CA2099704A1 - Zinc, iron and manganese stabilization using polymer polyamino methylene phosphonates - Google Patents
Zinc, iron and manganese stabilization using polymer polyamino methylene phosphonatesInfo
- Publication number
- CA2099704A1 CA2099704A1 CA002099704A CA2099704A CA2099704A1 CA 2099704 A1 CA2099704 A1 CA 2099704A1 CA 002099704 A CA002099704 A CA 002099704A CA 2099704 A CA2099704 A CA 2099704A CA 2099704 A1 CA2099704 A1 CA 2099704A1
- Authority
- CA
- Canada
- Prior art keywords
- polyether
- phosphonate
- iron
- zinc
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
Abstract
TITLE OF THE INVENTION
ZINC, IRON AND MANGANESE STABILIZATION USING POLYETHER
POLYAMINO METHYLENE PHOSPHONATES
ABSTRACT OF THE DISCLOSURE
Polyether polyamino methylene phosphonates, when added to various industrial water systems in concentrations between 3.1 mg/L and 50 mg/L, stabilize soluble zinc, manganese and iron ions and their reaction products, in desirable forms and reduced particle sizes. In particular, this stabilization can be achieved under severe conditions which include elevated pH, high dissolved solids content, and high saturation levels of calcium carbonate.
ZINC, IRON AND MANGANESE STABILIZATION USING POLYETHER
POLYAMINO METHYLENE PHOSPHONATES
ABSTRACT OF THE DISCLOSURE
Polyether polyamino methylene phosphonates, when added to various industrial water systems in concentrations between 3.1 mg/L and 50 mg/L, stabilize soluble zinc, manganese and iron ions and their reaction products, in desirable forms and reduced particle sizes. In particular, this stabilization can be achieved under severe conditions which include elevated pH, high dissolved solids content, and high saturation levels of calcium carbonate.
Description
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: 10 TITLE OF THE I~VENTION
.- ZINC, IRON AND MANG~NESE STABILIZATION USING POL~ET~ER
~: POL~MINO METHYLENE PHOSP~O~TES
.
, ~, .
,~
., 15 ~ACKGROUND Q~ TEE INVENTIQN
~: l. Field of the Invention .
i,...................................... .
STABILIZATIOM OF SOL~BL~ MANGANESE AND ITS
REACTION PRODUCTS - The present in~ention relate~ to the use of polyether polyamino methylene pho~pho~ates to:stabilize soluble manganese ion~ and their reaction products in de~irable forms and reduced :particle ~izes. Mangane~e exist~ in various 25~ oxi~dation s:tates ~rom l through 7, with the o~idation tates oX 2~and ~ being the moQt ~table, and the~r~ef:ore the p~edominant ~orms in nature. The 2~7'~ ~
2998H - ~ - C-1576 present invention .is inteTIded to include s~abilization of manganese ions for all of these oxida~ion s~ates. Manganese .ions ar~ o~ten found in well wateræ and coollng waters. Anionic species of carbonate, bicarbonate, sulfite, fluoride, chloride, sulfate, and so orth, and dissolved o~ygen may be present in both waters. Oxygen reaction produets of manganese and iron can collect on metal sur~aces and accelerate corrosion and reduce heat txans~er.
Oxidation leads to precipitation of dark brown or black hydrous oxides or hydroxides of the hlgher o o~idation ~tates o manganeæe which are ~ery insoluble. Man~anese hydro~ide, Mn~0~)2, is especially a problem. When these precipitates remain suspended in the water, they cause objectionable di~coloratio~ known as "black water"; when they settle out, black deposits form which can block lines, or act as catalystæ causing further manganese deposition. These deposits are very deleterious in tex~ile and laundry operations as they int2r~ere with dying processes and leave spots which are dif~icult 2a to remo~e. They appear to increase the corrosion o~
copper.. Manganese hydroxide, Mn(0~>2, while it is usually present as a colloidal ~uspension, when i~
does form a deposit, it readily becomes the site for the promotion of the deposit o~ other scaling ma~erials, thereby accelerating scaling in g~neral The polyether polyamino methylene phosphonates, when used in accordance wi~h the method o the present invention, can keep the reaction products of mangane~e described above in colloidal/fine dispersed : 30 ~orm rather than the normal flocculant, adherent species. The mangane~e thus remains soluble 90 that it will not ~orm particles which will precipitate out : ~: : ' ~ ' ' 7 ~ .~
of solution and form scale.
STABILIZATION OF SOLUBLE IRON AND ITS REACTION
PRODUCTS - The present in~ention further relates to the use of polyether polyamino methylene phospho~la:tes to stabilize soluble iro~ ion and its reaction products in desirable orms and reduced particle - 5 siæes. Ferrous and ferric ions are often found in well waters while cooling ~aters contain primarily the ferric species. Iron ions are often present as the result of rusting of the iro~ piping used to transport the ~ater in a cooling sy~tem. Anionic : 10 species of carbonate, bicarbonate, ~ulfite, fluoride, chloride, sulfate, and so ~orth, and dissolved oxygen may be present in both waters. Oxyge~ reaction products of iron can collect on metal surfaces and :: accelerate corrosion and reduce heat tran~fer.
; 15 Oxidation leads to precipitation of brown or red oxides of the higher oxidation states of iron which are insoluble. When these precipitates r~main suspended in ~he water, they cause objec~iona~le discoloration know~ a~ "red water"; when they settle QUt, red deposits foxm which can block lines, or act : as cataly~ts causing further iron reaction product deposition. The~e depo~its are very dele~erious in textile and laundry operations as they inter~ere wlth dying processes and leave spots which are dif~icult ! 25 to remove. Fe(OH)2, while it is usually prese~t as a colloidal su~pension, when it does form a deposit, : it readily becomes the 3ite for the promotion of the deposit of other scaling Materials ~ thereby acceleratin~ qcali~g in general.
The pol~ether polyamino methyleRe phosphonates, when used in accorda~ce with the.method of the preEent invention, can keep the reaction products of '7 ~ ~
~998H - 4 - C-1576 iron described above in colloidal/~ine dispersed ~orm rather than the n~rmal flocculant, adheren~ species.
The iron thus remains soluble so that it will not form par~icles which will precipitate out of solution and form scale.
STABILIZATION OF SOLUBLE ZINC AND ITS REACTION
PROD~CTS - The present invention ~urther relates to the use of polyether polyamino methy~ene pho3phonates to stabilize soluble zinc ion and its reaction pxoducts in desirable forms and reduced particle sizes. Zinc ions are o~ten found in well water~, while cooling waters can also contain zinc ionsO
Zn~ present in cooling waters is ofte~ derived : fxom the zinc metal used in making the copper and . brass alloy~ from whlch the piping used for ;i; tra~sporting the cooling water is co~structed.
Anionic species of carbonate, bicarbonat~ 9 sulfi-te, :~ ~luorîde, chloride, sulfate, and GO forth, and dissolved oxygen may be present in bo~h waters.
Oxygen reaction products of zlnc can collec~ on metal . 3urfaces and accelerate corrosion and reduce heat ~20 transf~r. Zinc hydroxide, Zn(0~)2, has been found to be a particular problem. While it is usually pr~sent as a colloidal ~uspension, when it doeæ form i a deposit, it readily becomes the site ~or the ~: promotion o~ the depo~it of other ~caling materials, thereby accelerati~g ~caling in general.
~:~ The combination products of the zinc îons and ~he anionic ~pecies recited above can often æettle out, c~eating deposits which can block lineQ~ or act as catalyst~ causing ~urther zinc reaction product ~depositio~. These depositæ can be ~ery deleterious :in textil~ and laundry operations as they interfere ; with dyinsg proCeæBeæ and lea~e spots ~hich are ~: ~
:
~$~
difICicult to remove.
The polye ther polyamino methylene phosphonates, when used in accordance with the method o:f tlle present inven~ion, can keep the reaction products of zinc described above in colloidal/f~ne diepersed form rather than the normal flocculant, adhexent ~pecies.
:~ 5 The zinc thus remains soluble ~o that it will not form par~icle~ which will precipi~ate out 0lc solution - and form scale.
The stabilizatio:n methods described above are especially use:L'ul under conditions OI high pH and 1~ hig~ calcite concen~ratio:lls, e.g. s thoæe found in cycled up cooling towers. Various indu~trial and ~;. commercial water-ca~ryiIlg systems are subjec~ to zinc, iron and ma~gane~e deposit formation problems.
These deposite form freguently in the tubes of heat e~change:rs and on other heat e~change eur~aceæ, ~uch a~ those in cooling towers. Particular systems or applications areas where severe conditions, especially h;gh alkaLirli~y, lead ~o exceptiorlal ;~ buildup OIC zinc, iron and manganese deposits, in addition to cycled up cooling towers, include reverse o~mosis systems9 sugar refinirlg evaporators, and certain types of ga~ scrubber~
The polyether polyamlno methylene phosphonates used in *he methods o~ the pre~ent invention, are usually used in greater amounts than threæhold -:
inhi~itor~ in the etabilizatio~ method~ of the $: pr~sent invention, more closely resembling ~eguestering or chelating age~ts in amour3ts. The compositions of ~he present invention have di~persant 30~ properties as well a~d signi:~icantly reduce the ~: adherency of any deposits which are formed , acilitating their ~asy removal.
, .
~ :
2~7~
2998H - 6 ~ C-1576 Pa~ticular problems are encountered when attempting to prevent deposits of zinc, iron and manganese compounds under severe conditions, where conventional treatments do not provide complete control, and where high alkalinity causes precipitation of hydro~ide ~altQ due to increased insolubility. Conven~ional trea~ment can be used to inhibit zinc, iron and mangane~e deposits un~er normal condi~ions o~ alkalini~y7 e.g. 9 Up to 100 to 120 times calcite sa~uration, i.e.~ a water containing Ca2~ and C03 presen~ a~ 100 times (100 x) their solubility limit of calcium as calcite (calcite is the most common crystalline form of calcium carbonate>. ~owever, what is desired are inhibitors effectiv2 in greater than 150X water, especially in greater than 250X water~ and more especially in greate~ than 300 X ~ater, i.e., where the calcite.ions can be preve~ted ~rom precipi~ating as calclum carbonate scale using æubs~oichiometric amounts of an inhibitor. The polyether phosphonate composi~ions used in the methods o~ the pre~ent invention are especially useful under se~ere conditions characterized by a calcite ~aturation level of 150 2 and above, especially 250~ and above, and more especially 300X and above~ as defined in the paragraph immediately below.
Ano~her characteristic feature of the se~ere cond~ions under which the ~olyether phosphonate compositions uæed in the methods of the prese~t invention are especially use~ul is high p~, i.e. a p~
0~ 8.5 and higher, particularly a p~ of 9 or 10 or even higherO
One of the particular advantages of the polyether phosphonate compositions used in the methods Qf the ,;,, ; ,. . ,, , , ; ,, .,, . , ,. ., , . , . , ",, ,"
2~19~7~ ~
preæent invention is the exceptional calcium tolerance which they exhibit. Calcium tolerance is a measure of a chemical compo~nd~s ability ~o remain soluble in the presenee of calcium ions (Ca~). As pH increases, calcium tolerance decreases rapidly for many compounds which might be used to control zinc, iron and manganese deposits, and they precipitate - with calcium at alkaline pE's, renderi~g them useless. While it is common practice to use an acid -: feed to the water of, e.g., a cooling tower system in ; order to lower p~ and thus avoid ~he calcium tolerance problem, the danger to handlers which suCh acid feeding poses ~ake3 it all the more important to find inhibitors o~ zinc~ iron and manganese deposits which operate at high p~s.
'-~
2. Brie~ Description of the Prior Art Methods which have been used heretofore to remove manganese include those whereby the manganous ion is oxidiæed to insoluble higher oxides, hydrous oxides, or hydroxides, which precipitate and may be removed by ~oagulation and settling, filtration, or both.
The oxidation has also been ef~ected by raising the p~ of t~e water to 8 or higher where naturally occurring diææolved oxygen or mechanical aeratlon ~:~ 25 brings about o~idation, or by the use of chlorine or permanganate. All of these me~hods, however, suffer from obvious disadvantages which limit ~heir ,~ ~ usefulness and effectiveness. For example, thie use of a high pH to ~acilitate oxidation by dissolved oxygen i~ expensive and tends to cause scale : deposition. Chlorine is only slightly more acti~e ~han dissolved o~ygen ~or oxidation of manganese and : : :
~98H 8 ~ C-1576 : also requires pH elevation. Permanganate is eæpensive and imparts to the water an intense color that may be unacceptable.
One method for removing the manganese by preCipitation and remo~al involves ~he addition of a salt o~ iron, copper, or cobalt and any compound yielding bi~ul~ite ions in solutlon to the manganese-containing water. See Hatch - ~S 3 9 349,031.
Soluble manganese ion and itæ reaction products have been stabilized in water sys~em~ using carbo~ylic acid/sulphonic acid copolymers. See Ralston - US 4,552,665.
US 4,080~375 discloses me~hylene phosphonates of amino-terminated oxyalkylate~ for use as scale inhibitors~ but these compositions are not the same as those of the present invention, nor is there any ~uggestion that such compositions would be useful for ~tabilizing zinc, iron and manganese. US 4,~31,189 disclo~es aminomethylene phosphonates o~ the type use~ in the method of th~ present in~ention, but ~or . inhibiting oil field scale formation involving a high brine en~iro ~ ent æusceptible to gypsum or barite ~cale formation. Such use in no way ~uggests the stabilization of zinc, ixvn and manganese described herein.
US 4,783,267 diæclose3 a method ~or stabili~ing metal ions in recirculating water ~ystems using 2-hydroxyphosphonacetic acid. The me~al ions stabilized include iron, zlnc, aluminum, and manganese. The~e is no suggestion, however, of use of the polyether phosphonates of the present ventiO~.
:: Th~ polyeth~r polyamino me~hylene ~hosphonates of ~the type ~hich are used to stabilize zinc, iron and . .:; ; . . . . ~. , ~ . .
7 ~ ~
.
:: .
~ .
~ - .
:: 5 ,~
~' :
. . .
: 10 TITLE OF THE I~VENTION
.- ZINC, IRON AND MANG~NESE STABILIZATION USING POL~ET~ER
~: POL~MINO METHYLENE PHOSP~O~TES
.
, ~, .
,~
., 15 ~ACKGROUND Q~ TEE INVENTIQN
~: l. Field of the Invention .
i,...................................... .
STABILIZATIOM OF SOL~BL~ MANGANESE AND ITS
REACTION PRODUCTS - The present in~ention relate~ to the use of polyether polyamino methylene pho~pho~ates to:stabilize soluble manganese ion~ and their reaction products in de~irable forms and reduced :particle ~izes. Mangane~e exist~ in various 25~ oxi~dation s:tates ~rom l through 7, with the o~idation tates oX 2~and ~ being the moQt ~table, and the~r~ef:ore the p~edominant ~orms in nature. The 2~7'~ ~
2998H - ~ - C-1576 present invention .is inteTIded to include s~abilization of manganese ions for all of these oxida~ion s~ates. Manganese .ions ar~ o~ten found in well wateræ and coollng waters. Anionic species of carbonate, bicarbonate, sulfite, fluoride, chloride, sulfate, and so orth, and dissolved o~ygen may be present in both waters. Oxygen reaction produets of manganese and iron can collect on metal sur~aces and accelerate corrosion and reduce heat txans~er.
Oxidation leads to precipitation of dark brown or black hydrous oxides or hydroxides of the hlgher o o~idation ~tates o manganeæe which are ~ery insoluble. Man~anese hydro~ide, Mn~0~)2, is especially a problem. When these precipitates remain suspended in the water, they cause objectionable di~coloratio~ known as "black water"; when they settle out, black deposits form which can block lines, or act as catalystæ causing further manganese deposition. These deposits are very deleterious in tex~ile and laundry operations as they int2r~ere with dying processes and leave spots which are dif~icult 2a to remo~e. They appear to increase the corrosion o~
copper.. Manganese hydroxide, Mn(0~>2, while it is usually present as a colloidal ~uspension, when i~
does form a deposit, it readily becomes the site for the promotion of the deposit o~ other scaling ma~erials, thereby accelerating scaling in g~neral The polyether polyamino methylene phosphonates, when used in accordance wi~h the method o the present invention, can keep the reaction products of mangane~e described above in colloidal/fine dispersed : 30 ~orm rather than the normal flocculant, adherent species. The mangane~e thus remains soluble 90 that it will not ~orm particles which will precipitate out : ~: : ' ~ ' ' 7 ~ .~
of solution and form scale.
STABILIZATION OF SOLUBLE IRON AND ITS REACTION
PRODUCTS - The present in~ention further relates to the use of polyether polyamino methylene phospho~la:tes to stabilize soluble iro~ ion and its reaction products in desirable orms and reduced particle - 5 siæes. Ferrous and ferric ions are often found in well waters while cooling ~aters contain primarily the ferric species. Iron ions are often present as the result of rusting of the iro~ piping used to transport the ~ater in a cooling sy~tem. Anionic : 10 species of carbonate, bicarbonate, ~ulfite, fluoride, chloride, sulfate, and so ~orth, and dissolved oxygen may be present in both waters. Oxyge~ reaction products of iron can collect on metal surfaces and :: accelerate corrosion and reduce heat tran~fer.
; 15 Oxidation leads to precipitation of brown or red oxides of the higher oxidation states of iron which are insoluble. When these precipitates r~main suspended in ~he water, they cause objec~iona~le discoloration know~ a~ "red water"; when they settle QUt, red deposits foxm which can block lines, or act : as cataly~ts causing further iron reaction product deposition. The~e depo~its are very dele~erious in textile and laundry operations as they inter~ere wlth dying processes and leave spots which are dif~icult ! 25 to remove. Fe(OH)2, while it is usually prese~t as a colloidal su~pension, when it does form a deposit, : it readily becomes the 3ite for the promotion of the deposit of other scaling Materials ~ thereby acceleratin~ qcali~g in general.
The pol~ether polyamino methyleRe phosphonates, when used in accorda~ce with the.method of the preEent invention, can keep the reaction products of '7 ~ ~
~998H - 4 - C-1576 iron described above in colloidal/~ine dispersed ~orm rather than the n~rmal flocculant, adheren~ species.
The iron thus remains soluble so that it will not form par~icles which will precipitate out of solution and form scale.
STABILIZATION OF SOLUBLE ZINC AND ITS REACTION
PROD~CTS - The present invention ~urther relates to the use of polyether polyamino methy~ene pho3phonates to stabilize soluble zinc ion and its reaction pxoducts in desirable forms and reduced particle sizes. Zinc ions are o~ten found in well water~, while cooling waters can also contain zinc ionsO
Zn~ present in cooling waters is ofte~ derived : fxom the zinc metal used in making the copper and . brass alloy~ from whlch the piping used for ;i; tra~sporting the cooling water is co~structed.
Anionic species of carbonate, bicarbonat~ 9 sulfi-te, :~ ~luorîde, chloride, sulfate, and GO forth, and dissolved oxygen may be present in bo~h waters.
Oxygen reaction products of zlnc can collec~ on metal . 3urfaces and accelerate corrosion and reduce heat ~20 transf~r. Zinc hydroxide, Zn(0~)2, has been found to be a particular problem. While it is usually pr~sent as a colloidal ~uspension, when it doeæ form i a deposit, it readily becomes the site ~or the ~: promotion o~ the depo~it of other ~caling materials, thereby accelerati~g ~caling in general.
~:~ The combination products of the zinc îons and ~he anionic ~pecies recited above can often æettle out, c~eating deposits which can block lineQ~ or act as catalyst~ causing ~urther zinc reaction product ~depositio~. These depositæ can be ~ery deleterious :in textil~ and laundry operations as they interfere ; with dyinsg proCeæBeæ and lea~e spots ~hich are ~: ~
:
~$~
difICicult to remove.
The polye ther polyamino methylene phosphonates, when used in accordance with the method o:f tlle present inven~ion, can keep the reaction products of zinc described above in colloidal/f~ne diepersed form rather than the normal flocculant, adhexent ~pecies.
:~ 5 The zinc thus remains soluble ~o that it will not form par~icle~ which will precipi~ate out 0lc solution - and form scale.
The stabilizatio:n methods described above are especially use:L'ul under conditions OI high pH and 1~ hig~ calcite concen~ratio:lls, e.g. s thoæe found in cycled up cooling towers. Various indu~trial and ~;. commercial water-ca~ryiIlg systems are subjec~ to zinc, iron and ma~gane~e deposit formation problems.
These deposite form freguently in the tubes of heat e~change:rs and on other heat e~change eur~aceæ, ~uch a~ those in cooling towers. Particular systems or applications areas where severe conditions, especially h;gh alkaLirli~y, lead ~o exceptiorlal ;~ buildup OIC zinc, iron and manganese deposits, in addition to cycled up cooling towers, include reverse o~mosis systems9 sugar refinirlg evaporators, and certain types of ga~ scrubber~
The polyether polyamlno methylene phosphonates used in *he methods o~ the pre~ent invention, are usually used in greater amounts than threæhold -:
inhi~itor~ in the etabilizatio~ method~ of the $: pr~sent invention, more closely resembling ~eguestering or chelating age~ts in amour3ts. The compositions of ~he present invention have di~persant 30~ properties as well a~d signi:~icantly reduce the ~: adherency of any deposits which are formed , acilitating their ~asy removal.
, .
~ :
2~7~
2998H - 6 ~ C-1576 Pa~ticular problems are encountered when attempting to prevent deposits of zinc, iron and manganese compounds under severe conditions, where conventional treatments do not provide complete control, and where high alkalinity causes precipitation of hydro~ide ~altQ due to increased insolubility. Conven~ional trea~ment can be used to inhibit zinc, iron and mangane~e deposits un~er normal condi~ions o~ alkalini~y7 e.g. 9 Up to 100 to 120 times calcite sa~uration, i.e.~ a water containing Ca2~ and C03 presen~ a~ 100 times (100 x) their solubility limit of calcium as calcite (calcite is the most common crystalline form of calcium carbonate>. ~owever, what is desired are inhibitors effectiv2 in greater than 150X water, especially in greater than 250X water~ and more especially in greate~ than 300 X ~ater, i.e., where the calcite.ions can be preve~ted ~rom precipi~ating as calclum carbonate scale using æubs~oichiometric amounts of an inhibitor. The polyether phosphonate composi~ions used in the methods o~ the pre~ent invention are especially useful under se~ere conditions characterized by a calcite ~aturation level of 150 2 and above, especially 250~ and above, and more especially 300X and above~ as defined in the paragraph immediately below.
Ano~her characteristic feature of the se~ere cond~ions under which the ~olyether phosphonate compositions uæed in the methods of the prese~t invention are especially use~ul is high p~, i.e. a p~
0~ 8.5 and higher, particularly a p~ of 9 or 10 or even higherO
One of the particular advantages of the polyether phosphonate compositions used in the methods Qf the ,;,, ; ,. . ,, , , ; ,, .,, . , ,. ., , . , . , ",, ,"
2~19~7~ ~
preæent invention is the exceptional calcium tolerance which they exhibit. Calcium tolerance is a measure of a chemical compo~nd~s ability ~o remain soluble in the presenee of calcium ions (Ca~). As pH increases, calcium tolerance decreases rapidly for many compounds which might be used to control zinc, iron and manganese deposits, and they precipitate - with calcium at alkaline pE's, renderi~g them useless. While it is common practice to use an acid -: feed to the water of, e.g., a cooling tower system in ; order to lower p~ and thus avoid ~he calcium tolerance problem, the danger to handlers which suCh acid feeding poses ~ake3 it all the more important to find inhibitors o~ zinc~ iron and manganese deposits which operate at high p~s.
'-~
2. Brie~ Description of the Prior Art Methods which have been used heretofore to remove manganese include those whereby the manganous ion is oxidiæed to insoluble higher oxides, hydrous oxides, or hydroxides, which precipitate and may be removed by ~oagulation and settling, filtration, or both.
The oxidation has also been ef~ected by raising the p~ of t~e water to 8 or higher where naturally occurring diææolved oxygen or mechanical aeratlon ~:~ 25 brings about o~idation, or by the use of chlorine or permanganate. All of these me~hods, however, suffer from obvious disadvantages which limit ~heir ,~ ~ usefulness and effectiveness. For example, thie use of a high pH to ~acilitate oxidation by dissolved oxygen i~ expensive and tends to cause scale : deposition. Chlorine is only slightly more acti~e ~han dissolved o~ygen ~or oxidation of manganese and : : :
~98H 8 ~ C-1576 : also requires pH elevation. Permanganate is eæpensive and imparts to the water an intense color that may be unacceptable.
One method for removing the manganese by preCipitation and remo~al involves ~he addition of a salt o~ iron, copper, or cobalt and any compound yielding bi~ul~ite ions in solutlon to the manganese-containing water. See Hatch - ~S 3 9 349,031.
Soluble manganese ion and itæ reaction products have been stabilized in water sys~em~ using carbo~ylic acid/sulphonic acid copolymers. See Ralston - US 4,552,665.
US 4,080~375 discloses me~hylene phosphonates of amino-terminated oxyalkylate~ for use as scale inhibitors~ but these compositions are not the same as those of the present invention, nor is there any ~uggestion that such compositions would be useful for ~tabilizing zinc, iron and manganese. US 4,~31,189 disclo~es aminomethylene phosphonates o~ the type use~ in the method of th~ present in~ention, but ~or . inhibiting oil field scale formation involving a high brine en~iro ~ ent æusceptible to gypsum or barite ~cale formation. Such use in no way ~uggests the stabilization of zinc, ixvn and manganese described herein.
US 4,783,267 diæclose3 a method ~or stabili~ing metal ions in recirculating water ~ystems using 2-hydroxyphosphonacetic acid. The me~al ions stabilized include iron, zlnc, aluminum, and manganese. The~e is no suggestion, however, of use of the polyether phosphonates of the present ventiO~.
:: Th~ polyeth~r polyamino me~hylene ~hosphonates of ~the type ~hich are used to stabilize zinc, iron and . .:; ; . . . . ~. , ~ . .
3 ~
2998~ - 9 - C~1576 manganese in the compositions of the preSeDt invention, are described in copending application Serial No. 07/708,527, filed May 31, 1991 (At~orney Docket No. C-1527). While their use for the control of calcium carbonate scale under severe conditions which include elevated pH and high calcium carkonate saturation levels, is described, there is no suggestion of their use to s~abilize æinc, i~on and manganese.
:
1o S ~ Y OF T~ INV~TIQN
The present in~ention relates to a method vf i~hibiting the precipitation of diæ~olved zinc, iron and manganese ions and their reaction products in an aqueous system, comprising the step of treating said ~: system with a~ effective precipitation-inhibi~ing amount of a polyether polyamino methylene phosphonate of the ~o~lowing fo~mula:
203P - ~2C R ~ CH2po3M~
~ C~ 2 -~- C~2 ~ ~ ~)n - N
`~ M203P - :~2C CE2P03M2 and optionally the N-o~ides therevf; wher~ n is an integer or fractional inte~er which is, or on a~erage om about 2 to about 12, inclusive; M is hyd~ogen or a suitable cation; and each R may be ~he same or differe~t and is independently selected from hydrogen and methy~. . -~ :A:preferred subclass o~ eomposàtio~s of the above :;
:
formula iæ ~hat wherein M is hydro~en, R is methyl, and n is from about 2 to about 3, most p~e~erably an average of about 2.6.
In particu~ar, the present invention relates to such a treatment method in which the aqueous system . being treated is characterized by the severe ; 5 conditions ofi a pH of at leas~ 8.5, especially 9~0 or ; greater, and a calcite concentration of at ~least - 250~, especially 300X or greater; and the polyethex p~osphona~e is u~ed in an amount su~icient to achieve a concentra~ion of from 0.1 to 50 mg/L in ~aid aqueous æystem, preferably from 1.0 o 10 mg/L, and most preferably from 2 to 5 mg/L.
The present invention further relates -to a metho~i o~ inhibiting the precipitation of dissolved zinc, iron and manganese ions and thelr reac~ion products l~ in an aqueous system, comprising the step of treating ~aid ~ystem with an effectlve ? precipitation-inhibiting amount of a composition compri~ing a polyether polyamino methylene phosphonate of the formula above, together wlth a polymer additive comprising one or more members ~ selected from the group consisting of: homo- and i, copolymers including terpolymeri comprising one or more of acrylamide ~AM)~ acrylic acid (AA), 2-acrylamide-methyl propane æulfon.ic acid ~MPSA), methacrylic acid (M~A), itaconic acid (IA), polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), ma~eic acid (~A), t-butyl acrylamide (TB~M), s~dium styrene sul~onate (SSS), sodium vinyl sulfo~ate, hydroxy propyl acrylate, hydroxy propyl methaerylate, 3-allyloxy-2-hydroxy propane ~ul~onic acid, sodium salt.~A~PS), and ~inyl phosphonic acid, wherein the weight average molecular weight for such ~ .
20997D~
2998H ~ C-1576 polymer additives i.s in the range of rom about 500 to 250,000.
In particular, the present invention relates to such a method in which for the above formula for the polyether phosphonate, M is hydrogen, R i9 methyl, and n is fxom about 2 to about 3, moæt preferably an average of about 2.6; the aqueou~ ~ystem being : treated is characterized by the severe conditions of a pE of at leaæt 8.5, especially 9.0 or greater, and a calcite concentra~ion of at least 250~, e~peeially 300X or greater; and the polyether phosphonate is used in an amount sufficient to achieve a concentration of from O.l to 50 m~/L in said agueous ~ystem, preferably from l.0 to 10 mg/L, and most :~ preferably from 2 to 5 mg/L; and ~aid po~.ymer additive is a member selected from the group consisting essentially of 90/lO to lO/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA, 100 M 9 75/25 SSS~MA, 33/33/34 AA/MAA/IA, 50/~0 AA/AM, 70/20/10 AA/~MPSA/P~M-5 (having 5 repeating oxyethylene ~nits), and AA/AMPSA/TBAM.
The present invention ~till ~urther relates to a composition $or inhibiting the precipitation of ,, dis~olved zinc, iron and manganese ions and their reaction products in an a~ueous-sy8tem, ~omprising a polyether polyamino methylene phosphonate o the formula above. The present invention also relates to a compo~ition comprising a polyeth~r phosphonate of the formula above in combl~ation with a polymer additive which is a member selected from the group eonsisting;es8entially of those enumerated above. In particular, the present invention relates to such a compositio~ in which for the abo~e formula or the polyether phosphonate, M is hydrogent R is methyl, ' :
.:
and n is from about 2 to about 3, most preferably an average of about 2.6; and said polymer additive is a member selected from the group consisting essentially of 90/10 to lO/90 AA/AMPSA, preferahly 75/25 and 60/40 AA/~IPSA, 100 A,9, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/:10 AA/AMPSA/PGM-5 (having 5 repeating oxyethylene UIlitS), and AA/AMPSA/TBAM.
DETAILED DESCRIPTION OF TEE INVENTI~N
~` 10 . . .
The acti~e ingredient in the compositions and methods.o~ the present i~vention for inhibiting the .: pxecipitation of dissolved æinc, iron and manganese .- 15 ions and their reaction products in a~ aqueous system, especially one characterized by se~ere conditions of high p~ and high calcite concentration, is a polyether polyamino methylene phosphonate of the f oralula:
M2O3P - H2C RR C~2PO~M2 , N - C~ - CX~OCH2 - CH ->~ - N
M203p - :EI2C C~2P03M2 25 and optionally th~ N-oxides thereof; where n is an ~, integer or fractiona~ integ~r which isl ~r on a~erage is, ~rom about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be th~
æame or diferent and is independently selected from hydrogen and methyï. A preferred subclass of compositior~ of the above formula is that wherein M
7 1a l.~
2998~ - 13 - C-1576 is hydrogen, R is methyl, and n is from a~out 2 to about 3~ most yre~erably an avexage of about 2,6.
In order to cbtain high levels of control of zinc, iron and manganese deposits, eæpecially under the severe condi-tions defined herein, it has been found that there are certain essential compone~ts of - 5 the structure of such polyether polyam~no methylene phosphonate or N-oxides which are necessary to provide that per~ormance. For e~ample, ~he N,N-bis(phosphonomethyl)amino portion of the structure is essential. Whether ~his group is present initially in the phosphonic acid form or as an alkali metal or other salt of the acid, has no critical bearing on ~he performance of ~he overall - molPcule. At the pH's under which the phosphonate compositions ~unction~ -~hey are, and must be, ln their ioni2ed form. Thus, .it is not critical whether ~M~ is hydrogen or a suitable cation, a~d the :: selection of an appropriate salt form i~ well within the skill o~ ~he art. Alkali metal salts are the most simple, and are preferred for that reason.
2~ Overall, however, it is preferred that M i3 hydrogen.
The poly~ther polyamino methylene phogphonate may ! be in the N-oxide ~orm: N $ O.. This group confers slgnifi~ant resistance to degradation by chlorine and bxomine bioeide~, or mixtures thereo~, which may be : 25 present in the aqueou~ system being treated, ~ presumahly by preventing o~idative attack on the : nitrogen atom of the group.
A preferred ~tructural feature of the polyether polyamino methylene phosphonates a~d N-oxides useful as deposit control agents is the isopropyl group which bridges the diphosphonomethylamino group and the polyether group. Thi~ group can also be an ~ .
2~
2998~ - C-1576 ethylene moiety.
: Another structural elemen~ o~ ~he phosphonate zinc, iron and manganese deposit inhibitors is the polyether moiety. Since the polyether polyamino methylene phosphonates are prepared by phosphonomethylation of the appropriate diamine, the character of the polyether moiety will depend UpOIl the way in which the amine startlng material is made. Processes for making such polyether diamine~
are known in the art; and attention i3 directed particularly to US 3,236,895, ~hich describes prepara~ion o~ a variety of polye~her diamines especially useful ~n preparing the phosphonate final products used as deposi~ con~rol agents ln ~he present invention.
In accordance with the processes ~et out in US
3,236,395 and related proCeBSe~ de~cribed in the prior art, ik is po~sible to prepare any on~ of a - number of desired polyether diamines within the ~cope of the present invention. In the ~eneral formula for the polyether polyamino methylene phosphonates used j 20 herein, the polyether moiety is simply represented by .the formula:
R
, _(-OCH2-C~-)n~
Since R may be hydrogen or methyl, both ethyleneoxy :~ and propyleneoxy units axe possible. Moreover, R is to be independently chosen, i.e., ethyleneoxy and propyleneoxy units may alternate in various patterns, : including blocks of each, or ~hey may be all one or ~:~ 30 the other. For e~ample, the following are ju~t ome o~ the polyether segments whic~ might be prepared to ; , : ~ :
:: : ....... : . ' 2~73l~
. .
form the basis for the corresponding diamines, which ~; would then be used to make phosphonate~ wi~hin the scope of the present invention (where E0 =
ethyleneoxy, and PO = propyleneoxy):
;` E0; P0; E0 E0; P0-P0; E0-P0; E0-E0-E0;
P0 P0-P0; E0-E0-P0; E0-P0-P0; EO~P0-E0;
.
P0-E0 P0, E0-E0-E0-E0; P0-P0-P0-P0~ E0-P0-P0-P0;
; ~0-E0-P0-P0; E0-E0-E0-P0; E0-P0-E0-P0;
:E;O-PO-PO-~;O, PO-EO-F.O-PO
.,~
In the above example~, "n" in the main ~ormula would be an integer of from 1 to 4. Since "n" is defined ~: as being from l to 12, an even larger numbex of possible polyether moie~ie~ i~ included. However9 it has been found that generally the polyether polyamino . 15 methylene pho3phonates of lower molecular weight, ,~ i.e., where ~n~ is a smaller i~tege~, are those which pro~ide the greatest amount o~ scale inhibition urlder ~` the severe conditions of high pH and high calcite J concentration, and thus are those which are ~'! 20 pre~erred. Examples of some of these preferred , pho~phona~es are shown in ~he table below, wherc Z =
methylenephosphonate:
~' .~ -$
, ~ . . .
~! .
~ 30 .
~;: : :
.
, 2 f~ J 7 ~ ~
Rz Ra ~b Z 2-N~ c~2-(oc~I2cH)a - (OC~;~CE)b -NZ2 Idf- No. _~ b Rz _ Ra_ Rb--; 5 2 1 CH3 ~ CE~3 :B 2 . 6* CH3 CE[3 - -C ~ f~H3 CH3 ---D 8 . 5* 1 ~3 ~ ~3 ~ 5 . 6* f~f C~3 G~.3 --~
2 o G 3 0 H H -~-E 3 ~f f~,~3 C~I3 ---1 S I 3 l E C~3 - J 4 G H C:E[3 ~--f ~ - the value of "n'9 on avera,g~e.
It ~ill be noted from ~he ;able above that in f 20 several cases 9 "n" has an average value , i . e ., thff~
number o~ repeatir~g ethyleneo~y or propy~eneoæy UllitS
may vary. Thus, it is pos~ible to have a mi~uxe o:E
varying c~ain lengths o~ polyox3rethy:Lelle or ~: polyo~propylene in the f inal product . This tf æ also ~5 co~templated tG be withln the ~cope of the pre~ellt invention, æo long aæ the requirementf~ with.respect to khe limit off "n" are observed. ConsegueIItly, whil;e ~n~ :is merely defined as an integ,er or fractional integer which is, or on average is, ~from 30: about :2 to about 12, it has two a~pects . It defineæ
the tota~ o~ the ~umber of repeating ethyleneo~
2 ~ 9 9 ~
2998~ - 17 - C-1576 and/ox propyleneoxy units considered separately, and ~hus if ~n~ is, e.g., 4, it includes 4 propyleneoxy units, 3 propyleneoxy units and 1 ethyleneo~y unit1 2 propyleneoxy units and 2 ethyleneoxy units, and so forth. The value o~ ~n~ may alsv represent an average number, and this is always the case, of course, when it is a fractional integer. In this case, for each of the ethyleneoxy and/or propyleneoxy units considered separately, mixtures of these unitsf may be presfent so as ~o give an average value for "n". For e~ample, in the table above, for Id. No. D, lO the total of "a" and "b" is 9.5, which is the value of "n". What is descri~ed is a mi~ture of polyether phosphonate~. in which all of ~hem have an i~opropyl hridging group and an e~hyleneoxy moiety, but ~he repea~ing propyleneoxy units are such that on average 15 thei~ value is about 8.5.
The number o~ repeati~g ethyleneo~y or oxypropylene units~ designated by the su~cript "n", determines the total molecular weight of the overall polyether polyamino methyl2ne phosphonate or 20 correfponding N-oxide, and thus plays a critical role in determining the scal~ inhibi ting per~ormance of that phosphonate. It has been ~ound that in order to provide adequate scale control under the fevere ~, conditions of use defined herein, it is neces~iary 1 25 that "n'l be an integer or fractional integer which i~,. or on average is, ~rom abou~ ~ to about 12, inclusive.
As discussed above, the rea~on ~ox ~n~ being potentially a fractional integer arises from the fact ~:~ 3~ that the primary diamine from which the polyether polyamino methylene phospho~ates are prepaxed by phosphonomethylation may be a mixture of polyethers ..
.
:::
.
.
.
299~X ~ C-157 ; in which "n~ two or more o~ 2, 3, 4, 5 and so forth, in varying proportions. For example, a preferred polyether polyamino methylene phosphonate for use in the compositions and method~ of the present invention has a molecular weight o~
approxîmately 632 and the value of i'n" on average is about 2.6. Thus, this type of polyether phosphonate has a molecular welgh~ distribution, i.e., of the various polyo~ypropylenes which make it up, and this distribution is represented by a fractional integer average value for "n". But, it is also within the scope of the present invention for "n" to be a whole integer, e.g., 1~3l~, which usually designates a single molecular wei~ht and not a mclecular weight ,~ distributlon.
~ The polyether polyamino methylene phosphonate and :, 15 corresponding N oxides of the compositions and methods of the present invention are prepared fir3t ~' by phosphonomethylation of the appropriate primary amine which already contains ~he polyo~yethylene and polyoxypropylene moieties, followed by an oxida~ion i 20 step which provides the N-oxide moieties.
'~ Such primary amine starting materials and their : method of preparation are well known. The ;I' phospho~omethylation o~ the primary amine is then carried out by a Mannich reactioll such as that i 25 described in ~. Moedritzer and R. Irani, ~. Org~nic .! ~hem. 31(5) 16G3-7, "The Direct Synthes ~ o~
-li alpha-Aminomethyl Pho~phonic Acids; Mannich-Type Reactions with Orthophosphorous Acid", May 1966. In ; a typical reaction, the primary amine is added to a mixture o~ phosphorous acid and water, and concentrated hydrochloric acid is then added slowly, : a~ter which the reaction:mixture is heated to reflux :
:~ :
20~7a~ -~wi~h addition of aqueous formaldehyde.
: Al~hough the general structural formula employed herein indicates ~ha~ the nitrogen atom is completely phosphonomethylated, as a practical matter, : preparation of the polyether polyamino methylene phosphonate and corresponding N-oxides of the present invention, as described in detail ~urther below, usually results in o~ly about 80 to 90%
phosphonomethylation. Other side products give N-substitution with H, CH3, C~20~, etc. It i8 not practical, as a matter of simple production economics, however, ~o isola~e and puri~y the completely phosphonomethylated compounds, since the ~ide products just described do not interfere with zinc, iron and manganese deposit inhibition. Such -side products, are consequently, usually allowed to remain, and the test data set out further below is ba~çd on test samples containing such side productæ.
Consequently, the activity levels obtained would be even higher were 100% acti~e compound being tested~
Once the desired phosphonomethylated polyoxypropylene diamine has been prepared as de~cribed above, the N-oxide ~inal product of ~he present invention is then prepared by a step of oxidation, which may be accomplished, e.g., simply by adding hydrogen peroxide to a basic solut~on of the 25 phosphonomethylated diamine and heating the reaction mixture, which gives high yields of the N-oæide final :-product. Of cour8e, it iB also posæibl~ to uæe other well known techniques for carrying out such a step of oxidation, and any number of these may be success~ully emplo~ed.
- ~The amounts o$ any particular polyether polyamino methylene phosphona~e that are required to be added :
:~:
2~7~
299~ - 20 - C-:L576 for the decired ma~imum inhibition of zinc, iron and ma~ganeæe deposit ~ormation will be such as to provide an ultimate concentration in the aqueous æystem being ~reated of between 0.1 and 50 mg/L, and preferably this concentration will be between 5 and 30 mg/L. Most preferably the concentration will be between 10 and 20 mg/L, although i t ie under~tood that many factors, of the type which have been explained in detail with regard to the background to . the present invention, will determine the actual s amount of polyether phosphonate which will be added to any particular aqueous system in order to achieve - the ma~imum amount o:F inhibitioIl of zinc, iron and manganese deposit formatiorl in that agueous system.
~he calculation of those amounts will be well wi~hin the skill of the artisan in this :Field.
When the polye ther polyamino methyl~ne phosphonate used in the me~hods and compositione of the present invention are used in combination with one or more of the polymers recited :further above, '3 ~he amounts of that combination which must be added in order to inhibit zinc, iron and manganese deposition i~ an a~ueous system, will as a ge~eral matter be within the ranges of amounts su~ficient to ~ establi~h the ranges of concentration3 of the 3 polyether phosphonates and corresponding N-oxides 1 2s used alone, as recited in detail above. Again, however, calculation of t~e actual amount iæ well j~ within th~ ekill of ~he ar~.
J~ The manner o~ addition of any particular polyether polyamino methylene phosphonate to an aqueous sy~tem will also be straightforward to a person o srdinary skill i~ this art. It may be added in ~inely subdivided solid form by mechanica~
dispensers of known design. It may also be added in solid form, but in ~he ~orm o~ a matri~ in which solid particles of the active ingredient are bonded or bound to~,ether by a material which is water : soluble, or optionally, does not dissolve at all.
Such a matrix allows for regular leaching out or disso~ving of the active ingredient particles, ~ whereby it is possible to obtain a sustained release ; and more unvarying concentration of the sodium monofluorophosphate in the water being treated. The par~icular polyether phosphollate may also ~e made up in the form of concentrated solutlons for di~pen3ing ;~ ln liquid foxm from dispensers well known in the ~:~ art. The polyether phosphonates may also be combined .~ with othe~ chemical treatment agent3 for dispensi~g - to the aqueous system, and these in combination may be dispensed in solid or liquid ~orm.
The phrase "aqueou~ system" as used herein i~
meant to ~nclude any system containin~ water;
.' including, but not limited to, cooling water systems ..
; including cooling to~ers, boiler water ~ystems, desalination systems, gas æcrubber units~ blast furnaceæ, ~ewage sludge dewatering æystems, thermal i, conditioning equipment, re~erse osmosis units, ~ugar ~: e~aporators, paper processing systems~ mining j circuits, and the li~e.
~ 25 1~ .
~:~ XQ~F,F~ 9F PREFERRED E~BODIMENTS.
The following e~amples demonstrate the effectiveness o~ the treatment mçthods of the pre~ent invention in reducing lead æolubility i~ water.
. , ' ' , : ~; ' ' -2'~ 4 ~998H - 22 - C-1576 The~e examples are illustrative only, and are not intended to be a limita~ion o the prese~ vention.
.
lEXAMPLEI
Manganese Stabilization PROCEDURE: Conditions: The 2 hour study was done using a gang stirrer at tempera~ure:-25~C and stagnant ~lasks a~ 60C; while ~he 24 hour study was lo done by incubating flasks at 60C. The p~ in all cases was 9.0, and the total alkalinity (~CO3/CO3) of 400 mg/L was added to 4~ Pittsburgh water of the following compositlon:
Ion Ion Con~en~ration (mg/L) Mg~ 24 Ca~ 88 : SO4- 329 Nal 56 25~ Cl- 70 IN~IBIl'OR: the polyether phosphonate test compound employed~wa~ that of the main formula wherein M = ~, CH3 in al~ cases, and n = on average about 2.6.
he~inhibitor:was added to a known volume (500 - ~:
[inhibl~tor volume + manganese volume ~ ECO3~CO3 olume3) of 4X Pittsburgh water (p~ adjusted to 8.8~, 7 ~ ~
followed by manganese solutions (1.0 g/L). ~sing a ~- 2.00 mL volumetric pipet, 2.00 mL of 1.00 g/L Mn ~2 stock solution was pipeted under the ~urface of the water. (The Mn~2 stock solution was prepared using 4.125 mL per lite~ of 50/O Manganous Nitrate, which equals 3.~57 g/L of Mn(NO3)2.) In order to oxi~ize the Mn up to oxidation state 7 and thereby duplicate natural aeration, ~here was added H202 . juSt prior to adjuæting the pH to 9.0 u~ing O.O50M
NaOH, followed by the addition of a~kalinity:
~ICO3/CO3 (80/20~ soiution. The H2O2 amount wa~ adjusted tf4 the ~moun~ of Mn (lppm ~22 per 1 ppm Mn). The total volume of the flask was 50G mL.
The flasks were clo~ed with rubber stoppers and incubated for 2 and 24 hours. For the 2 hour gang s-tirrer ~tudy, the total volume was brought up to 1000 mL in a bea~er. At the end o~ the equilibration time, 50 mL of each test solution was filtered through 0.25mm filter paper~ acidified with concentrated HCl, and analyzed ~y atomic ab~orption spectroscopy. The final result was calcula~ed in 2~ accordance with the following equation:
i ~/O Mn = Mn w/ Inh;b. - Mn w/ No Inhib -- X ~00 Stablæd. Mn Initially Added - Mn w/ No Inhih.
R~SULTS: Following the above procedure ~ the ,3 25 following results were obtained:
,. : , , .:
.! i ~ ' .
3 d :
: ~ .
,: ; :
7 3 ~
.
TABLE _l Mallganese Stabiliza~ion pH = 9.t); HC03/C03 - 40ûm~/L
: 5 TEST CONC~NTRATI~N M~TAL ION % RECO-DOSE INIT'L FINAL VERY IN SOLUTION % STABILIZATION
~mg/L) 2 ~Ir6~ 24 ~kZ Hrs.24 Hr6 ,2 Hr~. 24 Hr~s.
. ., 10.0 1.0 0.98 0.68 9B 68 90 57 .~ .
15 . O 1 . O O . 990 . 88 99 ~ 95 ~4 : .
10.0 2~0 l.g5 ~)o81 98 ~1 78 2~Q
20.0 2.0 .1.97 1.46, 99 72 ~7 ~2 ~ .
EXAMPI.E 2 :
~: ~ ; Iron Stabili7ation 25 ~ ~ . The same ge~eral procedures a~ de~cribed above or ~xample 1 were ~mployed.. Usia~g a 2 . 00 mL
volumetric pipet, 2 . 00 mL o~ 1. 00 g/L Fe~2 stoc,X
s~o~utioIl was pipeted under the surfa~e vî the water.
The~Fe+ ~tock æolution was prepared freæh using 30~ 7, oz ~g~ams of ~e(NH4)2($43~ 6EI2 ~nd ml, of concentrated ~S04 per total volume of 1 00 iter .:) The acidif ied f i~trates and diluted 2~97~
~9g8~ - 25 - C-1576 Fe+2 stock solution were analy~ed using atomic absorption spectroscopy. The values were multiplied by l.05 to account for dilution during acidification. The percent (%) stabilization was calculated as follows:
~; . ..
% Fe = Fe w/ Inhib. - Fe w/ No Inhib. X lO0 Stablzd Fe Initially Added - Fe wt No Inhib.
RESTJLTS: Following the above procedure the following results were obtained:
-~ 10 TABLE 2 I~on Stabilization pH = 9O0, HC03/C03 = ~sOO~ng/I.
l 5TEST CONCENTRATION IIETAL ION % RECO-, DOSE INIT ' L FINAL VERY IN SOLUTION % STABILI~ATION(mg/L2 ___ 2 Hr~ .. 24 ~r~ .. 2 Hr~, 24 EIr~ O 2 Hr~ ~ 24 Hr~
.0 l.O 1.0 0.5~ 100 59 lOO 59 ~i 2 0 15.0 l.O l.O 0.68 100 ~8 lOû 58 10.0 ~.0 1.96 o.ss 98 50 g8 50 25~20.0 2.0 1.98 1.59 99 80 99 80 2 ~
:EX~IPLE 3 Zinc Stabilization The same general procedures as de~cribed above 5 :for :3~ample 1 were employed. I'he ionie matrix was a water containing 160 mg/L of Ca and 200 mg/L O:e sulfate. Additionally, 400 mg/L of HC03/C03 Wt3S
added to ~he water and the pH was adjusted to 9 . û.
The percent (%) ~tabiliza~ion ~Jas calculated as 10 ~ollows:
% zn = Zn w/Jnhib. - Zn w/ No I~h~ ~ 100 Stablzd Zn Initially Added ~ Zn w/ No IIIhib.
RES~LTS: Following the above procedure the `~ 15 following r~sults were obtained:
., ;~' ! Zinc Stabilization pH = 9O0; ~C03/C03 = 400mg/1.
A ~: TESTCONCENTRATION ~qETAL ION ~ P~ECO-DOSEINIT'I. FINALVERY IN SOLUTION ~ STABILIZAT10l~l (mg/L ) ~= 2 l~r~ .24 ~ 2 Hrs ._4 ~r~ . 2 ~Ir~ O 24 H~ .
10.0 2.~ 1.67 1.66 ~34 84 83 82 15.0 ~.o 2.00 1.99 loo loo loo loo :30~ lO.0 5.0 2.05 2.07 41 41 38 3B
20 . 0 5 . 0 3 . 66 3 . 66 73 73 72 72 ~ . :
7 ~ ~
. A~rPLE 4 EP:f ect of T~mper~ure 5. ~he effect~ of temperature on ætabilization results were obsertred by selecting data from that set out in Examples 1-3 above and p:resentillg i~ to show temperature effects. That selected data is set out in the table of values below:
TABI.E 4 ~ffect o:E Temperature on ~inc/Mangan~se/lron 5tabili~ation (p~l = 9.û~ HC03/C03 a 40Qmg/L) TEST CONC~NTRATIaN (ing/L) DOSE METAL INITIAL FINAL AFTER 2 EIRS % STABII.IZATION
(mg/L~ ION25~C .~0C _~ 60~ 25~C
Zinc 2.02.0 1.67 1.66 83 82 ~::
Iron 2.02.0 1.96 1.26 98 ~3 Mng~ 2.02.0 1.g5 1.12 78 39 As æhown in the data abo~re, stabilization ~as studl~ed at two d;fferent :levels of metal ion .
30~ con~erltration and three levels of teæt do~e ~or the polyether phosphonate ~t~bilizer; The % . ..
stab~ilizat:ion wa :~ound to depend on both metal ion 2~9~'q concentration and stabilizer test dose. Metal ion recovery in solution was ound to incr~ase with increasing stabilizcr dose and was found to decrease with increasing metal ion concentration. Zinc stabilization did not change with time from 2 hours to 24 hours; however, for both manganese and iron, stabilization was found to be sharply reduced between 2 and 24 hours. It is conjectured that a slow oxidation of iron and manganese may have been responsible for precipitation of those ions with ~ime. This may represent the combined ef~ect o~ time and temperature on iron and manganese oxidation. The results in Table 4 indicate some deterioration ofi iron and manga~ese stabilization ak 60C af~er 2 hours1 while zinc stability remains unchanged af~er 2 hours, even at 60C. The polyether phosphonate stabilizer was found to be stable to H202 oxidation, since no breakdown o~ ~he stabilizer was observed in any of the above experiments.
.
~ 20 ., ~'I .
,.
, ~
~, 25 ' ' ., .
.
:~ 30 'i~;~
! ~ ~ . .
.:
2998~ - 9 - C~1576 manganese in the compositions of the preSeDt invention, are described in copending application Serial No. 07/708,527, filed May 31, 1991 (At~orney Docket No. C-1527). While their use for the control of calcium carbonate scale under severe conditions which include elevated pH and high calcium carkonate saturation levels, is described, there is no suggestion of their use to s~abilize æinc, i~on and manganese.
:
1o S ~ Y OF T~ INV~TIQN
The present in~ention relates to a method vf i~hibiting the precipitation of diæ~olved zinc, iron and manganese ions and their reaction products in an aqueous system, comprising the step of treating said ~: system with a~ effective precipitation-inhibi~ing amount of a polyether polyamino methylene phosphonate of the ~o~lowing fo~mula:
203P - ~2C R ~ CH2po3M~
~ C~ 2 -~- C~2 ~ ~ ~)n - N
`~ M203P - :~2C CE2P03M2 and optionally the N-o~ides therevf; wher~ n is an integer or fractional inte~er which is, or on a~erage om about 2 to about 12, inclusive; M is hyd~ogen or a suitable cation; and each R may be ~he same or differe~t and is independently selected from hydrogen and methy~. . -~ :A:preferred subclass o~ eomposàtio~s of the above :;
:
formula iæ ~hat wherein M is hydro~en, R is methyl, and n is from about 2 to about 3, most p~e~erably an average of about 2.6.
In particu~ar, the present invention relates to such a treatment method in which the aqueous system . being treated is characterized by the severe ; 5 conditions ofi a pH of at leas~ 8.5, especially 9~0 or ; greater, and a calcite concentration of at ~least - 250~, especially 300X or greater; and the polyethex p~osphona~e is u~ed in an amount su~icient to achieve a concentra~ion of from 0.1 to 50 mg/L in ~aid aqueous æystem, preferably from 1.0 o 10 mg/L, and most preferably from 2 to 5 mg/L.
The present invention further relates -to a metho~i o~ inhibiting the precipitation of dissolved zinc, iron and manganese ions and thelr reac~ion products l~ in an aqueous system, comprising the step of treating ~aid ~ystem with an effectlve ? precipitation-inhibiting amount of a composition compri~ing a polyether polyamino methylene phosphonate of the formula above, together wlth a polymer additive comprising one or more members ~ selected from the group consisting of: homo- and i, copolymers including terpolymeri comprising one or more of acrylamide ~AM)~ acrylic acid (AA), 2-acrylamide-methyl propane æulfon.ic acid ~MPSA), methacrylic acid (M~A), itaconic acid (IA), polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), ma~eic acid (~A), t-butyl acrylamide (TB~M), s~dium styrene sul~onate (SSS), sodium vinyl sulfo~ate, hydroxy propyl acrylate, hydroxy propyl methaerylate, 3-allyloxy-2-hydroxy propane ~ul~onic acid, sodium salt.~A~PS), and ~inyl phosphonic acid, wherein the weight average molecular weight for such ~ .
20997D~
2998H ~ C-1576 polymer additives i.s in the range of rom about 500 to 250,000.
In particular, the present invention relates to such a method in which for the above formula for the polyether phosphonate, M is hydrogen, R i9 methyl, and n is fxom about 2 to about 3, moæt preferably an average of about 2.6; the aqueou~ ~ystem being : treated is characterized by the severe conditions of a pE of at leaæt 8.5, especially 9.0 or greater, and a calcite concentra~ion of at least 250~, e~peeially 300X or greater; and the polyether phosphonate is used in an amount sufficient to achieve a concentration of from O.l to 50 m~/L in said agueous ~ystem, preferably from l.0 to 10 mg/L, and most :~ preferably from 2 to 5 mg/L; and ~aid po~.ymer additive is a member selected from the group consisting essentially of 90/lO to lO/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA, 100 M 9 75/25 SSS~MA, 33/33/34 AA/MAA/IA, 50/~0 AA/AM, 70/20/10 AA/~MPSA/P~M-5 (having 5 repeating oxyethylene ~nits), and AA/AMPSA/TBAM.
The present invention ~till ~urther relates to a composition $or inhibiting the precipitation of ,, dis~olved zinc, iron and manganese ions and their reaction products in an a~ueous-sy8tem, ~omprising a polyether polyamino methylene phosphonate o the formula above. The present invention also relates to a compo~ition comprising a polyeth~r phosphonate of the formula above in combl~ation with a polymer additive which is a member selected from the group eonsisting;es8entially of those enumerated above. In particular, the present invention relates to such a compositio~ in which for the abo~e formula or the polyether phosphonate, M is hydrogent R is methyl, ' :
.:
and n is from about 2 to about 3, most preferably an average of about 2.6; and said polymer additive is a member selected from the group consisting essentially of 90/10 to lO/90 AA/AMPSA, preferahly 75/25 and 60/40 AA/~IPSA, 100 A,9, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/:10 AA/AMPSA/PGM-5 (having 5 repeating oxyethylene UIlitS), and AA/AMPSA/TBAM.
DETAILED DESCRIPTION OF TEE INVENTI~N
~` 10 . . .
The acti~e ingredient in the compositions and methods.o~ the present i~vention for inhibiting the .: pxecipitation of dissolved æinc, iron and manganese .- 15 ions and their reaction products in a~ aqueous system, especially one characterized by se~ere conditions of high p~ and high calcite concentration, is a polyether polyamino methylene phosphonate of the f oralula:
M2O3P - H2C RR C~2PO~M2 , N - C~ - CX~OCH2 - CH ->~ - N
M203p - :EI2C C~2P03M2 25 and optionally th~ N-oxides thereof; where n is an ~, integer or fractiona~ integ~r which isl ~r on a~erage is, ~rom about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be th~
æame or diferent and is independently selected from hydrogen and methyï. A preferred subclass of compositior~ of the above formula is that wherein M
7 1a l.~
2998~ - 13 - C-1576 is hydrogen, R is methyl, and n is from a~out 2 to about 3~ most yre~erably an avexage of about 2,6.
In order to cbtain high levels of control of zinc, iron and manganese deposits, eæpecially under the severe condi-tions defined herein, it has been found that there are certain essential compone~ts of - 5 the structure of such polyether polyam~no methylene phosphonate or N-oxides which are necessary to provide that per~ormance. For e~ample, ~he N,N-bis(phosphonomethyl)amino portion of the structure is essential. Whether ~his group is present initially in the phosphonic acid form or as an alkali metal or other salt of the acid, has no critical bearing on ~he performance of ~he overall - molPcule. At the pH's under which the phosphonate compositions ~unction~ -~hey are, and must be, ln their ioni2ed form. Thus, .it is not critical whether ~M~ is hydrogen or a suitable cation, a~d the :: selection of an appropriate salt form i~ well within the skill o~ ~he art. Alkali metal salts are the most simple, and are preferred for that reason.
2~ Overall, however, it is preferred that M i3 hydrogen.
The poly~ther polyamino methylene phogphonate may ! be in the N-oxide ~orm: N $ O.. This group confers slgnifi~ant resistance to degradation by chlorine and bxomine bioeide~, or mixtures thereo~, which may be : 25 present in the aqueou~ system being treated, ~ presumahly by preventing o~idative attack on the : nitrogen atom of the group.
A preferred ~tructural feature of the polyether polyamino methylene phosphonates a~d N-oxides useful as deposit control agents is the isopropyl group which bridges the diphosphonomethylamino group and the polyether group. Thi~ group can also be an ~ .
2~
2998~ - C-1576 ethylene moiety.
: Another structural elemen~ o~ ~he phosphonate zinc, iron and manganese deposit inhibitors is the polyether moiety. Since the polyether polyamino methylene phosphonates are prepared by phosphonomethylation of the appropriate diamine, the character of the polyether moiety will depend UpOIl the way in which the amine startlng material is made. Processes for making such polyether diamine~
are known in the art; and attention i3 directed particularly to US 3,236,895, ~hich describes prepara~ion o~ a variety of polye~her diamines especially useful ~n preparing the phosphonate final products used as deposi~ con~rol agents ln ~he present invention.
In accordance with the processes ~et out in US
3,236,395 and related proCeBSe~ de~cribed in the prior art, ik is po~sible to prepare any on~ of a - number of desired polyether diamines within the ~cope of the present invention. In the ~eneral formula for the polyether polyamino methylene phosphonates used j 20 herein, the polyether moiety is simply represented by .the formula:
R
, _(-OCH2-C~-)n~
Since R may be hydrogen or methyl, both ethyleneoxy :~ and propyleneoxy units axe possible. Moreover, R is to be independently chosen, i.e., ethyleneoxy and propyleneoxy units may alternate in various patterns, : including blocks of each, or ~hey may be all one or ~:~ 30 the other. For e~ample, the following are ju~t ome o~ the polyether segments whic~ might be prepared to ; , : ~ :
:: : ....... : . ' 2~73l~
. .
form the basis for the corresponding diamines, which ~; would then be used to make phosphonate~ wi~hin the scope of the present invention (where E0 =
ethyleneoxy, and PO = propyleneoxy):
;` E0; P0; E0 E0; P0-P0; E0-P0; E0-E0-E0;
P0 P0-P0; E0-E0-P0; E0-P0-P0; EO~P0-E0;
.
P0-E0 P0, E0-E0-E0-E0; P0-P0-P0-P0~ E0-P0-P0-P0;
; ~0-E0-P0-P0; E0-E0-E0-P0; E0-P0-E0-P0;
:E;O-PO-PO-~;O, PO-EO-F.O-PO
.,~
In the above example~, "n" in the main ~ormula would be an integer of from 1 to 4. Since "n" is defined ~: as being from l to 12, an even larger numbex of possible polyether moie~ie~ i~ included. However9 it has been found that generally the polyether polyamino . 15 methylene pho3phonates of lower molecular weight, ,~ i.e., where ~n~ is a smaller i~tege~, are those which pro~ide the greatest amount o~ scale inhibition urlder ~` the severe conditions of high pH and high calcite J concentration, and thus are those which are ~'! 20 pre~erred. Examples of some of these preferred , pho~phona~es are shown in ~he table below, wherc Z =
methylenephosphonate:
~' .~ -$
, ~ . . .
~! .
~ 30 .
~;: : :
.
, 2 f~ J 7 ~ ~
Rz Ra ~b Z 2-N~ c~2-(oc~I2cH)a - (OC~;~CE)b -NZ2 Idf- No. _~ b Rz _ Ra_ Rb--; 5 2 1 CH3 ~ CE~3 :B 2 . 6* CH3 CE[3 - -C ~ f~H3 CH3 ---D 8 . 5* 1 ~3 ~ ~3 ~ 5 . 6* f~f C~3 G~.3 --~
2 o G 3 0 H H -~-E 3 ~f f~,~3 C~I3 ---1 S I 3 l E C~3 - J 4 G H C:E[3 ~--f ~ - the value of "n'9 on avera,g~e.
It ~ill be noted from ~he ;able above that in f 20 several cases 9 "n" has an average value , i . e ., thff~
number o~ repeatir~g ethyleneo~y or propy~eneoæy UllitS
may vary. Thus, it is pos~ible to have a mi~uxe o:E
varying c~ain lengths o~ polyox3rethy:Lelle or ~: polyo~propylene in the f inal product . This tf æ also ~5 co~templated tG be withln the ~cope of the pre~ellt invention, æo long aæ the requirementf~ with.respect to khe limit off "n" are observed. ConsegueIItly, whil;e ~n~ :is merely defined as an integ,er or fractional integer which is, or on average is, ~from 30: about :2 to about 12, it has two a~pects . It defineæ
the tota~ o~ the ~umber of repeating ethyleneo~
2 ~ 9 9 ~
2998~ - 17 - C-1576 and/ox propyleneoxy units considered separately, and ~hus if ~n~ is, e.g., 4, it includes 4 propyleneoxy units, 3 propyleneoxy units and 1 ethyleneo~y unit1 2 propyleneoxy units and 2 ethyleneoxy units, and so forth. The value o~ ~n~ may alsv represent an average number, and this is always the case, of course, when it is a fractional integer. In this case, for each of the ethyleneoxy and/or propyleneoxy units considered separately, mixtures of these unitsf may be presfent so as ~o give an average value for "n". For e~ample, in the table above, for Id. No. D, lO the total of "a" and "b" is 9.5, which is the value of "n". What is descri~ed is a mi~ture of polyether phosphonate~. in which all of ~hem have an i~opropyl hridging group and an e~hyleneoxy moiety, but ~he repea~ing propyleneoxy units are such that on average 15 thei~ value is about 8.5.
The number o~ repeati~g ethyleneo~y or oxypropylene units~ designated by the su~cript "n", determines the total molecular weight of the overall polyether polyamino methyl2ne phosphonate or 20 correfponding N-oxide, and thus plays a critical role in determining the scal~ inhibi ting per~ormance of that phosphonate. It has been ~ound that in order to provide adequate scale control under the fevere ~, conditions of use defined herein, it is neces~iary 1 25 that "n'l be an integer or fractional integer which i~,. or on average is, ~rom abou~ ~ to about 12, inclusive.
As discussed above, the rea~on ~ox ~n~ being potentially a fractional integer arises from the fact ~:~ 3~ that the primary diamine from which the polyether polyamino methylene phospho~ates are prepaxed by phosphonomethylation may be a mixture of polyethers ..
.
:::
.
.
.
299~X ~ C-157 ; in which "n~ two or more o~ 2, 3, 4, 5 and so forth, in varying proportions. For example, a preferred polyether polyamino methylene phosphonate for use in the compositions and method~ of the present invention has a molecular weight o~
approxîmately 632 and the value of i'n" on average is about 2.6. Thus, this type of polyether phosphonate has a molecular welgh~ distribution, i.e., of the various polyo~ypropylenes which make it up, and this distribution is represented by a fractional integer average value for "n". But, it is also within the scope of the present invention for "n" to be a whole integer, e.g., 1~3l~, which usually designates a single molecular wei~ht and not a mclecular weight ,~ distributlon.
~ The polyether polyamino methylene phosphonate and :, 15 corresponding N oxides of the compositions and methods of the present invention are prepared fir3t ~' by phosphonomethylation of the appropriate primary amine which already contains ~he polyo~yethylene and polyoxypropylene moieties, followed by an oxida~ion i 20 step which provides the N-oxide moieties.
'~ Such primary amine starting materials and their : method of preparation are well known. The ;I' phospho~omethylation o~ the primary amine is then carried out by a Mannich reactioll such as that i 25 described in ~. Moedritzer and R. Irani, ~. Org~nic .! ~hem. 31(5) 16G3-7, "The Direct Synthes ~ o~
-li alpha-Aminomethyl Pho~phonic Acids; Mannich-Type Reactions with Orthophosphorous Acid", May 1966. In ; a typical reaction, the primary amine is added to a mixture o~ phosphorous acid and water, and concentrated hydrochloric acid is then added slowly, : a~ter which the reaction:mixture is heated to reflux :
:~ :
20~7a~ -~wi~h addition of aqueous formaldehyde.
: Al~hough the general structural formula employed herein indicates ~ha~ the nitrogen atom is completely phosphonomethylated, as a practical matter, : preparation of the polyether polyamino methylene phosphonate and corresponding N-oxides of the present invention, as described in detail ~urther below, usually results in o~ly about 80 to 90%
phosphonomethylation. Other side products give N-substitution with H, CH3, C~20~, etc. It i8 not practical, as a matter of simple production economics, however, ~o isola~e and puri~y the completely phosphonomethylated compounds, since the ~ide products just described do not interfere with zinc, iron and manganese deposit inhibition. Such -side products, are consequently, usually allowed to remain, and the test data set out further below is ba~çd on test samples containing such side productæ.
Consequently, the activity levels obtained would be even higher were 100% acti~e compound being tested~
Once the desired phosphonomethylated polyoxypropylene diamine has been prepared as de~cribed above, the N-oxide ~inal product of ~he present invention is then prepared by a step of oxidation, which may be accomplished, e.g., simply by adding hydrogen peroxide to a basic solut~on of the 25 phosphonomethylated diamine and heating the reaction mixture, which gives high yields of the N-oæide final :-product. Of cour8e, it iB also posæibl~ to uæe other well known techniques for carrying out such a step of oxidation, and any number of these may be success~ully emplo~ed.
- ~The amounts o$ any particular polyether polyamino methylene phosphona~e that are required to be added :
:~:
2~7~
299~ - 20 - C-:L576 for the decired ma~imum inhibition of zinc, iron and ma~ganeæe deposit ~ormation will be such as to provide an ultimate concentration in the aqueous æystem being ~reated of between 0.1 and 50 mg/L, and preferably this concentration will be between 5 and 30 mg/L. Most preferably the concentration will be between 10 and 20 mg/L, although i t ie under~tood that many factors, of the type which have been explained in detail with regard to the background to . the present invention, will determine the actual s amount of polyether phosphonate which will be added to any particular aqueous system in order to achieve - the ma~imum amount o:F inhibitioIl of zinc, iron and manganese deposit formatiorl in that agueous system.
~he calculation of those amounts will be well wi~hin the skill of the artisan in this :Field.
When the polye ther polyamino methyl~ne phosphonate used in the me~hods and compositione of the present invention are used in combination with one or more of the polymers recited :further above, '3 ~he amounts of that combination which must be added in order to inhibit zinc, iron and manganese deposition i~ an a~ueous system, will as a ge~eral matter be within the ranges of amounts su~ficient to ~ establi~h the ranges of concentration3 of the 3 polyether phosphonates and corresponding N-oxides 1 2s used alone, as recited in detail above. Again, however, calculation of t~e actual amount iæ well j~ within th~ ekill of ~he ar~.
J~ The manner o~ addition of any particular polyether polyamino methylene phosphonate to an aqueous sy~tem will also be straightforward to a person o srdinary skill i~ this art. It may be added in ~inely subdivided solid form by mechanica~
dispensers of known design. It may also be added in solid form, but in ~he ~orm o~ a matri~ in which solid particles of the active ingredient are bonded or bound to~,ether by a material which is water : soluble, or optionally, does not dissolve at all.
Such a matrix allows for regular leaching out or disso~ving of the active ingredient particles, ~ whereby it is possible to obtain a sustained release ; and more unvarying concentration of the sodium monofluorophosphate in the water being treated. The par~icular polyether phosphollate may also ~e made up in the form of concentrated solutlons for di~pen3ing ;~ ln liquid foxm from dispensers well known in the ~:~ art. The polyether phosphonates may also be combined .~ with othe~ chemical treatment agent3 for dispensi~g - to the aqueous system, and these in combination may be dispensed in solid or liquid ~orm.
The phrase "aqueou~ system" as used herein i~
meant to ~nclude any system containin~ water;
.' including, but not limited to, cooling water systems ..
; including cooling to~ers, boiler water ~ystems, desalination systems, gas æcrubber units~ blast furnaceæ, ~ewage sludge dewatering æystems, thermal i, conditioning equipment, re~erse osmosis units, ~ugar ~: e~aporators, paper processing systems~ mining j circuits, and the li~e.
~ 25 1~ .
~:~ XQ~F,F~ 9F PREFERRED E~BODIMENTS.
The following e~amples demonstrate the effectiveness o~ the treatment mçthods of the pre~ent invention in reducing lead æolubility i~ water.
. , ' ' , : ~; ' ' -2'~ 4 ~998H - 22 - C-1576 The~e examples are illustrative only, and are not intended to be a limita~ion o the prese~ vention.
.
lEXAMPLEI
Manganese Stabilization PROCEDURE: Conditions: The 2 hour study was done using a gang stirrer at tempera~ure:-25~C and stagnant ~lasks a~ 60C; while ~he 24 hour study was lo done by incubating flasks at 60C. The p~ in all cases was 9.0, and the total alkalinity (~CO3/CO3) of 400 mg/L was added to 4~ Pittsburgh water of the following compositlon:
Ion Ion Con~en~ration (mg/L) Mg~ 24 Ca~ 88 : SO4- 329 Nal 56 25~ Cl- 70 IN~IBIl'OR: the polyether phosphonate test compound employed~wa~ that of the main formula wherein M = ~, CH3 in al~ cases, and n = on average about 2.6.
he~inhibitor:was added to a known volume (500 - ~:
[inhibl~tor volume + manganese volume ~ ECO3~CO3 olume3) of 4X Pittsburgh water (p~ adjusted to 8.8~, 7 ~ ~
followed by manganese solutions (1.0 g/L). ~sing a ~- 2.00 mL volumetric pipet, 2.00 mL of 1.00 g/L Mn ~2 stock solution was pipeted under the ~urface of the water. (The Mn~2 stock solution was prepared using 4.125 mL per lite~ of 50/O Manganous Nitrate, which equals 3.~57 g/L of Mn(NO3)2.) In order to oxi~ize the Mn up to oxidation state 7 and thereby duplicate natural aeration, ~here was added H202 . juSt prior to adjuæting the pH to 9.0 u~ing O.O50M
NaOH, followed by the addition of a~kalinity:
~ICO3/CO3 (80/20~ soiution. The H2O2 amount wa~ adjusted tf4 the ~moun~ of Mn (lppm ~22 per 1 ppm Mn). The total volume of the flask was 50G mL.
The flasks were clo~ed with rubber stoppers and incubated for 2 and 24 hours. For the 2 hour gang s-tirrer ~tudy, the total volume was brought up to 1000 mL in a bea~er. At the end o~ the equilibration time, 50 mL of each test solution was filtered through 0.25mm filter paper~ acidified with concentrated HCl, and analyzed ~y atomic ab~orption spectroscopy. The final result was calcula~ed in 2~ accordance with the following equation:
i ~/O Mn = Mn w/ Inh;b. - Mn w/ No Inhib -- X ~00 Stablæd. Mn Initially Added - Mn w/ No Inhih.
R~SULTS: Following the above procedure ~ the ,3 25 following results were obtained:
,. : , , .:
.! i ~ ' .
3 d :
: ~ .
,: ; :
7 3 ~
.
TABLE _l Mallganese Stabiliza~ion pH = 9.t); HC03/C03 - 40ûm~/L
: 5 TEST CONC~NTRATI~N M~TAL ION % RECO-DOSE INIT'L FINAL VERY IN SOLUTION % STABILIZATION
~mg/L) 2 ~Ir6~ 24 ~kZ Hrs.24 Hr6 ,2 Hr~. 24 Hr~s.
. ., 10.0 1.0 0.98 0.68 9B 68 90 57 .~ .
15 . O 1 . O O . 990 . 88 99 ~ 95 ~4 : .
10.0 2~0 l.g5 ~)o81 98 ~1 78 2~Q
20.0 2.0 .1.97 1.46, 99 72 ~7 ~2 ~ .
EXAMPI.E 2 :
~: ~ ; Iron Stabili7ation 25 ~ ~ . The same ge~eral procedures a~ de~cribed above or ~xample 1 were ~mployed.. Usia~g a 2 . 00 mL
volumetric pipet, 2 . 00 mL o~ 1. 00 g/L Fe~2 stoc,X
s~o~utioIl was pipeted under the surfa~e vî the water.
The~Fe+ ~tock æolution was prepared freæh using 30~ 7, oz ~g~ams of ~e(NH4)2($43~ 6EI2 ~nd ml, of concentrated ~S04 per total volume of 1 00 iter .:) The acidif ied f i~trates and diluted 2~97~
~9g8~ - 25 - C-1576 Fe+2 stock solution were analy~ed using atomic absorption spectroscopy. The values were multiplied by l.05 to account for dilution during acidification. The percent (%) stabilization was calculated as follows:
~; . ..
% Fe = Fe w/ Inhib. - Fe w/ No Inhib. X lO0 Stablzd Fe Initially Added - Fe wt No Inhib.
RESTJLTS: Following the above procedure the following results were obtained:
-~ 10 TABLE 2 I~on Stabilization pH = 9O0, HC03/C03 = ~sOO~ng/I.
l 5TEST CONCENTRATION IIETAL ION % RECO-, DOSE INIT ' L FINAL VERY IN SOLUTION % STABILI~ATION(mg/L2 ___ 2 Hr~ .. 24 ~r~ .. 2 Hr~, 24 EIr~ O 2 Hr~ ~ 24 Hr~
.0 l.O 1.0 0.5~ 100 59 lOO 59 ~i 2 0 15.0 l.O l.O 0.68 100 ~8 lOû 58 10.0 ~.0 1.96 o.ss 98 50 g8 50 25~20.0 2.0 1.98 1.59 99 80 99 80 2 ~
:EX~IPLE 3 Zinc Stabilization The same general procedures as de~cribed above 5 :for :3~ample 1 were employed. I'he ionie matrix was a water containing 160 mg/L of Ca and 200 mg/L O:e sulfate. Additionally, 400 mg/L of HC03/C03 Wt3S
added to ~he water and the pH was adjusted to 9 . û.
The percent (%) ~tabiliza~ion ~Jas calculated as 10 ~ollows:
% zn = Zn w/Jnhib. - Zn w/ No I~h~ ~ 100 Stablzd Zn Initially Added ~ Zn w/ No IIIhib.
RES~LTS: Following the above procedure the `~ 15 following r~sults were obtained:
., ;~' ! Zinc Stabilization pH = 9O0; ~C03/C03 = 400mg/1.
A ~: TESTCONCENTRATION ~qETAL ION ~ P~ECO-DOSEINIT'I. FINALVERY IN SOLUTION ~ STABILIZAT10l~l (mg/L ) ~= 2 l~r~ .24 ~ 2 Hrs ._4 ~r~ . 2 ~Ir~ O 24 H~ .
10.0 2.~ 1.67 1.66 ~34 84 83 82 15.0 ~.o 2.00 1.99 loo loo loo loo :30~ lO.0 5.0 2.05 2.07 41 41 38 3B
20 . 0 5 . 0 3 . 66 3 . 66 73 73 72 72 ~ . :
7 ~ ~
. A~rPLE 4 EP:f ect of T~mper~ure 5. ~he effect~ of temperature on ætabilization results were obsertred by selecting data from that set out in Examples 1-3 above and p:resentillg i~ to show temperature effects. That selected data is set out in the table of values below:
TABI.E 4 ~ffect o:E Temperature on ~inc/Mangan~se/lron 5tabili~ation (p~l = 9.û~ HC03/C03 a 40Qmg/L) TEST CONC~NTRATIaN (ing/L) DOSE METAL INITIAL FINAL AFTER 2 EIRS % STABII.IZATION
(mg/L~ ION25~C .~0C _~ 60~ 25~C
Zinc 2.02.0 1.67 1.66 83 82 ~::
Iron 2.02.0 1.96 1.26 98 ~3 Mng~ 2.02.0 1.g5 1.12 78 39 As æhown in the data abo~re, stabilization ~as studl~ed at two d;fferent :levels of metal ion .
30~ con~erltration and three levels of teæt do~e ~or the polyether phosphonate ~t~bilizer; The % . ..
stab~ilizat:ion wa :~ound to depend on both metal ion 2~9~'q concentration and stabilizer test dose. Metal ion recovery in solution was ound to incr~ase with increasing stabilizcr dose and was found to decrease with increasing metal ion concentration. Zinc stabilization did not change with time from 2 hours to 24 hours; however, for both manganese and iron, stabilization was found to be sharply reduced between 2 and 24 hours. It is conjectured that a slow oxidation of iron and manganese may have been responsible for precipitation of those ions with ~ime. This may represent the combined ef~ect o~ time and temperature on iron and manganese oxidation. The results in Table 4 indicate some deterioration ofi iron and manga~ese stabilization ak 60C af~er 2 hours1 while zinc stability remains unchanged af~er 2 hours, even at 60C. The polyether phosphonate stabilizer was found to be stable to H202 oxidation, since no breakdown o~ ~he stabilizer was observed in any of the above experiments.
.
~ 20 ., ~'I .
,.
, ~
~, 25 ' ' ., .
.
:~ 30 'i~;~
! ~ ~ . .
.:
Claims (7)
1. A method of inhibiting the precipitation of dissolved zinc, iron and manganese ions and their reaction products in an aqueous system having a pH of at least 8.5 and a calcite concentration of at least 250X, comprising the step of treating said system with an effective precipitation inhibiting amount of a polyether polyamino methylene phosphonate of the following formula:
and optionally the N-oxides thereof; where n is an integer or fractional integer which is, or on average is, from about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be the same or different and is independently selected from hydrogen and methyl.
and optionally the N-oxides thereof; where n is an integer or fractional integer which is, or on average is, from about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be the same or different and is independently selected from hydrogen and methyl.
2. A method according to Claim 1 wherein in the above formula for the polyether phosphonate, M is hydrogen, R is methyl, and n is an average of about 2.6.
3. A method according to Claim 1 in which the polyether phosphonate is used in an amount sufficient to achieve a concentration of from 0.1 to 50 mg/L in said aqueous system.
4. The method of Claim 1 wherein the concentration of polyether phosphonate is from 1.0 to 10 mg/L.
5. A method of inhibiting the precipitation of dissolved zinc, iron and manganese ions and their reaction products in an aqueous system having a pH of at least about 8.5 and a calcite concentration of at least 250X, comprising the step of treating said system with an effective precipitation-inhibiting amount of a composition comprising a polyether polyamino methylene phosphonate of the following formula:
and optionally the N-oxides thereof, where n is an integer or fractional integer which is, or on average is, from about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be the same or different and is independently selected from hydrogen and methyl;
TOGETHER WITH A POLYMER ADDITIVE COMPRISING:
one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide-methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), itaconic acid (IA), polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid, sodium salt (AHPS), and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000.
and optionally the N-oxides thereof, where n is an integer or fractional integer which is, or on average is, from about 2 to about 12, inclusive; M is hydrogen or a suitable cation; and each R may be the same or different and is independently selected from hydrogen and methyl;
TOGETHER WITH A POLYMER ADDITIVE COMPRISING:
one or more members selected from the group consisting of: homo- and copolymers including terpolymers comprising one or more of acrylamide (AM), acrylic acid (AA), 2-acrylamide-methyl propane sulfonic acid (AMPSA), methacrylic acid (MAA), itaconic acid (IA), polyethylene glycol monomethacrylate (PGM), maleic anhydride (MA), maleic acid (MA), t-butyl acrylamide (TBAM), sodium styrene sulfonate (SSS), sodium vinyl sulfonate, hydroxy propyl acrylate, hydroxy propyl methacrylate, 3-allyloxy-2-hydroxy propane sulfonic acid, sodium salt (AHPS), and vinyl phosphonic acid, wherein the weight average molecular weight for such polymer additives is in the range of from about 500 to 250,000.
6. A method according to Claim 5 in which for the above formula for the polyether phosphonate, M is hydrogen, R is methyl, and n is an average of about 2.6; the polyether phosphonate is used in an amount sufficient to achieve a concentration of from 0.1 to 50 mg/L in said aqueous system; and said polymer additive is a member selected from the group consisting essentially of the following weight percent compositions 90/10 to 10/90 AA/AMPSA, preferably 75/25 and 60/40 AA/AMPSA, 100 AA, 75/25 SSS/MA, 33/33/34 AA/MAA/IA, 50/50 AA/AM, 70/20/10 AA/AMPSA/P5M-5 (having 5 repeating oxyethylene units), and AA/AMPSA/TBAM.
7. A method according to Claim 6 wherein the polyether phosphonate is used in an amount sufficient to achieve a concentration of from 1.0 to 10 mg/L in said aqueous system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US907,257 | 1992-07-01 | ||
| US07/907,257 US5262061A (en) | 1992-07-01 | 1992-07-01 | Zinc, iron and manganese stabilization using polyether polyamino methylene phosphonates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2099704A1 true CA2099704A1 (en) | 1994-01-02 |
Family
ID=25423777
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002099704A Abandoned CA2099704A1 (en) | 1992-07-01 | 1993-06-29 | Zinc, iron and manganese stabilization using polymer polyamino methylene phosphonates |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5262061A (en) |
| EP (1) | EP0577422B1 (en) |
| JP (1) | JPH0699195A (en) |
| AU (1) | AU668568B2 (en) |
| CA (1) | CA2099704A1 (en) |
| DE (1) | DE69302526T2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE149148T1 (en) * | 1991-05-31 | 1997-03-15 | Calgon Corp | POLYETHER-POLYAMINO-METHYLENE PHOSPHONATES TO CONTROL DEPOSITS AT HIGH PH |
| US5322636A (en) * | 1992-03-30 | 1994-06-21 | Calgon Corporation | Polyether polyamino methylene phosphonate n-oxides for high pH scale control |
| US5368830A (en) * | 1992-10-15 | 1994-11-29 | Calgon Corporation | Scale control in gold and silver mining heap leach and mill water circuits using polyether polyamino methylene phosphonates |
| US5454954A (en) * | 1993-09-21 | 1995-10-03 | Calgon Corporation | Scale control in metal mining circuits using polyether polyamino methylene phosphonates |
| US5534157A (en) * | 1994-11-10 | 1996-07-09 | Calgon Corporation | Polyether polyamino methylene phosphonates for high pH scale control |
| US5593595A (en) * | 1995-10-06 | 1997-01-14 | Calgon Corporation | Method for controlling scale using a synergistic phosphonate combination |
| US5709814A (en) * | 1995-10-06 | 1998-01-20 | Calgon Corporation | Aqueous system containing a synergistic phosphonate scale control combination |
| US5702634A (en) * | 1995-10-06 | 1997-12-30 | Calgon Corporation | Aqueous system containing a synergistic combination including polyether polyamino methylene phosphates for controlling calcium carbonate and calcium phosphate scale |
| DE69607099T2 (en) * | 1995-10-06 | 2000-12-14 | Calgon Corp | Use of synergic composition for the control of scale |
| US5580462A (en) * | 1995-10-06 | 1996-12-03 | Calgon Corporation | Controlling calcium carbonate and calcium phosphate scale in an aqueous system using a synergistic combination |
| US5707529A (en) * | 1996-09-24 | 1998-01-13 | Calgon Corporation | Method for controlling scale in an aqueous system using a synergistic combination |
| US5772913A (en) * | 1996-09-24 | 1998-06-30 | Calgon Corporation | Aqueous system containing a synergistic combination for scale control |
| US9034805B2 (en) * | 2009-06-05 | 2015-05-19 | Kroff Chemical Company | Fluid treatment systems, compositions and methods for metal ion stabilization in aqueous solutions |
| CN102674519A (en) * | 2012-06-13 | 2012-09-19 | 何斌 | Preparation method of flocculant for sewage treatment |
| JP6357817B2 (en) * | 2014-03-14 | 2018-07-18 | 栗田工業株式会社 | Method for preventing zinc-based scale and zinc-based scale inhibitor |
| US11639464B2 (en) | 2018-12-07 | 2023-05-02 | Halliburton Energy Services, Inc. | Controlling the formation of polymer-metal complexes in wellbore operations |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3349031A (en) * | 1965-08-20 | 1967-10-24 | Calgon Corp | Method and composition for removal of manganese from water |
| US4080375A (en) * | 1971-02-05 | 1978-03-21 | Petrolite Corporation | Methylene phosphonates of amino-terminated oxyalkylates and uses therefor |
| US4552665A (en) * | 1984-05-04 | 1985-11-12 | Calgon Corporation | Stabilization of soluble manganese and its reaction products |
| US4872996A (en) * | 1987-03-13 | 1989-10-10 | The Dow Chemical Company | Use of aminophosphonic acids to inhibit scale formation and corrosion caused by manganese in water systems |
| US4783267A (en) * | 1987-06-29 | 1988-11-08 | Calgon Corporation | Method for stabilizing metal ions |
| US4931189A (en) * | 1988-11-02 | 1990-06-05 | Petrolite Corporation | Methods for inhibition of scale in high brine environments |
| US5112496A (en) * | 1988-11-02 | 1992-05-12 | Petrolite Corporation | Methods for inhibition of scale in high brine environments |
| ATE149148T1 (en) * | 1991-05-31 | 1997-03-15 | Calgon Corp | POLYETHER-POLYAMINO-METHYLENE PHOSPHONATES TO CONTROL DEPOSITS AT HIGH PH |
| CA2092492A1 (en) * | 1992-03-30 | 1993-10-01 | Ecc Specialty Chemicals Inc. | N-(2-hydroxyethyl)-n-bis (methylenephosphonic acid) and corresponding n-oxide thereof for high ph scale control |
| US5322636A (en) * | 1992-03-30 | 1994-06-21 | Calgon Corporation | Polyether polyamino methylene phosphonate n-oxides for high pH scale control |
-
1992
- 1992-07-01 US US07/907,257 patent/US5262061A/en not_active Expired - Fee Related
-
1993
- 1993-06-29 CA CA002099704A patent/CA2099704A1/en not_active Abandoned
- 1993-06-30 AU AU41638/93A patent/AU668568B2/en not_active Ceased
- 1993-07-01 JP JP5189117A patent/JPH0699195A/en active Pending
- 1993-07-01 EP EP93305171A patent/EP0577422B1/en not_active Expired - Lifetime
- 1993-07-01 DE DE69302526T patent/DE69302526T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0577422A1 (en) | 1994-01-05 |
| US5262061A (en) | 1993-11-16 |
| DE69302526T2 (en) | 1996-09-19 |
| AU4163893A (en) | 1994-01-06 |
| JPH0699195A (en) | 1994-04-12 |
| DE69302526D1 (en) | 1996-06-13 |
| EP0577422B1 (en) | 1996-05-08 |
| AU668568B2 (en) | 1996-05-09 |
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| FZDE | Discontinued |