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US 20090050853Al

(19) United States


(12) Patent Application Publication (10) Pub. No.: US 2009/0050853 A1
Itzhak et al. (43) Pub. Date: Feb. 26, 2009

(54) LIQUID COMPOSITION SUITABLE FOR USE (30) Foreign Application Priority Data
AS A CORROSION INHIBITOR AND A
METHOD FOR ITS PREPARATION Feb. 13, 2006 (IL) ........................................ .. 173706
Aug. 13, 2007
(76) Inventors: David Itzhak, Omer (IL); Sharon Oct. 30, 2007
Krumbein Rubin, KibutZ Naan Jan. 29, 2008 (IL) ........................................ .. 189119
(IL); Arieh Kampf, Tel Aviv (IL); Publication Classi?cation
Vered Atiya Zuckerman, Bet
Shikma (IL); Mira Bergstein (51) Int. Cl.
Freiberg, Omer (IL) C23F 11/12 (2006.01)
(52) US. Cl. ................................................. .. 252/389.54
Correspondence Address:
NIXON & VANDERHYE, PC (57) ABSTRACT
901 NORTH GLEBE ROAD, 11TH FLOOR A liquid composition comprising a high-capacity aqueous
ARLINGTON, VA 22203 (US) carrier in Which (i) a metalloid compound selected from the
group consisting of antimony and germanium compounds
(21) Appl. No.: 12/222,605 and (ii) morpholine or derivative thereof are dissolved in the
presence of (iii) unsaturated alcohol and (iv) Water-soluble
(22) Filed: Aug. 12, 2008 organic acid having reducing capacity, Wherein the total con
centration of said four components is preferably not less than
Related US. Application Data
5% relative to the total Weight of the composition. The com
(63) Continuation-in-part of application No. PCT/IL2007/ position is useful as a corrosion inhibitor. Also provided is a
000192, ?led on Feb. 12, 2007. process for preparing the composition.
US 2009/0050853 A1 Feb. 26, 2009

LIQUID COMPOSITION SUITABLE FOR USE g/cm3) at 300 degrees Fahrenheit (F), is too high for the most
AS A CORROSION INHIBITOR AND A demanding applications.A someWhat similar inadequacy Was
METHOD FOR ITS PREPARATION noted With US. Pat. No. 4,980,074, Which describes use of
soluble aliphatic or aromatic aldehydes reacted With primary
FIELD OF THE INVENTION amines, and claims a less than satisfactory corrosion rate of
28 mils per year for a 19.5 pounds per gallon (2.34 g/cm3)
[0001] This invention is pertaining primarily to corrosion brine at 250 degrees F. Only When supported by addition of
inhibitors, especially to corrosion inhibitors for concentrated sulfur compounds Was the corrosion rate loWered to a level of
salt solutions. It is particularly useful for certain oil drilling 10-13 mpy With the aforementioned brine at 250 degrees F.
and oil production systems, and for selected absorption US. Pat. No. 4,971,709 discloses use of some metallic poW
refrigeration systems Wherein Zinc bromide and mixtures of ders as inhibitors for Zinc containing brines. The main disad
Zinc bromide and other salt brines (such as calcium bromide) vantage of the method is the very loW solubility of those
are basic components, and When the protection of metallic poWders, Which cause precipitation of particles that might
surfaces at elevated temperatures is critical. plug or damage a producing formation. Also US. Pat. No.
4,539,122, Which proposes inhibiting heavy brines With
BACKGROUND OF THE INVENTION arsenic containing compositions, is handicapped by the accu
[0002] Well-drilling ?uids and especially completion, mulative toxicity of arsenic compounds. WO 01/46552
packer, and Workover ?uids are preferred in the form of clear claims use of heteropoly complex anions of transitional metal
salt aqueous solutions also commonly referred to as clear elements but omits to disclose the actual corrosion rates
brines. Those ?uids are called in accordance With the phases obtained in application simulations. EP 1038936 discloses
of the hydrocarbon extraction process in Which they are the use of ammonia or amines in an amount effective to raise
employed: completion ?uids are those used after the Well has the pH as additives in inhibiting corrosion in brines; hoWever,
been drilled and prior to the initiation of production; packer these additives can interfere With the stability of the brines.
?uids are utiliZed as ?uids in the annulus of the production Formulas combining antimony With acetylenic alcohols have
tubing; and Workover ?uids are used during remedial opera been proposed, for example in US. Pat. No. 4,498,997 and
tions on the Well. Of the multiple functions of the ?uid used in US. Pat. No. 4,522,658, for inhibiting oxidative effects of
the Well, a crucial one is balancing formation pressures to acidic aqueous environment.
prevent uncontrolled in?ux of underground ?uids, Which may [0007] In absorption refrigeration Where lithium bromide
result in a bloWout. When formation pres sure is high, as in the solution is the preferred ?uid, additions of Zinc bromide
deeper Wells, use of Zinc bromide is particularly useful, due to improve the saturation concentration and provide a desirable
its high density in concentrated solutions. While saturated loW vapor pressure at absorber high temperatures. HoWever,
brine density is 1.20 g/cm3 for NaCl solutions, 1.46 for CaCl2, such solutions are extremely corrosive and cannot be used in
1.50 for NaBr and 1.71 for CaBr2, the density of ZnCl2 brine the absence of very e?icient corrosion inhibitors. Known
at saturation attains 2.14 and the density of ZnBr2 is as high as additives include molybdates, chromates and nitrates. These
2.65 g/cm3. additives lessen corrosion, albeit not to a satisfactory level,
[0003] When in use, a technical problem associated With When signi?cant amounts of Zinc bromide are incorporated
the use of heavy brine ?uids is their high corrosiveness, into the Working ?uids.
especially toWard carbon steels, Which are Widely used in the [0008] It is, therefore, an object of the present invention to
construction of hydrocarbon Wells, and particularly at the provide a neW corrosion inhibitor formulation for reducing
elevated temperatures typically encountered in deep Wells. corrosion induced by heavy brine ?uids.
[0004] Known corrosion inhibitors, such as ?lm-forming [0009] It is further, an object of the present invention to
amines, Which have been used With high-density brines provide corrosion inhibition mixtures, Which are compatible
described in US. Pat. No. 4,304,677 and US. Pat. No. 4,292, With different applications of Working ?uids, particularly at
183 do not generally provide adequate protection from cor elevated temperatures.
rosion at those higher temperatures associated With the deep [0010] It is further another object of the present invention to
Wells in Which high-density brines are normally employed. provide corrosion inhibiting mixtures Which reduce corrosion
[0005] British Patent No. 2,027,686, US. Pat. No. 4,536, rate to beloW 25 mpy When comprised in heavy brine ?uids.
302, US. Pat. No. 4,728,446, US. Pat. No. 4,784,779 and [0011] Another object of the present invention is to provide
US. Pat. No. 4,980,074 have disclosed use of sulfur com corrosion inhibiting mixtures Which do not cause stress
pounds as the main inhibitor-formula component that has cracking to the apparatus in Which they are used.
been typical of the recent knoWn technology. Although the [0012] Still another object of the present invention is to
sulfur compounds are ef?cient corrosion inhibitors, there is provide use of combinations of corrosion inhibiting com
an increased risk of stress corrosion cracking. There have pounds in the manufacture of corrosion inhibiting mixtures.
been a number of catastrophic stress corrosion failures in the [0013] Still another object of the present invention is to
oil industry that have been attributed to sulfur containing provide concentrated aqueous salt solutions that are strongly
corrosion inhibitors. As a result, the industry is seeking effec inhibited to prevent unacceptable levels of corrosion on the
tive, non-sulfur corrosion inhibiting formulas. metallic apparatus in Which they are used.
[0006] Some non-sulfur corrosion-inhibition formulas are [0014] Still another object of the present invention is to
already knoWn, but they fall short in respect to the effective provide concentrated aqueous salt solutions in Which corro
ness considered necessary in the industry. Thus, US. Pat. No. sion of steel is strongly inhibited.
4,539,122 describes use of erythorbic acid salts in combina [0015] Another object of the present invention is to provide
tion With a molybdate salt, ferrous gluconate, and sodium strongly inhibited formulas of concentrated aqueous salt
gluconate. At more than 25 mpy (mili inches per year), the solutions that Would prevent catastrophic sul?de stress crack
corrosion rate claimed for 18.5 pounds per gallon brines (2.20 ing to the metallic apparatus in Which they are used.
US 2009/0050853 A1 Feb. 26, 2009

[0016] Another object of the present invention is to provide prise an antimony compound and three compounds selected
a method to use synergistic corrosion inhibitor formulations from three different families of said four families. Said three
that Would adapt the level of corrosion protection to the heavy compounds may comprise a combination selected from: a)
brine ?uids. propargyl alcohol, morpholine, selenium dioxide; b) propar
[0017] These and other objects of the present invention gyl alcohol, morpholine, isoascorbic acid; and c) morpholine,
shall become clear as the description proceeds. isoascorbic acid, selenium dioxide. An inhibitor according to
the invention may comprise an antimony compound and four
SUMMARY OF THE INVENTION compounds selected from four different families of said four
[0018] The invention provides an antimony-based corro families. Said four compounds may be propargyl alcohol,
sion inhibitor for reducing metal corrosion induced by salt morpholine, selenium dioxide, and isoascorbic acid.
solutions, comprising an antimony compound and at least tWo [0021] The invention relates to an inhibitor composition,
compounds selected from tWo of the four following com comprising an antimony compound and any combination of
pound families: i. morpholine and morpholine derivatives; ii. tWo or more compounds selected from the folloWing com
acetylenic alcohols; iii. ascorbic acid derivatives; and iv. sele pound families: i. morpholine and morpholine derivatives; ii.
nium compounds. acetylenic alcohols; iii. ascorbic acid derivatives; and iv. sele
[0019] Said antimony compound may be selected from nium compounds; Wherein at least tWo compounds of said
antimony trioxide, potassium antimony tartrate, antimony combination belong to different families. The inhibitor com
tartrate, and antimony trihalides. Said morpholine derivative position may comprise tWo or more compounds belonging to
may comprise alkylmorpholine derivatives, alkylmorpholine the same family. The antimony-based corrosion inhibitor
oxides, or other compounds comprising morpholinyl struc according to the invention essentially comprises a non-sulfur
ture in their molecule. Said acetylenic alcohols are preferably mixture. An antimony-based corrosion inhibitor or an anti
selected from 2-propyne alcohol and substituted 2-propyne mony-based anticorrosive composition according to the
alcohols. In a preferred embodiment of the invention said invention may comprise additional components that improve
acetylenic alcohol is propargyl alcohol. In another preferred its anticorrosive or other properties. Advantageously, the
embodiment of the invention said acetylenic alcohol is inhibitor composition may further comprise an amine. An
selected from l-alkyl substituted or l,l-dialkylsubstituted inhibitor according to the invention is preferably effective in
2-propyne alcohols, an example being 2-methyl-3-butyn-2 inhibiting or reducing corrosion rate in salt solutions used in
01. In still another preferred embodiment of the invention said hydrocarbon drilling, in completion ?uids, packer ?uids, and
acetylenic alcohol is selected from 3-substituted 2-propyne Workover ?uids. In a preferred embodiment of the invention,
alcohols, examples being 3-alkyl substituted or 3-hydroxyla the inhibitor is effective in inhibiting or reducing corrosion
lkyl substituted 2-propyne alcohols. In other preferred rate in salt solutions used in absorption refrigeration systems.
embodiment said acetylenic alcohol is selected from O-sub In another preferred embodiment of the invention, the inhibi
stituted 2-propyne alcohols. Said ascorbic acid derivatives tor is effective in inhibiting or reducing corrosion rate in
may be selected, Without being limited to them, from ascorbic heavy brine ?uids at elevated temperatures.
acid isomers, esters, and salts thereof. In a preferred embodi [0022] The invention is directed to the use of a mixture
ment of the invention, the derivatives of ascorbic acid are comprising an antimony compound and at least tWo com
selected from ascorbic acid, isoascorbic acid, and salts pounds selected from at least tWo of the four folloWing com
thereof. Said selenium compound is preferably selected from pound families: i. morpholine and morpholine derivatives; ii.
selenium oxide, selenium salts, such as selenium halides, and acetylenic alcohols; iii. ascorbic acid derivatives; and iv. sele
selenium oxychloride. nium compounds; in preparing a corrosion inhibitor for
[0020] A corrosion inhibitor according to the invention is reducing or inhibiting corrosion induced by salt solutions. In
preferably used in a solution comprising a salt selected from the use according to the invention, said mixture may, for
Zinc bromide, Zinc chloride, calcium bromide, calcium chlo example, comprise an antimony compound and tWo com
ride, and mixtures thereof. Said metal may be selected from pounds selected from morpholine or morpholine derivatives,
carbon steels and chromium-alloyed steels. An inhibitor and acetylenic alcohols, and may reduce the corrosion rate
according to the invention reduces the rate of corrosion, induced by said salt solution to a value of about 40 or loWer.
induced by said salt solution, to beloW 40 mpy, preferably to Said tWo compounds may be selected from the folloWing
beloW 25 mpy, and still more preferably to below 10 mpy. An combinations: a) propargyl alcohol, morpholine; b) morpho
inhibitor according to the invention may reduce the rate of line, isoascorbic acid; c) propargyl alcohol, isoascorbic acid;
corrosion induced by said salt solution to beloW 5 mpy. Said and d) propargyl alcohol, selenium dioxide; Wherein the rate
antimony compound is preferably selected from antimony of corrosion induced by said salt solution may be reduced
bromide and antimony chloride. In a preferred embodiment according to the invention to about 30 mpy or loWer. In
of the invention, the anticorrosive inhibitor comprises an another preferred use according to the invention, said mixture
antimony compound and tWo compounds selected from tWo may comprise an antimony compound and three compounds
different families of the above said four families. In a pre selected from morpholine or morpholine derivatives, acety
ferred embodiment of the invention, said tWo compounds are lenic alcohols, ascorbic acid derivatives, and selenium com
selected from morpholine, propargyl alcohol, isoascorbic pounds. Said three compounds may be selected from mor
acid, ascorbic acid, and selenium dioxide. In a preferred pholine or morpholine derivatives, acetylenic alcohols,
embodiment of the invention a preferred inhibitor according ascorbic acid or isoascorbic acid or a salt thereof, and a
to the invention may comprise an antimony compound and a selenium compound. Said three compounds may be selected
compound combination selected from: a) propargyl alcohol, from the folloWing combinations: a) propargyl alcohol, mor
morpholine; b) morpholine, isoascorbic acid; c) propargyl pholine, selenium dioxide; b) propargyl alcohol, morpholine,
alcohol, isoascorbic acid; and d) propargyl alcohol, selenium isoascorbic acid; and c) morpholine, isoascorbic acid, sele
dioxide. An inhibitor according to the invention may com nium dioxide; Wherein the rate of corrosion induced by a salt
US 2009/0050853 A1 Feb. 26, 2009

solution is reduced by using said corrosion inhibitor accord they are in this context interchangeably called in this appli
ing to the invention to about 25 mpy or loWer. In a preferred cation, Will have densities usually from about 1.20 to about
embodiment of the invention, the use of said mixture further 2.65 g/cm3 . Said antimony compound is preferably an anti
comprises admixing an amine into said inhibitor mixture or mony halide, such as antimony chloride (SbCl3) or antimony
into said brine. In the use of the invention the corrosion bromide (SbBr3). Said morpholine derivative may, for
inhibitor comprises an antimony compound and a compound example, comprise alkylmorpholine derivatives, said acety
combination selected from: a) propargyl alcohol, morpho lenic alcohol may comprise, for example, propyne or butyne
line, selenium dioxide, isoascorbic acid; and b) propargyl derivatives, said ascorbic acid derivative is preferably an iso
alcohol, morpholine, selenium dioxide, hexamine; Wherein mer or a salt of ascorbic acid. Said selenium compound may
the rate of corrosion induced by a salt solution is reduced by comprise a selenium salt or oxide. Optionally includable
the corrosion inhibitor used according to the invention to amine may comprise, for example, a tertiary amine such as
about 10 mpy or loWer. In the use according to the invention, hexamine.
the corrosion inhibitor is essentially a non-sulfur inhibitor. In [0025] The present invention is based on the discovery that
said use of the invention, the corrosion inhibitor is introduced mixtures containing an antimony compound together With
into a salt solution inducing corrosion, said salt solution com various combinations of morpholine compounds, antimony
prising, typically, salts selected from Zinc bromide, Zinc chlo compounds, acetylenic alcohols, ascorbic acid derivatives,
ride, calcium bromide, calcium chloride, and mixtures and selenium compounds, provide good corrosion protection
thereof. In said use, the corrosion inhibitor is effective in to metallic surfaces of apparatuses being in contact With
inhibiting or reducing the corrosion rate in salt solutions brines and Working ?uids, at relatively loW concentrations.
incorporated in hydrocarbon drilling, completion, production The corrosion inhibiting mixtures of the invention are par
and Workover, and in absorption refrigeration systems. Use of ticularly useful for heavy brine salts solutions containing Zinc
the invention comprises an effective corrosion inhibition in bromide and Zinc chloride, and especially When used at
salt solutions at elevated temperatures. elevated temperatures. The corrosion protection remains
[0023] The invention further relates to a salt solution com strong at those high temperatures that may be encountered in
prising a corrosion inhibitor as described above, Wherein the processes such as hydrocarbon drilling, completion, produc
corrosion induced by said salt solution is essentially reduced tion and Workover, as Well as in absorption refrigeration sys
by said corrosion inhibitor. A salt solution according to the tems. The present invention is further especially based on the
invention, having usually a density from about 1.20 to about discovery that When combined at the right ratios, said above
2.65 g/cm3, preferably comprises Zinc bromide, Zinc chlo mentioned compounds provide a synergistically enhanced
ride, calcium bromide, calcium chloride, and mixtures protection to metal surfaces coming in contact With a salt
thereof. The salt solution of the invention is usually incorpo solution, in particular With a concentrated solution containing
rated in technologies associated With hydrocarbon drilling, Zinc bromide that Was properly modi?ed by adding said syn
completion, production and Workover, and absorption refrig ergistic mixtures.
eration systems. A salt solution according to the invention is [0026] As Will be described in greater detail in the folloW
effective in inhibiting corrosion or reducing the rate of cor ing, compounds selected from among four compound fami
rosion induced by heavy brine ?uids at elevated temperatures. lies Were co-introduced to concentrated aqueous solutions
Said salt solution comprises a corrosion inhibitor Which is together With antimony compounds to form corrosion inhib
essentially a non-sulfur inhibitor. Said salt solution may fur iting mixtures of the present invention to be tested. Accord
ther comprise an amine. ingly, varying corrosion inhibiting rates Were obtained,
[0024] The invention provides a method of inhibiting metal depending on the compounds selection, and on their concen
corrosion in a heavy brine ?uid, comprising admixing to said trations. These tests enabled both setting the reduction in
?uid an antimony compound, and tWo or more compounds corrosion rate for each mixture and diagnosing the synergistic
selected from at least tWo of the four folloWing compound effect taking place in the addition of a compound of a certain
families: i. morpholine and morpholine derivatives; ii. acety family compared to a reference mixture. As Will be demon
lenic alcohols; iii. ascorbic acid derivatives; and iv. selenium strated, the mixtures used for corrosion inhibition reduced
compounds; Wherein said tWo or more selected compounds signi?cantly the rate of corrosion doWn to only several mpy in
belong to at least tWo of said four families. The invention is certain cases.
also directed to a formulation for use in inhibiting metal [0027] The invention relates to an anticorrosive mixture of
corrosion in heavy brine ?uids, comprising an antimony com compounds containing an antimony compound and at least
pound, and at least tWo compounds selected from at least tWo tWo compounds selected from the folloWing compound fami
of the four folloWing compound families: i. morpholine and lies: i) morpholine and morpholine derivatives; ii) acetylenic
morpholine derivatives; ii. acetylenic alcohols; iii. ascorbic alcohols; iii) ascorbic acid derivatives; and iv) selenium com
acid derivatives; and iv. selenium compounds. The invention pounds. Various effective corrosion inhibition combinations
thus relates to a method of inhibiting metal corrosion in may be produced from the compounds belonging to said
concentrated aqueous salt solutions, comprising adding, families, all being included Within the spirit of the present
together With an antimony compound, at least tWo other com invention. A combination of compounds Within the scope of
pounds, at relatively loW concentrations, to the solution, the invention may comprise more than one compound of one
Wherein said compounds belong to said compound families. family. A corrosion inhibitor according to the invention is
Including an amine may be sometimes useful. Said salt solu preferably used in a brine comprising a salt selected from Zinc
tions may, in various situations, combine With, Without being bromide, Zinc chloride, calcium bromide, calcium chloride,
limited to them, lithium, sodium, potassium, calcium, Zinc, and mixtures thereof. Said protected metal may be selected,
chlorides, bromides, acetates, and formates, and more typi for example, from carbon steels, chromium-alloyed steels,
cally Will comprise calcium or Zinc as cation, and chloride or and stainless steels of various types. The inhibitor of the
bromide as anion. Said salt solutions, or heavy brine ?uids, as invention reduces the rate of corrosion induced by said salt
US 2009/0050853 A1 Feb. 26, 2009

solution below 40 mpy, preferably below 25 mpy, and still determining the corrosion rate shoWn in the folloWing
more preferably below 10 mpy. Various combinations of the examples, mild steel C-4l30 corrosion coupons Were rinsed
compounds according to the invention may provide in various in acetone, dried and Weighed to the nearest 0.1 mg. One or
environments anticorrosive inhibition comprising values tWo coupons Were placed into a glass container containing
beloW 5 mpy. Said antimony compound is preferably an anti 125 ml or 250 ml of the test ?uid to thereby provide a volume
mony halide, such as antimony chloride or antimony bro to surface area ratio of 20 ml per sq. in. or in 200 ml of the test
mide. Said morpholine derivative may, for example, comprise ?uid to thereby provide a volume to surface area ratio of 45 .6
optionally substituted morpholine (for the sake of brevity, the ml per sq. in. The glass container holding the coupons and the
term morpholine derivative may be used for morpholine or test ?uid Was then placed into an aging cell and pressurized to
its derivative), said acetylenic alcohol may comprise, for 500 psi With an inert medium such as nitrogen. The cell Was
example, propyne derivatives, such as 2-methyl-3-butyn-2 next placed in an oven at the desired temperature for the
ol, 4-methyl- l -pentyn-3 -ol, l-hexyn-3 -ol, 4-ethyl-l -octyn-3 -
ol, propargyl alcohol, alkoxylated propargyl alcohols, ben required test period. When not indicated otherWise, the tem
Zylbutynol, l-ethynylcyclohexanol, 5-decyne-4,7-diol, and perature Was 177 C. (350 F.) and the test duration Was 7
mixtures thereof. Said ascorbic acid derivative is preferably days. After aging, the coupons Were removed from the cell,
an isomer or a salt of ascorbic acid. Optionally includable brushed and rinsed sequentially in hot Water and acetone.
amine may comprise, for example, a tertiary amine such as They Were later dried, re-Weighed to the nearest 0.1 mg and
hexamine. the Weight-loss Was calculated. For corrosion rate calcula
[0028] The invention provides a formulation to be added to tions the formula given beloW Was used:
brines to inhibit the corrosion rate, Which formulation may be mpy:5 34 W/DAT
a concentrated solution or a suspension of said compounds of
the mentioned four families. Said formulation may alterna Where mpy:corrosion rate in mili inches per year
tively be a solid comprising said compounds. [0033] Wqveight loss, mg
[0029] It is understood that said compounds may be present [0034] DIdensity of coupon, g/cm3
in various consistencies in an effective mixture or formula
[0035] AIarea of coupon, sq. in.
tion, and that they may interact or even react in the mixture to
form adducts or salts or complexes or other products of such [0036] T:exposure (aging) time, hr
interactions; the Words mixture and formulation are used [0037] As mentioned above, antimony compounds and
interchangeably in that context. compounds of four families Were used in preparing corrosion
[0030] In one preferred embodiment of the invention, the inhibiting mixtures, namely morpholine and morpholine
corrosion inhibitor of the invention comprises a combination derivatives, acetylenic alcohols, ascorbic acid derivatives
of compounds selected from antimony bromide, antimony such as isomers or salts, and selenium compounds, optionally
chloride, morpholine, propargyl alcohol, isoascorbic acid, using also amines. Without being limited to them, the folloW
hexamine, and selenium dioxide. Said inhibitor comprises at ing compounds may be included in the inhibiting mixtures:
least three compounds selected from three different com optionally substituted morpholine, antimony chloride, anti
pound families. In a preferred embodiment, the inhibitor of mony bromide, antimony trioxide, potassium antimony tar
the invention comprises a combination selected from the trate, antimony tartrate, propargyl alcohol, 2-methyl-3-bu
group of compound-triplets consisting of antimony bromide, tyn-2-ol, 4-methyl-l-pentyn-3-ol, l-hexyn-3-ol, 4-ethyl-l
propargyl alcohol, and morpholine; antimony bromide, mor octyn-3-ol, propargyl alcohol, alkoxylated propargyl
pholine, and isoascorbic acid; antimony bromide, propargyl alcohols, benZylbutylol, l-ethynylcyclohexanol, 5-decyne-4,
alcohol, and isoascorbic acid; and antimony bromide, prop 7-diol, isoascorbic acid, ascorbic acid, hexamine, selenium
argyl alcohol, and selenium dioxide. In other preferred dioxide, and selenium chloride.
embodiment of the invention, the anticorrosive inhibitor may
comprise four compounds selected from the group of com [0038] Effective corrosion inhibiting compositions may be
pound-quadruplets consisting of antimony bromide, propar obtained by combining different compounds detailed above,
gyl alcohol, morpholine, selenium dioxide; antimony bro particularly morpholine, antimony chloride or antimony bro
mide, propargyl alcohol, morpholine, isoascorbic acid; and mide, propargyl alcohol, isoascorbic acid, and selenium diox
antimony bromide, morpholine, isoascorbic acid, selenium ide, possibly With addition of an amine such as hexamine.
dioxide. An inhibitor according to the invention may com [0039] In one aspect of the present invention is provided a
prise more than four compounds selected from antimony three component composition for inhibiting corrosion in salt
compounds and said four compound families. In a preferred solutions. Particular examples of such three components
embodiment of the invention, the inhibitor is a compound compositions are as folloWs:
quintuplet consisting of antimony bromide, propargyl alco A composition that contains SbBr3, propargyl alcohol, and
hol, morpholine, selenium dioxide, and isoascorbic acid. In selenium dioxide.
another embodiment, the inhibitor is a compound quintuplet
consisting of antimony bromide, propargyl alcohol, morpho A composition that contains morpholine, SbBr3, and propar
line, selenium dioxide, and hexamine. It is understood that gyl alcohol.
other combinations, possibly comprising tWo or more mate A composition that contains SbBr3, propargyl alcohol, and
rials belonging to the same family, may be useful in various isoascorbic acid.
practical applications. [0040] In still another aspect, the present invention pro
[0031] Preferred examples of mixtures comprising such vides a four component composition for inhibiting corrosion
corrosion inhibiting combinations, Will noW be described in in salt solutions. Particular examples of such four compo
greater detail. nents compositions are as folloWs:
DESCRIPTION OF THE PREFERRED A composition that contains morpholine, SbBr3, propargyl
EMBODIMENTS alcohol, and isoascorbic acid.
[0032] To more fully illustrate the present invention, sev A composition that contains morpholine, SbBr3, propargyl
eral non-limiting examples are subsequently presented. In alcohol, and selenium dioxide.
US 2009/0050853 A1 Feb. 26, 2009

A composition that contains morpholine, SbBr3, isoascorbic of Zinc bromide, Zinc chloride, calcium bromide, calcium
acid, and selenium dioxide. chloride and mixtures thereof, and any of the compositions
[0041] In still another aspect, the present invention pro detailed above.
vides a composition for inhibiting corrosion in salt solutions [0048] The folloWing Examples 1-7 demonstrate the syn
comprising more than four components. Particular examples ergistic effect observed inparticular corrosion inhibiting mix
of such compositions are as folloWs: tures introduced into Zinc bromide and calcium bromide salt
A composition that contains morpholine, SbBr3, propargyl solutions and tested according to the above described proce
dure. The corrosion inhibiting components in these mixtures
alcohol, selenium dioxide, and hexamine. are selected from morpholine, antimony chloride or antimony
A composition that contains morpholine, SbBr3, propargyl bromide, propargyl alcohol, isoascorbic acid, hexamine, and
alcohol, isoascorbic acid, and selenium dioxide. selenium dioxide, and the mixtures tested, Whether incorpo
[0042] From the vieWpoint of corrosion inhibition, anti rating only part of the components or all, Were compared to a
mony bromide may usually be replaced by antimony chlo reference example Where no corrosion inhibiting compound
ride. is introduced.
[0043] A suitable combination of at least three components [0049] The above-described procedure Was employed With
selected from antimony compounds and the four families an 18.2 ppg (pounds per gallon) salt solution made of 44.3 Wt.
according to the invention may provide the desired corrosion % Zinc bromide and 25.8 Wt. % calcium bromide. The cou
inhibitor for various practical situations, as a skilled person pons Were of carbon steel C-4130, the temperature 3500 E,
Will appreciate. the pressure 500 psi and the duration of exposure 168 hours.
[0044] In a preferred embodiment of the invention, a salt [0050] The experiments Which Were designed to look for
solution containing Zinc bromide at 10 Wt. % to 82 Wt. %, any Environment-Assisted Cracking (EAC) used U-bend
preferably 30 Wt. % to 78 Wt. %, and/or calcium bromide at 1 coupons that Were prepared as recommended in ASTM No.
Wt. % to 56 Wt. %, preferably 15 Wt. % to 35 Wt. %, and/or GM 58 from 309, 310 and 410 stainless steels and exposed for
calcium chloride at 0 Wt. % to 20 Wt. % is inhibited by a 1 Week at 3500 F. to the cited synergistically inhibited 18.2
corrosion inhibitor comprising tWo or more compounds ppg salt solution. No signs of cracking Were observed on any
selected from groups i. to iv. de?ned above, Wherein said salt of the mentioned coupons after aging.
solution preferably contains less than 1 Wt. % of said com
pounds, for example less than 0.8 Wt. %, preferably 0.5 Wt % Example 1
or less. Said compounds constituting the inhibitor may be Reference Example
present in the brine in amounts, e.g., from 50 ppm to 0.5 Wt. [0051] Corrosion inhibition Was ?rst tested for a blank salt
%. Said corrosion inhibitor preferably reduces the corrosion solution. The corrosion rate Was 46.2 mpy.
rate of steel, even at elevated temperatures, Wherein said steel [0052] Three components selected from morpholine, anti
may be for example carbon steel, or chromium-alloyed steel, mony compound, and propargyl alcohol Were then tested
such as 13% chromium steel (Alloy 410). separately. Table 1 herein shoWs that use of one component
[0045] In still another embodiment of the invention, a salt loWered the corrosion rate to 37-43 mpy. A small amount of
solution containing Zinc bromide at 10 Wt. % to 82 Wt. %, antimony chloride (100-200 ppm) and propargyl alcohol
preferably 30 Wt. % to 78 Wt. %, and/or calcium bromide at 1 resulted in a small decrease in the corrosion rate to 41-45 mpy.
Wt. % to 56 Wt. %, preferably 15 Wt. % to 35 Wt. %, and/or A larger amount of antimony bromide (500 ppm) and prop
calcium chloride at 0 Wt. % to 20 Wt. % is inhibited by a argyl alcohol resulted in a larger decrease in the corrosion
corrosion inhibitor comprising selenium dioxide, When in rate, to 30 mpy.
contact at 177 C. With carbon steel used in oil?eld installa
tion, Wherein no more than half a percent of each of said TABLE 1
components selected from said four families is added in either
solid form or dissolved in a suitable aqueous or organic sol Corrosion Rate Morpholine SbBr3 SbCl3 Propargyl Alcohol
vent. It is for those skilled in the art to choose the most (mpy) (Wt- %) (W11) (W11) (Wt- %)
effective inhibitor dosage for the particular salt solution com 46.2 i i i i

position and the speci?c temperature of use. In a variation of 42.5 0.25 i i i

37.0 i 2500 i i
the aforementioned embodiment, the anti-corrosion effect is 41.9 i i i 0.25

synergistically augmented by further addition of no more 30.1 i 500 i 0.2

than 1 Wt. %, preferably no more than 0.4 Wt. % of a 1:20 40.8 i i 100 0.2

Weight per Weight (W/W) solution of antimony chloride in 45.3 i i 200 0.2

propargyl alcohol. Here also, it is for those skilled in the art to


choose the most effective inhibitor dosage for the particular
salt solution composition and the speci?c temperature of use. Example 2
[0046] Salt solutions that are corrosion inhibited may be Three Components-Mixture
prepared by introducing and mixing the components in any [0053] A three component mixture Was tested for decrease
order. For example, a process for the preparation of an inhib in corrosion rate. The combination of morpholine+propargyl
ited brine may comprise introducing a concentrated aqueous alcohol+isoascorbic acid had no effect on the corrosion rate
or non-aqueous solution of some of the inhibiting compounds but other combinations of three components resulted in
into the brine, or the process may also comprise introducing decreases in the corrosion rate. Using antimony compounds
solids or liquids into the brine. One or more of the inhibiting together With either morpholine and propargyl alcohol, pro
compounds may serve as a solubiliZing or suspending pargyl alcohol and isoascorbic acid, or morpholine and
medium for one or more other inhibiting compounds. isoascorbic acid, resulted in signi?cantly reduced corrosion
[0047] In one particular embodiment of the present inven rate values doWn to loWer than 15 mpy, and in certain cases
tion the corrosion inhibited salt solutions may comprise any loWer than 10 mpy, as can be appreciated from Table 2 beloW.
US 2009/0050853 A1 Feb. 26, 2009

TABLE 2
Corrosion Rate Morpholine SbBr3 SbCl3 Propargyl Alcohol Isoascorbic acid
(mpy) (Wt- %) (ppm) (ppm) (Wt- %) (Wt- %)
47.5 0.3 i i 0.2 0.5
45.0 0.3 i i 0.2 0.5
26.8 0.3 i 100 0.2 i
27.5 0.3 i 100 0.2 i
18.0 i i 100 0.2 0.5
31.7 i i 100 0.2 0.5
12.5 0.3 150 i i 0.4
11.0 0.3 150 i i 0.5
8.1 0.3 150 i i 0.5
13.9 0.3 150 i i 0.5
15.5 0.3 150 i i 0.5
10.9 0.3 150 i i 0.6
12.6 0.3 i 100 i 0.5
13.8 0.3 i 100 i 0.5
9.6 0.3 i 100 i 0.5
10.2 0.3 i 100 i 0.5

[0054] Based on the above results, the following conclu- lower corrosion rate (11 mpy) than the combination of anti
sions regarding the above different combinations Were mony bromide and propargyl alcohol (30 mpy).
draWn:
[0055] a) morpholine+propargyl alcohol+isoascorbic acid TABLE 4
had little effect on the corrosion rate. Corrosion Rate SeO2 SbBr3 Propargyl Alcohol
[0056] b) morpholine+antimony chloride+propargyl alco (mpy) (ppm) (ppm) (Wt- %)
hol decreased the corrosion rate to 27-28 mpy. 40.4 2500 i i

[0057] c) antimony chloride+propargyl alcohol+isoascor 42.5 i i i

37.0 i 2500 i
bic acid decreased the corrosion rate to 18-32 mpy. 41.9 i i 0.25

[0058] d) morpholine+antimony bromide or antimony 30.1 500 0.2


chloride+isoascorbic acid decreased the corrosion rate to 11.1 250 250 0.2

8-16 mpy.

Example 3 Example 5
Four Components-Mixture
Four Components -Mixture
[0061] Four components, chosen from selenium dioxide,
[0059] A four-component mixture, consisting of morpho morpholine, antimony bromide, propargyl alcohol, and
line, antimony chloride, propargyl alcohol, and isoascorbic isoascorbic acid, Were tested. The corrosion rate results are
acid Was tested and resulted in a very loW corrosion rate (3-6 summarized in Table 5 beloW.
mpy)
TABLE 5
TABLE 3
Propargyl Isoascorbic
Propargyl Corrosion SeO2 Morpholine SbBr3 Alcohol acid
Corrosion Rate Morpholine SbCl3 Alcohol Isoascorbic acid Rate (mpy) (ppm) (Wt- %) (ppm) (Wt- %) (Wt- %)
(mpy) (Wt. %) (ppm) (Wt. %) (Wt. %) 8.7 100 0.2 150 i 0.4
17.0 150 0.2 150 i 0.4
3.1 0.3 100 0.2 0.5
9.6 250 0.2 250 0.2 i
3.2 0.3 100 0.2 0.5
10.4 100 0.2 150 0.2 i
5.5 0.3 100 0.2 0.5
6.9 100 0.2 150 0.2 i
5.2 0.3 100 0.2 0.5
17.2 50 0.15 120 0.2 i
19.4 50 0.15 120 0.2 i
15.3 50 0.15 120 0.2 i
35.0 50 0.15 45 0.2 i
Example 4
Use of Selenium Dioxide [0062] The results for this set of tests may be summarized
as folloWs:
[0060] The positive effect of selenium dioxide Was tested Selenium dioxide+morpholine+antimony bromide+
alone and in a three component combination With antimony isoascorbic acid resulted in a corrosion rate of 9-17 mpy;
bromide and propargyl alcohol. Table 4 shoWs that the use of selenium dioxide+morpholine+antimony bromide+propar
selenium dioxide by itself decreased the corrosion rate gyl alcohol resulted in a corrosion rate decreasing from 35
slightly to 40 mpy. The combination of selenium dioxide+ mpy to 7 mpy, as amounts of morpholine and antimony bro
antimony bromide+propargyl alcohol resulted in a much mide increased.
US 2009/0050853 A1 Feb. 26, 2009
7

Example 6 [0067] The corrosion inhibitors for lowering the corrosion


Five Components-Mixture rate below 25 mpy may contain d) antimony compound,
[0063] A ?ve-component mixture consisting of selenium morpholine, and isoascorbic acid; 6) antimony Compound,
dioxide, morpholine, antimony bromide, propargyl alcohol, propargyl 211001101, and Selenium dioxide; or f) antimony C0111
and isoascorbic acid Was tested. Corrosion rates are summa- pound, morpholine, selenium dioxide, and isoascorbic acid.
nZed m_ Table 6 Showmg a 10W Corroslon rate of 9'? mPY [0068] The corrosion inhibitors that can loWer the corro
decreasing to a value as loW as 3.5, When further adjusting sion rate below 10 mpy may Contain g) antimony Compound
morpholine and1soascorb1c ac1d. . . . . _
propargyl alcohol, morpholine, and isoascorbic acid, or h)
TABLE 6 antimony compound, propargyl alcohol, morpholine, and
selenium dioxide i) antimony compound, propargyl alcohol,
Propargyl Isoascorbic Morpholine, selenium dioxide, and isoascorbic acid; or j)
C ' S O M h l' SbB Al h l 'd - -
Razirzilg; (pin?) :23 (pp (W051i) (351% antimony compound, propargyl alcohol, morpholine, sele
nium d1ox1de, and hexam1ne.
[88 855 [28 8:; 8:41; [0069] Table 8 shoWs the above conclusions about corro
sion rates, denoting the presence of a compound by x. SbX3
may be SbCl3 or SbBr3.

TABLE 8
Corrosion Propargyl
Rate (mpy) SbX3 Alcohol Morpholine Isoascorbic acid SeO2 Hexamine
a <30 x x
b <30 x x x
c <30 x x x
d <20 x x x
e <20 x x x
f <20 x x x x
g <l0 x x x x
h <l0 x x x x
i <l0 x x x x x
j <l0 x x x x x

Example7 [0070] Besides the above tested mixtures, aqueous salt


mixtures With inhibitors according to prior art recipes Were
Five Components-Mixture, Introducing Hexamine prepared but they either didnot produce loW corrosion rates or
they shoWed disadvantageous features (such as undesired
[0064] Hexamine Was added to a four component mixture surface and interphase phenomena).
consisting of selenium dioxide, morpholine, antimony bro [0071] A skilled person Will utiliZe the potential of the
mide, and propargyl alcohol. The corrosion rate decreased invention, Which can provide an anticorrosive composition
from 10.4 mpy to 5.7 mpy. for various situations, taking into account the desired corro
sion rate, phenomena other than corrosion, behavior of the
TABLE 7 inhibited brine, physical conditions during the intended use
Propargyl
(temperature, pressure, additional chemical components
Corrosion SeO2 Morpholine SbBr3 Alcohol Hexamine from the environment, etc.), as Well as other aspects, includ
Rate (mpy) (ppm) (Wt- %) (ppm) (Wt- %) (ppm) ing economic, environmental, and safety aspects. For
10.4 100 0.2 150 0.2 i
example, some speci?c applications Will require very loW
5.7 100 0.2 150 0.2 150 mpy values, other may necessitate loW costs While doing With
relatively higher mpy values, taking advantage of ?exibility
enabled by the invention. Said variety of practical aspects Will
affect the selection of chemicals and their quantities effected
SUMMARY according to the invention by a skilled person.
[0072] While examples of the invention have been
[0065] Summarizing the results obtained for the different described for purposes of illustration, it Will be apparent that
combinations tested for corrosion inhibition, the folloWing many modi?cations, variations and adaptations canbe carried
conclusions may be draWn (the mpy values relating to 350 out by persons skilled in the art, Without exceeding the scope
F.): of the claims.
[0066] Non-sulfur corrosion inhibitors for loWering the
corrosion rate beloW 30 mpy may contain, for example, a)
antimony compound, and propargyl alcohol; or b) antimony 1-48. (canceled)
compound, propargyl alcohol, and morpholine; or c) anti 49) A liquid composition comprising a hi gh-capacity aque
mony compound, propargyl alcohol, and isoascorbic acid. ous carrier in Which (i) a metalloid compound selected from
US 2009/0050853 Al Feb. 26, 2009

the group consisting of antimony and germanium compounds wherein R1 is hydrogen or C l-C3 alkyl and R2 is indepen
and (ii) morpholine or derivative thereof are dissolved in the dently selected from the group consisting of hydrogen,
presence of (iii) unsaturated alcohol and (iv) Water-soluble Cl-C3 alkyl and phenyl group and n is 0, 1,2,3 or 4, said
organic acid having reducing capacity. Cl-C3 alkyl and phenyl groups being optionally substi
50) A composition according to claim 49, Wherein the tuted;
composition is in the form of a clear solution. (iii) unsaturated alcohol selected from the group consisting
51) A composition according to claim 50, Wherein the total of alkenols having from 3 to 7 carbon atoms, alkynols
concentration of the four components in the aqueous compo having from 3 to 7 carbon atoms, and mixtures thereof;
sition is not less than 30% by Weight and the Water content of and
the composition is not less than 30% by Weight. (iv) (iso)ascorbic acid.
52) A composition according to claim 49, Wherein the 62) A composition according to claim 63, Wherein the
metalloid compound is antimony halide. morpholine of Formula I is selected from the group consisting
53) A composition according to claim 49, Wherein the of morpholine and 4-(2-hydroxyalkyl) morpholines, and the
morpholine and derivative thereof are represented by the unsaturated alcohol comprises a straight chain primary alk
structure of Formula I: enol having from 3 to 5 carbon atoms.
63) A composition according to claim 60, Which is a clear
(I)
solution containing about 30-60% by Weight Water; (i) 0.40
0.60% by Weight antimony halide; (ii) 10-25% by Weight
morpholine or 4-(2-hydroxyalkyl) morpholine; (iii) 7-18%
by Weight straight chain primary alkenol having from 3 to 5
carbon atoms and (iii) 20-30% by Weight (iso)ascorbic acid.
64) A composition according to claim 63, Wherein the
antimony halide is SbCl3, the morpholine derivative is 4-(2
wherein R1 is hydrogen or C l-C3 alkyl and R2 is indepen hydroxyethyl) morpholine and the alkenol is selected from
dently selected from the group consisting of hydrogen,
Cl-C3 alkyl and phenyl group and n is 0, 1,2,3 or 4, said
group consisting of allyl alcohol (CH2:CHCH2OH), crotyl
alcohol (CH3CH:CHCH2OH) and a mixture thereof.
Cl-C3 alkyl and phenyl groups being optionally substi
tuted. 65) A process for preparing a clear aqueous composition,
Which comprises mixing in a vessel a high-capacity aqueous
54) A composition according to claim 53, Wherein in For
mula (1) R1 is hydrogen or C 1 -C3 alkyl substituted With one or
carrier, Water-soluble organic acid having reducing capacity,
a metalloid compound Which is antimony or germanium com
more hydroxy groups and R2 is hydrogen. pound, unsaturated alcohol and morpholine or derivative
55) A composition according to claim 49, Wherein the thereof, such that the dissolution of said metalloid compound
unsaturated alcohol comprises alkenol or alkynol having in said aqueous carrier is accomplished under acidic environ
from 3 to 7 carbon atoms, or a mixture thereof. ment.
56) A composition according to claim 55, Wherein the
unsaturated alcohol is alkynol. 66) A process according to claim 65, Which comprises
mixing (iso)ascorbic acid in the aqueous carrier to form an
57) A composition according to claim 56, Wherein the acidic aqueous carrier, dissolving the metalloid compound in
alkynol is selected from the group consisting of propargyl said carrier, introducing unsaturated alcohol into the resulting
alcohol, 3-butyn-2-ol and 2-butyn-l -ol. solution and subsequently adding morpholine or derivative
58) A composition according to claim 55, Wherein the thereof, to form an essentially homogeneous liquid compo
unsaturated alcohol is a straight chain primary alkenol having sition With a pH in the range betWeen 6 to 12.
from 3 to 5 carbon atoms.
67) A process according to claim 66, Wherein the metalloid
59) A composition according to claim 58, Wherein the compound is antimony halide, the unsaturated alcohol is
alkenol is allyl alcohol (CH2:CHCH2OH), crotyl alcohol selected from the group consisting of alkenols and alkynols
(CH3CH:CHCH2OH) or a mixture thereof. having from 3 to 7 carbon atoms and the morpholine or
60) A composition according to claim 49, Wherein the derivative thereof is represented by Formula I
Water-soluble organic acid having reducing capacity is (iso)
ascorbic acid.
61) A composition according to claim 51 Which is a clear (I)
solution comprising Water and
(i) a metalloid compound Which is antimony compound;
(ii) morpholine or derivative thereof as represented by the
structure of Formula I:

(1)
wherein R1 is hydrogen or C l-C3 alkyl and R2 is indepen
dently selected from the group consisting of hydrogen,
Cl-C3 alkyl and phenyl group and n is 0, 1,2,3 or 4, said
Cl-C3 alkyl and phenyl groups being optionally substi
tuted.
68) A process according to claim 67, Wherein the alkenol is
straight chain primary alkenol containing from 3 to 5 carbon
US 2009/0050853 A1 Feb. 26, 2009

atoms and the morpholine of Formula I is selected from the 74) A corrosion inhibiting composition according to claim
group consisting of morpholine, 4-(2 -hydroxyethyl) morpho 71, Wherein the morpholine derivative is 4-(hydroxyalkyl)
line and mixtures thereof. morpholine.
69) A method for inhibiting the corrosion of metals in 75) A composition according to claim 71, Wherein the
contact With a corrosive ?uid, Which method comprises: antimony compound is SbCl3, the morpholine derivative is
(a) providing a solution comprising: 4-(2-hydroxyethyl) morpholine, the alkenol is selected from
(i) a metalloid compound selected from the group con group consisting of allyl alcohol (CH2:CHCH2OH), crotyl
sisting of antimony and germanium compounds; alcohol (CH3CH:CHCH2OH) and a mixture thereof and the
(ii) morpholine or derivative thereof; Water-soluble organic acid is (iso)ascorbic acid.
76) A method for inhibiting the corrosion of metals in
(iii) unsaturated alcohol; and contact With a corrosive ?uid, Which method comprises add
(iv) Water-soluble organic acid having reducing capac
ing to said corrosive ?uid a corrosion-inhibiting effective
1W; amount of a metalloid compound selected from the group
Wherein said components are dissolved in a high-capac
ity aqueous carrier at a concentration of not less than
consisting of antimony and germanium compounds; Water
5% by Weight, and soluble organic acid having reducing capacity; C3-C7 alk
(b) adding to said corrosive ?uid a corrosion-inhibiting enol; and morpholine or a derivative thereof as represented by
the structure of Formula I:
effective amount of said solution.
70) A method according to claim 69, Wherein the corrosion
to be inhibited is stress-corrosion cracking and the corrosive
brine is calcium bromide brine.
71) A corrosion inhibiting composition comprising:
(i) a metalloid compound selected from the group consist
ing of antimony and germanium compounds;
(ii) morpholine or derivative thereof as represented by the
structure of
Formula I:
wherein R1 is hydrogen or C l-C3 alkyl and R2 is indepen
dently selected from the group consisting of hydrogen,
Cl-C3 alkyl and phenyl group and n is 0, 1,2,3 or 4, said
Cl-C3 alkyl and phenyl groups being optionally substi
tuted.
77) A method according to claim 76, Wherein the alkenol is
a straight chain primary alkenol having from 3 to 5 carbon
atoms and the morpholine derivative is 4-(hydroxyalkyl)
morpholine.
78) A method according to claim 77, Wherein the alkenol is
wherein R1 is hydrogen or Cl-C3 alkyl and R2 is inde selected from the group consisting of allyl alcohol
pendently selected from the group consisting of (CH2:CHCH2OH), crotyl alcohol (CH3CH:CHCH2OH)
hydrogen, C l-C3 alkyl and phenyl group and n is 0, l, or a mixture thereof and the morpholine is 4-(2-hydroxy
2, 3 or 4, said Cl-C3 alkyl and phenyl groups being ethyl) morpholine.
optionally substituted; 79) A method according to claim 76, Wherein the corrosion
(iii) C3 -C7 alkenol; and to be inhibited is stress-corrosion cracking.
(iv) Water-soluble organic acid having reducing capacity. 80) A method according to claim 79, Wherein the corrosive
72) A corrosion inhibiting composition according to claim ?uid is calcium bromide brine.
71, Wherein the alkenol is a straight chain primary alkenol 81) Halide brine, Which comprises one or more of the
having from 3 to 5 carbon atoms. folloWing salts: NaCl, NaBr, CaCl2, CaBr2, ZnCl2 and ZnBr2,
73) A composition according to claim 72, Wherein the and further comprises a corro sion-inhibiting effective amount
alkenol is selected from the group consisting of allyl alcohol of the composition according to claim 71.
(CH2:CHCH2OH), crotyl alcohol (CH3CH:CHCH2OH)
* * * * *
and a mixture thereof.