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    • 专利摘要:
    The invention provides the use of a surfactant as a corrosion inhibitor, wherein the surfactant is selected from derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, and mixtures thereof, provided that the derivatives are not sulfosuccinates. Also provided is a method of preventing or reducing corrosion of a metal component that is in contact with, or will be in contact with, an aqueous fluid, wherein the method comprises providing a surfactant and applying the surfactant to the metal component or adding the surfactant to the aqueous fluid that is in contact with, or will be in contact with, the metal component, wherein the surfactant is selected from derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, and mixtures thereof, provided that the derivatives are not sulfosuccinates.
    公开号:AU2013214288A1
    申请号:U2013214288
    申请日:2013-01-30
    公开日:2014-07-31
    发明作者:Gareth Collins；Alan Fellows；Kevan Hatchman；Christopher Raymond Jones
    申请人:Rhodia Operations SAS；
    IPC主号:C23F11-10
    专利说明:
    WO 2013/113740 PCT/EP2013/051758 1 CORROSION INHIBITORS [001] The present invention relates to the use of surfactants as corrosion inhibitors, especially in oilfield applications, wherein the corrosion inhibiting surfactants are selected from 5 derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, where the derivatives are not sulfosuccinate derivatives. Background to the Invention 10 [002] Alkyl polyglucosides (APGs) are surfactants known for use in the personal care industry, e.g. for hair and skin cleaning and conditioning products. APGs are synthesised from the reaction of glucose and a fatty alcohol. APGs are polymeric in nature and can contain one or more glucoside units. APGs are usually provided as a mixture of products that differ in terms of the extent of polymerisation. Therefore when referring to the degree of polymerisation 15 (dp) for APGs this will be given as the average (mean) degree of polymerisation of the mixture. For example, a 50:50 mixture of an APG with a dp=1 and an APG with a dp=2 will provide an average degree of polymerisation of 1.5. OH HO OH OH OH 20 HO OH HOOC OH OH OH RO O RO 0 APG with dp=1 APG with dp=2 25 [003] An APG can be reacted with a functionalising agent to create a functionalised polymer. A cross-linking agent will usually be used in such a reaction to create a 'cross-polymer'. [004] Functional groups that can be added include quaternary compounds, phosphates, 30 carboxmethylates, maleates, sulfonates (including hydroxyalkylsulfonates), succinates and sulfosuccinates. The synthesis of these functionalised APGs is described in US 6,627,612 and US 7,507,399. [005] Alkoxylated terpenes are primarily used as emulsifiers, solubilisers, wetting agents and 35 low foaming surfactants in agrochemical, home care, institutional and industrial applications. These terpene alkoxylates are obtained by the reaction of the terpene (nopol) with alkoxides WO 2013/113740 PCT/EP2013/051758 2 such as ethylene oxide, propylene oxide and/or butylene oxide. This is described in, for example, US patent publication 2006/0135683. [006] A derivative of a terpene alkoxylate can be obtained by reacting the terpene alkoxylate 5 with a functionalising agent. For example, an ether carboxylic acid derivative can be prepared by the reaction of the terpene alkoxylate with sodium monochloroacetate (SMCA) at 80 0 C. The alkyl ether carboxylate may be prepared using a slight molar excess (1.1 - 1.2 moles) of SMCA per mole of alkoxylate in the presence of an alkali (NaOH). The resultant mixture can be acidified and washed with water to remove any residual sodium chloride. 10 [007] It is well known that steel and other metal surfaces can corrode in the presence of aqueous environments; especially acidic aqueous environments such as those found in subterranean wells, which can pass through formations containing high concentrations of corrosive materials such as hydrogen sulphide, carbon dioxide, brine, and the like. 15 [008] Alloy technology and galvanisation have resulted in materials that can withstand some incidental contact with corrosive environments, but in a number of industrial applications (such as hydrocarbon exploration, recovery and refining, and chemical processing) more prolonged contact with corrosive environments occurs. In particular, during the working life of 20 an oil or gas well various conduits and other components in the production zone encounter considerable acidic corrosion. [009] Corrosion inhibitors are therefore widely used in oil and gas production wells and pipelines to reduce corrosion of metal components and therefore prevent consequential 25 production equipment failures. [010] Imidazolines are commonly used as corrosion inhibitors, and are viewed as the industry standard, but are known to have poor aquatic toxicity. Other known corrosion inhibitors for use in oilfields are based on fatty amine, fatty amidoamine or quaternary ammonium 30 chemistries. However, these compounds are also harmful to aquatic species. These known corrosion inhibitors can also exhibit poor biodegradability. [011] There is therefore a continuing need for corrosion inhibitors, for use in the oil and gas industry and other industrial applications, which have improved aquatic toxicity and 35 biodegradability.
    WO 2013/113740 PCT/EP2013/051758 3 Summary of the Invention [012] The present invention provides, in a first aspect, the use of a surfactant as a corrosion inhibitor, wherein the surfactant is selected from derivatives of alkyl polyglucosides and 5 derivatives of terpene alkoxylates, and mixtures thereof. [013] In particular, the corrosion inhibiting surfactant can be used to inhibit the corrosion of a metal component, that is, or will be, in contact with an aqueous fluid, in order to prevent or reduce corrosion of the metal component. 10 [014] The present invention also provides, in a second aspect, a method of preventing or reducing corrosion of a metal component that is in contact with, or will be in contact with, an aqueous fluid, wherein the method comprises: - providing a surfactant, wherein the surfactant is selected from derivatives of alkyl 15 polyglucosides and derivatives of terpene alkoxylates, and mixtures thereof; and - applying the surfactant to the metal component or adding the surfactant to the aqueous fluid that is in contact with, or will be in contact with, the metal component. [015] The corrosion inhibiting surfactants of the present invention can have good 20 compatibility with non-ionic, anionic and amphoteric corrosion inhibitors, therefore permitting corrosion inhibitor formulations to be produced that comprise combinations of two or more different corrosion inhibitors. [016] Accordingly, in a third aspect there is provided a corrosion inhibitor formulation that 25 comprises one or more corrosion inhibiting surfactant, wherein the surfactant is selected from derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, and mixtures thereof, together with a corrosion inhibitor that is not a corrosion inhibiting surfactant in accordance with the invention. 30 [017] The surfactants of the present invention have been surprisingly identified as effective corrosion inhibitors. Further, they exhibit lower aquatic toxicity than imidazolines. Information regarding the toxicity of surfactants can be found in Chapter 9, Anionic surfactants, Ed: H W Stache, Surfactant Science Series, Vol: 56, Marcel Dekker (1996). 35 [018] A further benefit is that the corrosion inhibiting surfactants of the invention can be tailored to have a molecular weight of greater than 700Da, which would mean they would be WO 2013/113740 PCT/EP2013/051758 4 classified as non bio-accumulating (according to the OSPAR Guidelines for Completing the Harmonised Offshore Chemical Notification Format (HOCNF) (Reference number: 2008-5), paragraph 38). In particular, derivatives of alkyl polyglucosides can be prepared having molecular weights of the order of about 2000 to 6000Da and therefore these do not bio 5 accumulate in the environment. [019] Additionally, the corrosion inhibiting surfactants of the invention are beneficial in that they are biodegradable. It may also be that they can be cleaved by hydrolysis by acids or by bases. 10 [020] Therefore the corrosion inhibiting surfactants provide a number of advantages over known corrosion inhibitors. Detailed description of the invention 15 [021] The corrosion inhibiting surfactant used in the present invention may be one or more surfactant which is a derivative of an alkyl polyglucoside and/or one or more surfactant which is a derivative of a terpene alkoxylate, wherein the derivative is not a sulfosuccinate. 20 [022] Only one corrosion inhibiting surfactant may be used, or a combination of more than one corrosion inhibiting surfactant may be used. When more than one is used, these may all be derivatives of alkyl polyglucosides or may all be derivatives of terpene alkoxylates or they may be a mixture of derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates. 25 [023] In one embodiment, the total number of carbon atoms in the (or each) corrosion inhibiting surfactant is from 12 to 500, such as from 13 to 450, or from 14 to 400, or from 15 to 350. It may be from 12 to 300, or from 16 to 250, or from 18 to 200. Preferably it is from 20 to 300, such as from 22 to 250, or from 24 to 200. 30 [024] In one embodiment, the corrosion inhibiting surfactant has a molecular weight of greater than 700Da. This can be beneficial for some applications, as it means they would be classified as non bio-accumulating. However, in an alternative embodiment, the surfactant has a molecular weight of 700Da or less. 35 [025] It may be that the corrosion inhibiting surfactant has a molecular weight of from 300 to 3000Da, such as from 350 to 2500Da, or from 400 to 2200Da, or from 450 to 2000Da.
    WO 2013/113740 PCT/EP2013/051758 5 [026] In one embodiment, the corrosion inhibiting surfactant has a molecular weight of greater than 700Da and less than or equal to 3000Da. In one such embodiment, it has a molecular weight of from 705 to 3000Da, such as from 710 to 2500Da, or from 715 to 5 2200Da, or from 720 to 2000 Da. [027] In another embodiment, the corrosion inhibiting surfactant has a molecular weight of from 300 to 700Da, such as from 350 to 675Da or from 400 to 650Da. 10 [028] When the corrosion inhibiting surfactant comprises a derivative of an alkyl polyglucoside, this surfactant may suitably be selected from reaction products of an alkyl polyglucoside with a cross linking agent and a functionalising agent. [029] The crosslinking agent is suitably of formula X-Ra-X, where each X, which may be the 15 same or different, is a halogen (e.g. chloro, fluoro or bromo) and Ra is a C2-C18 hydrocarbon (e.g. alkyl or alkenyl), that may optionally be substituted and that may be branched or unbranched. Optional substituent groups which may replace one or more hydrogens in the hydrocarbon include hydroxy, amino, amido, nitro and alkoxy. Optional substituent groups which may replace one or more carbons in the hydrocarbon include 0, N and S. 20 [030] It may be that Ra comprises a C2-C18 (e.g. C2-C12) alkanyl or alkenyl group, or an alkoxylated (e.g. ethoxylated, propoxylated or butoxylated) derivative thereof, and it may optionally be substituted (e.g. one or more one or more hydrogen may be replaced with substituent groups selected from hydroxy, amino, amido, nitro and alkoxy groups) and it may 25 be branched or unbranched. Ra may, for example, be a C2-C12 alkanyl or alkenyl group that may optionally be substituted (e.g. with one or more one or more hydrogen being replaced with substituent groups selected from hydroxy groups and amino groups) and that may be branched or unbranched. 30 [031] In one embodiment Ra is a branched or unbranched C2-C8 alkanyl (e.g. C2, C3, C4 or C5 alkanyl) that may optionally be substituted (e.g. with one or more one or more hydrogen being replaced with substituent groups selected from hydroxy groups and amino groups). In one such embodiment X is chloro. 35 [032] In one embodiment the crosslinking agent is: WO 2013/113740 PCT/EP2013/051758 6 [033] The functionalising agent is suitably of formula X-Ra-Y, where X is a halogen (e.g. chloro, fluoro or bromo), Ra is a C2-C18 hydrocarbon (e.g. alkyl or alkenyl), that may 5 optionally be substituted and that may be branched or unbranched, and Y is selected from quaternary ammonium groups, sulfonate groups, sulfate groups, phosphate groups, and hydroxy groups. Optional substituent groups which may replace one or more hydrogens in the hydrocarbon include hydroxy, amino, amido, nitro and alkoxy. Optional substituent groups which may replace one or more carbons in the hydrocarbon include 0, N and S. 10 [034] In one embodiment, one or more carbon atoms in the hydrocarbon chain are replaced with oxygen. [035] It may be that Ra comprises a C2-C18 (e.g. C2-C12) alkanyl or alkenyl group, or an 15 alkoxylated (e.g. ethoxylated, propoxylated or butoxylated) derivative thereof, and it may optionally be substituted (e.g. one or more one or more hydrogen may be replaced with substituent groups selected from hydroxy, amino, amido, nitro and alkoxy groups) and it may be branched or unbranched. 20 [036] Ra may, for example, be a C2-C12 alkanyl or alkenyl group that may optionally be substituted (e.g. with one or more one or more hydrogen being replaced with substituent groups selected from hydroxy groups and amino groups) and that may be branched or unbranched. 25 [037] In one embodiment Ra is a branched or unbranched C2-C8 alkanyl (e.g. C2, C3, C4 or C5 alkanyl) that may optionally be substituted (e.g. with one or more one or more hydrogen being replaced with substituent groups selected from hydroxy groups and amino groups). In one such embodiment X is chloro. 30 [038] Y is selected from quaternary ammonium groups, sulfonate groups, sulfate groups, phosphate groups, and hydroxy groups. [039] Quaternary ammonium groups may be of formula -N R' 3 where each R' may be the same or different and may be selected from C1-C36 hydrocarbon groups (e.g. alkyl or alkenyl), 35 that may optionally be substituted and that may be branched or unbranched. Optional WO 2013/113740 PCT/EP2013/051758 7 substituent groups which may replace one or more hydrogens in the hydrocarbon include hydroxy, amino, amido, carboxy, nitro and alkoxy. Optional substituent groups which may replace one or more carbons in the hydrocarbon include 0, N and S. 5 [040] In one embodiment, each R' may be the same or different and is selected from C1-C36 branched or unbranched alkyl groups that may optionally be substituted (e.g. one or more one or more hydrogen may be replaced with substituent groups selected from hydroxy, amino, amido, carboxy, nitro and alkoxy groups). 10 [041] Preferably one or more of the R' groups are selected from methyl, ethyl or propyl. It may be that two of the R' groups are selected from methyl, ethyl or propyl and the third R' group is selected from C1-C36 branched or unbranched alkyl groups, especially unbranched alkyl groups, more especially C6-C36 unbranched alkyl groups and most especially C10-C36 unbranched alkyl groups (e.g. C12-C30 unbranched alkyl groups). 15 [042] Preferably at least some of the R' groups are unsubstituted. In one preferred embodiment all of the R' groups are unsubstituted. [043] Sulfonate groups may be of formula -S0 3 M where M is selected from H and 20 monovalent cations such as Na, K, and NH 4 . [044] Sulfate groups may be of formula -S0 4 M where M is selected from H and monovalent cations such as Na, K, and NH 4 . 25 [045] Phosphate groups may be of formula -OPO(OM) 2 where each M is independently selected from H and monovalent cations such as Na, K, and NH 4 . [046] In one embodiment, the functionalising agent is selected from: WO 2013/113740 PCT/EP2013/051758 8 and mixtures thereof, wherein R1 is selected from C6-C36 unbranched alkyl groups, and 5 M is selected from H and monovalent cations such as Na, K, and NH 4 . [047] The reactions that take place between alkyl polyglucosides and crosslinking agents and functionalising agents are described in more detail in US 7,507,399 Bi. As described in that document, the resultant product is a cross-linked polymer (crosslinked by -Ra- groups) but the 10 degree of crosslinking depends of the ratio of crosslinking agent to hydroxy groups in the glucoside. Likewise, the functionalising agent will react with hydroxy groups in the glucoside and the number of groups -Ra-Y that replace hydroxy groups in the crosslinked glucosides will depend on the ratio of functionalising agent to hydroxy groups in the glucoside. 15 [048] The alkyl polyglucosides from which the corrosion inhibiting surfactant can be derived may suitably have an alkyl group that is a C8 to C30 branched or unbranched alkyl group, such as a C8 to C25, C8 to C22, C9 to C20, C1O to C18, or C1O to C16 branched or unbranched alkyl group. In one embodiment it may be a C1O to C30 branched or unbranched alkyl group, such as a C10 to C24, or C10 to C18 branched or unbranched alkyl group. 20 [049] In a preferred embodiment the alkyl polyglucoside from which the corrosion inhibiting surfactant is derived has an alkyl group that is a C12 to C30 branched or unbranched alkyl group, such as a C12 to C25, C12 to C24, C12 to C22, C12 to C20, C12 to C18, or C12 to C16 branched or unbranched alkyl group. In one such preferred embodiment the alkyl WO 2013/113740 PCT/EP2013/051758 9 polyglucoside may have an alkyl group that is a C12 to C24 branched or unbranched alkyl group. [050] Preferably the alkyl group is unsubstituted. 5 [051] The skilled reader will understand that, due to the method by which they are synthesized, alkyl polyglucosides are generally present as mixtures of alkyl polyglucosides, where there are varying numbers of carbon atoms in the alkyl radical and where there are varying degrees of polymerisation. Thus, when referring to alkyl polyglucosides, the alkyl 10 radical is generally referred to as having a range of carbon atoms, which cover the minimum and maximum length of alkyl carbon chains present in the mixture, and the degree of polymerisation is the average (mean) degree of polymerisation of the mixture. [052] For the alkyl polyglucoside derived products, the polyglucoside may in one 15 embodiment have a degree of polymerisation of from I to 15, and preferably from I to 10, e.g. from 1 to 9, from 1 to 8, from 1 to 7 or from 1 to 6. Typically it may be from 1 to 5 or from 1 to 4. In one embodiment for the alkyl polyglucoside derived products, the polyglucoside has a degree of polymerisation of from 1 to 3; more preferably from 1 to 2; for example from 1.1 to 1.8 or from 1.1 to 1.7; such as from 1.2 to 1.6; most preferably from 1.2 to 1.5. 20 [053] As the skilled reader will appreciate, the degree of polymerisation can be measured by known techniques such as gel permeation chromatography. [054] In one embodiment, the alkyl polyglucoside is made up of units of formula (I) and/or 25 (II): WO 2013/113740 PCT/EP2013/051758 10 I) (II R~~~~~1 -I N k-%t6 H wherein R is a C8-30 alkyl group; 5 R', R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen and 12
    CH
    2
    CH(OH)CH
    2 -R with the proviso that R' , R2 , R 3 and R 4 are not all hydrogen;
    R
    5 , R', R 7 R', R 9 and R" are independently selected from the group consisting of hydrogen and 12
    -CH
    2
    CH(OH)CH
    2 -R 10 and R' 0 is selected from the group consisting of hydrogen, -CH 2 CH(OH)(CH2 -R"1, and I I with the proviso that R , R', R' R', R9, R and R" are not all hydrogen, wherein x = 0 or 1, and R 2 is a functional group selected from: 15 WO 2013/113740 PCT/EP2013/051758 11 5 wherein RI is selected from C6-C36 unbranched alkyl groups, and M is selected from H and monovalent cations such as Na, K, and NH 4 , and wherein the overall degree of polymerisation of the surfactant product (i.e. the average number of glucose units per alkyl group R) is from 1ito 15, preferably from 1ito 10, e.g. from 1ito 5. 10 [055] In one embodiment the degree of polymerisation is from 1 to 5, e.g. from 1.1 to 1.8 (such as from 1.2 to 1.5). [056] The alkyl groups R in formula (I) and (II) are C8 to C30 branched or unbranched alkyl 15 groups, such as C8 to C25 branched or unbranched alkyl groups, e.g. C9 to C22 branched or unbranched alkyl groups; more preferably C1O to C24 branched or unbranched alkyl groups, e.g. C10 to C18 branched or unbranched alkyl groups. [057] In a preferred embodiment the alkyl groups R (i.e. the alkyl group for the alkyl 20 polyglucosides) are C12 to C30 branched or unbranched alkyl groups, such as C12 to C25, and most preferably C12 to C24 branched or unbranched alkyl groups. In one such embodiment the alkyl groups R in formula (III) and (IV) are C12 to C22 branched or unbranched alkyl groups, such as C12 to C20 branched or unbranched alkyl groups, e.g. C12 to C18 branched or unbranched alkyl groups or C12 to C16 branched or unbranched alkyl groups. 25 [058] In one embodiment, the alkyl polyglucoside derivative is based on decyl polyglucoside or lauryl polyglucoside. In one preferred embodiment, the alkyl polyglucoside derivative is based on lauryl polyglucoside. 30 [059] In one embodiment, the alkyl polyglucoside derivative is selected from those described in US 7,507,399 Bi.
    WO 2013/113740 PCT/EP2013/051758 12 [060] It may be that the alkyl polyglucoside derivative is of formula (III): 5 Y OH y H 10 0 HO OH OH O HO O O OH RO 0 L 15 RO 0 J (III) 20 wherein n is an integer of 1 or more (e.g. from I to 20 or from I to 10), such as 2 or more, or 3 or more, and typically 4 or more; R is selected from C8 to C30 branched or unbranched alkyl groups; Y is selected from quaternary ammonium groups, sulfonate groups, sulfate groups, 25 phosphate groups, and hydroxy groups. [061] Preferred options for R and Y are as described above. It may be that R is selected from C1O to C24 branched or unbranched alkyl groups; most preferably C12 to C24 branched or unbranched alkyl groups, e.g. C12 to C22 branched or unbranched alkyl groups. It may be that 30 Y is a functional group selected from: C35 S( -M- and SO4-M 35 WO 2013/113740 PCT/EP2013/051758 13 wherein RI is selected from C6-C36 unbranched alkyl groups, and M is selected from H and monovalent cations such as Na, K, and NH 4 . 5 [062] In one embodiment, the alkyl polyglucoside derivative is selected from: * Sodium Hydroxypropylsulfonate Decyl-Glucoside Crosspolymer * Sodium Hydroxypropylsulfonate Lauryl-Glucoside Crosspolymer * Sodium Hydroxypropylphosphate Laurylglucoside Crosspolymer * Sodium Bis-Hydroxyethylglycinate Lauryl-Glucosides Crosspolymer 10 * Hydroxypropyltrimethylammmonium Coco glucosides Chloride . Stearyldimethylammoniumhydroxypropyl Lauryl glucosides Chloride. [063] In one such embodiment, the alkyl polyglucoside derivative is selected from: * Sodium Hydroxypropylsulfonate Lauryl-Glucoside Crosspolymer 15 * Sodium Hydroxypropylphosphate Laurylglucoside Crosspolymer * Sodium Bis-Hydroxyethylglycinate Lauryl-Gluco sides Crosspolymer . Stearyldimethylammoniumhydroxypropyl Lauryl glucosides Chloride. [064] In one such embodiment, the alkyl polyglucoside derivative is selected from: 20 * Sodium Hydroxypropylsulfonate Lauryl-Glucoside Crosspolymer . Stearyldimethylammoniumhydroxypropyl Lauryl glucosides Chloride. [065] When the corrosion inhibiting surfactant comprises a derivative of a terpene alkoxylate, the (or each) surfactant may suitably be an ester or ether of a terpene alkoxylate, provided that 25 it is not a sulfosuccinate mono-ester or di-ester. [066] The ester may, in one embodiment, be a phosphate ester or a sulfate ester or a carbonate ester or a carboxylate ester. 30 [067] The ether may, in one embodiment, be of formula -O-Rm-R, wherein Rm is a C1-20 hydrocarbon divalent linking group and R, is a carboxylate or amide group. [068] Rm may optionally be substituted and may be branched or unbranched. Optional substituent groups which may replace one or more hydrogens in the hydrocarbon include 35 hydroxy, amino, amido, nitro and alkoxy. Optional substituent groups which may replace one WO 2013/113740 PCT/EP2013/051758 14 or more carbons in the hydrocarbon include 0, N and S. Rm may suitably be a C1-20 alkylene or C2-20 alkenylene group, or C1-20 alkoxyene group; e.g. a C1-C12 or a C1-C8 alkylene or alkoxyene; more preferably a C2, C3, C4, C5 or C6 alkylene or alkoxyene group; most preferably a C2, C3, or C4 alkylene or alkoxyene group. 5 [069] R, is a carboxylate or amide group and is therefore suitably of formula -CO 2 Rp or -C(=O)NHRp or -C(=O)N(Rp) 2 where Rp is selected from C1-C36 hydrocarbon groups (e.g. alkyl or alkenyl) that may optionally be substituted and that may be branched or unbranched. When there is more than one Rp these may be the same or different. Optional substituent 10 groups which may replace one or more hydrogens in the hydrocarbon include hydroxy, amino, amido, carboxy, nitro and alkoxy. Optional substituent groups which may replace one or more carbons in the hydrocarbon include 0, N and S. [070] In one embodiment, Rp is selected from C1-C36 branched or unbranched alkyl groups 15 that may optionally be substituted, more especially C6-C36 unbranched alkyl groups and most especially C10-C36 unbranched alkyl groups (e.g. C12-C30 unbranched alkyl groups). [071] The terpene alkoxylate derivative used as a corrosion inhibiting surfactant in the present invention may be of formula (III): 20 Rx-Z (III) wherein Rx is selected from: (a) R'-(O-C 2
    H
    4 )x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or (b) R'-(O-C 3
    H
    6 )x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or 25 (c) R'-(O-C 4 Hg)x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or (d) R'-(O-CyH 2 y)x' (0-C 2
    H
    4 )x" -, where R' is a C8-C30 terpene group, y is 3 or 4, x' is an integer from I to 50, and x" is an integer from I to 50, and wherein Z is an ester group (e.g. a phosphate ester group or a sulfate ester group or a carbonate ester group or a carboxylate ester group) or an ether group, provided that it is not a 30 sulfosuccinate mono-ester or di-ester. [072] Z may, in one embodiment, be an ether of formula -O-Rm-Rn, as defined above. [073] In one preferred embodiment, Z is an ester group (e.g. a phosphate ester group or a 35 sulfate ester group or a carbonate ester group or a carboxylate ester group).
    WO 2013/113740 PCT/EP2013/051758 15 [074] Z may be of formula (IV-a): 0 II -0- P -OR I OR " (IV-a) where R m is selected from H and C1-C30 branched or unbranched alkyl and C2-C30 branched 5 or unbranched alkenyl groups, which may optionally be substituted, and R" is selected from H, RX and C1-C30 branched or unbranched alkyl and C2-C30 branched or unbranched alkenyl groups, which may optionally be substituted, wherein optional substituent groups (which may replace one or more hydrogens) include hydroxy, amino, nitro, halo and alkoxy. 10 [075] Z may be of formula (IV-b): 0 II -O-S -ORm II (IV-b) where R m is selected from H and C1-C30 branched or unbranched alkyl and C2-C30 branched 15 or unbranched alkenyl groups, which may optionally be substituted, wherein optional substituent groups (which may replace one or more hydrogens) include hydroxy, amino, nitro, halo and alkoxy. [076] Z may be of formula (IV-c):
    O-R
    m O= 0 20 (IV-c) where R m is selected from H and C1-C30 branched or unbranched alkyl and C2-C30 branched or unbranched alkenyl groups, which may optionally be substituted, WO 2013/113740 PCT/EP2013/051758 16 wherein optional substituent groups (which may replace one or more hydrogens) include hydroxy, amino, nitro, halo and alkoxy. [077] Z may be of formula (IV-d): 5 0 R C (IV-d) where R m is selected from H and C1-C30 branched or unbranched alkyl and C2-C30 branched or unbranched alkenyl groups, which may optionally be substituted, wherein optional substituent groups (which may replace one or more hydrogens) include 10 hydroxy, amino, nitro, halo and alkoxy, provided that Z is not a sulfosuccinate mono-ester or di-ester. [078] Preferably, if Z is of formula (IV-d), then if R m is substituted the substituent groups are not carboxy or sulfonate groups. 15 [079] Preferably, if Z is of formula (IV-d), then if R m is substituted this is only with groups selected from hydroxy, amino, amido, nitro, halo, alkoxy, ether or ester. [080] More preferably, if Z is of formula (IV-d), then if R m is substituted this is only with 20 groups selected from hydroxy, amino, nitro, halo and alkoxy. [081] In one embodiment, which may apply to any of the above options (IV-a) to (IV-d), any alkyl or alkenyl groups present in the group Z are selected from C1-C24 branched or unbranched alkyl and C2-C24 branched or unbranched alkenyl groups, which may optionally 25 be substituted; preferably they are selected from C1-C18 branched or unbranched alkyl and C2 C18 branched or unbranched alkenyl groups, which may optionally be substituted; most preferably they are selected from C1-C12 branched or unbranched alkyl and C2-C12 branched or unbranched alkenyl groups, which may optionally be substituted. 30 [082] In one embodiment, which may apply to any of the above options (IV-a) to (IV-d), R m is H.
    WO 2013/113740 PCT/EP2013/051758 17 [083] In one embodiment, option (IV-a) applies and R is H or R'. [084] The terpene alkoxylate from which the surfactant can be derived preferably has an HLB 5 of less than 10, e.g. from 0 to 7, more preferably 5 or less, e.g. from 1 to 5, such as from 2 to 4 or from 3 to 5 or from 3 to 4. [085] The degree of alkoxylation for the terpene alkoxylate is suitably from 1 to 50, such as from 1 to 40, from 1 to 30, from 1 to 24, from 1 to 20, or from 1 to 12. The alkoxylating 10 groups may suitably be selected from C1-C4 alkoxy group, such as ethoxy, propoxy or butoxy, or combinations thereof. For example, the invention envisages, inter alia, ethoxylation, propoxylation, butoxylation, and block alkoxylation with (EO)(PO), (EO)(BO), (PO)(EO) and (BO)(EO). 15 [086] In one embodiment, the (or each) surfactant is derived from an ethoxylated terpene group, a propoxylated terpene group, a butoxylated terpene group, an (EO)(PO), (EO)(BO), (PO)(EO) or (BO)(EO) block alkoxylated terpene group. [087] In one preferred embodiment, the (or each) surfactant is derived from an ethoxylated 20 C8-30 terpene group, a propoxylated C8-30 terpene group, a butoxylated C8-30 terpene group, an (EO)(PO), (EO)(BO), (PO)(EO) or (BO)(EO) block alkoxylated C8-30 terpene group. [088] In one preferred embodiment, the (or each) surfactant is derived from an ethoxylated C8-22 terpene group, a propoxylated C8-22 terpene group, a butoxylated C8-22 terpene group, 25 an (EO)(PO), (EO)(BO), (PO)(EO) or (BO)(EO) block alkoxylated C8-22 terpene group. [089] The skilled reader will also understand that alkoxylated terpenes are generally present as mixtures where there are varying numbers of alkoxylation. Thus, when referring to these alkoxylated products, the degree of alkoxylation is the average (mean) degree of alkoxylation 30 of the mixture. [090] As the skilled reader will appreciate, for the options a, b and c for the product of formula (III), the value of x is the degree of alkoxylation, whilst for option d the combined value of x' and x" is the degree of alkoxylation. Preferably, x, x' and x" are each 35 independently from 1 to 30, more preferably from 1 to 20, such as from 1 to 15, e.g. from 1 to 12. In one embodiment, therefore, x, x' and x'' are each independently 1, 2, 3, 4, 5, 6, 7, 8, 9, WO 2013/113740 PCT/EP2013/051758 18 10, 11 or 12. It may be that x, x' and x" are each independently from I to 6 or alternatively it may be that x, x' and x" are each independently from 7 to 12. [091] As the skilled reader will appreciate, the degree of alkoxylation can be measured by 5 known techniques such as gel permeation chromatography. [092] In one embodiment, the surfactant is derived from an ethoxylated terpene, a propoxylated terpene or a butoxylated terpene, and the degree of alkoxylation is from 1 to 30, more preferably from 1 to 20, such as from 1 to 15, e.g. from 1 to 12 and most preferably from 10 1 to 10. In one embodiment, therefore, the degree of alkoxylation is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. [093] In another embodiment, the surfactant is derived from a block alkoxylated terpene, and the degree of alkoxylation from each alkoxylating group is independently from 1 to 20, such as 15 from 1 to 15, e.g. from 1 to 12 and most preferably 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The total degree of alkoxylation may be from 1 to 30, more preferably from 1 to 20, such as from 1 to 15, e.g. from I to 12. [094] The terpene group of the alkoxylated terpene may be a C8 to C30 terpene group. The 20 skilled reader will appreciate that this group is a hydrophobic group. The terpene group may be acyclic or cyclic. [095] In one embodiment, the surfactant is an alkoxylated terpene based on a C8 to C24 terpene group. In one embodiment, the surfactant is an alkoxylated terpene based on a C8 to 25 C22 terpene group. In one embodiment, the terpene is a C9 to C24 terpene group, C9 to C22 terpene group, or C9 to C15 terpene group. [096] In one embodiment the terpene group is a C8 to C22 terpene group, such as a C8 to C20 terpene group; preferably a C8 to C16 terpene group, such as a C9, C1O, C1i, C12, C13, C14 30 or C15 terpene group. [097] In one embodiment the terpene group may comprise a C1O acyclic, monocyclic or bicyclic terpene radical (e.g. geraniol, limonene, terpineol, linalool, pinene, carene, sabinene, camphene or thujene); a C15 acyclic, monocyclic, bicyclic or tricyclic terpenene radical (e.g. 35 farnesene, farnesol, zingiberene, humulene, caryophyllene, vetivazulene, guaiazulene, longifolene, copaene or patchoulol), or a C20 acyclic, monocyclic, bicyclic, tricyclic or WO 2013/113740 PCT/EP2013/051758 19 tetracyclic terpene radical (e.g. cafestol, kahweol, cembrene, sclareol, lagochilin, labdane, stemarene, steviol, or taxadiene). [098] The terpene group may, in one embodiment, comprise a C8-C15 monocyclic or bicyclic 5 terpene radical, which may optionally further comprise a C1-20 hydrocarbon divalent linking group, which links the cyclic radical to the alkoxylating groups. This C1-20 hydrocarbon divalent linking group may suitably be a C1-20 alkylene, C2-20 alkenylene, or C1-20 alkoxyene group, for example a C1-12 alkylene, C2-12 alkenylene, or C1-12 alkoxyene group, such as a C2-10 alkylene, C2-10 alkenylene, or C2-10 alkoxyene group; preferably a C2-8 10 alkylene, C2-8 alkenylene, or C2-8 alkoxyene group; more preferably a C2, C3, C4, C5 or C6 alkylene or alkoxyene group; most preferably a C2, C3, or C4 alkylene or alkoxyene group. [099] In one embodiment the terpene group comprises a bicyclo[a,b,c,]heptenyl or bicyclo[a,b,c]heptyl radical, wherein a+b+c=5 and a=2, 3, or 4; b=2 or 1; and c=0 or 1. The 15 terpene group in this embodiment may further comprise a C1-20 hydrocarbon divalent linking group, which links the cyclic radical to the alkoxylating groups. This C1-20 hydrocarbon divalent linking group may suitably be a C1-20 alkylene, C2-20 alkenylene, or C1-20 alkoxyene group, for example a C1-12 alkylene, C2-12 alkenylene, or C1-12 alkoxyene group, such as a C2-10 alkylene, C2-10 alkenylene, or C2-10 alkoxyene group; preferably a C2-8 20 alkylene, C2-8 alkenylene, or C2-8 alkoxyene group; more preferably a C2, C3, C4, C5 or C6 alkylene or alkoxyene group; most preferably a C2, C3, or C4 alkylene or alkoxyene group. [0100] Thus the terpene group may, for example, be of formula Z-Y- in which Z represents a bicyclo[a,b,c,]heptenyl or bicyclo[a,b,c]heptyl radical, wherein a+b+c=5 and a=2, 3, or 4; b=2 25 or 1; and c=0 or 1; and Y represents -CH 2
    -C(R
    20 )(R 2 1)- or -O-CH(R 22
    )-CH(R
    2 1 )-, wherein R 2 0 , R , R 2 2 , and R2, which may be identical or different, represent hydrogen or a C1-8 (preferably 20 21 223 C1-6 or C1-5) alkyl. Preferably, R , R , R , and R , which may be identical or different, represent hydrogen or a C1, C2, C3 or C4 alkyl. Most preferably R 2 0 , R ', R , and R , which may be identical or different, represent hydrogen or a Cl or C2 alkyl. 30 [0101] In one embodiment, the surfactant is derived from a block alkoxylated terpene, and that alkoxylated terpene is of the following formula: Z-Y-[OCH(R )-CH(R 2 5 )]n-[OCH 2
    CH
    2 ]m 35 WO 2013/113740 PCT/EP2013/051758 20 in which Z represents a bicyclo[a,b,c,]heptenyl or bicyclo[a,b,c]heptyl radical, wherein a+b+c=5 and a=2, 3, or 4; b=2 or 1; and c=0 or 1; Y represents CH 2
    -C(R
    2 0 )(R 2 1)- or -0 CH(R )-CH(R 2 1 )-, wherein R 20, R , R , and R 2 , which may be identical or different, represent hydrogen or a C1-8 (preferably C1-6 or C1-4, more preferably Cl or C2) alkyl; R 24 5 and R , which may be identical or different, represent hydrogen or a Cl or C2 alkyl, provided that at least one of the radicals R 2 4 and R 25 is not hydrogen and provided that the total number of carbon atoms in the radicals R 2 4 and R 25 is 1 or 2; n is an integer from 0 to 20; and m is an integer from I to 50. The HLB of the alkoxylated terpene is preferably less than 10, such as 5 or less; preferably from 1 to 5 and more preferably from 3 to 5 10 [0102] This type of terpene product is, for example, described in US Patent Publication No: 2006/0135683 and in WO 2009/023724. [0103] In one such embodiment, Z represents a bicyclo[a,b,c,]heptenyl or bicyclo[a,b,c]heptyl 15 radical, wherein a+b+c=5 and a=2, 3, or 4; b=2 or 1; and c=0 or 1; Y represents -CH 2
    -CH
    2 - or O-CH 2
    -CH
    2 -; R 2 4 and R 25 , which may be identical or different, represent hydrogen, CH 3 or
    C
    2
    H
    5 , provided that at least one of the radicals R 24 and R 25 is not hydrogen and provided that the total number of carbon atoms in the radicals R 2 4 and R 25 is 1 or 2; n is an integer from 1 to 20; and m is an integer from 1 to 20. 20 [0104] Preferably, in this embodiment the alkoxylated terpene is of the following formula: wherein RS is CH 3 or C 2
    H
    5 , n is an integer from 1 to 20 and m is an integer from 1 to 30. Most preferably, RS is CH 3 , n is an integer from 1 to 20 and m is an integer from 1 to 20. For 25 example, it may be that RS is CH 3 , n is an integer from I to 10 and m is an integer from 1 to 10. [0105] Accordingly, in one embodiment it is preferred that the terpene is 6,6 dimethylbicyclo[3.1.1]hept-2-ene-2-ethanol (CAS No: 128-50-7).
    WO 2013/113740 PCT/EP2013/051758 21 [0106] In this embodiment, therefore the surfactant is derived from a block alkoxylated (PO)(EO) terpene based on 6,6-dimethylbicyclo[3.1.1]hept-2-ene-2-ethanol (CAS No: 128-50 7). The number of propoxy groups is preferably from 1 to 20 (e.g. from 1 to 10) and the number of ethoxy groups is preferably from 1 to 20 (e.g. from 1 to 10). The HLB of the 5 alkoxylated terpene is preferably less than 10, such as 5 or less; preferably from 1 to 5 and more preferably from 3 to 5. [0107] In one embodiment, the terpene alkoxylate derivative is based on the following alkoxylated terpene:
    H
    3 C CH 3 CH 10 and the derivative is an ester thereof, e.g. a phosphate ester or a sulfate ester or a carbonate ester or a carboxylate ester. It may suitably be any of the options for Z defined above. In particular, it may be a phosphate ester in accordance with formula (IV-a) above. 15 [0108] The surfactants used in the invention can be prepared using conventional methods. [0109] The synthesis of these functionalised APGs is described in US 6,627,612 and US 7,507,399. An example of synthesising a hydroxypropyl sulfonate co-polymer APG is set out in Figure 1. 20 [0110] A phosphate ester derivative of a terpene alkoxylate can be made by the reaction of the terpene alkoxylate with polyphosphoric acid. The use of a 3:1 molar ratio will predominantly obtain the monoester product. The reaction is carried out at 50 - 70 0 C, with the polyphosphoric acid being added slowly to avoid excessive temperature rises and thermal 25 degradation of the terpene alkoxylate. The viscosity of the reaction product may be adjusted using a suitable solvent, e.g. ethylene glycol. The preferred purity of the polyphosphoric acid is 95 - 118%, expressed as the apparent H 3
    PO
    4 content. [0111] A reaction scheme for obtaining a phosphate ester functionalised terpene alkoxylate is 30 shown in Figure 2.
    WO 2013/113740 PCT/EP2013/051758 22 [0112] The skilled reader will appreciate that the starting raw materials for these syntheses are readily available. Additionally, many of the surfactants of the invention are commercially available and reaction chemistries are well known, as well as manufacturing routes being described in text books on surfactants. Synthesis of alkyl polyglucosides is well known and can 5 be found in any text book covering such surfactants, e.g. Alkyl Polyglucosides: Technology, Properties and Applications, eds K Hill, W von Rybinski and G Stoll (Wiley, (1996)). [0113] The amount of surfactant used may be any suitable amount to reduce or inhibit corrosion of the metal component. In one embodiment it may be used at a level of 1ppm or 10 more with respect to the aqueous fluid, such as from 1ppm to 1000ppm, e.g. from 1ppm to 500ppm. It may be that the amount of surfactant is from 2 to 200ppm, such as from 3 to 150pmm or from 4 to 100ppm. In one embodiment, the amount of surfactant is from 5 to 50ppm, such as from 10 to 40ppm or from 15 to 30ppm. 15 [0114] The surfactant may be used in the same manner as a conventional corrosion inhibitor. [0115] The surfactant may suitably be used to inhibit corrosion of a metal component in an industrial aqueous system, where the metal component is (or will be) in contact with an aqueous fluid. 20 [0116] The industrial aqueous system may, in one embodiment, be an aqueous system in a hydrocarbon plant; this may be a plant for exploration, recovery, refining or distribution of hydrocarbon. For example, the aqueous system may be an oil or gas plant. In one such embodiment the aqueous system is an oilfield system, such as an oilfield production system or 25 an oilfield distribution system. In another such embodiment the aqueous system is a downstream oil-related system, such as an oil refining system. Preferred industrial aqueous systems may be aqueous systems in topside oilfield locations. [0117] The industrial aqueous system may in an alternative embodiment be an aqueous system 30 in a chemical plant, e.g. a chemical manufacturing, processing or distribution plant. [0118] The industrial aqueous system may in another alternative embodiment be a water plant, e.g. an industrial water treatment or distribution system. 35 [0119] The industrial aqueous system may in another alternative embodiment be a paper manufacturing plant.
    WO 2013/113740 PCT/EP2013/051758 23 [0120] In one embodiment, the aqueous fluid is at a temperature of 100 0 C or less, such as 90 0 C or less, e.g. 80 0 C or less, or 70 0 C or less, or 60 0 C or less. 5 [0121] The aqueous fluid may be flowing or may be stationery. Thus the aqueous fluid may, for example, be in a pipe or other conduit or may be in a tank or other storage container. [0122] The metal component may therefore be a pipe or other conduit or may be a tank or other storage container. 10 [0123] The aqueous fluid may be acidic, neutral or basic. In one embodiment the aqueous fluid has, or will have, acidic conditions, i.e. a pH of less than 7. [0124] In one embodiment, the aqueous fluid comprises water and further comprises, or will 15 further comprise, one or more acidifying compounds, such as carbon dioxide or hydrogen sulphide. [0125] In one embodiment, the aqueous fluid comprises water and a hydrocarbon, such as oil, and further comprises, or will further comprise, one or more acidifying compounds, such as 20 carbon dioxide or hydrogen sulphide. [0126] The metal component may comprise any metal that is prone to corrode following a time of exposure to an aqueous fluid, especially an acidic aqueous fluid. It may comprise a metal alloy or a single metal. The metal component may in particular comprise ferrous materials (e.g. 25 steel), copper, and/or aluminium. [0127] In one embodiment the metal component comprises steel, such as mild steel, carbon steel, stainless steel (including precipitation-hardened stainless steel), chrome steel, duplex steel, martensitic alloy steel, ferritic alloy steel, austenitic stainless steel, or high nickel 30 content steel. [0128] The surfactant may be applied to the metal component and/or may be added to the aqueous fluid. In one embodiment the surfactant is added to the aqueous fluid.
    WO 2013/113740 PCT/EP2013/051758 24 [0129] The surfactant may be applied to the metal component before the metal component is in contact with the aqueous fluid and/or may be applied once the metal component is in contact with the aqueous fluid. 5 [0130] The surfactant may be added to the aqueous fluid before the aqueous fluid is in contact with the metal component and/or may be added to the aqueous fluid once the aqueous fluid is in contact with the metal component. [0131] The surfactant may be used with one or more additional components. These additional 10 components may have been pre-mixed with the surfactant, or may be added simultaneously with the surfactant, or sequentially with the surfactant, or separately from the surfactant. They may be added before the surfactant or after the surfactant. [0132] The additional components may, for example, be selected from: corrosion inhibitors 15 that are not the surfactants of the invention; additional surfactants; solvents; demulsifiers; antifoam agents; scale inhibitors; dispersants; and biocides. [0133] When a corrosion inhibitor that is not the surfactant of the invention is used as an additional component, that additional corrosion inhibitor may be selected from non-ionic, 20 anionic, cationic and amphoteric corrosion inhibitors. It may, for example, be selected from: sodium tripolyphosphate, sodium ethylenediamine tetracetate, sodium nitrilo triacetate, tetra potassium pyrophosphate, acetodiphosphonic acid and its salts, ammonium trismethylene phosphonic acid and its salts, ethylenediamine tetrakis (methylene phosphonic) acid and its salts, diethylenetriamine pentakis (methylene phosphonic) acid, hexamethylenediamine tetrakis 25 (methylene phosphonic) acid, bishexamethylenetriamine pentakis (methylene phosphonic) acid, and ethanolamine bis(methylenephosphonic) acid and its salts. [0134] In one embodiment, the additional corrosion inhibitor is an amphoteric corrosion inhibitor, such as an inhibitor selected from alkylamidopropyl betaines, alkylamidopropyl 30 sultaines, alkyl ampho(di)acetates, and alkyl amphohydroxypropyl sulfonates and propionates, which may be based on lauric acid, coconut oil, palm oil, oleic acid, castor oil, tall oil or ricinoleic acid. [0135] In one embodiment, the additional corrosion inhibitor is a non-ionic corrosion 35 inhibitor, such as an inhibitor selected from fatty diamine derivatives of oleic or tall oil fatty acids, and fatty acid alkanolamides such as monoisopropyl oleamide.
    WO 2013/113740 PCT/EP2013/051758 25 [0136] In one embodiment, the additional corrosion inhibitor is an anionic corrosion inhibitor, such as an inhibitor selected from alkyl and alkyl ether phosphate esters, acyl sarcosinates, taurides and alkyl ether carboxylic acids. 5 [0137] In one embodiment, the additional corrosion inhibitor is a cationic corrosion inhibitor, such as an inhibitor selected from quaternary ammonium salts, such as alkyl trimethyl ammonium halides or benzalkonium derivatives, fatty amines, amidoamines (including alkylamidopropyl amines and imidazolines). For example, it may be an alkyl hydroxyethyl or 10 alkyl aminoethyl derivative of oleic or tall oil fatty acids. [0138] When an additional surfactant is used as well as the corrosion inhibiting surfactant of the invention, the additional surfactant may be a cationic surfactant (for example it may be selected from benzalkonium salts, C10-20 alkyl trimethyl ammonium salts, and C10-20 alkyl 15 trimethyl or tris (hydroxymethyl) phosphonium salts). [0139] Alternatively, the additional surfactant may be anionic (for example it may be selected from C10-20 alkyl benzene sulphonates, C10-20 olefin sulphonates, C10-20 alkyl sulfates, C10-20 alkyl 1 to 25 mole ether sulfates, C10-20 paraffin sulphonates, C10-20 alkyl phenol 20 sulfates, lignin sulphonates, fatty ester sulphonates, C10-20 alkyl phenol ether sulfates, C10-20 alkyl ethanolamide sulfates, and C10-20 alpha sulphofatty acid salts). [0140] The additional surfactant might also be amphoteric (for example it may be selected from betaines, sulphobetaines, and quaternized imidazoline). 25 [0141] The additional surfactant might alternatively be non-ionic (for example it may be selected from ethoxylated fatty acids, ethoxyl/propyleneoxy block copolymers, ethoxylated fatty amines, mono- and di-alkanolamides, amine oxides and C 10-20 acyl sorbitan and glyceryl ethoxylates). 30 [0142] When a solvent is used as an additional component, the solvent may be aqueous or may be organic. The solvent may be any suitable solvent that is compatible with the aqueous fluid. Examples of solvents include water, dimethyl sulfoxide (DMSO), alkylene glycols, glycol ethers, and tetrahydrofuran (THF). 35 WO 2013/113740 PCT/EP2013/051758 26 [0143] A demulsifier may, in particular, be beneficial as an additional component when the surfactant is being used in oilfield applications. Examples of demulsifers include phenol formaldehyde resins; polyamines; di-epoxides; and polyols. 5 [0144] When an antifoam agent is used as an additional component, the antifoam agents that may be considered include silicone defoamers and acetylenic diols. [0145] When a scale inhibitor is used as an additional component, the scale inhibitor may, for example, be selected from polyacrylates; polymaleates; polysulfonates; phosphonates; and 10 bisphosphonates [0146] When a dispersant is used as an additional component, the dispersant may, for example, be selected from polymaleic acids, polyacrylic acids and polyvinylsulphonic acids. 15 [0147] When a biocide is used as an additional component, the biocide may, for example, be a quaternary ammonium or phosphonium compound, such as an ADBAC quaternary ammonium compound, or a tetrakis (hydroxymethyl) phosphonium salt, or formaldehyde glutaraldehyde. [0148] The corrosion inhibitor formulation of the third aspect may be used in the inventions of 20 the first or second aspect. Alternatively, the inventions of the first and second aspect may add or apply the surfactant of the invention and any additional corrosion inhibitors separately. Alternatively, the inventions of the first and second aspect may use only the surfactants of the invention as the corrosion inhibitor. 25 [0149] The corrosion inhibitor formulation of the third aspect may comprise the corrosion inhibiting surfactant of the invention together with a corrosion inhibitor that is not a corrosion inhibiting surfactant according to the invention, wherein this corrosion inhibitor is selected from non-ionic, anionic, cationic and amphoteric corrosion inhibitors. 30 [0150] The corrosion inhibitor formulation may in one embodiment comprise from 10 to 99wt% corrosion inhibiting surfactant, such as from 50 to 95wt% corrosion inhibiting surfactant. The corrosion inhibitor formulation may in one embodiment comprise from 1 to 90wt% of corrosion inhibitor that is not the corrosion inhibiting surfactant, such as from 5 to 50wt% of corrosion inhibitor that is not the corrosion inhibiting surfactant. 35 WO 2013/113740 PCT/EP2013/051758 27 [0151] The formulation may further include additional components, which may for example be selected from: surfactants; solvents; demulsifiers; antifoam agents; scale inhibitors, dispersants, and biocides. These components are discussed in more detail above. 5 [0152] The invention will now be further described, in a non-limiting manner, with reference to the following Examples. Examples 10 Example 1 - Linear polarisation resistance (LPR) test A modified version of the bubble test was used to compare the corrosion inhibition performance of various corrosion inhibiting surfactants according to the invention with the industry standard corrosion inhibitor, tall oil aminoethyl imidazole, under oilfield conditions. 15 The products tested were as set out in Table 1 below: Acti ity Product Chemical name PolySugaNate looP (from Sodium hydroxypropyl sulfonate Decyl glucose 40.5 Colonial Chemicals) crosspolymer PolySugaNate 160P (from Sodium hydroxypropyl sulfonate Lauryl glucose 38.6 Colonial Chemicals) crosspolymer PolySugaPhos 1200P (from Poly sodium Lauryl glucoside hydroxypropyl 40.1 Colonial Chemicals) phosphate PolySugaBetaine L (from Lauryl Glucoside Betaine crosspolymer 40 Colonial Chemicals) PolySugaQuat TM8610P Hydroxypropyltrimonium Coco glucosides 41.8 (from Colonial Chemicals) Chloride PolySugaQuat S-1210P Stearyldimoniumhydroxypropyl Lauryl 30 (from Colonial Chemicals) glucosides Chloride Rhodoline HP Half ester Terpene alkoxylate half ester sulfosuccinate (based on block alkoxylated (EO)(PO) C9 Sulfosuccinate (from 35 terpene, where the terpene alkoxylate has an Rhodia Novecare) HLB in the range of from 3 to 5) WO 2013/113740 PCT/EP2013/051758 28 Terpene alkoxylate phosphate ester (based on Rhodoner Hm Phohae block alkoxylated (EO)(PO) C9 terpene, where Ester (from Rhodia 99.7 Novecare) the terpene alkoxylate has an HLB in the range of from 3 to 5) Mackterra TDI Tall oil aminoethyl imidazoline (industry 100 standard) Table 1: Products tested The alkoxylated terpene used in the terpene-based products is shown below: 5
    H
    3 C CH 3 CH 10 Method * Each cell was charged with the desired weight of brine (5% NaCl solution) and oil (C11-15 isoparaffin fluid Isopar M). 15 * Every cell had a stirring bar, auxiliary electrode, reference electrode, gas sparge tube, and glass periscope inserted. * The cells were placed in a water bath set at 60 0 C and set to stir at approximately 300rpm. * Each cell was connected to a constant sparge of CO 2 and then left for 1 hour to reach 20 equilibrium. * C1018 mild steel coupons were washed with xylene and acetone and allowed to dry to ensure the surfaces were free from oils / grease. * After the cells reached equilibrium, the mild steel coupons were connected to the working electrodes and inserted into each cell using the glass periscopes (to avoid getting the 25 electrode oil wet). * The LPR run was started and baseline corrosion data was collected for approximately 2.5 hours. * During this time 20000ppm w/w active stock solutions of the surfactants and the tall oil aminoethyl imidazole were made up. The tall oil aminoethyl imidazole was made up in 30 isoparaffin fluid IsoparTM M, because it is not water soluble. The alkyl polygluconate WO 2013/113740 PCT/EP2013/051758 29 surfactants were made up in a 5% NaCl brine. The terpene alkoxylated surfactants were made up in methanol. * After the baseline corrosion data was collected the stock solutions were injected into the cells at a concentration of 20ppm actives and the corrosion rate in each cell was recorded for a 5 further 12.5 hours. * Corrosion efficiency was also calculated as: [Baseline corrosion - corrosion at 15 hours] x 100 Baseline corrosion 10 where baseline corrosion was calculated by taking the average corrosion rate of each cell before the corrosion inhibitors were introduced. A summary of the conditions for the LPR test is shown in Table 2. 15 Condition Description Brine 5% NaCl Oil phase Isopar M Brine Oil Ratio 9:1 Temperature 60 0 C Gas Sparge Constant CO 2 Stirring speed ~300rpm Working electrode Mild Steel C1018 Reference electrode Ag/AgC1 (saturated in KCl) Auxiliary electrode Platinum Inhibitor Concentration 20ppm actives Test period 15 hours Table 2: Tabulated LPR Conditions Results and discussion 20 The results are shown in Figures 3-6 (corrosion rate) and Figure 7 (corrosion efficiency). In Figure 3 it can be seen that both Sodium hydroxypropyl sulfonate Decyl glucose crosspolymer and Sodium hydroxypropyl sulfonate Lauryl glucose crosspolymer reduce the observed corrosion rates under oilfield conditions. Sodium hydroxypropyl sulfonate Lauryl WO 2013/113740 PCT/EP2013/051758 30 glucose crosspolymer acts to form a protective film around the working electrode quicker than the industry standard (tall oil aminoethyl imidazole). In Figure 4 it can be seen that Poly sodium Lauryl glucoside hydroxypropyl phosphate reduces 5 the observed corrosion rates under oilfield conditions. In Figure 5 it can be seen that Lauryl Glucoside Betaine crosspolymer, Hydroxypropyltrimonium Coco glucosides Chloride and Stearyldimoniumhydroxypropyl Lauryl glucosides Chloride reduce the observed corrosion rates under oilfield conditions. 10 Stearyldimoniumhydroxypropyl Lauryl glucosides Chloride acts to form a protective film around the working electrode quicker than the industry standard (tall oil aminoethyl imidazole). In Figure 6 it can be seen that the terpene alkoxylate phosphate ester reduces the observed 15 corrosion rates under oilfield conditions. This acts to form a protective film around the working electrode quicker than the industry standard (tall oil aminoethyl imidazole). The half ester sulfosuccinate is also effective (but is not claimed in the present application). Figure 7 shows that various surfactants in accordance with the invention have good corrosion 20 efficiencies. The sodium hydroxypropyl sulfonate lauryl glucose crosspolymer, the stearyldimoniumhydroxypropyl lauryl glucosides chloride, and the terpene alkoxylate phosphate ester can all be seen to significantly reduce the corrosion rate and these have a performance very similar to the industry standard (tall oil aminoethyl imidazoline). 25 The effects for the poly sodium lauryl glucoside hydroxypropyl phosphate are still good and a larger molecular weight will reduce bioaccumulation. Therefore in at least some situations the advantage of non-bioaccumulation would be considered to outweigh the slight reduction in effectiveness as a corrosion inhibitor. 30 Conclusion These examples show that a range of surfactants which are derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates exhibit corrosion inhibition properties for metal in an aqueous environment.
    权利要求:
    Claims (26)
    [1] 1. The use of a surfactant as a corrosion inhibitor, wherein the surfactant is selected from derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, and mixtures 5 thereof, provided that the derivatives are not sulfosuccinates.
    [2] 2. The use of claim 1, wherein the surfactant is used to inhibit the corrosion of a metal component, that is, or will be, in contact with an aqueous fluid, in order to prevent or reduce corrosion of the metal component. 10
    [3] 3. A method of preventing or reducing corrosion of a metal component that is in contact with, or will be in contact with, an aqueous fluid, wherein the method comprises: - providing a surfactant; and - applying the surfactant to the metal component or adding the surfactant to the 15 aqueous fluid that is in contact with, or will be in contact with, the metal component wherein the surfactant is selected from derivatives of alkyl polyglucosides and derivatives of terpene alkoxylates, and mixtures thereof, provided that the derivatives are not sulfosuccinates. 20
    [4] 4. The use or method of any of claims 1 to 3 wherein the surfactant is selected from: (a) reaction products of an alkyl polyglucoside with a cross linking agent and a functionalising agent; and (b) terpene alkoxylate esters or ethers; and (c) mixtures of (a) and (b).
    [5] 5. The use or method of claim 4, option (a) or (c), wherein the crosslinking agent is of 25 formula X-Ra-X, where each X, which may be the same or different, is a halogen and Ra is a C2-C18 hydrocarbon group that may optionally be substituted and that may be branched or unbranched.
    [6] 6. The use or method of claim 4, option (a) or (c), or claim 5, wherein the functionalising 30 agent is of formula X-Ra-Y, where X is a halogen, Ra is a C2-C18 hydrocarbon group that may optionally be substituted and that may be branched or unbranched, and Y is selected from quaternary ammonium groups, sulfonate groups, sulfate groups, phosphate groups, and hydroxy groups. WO 2013/113740 PCT/EP2013/051758 32
    [7] 7. The use or method of claim 4, option (a) or (c), or claim 5, or claim 6, wherein the alkyl polyglucoside has a degree of polymerisation of from I to 10.
    [8] 8. The use or method of claim 4, option (a) or (c), or any of claims 5 to 7, wherein the 5 alkyl polyglucoside has an alkyl group that is a C8 to C30 branched or unbranched alkyl group,
    [9] 9. The use or method of claim 8 wherein the alkyl polyglucoside has an alkyl group that is a C12 to C30 branched or unbranched alkyl group. 10
    [10] 10. The use or method of claim 4, option (b) or (c), wherein the terpene alkoxylate ester is selected from phosphate esters, sulfate esters, carbonate esters, and carboxylate esters of terpene alkoxylates. 15
    [11] 11. The use or method of claim 4, option (b) or (c), or claim 10, wherein the terpene group is a C8-C30 terpene group.
    [12] 12. The use or method of claim 4, option (b) or (c), or claim 10, or claim 11, wherein the degree of alkoxylation for the terpene alkoxylate is from 1 to 50. 20
    [13] 13. The use or method of claim 11 or claim 12, wherein the terpene alkoxylate ester is of formula (III): Rx-Z (III) 25 wherein Rx is selected from: (a) R'-(O-C 2 H 4 )x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or (b) R'-(O-C 3 H 6 )x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or (c) R'-(O-C 4 Hg)x -, where R' is a C8-C30 terpene group, and x is an integer from 1 to 50; or (d) R'-(O-CyH 2 y)x' (0-C 2 H 4 )x" -, where R' is a C8-C30 terpene group, y is 3 or 4, x' is an 30 integer from 1 to 50, and x" is an integer from 1 to 50, and wherein Z is a phosphate ester group or a sulfate ester group or a carbonate ester group or a carboxylate ester group.
    [14] 14. The use or method of claim 4, option (b) or (c), or any of claims 11 to 13, wherein the 35 terpene group is a C8-C16 terpene group. WO 2013/113740 PCT/EP2013/051758 33
    [15] 15. The use or method of claim 4, option (b) or (c), or any of claims 11 to 14, wherein the degree of alkoxylation for the terpene alkoxylate is from 1 to 30.
    [16] 16. The use or method of any one of claims 1 to 15 wherein the surfactant is used to 5 inhibit corrosion of a metal component in an industrial aqueous system, wherein the metal component contacts the aqueous fluid within the industrial aqueous system.
    [17] 17. The use or method of claim 16 wherein the industrial aqueous system is an aqueous system in a hydrocarbon plant; a chemical plant; a water plant; or a paper manufacturing 10 plant.
    [18] 18. The use or method of claim 17 wherein the industrial aqueous system is an oilfield system or a downstream oil-related system. 15
    [19] 19. The use or method of claim 18 wherein the industrial aqueous system is an oilfield production system or an oilfield distribution system or an oil refining system.
    [20] 20. The use or method of any one of claims 1 to 19 wherein the aqueous fluid is acidic. 20
    [21] 21. The use or method of any one of claims 1 to 20 wherein the metal component comprises ferrous material, copper, and/or aluminium.
    [22] 22. The use or method of claim 21 wherein the metal component comprises steel. 25
    [23] 23. The use or method of any one of claims 1 to 22 wherein the surfactant is used together with one or more component selected from: corrosion inhibitors that are not surfactants as defined in any one of claims 1 to 15, surfactants that are not as defined in any one of claims 1 to 15; solvents; antifoam agents; demulsifiers; scale inhibitors; dispersants and biocides. 30
    [24] 24. The use or method of any one of claims 1 to 22 wherein the amount of surfactant used is from lppm to 1000ppm.
    [25] 25. A corrosion inhibitor formulation that comprises a surfactant as defined in any one of claims 1 to 15, together with a corrosion inhibitor that is not a surfactant as defined in any 35 one of claims I to 15. WO 2013/113740 PCT/EP2013/051758 34
    [26] 26. The corrosion inhibitor formulation of claim 25 which further comprises one or more component selected from: surfactants; solvents; antifoam agents; demulsifiers; scale inhibitors; dispersants and biocides.
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    同族专利:
    公开号 | 公开日
    EP2809829B1|2022-01-19|
    US10550482B2|2020-02-04|
    BR112014018436B1|2021-02-23|
    US20150010429A1|2015-01-08|
    EP2809829A2|2014-12-10|
    CA2860930C|2016-12-20|
    GB201201542D0|2012-03-14|
    CA2860930A1|2013-08-08|
    GB2506096A|2014-03-26|
    WO2013113740A2|2013-08-08|
    WO2013113740A3|2013-10-03|
    AU2013214288B2|2017-06-29|
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    法律状态:
    2017-10-26| FGA| Letters patent sealed or granted (standard patent)|
    优先权:
    申请号 | 申请日 | 专利标题
    GB1201542.6A|GB2506096A|2012-01-30|2012-01-30|A surfactant as a corrosion inhibitor|
    GB1201542.6||2012-01-30||
    PCT/EP2013/051758|WO2013113740A2|2012-01-30|2013-01-30|Corrosion inhibitors|
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