce a solution of a quaternary compound in liquid form. Sixty percent (60%) in isopropanol has been found to be a convenient concentration.
The corrosion inhibitor, dissolved or dispersed in the solvent may be introduced into the aqueous acid at a concentration to provide protection of ferrous metals against acid corrosion.
Other additives which may be included in the aqueous acid package are acetylenic alcohol, surfactants, hydrocarbons, formic acid derivatives (e.g. formamide), other quaternary compounds, etc. In addition, other additives for well stimulation and workover treatments may be included in the package. These include compounds such as mutual solvents (e.g. ethylene glycol monobutyl ether) and complex surfactant formulations designed to prevent formation of emulsions. These additives as well as many others are routinely used in acid corrosion formulation packages.
The preferred corrosion inhibitor additive components for introduction into an aqueous acid include the following:
______________________________________                                    
             Broad Range                                                  
                        Preferred Range                                   
             (Vol % of Acid                                               
                        (Vol % of Acid                                    
             Soln.)     Soln.)                                            
______________________________________                                    
Corrosion inhibitor of                                                    
               0.01-4.0     0.1-2.0                                       
the present invention                                                     
Acetylenic Alcohols                                                       
               0-4.0        0.1-2.0                                       
Hydrocarbon liquid                                                        
               0-1.0        0-0.5                                         
Surfactant     0-1.0        0-0.5                                         
Formamide or formic acid                                                  
               0-20.0       0-10.0                                        
______________________________________
The purpose of these additives are as follows:
acetylenic alcohols: improves effect of quaternary compound
surfactant: water soluble; dispersant; contributes to pitting control to reduce corrosion rates
formamide or formic acid: inhibitor intensifier
hydrocarbon liquid: oil wet metal surface (e.g. heavy aromatic naphtha, pine oil, mineral oil and C14 -C20 fatty acids such as tall oil fatty acid.
The corrosion inhibitor may be used alone but preferably is used in a package (containing one or more of the the above additives), which is especially formulated for optimum performance. The entire package may be added to the acid solution. The preferred corrosion inhibitor packages are as follows:
______________________________________                                    
           Broad Range Preferred Range                                    
           (wt % of Package)                                              
                       (wt % of Package)                                  
______________________________________                                    
Corrosion inhibitor of                                                    
             2-100         5-50                                           
the present invention                                                     
Acetylenic Alcohols                                                       
             0-80          5-25                                           
Hydrocarbon liquid                                                        
             0-30          5-20                                           
Surfactant   0-20          1-10                                           
Formamide or formic                                                       
             0-90          10-50                                          
acid                                                                      
______________________________________
In connection with well treating operations, the corrosion inhibitor package may be added to the acid solution and transported to the well site. The aqueous acid solution with the corrosion inhibitor package may then be pumped into the well using conventional techniques and equipment.
EXPERIMENTS
The samples of the corrosion inhibitors listed in Table I were prepared in isopropyl alcohol by the method described above.
              TABLE I                                                     
______________________________________                                    
Quaternary Compounds                                                      
SAMPLE  HETEROCYCLIC    QUATERNIZATION                                    
NO.     AMINE           AGENT                                             
______________________________________                                    
1       Coal Tar Bases  Benzyl Chloride                                   
2       Coal Tar Bases  2-Chlorobenzyl Chloride                           
3       Coal Tar Bases  3-Chlorobenzyl Chloride                           
4       Coal Tar Bases  4-Chlorobenzyl Chloride                           
5       Coal Tar Bases  2-Fluorobenzyl Chloride                           
6       Coal Tar Bases  3-Fluorobenzyl Chloride                           
7       Coal Tar Bases  4-Fluorobenzyl Chloride                           
8       Coal Tar Bases  2-Bromobenzyl Bromide                             
9       Coal Tar Bases  3-Bromobenzyl Bromide                             
10      Coal Tar Bases  4-Bromobenzyl Bromide                             
11      Coal Tar Bases  a-2,6-Trichlorotoluene                            
12      Coal Tar Bases  a-2,4-Trichlorotoluene                            
13      Coal Tar Bases  a-3,4-Trichlorotoluene                            
14      Isoquinoline    2-Chlorobenzyl Chloride                           
15      Quinaldine      2-Chlorobenzyl Chloride                           
16      Quinoline       2-Chlorobenzyl Chloride                           
17      2,3-Cyclohexenopyridine                                           
                        2-Chlorobenzyl Chloride                           
18      2,3-Cyclohexenopyridine                                           
                        Benzyl Chloride                                   
19      6-Methylquinoline                                                 
                        2-Chlorobenzyl Chloride                           
20      4-Methylquinoline                                                 
                        2-Chlorobenzyl ChIoride                           
21      Acridine        2-Chlorobenzyl Chloride                           
22      Phenanthridine  2-Chlorobenzyl Chloride                           
23      Coal Tar Bases  2-Iodobenzyl Chloride                             
24      Coal Tar Bases  Chloromethyl Chloronaph-                          
                        thalene                                           
25      4-Chloroquinoline                                                 
                        2-Chlorobenzyl Chloride                           
26      4-Ethylpyridine 2-Chlorobenzyl Chloride                           
27      4-Ethylpyridine Benzyl Chloride                                   
______________________________________
Note that Samples 1, 18, and 27 represent prior art corrosion inhibitors.
Samples 1 through 27 were prepared as a 60% concentrated solution in isopropyl alcohol and tested in an acid corrosion testing autoclave. Certain test samples included corrosion inhibitor and additives and other test samples included only the corrosion inhibitor. The corrosion inhibitor sample and other additives, if used, were added to a 15% HCl acid solution at a concentration as indicated in Table II based on the total weight of the final solution. The additive, identified as Formula A, had the following composition
______________________________________                                    
                wt %                                                      
______________________________________                                    
Formula A                                                                 
Acetylenic Alcohol                                                        
                  14.6                                                    
Surfactant        7.4                                                     
Hydrocarbon Liquid                                                        
                  19.4                                                    
Formamide         39.6                                                    
Solvent (alcohol) 19.0                                                    
TOTAL             100.0                                                   
______________________________________
Metal coupons made from schedule N80 steel tubing were exposed to the inhibited acid mixture. After the test exposure, the coupons were cleaned, dried, weighed and visually evaluated for corrosion effects. The corrosion rate (in pounds of steel lost per square foot of area) was calculated from the weight loss data.
The HCl solution with additives thus prepared were tested under various test conditions at various treating rates as shown in Table II.
                                  TABLE II                                
__________________________________________________________________________
                            TEST CONDITIONS                               
    SAMPLE       ADDITIVE   TEMP.                                         
                                 PRESS.                                   
                                      TIME                                
TESTS                                                                     
    wt %  ADDITIVE                                                        
                 wt %  ACID °F.                                    
                                 Psig Hrs.                                
__________________________________________________________________________
Series                                                                    
A   0.9   Formula A                                                       
                 2.1   15% HCl                                            
                            325  4000 6                                   
B   0.9   Formula A                                                       
                 2.1   15% HCl                                            
                            300  4000 6                                   
Series                                                                    
C   1.0   --     --    15% HCl                                            
                            180  atm  6                                   
D   2.0   --     --    15% HCl                                            
                            300  4000 4                                   
E   2.0   Formic acid                                                     
                 2.0   15% HCl                                            
                            300  4000 4                                   
F   2.0   Surfactant.sup.1                                                
                 1.0   15% HCl                                            
                            300  4000 4                                   
G   2.0   PA.sup.2                                                        
                 2.0   15% HCl                                            
                            300  4000 4                                   
H   2.0   KI     1.0.sup.3                                                
                       15% HCl                                            
                            300  4000 4                                   
I   2.0   Cu.sub.2 I.sub.2                                                
                 1.03  15% HCl                                            
                            300  4000 4                                   
__________________________________________________________________________
 .sup.1 ethoxylated nonyl phenol (10 moles EO)                            
 .sup.2 Propargyl alcohol                                                 
 .sup.3 1 gram/100 ml
The corrosion coupon test data are presented in Tables III through XI.
              TABLE III                                                   
______________________________________                                    
Series A                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .2896                                                       
2             .1577                                                       
3             .1822                                                       
4             .2167                                                       
5             .2858                                                       
6             .2168                                                       
7             .3298                                                       
8             .2840                                                       
9             .2803                                                       
10            .2126                                                       
11            .1480                                                       
12            .2095                                                       
13            .1939                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE IV                                                    
______________________________________                                    
Series B                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .0798                                                       
2             .0349                                                       
3             .0572                                                       
4             .0440                                                       
5             .0552                                                       
6             .0378                                                       
7             .0806                                                       
10            .0381                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE V                                                     
______________________________________                                    
Series C                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .0935                                                       
2             .0559                                                       
3             .0143                                                       
4             .0192                                                       
5             .1106                                                       
6             .0690                                                       
7             .0659                                                       
8             .1281                                                       
9             .1146                                                       
10            .0788                                                       
11            .1081                                                       
13            .0150                                                       
14            .2550                                                       
15            .0951                                                       
16            .0192                                                       
17            .3077                                                       
18*           .3648                                                       
19            .0168                                                       
20            .0645                                                       
21            .5980                                                       
22            .0575                                                       
23            .0583                                                       
24            .0657                                                       
25            .3731                                                       
26            .2933                                                       
27*           .4038                                                       
28            .3648                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE VI                                                    
______________________________________                                    
Series D                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .3261                                                       
2             .2139                                                       
3             .1696                                                       
4             .1530                                                       
5             .3801                                                       
6             .3689                                                       
7             .3839                                                       
8             .4425                                                       
9             .3492                                                       
10            .3716                                                       
11            .2731                                                       
13            .2603                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE VII                                                   
______________________________________                                    
Series E                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .0479                                                       
2             .0255                                                       
3             .0301                                                       
4             .0254                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE VIII                                                  
______________________________________                                    
Series F                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .7441                                                       
2             .6404                                                       
3             .2309                                                       
4             .2098                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE IX                                                    
______________________________________                                    
Series G                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .1720                                                       
2             .0765                                                       
3             .0771                                                       
4             .0805                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE X                                                     
______________________________________                                    
Series H                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .1575                                                       
2             .2046                                                       
3             .1476                                                       
4             .1024                                                       
______________________________________                                    
 *Prior art corrosion inhibitor                                           

              TABLE XI                                                    
______________________________________                                    
Series I                                                                  
              CORROSION                                                   
SAMPLE        RATE                                                        
NO.           (LB/SQ FT)                                                  
______________________________________                                    
1*            .0335                                                       
2             .0276                                                       
3             .0300                                                       
4             .0284                                                       
______________________________________                                    
 *Prior art corrosion inhibitor
The above corrosion tests show that the corrosion inhibitor of the present invention is quite effective alone or with additives in providing protection over a wide range of test conditions.

Claims (21)

What is claimed is:
1. A method of inhibiting corrosion of ferrous metals which comprises treating a system wherein metals are susceptible to corrosion with a corrosion inhibiting amount of a quaternary compound prepared by reacting a tertiary aromatic heterocyclic amine with a (halo-substituted-aryl) alkyl halide wherein the halogen substitution on the aromatic ring of the (halo-substituted -aryl) alkyl halide does not enter into the reaction and remains intact on said aromatic ring, and the alkyl group contains from 1 to 3 carbon atoms.
2. The method of claim 1 wherein the heterocyclic amine is selected from the group consisting of quinoline, isoquinoline, quinaldine, pyridine, acridine, phenanthridine, and coal tar bases, with or without substituents, and mixtures of the foregoing.
3. The method of claim 1, wherein the quaternary compound has the formula of: ##STR5## wherein ARYL is a heterocyclic ring or rings; N+ is a positively charged nitrogen atom and is part of ARYL; ARYL' is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'.
4. The method of claim 1 wherein the quaternary compound has a formula selected from the group consisting of ##STR6## wherein R is an alkyl group containing from 1 to 3 carbon atoms; X and Y are halogens; and Z is a halogen or hydrogen.
5. The method of claim 1 wherein the (halo-substituted-aryl) alkyl halide is halobenzyl halide.
6. A method of acidizing a subterranean formation penetrated by a well having pipe extending from the surface to said formation, which comprises injecting through the pipe and into said formation an aqueous acid solution having dissolved or dispersed therein an acid inhibiting amount of a quaternary compound prepared by the reaction of a tertiary heterocyclic amine with a halogen substituted benzyl halide wherein the substituted halogen is on the aromatic ring and the halide on the benzyl methylene carbon reacts with the amine to form the quaternary compound.
7. The method of claim 6 wherein the halogen substituted benzyl halide is selected from the group consisting of a chlorobenzyl chloride, a fluorobenzyl chloride, bromobenzyl chloride, an iodobenzyl chloride, a chlorotoluene, and a chloromethyl chloronaphthalene.
8. The method of claim 6 wherein the aqueous acid is selected from the group consisting of hydrochloric acid, hydrofluoric acid, acetic acid, formic acid, and mixture of these.
9. The method of claim 8, wherein the quaternary compound comprises from 0.01 to 10.0 vol % of the aqueous acid solution.
10. The method of claim 7 wherein the quaternary compound comprises from 0.05 to 3.0 vol % of the aqueous acid solution.
11. The method of claim 6 wherein the heterocyclic amine is selected from the group consisting of coal tar bases, quinoline, quinaldine, isoquinoline, pyridine, acridene, phenanthradine, and mixtures and substitutions thereof.
12. An inhibited acid comprising
(a) an aqueous solution of a well treating acid selected from the group consisting of hydrochloric acid, hydrofluoric acid, acetic acid, formic acid, and mixtures thereof; and
(b) from about 0.01 to 10.0 vol % of the treating acid of a quaternary compound prepared by reacting a tertiary aromatic heterocyclic amine with a (halo-substituted-aryl) alkyl halide wherein the halogen substitution is on the aromatic ring and the alkyl halide does not enter into the reaction and remains intact on the aromatic ring and the alkyl group contains from 1 to 3 carbon atoms.
13. The inhibited acid of claim 12 wherein the quaternary compound has the formula consisting of ##STR7## wherein ARYL is a heterocyclic ring or rings; N+ is a positively charged nitrogen atom and is part of ARYL; ARYL' is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'.
14. The inhibited acid of claim 12 and further comprising a water soluble surfactant.
15. The inhibited acid of claim 12, further comprising an effective amount of acetylenic alcohol.
16. The inhibited acid of 12, and further comprising formic acid or formamide.
17. The inhibited acid of claim 12, and further comprising potassium iodide or aqueous iodide.
18. The inhibited acid of claim 12 and further comprising a hydrocarbon liquid.
19. The inhibited acid of claim 12 and further comprising acetylenic alcohol, a hydrocarbon liquid, a water wetting surfactant, and formic acid or formamide.
20. A formulation for inhibiting aqueous acid solutions selected from the group consisting of hydrochloric acid, hydrofluoric acid, acetic acid, formic acid and mixtures thereof which comprises
(a) a quaternary compound having the formula ##STR8## wherein ARYL is a heterocyclic ring or rings; N+ is a positively charged nitrogen atom and is part of ARYL; ARYL' is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'; and
(b) an additive selected from the group consisting of acetylenic alcohol, hydrocarbon liquid, water wetting surfactant, formic acid, formamides, and mixtures thereof.
21. A corrosion inhibitor formulation comprising
(a) from 5 to 50 wt % of the corrosion inhibitor having the formula of ##STR9## wherein ARYL is a heterocyclic ring or rings; N+ is a positively charged nitrogen atom and is part of ARYL; ARYL' is an aromatic ring or rings; R is an alkyl group containing from 1 to 3 carbon atoms and connects N+ to ARYL'; X is a halogen; Y is a halogen substituted on ARYL'; and Z is a halogen or hydrogen substituted on ARYL'.
(b) from 5 to 25 wt % of acetylenic alcohol;
(c) from 5 to 20 wt % of a hydrocarbon liquid selected from the group consisting of mineral oil, pine oil, aromatic naptha, and C14 to C20 fatty acids;
(d) from 1 to 10 wt % of a surfactant capable of dispersing the corrosion inhibitor; and
(e) from 10 to 50 wt % of formic acid or formamide.
US07/204,839 1988-06-10 1988-06-10 Method of inhibiting acid corrosion of ferrous metals Abandoned USH751H (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US07/204,839 USH751H (en) 1988-06-10 1988-06-10 Method of inhibiting acid corrosion of ferrous metals

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/204,839 USH751H (en) 1988-06-10 1988-06-10 Method of inhibiting acid corrosion of ferrous metals

Publications (1)

Publication Number Publication Date
USH751H true USH751H (en) 1990-03-06

Family

ID=22759667

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/204,839 Abandoned USH751H (en) 1988-06-10 1988-06-10 Method of inhibiting acid corrosion of ferrous metals

Country Status (1)

Country Link
US (1) USH751H (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5084210A (en) * 1990-02-07 1992-01-28 Chemlink Incorporated Corrosion inhibitor
US5089153A (en) * 1990-03-16 1992-02-18 Williams Dennis A Method of inhibiting corrosion in acidizing wells
US5120471A (en) * 1985-08-14 1992-06-09 Dowell Schlumberger Incorporated Process and composition for protecting chrome steel
US5756004A (en) * 1997-05-13 1998-05-26 Halliburton Energy Services, Inc. Quaternary ammonium compounds useful for inhibiting metal corrosion
US5939362A (en) * 1995-03-27 1999-08-17 Nalco/Exxon Energy Chemicals, L.P. Enhanced corrosion protection by use of friction reducers in conjuction with corrosion inhibitors
US20030183808A1 (en) * 2002-03-28 2003-10-02 Walker Michael L. Corrosion inhibitor
US20040138071A1 (en) * 2003-01-15 2004-07-15 Gupta D. V. Satyanarayana Surfactant based viscoelastic fluids
US20080146464A1 (en) * 2006-12-19 2008-06-19 Malwitz Mark A Corrosion inhibitor composition comprising a built-in intensifier
US20110114322A1 (en) * 2009-11-17 2011-05-19 Ronald Casey Plasier Surfactant based viscoelastic fluids and methods of using the same
US9074289B2 (en) 2011-11-08 2015-07-07 Nalco Company Environmentally friendly corrosion inhibitor
US10947446B2 (en) * 2011-11-23 2021-03-16 Saudi Arabian Oil Company Dual-phase acid-based fracturing composition with corrosion inhibitors and method of use thereof
CN115161644A (en) * 2021-12-17 2022-10-11 青岛华节鼎孚节能科技有限公司 Pipeline corrosion inhibitor for vapor-liquid two-phase transportation and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2037762A (en) 1932-06-02 1936-04-21 Barrett Co Pickling compound and method of making and using same
US2814593A (en) 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition
US4071746A (en) 1972-03-06 1978-01-31 Petrolite Corporation Alkylbenzyl pyridinium compounds and uses
US4498997A (en) 1983-06-24 1985-02-12 Halliburton Company Method and composition for acidizing subterranean formations
US4552672A (en) 1984-06-21 1985-11-12 Halliburton Company Method and composition for acidizing subterranean formations
US4698168A (en) 1986-08-29 1987-10-06 Hughes Tool Company Corrosion inhibitor for well acidizing treatments

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2037762A (en) 1932-06-02 1936-04-21 Barrett Co Pickling compound and method of making and using same
US2814593A (en) 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition
US4071746A (en) 1972-03-06 1978-01-31 Petrolite Corporation Alkylbenzyl pyridinium compounds and uses
US4498997A (en) 1983-06-24 1985-02-12 Halliburton Company Method and composition for acidizing subterranean formations
US4552672A (en) 1984-06-21 1985-11-12 Halliburton Company Method and composition for acidizing subterranean formations
US4698168A (en) 1986-08-29 1987-10-06 Hughes Tool Company Corrosion inhibitor for well acidizing treatments

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5120471A (en) * 1985-08-14 1992-06-09 Dowell Schlumberger Incorporated Process and composition for protecting chrome steel
US5084210A (en) * 1990-02-07 1992-01-28 Chemlink Incorporated Corrosion inhibitor
US5089153A (en) * 1990-03-16 1992-02-18 Williams Dennis A Method of inhibiting corrosion in acidizing wells
US5939362A (en) * 1995-03-27 1999-08-17 Nalco/Exxon Energy Chemicals, L.P. Enhanced corrosion protection by use of friction reducers in conjuction with corrosion inhibitors
US5756004A (en) * 1997-05-13 1998-05-26 Halliburton Energy Services, Inc. Quaternary ammonium compounds useful for inhibiting metal corrosion
US20030183808A1 (en) * 2002-03-28 2003-10-02 Walker Michael L. Corrosion inhibitor
US20040138071A1 (en) * 2003-01-15 2004-07-15 Gupta D. V. Satyanarayana Surfactant based viscoelastic fluids
US7638468B2 (en) * 2003-01-15 2009-12-29 Bj Services Company Surfactant based viscoelastic fluids
WO2008077005A1 (en) * 2006-12-19 2008-06-26 Nalco Company Corrosion inhibitor composition comprising a built-in intensifier
US20080146464A1 (en) * 2006-12-19 2008-06-19 Malwitz Mark A Corrosion inhibitor composition comprising a built-in intensifier
US7842127B2 (en) 2006-12-19 2010-11-30 Nalco Company Corrosion inhibitor composition comprising a built-in intensifier
US20110114322A1 (en) * 2009-11-17 2011-05-19 Ronald Casey Plasier Surfactant based viscoelastic fluids and methods of using the same
US8196662B2 (en) 2009-11-17 2012-06-12 Baker Hughes Incorporated Surfactant based viscoelastic fluids and methods of using the same
US9074289B2 (en) 2011-11-08 2015-07-07 Nalco Company Environmentally friendly corrosion inhibitor
US10947446B2 (en) * 2011-11-23 2021-03-16 Saudi Arabian Oil Company Dual-phase acid-based fracturing composition with corrosion inhibitors and method of use thereof
CN115161644A (en) * 2021-12-17 2022-10-11 青岛华节鼎孚节能科技有限公司 Pipeline corrosion inhibitor for vapor-liquid two-phase transportation and preparation method and application thereof
CN115161644B (en) * 2021-12-17 2023-05-30 青岛华节鼎孚节能科技有限公司 Pipeline corrosion inhibitor for gas-liquid two-phase transportation and preparation method and application thereof

Similar Documents

Publication Publication Date Title
US4522658A (en) Method and composition for protecting metal surfaces from oxidative environments
US4498997A (en) Method and composition for acidizing subterranean formations
US5009799A (en) Inorganic acid solution viscosifier and corrosion inhibitor and method
Singh et al. Acidizing corrosion inhibitors: a review
US5543388A (en) Intensified corrosion inhibitor and method of use
USH751H (en) Method of inhibiting acid corrosion of ferrous metals
US7842127B2 (en) Corrosion inhibitor composition comprising a built-in intensifier
US6180057B1 (en) Corrosion inhibiting compositions and methods
US6192987B1 (en) Metal corrosion inhibitors, inhibited acid compositions and methods
CA2237542C (en) Quarternary ammonium compounds useful for inhibiting metal corrosion
US20090221455A1 (en) Methods and compositions for protecting steels in acidic solutions
US5058678A (en) Method for preventing the formation of sludge in crude oil
US4698168A (en) Corrosion inhibitor for well acidizing treatments
US7655158B2 (en) Corrosion inhibitor
US5096618A (en) Process and composition for inhibiting high-temperature iron and steel corrosion
CA2237561C (en) Metal corrosion inhibitor for use in aqueous acid solutions
US2955083A (en) Corrosion inhibitors in well treating compositions
US4919827A (en) Multicomponent organic liquid and use thereof in treating wells and subterranean formations
US5209859A (en) Inhibited acid system for acidizing wells
AU649266B2 (en) Method of inhibiting corrosion in acidizing wells
US5084192A (en) Method and composition for preventing the formation of sludge in crude oil
EP0593230A1 (en) Metal corrosion inhibiting compositions
US5200096A (en) Method of inhibiting corrosion in acidizing wells
CA1336039C (en) High temperature corrosion inhibitor
Yao et al. Development of a new multifunctional cationic surfactant system with corrosion inhibiting ability

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE