WO1997004055A1 - Oxime containing inhibitors for acid pickling - Google Patents

Oxime containing inhibitors for acid pickling Download PDF

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Publication number
WO1997004055A1
WO1997004055A1 PCT/US1996/011426 US9611426W WO9704055A1 WO 1997004055 A1 WO1997004055 A1 WO 1997004055A1 US 9611426 W US9611426 W US 9611426W WO 9704055 A1 WO9704055 A1 WO 9704055A1
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WIPO (PCT)
Prior art keywords
component
contain
carbon atoms
moiety
molecules
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Application number
PCT/US1996/011426
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French (fr)
Inventor
William G. Johnston
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Henkel Corporation
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Publication date
Application filed by Henkel Corporation filed Critical Henkel Corporation
Priority to AU65434/96A priority Critical patent/AU6543496A/en
Publication of WO1997004055A1 publication Critical patent/WO1997004055A1/en

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    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/061—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors nitrogen-containing compounds

Definitions

  • This invention relates to the treatment of metal surfaces with aqueous acids to remove scale and like materials from the surface, a process commonly known in the art as "pickling", and to corrosion inhibitors used in such processes.
  • Advantageous inhibitors reduce the rate of dissolution of clean metal as much as possible while reducing the rate of dissolution of surface scale and like contaminating materials as little as possible.
  • One common quantitative method of rating inhibitors used in the art, and in this description below, involves measuring the corrosion rate of the metal to be pickled in a solution containing the type and concentration of acid to be used for pickling, measuring the corrosion rate in a solution otherwise the same except for adding the inhibitor to be used, and then reporting the results as the percent "protection" ofthe inhibitor.
  • a major object of this invention is to provide pickling inhibitors and pickling compositions that are free from carcinogens and as free as possible from otherwise toxic ingredients, while still achieving protection levels at least as high as have been achieved with high quality inhibitors ofthe prior art that are undesirable because of containing in ⁇ gredients, such as thiourea and propargyl alcohol (i.e., 2-propyn-l-ol), that are now known to be carcinogenic.
  • the desired freedom from carcinogens includes freedom from carcinogenic products formed by reaction among the components ofthe inhibitor within 1000 hours of mixing, as well as freedom from known carcinogens directly added to the inhibitor mixtures.
  • Another concurrent or alternative object is to provide effective inhi ⁇ bition at low cost, particularly by utilizing combinations of ingredients that are more ef- fective than any single ingredient in the combination would be alone, or in other words, are synergistic. Other objects will appear from the description below. Summary ofthe Invention
  • (A) a first component selected from the group consisting of oximes, i.e., molecules containing a moiety with the formula C N-O; and
  • One major embodiment of the invention is a concentrate useful for adding to aqueous acid solutions to produce a working pickling composition.
  • a second major em- bodiment is a working pickling composition containing a combination inhibitor accord ⁇ ing to the invention, and a third major embodiment is a process of pickling with such a working pickling composition.
  • a concentrate according to the invention is preferably liquid at 25° C.
  • any composition according to the invention preferably contains amounts of com ⁇ ponents (A) and (B) that produce a synergistic effect, i.e., so that the percent inhibition value as already defined above is greater for the combination A a + B b than for either A a or B b alone, where capital letters represent the component selected from the group desig ⁇ nated with the same capital letter in parentheses as defined above and lower case sub- scripts represent the quantitative concentration ofthe component represented by the cap ⁇ ital letter to which they are appended.
  • a a represents a concentration "a” of a particular selection “A” from the group “(A)” as defined above and B b represents a concentration “b” of a particular composition “B” from the group “(B)” as defined above.
  • B b represents a concentration "b” of a particular composition “B” from the group “(B)” as defined above.
  • the combination A a + B b has a greater percent inhibition than either A (a+b) or B (a+b) .
  • Aliphatic and aromatic oximes, oximes with a single oxime moiety or with more than one, oximes in which either hydrogen or an alkyl group is bonded to the nitrogen atom(s) in the oxime moiety, and oximes including heteroatoms are all effective in the combinations according to the invention. Largely because of their lower cost, oximes with from 2 to 6, or more preferably 2 to 4, carbon atoms are somewhat preferred.
  • the total concentration of oximes component (A) in a working composition according to the invention preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, or 0.30 grams per liter (hereinafter usually abbreviated "g/L") ofthe working composition.
  • g/L grams per liter
  • 5 concentration of component (A) in a working composition according to the invention is, with increasing preference in the order given, not greater than 1.0, 0.9, 0.8, 0.7, 0.6, 0.5,
  • Component (B) is preferably selected from surface active compounds, i.e., com- o pounds that reduce the surface tension of an otherwise similar composition to which they are added. More preferably, component (B) is selected from molecules that contain at least one moderate size hydrocarbyl moiety, i.e., a moiety including a number of carbon atoms that is, with increasing preference in the order given, at least 6, 9, 10, 12, 14, 16, 18, or 20 and independently preferably is, with increasing preference in the order given, 5 not more than 50, 40, 30, 25, or 22, and this moderate sized hydrocarbyl moiety is chem ⁇ ically bonded directly to a nitrogen atom by a carbon-nitrogen single bond.
  • surface active compounds i.e., com- o pounds that reduce the surface tension of an otherwise similar composition to which they are added. More preferably, component (B) is selected from molecules that contain at least one moderate size hydrocarbyl moiety, i.e., a moiety including a number of carbon atoms that is, with increasing
  • the other hydrocarbyl moieties in the molecules that (i) are chemically bonded directly to the same nitrogen atom as the moderate size hydrocarbyl moiety and (ii) do 0 not contain any aromatic ring preferably contain no more than, with increasing preference in the order given, 5, 4, 3, 2, or 1 carbon atom(s) each; a cyclic hydrocarbyl moiety that is bonded twice or more to the same nitrogen atom is considered to be a single moiety, and at least one ofthe bonds between the cyclic hydrocarbyl moiety and the nitrogen atom is considered to be a single bond, for the purpose of satisfying this 5 preference.
  • hydrocarbyl moiety in a molecule means a collection of carbon and hydrogen atoms in the molecule in which (i) each of the carbon atoms is directly bonded to at least one of the other carbon atoms in the collection without any intervening atoms; (ii) the number of carbon atoms in the collection is as large as it can be in the particular part ofthe molecule concerned without 0 violating criterion (i); and (iii) the collection includes all the hydrogen atoms bonded to any one ofthe carbon atoms that are present as a result of satisfying criteria (i) and (ii).
  • component (B) preferably is selected from molecules that contain a number of carbon atoms per molecule that is, with increasing preference in the order given, at least 8, 10, 12, 14, 15, 16, 17, 18, 19, or 20 and inde ⁇ pendently preferably is, with increasing preference in the order given, not more than 60, 50, 40, 35, or 30.
  • the molecules of component (B) it has been found preferable for the molecules of component (B) to include at least one aromatic ring, which term is to be understood as including rings with heteroatoms such as nitrogen, sulfur, and oxygen that chemically behave similarly to all-carbon aromatic ring moieties such as phenyl and napthyl.
  • component (B) The most preferred chemical class from which the molecules of component (B) can be selected are ketonylated rosin amines as described in U. S. Patent 2,975,125 of Mar. 14, 1961 to Saukaitis et al., the entire disclosure of which, to the extent that it de ⁇ scribes ketonylated abietyl, hydroabietyl, and dihydroabietyl amines and is not inconsist ⁇ ent with any explicit statement herein, is hereby incorporated herein by reference.
  • An ⁇ other highly preferred chemical class for component (B) is that constituted of molecules including nitrogen and/or sulfur atom containing aromatic rings such as thiophene, pyr ⁇ role, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, and pyridazine, preferably along with a ring-substituent alkyl group in which the number of carbon atoms is, with increasing preference in the order given, at least 6, 9, 10, 12, 14, 16, 18, or 20 and inde ⁇ pendently preferably is, with increasing preference in the order given, not more than 50, 40, 30, 25, or 22.
  • mixed alkyl pyridines are particular favored from this class of constituents for component (B).
  • any quaternary salt has somewhat greater steric hindrance around the nitrogen atom than the protonated form of ammonium ion expected to be formed, in a highly acid ⁇ ic working pickling composition according to this invention, from any constituent added initially as an amine.
  • the total concentration of component (B) in a working composition according to the invention preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, or 0.26 g/L ofthe working composition.
  • concentration of component (B) in a working composition according to the invention is not greater than 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.45, 0.40, 0.35, 0.32, 0.30, or 0.28 g/L.
  • compositions according to the invention In a concentrate composition according to the invention, of course, substantially higher concentrations of component (B) would normally be used. It has generally been found preferable for working compositions according to the invention to contain at least one additional optional component (C) in addition to the two necessary components (A) and (B).
  • Component (C) is selected from molecules that are not part of components (A) or (B) and contain a moiety having the general formula -(C n H 2n O) m -, where n is 2, 3, or 4, preferably 2 or 3, more preferably 2, and m represents a positive integer that, if there is only one such polyoxyalkylene moiety in the molecule, preferably is, with increasing preference in the order given, at least 2, 3, 4, 5, 6, 7, 8, or 9.
  • each molecule of component (C) contains a hydrocarbyl moiety that has a number of carbon atoms that is at least, with increasing preference in the order given, 6, 8, 10, 12, or 14 and independently preferably is not more than, with increasing preference in the order given, 24, 22, 20, 18, or 16, and when such a hydrocarbyl moiety is present it independently preferably either contains at least one aromatic ring or is directly chemically bonded to a nitrogen atom.
  • ethoxylates of octyl and nonyl phenols and (ii) ethoxylated derivatives of fatty amines in which a hydrocarbyl group with the same chemical structure as one in a fatty acid produced by hydrolysis of natural fats and/or oils is bonded directly to a first nitrogen atom and the molecule also contains a second nitrogen atom that is separated by not more than three carbon atoms from the first nitrogen atom.
  • Suitable and preferred materials for component (C) are readily available commer ⁇ cially as surfactants, and their surfactant activity is believed also to be useful in the com- positions. Unexpectedly, however, such materials have been found to reduce or elimin ⁇ ate an otherwise troublesome tendency, exhibited by many inhibitor compositions con ⁇ taining substances of the type used for component (B) according to this invention, to form tarry materials on long continued use. Such tarry materials often float on the sur ⁇ face of a pickling composition and can soil the desirably clean pickled metal surfaces as these are removed from the pickling tank. Other kinds of tarry material appear to be formed directly on the pickled surfaces and are equally undesirable.
  • polyoxyalkylene block containing component (C) has been observed substantially to reduce the danger of tarry contamination ofthe pickled surfaces. Relatively little of this material is needed for a beneficial effect; the concentration of component (C) in a working composition preferably is, with increasing preference in the order given, at least 0.001, 0.002, 0.004, 0.008, 0.015, 0.025, 0.035, 0.045, 0.055, 0.065, 0.075, 0.085, 0.090, or 0.095 g/L.
  • the amount of component (C) in a working composition according to the invention preferably is, with increasing preference in the order given, not more than 1, 0.5, 0.4, 0.3, or 0.2 g/L.
  • Another optional component (D) that can be advantageous in working composi- tions according to the invention, especially if they contain sulfuric acid as a major ingred ⁇ ient, is selected from organic compounds that are not part of components (A), (B), or (C) but contain divalent sulfur atoms.
  • Thiourea has been a common constituent of prior in ⁇ hibitors but should be avoided because it is now known to be carcinogenic.
  • Dialkylthio- ureas however, have not been found to be carcinogenic and can be useful in composi- tions according to this invention. Dibutyl thiourea is especially preferred.
  • Another optional component (E) is selected from noncarcinogenic and low toxic ⁇ ity materials that are not part of components (A), (B), (C), or (D) but whose molecules contain the moiety C ⁇ C-C-OH.
  • Propargyl alcohol is a conventional ingredient for pick ⁇ ling inhibitors but is preferably avoided in compositions according to this invention be- cause of its high toxicity.
  • a preferred, readily available, and much less toxic alternative is 3-methyl-l-butyne-3-ol.
  • the ratio by weight ofthe total of components (D) and (E), if either is present, to component (A) in a composition according to the invention is, with increasing preference in the order given, not more than 10, 5, 4, 3, 2, 1.5, or 1.1.
  • the ratio of component (B) as described above to the total of components (A), (D), and (E) preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.08, 0.15, 0.25, 0.30, 0.35, 0.40, 0.43, 0.46, 0.49, 0.52, 0.55, 0.58, or 0.61 and independently preferably is, with increasing preference in the order given, not more than 10, 5, 4, 3.0, 2.5, 2.0, 1.4, 1.3, 1.2, 1.1, 1.0, 0.95, 0.93, 0.91, 0.89, or 0.88.
  • a working pickling composition according to this invention preferably contains, with increasing preference in the order given, at least 1, 2, 4, 5.0, 6.0, 7.0, 8.0, 9.0, or 9.9 % and independently preferably contains, with increasing preference in the order given, not more than 50, 45, 40, 36, 33, 30, or 28.8, % of acid, preferably selected from hydro ⁇ chloric acid, sulfuric acid, alkali metal bisulfates, phosphoric acid, oxalic acid, formic acid, citric acid, acetic acid, tartaric acid, hydroxyacetic acid, sulfamic acid, and mixtures thereof; more preferably, the acid is either sulfuric or hydrochloric.
  • a concentrate composition according to the invention preferably comprises, more preferably consists essentially of, or still more preferably consists of, components (A) and (B) as defined above, and, optionally, one or more of components (C) through (E) as defined above, acids and organic solvents as described above, and water, except that the concentrations of each of components (A) through (E) independently in a concentrate preferably are, with increasing preference in the order given, at least 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, 190, or 195 times greater than those specified above for the con ⁇ centration ofthe corresponding component in a working pickling composition.
  • all ofthe preferences given above for ratios among or between any two or more of components (A) through (E) also apply, independently for each ratio specified, to concentrate compositions according to the invention.
  • a process according to the invention comprises contacting a metal workpiece to be pickled with a working pickling composition according to the invention as described above, preferably at a temperature that is, with increasing preference in the order given, at least 16, 30, 52, 60, 66, 70, 74, 78, or 81 °C and independently preferably is, with in ⁇ creasing preference in the order given, not more than 93, 88, or 83, °C for a time suffi- cient to remove scale and other bulk oxide coatings from the workpiece surface.
  • the time of contact preferably is in the range from 10 to 60, more preferably from 15 to 45, or still more preferably from 25 to 35, minutes, although the time naturally will vary considerably as a function ofthe amount and type of surface contamination to be removed.
  • Contact between the workpiece and the working pickling composition is generally by immersion, but any process of establishing the requisite contact, as known per se in the art, may be used.
  • This concentrate according to the invention was formulated to be highly effective in both hydrochloric and sulfuric acid pickling compositions. Its constituents are: 5 parts of methyl ethyl ketone oxime; 8 parts of a solution containing about 65 % of mixed ketonylated rosin amines, made substantially according to the directions of column 2 lines 7 - 20 of U. S. Patent 2,975,125; 8 parts of dibutyl thiourea; 5 parts of 3-methyl-l- butyn-3-ol; 6 parts of ETHODUOMENTM T/20 surfactant; and 34 parts each of water and of the monobutyl ether of ethylene glycol.
  • ETHODUOMENTM T/20 surfactant was obtained commercially from AKZO Chemicals Division and is reported by its supplier to contain: from 90 - 93 % of ethoxylated tallow amine-trimethylene diamine derivatives conforming to the general formula:
  • R represents an alkyl group conforming to that in a fatty acid made by hydroly ⁇ sis of natural tallow and each of x, y, and z represents a positive integer; from 5 - 10 % of ethoxylated tallow alkyl amines; and from 2 - 6 % of polyoxyethylene glycols.
  • Methylethylketoxime g/L 0.30 0.20 0.20 0.20
  • Trimethyldodecylammonium chloride 5 g/L 0.20 0.40
  • Nonylphenoxy-ol igo(oxyethy lene)ethanol 7 g/L 0.30 0.10 0.10 0.10 0.10 0.10 0.20
  • Polyoxyethylene surfactant 9 g/L 0.30
  • AKOLIDINETM 12 Commercially supplied as AKOLIDINETM 12 by Lonza.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
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Abstract

A combination of (i) oximes and (ii) non-carcinogenic and low toxicity amines and/or quaternary ammonium salts provides effective pickling inhibition. The addition of surfactant materials containing at least one polyoxyalkylene moiety per molecule substantially reduces any tendency that the working pickling compositions containing this inhibitor combination might otherwise have to form undesirable tarry materials that can contaminate the pickled surfaces.

Description

Description OXIME CONTAINING INHIBITORS FOR ACID PICKLING
BACKGROUND OF THE INVENTION Field ofthe Invention
This invention relates to the treatment of metal surfaces with aqueous acids to remove scale and like materials from the surface, a process commonly known in the art as "pickling", and to corrosion inhibitors used in such processes. Statement of Related Art
Strong mineral acids such as hydrochloric and sulfuric acids, together with an in¬ hibitor component that substantially reduces the rate of dissolution of clean metal surface from the rate that would prevail in the same type of acid solution without the inhibitor, are normally used as pickling compositions.
Advantageous inhibitors reduce the rate of dissolution of clean metal as much as possible while reducing the rate of dissolution of surface scale and like contaminating materials as little as possible. One common quantitative method of rating inhibitors used in the art, and in this description below, involves measuring the corrosion rate of the metal to be pickled in a solution containing the type and concentration of acid to be used for pickling, measuring the corrosion rate in a solution otherwise the same except for adding the inhibitor to be used, and then reporting the results as the percent "protection" ofthe inhibitor. The percent protection is defined by the following equation: P = 100[1- (Rj/RJ], where P = percent protection, R; = corrosion rate ofthe metal in the inhibited solution, and Ru = the corrosion rate ofthe metal in the uninhibited solution, expressed in the same units as Rs.
A very wide variety of inhibitors for pickling compositions are known in the art. A useful review is given by G. Trabanelli and V. Carassiti, "Mechanism and Phenomenology of Organic Inhibitors", in Advances in Corrosion Science and Technology, Volume 1 (Plenum Press, New York, 1970).
DESCRIPTION OF THE INVENTION General Principles of Description
Except in the claims and the operating examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word "about" in describing the broadest scope ofthe invention. Practice within the numerical limits stated is generally preferred, however. Also, unless expressly stated to the contrary: per¬ cent, "parts of, and ratio values are by weight; the term "polymer" includes "oligomer", "copolymer", "terpolymer", and the like; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more ofthe members ofthe group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; specifi¬ cation of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole; and any counterions thus implicitly specified preferably are selected from among other constituents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, ex- cept for avoiding counterions that act adversely to the objects ofthe invention; and the terms "solution", "soluble", and the like are to be understood as including not only true equilibrium solutions but also dispersions that show no visually detectable tendency to¬ ward phase separation over a period of observation of at least 1000 hours. Objects ofthe Invention A major object of this invention is to provide pickling inhibitors and pickling compositions that are free from carcinogens and as free as possible from otherwise toxic ingredients, while still achieving protection levels at least as high as have been achieved with high quality inhibitors ofthe prior art that are undesirable because of containing in¬ gredients, such as thiourea and propargyl alcohol (i.e., 2-propyn-l-ol), that are now known to be carcinogenic. The desired freedom from carcinogens includes freedom from carcinogenic products formed by reaction among the components ofthe inhibitor within 1000 hours of mixing, as well as freedom from known carcinogens directly added to the inhibitor mixtures. Another concurrent or alternative object is to provide effective inhi¬ bition at low cost, particularly by utilizing combinations of ingredients that are more ef- fective than any single ingredient in the combination would be alone, or in other words, are synergistic. Other objects will appear from the description below. Summary ofthe Invention
It has been found that particularly effective inhibition can be achieved by a com¬ bination of:
(A) a first component selected from the group consisting of oximes, i.e., molecules containing a moiety with the formula C=N-O; and
(B) a second component selected from the group of non-oxime and non-carcinogenic organic amines and quaternary ammonium salts.
One major embodiment of the invention is a concentrate useful for adding to aqueous acid solutions to produce a working pickling composition. A second major em- bodiment is a working pickling composition containing a combination inhibitor accord¬ ing to the invention, and a third major embodiment is a process of pickling with such a working pickling composition. Description of Preferred Embodiments
A concentrate according to the invention is preferably liquid at 25° C. Independ- ently, any composition according to the invention preferably contains amounts of com¬ ponents (A) and (B) that produce a synergistic effect, i.e., so that the percent inhibition value as already defined above is greater for the combination Aa + Bb than for either Aa or Bb alone, where capital letters represent the component selected from the group desig¬ nated with the same capital letter in parentheses as defined above and lower case sub- scripts represent the quantitative concentration ofthe component represented by the cap¬ ital letter to which they are appended. Thus, for example, Aa represents a concentration "a" of a particular selection "A" from the group "(A)" as defined above and Bb represents a concentration "b" of a particular composition "B" from the group "(B)" as defined above. Still more preferably, the combination Aa + Bb has a greater percent inhibition than either A(a+b) or B(a+b).
Aliphatic and aromatic oximes, oximes with a single oxime moiety or with more than one, oximes in which either hydrogen or an alkyl group is bonded to the nitrogen atom(s) in the oxime moiety, and oximes including heteroatoms are all effective in the combinations according to the invention. Largely because of their lower cost, oximes with from 2 to 6, or more preferably 2 to 4, carbon atoms are somewhat preferred. The total concentration of oximes component (A) in a working composition according to the invention preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, or 0.30 grams per liter (hereinafter usually abbreviated "g/L") ofthe working composition. In a working com¬ position, little or no benefit is generally obtained from substantially higher concentra¬ tions, so that, primarily for reasons of economy, it is independently preferred that the
5 concentration of component (A) in a working composition according to the invention is, with increasing preference in the order given, not greater than 1.0, 0.9, 0.8, 0.7, 0.6, 0.5,
0.45, 0.40, or 0.35 g/L. In a concentrate composition according to the invention, of course, substantially higher concentrations of component (A) would normally be used.
Component (B) is preferably selected from surface active compounds, i.e., com- o pounds that reduce the surface tension of an otherwise similar composition to which they are added. More preferably, component (B) is selected from molecules that contain at least one moderate size hydrocarbyl moiety, i.e., a moiety including a number of carbon atoms that is, with increasing preference in the order given, at least 6, 9, 10, 12, 14, 16, 18, or 20 and independently preferably is, with increasing preference in the order given, 5 not more than 50, 40, 30, 25, or 22, and this moderate sized hydrocarbyl moiety is chem¬ ically bonded directly to a nitrogen atom by a carbon-nitrogen single bond. Independent¬ ly, when the molecules of component (B) include such a moderate size hydrocarbyl moiety, the other hydrocarbyl moieties in the molecules that (i) are chemically bonded directly to the same nitrogen atom as the moderate size hydrocarbyl moiety and (ii) do 0 not contain any aromatic ring preferably contain no more than, with increasing preference in the order given, 5, 4, 3, 2, or 1 carbon atom(s) each; a cyclic hydrocarbyl moiety that is bonded twice or more to the same nitrogen atom is considered to be a single moiety, and at least one ofthe bonds between the cyclic hydrocarbyl moiety and the nitrogen atom is considered to be a single bond, for the purpose of satisfying this 5 preference. For the definitions above, the term "hydrocarbyl moiety" in a molecule means a collection of carbon and hydrogen atoms in the molecule in which (i) each of the carbon atoms is directly bonded to at least one of the other carbon atoms in the collection without any intervening atoms; (ii) the number of carbon atoms in the collection is as large as it can be in the particular part ofthe molecule concerned without 0 violating criterion (i); and (iii) the collection includes all the hydrogen atoms bonded to any one ofthe carbon atoms that are present as a result of satisfying criteria (i) and (ii).
Independently of all other preferences, component (B) preferably is selected from molecules that contain a number of carbon atoms per molecule that is, with increasing preference in the order given, at least 8, 10, 12, 14, 15, 16, 17, 18, 19, or 20 and inde¬ pendently preferably is, with increasing preference in the order given, not more than 60, 50, 40, 35, or 30. Independently ofthe other preferences stated above, it has been found preferable for the molecules of component (B) to include at least one aromatic ring, which term is to be understood as including rings with heteroatoms such as nitrogen, sulfur, and oxygen that chemically behave similarly to all-carbon aromatic ring moieties such as phenyl and napthyl. The most preferred chemical class from which the molecules of component (B) can be selected are ketonylated rosin amines as described in U. S. Patent 2,975,125 of Mar. 14, 1961 to Saukaitis et al., the entire disclosure of which, to the extent that it de¬ scribes ketonylated abietyl, hydroabietyl, and dihydroabietyl amines and is not inconsist¬ ent with any explicit statement herein, is hereby incorporated herein by reference. An¬ other highly preferred chemical class for component (B) is that constituted of molecules including nitrogen and/or sulfur atom containing aromatic rings such as thiophene, pyr¬ role, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, and pyridazine, preferably along with a ring-substituent alkyl group in which the number of carbon atoms is, with increasing preference in the order given, at least 6, 9, 10, 12, 14, 16, 18, or 20 and inde¬ pendently preferably is, with increasing preference in the order given, not more than 50, 40, 30, 25, or 22. Largely because of availability and relatively low cost, mixed alkyl pyridines are particular favored from this class of constituents for component (B). How¬ ever, even simple aliphatic amines and quaternary ammonium salts are fully suitable for component (B), although the quaternary salts are somewhat less preferred, possibly be¬ cause any quaternary salt has somewhat greater steric hindrance around the nitrogen atom than the protonated form of ammonium ion expected to be formed, in a highly acid¬ ic working pickling composition according to this invention, from any constituent added initially as an amine.
The total concentration of component (B) in a working composition according to the invention preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, or 0.26 g/L ofthe working composition. In a working composition, little or no benefit is generally obtained from substantially higher concentrations, so that, primarily for reasons of economy, it is inde- pendently preferred that the concentration of component (B) in a working composition according to the invention is not greater than 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.45, 0.40, 0.35, 0.32, 0.30, or 0.28 g/L. In a concentrate composition according to the invention, of course, substantially higher concentrations of component (B) would normally be used. It has generally been found preferable for working compositions according to the invention to contain at least one additional optional component (C) in addition to the two necessary components (A) and (B). Component (C) is selected from molecules that are not part of components (A) or (B) and contain a moiety having the general formula -(CnH2nO)m-, where n is 2, 3, or 4, preferably 2 or 3, more preferably 2, and m represents a positive integer that, if there is only one such polyoxyalkylene moiety in the molecule, preferably is, with increasing preference in the order given, at least 2, 3, 4, 5, 6, 7, 8, or 9. Independently, each molecule of component (C) contains a hydrocarbyl moiety that has a number of carbon atoms that is at least, with increasing preference in the order given, 6, 8, 10, 12, or 14 and independently preferably is not more than, with increasing preference in the order given, 24, 22, 20, 18, or 16, and when such a hydrocarbyl moiety is present it independently preferably either contains at least one aromatic ring or is directly chemically bonded to a nitrogen atom. Particularly preferred are (i) ethoxylates of octyl and nonyl phenols and (ii) ethoxylated derivatives of fatty amines in which a hydrocarbyl group with the same chemical structure as one in a fatty acid produced by hydrolysis of natural fats and/or oils is bonded directly to a first nitrogen atom and the molecule also contains a second nitrogen atom that is separated by not more than three carbon atoms from the first nitrogen atom.
Suitable and preferred materials for component (C) are readily available commer¬ cially as surfactants, and their surfactant activity is believed also to be useful in the com- positions. Unexpectedly, however, such materials have been found to reduce or elimin¬ ate an otherwise troublesome tendency, exhibited by many inhibitor compositions con¬ taining substances of the type used for component (B) according to this invention, to form tarry materials on long continued use. Such tarry materials often float on the sur¬ face of a pickling composition and can soil the desirably clean pickled metal surfaces as these are removed from the pickling tank. Other kinds of tarry material appear to be formed directly on the pickled surfaces and are equally undesirable. The addition of polyoxyalkylene block containing component (C) has been observed substantially to reduce the danger of tarry contamination ofthe pickled surfaces. Relatively little of this material is needed for a beneficial effect; the concentration of component (C) in a working composition preferably is, with increasing preference in the order given, at least 0.001, 0.002, 0.004, 0.008, 0.015, 0.025, 0.035, 0.045, 0.055, 0.065, 0.075, 0.085, 0.090, or 0.095 g/L. Larger amounts are not harmful, but, primarily for reasons of economy, the amount of component (C) in a working composition according to the invention preferably is, with increasing preference in the order given, not more than 1, 0.5, 0.4, 0.3, or 0.2 g/L.
Another optional component (D) that can be advantageous in working composi- tions according to the invention, especially if they contain sulfuric acid as a major ingred¬ ient, is selected from organic compounds that are not part of components (A), (B), or (C) but contain divalent sulfur atoms. Thiourea has been a common constituent of prior in¬ hibitors but should be avoided because it is now known to be carcinogenic. Dialkylthio- ureas, however, have not been found to be carcinogenic and can be useful in composi- tions according to this invention. Dibutyl thiourea is especially preferred.
Another optional component (E) is selected from noncarcinogenic and low toxic¬ ity materials that are not part of components (A), (B), (C), or (D) but whose molecules contain the moiety C≡C-C-OH. Propargyl alcohol is a conventional ingredient for pick¬ ling inhibitors but is preferably avoided in compositions according to this invention be- cause of its high toxicity. A preferred, readily available, and much less toxic alternative is 3-methyl-l-butyne-3-ol.
Primarily for reasons of economy, it is preferred that the ratio by weight ofthe total of components (D) and (E), if either is present, to component (A) in a composition according to the invention is, with increasing preference in the order given, not more than 10, 5, 4, 3, 2, 1.5, or 1.1.
Strong acidity is of course a necessity in working compositions according to the invention in order for them to pickle effectively. Acids, although not a necessary com¬ ponent in concentrates according to the invention, may be useful in concentrates also to promote solubility of some ofthe amines used. Many organic solvents, although not nec- essary or apparently advantageous in working compositions according to the invention also are not harmful in such working compositions and may be useful in concentrates ac¬ cording to the invention to solubilize some ofthe other ingredients in high concentra- tions. When solvent is needed or desired, monoethers of ethylene and/or propylene gly¬ col, such as the particularly preferred monobutyl ether of ethylene glycol, are preferred. Independently ofthe concentrations of individual components of a composition according to the invention given above, certain ratios among various components are preferred. In particular, the ratio of component (B) as described above to the total of components (A), (D), and (E) preferably is, with increasing preference in the order given, at least 0.02, 0.04, 0.08, 0.15, 0.25, 0.30, 0.35, 0.40, 0.43, 0.46, 0.49, 0.52, 0.55, 0.58, or 0.61 and independently preferably is, with increasing preference in the order given, not more than 10, 5, 4, 3.0, 2.5, 2.0, 1.4, 1.3, 1.2, 1.1, 1.0, 0.95, 0.93, 0.91, 0.89, or 0.88. A working pickling composition according to this invention preferably contains, with increasing preference in the order given, at least 1, 2, 4, 5.0, 6.0, 7.0, 8.0, 9.0, or 9.9 % and independently preferably contains, with increasing preference in the order given, not more than 50, 45, 40, 36, 33, 30, or 28.8, % of acid, preferably selected from hydro¬ chloric acid, sulfuric acid, alkali metal bisulfates, phosphoric acid, oxalic acid, formic acid, citric acid, acetic acid, tartaric acid, hydroxyacetic acid, sulfamic acid, and mixtures thereof; more preferably, the acid is either sulfuric or hydrochloric.
A concentrate composition according to the invention preferably comprises, more preferably consists essentially of, or still more preferably consists of, components (A) and (B) as defined above, and, optionally, one or more of components (C) through (E) as defined above, acids and organic solvents as described above, and water, except that the concentrations of each of components (A) through (E) independently in a concentrate preferably are, with increasing preference in the order given, at least 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, 190, or 195 times greater than those specified above for the con¬ centration ofthe corresponding component in a working pickling composition. Inde- pendently, all ofthe preferences given above for ratios among or between any two or more of components (A) through (E) also apply, independently for each ratio specified, to concentrate compositions according to the invention.
A process according to the invention comprises contacting a metal workpiece to be pickled with a working pickling composition according to the invention as described above, preferably at a temperature that is, with increasing preference in the order given, at least 16, 30, 52, 60, 66, 70, 74, 78, or 81 °C and independently preferably is, with in¬ creasing preference in the order given, not more than 93, 88, or 83, °C for a time suffi- cient to remove scale and other bulk oxide coatings from the workpiece surface. Inde¬ pendently, the time of contact preferably is in the range from 10 to 60, more preferably from 15 to 45, or still more preferably from 25 to 35, minutes, although the time naturally will vary considerably as a function ofthe amount and type of surface contamination to be removed. Contact between the workpiece and the working pickling composition is generally by immersion, but any process of establishing the requisite contact, as known per se in the art, may be used.
The practice and benefits ofthe invention may be further appreciated by consider¬ ation ofthe following non-limiting examples. Examples of Pickling and Working Compositions Therefor
Concentrations in the working compositions of any components present other than acid and water are shown in Table 1. All of the working compositions for these examples also contained 29 % HCl and were used at 82 °C on Type 1008 cold rolled steel panel substrates. The percent protection values achieved are shown in Table 1. Concentrate Inhibitor Example
This concentrate according to the invention was formulated to be highly effective in both hydrochloric and sulfuric acid pickling compositions. Its constituents are: 5 parts of methyl ethyl ketone oxime; 8 parts of a solution containing about 65 % of mixed ketonylated rosin amines, made substantially according to the directions of column 2 lines 7 - 20 of U. S. Patent 2,975,125; 8 parts of dibutyl thiourea; 5 parts of 3-methyl-l- butyn-3-ol; 6 parts of ETHODUOMEN™ T/20 surfactant; and 34 parts each of water and of the monobutyl ether of ethylene glycol. ETHODUOMEN™ T/20 surfactant was obtained commercially from AKZO Chemicals Division and is reported by its supplier to contain: from 90 - 93 % of ethoxylated tallow amine-trimethylene diamine derivatives conforming to the general formula:
R-N-(C2H4O)x-H \
(CH2)3 \ H-(C2H4O)y-N-(C2H4O)z-H wherein R represents an alkyl group conforming to that in a fatty acid made by hydroly¬ sis of natural tallow and each of x, y, and z represents a positive integer; from 5 - 10 % of ethoxylated tallow alkyl amines; and from 2 - 6 % of polyoxyethylene glycols. TABLE 1
Ingredient and Units Amount of Ingredient in Working Composition No.:
1 2 3 4 5 6 7 8 9 10 11 12 13
Butyraldehyde oxime, g L 0.25 0.30 0.30
Figure imgf000012_0001
Dimethyiglyoxime, g L 0.30
Acetaldehyde oxime, g/L 0.30 0.15
Methylethylketoxime, g/L 0.30 0.20 0.20 0.20
Benzaldehyde oxime, g L 0.30
2-Methyl-2-methylthiopropionaldehyde oxime1, g/L 0.30 0.20
Mixed alkyl pyridines2, g/L 0.10 0.30 0.30 0.20 0.20
Mixed ketonylated rosin amines3, g/L 0.26 0.26 0.26 0.26 0.26 0.26 0.20
Na2N-lauryl-P-iminopropionate4, g L 0.10 0.10
Trimethyldodecylammonium chloride5, g/L 0.20 0.40
Average Cl4-alkyl monoamines mixture6, g L 0.30
3-Methyl-l-butyne-3-ol, g L 0.30 0.30 0.20
Nonylphenoxy-ol igo(oxyethy lene)ethanol7, g/L 0.30 0.10 0.10 0.10 0.10 0.10 0.20
Ethoxylated rosin8, g L 0.30 0.30
Polyoxyethylene surfactant9, g/L 0.30
Percent of Inhibition Achieved by the Working Composition:
98.9 99.4 98.6 99.8 99.7 99.7 99.8 99.7 88.1 98.9 98.6 95.1 60.5
Footnotes for Table 1 are on the next page ...
Footnotes for Table 1
'Commercially supplied under the trade name Aldicarb Oxime by Allied-Signal.
Commercially supplied as AKOLIDINE™ 12 by Lonza.
3Made substantially according to the directions of column 2 lines 7 - 20 of U. S. Patent 2,975,125.
Commercially supplied as DERIPHAT™ 160 by.Henkel Corp.
Commercially supplied as ARQUAD™ 12/50 by Chemax, Inc., Greenville, SC
Commercially supplied as EXXON™ PA- 14 by Exxon Chemical Co.
'Commercially supplied as TRITON™ N-l 01 by Van Waters and Rogers, Kirkland, Washington.
Commercially supplied as EMULSOGEN™ 2144 by Hoechst Celanese or
CHEMAX™ AR-497 by Chemax, Inc., Greenville, SC.
Commercially supplied as HOSTAWET™ TDC by Hoechst Celanese.
Concentrations from about 0.2 to about 1 % of this concentrate effectively inhibit most acid pickling compositions.

Claims

The invention claimed is:
1. A concentrate inhibitor composition, comprising:
(A) a first component selected from the group consisting of molecules containing a moiety with the formula C=N-O; and (B) a second component selected from the group of non-oxime and non-carcinogenic organic amines and quaternary ammonium salts.
2. A concentrate inhibitor composition according to claim 1 , additionally compris¬ ing:
(C) a third component selected from the group consisting of molecules that are not part of either of the first or second components and that contain at least one moiety having the general formula -(CnH2nO)m-, where n is 2, 3, or 4 and m represents a positive integer that, if there is only one such moiety in the molecule, is at least 2, and, optionally, also comprising one or more of:
(D) a fourth component selected from the group consisting of organic molecules that are not part of any ofthe previously recited components and that contain divalent sulfur atoms;
(E) a fifth component selected from the group consisting of non-carcinogenic and low toxicity molecules that are not part of any ofthe previous recited components and that contain a moiety having the chemical formula C≡C-C-OH; (F) a sixth component selected from the group consisting of water soluble acids that are not part of any ofthe previously recited components; (G) a seventh component selected from the group consisting of organic solvents that are not part of any ofthe previously recited components; and (H) water, wherein components (A) through (E) are present in amounts, each of which amounts except those of components (A), (B), and (C) may be zero, such that (i) the amounts of components (A), (D), and (E) have a sum, (ii) the amount of component (B) has a ratio to the sum ofthe amounts of components (A), (D), and (E) that is in a range from about 0.15:1.0 to about 3.0:1.0, (iii) the amounts of components (D) and (E) have a sum, and (iv) the sum of the amounts of components (D) and (E) has a ratio to the amount of component (A) that is not more than about 10:1.0. 3. A concentrate inhibitor composition according to claim 2, wherein: (1) compon¬ ent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 8 to 60 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 6 to 50 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.
3) contains more than 5 carbon atoms; (3) component (C) is selected from molecules that (3.1) contain at least one hydrocarbyl moiety having from 6 to 24 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 3; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.25 : 1.0 to about 2.5:1.0, and (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component
(A) is not more than about 5:1.0.
4. A concentrate inhibitor composition according to claim 3, wherein: (1) compon¬ ent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 10 to 50 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 9 to 40 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 4 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 8 to 22 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 4; (4) the ratio of the amount of component (B) to the sum of the amounts of components (A), (D), and (E) is in a range from about 0.35: 1.0 to about 2.0: 1.0, and (5) the ratio of the sum of the amounts of components (D) and (E) to the amount of component (A) is not more than about 4: 1.0.
5. A concentrate inhibitor composition according to claim 4, wherein: (^ compon¬ ent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 14 to 40 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 12 to 30 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 3 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 10 to 20 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and. if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 5; (4) the ratio of the amount of component (B) to the sum of the amounts of components (A), (D), and (E) is in a range from about 0.40: 1.0 to about 1.4: 1.0, and (5) the ratio of the sum of the amounts of components (D) and (E) to the amount of component (A) is not more than about 4:1.0.
6. A concentrate inhibitor composition according to claim 5, wherein: (1) compon¬ ent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 15 to 35 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 12 to 30 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 3 carbon atoms;
(3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and. if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 6; (4) the ratio of the amount of component (B) to the sum of the amounts of components (A), (D), and (E) is in a range from about 0.40: 1.0 to about 1.4: 1.0, and (5) the ratio of the sum of the amounts of components (D) and (E) to the amount of component (A) is not more than about 4:1.0.
7. A concentrate inhibitor composition according to claim 6, wherein: (1) compon¬ ent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 16 to 30 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 14 to 25 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 3 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 7; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.46: 1.0 to about 1.2: 1.0, and (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component (A) is not more than about 3:1.0.
8. A concentrate inhibitor composition according to claim 7, wherein: (1) compon- ent (A) is selected from oximes containing from 2 to 4 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 17 to 30 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 14 to 22 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 2 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 8; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com- ponents (A), (D), and (E) is in arange from about 0.55:1.0 to about 1.0:1.0, and (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component (A) is not more than about 2: 1.0.
9. A concentrate inhibitor composition according to claim 8, wherein: (1) compon- ent (A) is selected from oximes containing from 2 to 4 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 18 to 30 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 16 to 22 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 2 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 9; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.61 : 1.0 to about 0.89:1.0, and (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component
(A) is not more than about 1.5: 1.0.
10. A concentrate inhibitor composition according to claim 9. wherein: (1) component
(B) is selected from the group consisting of (1.1) ketonylated rosin amines and (1.2) alkyl pyridines in which the alkyl groups have from 12 to 15 carbon atoms each; (2) component (C) is selected from the group consisting of (2.1 ) ethoxylates of octyl and nonyl phenols and (2.2) ethoxylated compounds in which (2.2.1) a hydrocarbyl group with the same chemical structure as one in a fatty acid produced by hydrolysis of natural fats and/or oils is bonded directly to a first nitrogen atom in each molecule and (2.2.2) each molecule also contains a second nitrogen atom that is separated by not more than three carbon atoms from the first nitrogen atom.
11. A working metal pickling composition, comprising water, at least 1 % of an acid component selected from the group consisting of hydrochloric acid, sulfuric acid, alkali metal acid sulfates, phosphoric acid, oxalic acid, formic acid, citric acid, acetic acid, tar- taric acid, hydroxyacetic acid, sulfamic acid, and mixtures of any two or more thereof; and:
(A) a first component selected from the group consisting of molecules containing a moiety with the formula C=N-O; and 5 (B) a second component selected from the group of non-oxime and non-carcinogenic organic amines and quaternary ammonium salts.
12. A working metal pickling composition according to claim 11 , additionally com¬ prising:
(C) a third component selected from the group consisting of molecules that are not o part of either of the first or second components and that contain at least one moie¬ ty having the general formula -(CnH2nO)m-, where n is 2, 3, or 4 and m represents a positive integer that, if there is only one such moiety in the molecule, is at least 2, and, optionally, also comprising one or more of:
(D) a fourth component selected from the group consisting of organic molecules that 5 are not part of any of the previously recited components and that contain divalent sulfur atoms;
(E) a fifth component selected from the group consisting of non-carcinogenic and low toxicity molecules that are not part of any ofthe previous recited components and that contain a moiety having the chemical formula C≡C-C-OH; 0 (F) a sixth component selected from the group consisting of water soluble acids that are not part of any ofthe previously recited components; and (G) a seventh component selected from the group consisting of organic solvents that are not part of any ofthe previously recited components, wherein: (1) components (A) through (E) are present in amounts, which amounts for 5 components (D) and (E) may be zero, such that (1.1) the amounts of components (A),
(D), and (E) have a sum, (1.2) the amount of component (B) has a ratio to the sum ofthe amounts of components (A), (D), and (E) that is in a range from about 0.15 : 1.0 to about 3.0:1.0, (1.3) the amounts of components (D) and (E) have a sum, and (1.4) the sum of the amounts of components (D) and (E) has a ratio to the amount of component (A) that 0 is not more than about 10:1.0; (2) said acid component is present in an amount from about 2 to about 50 % ofthe total working pickling composition; (3) component (A) is present in a concentration from about 0.02 to about 1.0 g/L ofthe total working pickling composition; (4) component (B) is present in a concentration from about 0.02 to about 1.0 g/L of the total working pickling composition; (5) component (C) is present in a concentration from about 0.001 to about 1 g/L ofthe total working pickling composition, and (6) the working pickling composition contains at least 4 % of the acid component selected from the group consisting of hydrochloric acid, sulfuric acid, alkali metal acid sulfates, phosphoric acid, oxalic acid, formic acid, citric acid, acetic acid, tartaric acid, hydroxyacetic acid, sulfamic acid, and mixtures of any two or more thereof.
13. A working metal pickling composition according to claim 12, wherein: (1) com¬ ponent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 8 to 60 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 6 to 50 carbon atoms chemically bonded directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not con¬ tain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 5 carbon atoms; (3) component (C) is selected from molecules that (3.1) contain at least one hydrocarbyl moiety having from 6 to 24 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 3; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.25: 1.0 to about 2.5: 1.0, (5) the ratio ofthe sum of the amounts of components (D) and (E) to the amount of component (A) is not more than about 5:1.0, (6) component (A) is present in a concentration from about 0.06 to about 0.9 g/L of the total working pickling composition, (7) component (B) is present in a concentration from about 0.06 to about 0.9 g/L ofthe total working pickling composition, (8) component (C) is present in a concentration from about 0.004 to about 1 g/L ofthe total working pickling composition, and (9) the working pickling composi¬ tion contains at least about 4 % ofthe acid component selected from the group consisting of hydrochloric acid, sulfuric acid, alkali metal acid sulfates, phosphoric acid, oxalic ac- id, formic acid, citric acid, acetic acid, tartaric acid, hydroxyacetic acid, sulfamic acid, and mixtures of any two or more thereof.
14. A working metal pickling composition according to claim 13, wherein: (1) com¬ ponent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 14 to 40 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 12 to 30 carbon atoms chemically bond- ed directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 3 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 10 to 20 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 or 3 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 5; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.40:1.0 to about 1.4:1.0, (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component (A) is not more than about 4:1.0, (6) component (A) is present in a concentration from about 0.12 to about 0.7 g/L of the total working pickling composition, (7) component (B) is present in a concentration from about 0.12 to about 0.7 g/L ofthe total working pickling composition, (8) component (C) is present in a concentration from about 0.015 to about 0.4 g/L ofthe total working pickling composition, and (9) the working pickling composi¬ tion contains from about 5.0 % to about 36 % ofthe acid component selected from the group consisting of hydrochloric acid, sulfuric acid, alkali metal acid sulfates, phosphoric acid, oxalic acid, formic acid, citric acid, acetic acid, tartaric acid, hydroxyacetic acid, sulfamic acid, and mixtures of any two or more thereof.
15. A working metal pickling composition according to claim 14, wherein: (^ com¬ ponent (A) is selected from oximes containing from 2 to 6 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 16 to 30 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 14 to 25 carbon atoms chemically bond¬ ed directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 3 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 7; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.46: 1.0 to about 1.2: 1.0, (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component (A) is not more than about 3:1.0, (6) component (A) is present in a concentration from about 0.18 to about 0.6 g/L ofthe total working pickling composition, (7) component (B) is present in a concentration from about 0.16 to about 0.6 g/L of the total working pickling composition, (8) component (C) is present in a concentration from about 0.045 to about 0.4 g/L ofthe total working pickling composition, and (9) the working pickling composi¬ tion contains from about 5.0 % to about 36 % of an acid component selected from the group consisting of hydrochloric acid, sulfuric acid, and mixtures thereof.
16. A working metal pickling composition according to claim 15, wherein: (1) com¬ ponent (A) is selected from oximes containing from 2 to 4 carbon atoms; (2) component (B) is selected from molecules that (2.1) contain a total of from 18 to 30 carbon atoms, (2.2) contain a hydrocarbyl moiety having from 16 to 22 carbon atoms chemically bond- ed directly to a nitrogen atom, (2.3) contain at least one aromatic ring, and (2.4) do not contain any hydrocarbyl group, other than the one recited in part (2.2), that (2.4.1) is bonded directly to the same nitrogen atom as the hydrocarbyl group recited in part (2.2), (2.4.2) does not contain an aromatic ring, and (2.4.3) contains more than 2 carbon atoms; (3) component (C) is selected from molecules (3.1) that contain at least one hydrocarbyl moiety having from 12 to 18 carbon atoms and (3.2) in which n in the general formula for the necessary moiety in the molecules is 2 and, if there is only one such moiety in each molecule, m in the general formula for the necessary moiety in the molecules is at least 9; (4) the ratio ofthe amount of component (B) to the sum ofthe amounts of com¬ ponents (A), (D), and (E) is in a range from about 0.61 : 1.0 to about 0.89: 1.0, (5) the ratio ofthe sum ofthe amounts of components (D) and (E) to the amount of component (A) is not more than about 1.5:1.0, (6) component (A) is present in a concentration from about 0.26 to about 0.5 g/L ofthe total working pickling composition, (7) component (B) is present in a concentration from about 0.24 to about 0.40 g/L ofthe total working pick¬ ling composition, and (8) component (C) is present in a concentration from about 0.075 to about 0.4 g/L ofthe total working pickling composition.
17. A working metal pickling composition according to claim 16, wherein: (1 ) com- ponent (B) is selected from the group consisting of (1.1) ketonylated rosin amines and
(1.2) alkyl pyridines in which the alkyl groups have from 12 to 15 carbon atoms each; (2) component (C) is selected from the group consisting of (2.1) ethoxylates of octyl and nonyl phenols and (2.2) ethoxyated compounds in which (2.2.1) a hydrocarbyl group with the same chemical structure as one in a fatty acid produced by hydrolysis of natural fats and/or oils is bonded directly to a first nitrogen atom in each molecule and (2.2.2) each molecule also contains a second nitrogen atom that is separated by not more than three carbon atoms from the first nitrogen atom.
18. A process of pickling a metal surface, said process comprising steps of:
(I) bringing the metal surface into contact with a working metal pickling composi- tion according to any one of claims 11 - 17 at a temperature of at least 18 °C for a time sufficient to remove any scale and other bulk oxide coatings from the met¬ al surface; and
(II) separating the metal surface as modified in step (I) from contact with the working metal pickling composition.
19. A process according to claim 18, wherein the temperature during the contact in step (I) is from about 60 to about 93 °C and the time of contact is from about 15 to about 45 minutes.
20. A process according to claim 19, wherein the temperature during the contact in step (I) is from about 74 to about 83 °C and the time of contact is from about 25 to about 35 minutes.
PCT/US1996/011426 1995-07-21 1996-07-12 Oxime containing inhibitors for acid pickling WO1997004055A1 (en)

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Citations (6)

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US3031411A (en) * 1958-06-10 1962-04-24 Detrex Chem Ind Composition and method of inhibiting corrosion of ferrous metals by aminestabilized unsaturated chlorinated hydrocarbons
US3062748A (en) * 1959-08-24 1962-11-06 Dow Chemical Co Inhibited aqueous acidic composition
US3107221A (en) * 1958-04-18 1963-10-15 Dow Chemical Co Corrosion inhibitor composition
US3676354A (en) * 1970-10-02 1972-07-11 Basf Wyandotte Corp Corrosion inhibitor for hydrochloric acid pickling of steel
US3876371A (en) * 1970-09-25 1975-04-08 Ici Ltd Inhibition of corrosion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2975125A (en) * 1957-03-01 1961-03-14 Amchem Prod Inhibitor compositions
US3107221A (en) * 1958-04-18 1963-10-15 Dow Chemical Co Corrosion inhibitor composition
US3031411A (en) * 1958-06-10 1962-04-24 Detrex Chem Ind Composition and method of inhibiting corrosion of ferrous metals by aminestabilized unsaturated chlorinated hydrocarbons
US3062748A (en) * 1959-08-24 1962-11-06 Dow Chemical Co Inhibited aqueous acidic composition
US3876371A (en) * 1970-09-25 1975-04-08 Ici Ltd Inhibition of corrosion
US3676354A (en) * 1970-10-02 1972-07-11 Basf Wyandotte Corp Corrosion inhibitor for hydrochloric acid pickling of steel

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AU6543496A (en) 1997-02-18
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