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Adducts of Propargyl Alcohol and Their Use As Corrosion Inhibitors in Acidizing Systems

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Adducts of Propargyl Alcohol and Their Use As Corrosion Inhibitors in Acidizing Systems Europaisches Patentamt 19) s European Patent Office © Publication number: 0 239 770 Office europeen des brevets A1 © EUROPEAN PATENT APPLICATION © Application number: 87102356.0 © Int. CI.3: C 23 F 11/12 E 21 B 41/02, E 21 B 37/06 © Date of filing: 19.02.87 © Priority: 28.02.86 US 834526 © Applicant: BASF Corporation 9 Campus Drive Parsippany, NJ 07054(US) © Date of publication of application: 07.10.87 Bulletin 87/41 © Inventor: Perry, Christine 22335 Nixon © Designated Contracting States: Riverview Michigan 481 92(US) DE FR GB NL © Inventor: Crema,Stefano Carlo 1874 20th Street Wyandotte Michigan 48192(US) © Inventor: Davis, Pauls 30027 White Gibraltar Michigan 48173(US) @ Representative: Holler, Klaus, Dr. et al, BASF Aktiengesellschaft Carl-Bosch-Strasse 38 D-6700 Ludwigshafen(DE) © Adducts of propargyl alcohol and their use as corrosion inhibitors in acidizing systems. © The invention relates to an acidizing system comprising: (a) an acidizing solution; and (b) an effective corrosion inhibiting amount of a prop- argyl alcohol adduct having the following structural formula I: _ _ HC a C-CH2-0- -(CH2)5C-^ -H (I) wherein n = 1 or 3 and R = H if n = 3 and R = CH3 if n = 1 ; and x = 1 to 5. Corrosion of ferrous metals is inhibited by treating the surface thereof with the acidizing system. o IN M CM 0. Ul Croydon Printing Company Ltd. BASF Corporation ADDUCTS OF PROPARGYL ALCOHOL AND THEIR USE AS CORROSION INHIBITORS IN ACIDIZING SYSTEMS This invention relates to acidizing systems for oil and gas recovery containing propylene oxide and/or butylene oxide adducts of propargyl alcohol as corrosion inhibitors. It is known to use propargyl alcohol as a corro- sion inhibitor in acidizing systems used in oil and gas recovery. The propargyl alcohol is effective at preventing the corrosion of ferrous metal tank cars used to transport the highly corrosive acidizing systems which are used to break up deposits in oil arid gas wells, and also protects ferrous metal pipe and equipment which comes into contact with the acidizing system at the site of the oil and gas well- Although propargyl alcohol is an effective corrosion inhibitor in acidizing systems/ there is always a need to discover more effective corrosion inhibitors (particularly those effective at higher use temperatures such as 80°C and above) which are more economical to use. The invention relates to an acidizing system comprising: (a) an acidizing solution: and I.Z. 2063/01514 0239770 [b; propargyl alcohol adducts , having the following structural formula I: R 1 [CH_ )-C-0 ID HC £ C-CH2-C— 2 -n n, H __ where n=l or 3 and R=H if n=3 and R=CH3 if n=l; and x=i to b, preferably 1 to 2. A. surfactant and a C3~c12 aliPnatic alcohol are also preferably used as components of the acidizing system. The propargyl alcohol adducts are more effective as corrosion inhibitors in the acidizing system than propargyl alcohol. The invention also relates to a process for inhibiting the corrosion of ferrous metals from the effects of acids which comprises treating the ferrous metal surface with an acidizing system containing the propargyl alcohol alcohol adducts. It further relates to the use of the propargyl inhibitors for adducts of general formula I as corrosion acidizing systems and to the use of said acidizing systems in oil and gas recovery. As was previously indicated/ the propargyl alcohol adducts have the following structural formula I: R I HC = C-CH2~0- (CH,)-C-C- -H (I) & n| H - 2 - 0239770 0.2. 2033/01514 where n = 1 or 3 and R = H if n = 3 and R = CH3 if n = 1; and x = 1-5. These compositions are prepared according to well known methods. Propargyl alcohol is preferably reacted with propylene oxide/ butylene oxide/ or mixtures thereof in the presence of an oxyalkylation catalyst. It is also contem- plated that other lower alkylene oxides such as ethylene oxide may be included, provided they are used in amounts which do not significantly reduce the effectiveness of the corrosion inhibitor. Examples of such catalysts are tertiary amines such as pyridine/ triethylamine / and the like; alkali metal such as sodium/ potassium, and lithium; and alkali metal hydroxides such as sodium hydroxide/ potassium hydroxide/ lithium hydroxide/ and the like. The amount of oxyalkylation catalyst employed is generally within the range of about 0.001 part to about 1.0 part by weight of catalyst per 100 parts by weight of propargyl alcohol. For those who need more details regarding the preparation of the subject compositions/ such details are disclosed in Encyclopedia of Chemical Technology/ vol. 1 , pp. 257-262/ published by Interscience Publishers/ Inc./ (1951). To prepare an acidizing system/ the propargyl alcohol adducts are combined with an acidizing solution. J - 3 - 023.9770 }.Z. 2063/01514 Generally, the acidizing solution will contain an acid such as hydrochloric acid/ phosphoric acid/ or sulfuric acid in a concentration of about 3 to about 30 percent by volume based upon the total volume of the acidizing solution which will contain water in addition to the acid. The propargyl alcohol adduct is used in an amount effective to inhibit the corrosion of the ferrous metal/ generally in amount of about 0.1 part by weight to about 10.0 parts by weight based upon the total weight of the acidizing system. As was mentioned/ a surfactant is preferably used in the acidizing system along with a C2"C12 aliPnatic alcohol. Although aany anionic and nonionic surfactants/ and mixtures thereof/ can be used in the acidizing systems/ particularly useful ones are described in GB-A-2141731 . These surfactants are oxyalkylated alcohols or phenols which may or may not be terminally esterified thus potentially forming mixtures of mono- and diesters. In the esterified form, the surfactant is an anionic detergent and in the nonesterif ied form can be considered a nonionic detergent wherein the hydrophilic or water soluble moiety is a terminal ethylene oxide chain. Thus, the particularly preferred surfactants of the present invention are charac- terized by the chemical formula II: ).Z. 2063/01514 CH3 ( H ) l-O- (CH-CH2-0- )x- (-CH2-CH2-0- )y-A nrhere R is an alkyl or alkyl-aryl radical ot about to Cork; A is a radical selected from the CH„ 6 20 I J -PO(OH) group consisting of -P0(0H>2, [0CH2CH2]y[0CH2CH]x0R, is a number corresponding .herein R has the same meaning as above, x and is a number corresponding to the degree of propoxylation y and -SOgH. to the degree of ethoxylation , hydrogen, -SO3H In the broadest sense, R is any hydroxylated organic substitutent that after oxyalkylation represents or contributes to the necessary hydrophobic character at one end of the resulting surfactant molecule. Commercially, fatty alcohols and alkyl phenols are frequently employed as starting materials for the subsequent oxyalkylation. In principle, the oxyalkylation can involve alkylene oxides other than propylene oxide and ethylene oxide provided the oxide for water terminal sequence is predominantly ethylene solubility or hydrophilic character. Preferably, the followed oxyalkylation is a block polymer of propylene oxide the by ethylene oxide. However, in addition to incorpora- tion of other alkylene oxides, particularly near the oxide starting alcohol moiety, one or more moles of ethylene to can be readily and advantageously employed initially well known in the promote the oxyalkylation reaction as the art. Thus, the term block polymer when used to describe - 5 - 023.9770 3.Z. 2063/01514 Dolyether moiety of the surfactant molecule is referring generally to the presence of a terminal ethylene oxide chain and the reference to block propylene oxide/ethylene oxide also includes other alkylene oxides in the propylene oxide portion including initiation of the oxyalkylation reaction with an ethylene oxide. The presence and degree of the terminal esterifi- cation and the selection of the acid or equivalent used to esterify the ethylene oxide chain will depend on the particular end use of the surfactant and acidic surfactant/alcohol solution. If high surface absorption is desired, then the sulfate ester and/or phosphate ester may be appropriate. If no surface absorption is desired/ then the nonesterif ied nonionic form of the surfactant may be preferred. In such cases/ the relative degree of ethoxyla- tion can be increased to ensure water solubility. Simi- larly/ the viscosity/ solubility and absorptivity of the resulting acidic solution can be adjusted by varying the degree of oxyalkylation and esterif ication of the surfac- tant. Thus# it is envisioned that for example in enhanced oil recovery applications/ such as a CO^ flood/ the nonionic (non-esterif ied) surfactant would be preferred (minimum adsorption)/ while for well stimulation and cleaning/ the phosphate ester seems to be the best approach. Selected other end uses may dictate the employment of the sulphate O.Z. 2063/01514 ester. The actual method of es terif ication can be by any technique well known in the art. The particularly preferred phosphate ester • v • • * .. • , ■ < . * "' surfactants useful in the present invention are the phos- * phate esters of the oxyalkylated fatty alcohols and the like as described in US-A-3629127 , herein incorporated by reference as descriptive thereof. alc°hoi As was mentioned/ generally any C3~C22 can be used in the acidizing system along with the surfactant. 5 ( However/ it is preferable to use a mixture consisting of a' 1 branched C--C- alcohol/ preferably isopropanol/ and a branched C^-C^q alcohol/ preferably isoctyl alcohol. The ratio of the alcohol to a^coho^ weight C^-C^ C7-C3.0 may vary oyer wide ranges/ but generally is from 0.1:1 to 10.0:1.
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