US2873252A - Method of inhibiting corrosion of ferrous metal surfaces - Google Patents
Method of inhibiting corrosion of ferrous metal surfaces Download PDFInfo
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- US2873252A US2873252A US439158A US43915854A US2873252A US 2873252 A US2873252 A US 2873252A US 439158 A US439158 A US 439158A US 43915854 A US43915854 A US 43915854A US 2873252 A US2873252 A US 2873252A
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- 238000005260 corrosion Methods 0.000 title claims description 25
- 230000007797 corrosion Effects 0.000 title claims description 25
- 229910052751 metal Inorganic materials 0.000 title claims description 24
- 239000002184 metal Substances 0.000 title claims description 24
- 238000000034 method Methods 0.000 title claims description 7
- 230000002401 inhibitory effect Effects 0.000 title claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title description 9
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007795 chemical reaction product Substances 0.000 claims description 23
- 150000005846 sugar alcohols Polymers 0.000 claims description 19
- -1 FERROUS METALS Chemical class 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 description 20
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 19
- 229960002594 arsenic trioxide Drugs 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000012895 dilution Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229910052787 antimony Inorganic materials 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical class O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013000 chemical inhibitor Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229960004903 invert sugar Drugs 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/122—Alcohols; Aldehydes; Ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/939—Corrosion inhibitor
Definitions
- This invention relates to an improved method of inhibiting corrosion of ferrous metals and particularly the terrous metal equipment associated with the production of petroleum hydrocarbons, as in a producing oil well. Additionally, the invention relates to an improved arsenical composition which is adapted for aqueous dilution and suitable for application as a corrosion inhibitor for ferrous metals and particularly as an inhibitor for carbon dioxide-inducedmetal corrosion.
- Ferrous metal corrosion has long been recognized as one of the most serious problems associated with the production and recovery of petroleum hydrocarbons from subsurface formations.
- the corrosive attack upon the ferrous metal surfaces in contact with the production fluid is primarily due to the action of the weak acidic solutions, such as the aqueous solutions of carbon dioxide, normally present in the production fluid.
- the weak acidic solutions such as the aqueous solutions of carbon dioxide
- PI'ESUH'ICSZIII acid attack upon the ferrous metal surfaces other integral and contributing corrosive actions have been recognized.
- electrochemical corrosive action is also a major factor.
- alkaline arsenical inhibitors In the practical or field application of these alkaline arsenical inhibitors, certain difilculties have been encountered which have prevented the full utilization of the arsenious oxide content of the inhibitor. It has been found that under certain conditions the alkaline arsenicals will form deposits in the form of flocculent precipitates and sludges in the dilution tanks and throughout the injection system associated with the introduction of the inhibitor into a producing oil well.
- Another contributing factor to the formation of tie posits on dilution of the alkaline arsenical inhibitors is the presence of antimony impurities associated with the arsenic.
- the commercial grades of arsenious oxide contain about 1 to 3 percent of the oxides of antimony and, in the preparation of the alkaline arsenical inhibitors, the conditions of reaction are conducive to the solution of the oxides of antimony with the arsenious oxide.
- the very low solubility of Sb O is approached and the metal surfaces of the tanks, pumps and piping become coated with a sludge high in antimony.
- the properties of the reaction product will vary' according to "the type of polyhydric alcohol and the mol ratio of reactants employed.
- the reaction products may vary from a water-miscible, low-viscosity liquid product to a water-miscible, solid or glass-like product.
- it is proferred, to react the polyhydric alcohol at such a mol ratio as to provide at least one free hydroxyl group available in the reaction product.
- the preferred mol ratios of reactants to produce a stable, water-miscible corrosion inhibitor will lie within the range of 1 mol of arsenious oxide to from 3 to- 8 mols of the normally-liquid polyhydric alcohols, and in the range of 1 mol of arsenious oxide to 0.5 to 4 mols of normally-solidpolyhydric alcohols.
- the reaction will result in a water-miscible, glass-like reaction product which is eminently suited as a solid arsenical corrosion inhibitor which may be introduced into a producing well in the form of a molded stick and is gradually dissolved in the production fluid to provide corrosion inhibition to the ferrous metal surfaces in contact with the production fluid.
- An additional advantage of the'pentaterythritol arsenical composition is the fact that under ccrtain'conditions of operation the solid inhibitor will gradually decompose and release formaldehyde which will aflord additional hydrogen sulfide corrosion protection.
- the dihydric alcohols or the glycols containing from 2 to 4 carbon atoms are the most desirable.
- the glycols when reacted with arsenious oxide in the mol ratio range of from 3 to 8 mols of glycol per mol of arsenious oxide, will result in a stable, Water-miscible, free-flowing product whichis readily compounded in concentrations of at least 4 pounds of AS203 per gallon, and may be diluted Without deposit formation at the conventional field dilutions of 1 to 30 or greater.
- the reaction of the polyhydric alcohols and the arsenous oxide to form the arsenical corrosion inhibitor of the invention inherently avoids the presence of normallyassociated antimony in the I reaction product. H Under the conditions of the reaction, the oxides of antimony do not esterify with the polyhydric alcohols, and theantirnony is substantially eliminated in the reaction residue or sludge.
- the reaction is conducted by heating the reactants together in the presence of catalytic amounts of a condensing agent, such as about 0.01 to 0.5 percent by weight of a strong mineral acid or a strong base, at atemperature. of at least 100 C. and below the boiling point of the polyhydric alcohols. At temperatures approaching 100i. C .,.'the reaction is exothermic and-proceeds rapidly with the elimination of water.
- the reaction productv is immediately applicableas an arsenicalcorrosion inhibitor.
- Example 7 The reaction mass was heated and, as the temperature approached 100 C., catalytic amounts 'of 50 percent caustic were added. An instantaneous 'exotherrni'o'reaction occurred. The reaction temperature was controlled so that it remained below the boiling point of the propylene glycol. Steam was driven off, and the reaction mass was stirred for to 10 minutes and then cooled. The resulting reaction product was clear, water-white, slightly viscous, but flowable, and water-miscible. When diluted to a l to 40 dilution, it did not precipitate either in hard water or when carbon dioxide was bubbled through the solution. When employing technical-grade arsenious oxide containing about 1 to 3 percent of the oxides of antimony, the reaction product is separated from the reaction sludge in which substantially all of the antimony is present.
- I claim: v 1. -A method of inhibitingthe corrosion of ferrous metals subject to contact with aqueous solutions of car bon dioxide which comprises introducing into contact with said ferrous metals a water-miscible reaction productof As O and a polyhydric alcohol obtained'at reaction 'te'rnper'atures of at least about C. and below the boilingp'oint of said polyhydric alcohol, said reaction product containing at least one free hydroxyl radical.
- a method of inhibiting corrosion'of ferrous metals which comprises introducing into contactwith said ferrous metals a water-miscible reaction product of arsenious oxide and a dihydric alcohol containing from 2 to 4 carbon atoms, said reaction product being obtained bythe reaction'of 1 mol of arsenious oxide for every3 to' 8 mols of said dihydric alcohol and at'reaction temperatures of atleast about 100 C. and below'th'e boiling point of said dihydric alcohol.
- a stable arsenrcal composition comprising a watermiscible reaction product of arsenious oxide and 21 nor mally-solid polyhydric'alcohol obtained by the reaction of 1 mol of arsenious oxide to 0.5 to 4 mols of the normally-solid polyhydric alcohol at reaction temperatures of at least 100 C. and below the boiling point of said polyhydric alcohol.
- a solid arsenical corrosion inhibitor suitable for gradual solution in the production fluid of a producing oil well which comprises a water-miscible reaction product of arseniousfoxide and 'pentaerythritol, said reaction product being obtained by the reaction of 1 mol of arsenious oxide for every 0.5 to 4 mols of pentaerythri tol and at reaction temperatures of at least 100 C. and below the boiling point of pentaerythritol.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
METHOD F INHIBITING CORROSION OF FERROU METAL SURFACES N0 Drawing; Application June 24,1954
Serial No. 439,158
'Claims. (Cl.252--8.55)
This invention relates to an improved method of inhibiting corrosion of ferrous metals and particularly the terrous metal equipment associated with the production of petroleum hydrocarbons, as in a producing oil well. Additionally, the invention relates to an improved arsenical composition which is adapted for aqueous dilution and suitable for application as a corrosion inhibitor for ferrous metals and particularly as an inhibitor for carbon dioxide-inducedmetal corrosion.
Ferrous metal corrosion has long been recognized as one of the most serious problems associated with the production and recovery of petroleum hydrocarbons from subsurface formations. The corrosive attack upon the ferrous metal surfaces in contact with the production fluid is primarily due to the action of the weak acidic solutions, such as the aqueous solutions of carbon dioxide, normally present in the production fluid. While the presence of the carbonic acid solutions PI'ESUH'ICSZIII acid attack upon the ferrous metal surfaces, other integral and contributing corrosive actions have been recognized. Thus, electrochemical corrosive action is also a major factor.
Although numerous chemical inhibitors have been previously proposed for the treatment of ferrous metal sur faces in contact with corrosive well fluids, it is only recently that any measure of success has been obtained in the practical solution of this problem. It has recently been proposed to inject into the production fluid and circulate throughout the production system an arsenical composition comprising the alkali metal arsenites or alkaline solutions of arsenious oxide. These alkaline arsenical compositions have been used successfully both in the form of dilute aqueous solutions which are pumped or lubricated, intermittently or continuously, into a producing well, or in the form of solid compositions which are dropped into the production tubing and gradually are dissolved into the production fluid. These arsenical corrosion inhibitors provided a tenacious protective film upon the ferrous metal surfaces which successfully inhibits the corrosive action of the contacting production fluid.
In the practical or field application of these alkaline arsenical inhibitors, certain difilculties have been encountered which have prevented the full utilization of the arsenious oxide content of the inhibitor. It has been found that under certain conditions the alkaline arsenicals will form deposits in the form of flocculent precipitates and sludges in the dilution tanks and throughout the injection system associated with the introduction of the inhibitor into a producing oil well.
Basically, in order to achieve a water-soluble, highlyconcentrated formulation of arsenious oxide (at least 2 pounds As O per gallon), it is necessary to employ a high alkali-arsenic ratio in the formulations. When employing hard waters of at least 70 p. p. m. for dilution in the field mixing tanks, it is noted that deposits are formed throughout the inhibitor system which are largely composed of compounds containing the alkaline earth and heavy metal cations of the dilution water. In extrernely hard waters (several hundred p. p. m.), precipitaiii Fatented Feb. it 'lfiSQ 2 tion and sludge deposition are almost immediate and voluminous.
Another contributing factor to the formation of tie posits on dilution of the alkaline arsenical inhibitors is the presence of antimony impurities associated with the arsenic. Generally, the commercial grades of arsenious oxide contain about 1 to 3 percent of the oxides of antimony and, in the preparation of the alkaline arsenical inhibitors, the conditions of reaction are conducive to the solution of the oxides of antimony with the arsenious oxide. On dilution, irrespective of the hardness of the diluting water, the very low solubility of Sb O is approached and the metal surfaces of the tanks, pumps and piping become coated with a sludge high in antimony.
A typical analysis of such a coatingis as follows:
Tank Valve Deposit Deposit Percent Percent In contrast to the foregoing difliculties in field application of the alkaline arsenical corrosion inhibitors, it has now been found possible to provide a water-miscible arsenical corrosion inhibitor which may be formulated as a concentrate containing at least 2 pounds of As O per gallon which is stable in storage; contains negligible quantities of antimony oxides; on dilution with waters having a hardness greater than 70 p. p. m., will not precipitate the alkaline earth and heavy metal cations; and, in general, provides deposit-free operation as a corrosion inhibitor for ferrous metals and particularly the ferrous metal equipment associated with the production of petroleum hydrocarbons.
In accordance with the present invention, it has been discovered that the water-miscible reaction products of arsenious oxide and polyhydric alcohols will provide an arsenical corrosion inhibitor for ferrous metals which ossesses materially improved performance characteristics and more universal application over the conventional alkaline arsenical compositions. Although these reaction products result in the formation of arsenite esters, these esters are not necessarily the sole component of the reac tion product, which more than likely consists of a mixture of esters and dissolved arsenious oxide.
The properties of the reaction product will vary' according to "the type of polyhydric alcohol and the mol ratio of reactants employed. The reaction products may vary from a water-miscible, low-viscosity liquid product to a water-miscible, solid or glass-like product. Generally, in order to provide a reaction product possessing op timum water-miscibility and a lower viscosity, it is proferred, to react the polyhydric alcohol at such a mol ratio as to provide at least one free hydroxyl group available in the reaction product.
The types of polyhydric alcohols which have been found suitable in the preparation of the arsenical reaction products'may be classified into the normally-liquid polyhydroxy aliphatic compounds and the normally-solid polyhydroxy aliphatic compounds. The preferred mol ratios of reactants to produce a stable, water-miscible corrosion inhibitor will lie within the range of 1 mol of arsenious oxide to from 3 to- 8 mols of the normally-liquid polyhydric alcohols, and in the range of 1 mol of arsenious oxide to 0.5 to 4 mols of normally-solidpolyhydric alcohols. a
In the case of the reaction products obtained from the reaction of the normally-solid polyhydric alcohols, as represented by pentaterythritol, the reaction will result in a water-miscible, glass-like reaction product which is eminently suited as a solid arsenical corrosion inhibitor which may be introduced into a producing well in the form of a molded stick and is gradually dissolved in the production fluid to provide corrosion inhibition to the ferrous metal surfaces in contact with the production fluid. An additional advantage of the'pentaterythritol arsenical composition is the fact that under ccrtain'conditions of operation the solid inhibitor will gradually decompose and release formaldehyde which will aflord additional hydrogen sulfide corrosion protection.
Of the normally-liquid polyhydric alcohols, the dihydric alcohols or the glycols containing from 2 to 4 carbon atoms are the most desirable. The glycols, when reacted with arsenious oxide in the mol ratio range of from 3 to 8 mols of glycol per mol of arsenious oxide, will result in a stable, Water-miscible, free-flowing product whichis readily compounded in concentrations of at least 4 pounds of AS203 per gallon, and may be diluted Without deposit formation at the conventional field dilutions of 1 to 30 or greater.
The reaction of the polyhydric alcohols and the arsenous oxide to form the arsenical corrosion inhibitor of the invention inherently avoids the presence of normallyassociated antimony in the I reaction product. H Under the conditions of the reaction, the oxides of antimony do not esterify with the polyhydric alcohols, and theantirnony is substantially eliminated in the reaction residue or sludge. In general, the reaction is conducted by heating the reactants together in the presence of catalytic amounts of a condensing agent, such as about 0.01 to 0.5 percent by weight of a strong mineral acid or a strong base, at atemperature. of at least 100 C. and below the boiling point of the polyhydric alcohols. At temperatures approaching 100i. C .,.'the reaction is exothermic and-proceeds rapidly with the elimination of water. Upon comple tion of the reaction, the reaction productv is immediately applicableas an arsenicalcorrosion inhibitor. T
A number of variations have been employed. in carrying out the reaction which may find practical application. Thus, an entraining solvent may be incorporated in the reaction to remove the water formed, and therebylallow a greater control of reaction temperatures. Preparations havebeen madeinthc absence of a condensing agent, but such reactions require prolonged heating ofthe reaction mass in order to complete removal of the reaction Water. v The following example is presented as .an illustration of the details of the invention.
Example 7 The reaction mass was heated and, as the temperature approached 100 C., catalytic amounts 'of 50 percent caustic were added. An instantaneous 'exotherrni'o'reaction occurred. The reaction temperature was controlled so that it remained below the boiling point of the propylene glycol. Steam was driven off, and the reaction mass was stirred for to 10 minutes and then cooled. The resulting reaction product was clear, water-white, slightly viscous, but flowable, and water-miscible. When diluted to a l to 40 dilution, it did not precipitate either in hard water or when carbon dioxide was bubbled through the solution. When employing technical-grade arsenious oxide containing about 1 to 3 percent of the oxides of antimony, the reaction product is separated from the reaction sludge in which substantially all of the antimony is present.
Additional preparations were conducted employing a condensing system on the reaction vessel whereby the reaction temperature was controlled to allow the water to escape and refluxing the glycol.
Additional preparations were conducted with ethylene glycol, glycerol, 70 percent commercial sorbitol, percent invert sugar glucose, and pentaerythritol with varying mol ratios to produce stable, water-miscible arsenical corrosion inhibitors which, when evaluated for corrosion inhibition according to the test procedure of Scott and Rohrback published in Corrosion, vol. 8, No. 7, pages 234-239, July 1952, showed at least 85 percent corrosion inhibition of ferrous metal surfaces.
Obviously, many modifications and variations of the invention, as hereinbe fore set forth,'may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
I claim: v 1. -A method of inhibitingthe corrosion of ferrous metals subject to contact with aqueous solutions of car bon dioxidewhich comprises introducing into contact with said ferrous metals a water-miscible reaction productof As O and a polyhydric alcohol obtained'at reaction 'te'rnper'atures of at least about C. and below the boilingp'oint of said polyhydric alcohol, said reaction product containing at least one free hydroxyl radical.
2. A method of inhibiting corrosion'of ferrous metals which comprises introducing into contactwith said ferrous metals a water-miscible reaction product of arsenious oxide and a dihydric alcohol containing from 2 to 4 carbon atoms, said reaction product being obtained bythe reaction'of 1 mol of arsenious oxide for every3 to' 8 mols of said dihydric alcohol and at'reaction temperatures of atleast about 100 C. and below'th'e boiling point of said dihydric alcohol.
, 3. A stable arsenrcal composition comprising a watermiscible reaction product of arsenious oxide and 21 nor mally-solid polyhydric'alcohol obtained by the reaction of 1 mol of arsenious oxide to 0.5 to 4 mols of the normally-solid polyhydric alcohol at reaction temperatures of at least 100 C. and below the boiling point of said polyhydric alcohol. a
4. A solid arsenical corrosion inhibitor suitable for gradual solution in the production fluid of a producing oil well which comprises a water-miscible reaction product of arseniousfoxide and 'pentaerythritol, said reaction product being obtained by the reaction of 1 mol of arsenious oxide for every 0.5 to 4 mols of pentaerythri tol and at reaction temperatures of at least 100 C. and below the boiling point of pentaerythritol.
5. 'A method of inhibit'ng the corrosion of ferrous metals which comprises introducing into contact with said ferrous metals a water-miscible reaction product of arsenious oxide and a polyhydric alcohol obtained by the r'eaction'of arsenious oxide with a polyhydric alcohol atreaction'te'mperatures of at least 100 C. and below the boiling point of said polyhydric alcohol and at mol ratios such that said reaction product contains at least one free hydroxyl radical.
' References Cited in the file of this patent .UNITED STATES PATENTS 20,665/34- Australia a Aug. 21, 1935
Claims (1)
1. A METHOD OF INHIBITING THE CORROSION OF FERROUS METALS SUBJEC TO CONTACT WITH AQUEOUS SOLUTIONS OF CARBON DIOXIDE WHICH COMPRISES INTRODUNCING INTO CONTACT WITH SAID FERROUS METALS A WATER-SOLUBLE REACTION PRODUCT OF AS2O3 AND A POLYHYDRIC ALCOHOL OBTAINED AT REACTION TEMPERATURES OF AT LEAST ABOUT 100*C. AND BELOW THE BOILING POINT OF SAID POLYHYDRIC ALCOHOL, SAID REACTION PRODUCT CONTAINING AT LEAST ONE FREE HYDROXYL RADICAL.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US439158A US2873252A (en) | 1954-06-24 | 1954-06-24 | Method of inhibiting corrosion of ferrous metal surfaces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US439158A US2873252A (en) | 1954-06-24 | 1954-06-24 | Method of inhibiting corrosion of ferrous metal surfaces |
Publications (1)
Publication Number | Publication Date |
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US2873252A true US2873252A (en) | 1959-02-10 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US439158A Expired - Lifetime US2873252A (en) | 1954-06-24 | 1954-06-24 | Method of inhibiting corrosion of ferrous metal surfaces |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20030143865A1 (en) * | 2000-10-25 | 2003-07-31 | International Business Machines Corporation | Ultralow dielectric constant material as an intralevel or interlevel dielectric in a semiconductor device and electronic device made |
US6620341B1 (en) * | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US63084A (en) * | 1867-03-19 | Improvement in dyeing and printing textile fabrics, and in compounds therefor | ||
CH156339A (en) * | 1930-04-08 | 1932-07-31 | Ig Farbenindustrie Ag | Process for the preparation of an arsenic complex salt. |
US1988176A (en) * | 1932-02-23 | 1935-01-15 | Union Oil Co | Polyglycol arsenite and method for producing same |
AU2066534A (en) * | 1934-12-21 | 1935-08-29 | Hart & Company Proprietary Limited | Arsenical compounds for destruction of pests and parasites and process forthe production ofthese compounds |
US2346157A (en) * | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded oil |
US2635999A (en) * | 1951-12-22 | 1953-04-21 | California Research Corp | Corrosion inhibiting composition containing arsenous oxide and potassium hydroxide |
-
1954
- 1954-06-24 US US439158A patent/US2873252A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US63084A (en) * | 1867-03-19 | Improvement in dyeing and printing textile fabrics, and in compounds therefor | ||
CH156339A (en) * | 1930-04-08 | 1932-07-31 | Ig Farbenindustrie Ag | Process for the preparation of an arsenic complex salt. |
US1988176A (en) * | 1932-02-23 | 1935-01-15 | Union Oil Co | Polyglycol arsenite and method for producing same |
AU2066534A (en) * | 1934-12-21 | 1935-08-29 | Hart & Company Proprietary Limited | Arsenical compounds for destruction of pests and parasites and process forthe production ofthese compounds |
US2346157A (en) * | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded oil |
US2635999A (en) * | 1951-12-22 | 1953-04-21 | California Research Corp | Corrosion inhibiting composition containing arsenous oxide and potassium hydroxide |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6620341B1 (en) * | 1999-12-23 | 2003-09-16 | Fmc Corporation | Corrosion inhibitors for use in oil and gas wells and similar applications |
US20030143865A1 (en) * | 2000-10-25 | 2003-07-31 | International Business Machines Corporation | Ultralow dielectric constant material as an intralevel or interlevel dielectric in a semiconductor device and electronic device made |
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