Corrosion Inhibition

Abstract

Corrosion of steel in acidic solution is inhibited using a mixture of a compound in which a plurality of heterocyclic aromatic groups with a quaternary nitrogen atom are connected together, such as by a linking group which may be covalently attached to the quaternary nitrogen atoms of the aromatic heterocyclic rings, and a polarizable adsorption-intensifying anion.

Claims

1. A method of inhibiting corrosion of metal exposed to aqueous acidic solution comprising including in the solution: at least one compound comprising two to five groups which are connected together and each contain a heterocyclic aromatic ring or ring system comprising at least one ring nitrogen atom which is quaternary in the aqueous acidic solution; and at least one adsorption-intensifying anion which comprises at least one atom of atomic number of 52 or above and/or an anionic group conjugated with an aromatic ring or ring system; wherein the concentration, in equivalents, of the at least one adsorption-intensifying anion is at least equal to the concentration, in equivalents, of the at least one ring nitrogen atom.

2. The method according to claim 1 wherein the at least one ring nitrogen atom is tertiary in aqueous neutral or alkaline solutions.

3. The method according to claim 1 wherein the concentration, in equivalents, of the at least one adsorption-intensifying anion is at least twice the concentration, in equivalents, of the at least one ring nitrogen atom.

4. The method according to claim 1 wherein the molar concentration of the at least one adsorption-intensifying anion is at least twice the concentration, in equivalents, of the at least one ring nitrogen atom.

5. The method according to claim 1 wherein the at least one adsorption-intensifying anion carries a single negative charge.

6. The method according to claim 1 wherein the at least one adsorption-intensifying anion comprises iodide.

7. The method according to claim 1 wherein the at least one adsorption-intensifying anion comprises an aromatic sulphonate.

8. The method according to claim 1 wherein the number of quaternary nitrogen-containing groups which are connected together is from two to four.

9. The method according to claim 1 wherein each of the quaternary nitrogen-containing groups contains only a single ring nitrogen atom.

10. The method according to claim 1 wherein each group is covalently bonded through its quaternary nitrogen atom to a linking group which comprises a plurality of carbon atoms.

11. The method according to claim 10 wherein the linking group comprises a chain of at least three carbon atoms.

12. The method according to claim 1 wherein at least one of the quaternary nitrogen-containing groups contains a heterocyclic ring or ring system which is any one of pyridine, pyridinium, quinoline, quinolinium, isoquinoline, isoquinolinium, anthradine, anthradinium, phenanthradine, phenanthradinium, tetrahydroquinoline, or decahydroquinoline.

13. The method according to claim 1 wherein each quaternary nitrogen-containing group contains a heterocyclic ring or ring system which is any one of pyridine, pyridinium, quinoline, quinolinium, isoquinoline, isoquinolinium, anthradine, anthradinium, phenanthradine, phenanthradinium, tetrahydroquinoline, or decahydroquinoline and each quaternary nitrogen-containing group is connected through the quaternary nitrogen atom to a linking group which comprises a plurality of carbon atoms.

14. The method according to claim 1 wherein the solution is an acidic solution with a pH below zero.

15. The method according to claim 14 wherein the solution is a matrix acidizing fluid.

16. The method according to claim 1 wherein the metal is steel tubing located within, connected to or delivering into a subterranean borehole and the method includes pumping the solution through the metal tubing.

17. The method according to claim 1 wherein the metal is duplex alloy steel.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0049] FIG. 1 is a graph showing weight loss results obtained in Examples 1 and 2 below, with lb/ft.sup.2 on the left hand axis and corresponding gm/m.sup.2 at the right;

[0050] FIG. 2 is the equivalent circuit referred to in Example 6 below;

[0051] FIG. 3 is a graph showing results obtained in Example 6 below; and

[0052] FIG. 4 is a graph showing results obtained in Example 7 below.

DETAILED DESCRIPTION

[0053] As indicated in the summary above, the present disclosure is concerned with mixtures in which there are one or more compounds which contain a plurality of groups each of which contains charged quaternary nitrogen. This disclosure is also concerned with the use of such mixtures as corrosion inhibitors in a corrosive solution, in particular in a corrosive acidic aqueous solution. Surfaces to be protected from corrosion will ordinarily be metallic and the metal may be an alloy. For instance surfaces to be protected may be steel and the steel may be a single phase steel or a duplex alloy steel. An alloy steel may contain nickel, chromium, molybdenum and possibly other alloying metals.

[0054] In some embodiments, such a quaternary nitrogen-containing compound is included in an inhibitor composition which is used to protect a system in which there are a plurality of metals which come into contact with corrosive aqueous acidic liquid. The metals may be steel or steel alloys and they may be located within a subterranean borehole.

[0055] Quaternary nitrogen in heterocyclic aromatic rings or fused ring systems is often written as having three bonds to other atoms of a ring. A pyridine ring is a single six membered ring containing one such nitrogen. It may be incorporated into a larger molecule through a covalent bond to its nitrogen atom, thereby quaternizing the nitrogen atom.

[0056] Thus the following reactions lead to instances of inhibitor compounds with a plurality of connected groups containing quaternary nitrogen in an aromatic ring:

##STR00005##

[0057] The products of both these reactions are possibilities within the abovementioned general formula

[0058] YB).sub.m

where in this case Y is the polymethylene group shown as (CH.sub.2).sub.n, B is a pyridine ring and m is 2.

[0059] The above compound of formula

##STR00006##

may be obtained by a synthetic route including synthesis of the pyridine ring with the polymethylene group attached.

[0060] Instances of fused aromatic ring systems which contain nitrogen atoms which can become quaternary when joined to a linking group are

##STR00007##

[0061] These fused ring systems can be connected by linking groups covalently attached to nitrogen atoms which then become quaternary. The reaction may be directly analogous to the reaction of two molecules of pyridine with a polymethylene dibromide as shown above.

[0062] Heterocyclic rings and rings systems may contain more than one nitrogen atom, as is the case with pyrimidine which has two ternary nitrogen atoms:

##STR00008##

[0063] Purine consists of a pyrimidine ring fused to an imidazole ring and has three ternary nitrogen atoms and also a secondary nitrogen atom. Purine itself may be used as a nitrogen-containing group and so can other compounds with a purine structure, shown below:

##STR00009##

[0064] A heterocyclic aromatic ring may contain another hetero atom as well as nitrogen. An example is oxazole which contains one nitrogen atom and one oxygen atom in a five membered ring.

[0065] It is also possible that quaternary nitrogen-containing heterocyclic groups are attached by an unsaturated linking group attached to carbon atoms of heterocyclic rings. The following structure is an example of this in which the two nitrogen containing groups are quinolinium groups quaternized with naphthyl groups

##STR00010##

[0066] A further possibility for the inhibitor compounds is that some or all of the nitrogen-containing groups have additional groups attached which are intended to enhance adsorption onto a metal surface or add further functionality. For instance a quinolinium group could have an electron-rich naphthylmethoxy group attached, as illustrated by the partial structure

##STR00011##

[0067] A naphthyl methoxy group may be introduced by reaction of 1-(chloromethyl) naphthalene with 6-hydroxyquinoline as will be exemplified below.

[0068] A benzyloxy group could be attached in the same way as the naphthylmethoxy group above. These electron rich groups will be able to chemisorb to the metal surface, enhancing the protection of the surface.

[0069] Another possibility for an additional group attached to a nitrogen-containing heterocyclic ring is a styryl group. The styryl group may be introduced by reaction of benzaldehyde with a methyl substituent on a heterocyclic ring, as illustrated by the following reaction scheme leading to a structure in which styryl groups are attached to two quinolinium groups

##STR00012##

[0070] Optionally, the at least one ring nitrogen atom may be tertiary in aqueous neutral or alkaline solutions.

[0071] One dimer example is shown below:

##STR00013##

[0072] The ring nitrogen atoms in the above molecule protonate in aqueous acidic solutions and become quaternary nitrogen atoms. This provides solubility and thus allows the molecule to act as an acid corrosion inhibitor.

[0073] Optionally, further groups can be attached to the structure. A trimer example is shown below:

##STR00014##

[0074] As already noted, a linking group which connects nitrogen-containing groups in an inhibitor compound as disclosed herein may contain a chain of carbon atoms. A linking group may be aliphatic or aromatic. Specific possibilities for a linking group joining two nitrogen-containing groups are a saturated polymethylene chain

(CH.sub.2).sub.n

an unsaturated alkylene chain, i.e. a chain of aliphatic carbon atoms with at least one olefinic double bond in the chain such as

CH.sub.2CHCHCH.sub.2

and a mixed aliphatic aromatic chain in which two aliphatic groups are connected by an aromatic ring, such as

##STR00015##

[0075] A linking group may join three or more nitrogen-containing groups. For joining three or more such groups a linking group could be a branched aliphatic structure such as

##STR00016##

or could be a mixed aliphatic aromatic structure with methylene groups joined to an aromatic ring, for example

##STR00017##

[0076] The examples of synthesis below mention two compounds in which three heterocyclic groups are attached to a linking group.

[0077] A further instance of such a compound is the structure:

##STR00018##

[0078] This has been disclosed as a dye, by Mishra and Haram in Dyes and Pigments (2004), 63(2), pp 191-202.

[0079] The linking groups referred to above would allow three or four nitrogen-containing groups to be connected by covalent bonding to a single linking group. In an alternative possibility, a plurality of groups are connected together as an oligomeric chain, for example as illustrated by the following structure:

##STR00019##

[0080] in which p is 1 to 4. This compound is an oligomer derivable from a bromoalkylisoquinoline

##STR00020##

[0081] The inhibitor compounds described above are used in conjunction with a polarisable anion. The polarisable character may come about because the anion comprises an atom of atomic number 52 or more. Such an atom is large enough that some of its electrons occupy orbitals at distance from the nucleus. Iodine has atomic number 53 and iodide ion may be the most readily accessible ion of this character. The inhibitor compound may be provided as an iodide salt or it may be mixed with another iodide such as potassium iodide. If the inhibitor compound is provided as an iodide salt, additional iodide may be added to the mixture. Another possible anion is tri-iodide, which may be made by reacting iodine with potassium iodide in aqueous solution.

[0082] Polarisable character of an anion can also come about when an ion contains an anionic group such as sulfonate, attached to an aromatic ring or ring system. One anion which may be used is para-toluene methyl sulphonate, often referred to as tosylate, having the formula

##STR00021##

[0083] Another possibility is naphthalene sulphonate, having formula:

##STR00022##

[0084] In addition, one or more of the two to five nitrogen-containing groups may have one or more additional groups attached which are intended to enhance adsorption onto a metal surface or provide an additional function:

##STR00023##

[0085] For instance, the group below could have an additional polymerisable group attached to one of its rings, as illustrated below:

##STR00024##

[0086] Possible polymerisable groups for example include C(OH)CCH, CC, and/or CN. Such a polymerisable group is intended to polymerise with other polymerisable groups after adsorption onto a metal surface, and this enables the molecules to combine together as a protective film which enhances acid corrosion inhibition.

Examples of Synthesis of Inhibitor Compounds

[0087] A general method of synthesis of compounds in which a linking group connects to nitrogen atoms of the nitrogen containing groups is based on a paper by Hartwell and Pogorelskin, J.A.C.S. vol 72 pp 2040-2044 [1950].

[0088] A nitrogen containing compound (used with 20% excess) and a precursor of the linking group terminating in halogen atoms are reacted as a suspension in dimethylformamide (DMF) which is an aprotic solvent. The product is collected by addition of acetone and filtration.

[0089] A number of compounds were prepared by this general method and details of some preparations are given by way of example below.

1,1-(Propane-1,3-diyl) di-quinolinium bromide

[0090] ##STR00025##

[0091] Quinoline (5 g, 38.7 mmol) and 1,3-dibromopropane (3.26 g, 16.1 mmol) were mixed together in N,N-dimethylformamide (8 ml) as solvent and heated at 90 C. for 18 hr. The suspension was cooled, acetone was added, and the solid filtered off then washed with acetone and diethyl ether to give a solid product (6.63 g). The solid was crystallised from ethanol (32 ml), filtered, washed with ethanol and diethyl ether and dried to give 1,1-(propane-1,3-diyl)diquinolinium bromide, 4.95 g (66%).

[0092] .sup.1H NMR 400 MHz (DMSO.sub.d6) =9.72 (d, 2H J=8 Hz), 9.34 (d, 2H, J=8 Hz), 8.90 (d, 2H, J=8 Hz), 8.53 (d, 2H J=8 Hz), 8.31 (bt, 2H J=8 Hz), 8.24 (dd, 4H J=8 Hz), 8.08 (t, 2H J=8 Hz), 5.41 (t, 4H J=8 Hz)

1,1-(Propane-1,3-diyl) di-quinolinium iodide

[0093] ##STR00026##

[0094] Quinoline (5 g, 38.7 mmol) and 1,3-diiodopropane (4.77 g, 16.1 mmol) were mixed together in N,N-dimethylformamide (8 ml) and heated at 90 C. for 18 hr. The suspension was cooled and the solid filtered, washed with acetone and dried to give the product 1,1-(propane-1,3-diyl)diquinolinium iodide, 7.3 g (81%) which was used without further purification.

[0095] .sup.1H NMR 400 MHz (D.sub.2O) =9.36 (d, 2H J=8 Hz), 9.17 (d, 2H J=8 Hz), 8.44 (d, 2H J=8 Hz), 8.41 (d, 2H J=8 Hz), 8.27 (t, 2H J=8 Hz), 8.07 (t, 2H J=8 Hz), 8.05 (t, 2H J=8 Hz), 5.39 (t, 4H J=8 Hz), 3.04 (bm, 2H)

1,1-(Butane-1,4-diyl)diquinolinium bromide

[0096] ##STR00027##

[0097] Quinoline (5 g, 38.7 mmol) and 1,4-dibromobutane (3.48 g, 16.1 mmol) were mixed together in N,N-dimethylformamide (8 ml) and heated at 90 C. for 18 hr. The suspension was cooled, the solid filtered, washed with acetone and diethyl ether to give a solid. The solid was triturated with hot ethanol (80 ml), cooled, filtered washed with ethanol and diethyl ether and dried to give the product 1,1-(butane-1,4-diyl)diquinolinium bromide 6.2 g (81% yield) which was used without further purification.

[0098] .sup.1H NMR 400 MHz (D.sub.2O) =9.55 (d, 2H J=8 Hz), 9.31 (d, 2H J=8 Hz), 8.70 (d, 2H J=8 Hz), 8.52 (d, 2H J=8 Hz), 8.31 (t, 2H J=8 Hz), 8.18 (dd, 2H J=8 Hz), 8.08 (t, 2H J=8 Hz), 5.12 (bs, 4H), 2.28 (bs, 4H)

(E)-1,1-(But-2-ene 1,4-diyl)diquinolinium bromide

[0099] ##STR00028##

[0100] Quinoline (3.1 g, 24 mmol) and 1,4-dibromobut-2-ene (2.14 g, 10 mmol) were mixed together in N,N-dimethylformamide (8 ml) and heated at 90 C. for 18 hr. The suspension was cooled, the solid filtered, washed with acetone and diethyl ether to give the product (E)-1,1-(but-2-ene 1,4-diyl)diquinolinium bromide, 4.3 g (92% yield) which was used without further purification.

1,1-(1-4-phenylenebis(methylene)diquinolinium bromide

[0101] ##STR00029##

[0102] Quinoline (1.52 g, 11.6 mmol) and 1,4-bis(bromomethyl)benzene (1.3 g, 4.9 mmol) were combined in N,N-dimethylformamide (4 ml) and heated at 90 C. for 18 hr. The suspension was cooled, the solid filtered, washed with acetone, diethyl ether and dried to 1,1-(1-4-phenylenebis(methylene) diquinolinium bromide, 2.4 g (93% yield) which was used without further purification.

6-(Naphthalen-1-ylmethoxy)-1-(3-(6-naphthalen-2-ylmethoxy) quinolinium-1-yl) propyl) quinolinium bromide (14)

[0103] This compound was prepared in two stages, by the following reaction scheme.

##STR00030##

[0104] In the first stage, 6-Hydroxyquinoline (11) (5 g, 34.4 mmol) was added to acetone (200 ml) and heated to just below reflux. Potassium carbonate (24 g, 0.17 mol) was added portion wise and heated at reflux for 5 min. 1-(Chloromethyl) naphthalene (12) (6.07 g, 34 mmol) was added portion wise and the suspension heated at reflux for 23 hr. The suspension was cooled, the solid filtered and washed with acetone and the filtrated evaporated. The crude product was purified by column chromatography eluting with 0-10% methanol in dichloromethane. The combined column fractions were evaporated and the residue triturated with hexane to give a solid which was filtered and washed with hexane to give 6-(naphthalen-2-ylmethoxy) quinoline (13), 6.7 g (68% yield).

[0105] In the second stage, 6-(Naphthalen-2-ylmethoxy) quinoline (13) (1.3 g, 4.55 mmol) and 1,3-dibromopropane (402 mg, 1.99 mmol) were added to in N,N-dimethylformamide (2 ml) and heated at 90 C. for 22 hr. The suspension was cooled and the solid filtered, washed with acetone, diethyl ether and dried to give 6-(naphthalen-1-ylmethoxy)-1-(3-(6-naphthalen-2-ylmethoxy) quinolinium-1-yl) propyl) quinolinium bromide (14), 1.35 g (87% yield) which was used without further purification.

Tri-Quinolinium Inhibitors

[0106] ##STR00031##

[0107] Quinoline (1) in small excess was reacted with 1,3,5-tris(bromomethyl)benzene (2) in dimethylformamide with procedure as before to form the trisquinolinium species (3), 8.9 g (100% yield). An aliquot of the trisquinolinium bromide species (3) was dissolved in methanol and KI added. The resultant solid (iodide salt) was filtered off and dried

[0108] In the same way quinoline (1) was reacted with 2,4,6-tris(bromomethyl)mesitylene (4) to obtain the trisquinolinium species (5), 8.3 g (84% yield).

##STR00032##

Tri-Phenanthridinium Inhibitor

[0109] The same procedure was used to react phenanthridine (6) with 1,3,5-tribromomethylbenzene (2) to obtain the trisphenanthridium species (7), 5.0 g (94% yield).

##STR00033##

EXPERIMENTAL EXAMPLES

[0110] Experiments were carried out with coupons of the following steels: [0111] HS80, a low carbon steel used to fabricate coiled tubing. [0112] N80, a medium carbon steel used to fabricate borehole casing. [0113] 13Cr80, an alloy steel containing chromium without nickel, also used to fabricate borehole casing. [0114] 22Cr125 also designated 2205, a duplex alloy steel which is an iron-chromium-nickel-molybdenum alloy, also used (among other things) to fabricate casing.

Example 1

[0115] Experiments were carried out to observe corrosion rates on coupons of the steels above. Corrosion test coupons with surface area of 25-30 cm.sup.2 were glass bead blasted to ensure a clean and homogeneous surface, measured to determine their exact surface area, weighed and then exposed to 4 molar hydrochloric acid solution in a continuously stirred corrosion cell containing 200 mL acid solution per test coupon. The temperature was held at 78 C. with the acid solution pre-heated to this temperature before immersing the test coupon. The acid solution contained a corrosion inhibiting material or mixture of materials. After a test period of three hours, the coupons were removed from the solution, washed and dried and re-weighed so as to determine the weight loss. Results were expressed as weight loss per unit area.

[0116] This test procedure was used to compare corrosion inhibition in an acid solution which contained 5 mM hexanediyl di-quinolinium bromide (a quinolinium dimer embodying the concepts disclosed herein) in the presence of 20 mM potassium iodide. The tests on 22Cr 125 steel also included a comparative test of corrosion inhibition in a solution which contained 10 mM propyl-quinolinium bromide (twice the concentration because it is a mono-quinolinium compound) again in the presence of 20 mM potassium iodide. The measurements of weight loss per unit area, over the three hour test period, are given in the following table.

TABLE-US-00003 Total Weight Weight iodide loss loss Inhibitor in acid solution Steel conc. (lbs/ft.sup.2) (gm/m.sup.2) 5 mM hexanediyl di- HS80 20 mM 0.013 63.4 quinolinium bromide 5 mM hexanediyl di- N80 20 mM 0.008 39.0 quinolinium bromide 5 mM hexanediyl di- 13Cr 20 mM 0.032 156 quinolinium bromide 5 mM hexanediyl di- 22Cr125 20 mM 0.005 24.4 quinolinium bromide 10 mM propyl mono- 22Cr125 20 mM 0.019 92.7 quinolinium bromide

[0117] It is apparent that weight loss was lowest on 22Cr125 steel and that on this steel the di-quinolinium compound gives much improved corrosion inhibition as compared to the comparative mono-quinolinium compound.

[0118] A similar comparison was made using decanediyl di-quinolinium bromide (another quinolinium dimer embodying the concepts disclosed herein) in the presence of added potassium iodide and isopentyl mono-quinolinium iodide in the presence of some additional iodide provided as potassium iodide.

[0119] The following table gives the concentrations of the inhibitor molecules, the total concentration of iodide in solution (introduced both as counterion of the inhibitor and as potassium iodide) and the measurements of weight loss per unit area over the three hour test period.

TABLE-US-00004 Total Weight Weight iodide loss loss Inhibitor in acid solution Steel conc. (lbs/ft.sup.2) (gm/m.sup.2) 2 mM decanediyl di- 22Cr125 16 mM 0.0062 30.2 quinolinium bromide 5 mM isopentyl mono- 22Cr125 15 mM 0.0098 47.8 quinolinium iodide 5 mM isopentyl mono- 22Cr125 25 mM 0.0064 31.2 quinolinium iodide 5 mM decanediyl di- HS80 20 mM 0.0059 28.8 quinolinium bromide 5 mM decanediyl di- N80 20 mM 0.0045 22.0 quinolinium bromide 5 mM decanediyl di- 13Cr 20 mM 0.0090 43.9 quinolinium bromide 5 mM decanediyl di- 22Cr125 20 mM 0.0044 21.5 quinolinium bromide

[0120] The first three rows in the table above show that 2 mM decanediyl di-quinolinium bromide with 16 mM iodide matched the efficacy of 5 mM isopentyl mono-quinolinium iodide with 25 mM iodide, even though the diquinolinium compound was used at a concentration such that the concentration of quaternary nitrogen atoms was slightly less than with the monoquinolinium compound, and the concentration of iodide was also lower.

Example 2

[0121] Weight loss testing as in the previous example was carried out on 22Cr125 steel with 5 mM concentrations of diquinolinium compounds listed below and with varying concentrations of potassium iodide in solution. The diquinolinium compounds were [0122] propanediyl diquinolinium bromide [0123] butanediyl diquinolinium bromide [0124] hexanediyl diquinolinium bromide [0125] decanediyl diquinolinium bromide

[0126] The results are shown graphically in FIG. 1. The data points for 5 mM propanediyl diquinolinium bromide are shown connected by a line. As is apparent, corrosion inhibition is enhanced by increasing concentrations of iodide. As shown, when 5 mM propanediyl diquinolinium bromide was used with 10 mM iodide, which is the equivalent quantity of iodide ion, the weight loss was reduced by a factor of about 5 compared to 5 mM propanediyl diquinolinium bromide without added iodide.

[0127] The same weight loss test was carried out on 22Cr125 steel with 5 mM concentration of propanediyl diquinolinium iodide without addition of any potassium iodide. The weight loss measured was almost the same as the weight loss measured with 5 mM propanediyl diquinolinium bromide and 10 mM potassium iodide, demonstrating that the enhanced corrosion protection in the presence of iodide results from the presence of this ion, and not merely from increased concentration of halide ions.

[0128] The corrosion inhibition was further improved as the length of the linking group increased from three to six and from six to ten carbon atoms. The comparative result for 10 mM propylquinolinium bromide with 20 mM iodide in Example 1 has been included in FIG. 1, with a filled circle as the data point.

Example 3

[0129] Weight loss testing as in the previous examples was carried out on a range of steels using decanediyl diquinolinium bromide with varying concentrations of potassium iodide in solution. Results are set out in the following table which includes some results from previous examples.

TABLE-US-00005 Total Weight Weight iodide loss loss Inhibitor in acid solution Steel concentration (lbs/ft.sup.2) (gm/m.sup.2) 5 mM decanediyl di- HS80 none 0.042 204 quinolinium bromide N80 none 0.025 122 13Cr none 0.048 234 22Cr125 none 0.057 278 HS80 20 mM 0.0059 28.8 N80 20 mM 0.0045 22.0 13Cr 20 mM 0.0090 43.9 22Cr125 20 mM 0.0044 21.5 22Cr125 30 mM 0.0029 14.2 HS80 40 mM 0.0050 24.4 N80 40 mM 0.0033 16.1 13Cr 40 mM 0.0061 29.8 22Cr125 40 mM 0.0023 11.2

[0130] These results show that the presence of iodide leads to a very considerable reduction in weight loss (i.e. enhanced corrosion protection). With all the steels, the presence of 20 mM iodide reduced the weight loss by a factor of four or more. There is some further improvement with higher concentrations of iodide.

Example 4

[0131] The weight loss testing procedure as in previous examples was carried out using 5 mM butenediyldiquinolinium bromide (formula and preparation given previously) which has an olefinic unsaturation in the linking group and also 5 mM phenylenebis methylene diquinolinium bromide which has the structure below with an aromatic ring in the linking group.

##STR00034##

[0132] The weight loss results are given in the following table which also includes some results shown in FIG. 1.

TABLE-US-00006 Total Weight Weight iodide loss loss Inhibitor in acid solution Steel conc. (lbs/ft.sup.2) (gm/m.sup.2) 5 mM butanediyl di- 22Cr125 none 0.050 244 quinolinium bromide 5 mM butenediyl di- 22Cr125 none 0.057 278 quinolinium bromide 5 mM phenylenebismethylene HS80 none 0.053 259 di-quinolinium bromide N80 none 0.035 171 22Cr125 none 0.019 93 HS80 20 mM 0.0097 47.3 N80 20 mM 0.0048 23.4 22Cr125 20 mM 0.0043 21.0 HS80 40 mM 0.0073 35.6 N80 40 mM 0.0043 21.0

[0133] Once again, these results show that the presence of iodide leads to a very considerable reduction in weight loss (i.e. enhanced corrosion protection).

Example 5

[0134] The weight loss testing procedure as in previous examples was also carried out with a di-isoquinolinium compound, namely with 5 mM hexanediyl di-isoquinolinium. The results, together with the results for the corresponding quinolinium compound is given in the following table.

TABLE-US-00007 Total Weight Weight iodide loss loss Inhibitor in acid solution Steel conc. (lbs/ft.sup.2) (gm/m.sup.2) 5 mM hexanediyl di- 22Cr125 none 0.016 78.1 isoquinolinium bromide HS80 20 mM 0.011 53.7 N80 20 mM 0.0065 31.7 22Cr125 20 mM 0.0034 16.5 22Cr125 30 mM 0.0030 14.6 22Cr125 40 mM 0.0024 11.7 5 mM hexanediyl di- 22Cr125 none 0.023 112 quinolinium bromide HS80 20 mM 0.013 63.4 N80 20 mM 0.0083 40.5 22Cr125 20 mM 0.0054 26.35 22Cr125 30 mM 0.0037 18.1 22Cr125 40 mM 0.0030 14.6

[0135] As can be seen, the isoquinolinium compound was even better than its quinolinium counterpart.

Example 6

[0136] Corrosion inhibition by some of the above mentioned di-quinolinium and di-isoquinolinium compounds was also examined by Electrochemical Impedance Spectroscopy. The steel sample, subjected to corrosion, was in the form of a rotating cylinder electrode, that is to say it was in the form of a cylinder, partially immersed in the corrosive acid solution, and rotated at 2000 rpm. This electrode was made of 22Cr125 steel. The surface area in contact with acid solution was 1.88 cm.sup.2. The rotation provided dynamic flow of the electrolyte relative to the steel, representing flow of acid over fixed tubing. The rotating cylinder was used as the working electrode of a three-electrode electrochemical cell. The other electrodes were a Ag/AgCl, KCl (3M) reference electrode and a graphite counter electrode. The electrolyte was the corrosive acid, which in these experiments was 4M hydrochloric acid solution containing the corrosion inhibitor being tested. The cell was maintained at 80 C. The impedance of the cell was determined using a potentiostat to measure current and phase when a 2 mV alternating potential was superimposed on direct bias potential (equal to the open circuit potential of the system) applied to the working electrode. This was done while the frequency of the alternating potential was varied in steps from 10 KHz to 0.1 Hz.

[0137] The experimental data was fitted to the theoretical impedance of an equivalent circuit shown in FIG. 2 where Ew is the working electrode, Eref is the reference electrode, Rs, Rct, and RL are the solution resistance, charge transfer resistance and the inductor resistance respectively, Cdl is the double layer capacitance and L is the inductor associated with the corrosion intermediates. Fitting the data, using a Nyquist plot allowed the charge transfer resistance to be determined. Charge transfer resistance is the parameter of interest because it is inversely proportional to the corrosion rate at the time of the test.

[0138] FIG. 3 is a plot of the reciprocal of charge transfer resistance for a number of compounds mentioned above, with varying iodide concentrations. Similarity to the weight loss data in previous examples was clearly apparent as was the enhancement of corrosion protection in the presence of iodide ion.

[0139] The compounds tested, as named herein, were the following:

butenediyl diquinolinium bromide (with double bond in linking group)
butanediyl quinolinium bromide
hexanediyl diquinolinium bromide
hexanediyl diisoquinolinium bromide
phenylenebis methylene diquinolinium bromide
decanediyl diquinolinium bromide

Example 7

[0140] Electrochemical Impedance Spectroscopy was also used to examine corrosion inhibition by the two tris-quinolinium compounds referred to as (3) and (5) in the examples of synthesis given earlier. The results, at varying iodide concentrations, for these two compounds and also for two diquinolinium compounds are shown in FIG. 4. Yet again the presence of iodide ion greatly enhances corrosion protection.

[0141] This technique was also used to examine corrosion inhibition by the tris phenathridium compound shown as compound (7) in the examples of synthesis. The tests were carried out at 30 mM iodide and at 60 mM iodide. At both iodide concentrations, the tris phenanthridium inhibitor was as good as, or better than, the tris quinolinium compounds.

[0142] It will be appreciated that the embodiments and examples described in detail above can be modified and varied within the scope of the concepts which they exemplify. Features referred to above or shown in individual embodiments above may be used together in any combination as well as those which have been shown and described specifically. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.

Example 8

[0143] ##STR00035##

1,6-Bis (octahydroquinolin-1(2H)-yl)hexane

[0144] In the hydroquinoline dimer shown above, the two hydroquinoline sub-structures are linked by a linear hexyl chain.

[0145] (bisOHQyl)hexane contains two ring nitrogen atoms which convert to the protonated form under acid conditionsthis reversible process leads to good acid solubility and insolubility (and low toxicity) under neutral pH conditions.

(bisOHQyl)hexane Synthesis:

##STR00036##

[0146] 1,2,3,4-Tetrahydroquinoline (639 mg, 4.8 mmol), 1,6-dibromohexane (488 mg, 2 mmol) and potassium carbonate (800 mg, 5.8 mmol) were heated, in dimethylformamide at 90 C. for 17 hr. The suspension was filtered and the solid was washed with diethyl ether. Water was added to the filtrate, the aqueous phase was removed and extracted with diethyl ether. The organic phase was evaporated and residue applied to silica column and eluted with hexane to give 1,6-bis (octahydroquinolin-1(2H)-yl)hexane (3), 85 mg (12% yield).