EP2242728A1

EP2242728A1 - Method of water treatment

Info

Publication number: EP2242728A1
Application number: EP09704743A
Authority: EP
Inventors: Patrick NOTTÉ; Tessa Johnson; Albert Devaux
Original assignee: Dequest AG
Current assignee: Italmatch Chemicals SpA
Priority date: 2008-01-22
Filing date: 2009-01-21
Publication date: 2010-10-27
Also published as: RU2010134907A; EP2082991A1; CN103011428B; CA2712617A1; WO2009092738A1; BRPI0907437A8; BRPI0907437A2; CN101925541A; VN25747A1; RU2494049C2; AU2009207667A1; CN103011428A; AU2014202547B2; AU2009207667B2; WO2009092738A9; MX2010007809A; CN101925541B; AU2014202547A1

Abstract

A method for securing the use of an aqueous medium under any substantial exclusion of metal ion interference is disclosed. A phosphonic acid compound containing: a selected phosphonate moiety and a moiety selected from a limited number of species; or hydrocarbon chains containing aminoalkylene phosphonic acid substituents; or alkylamino alkylene phosphonic acids containing an active moiety embodying N, O, and S. The technology can, by way of illustration, be used in numerous applications including secondary oil recovery, scale inhibition, industrial water treatment, paper pulp bleaching, dispersant treatment, sequestering application, brightness reversion avoidance and paper pulp treatment.

Description

Method of Water Treatment

This invention relates to a method of water treatment to thereby substantially inactivate selected metal ions. In particular, the method comprises adding to an aqueous phase of from 0.1 to 100,000 ppm (part per million) of a phosphonate compound having the formula E - B wherein E is selected from: specific organic moieties, termed T; linear or branched hydrocarbon chain moieties having from 6 to 2.10 carbon atoms; and moieties comprising N, O and S; and B is represented by a specifically defined phosphonate containing moiety.

The technology can be used beneficially in numerous well known applications based on a predominantly aqueous medium wherein metal ions can adversely interfere with the reactants, the medium, catalysts, the end products and the objective of the intended use of the medium. Examples of such treatments are secondary oil recovery, scale inhibition, industrial water treatment, reverse osmosis, paper pulp bleaching, dispersants, sequestrent and brightness reversion avoidance in paper pulp treatment. Examples of controllable metal ions include earth alkali metal ions such as calcium, strontium, barium and magnesium and metal ions such as iron, chromium, manganese, cobalt, nickel and copper.

The domain of effectively controlling the formation of inorganic deposits, in particular inhibiting the formation of undesirable levels of the like deposits, including frequently calcium carbonate and barium sulphate, in water is well known and has been around for a long time. As one can consequen expect, the relevant art is fairly crowded.

WO 01/49756 discloses scale inhibitors comprising a hy soluble copolymer consisting of major amounts of styr sulfonic acid and vinyl sulfonic acid and, optionally, mi levels of non-ionisable monomers. These inhibitor combinati can be used in a squeeze treatment. US 5,112,496 descri compositions and methods for inhibiting oil field sc formation, particularly in high brine environmen Aminomethylene phosphonates containing 2 or more am moieties, wherein substantially all of the available functions have been phosphonated, are suitable for use. 4,080,375 pertains to methylene phosphonates of ami terminated oxyalkylates, having at least two amino groups, the use thereof as scale inhibitors in marine oil recov activities as well as their use for chelation in biologi systems. As an example, the phosphonates can effectiv sequester iron ions within the context of secondary recovery by means of water floods.

US 5,263,539 describes method and composition technol useful for controlling and reducing the occurrence of scale subterranean formations. The inhibitor compositions compr an amino phosphonic acid and a copolymer of an alke sulfonic acid compound and an ethylenically unsatura monomer. The phosphonic acid can be represented bishexamethylene triamine pentamethylene phosphonic acid. Gl 306 465 pertains to a method of scale inhibition for use oil field operations where water can contain h concentrations of alkaline earth metal salts such as bar salts. Preferred scale inhibitors can be represented hydroxyl alkylated phosphonomethyl amines. US 6,022,401 discloses biodegradable corrosion inhibitors anti-sealants for use in oil field fluid systems and ot industrial water applications. The corrosion inhibitors/an sealants are represented by modified poly (aspartic ac polymers and modified aspartic acid units. The modif aspartic acid can be substituted by selected side chains s as methyl phosphonic acids/salts.

EP 0 408 297 describes scale inhibitors suitable inhibiting calcium and barium scale formation in aqua systems in which iron can be present. The inhibitor represented by a methylene phosphonate, prefera carboxybisnitrilo tetra (methylene phosphonic acid) , also kn as urea (tetramethylene phosphonic acid). WO 01/85616 divul a scale- and corrosion-inhibitor for application, inter al in water used in oilfield activities, containing, at lea one oxyalkylene unit and one phosphonate unit. The oxyalkyl can be represented by triethylene glycol or tetraethyl glycol. The phosphonate can be represented by vinyl phospho acid or vinylidene diphosphonic acid. In a preferred approa the phosphonate and the oxyalkylene constituents can reacted to thus yield a single compound for use.

Kulin Huang et al . , Eur. J. Inorg. Chem. 2004, 2956-29 describe the synthesis of functionalized γ-zircon phosphate-phosphonates based on N-phosphonomethyl-L-proline from proline and N-phosphonomethyl-1, 3-thiazolidine carboxylic acid from cysteine. A method for producing phosphonomethylglycine by reaction of hexahydrotriazine w triacyl phosphate is described in WO 2003 000704. Along same lines, DD 141 930 describes the manufacture monophosphonated amino acids or the esters thereof. The am acid moiety can, in the final product, be represented by alanine, β-alanine, phenylalanine and asparagine. The purp of the study was the preparation of monophosphonates hav one residual N-H function.

DE 41 31 912 discloses mixtures of carboxyalkane aminometh phosphonic acids prepared by reacting natural proteins, particular from waste such as e.g. leather, corn and soya, white, skimmed and sugar-free milk powder, wool and s waste, animal hair and other protein wastes. US 5,087, discloses a method of inhibiting the formation of sea forming salts by means of a low level of diphosphonomet derivatives of taurine or cysteic acid.

US 5 414 112 discloses N-bis (phosphonomethyl) amino acids their use to control calcium carbonate scale in contact w industrial process waters. Specific compounds described N, N-bis (phosphonomethyl) -L-glutamic acid, N bis (phosphonomethyl) -L-serine and N, N, N', bis (phosphonomethyl) -L-lysine . The L-lysine compound represented by species carrying one phosphonomethyl moi attached to one amino radical.

WO 2005/061782 describes a method for reducing brightn reversion of mechanical and chemical pulps. In essence, process comprises the sequence of activating the fibres w an oxidizing agent followed by attaching to the oxidized si a modifying agent to block the reactivity of the activa sites. US 5,062,962 discloses a principle of inhibiting sc formation in industrial water systems by introducing into circulating aqueous system a polyepoxy succinic acid. EP 0 304 pertains to a process for the bleaching of chemical p whereby in the final bleaching stage hydrogen peroxide applied in the presence of a stabilizing agent whereby pulp has, preparatory to the hydrogen peroxide treatment, b purified by reducing the manganese content to below 3 ppm.

The art, in essence, aims at adding cumulative functionalit to thus secure additive results without providing remedy known performance deficiencies, such as within the context marine oil recovery activities and/or water treatm applications, and/or avoiding multi component systems wh are known to exhibit material deficiencies which inherently attached to such known active combinations.

It is a major object of this invention to provide a benefic method for scale inhibition capable of effectively limit scale in aqueous environment under a broad range of conditi including temperature, hardness levels and alkalinity. It another object of this invention to provide an effective sc control method thereby substantially using a single act scale inhibitor. Another object of the invention aims providing effective oil scale control without any substant secondary negatives in relation to e.g. the medium application. Still another object of this invention aims providing effective means for water treatment control, another object of this invention concerns a provision of sc control under severe temperature conditions. Still furt objects of this invention aim at providing benefic dispersants, agents for the avoidance of brightness reversi paper pulp bleaching additives and effective sequester agents, in particular in relation to heavy metals.

The term "percent" or "%" as used throughout this applicat stands, unless defined differently, for "percent by weight" "% by weight". The terms "phosphonic acid" and "phosphona are also used interchangeably depending, of course, u medium prevailing alkalinity/acidity conditions, and b terms comprise the free acids, salts and esters of phospho acids. The term "ppm" stands for "parts per million".

The foregoing and other objects of this invention can now met by the provision of a method for securing an aque medium under substantial exclusion of metal ion comprisinς selected phosphonic acid compound. In more detail, technology herein contemplates adding to the water of from to 100000 parts per million (ppm) of a phosphonate compo selected from the group of:

(a) a phosphonate compound of the general formula:

T-B

wherein B is a phosphonate containing moiety having formula :

-X-N(W) (ZPO₃M₂)

wherein X is selected from C2-C50 linear, branched, cyclic aromatic hydrocarbon moiety, optionally substituted by a Ci- linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR' and SR' moieties, wherein R' is a C1-C12 line branched, cyclic or aromatic hydrocarbon chain; and [A-O] wherein A is a C2-C9 linear, branched, cyclic or aroma hydrocarbon chain and x is an integer from 1 to 200;

Z is a Ci-Cε alkylene chain; M is selected from H, C1-C20 linear, branched, cyclic aromatic hydrocarbon moieties and from alkali, earth alk and ammonium ions and from protonated amines;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V selected from: a C2-C50 linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C1-C12 line branched, cyclic or aromatic groups, which moieties and groups are optionally substituted by OH, COOH, F, OR' or moieties wherein R' is a C1-C12 linear, branched, cyclic aromatic hydrocarbon moiety; and from [A-O]_x-A wherein A i, C2-C9 linear, branched, cyclic or aromatic hydrocarbon moi< and x is an integer from 1 to 200; and

K is ZPO₃M₂ or H and n is an integer from 0 to 200;

and wherein T is a moiety selected from the group of:

(i) MOOC-X-N(U)-;

;ii) MOOC-C (X²) 2-N (U) -;

(iii) MOOC-X-S-;

(iv) [X(HO)_n-(N-U) n J n f

(v) U-N(U)-[X-N(U) n r

(vi) D-S-;

(vii) CN-;

(viii) MOOC-X-O-; ; ix ) MOOC-C ( X² ) 2 -0- ;

( x ) NHR' ' - ; and

( xi ) ( DCO ) ₂ -N- ;

wherein M, Z, W and X are as defined above; U is selected f linear, branched, cyclic or aromatic C1-C12 hydrocar moieties, H and X-N(W) (ZPO₃M₂); X² is independently selec from H, linear, branched, cyclic or aromatic Ci-C₂O hydrocar moieties, optionally substituted by Ci-Ci₂ linear, branch cyclic or aromatic hydrocarbon groups, optionally substitu by OH, COOH, R'O, R' S and/or NH₂ moieties; n' , n" and n' ' ' independently selected from integers of from 1 to 100; D R' ' are independently selected from C1-C50 linear, branch cyclic or aromatic hydrocarbon moieties, optiona substituted by a Ci-Ci₂ linear, branched, cyclic, or aroma group, which moiety and/or which group can be optiona substituted by OH, COOH, F, OR' and SR' moieties, wherein is a Ci-Ci₂ linear, branched, cyclic or aromatic hydrocar moiety; and A' 0-[A-O]_x-A wherein A is a C₂-Cg linear, branch cyclic or aromatic hydrocarbon moiety, x is an integer froi to 200 and A' is selected from C1-C50 linear, branched, eye or aromatic hydrocarbon moiety, optionally substituted by a Ci₂ linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR' and SR' moieties, wherein R' has the meaning gi above; with the further proviso that D can also be represen by H;

(b) linear or branched hydrocarbon compounds having f 6 to 2.1O⁶ carbon atoms containing amino groups substituted alkylene phosphonate substituents, and/or -X-N(W) (ZPO3M2) w respect to the hydrocarbon chain, in either terminal branched positions whereby the molar ratio of aminoalkylene phosphonate substituents to the number of car atoms in the hydrocarbon chain is in the range of from 2 to 1 : 40 whereby at least 30 % of the available functionalities have been converted into the correspond aminoalkylene phosphonate acid; or/and into X-N(W) (ZPO: substituted groups; and wherein the alkylene moiety selected from Ci-β; and X, W, Z and M have the same meaning given above; and

(c) alkylamino alkylene phosphonates having the formula:

Y- [X-N(W) (ZPO₃M₂) ] _s

the structural elements having the following meaning:

X is selected from C2-C50 linear, branched, cyclic or aroma hydrocarbon moieties, optionally substituted by a CV linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR', R²O[A-O]_x- wherein R² is a Ci-C₅₀ linear, branch cyclic or aromatic hydrocarbon moiety, and SR' moieti wherein R' is a C1-C50 linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C1-C12 line branched, cyclic or aromatic hydrocarbon groups, said moiet and/or groups can be optionally substituted by COOH, OH, OR' and SR'; and [A-O]_x-A wherein A is a C₂-C₉ line branched, cyclic or aromatic hydrocarbon moiety and x is integer from 1 to 200;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V selected from: a C2-C50 linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C1-C12 line branched, cyclic or aromatic groups, which moieties and groups can be optionally substituted by OH, COOH, F, 0 R²O[A-O]_x- wherein R² is a C1-C50 linear, branched, cyclic aromatic hydrocarbon moiety, and SR' moieties; and from [A-C A wherein A is a C2-C9 linear, branched, cyclic or aroma hydrocarbon moiety and x is an integer from 1 to 200;

K is ZPO3M2 or H and n is an integer from 0 to 200; and

Y is a moiety selected from NH₂, NHR', N (R') 2, NH, N, OH, 0 S, SH, and S-S wherein R' is as defined above with proviso that when Y is OH or OR' , X is, at least, C₄; and

s is 1 in the event Y stands for NH₂, NHR', N (R') 2, HS, OR', OH; s is 2 in the event Y stands for NH, S or S-S; and s i: in the event Y stands for N.

In one aspect of the method herein, the precursor for Y selected from: NH₃; NH₂R; NH (R') 2; OH^"; HOR; Na₂S; thiourea; Na₂S₂.

In the definition of X, X², D, R', R'', A, U, M and V, the Cy linear or branched hydrocarbon moiety is preferably lin or branched alkane-diyl with a respective chain length. Cyc hydrocarbon moiety is preferably C3-Cio-cycloalkane-di Aromatic hydrocarbon moiety is preferably C6-Ci2-arene-di When the foregoing hydrocarbon moieties are substituted, it preferably with linear or branched alkyl of a respective ch length, C3-Cio-cycloalkyl, or C6-Ci2-aryl . All these groups be further substituted with the groups listed with respective symbols.

More and particularly preferred chain lengths for alk moieties are listed with the specific symbols. A cyclic moi< is more preferred a cyclohexane moiety, in case cyclohexane-diyl in particular a cyclohexane-1, 4-diyl moie An aromatic moiety is preferably phenylene or phenyl, as case may be, for phenylene 1, 4-phenylene is particula preferred.

In preferred embodiments, the individual moieties in phosphonate reaction partner of the (c) component are selec as follows: X is C₂-C₃₀ or [A-O]_x-A; V is C₂-C₃₀ or [A-O]_x wherein for both, X and V are independently selected, A is C₆ and x is 1-100; R² is Ci-C₃₀; Z is Ci-C₃; M is H or Ci-C₆; . n is 1-100. In yet another more preferred embodiment, individual moieties in the phosphonate reaction partner of (c) component are selected as follows: X is C₂-Ci₂ or [A-O]_x V is C₂-Ci₂ or [A-O]_x-A; wherein for both, X and V independently selected, A is C₂-C₄ and x is 1-100; R² is Ci-C Z is Ci; M is H or Ci-C₄; and n is 1-25.

M is selected from H, Ci-C₂₀ linear, branched, cyclic aromatic hydrocarbon moieties and from alkali, earth alk and ammonium ions and from protonated amines.

In more detail, the essential phosphonate compound herein be neutralized, depending upon the degree alkalinity/acidity required by means of conventional age including alkali hydroxides, earth alkali hydroxides, ammo and/or amines. Beneficial amines can be represented by alk dialkyl and tri alkyl amines having e.g. from 1 to 20 car! atoms in the alkyl group, said groups being in straight and branched configuration. Alkanol amines such as ethanol amin< di- and tri-ethanol amines can constitute one preferred cl of neutralizing agents. Cyclic alkyl amines, such cyclohexyl amine and morpholine, polyamines such as 1 ethylene diamine, polyethylene imine and polyalkoxy mono- . poly-amines can also be used.

Preferred species of the reaction partner T in phosphon compounds (a) herein are selected from:

(i) : caprolactam or 6-amino hexanoic acid; 2-pyrrolid or 4-amino butanoic acid; and lauryl lactam or 12-am dodecanoic acid;

(ii) : glutamic acid; methionine; lysine; aspartic ac phenylalanine; glycine; and threonine;

(iv) : 2-ethanol amine; 6-amino hexanol; 4-amino butan di- (2-ethanolamine) ; dipropanolamine; 2- (2-aminoetho ethanol; and 3-propanol amine;

(v) : diaminotoluene; 1, 6-hexamethylene diamine; 1,4-but diamine; and 1,2-ethylene diamine;

(x) : methylamine; ethylamine; propylamine; butylami hexylamine; heptylamine; octylamine; nonylamine; decylami dodecylamine; aniline; and C12-C22 fatty amines including lin and branched species; and (xi) : phthalimide; succinimide; and maleimide.

In another embodiment, preferred species of the react partner T can be selected from the group of (iii) , (v (viii) and (ix) . Specifically preferred examples of reaction partner T can be selected from:

(iii) : thioglycolic acid; and cysteine;

(vi) : methylthiol; ethylthiol; propylthiol; pentylthi hexylthiol; octylthiol; thiophenol; thionaphthol; decylthi and dodecylthiol;

(viii) : 3-hydroxy propanoic acid; 4-hydroxy butanoic acid; hydroxy pentanoic acid; and 2-hydroxy acetic acid; and

(ix) : tartaric acid; hydroxysuccinic acid; and α-hydr isobutyric acid.

Specific and preferred embodiments of the (b) alkyl< phosphonic acids can be represented by species wherein hydrocarbon compound in (b) containing amino groups selected from: poly (amino) alkanes; poly(allyl) amines; poly (vinyl amines); and poly (ethylene imines) , branched or linear or combinations thereof whereby the alkylene phosphonates acids are represented by phosphonates and whereby X is C₂-C30 or [A-O]_x-A.

Individual and preferred species of the (b) compounds selected from the group of: -4-aminomethyl 1,8-octane diamine hexa (methylene phospho acid) ;

-4-aminomethyl 1,8-octane diamine hexa (alkylene im bis (methylene phosphonic acid) ) ;

-poly [vinylamine bis (methylene phosphonic acid)]; -polyethylene imine poly (alkylene imino bis (methyl phosphonic acid) ) ;

-polyethylene imine poly (methylene phosphonic acid); -poly [vinylamine bis (alkylene imino bis (methylene phospho acid) ) ] ; and -poly [vinylamine bis (methylene phosphonic acid)] .

One or more, preferably one to five, phosphonates of invention are used in the method of the invention.

Scale formation, such as carbonate and sulphate scales, can a major problem in oil field production facilities that result in a significant well productivity decline. This c in particular, apply when sea water is injected into the bearing formation to compensate e.g. for a loss in pressure. As a result of the presence of important quantit of barium and calcium ions in the down-hole formation wat calcium sulphate and especially barium sulphate and stront sulphate can become a major problem in the operation of well. Whereas sulphate scales prevail upon seawater inject during the enhanced oil recovery treatment, milder conditions, prevailing closer to the surface, press differences and high temperatures in the down-hole format usually lead to the formation of mixtures of carbonate sulphate scale. The scale inhibitors shall therefore exhi performance over a broad range of conditions such as can oc in the oil wells and production facilities. The inhibitor be introduced into the oil bearing formation by any suita treatment including a "squeeze" treatment. In general suet method for oil recovery requires injecting into a marine well an aqueous solution of the phosphonic acid sc inhibitor of this invention in a usual level of from 0.1 100000 ppm. Frequently, the production oil well activity stopped and the inhibitor solution is injected into the well formation. It was established that the scale inhibit in accordance with this invention can be used effectively singly. The squeeze treatment generally consists of inject a scale inhibitor solution into the wellbore of the produc well to place the inhibitor into the formation. The sc inhibitor released from the formation is present, in return water, in a concentration of, at least, 0.1, usually least 0.5, frequently from 10 to 100 ppm to thus exhi effective scale control and consequently secure oil w production continuity with levels of inhibitor means redu by one order of magnitude compared to actually prevail practice .

In more detail, a beneficial method for oil recovery can done by injecting into marine oil wells an aqueous solution the phosphonic acid compound of the invention in a level from 0.1 to 100000 ppm. The method can be conducted continuously injecting into the well an aqueous solution from 0.1 to 800 ppm of the phosphonic acid compound, continuous injection frequently means that the scale inhibi solution is injected into the water injection well. Howev< it is understood that the continuous injection can also ap to the surroundings of the production well such as the we head arrangement including under-water equipment for exam pumps and pipes. The scale inhibitors of this invention also be used in squeeze oil recovery methods. Such sque method comprises, in sequence: stopping the product wellbore activity; introducing through the production wellb the aqueous treatment solution containing the phosphonic a scale inhibitor in a level of from 100 to 100000 p^' injecting sea water through the production wellbore to pi the scale inhibitor within the targeted area of the formati restarting the oil extraction activity; and producing ret fluids, containing oil and return water, through production wellbore.

In one aspect of the invention, the method can gener appreciable benefits for reducing the susceptibility materials, such as lignocellulosic materials, to unwan brightness reversion, in particular to brightness revers caused by light or heat. The brightness reversion problem well-known in the relevant domain and can be caused by lig in particular UV light, heat, moisture and chemicals, reversion can translate in reduced reflectivity, particula in blue light. This reversion, or yellowing, can vary upon type of pulp used, the raw material used, the production after treatment methods used. The method of this invent aims at eliminating the known reversion problems to thus yi< superior color stability. The inventive method thus provide, resulting from the use of the inventive phosphona to the aqueous medium, superior color properties. While wishing to be bound by any structural hypothesis, it believed that contrary to the principles underlying revers control in accordance with the art, the present method unexpectedly and beneficially controlled through interaction of the phosphonate/metal ion/reactive site on bleached compound. The inventive phosphonate is, for ble reversal avoidance purposes, generally used in levels fron to 10000 ppm. Preferred usage ranges require from 5 to 5 ppm, more preferably from 50 to 1000 ppm of the phosphonate this invention. The pulp can be used in common art establis concentrations in such aqueous medium, e.g. from 0.1 to K based of the treatment medium.

In another aspect, the inventive method contemplates treatm of water to inhibit and control the nuisance attached to sc formation. To that effect, the phosphonic acid of t invention is introduced into an industrial water system levels which can broadly and preferably range from about up to about 10000 ppm, usually from about 0.1 to about 1 ppm frequently from about 1 to about 200 ppm and prefera from 20 to 200 ppm.

In yet another aspect, the method herein can be u beneficially in connection with paper pulp bleaching broad Paper pulp bleaching technology is well established and been used for a long time. The phosphonates serve to stabil and enhance the performance of the paper pulp bleaching age used. The phosphonates can be used beneficially in s additive levels of e.g. from 1 to 5000 ppm, preferably of f 10 to 2000 ppm.

The method herein can also be used for dispersant purposes. particular, the phosphonates herein can serve as effect dispersants and thus reduce the viscosity of phyllosilicate slurries and aqueous medium in general. The dispers moieties, such as the phosphonate groups, can incre dispersion and exfoliation properties of the said silica and consequently decrease the viscosity. To that effect phosphonates herein are preferably used in low leve frequently in the range up to 10000 ppm starting from e.g ppm, or differently expressed in a range possible of from 0 to 3 % based on the level of the phyllosilicates .

The method can also beneficially serve for the sequestering undesirable metal ions which can be present in very low lev> e.g. l-500ppm or higher. The phosphonates herein beneficially serve for effectively hindering such undesirai metal ions to thus reduce the level of free metal ions to ppm levels.

In a further aspect of the invention, there is provided use of one or more phosphonate compound as described above deactivating metal ions in an aqueous medium, where the one more phosphonate compound is added to the aqueous medium in amount of from 0.1 to 100 000 ppm.

To deactivate as used herein means to suppress an adve effect of the metal ions on the aqueous medium, its compone or intended use, such as scale formation, increased viscosi or unwanted brightness reversion in pulp.

Accordingly, the use for deactivating metal ions in an aque medium includes the use as scale inhibitor, dispersa exfoliating agent, sequestering agent and/or stabiliser.

The aqueous medium comprising one or more phosphon compounds of the invention is preferably applied in production, such as secondary oil recovery, industrial wa treatment, reverse osmosis, or paper pulp treatment, such paper pulp bleaching.

The invention is further illustrated by the follow examples . Examples

Throughout the example section, the following abbreviati are used.

PIBMPA stands for propyl imino bis (methylene phosphonic aci

EIBMPA stands for ethyl imino bis (methylene phosphonic acid

AMODHMPA stands for 4-aminomethyl 1,8-octane diamine h (methylene phosphonic acid)

HEIBMPA stands for 2-hydroxy ethyl imino bis (methyl phosphonic acid)

The preparation of phosphonate species which can be used the invention herein is illustrated in the following synthe examples .

1. "6-Amino hexanoic acid PIBMPA" (Mixture of mono and alkylation product)

Solution 1 is prepared by mixing 22.63g (0.2 moles) of caprolactam with 50ml of water and 64g (0.8 moles) of a NaOH solution in water and heated for 3 hours at 100⁰C. slurry is prepared by mixing 117.3g (0.4 moles) of 96% pure chloro propyl imino bis (methylene phosphonic acid) and 150 of water. 64g (0.8 moles) of 50% NaOH solution in wa diluted to 150ml with water are gradually added to this slu between 5 and 10⁰C. Solution 2 so obtained is mixed w Solution 1 between 8 and 10⁰C. At the end of the addition (0.2 moles) of 50% NaOH solution in water are added bef heating the resulting mixture to 105⁰C for 6 hours. ³¹P analysis of the crude reaction mixture shows 68% mo hexanoic acid 6-imino bis [propyl 3- imino bis (methyl phosphonic acid) ] ; 15% molar hexanoic acid 6-amino propyl imino bis (methylene phosphonic acid) and 9% molar hydroxypropyl imino bis (methylene phosphonic acid) .

2. ^λλ11-Amino undecanoic acid PIBMPA" (Mixture of mono and alkylation product)

Slurry 1 is prepared by mixing at room temperature of 40. (0.2 moles) of 11-amino undecanoic acid with 75ml of water 64g (0.8 moles) of a 50% NaOH solution in water. Slurry 2 prepared by mixing 117.3g (0.4 moles) of 96% pure 3-chl propyl imino bis (methylene phosphonic acid) and 150 cc water. To this slurry 64g (0.8 moles) of 50% NaOH solution water diluted to 150ml with water are gradually added betw 5 and 10⁰C. Solution 2 so obtained is mixed with Slurry between 8 and 10⁰C. At the end of this addition 24g ( moles) of 50% NaOH solution in water are added to the react mixture along with 2g of KI before heating to 90⁰C for hours. ³¹P NMR analysis of the crude reaction mixture shows molar undecanoic acid 11-imino bis [propyl 3- imino (methylene phosphonic acid)] and 16% molar undecanoic acid amino propyl 3-imino bis (methylene phosphonic acid) .

3. "2- (2-amino ethoxy) ethanol PIBMPA" (Mixture of mono bis alkylation product)

Solution 1 is prepared by mixing at room temperature 21. (0.2 moles) of 2- (2-amino ethoxy) ethanol with 75ml of wa and 8Og (1 mole) of a 50% NaOH solution in water. Slurry 1 prepared by mixing 117.3g (0.4 moles) of 96% pure 3-chl propyl imino bis (methylene phosphonic acid) and 150 cc water. To this slurry 48g (0.6 moles) of 50% NaOH solution water diluted to with water 120ml are gradually added betw 5 and 10⁰C. Solution 2 so obtained is mixed with Solutior between 8 and 10⁰C. At the end of this addition 16g ( moles) of 50% NaOH solution in water are added and resulting mixture heated to 90⁰C for 5 hours. ³¹P NMR analy of the crude reaction mixture shows 55% molar 2- (2-im ethoxy) ethanol bis [propyl 3-imino bis (methylene phospho acid)]; 19% molar 2- (2amino ethoxy) ethanol propyl 3-imino (methylene phosphonic acid) and 16% molar of the correspond azetidinium salt.

4. "Glycine PIBMPA" (Mixture of mono and bis alkylat product)

Solution 1 is prepared by mixing at room temperature 15. (0.2 moles) of glycine with 75ml of water and 96g (1.2 moL of a 50% NaOH solution in water. Slurry 1 is prepared mixing 117.3g (0.4 moles) of 96% pure 3-chloro propyl im bis (methylene phosphonic acid) and 150 cc of water. To t slurry 48g (0.6 moles) of 50% NaOH solution in water dilu to 100ml with water are gradually added between 5 and 10

Solution 2 so obtained is mixed with Solution 1 between 5

10⁰C. At the end of this addition 8g (0.1 moles) of 50% N solution in water are added to the mixture which is heated

105°C for 5 hours. ³¹P NMR analysis of the crude react mixture shows 67.4%w/w glycine bis [propyl 3-imino ;

(methylene phosphonic acid)]; 2.2% w/w glycine propyl 3- im bis (methylene phosphonic acid) and 3%w/w of the correspond azetidinium salt.

5. "Imino bis ( EIBMPA)" (Mixture of mono and bis alkylat product)

Solution 1 is prepared by mixing between 5 and 8° C 111

(0.4 moles) of 96% pure 2-chloro ethyl imino bis (methyl* phosphonic acid); 300ml of water and 30g (0.375 moles) oi

50% NaOH solution in water. Solution 2 is prepared by mix

130g (1.625 moles) of 50% aqueous sodium hydroxide with wa to get a final volume of 250 ml. Ammonia solution is prepa by mixing 13.6g (0.8 moles) of 25% ammonia solution in wa with 200 ml of water. Solutions 1 and 2 are gradually ad to the ammonia solution with good stirring between 8 and Y. C. This mixture is heated to 80⁰C for 5 hours. ³¹P analysis of the crude reaction mixture shows 56.2%w/w im bis [ethyl 2-imino bis (methylene phosphonic acid)]; 22.2% amino ethyl 2-imino bis (methylene phosphonic acid) 11.8%w/w of the nitrilo tris [ethyl 2-imino bis (methyl phosphonic acid) ] .

6. "Glycine EIBMPA" (Mixture of mono and bis alkylat product) A glycine solution is prepared by mixing at room temperat 7.51g (0.1 moles) of glycine with 30 ml of water and 8 g ( moles) of a 50% NaOH solution in water. Slurry 1 is prepa by mixing 55.72g (0.2 moles) of 96% pure 2-chloro ethyl im bis (methylene phosphonic acid) and 150 cc of water. To t slurry 15g (0.1875 moles) of 50% NaOH solution in wa diluted to 100ml with water are gradually added between 5 10⁰C. Solution 1 is prepared by diluting 53g (0.6625 mol of 50% NaOH in water to a total volume of 110 ml. Solutioi and slurry 1 are gradually added under stirring to the glyc solution between 8 and 12°C. At the end of this addition (0.25 moles) of 50% NaOH solution in water are added to mixture which is heated to 100⁰C for 5 hours. ³¹P NMR analy of the crude reaction mixture shows 74.5%w/w glycine ^'. [ethyl 2- imino bis (methylene phosphonic acid)]; 7.1% glycine ethyl 2- imino bis (methylene phosphonic acid) 4.8%w/w of the 2-hydroxy ethyl imino bis (methylene phospho acid)

7. 4-Aminomethyl 1,8-octane diamine hexa (methylene phospho acid)

173.5 g (1 mole) of 4-aminomethyl 1,8-octane diamine w> mixed under stirring with 492 g (6 moles) of phosphorous ac 413.87 g (4.2 moles) of 37% hydrochloric acid and 200 ml water. The resulting mixture is heated up to 110 ⁰C. 541.5; of 36.6 % aqueous (6.6 moles) formaldehyde were added in minutes while maintaining the reaction temperature around ⁰C. Upon completion of the formaldehyde addition, the react mixture is heated for an additional 60 minutes at 114 ³¹PNMR analysis of the crude product shows 93.2 % of aminomethyl 1,8-octane diamine hexa (methylene phospho acid) . 8. Poly [vinyl amine bis (methylene phosphonic acid)]

222.67 g (1 mole based on the monomer unit) of a 32.2 % polyvinyl formamide (Lupamin 4500 from BASF) were mixed un< stirring with 164 g (2 moles) of phosphorous acid, 221.7] (2.25 moles) of 37 % hydrochloric acid and 50 ml of water, resulting mixture was heated up to 110 ⁰C. 168 ml of 36. ( aqueous (2.2 moles) formaldehyde was added in 120 minu while maintaining the reaction temperature between 108 and ⁰C. Upon completion of the formaldehyde addition, the react mixture was heated for an additional 60 minutes at 105 ³¹PNMR analysis of the crude reaction product showed presence of 60 % of polyvinyl amine bis (methylene phospho acid) in the reacted product mixture.

9. 2-Hydroxy ethyl imino bis (methylene phosphonic acid)

111.48g (0.4 mole) Of 96% pure 2-chloro ethyl im bis (methylene phosphonic acid) (CEIBMPA) were mixed un stirring with 300 ml of water. 30g of a 50% aqueous solut of sodium hydroxide (0.375mole) was diluted with water 100ml and added, under stirring below 10⁰C, to the CEIB aqueous solution. This mixture was then added over a period 160 minutes to 162g (2.025 moles) of 50% sodium hydrox under good stirring at a temperature between 95°C and 100 Heating was further continued for 60 minutes at 100⁰C. ³¹P of the crude reaction product showed the presence of 88.3% the hydroxy homologue of CEIBMPA; the corresponding eye phosphonate ester is absent from the crude product. 10. Polyethylene imine poly (propyl imino bis (methylene phosphonic acid) )

146.65g (0.50 mole) of 96% pure 3-chloro propyl im bis (methylene phosphonic acid) were added under stirring o 100 minutes to a mixture of 29.25g of linear polyethyl imine (Mw=423, 0.66 mole based on -CH₂-CH₂-NH₂ unit) w 160.8g (2.01 moles) of 50% sodium hydroxide and lOOg of wa while maintaining the temperature between 35°C and 40⁰C. W addition was complete, the mixture was heated at reflux fo. hours. ³¹P NMR analysis of the crude product indicated 92% polymer bound propyl imino bis (methylene phosphonic acid) w 7% of the 3-hydroxy propyl imino bis (methylene phospho acid) (HPIBMPA) .

11. Polyethylene imine poly (propyl imino bis (methyl phosphonic acid) )

146.65g (0.50 mole) of 96% pure 3-chloro propyl im bis (methylene phosphonic acid) were added under stirring o

100 minutes to a mixture of 19.5g of linear polyethylene im

(Mw=423, 0.44 mole based on -CH₂-CH₂-NH₂ unit) with 160

(2.01 moles) of 50% sodium hydroxide and lOOg of water wh maintaining the temperature between 35 and 40⁰C. W addition was complete, the mixture was heated at reflux fo. hours. ³¹P NMR analysis of the crude product indicated 93% polymer bound propyl imino bis (methylene phosphonic acid) w

5% of the hydroxy propyl imino bis (methylene phosphonic ac

(HPIBMPA) . 12. "6-Amino hexanoic acid EIBMPA" (Mixture of mono and alkylation product)

Solution 1 is prepared by mixing 22.63g (0.2 moles) of caprolactam with 70ml of water and 32g (0.4 moles) of a NaOH solution in water and heated for 3 hours at 100⁰C. slurry is prepared by mixing 111.44 g (0.4 moles) of 96% p 2-chloro ethyl imino bis (methylene phosphonic acid) and cc of water. 3Og (0.375 moles) of 50% NaOH solution in wa diluted to 100ml with water are gradually added to this slu between 5 and 8°C. Solution 3 is prepared by diluting

(1.225 moles) of a 50% NaOH solution with 250 ml of wat

Solutions 2 and 3 are gradually added to Solution 1 un mixing between 8 and 10⁰C. The resulting mixture is t heated to about 100⁰C for 5 hours. ³¹P NMR analysis of crude reaction mixture shows 42.7%w/w of hexanoic acid 6-im bis [ethyl 2- imino bis (methylene phosphonic acid)]; 28.5% hexanoic acid 6-amino ethyl 2-imino bis (methylene phospho acid) and 13%w/w of 2-hydroxy ethyl imino bis (methyl phosphonic acid) .

Thermal stability assessment.

This is a test to assess the thermal stability of phosphona in the presence of synthetic North Sea water. The test carried out by submitting mixtures of North Sea water phosphonates stabilized at pH 5.5 to a one week heating at °C. The thermal degradation is determined by ³¹P NMR analys The results give the percentage by weight of product which decomposed after the treatment. Test details are as follows:

- prepare an aqueous solution containing 20 % of active a phosphonate (AA) at pH 5.5 (solution 1);

prepare synthetic North Sea water having a pH of (solution 2) ;

- prepare a sample of 1 % active acid phosphonate by mixinc g of solution 1 with 19 g of solution 2 ;

- put the sample so prepared in an oven at 140 ⁰C for week; and

- analyze the sample, after the heat treatment, for then decomposition by means of ³¹P NMR spectroscopy.

Brine/sea water compatibility.

This test assesses sea water compatibility of the phosphona added at: 100; 1000; 10000; and 50000 ppm to North Sea wa after 22 hours at 90 ⁰C. Calcium left in solution is measu by ICP.

Test details are as follows:

- prepare synthetic North Sea water at pH 5.5;

- add the phosphonate at 100, 1000, 10000 and 50000 ppm act acid to the synthetic North Sea water solution;

- prepare 5 blank solutions made by mixing the required amo of distilled water with North Sea water to obtain the s dilution as obtained by the addition of 1, 100, 1000, 10 and 50000 ppm active acid phosphonate to the synthetic No Sea water solution;

- the phosphonate samples with the respective phosphonates the 4 concentrations as well as the 5 blanks are stored in oven at 90 ⁰C for a period of 22-24 hours;

upon completion of the test, the samples are obser visually;

after completion of the test, the pH values are be carefully monitored and 50 ml are drawn from each samp filtered through a 40 μm Millipore filter and stabilized pH< 2 by addition of 37 % aqueous hydrochloric acid;

- Ca tolerance values are calculated as follows:

V₁

% Ca tolerance = x 100

V₀

where V₀ = ppm Ca found in the blank solution; and

where Vo = ppm Ca found in the blank solution; and

Vi = ppm Ca found in the solution with the phosphonate, Barium sulphate scale inhibition.

This is a static test to evaluate the efficiency phosphonates in preventing barium and strontium sc inhibition in oil field scaling conditions. The test carried out by determining the amount of BaSO₄ and SrSO₄ t has precipitated after 22 hours at 90 ⁰C in a 50/50 mixture synthetic North Sea water and Formation water containing phosphonates to be tested at 5 different concentrations. amount of soluble Ba and Sr ions is determined by ICP. results stand for the minimum phosphonate concentration 100 % barium sulphate scale inhibition or give the sc inhibition at 100 ppm loading of phosphonate.

Test details are as follows:

Synthetic North Sea water:

Salts iπmol/1

NaCl 420.1

CaCl₂ . 2H₂O 10 . 08 MgCl₂ . 6H₂O 54 . 32

KCl 8 . 7

Na₂SO₄ - I OH₂O 25 . 8

NaHCO₃ 2 . 21 Formation water:

S al t s mmo 1 / 1 NaCl 1313

CaCl₂ . 2 H₂O 77 . 75

MgCl₂ . 6H₂O 1 9 . 74

KCl 1 1

BaCl₂.2H₂O 1.82

SrCl₂.6H₂O 7.53

- synthetic North Sea and Formation water are prepared hav a pH of 6. These water solutions are preheated at 90 ⁰C bef starting the test. An acetic acid/sodium acetate buffer prepared and added to the North Sea water in order to give required pH;

- add to a glass bottle the required amount of scale inhibi to obtain the test concentrations (15, 30, 50, 70 and 100 ; active phosphonic acid) of the scale inhibitor in the fi test mixture;

- to this glass bottle, add 50 ml of North Sea water wh stirring. Then add to this glass bottle 50 ml of Format water;

- also prepare one blank solution by mixing 50 ml of North water with 50 ml of Formation water; - put the sample bottles in an oven for 22 hours at 90 ⁰C;

- after 22 hours, take 3 ml of each test solution from surface, filter through a 0.45 μm Millipore filter and add a stabilizing solution. The samples are then analyzed by for Ba and Sr;

-the phosphonate efficiencies as BaSO₄ and SrSO₄ sc inhibition are calculated as follows:

V₁ - V₀ % Scale inhibition = x 100

V₂ - V₀

where

Vo = ppm Ba (or Sr) found in the blank solution;

Vi = ppm Ba (or Sr) found in the solution with inhibitor;

V₂ = ppm Ba (or Sr) present in the Formation water.

Testing method for calcium carbonate scale inhibition.

This is a static test to evaluate the efficiency phosphonates in preventing calcium carbonate scale inhibit in industrial water treatment conditions. The test is carr out by determining the amount of CaCθ3 that has precipita after 22 hours at 50⁰C in a 50/50 mixture of cationic anionic waters with the test phosphonates at 5 differ concentrations. The amount of soluble Ca ions is analyzed titration. Result indicates the % Ca scale inhibit provided by the 5 phosphonate concentrations. Reported resu give the minimum phosphonate concentration for 100% calc carbonate scale inhibition.

Test details are as follows:

Cationic water composition

Salt g/l

CaCl₂.2H₂O 1.76

Anionic water composition

Salt g/l

NaHCO3 2.02

Cationic and anionic waters are prepared at pH 9. 10 of buffer are added to the anionic water before bring water to its final 1 liter final volume. - Prepare a lOOOppm phosphonate solution in water at pH 9 Add to a glass bottle the required amount of the sc inhibitor mother phosphonate solution to obtain the t< concentration (1, 2, 2.5, 3 and 3.5 ppm active phospho acid) of the scale inhibitor in the final test mixture. - To this glass bottle add 50ml of anionic water wh stirring and then 50 ml of cationic water while stirrin

Put the sample bottles in an oven for 22 hours at 50⁰C. After 22 hours, take 50 ml of each test solution from surface, filter through a 0.45 μm Millipore filt measure and note the weight of the solution (Wtsam) acidify to pH 1 with an HCl solution Measure and n the HCl solution weight added (Wta) . Analyze Ca by titration (Caf) . The phosphonate efficiency as CaCθ3 scale inhibition then calculated using the following equation:

% CaCO₃ scale inhibition = {Cat -Cab)xlOθ)÷{Cai -Cab))

where

Cat = Calcium remaining in solution of the t sample, where the dilution with acid has b< corrected Cab = Calcium remaining in the blank where phosphonate was added.

Cai = Total calcium present in the original t sample

Cat = (Caf) x (Wta) /Wtsam

Peroxide stabilization procedure

In a 250 ml glass bottle filled with 200ml deionised wa stabilized at 40⁰C add the following ingredients: 0.4g iron, 35ppm of the tested bleach stabilizer, 0.53g of sod bicarbonate, 0.42g of sodium carbonate, 0.14g of sod perborate tetrahydrate and 0.06g of tetra-acetyl ethyl diamine (TAED) . Dissolve these ingredients in the water using an ultrasonic bath. After one minute of such treatm the bottle is transferred to the water bath set at 40⁰C samples (10 ml each) are taken from the test bottle 6,10,15,20 and 30 minutes thereafter. To these samples added 10ml of IM potassium iodide and 10ml of 20% aque sulphuric acid before immediate titration with a standardi 0.01N thiosulphate solution. Clay Dispersion.

This test is used to determine and compare the effectiven of the phosphonate agents of this invention.

A one liter 0.15%w/w solution of the selected phosphonate prepared in tap water. The solution pH is brought to 11.5 addition of a 50% sodium hydroxide aqueous solution. Kao

(Ig) is added and the liquid is agitated, at ambi temperature, till a homogeneous suspension is obtained. suspension is then introduced in an Imhoff cone. Gradually second phase appears at the bottom of the cone and its Ie is recorded at regular intervals (5, 15, 30, 60 and minutes) . The aspect and color of the two phases were also recorded at the same intervals. The percentage of dispers provided by the tested product after 120 minutes is calcula as follows by reference to a blank test which does not cont a phosphonate.

% Dispersion = 100 - (level of the bottom phase (in ml) x / level of the bottom phase in the blank (in ml) ) .

Phosphonate samples for use in the method of this invent were performance tested by means of the foregoing test procedures. The performance data illustrated in Application Examples were as follows.

Example I .

N° Phosphonate Ba Scale (***) Ca Tolerance in %

Inhibition 100 1000 10000 50000

1. 2-aminoethoxy 15ppm 100 95 94 86 ethanol PIBMPA (*) full scale 2. 11-amino 75% @100ppm 100 92 32 undecanoic acid PIBMPA

3. Glycine PIBMPA 100% ΘlOOppm 100 94 32 91

4. 6-Amino hexanoic 15ppm 100 96 63 100 acid PIBMPA full scale

5. Glycine EIBMPA (*) 100% glOOppm

6. Amino EIBMPA 100% glOOppm 100 98 38 63

7. Dequest 2066A (****) 15ppm 100 89 24 100 full scale

8. AMODHMPA (*****) 30ppm 99 83 21 100 full scale

9. HEIBMPA(******) 30ppm 100 79 100 100 full scale

10. PEI IBMPA I (+) 30ppm 95 93 70 95 full scale

11. PEI IBMPA II (++) 30ppm 89 85 38 95 full scale

(*) PIBMPA stands for propyl imino bis (methylene phospho acid) (**) EIBMPA stands for ethyl imino bis (methylene phospho acid)

(***) expressed as: - ppm phosphonate needed for 100% BaSO₄ scale inhibiti or

- % scale inhibition for 100 ppm phosphonate. (****) -j__s diethylene triaminopentamethylene phosphonate. (*****) AMODHMPA stands for 4-aminomethyl 1,8-octane diam hexa (methylene phosphonic acid)

(******) HEIBMPA stands for 2-hydroxy ethyl imino bis (methyl phosphonic acid

(+) PEI IBMPA stands for polyethylene imine poly (propyl im bis (methylene phosphonic acid)) with molar ratio 3-chl propyl imino bis (methyelene phosphonic acid) /PEI=O .75

(++) PEI IBMPA stands for polyethylene imine poly (propyl im bis (methylene phosphonic acid)) with molar ratio 3-chl propyl imino bis (methyelene phosphonic acid) /PEI=I .14

Example I I .

N° Phosphonate Ca Scale (***)

Inhibition

1. 2-aminoethoxy 2 ppm ethanol PIBMPA full scale 2. 11-amino 2 ppm undecanoic acid PIBMPA full scale

3. Glycine PIBMPA 2 ppm full scale

4. 6-Amino hexanoic 2 ppm acid PIBMPA full scale

5. Amino EIBMPA 2 ppm full scale

7. Dequest 2066A 2 ppm full scale

A series of phosphonate inhibitors were tested for ther stability thereby using the method set forth above, testing results were as follows.

Example III .

Test Phosphonate Thermal Stability at 140⁰C 1 week

N° Decomposition in %

1. 2-aminoethoxy ethanol PIBMPA 17

2. 11-amino undecanoic acid PIBMPA 35

3. Glycine PIBMPA 27

4. 6-Amino hexanoic 38 acid PIBMPA

5. Glycine EIBMPA 13

7. Dequest 2066A 24 8. AMODHMPA

9. HEIBMPA 1 9

A series of phosphonates were tested for perox stabilization thereby using the method set forth above, testing results were as follows.

Example IV.

Phosphonate Time (min) % remaining act . oxygen

None 0 100

2 92

6 80

10 71 15 61 20 53 30 53

+ 35ppm Dequest 2066 0 100 2 100 6 99

10 97 15 95 20 94 30 90

+45.5ppm 6-amino hexanoic acid PIBMPA 100 2 88

6 83 10 79

15 73

20 71

30 67

+35ppm Imino bis (EIBMPA) 0 100

2 100

6 93 10 91

15 91

20 90

30 89

+17.5ppm Imino bis (EIBMPA) 0 100

2 100

6 97 10 96

15 96

20 94

30 94

+ 35ppm of 6-amino hexanoic acid EIBMPA 0 100 2 100

6 98

10 98 15 96 20 95 30 93

Example V.

Clay dispersion

Time Blank test 6-Amino hexanoic Glycine PIB acid PIBMPA

(Min) ml(l) (2) ml(l) (2) ml(l) (2)

5 6 cloudy 0.15 cloudy 0.4 clou

15 7 cloudy 0.4 cloudy 0.6 clou

30 6 cloudy 0.55 cloudy 0.9 clou

60 6 clear 0.8 cloudy 1.1 clou

120 6 clear 1 cloudy 1.2 clou

% Dispersion 0.0 82 78

Time Blank test Glycine EIBMPA 2- (2-Amino ethoxy) ethano PIBMPA

(Min) ml(l) (2) ml(l) (2) ml(l) (2)

5 6 cloudy 0.2 cloudy 0.5 cloudy

15 7 cloudy 0.5 cloudy 0.75 cloudy

30 6 cloudy 0.7 cloudy 1.0 cloudy

60 6 clear 1.0 cloudy 1.0 cloudy 120 clear 1.2 cloudy 1.4 cloudy

Dispersion 0.0 74

Time Blank test Imino bis (EIBMPA) 11-Amino undecanoic

Acid PIBMPA

(Min) ml(l) (2) ml(l) (2) ml(l) (2)

5 6 cloudy 0.2 cloudy 0.4 cloudy

15 7 cloudy 0.3 cloudy 0.7 cloudy

30 6 cloudy 0.5 cloudy 1.0 cloudy

60 6 clear 0.7 cloudy 1.2 cloudy

120 6 clear 0.9 cloudy 1.3 cloudy

Dispersion 0.0 80 71

Claims

1. A method for securing the use of an aqueous med under substantial exclusion of metal ion interferen comprising adding to the water of from 0.1 to 100000 parts million (ppm) of a phosphonate compound selected from group of:

(a) a phosphonate compound of the general formula:

T-B

wherein B is a phosphonate containing moiety having formula:

-X-N(W) (ZPO₃M₂)

wherein X is selected from C₂-C₅O linear, branched, cyclic aromatic hydrocarbon moiety, optionally substituted by a Ci- linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR' and SR' moieties, wherein R' is a Ci-Ci₂ line branched, cyclic or aromatic hydrocarbon moiety; and [A-O] wherein A is a C₂-Cg linear, branched, cyclic or aroma hydrocarbon moiety and x is an integer from 1 to 200;

Z is a Ci-Cε alkylene chain;

M is selected from H, Ci-C₂O linear, branched, cyclic aromatic hydrocarbon moieties and from alkali, earth alk and ammonium ions and from protonated amines;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V selected from: a C₂-C₅Q linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C₁-C₁₂ line branched, cyclic or aromatic groups, which moieties and groups are optionally substituted by OH, COOH, F, OR' or moieties wherein R' is a C₁-C₁₂ linear, branched, cyclic aromatic hydrocarbon moiety; and from [A-O]_x-A wherein A i, C₂-C9 linear, branched, cyclic or aromatic hydrocarbon moi< and x is an integer from 1 to 200; and

K is ZPO₃M₂ or H and n is an integer from 0 to 200;

and wherein T is a moiety selected from the group of:

:i⁾ MOOC-X-N(U) -;

(ii) MOOC-C(X^)₂-N(U) -;

:iϋ) MOOC-X-S-;

:iv) [X(HO)_n- (N-U) n J n r

(v) U-N(U) - [X-N(U) n r

(vi) D-S-;

(vii) CN-;

(viii) MOOC-X-O-;

:i^χ) MOOC-C(X^)₂-O-;

(x) NHR''-; and

(xi) (DCO)₂-N-; wherein M, Z, W and X are as defined above; U is selected f linear, branched, cyclic or aromatic C1-C12 hydrocar moieties, H and X-N(W) (ZPO3M2) ; X² is independently selec from H, linear, branched, cyclic or aromatic C1-C20 hydrocar moieties, optionally substituted by C1-C12 linear, branch cyclic or aromatic hydrocarbon groups, optionally substitu by OH, COOH, R'O, R' S and/or NH₂ moieties; n' , n" and n' ' ' independently selected from integers of from 1 to 100; D R' ' are independently selected from C1-C50 linear, branch cyclic or aromatic hydrocarbon moieties, optiona substituted by a C1-C12 linear, branched, cyclic, or aroma group, which moiety and/or which group can be optiona substituted by OH, COOH, F, OR' and SR' moieties, wherein is a C1-C12 linear, branched, cyclic or aromatic hydrocar moiety; and A' 0-[A-O]_x-A wherein A is a C₂-C₉ linear, branch cyclic or aromatic hydrocarbon moiety, x is an integer froi to 200 and A' is selected from C1-C50 linear, branched, eye or aromatic hydrocarbon moiety, optionally substituted by a C12 linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR' and SR' moieties, wherein R' has the meaning gi above; with the further proviso that D can also be represen by H;

(b) linear or branched hydrocarbon moieties having froi to 2.1O⁶ carbon atoms containing amino groups substituted alkylene phosphonic acid substituents and/or -X-N(W) (ZPO: with respect to the hydrocarbon moiety, in either terminal branched positions whereby the molar ratio of the am moieties to the number of carbon atoms in the hydrocar chain is in the range of from 2 : 1 to 1 : 40 whereby at Ie 30 % of the available NH functionalities have been conver into the corresponding aminoalkylene phosphonic acid or/ into X-N(W) (ZPO3M2) substituted groups; and wherein alkylene moiety is selected from Ci-ε; and X, W, Z and M h the same meaning as given above; and

(c) alkylamino alkylene phosphonic acids having the formula

Y- [X-N(W) (ZPO₃M₂) ] _s

the structural elements having the following meaning:

X is selected from C2-C50 linear, branched, cyclic or aroma hydrocarbon moieties, optionally substituted by a Ci- linear, branched, cyclic, or aromatic group, which moi and/or which group can be optionally substituted by OH, CO F, OR', R²O[A-O]_x- wherein R² is a Ci-C₅₀ linear, branch cyclic or aromatic hydrocarbon moiety, and SR' moieti wherein R' is a C1-C50 linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C1-C12 line branched, cyclic or aromatic hydrocarbon groups, said moiet and/or groups can be optionally substituted by COOH, OH, OR' and SR'; and [A-O]_x-A wherein A is a C₂-C₉ line branched, cyclic or aromatic hydrocarbon moiety and x is integer from 1 to 200;

Z is a Ci-Cε alkylene chain;

M is selected from H, C1-C20 linear, branched, cyclic aromatic hydrocarbon chains and from alkali, earth alkali ammonium ions and from protonated amines;

W is selected from H, ZPO₃M₂ and [V-N(K)J_nK, wherein V selected from: a C₂-C₅Q linear, branched, cyclic or aroma hydrocarbon moiety, optionally substituted by C1-C12 line branched, cyclic or aromatic groups, which moieties and groups can be optionally substituted by OH, COOH, F, 0 R²O[A-O]_x- wherein R² is a C1-C50 linear, branched, cyclic aromatic hydrocarbon moiety, and SR' moieties; and from [A-C A wherein A is a C2-C9 linear, branched, cyclic or aroma hydrocarbon moiety and x is an integer from 1 to 200;

K is ZPO3M2 or H and n is an integer from 0 to 200; and

2. The method in accordance with Claim 1 wherein the phosphonic acid compound is added in an amount of from 1

10000 ppm.

3. The method in accordance with Claim 1 or 2 wherein component (a) the reaction partner T is selected from group of (i) , (ii) , (iv) , (v) , (x) and (xi) .

4. The method in accordance with any one of Claims 1 3, wherein the individual moieties in the phosphonate react partner of the component (c) are selected as follows: X is C₃₀ or [A-O]_x-A; V is C₂-C₃₀ or [A-O]_x-A; wherein for both, X

V are independently selected, A is C₂-C₆ and x is 1-100; R² Ci-C₃₀; Z is Ci-C₃; M is H or Ci-C₆; and n is 1-100.

5. The method in accordance with Claim 4 wherein individual moieties in the phosphonate reaction partner of component (c) are selected as follows: X is C2-C12 or [A-O]_x V is C₂-Ci₂ or [A-O]_x-A; wherein for both, X and V independently selected, A is C₂-C₄ and x is 1-100; R² is Ci-C Z is Ci; M is H or Ci-C₄; and n is 1-25.

6. The method in accordance with any one of Claims 1, 4, or 5 wherein the precursor for Y is selected from: N NH₂R; NH (R') 2; OH^"; HOR; Na₂S; thiourea; and Na₂S₂.

7. The method in accordance with Claim 3 wherein reaction partner T is selected from:

(x) : methylamine; ethylamine; propylamine; butylami hexylamine; heptylamine; octylamine; nonylamine; decylami dodecylamine; aniline; and Ci₂-C₂₂ fatty amines including lin and branched species; and (xi) : phthalimide; succinimide; and maleimide.

8. The method in accordance with Claims 1 or 2 wher in component (a) the reaction partner T is selected from group of (iii) , (vi) , (viii) and (ix) .

9. The method in accordance with Claim 8 wherein reaction partner T is selected from:

(iii) : thioglycolic acid; and cysteine;

(ix) : tartaric acid; hydroxysuccinic acid; and α-hydr isobutyric acid.

10. The method in accordance with any one of Claims 1 3 or 7 to 9 wherein the structural elements of T are selec from: X² is H or Ci-Ci₀; n' , n" are independently 1-25; n' ' ' 1-50; R'' is Ci-Ci₆ or AO-[A-O]_x-A; D is H, C_x-Ci₆ or A'O- O]_x-A, wherein for both, R'' and D independently, A is C₂ and x is 1-100; X is C₂-Ci₂; and Z is Ci-C₃.

11. The method in accordance with Claims 1 or 2 wher the hydrocarbon chain in component (b) containing amino gro is selected from: poly (amino) alkanes; poly(allyl) amines; poly (vinyl amines); and poly (ethylene imines) , branched or linear or combinations thereof whereby the alkylene phosphonic acids are represented by i phosphonic acid moieties and whereby X is C2-C30 or [A-O]_x-A.

12. The method in accordance with any one of Claims 1 or 11 wherein component (b) is selected from the group of:

- 4-aminomethyl 1,8-octane diamine hexa (methylene phospho acid) ;

4-aminomethyl 1,8-octane diamine hexa (alkylene im bis (methylene phosphonic acid) ) ;

- poly [vinylamine bis (methylene phosphonic acid)]; - polyethylene imine poly (alkylene imino bis (methyl phosphonic acid) ) ;

- polyethylene imine poly (methylene phosphonic acid);

- poly [vinylamine bis (alkylene imino bis (methylene phospho acid) ) ] ; and - poly [vinylamine bis (methylene phosphonic acid)].

13. The use of a phosphonate compound according to one of Claims 1 or 3 to 12 for deactivating metal ions in aqueous medium, where the phosphonate compound is added to aqueous medium in an amount of from 0.1 to 100000 ppm.

14. The use according to Claim 13, where the phosphon compound acts as a scale inhibitor, dispersant, exfoliat agent, sequestering agent or stabilizer.

15. The use according to Claims 13 or 14, where aqueous solution is applied in oil production, industr water treatment, reverse osmosis, or paper pulp treatment.