CA1222620A - Method and compositions for cleaning organically fouled anion exchange resins - Google Patents
Method and compositions for cleaning organically fouled anion exchange resinsInfo
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- CA1222620A CA1222620A CA000460186A CA460186A CA1222620A CA 1222620 A CA1222620 A CA 1222620A CA 000460186 A CA000460186 A CA 000460186A CA 460186 A CA460186 A CA 460186A CA 1222620 A CA1222620 A CA 1222620A
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- group
- sodium
- fouled
- perborate
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Abstract
Abstract of The Disclosure A method and composition for cleansing organically fouled anion exchange resins are disclosed. In addition to cleansing with brine and/or caustic, the resins are contacted with an aqueous com-position comprising a water soluble inorganic peroxide salt have a peroxy containing anion selected from the group consisting of per-borate, persulfate and percarbonate anions.
Description
~26~2~
IMPROVED METHOD AND COMPOSITIONS FOR
CLEA~ING ORGANICALLY FOULED ANION
EXCHANGE RESINS
Field of The Invention:
The present invention pertains to an improved method and composltlons for cleaning organically fouled anionlc exchange resins.
Background: The fouling of anion resins-has posed a prob-lem that has confronted ion exchange applications since their incep-tion. Humic substances found in surface waters are high molecular weight polyfunctional organic ac~ds (both carbo~ylic and phenolic) formed ~rom the breakdo~n of plant and animal materials. In deminer~
alizer operations, the large organic molecules may coat the resin bead, block~ng and/or entering the pores of an an~on exchange resln.
These organics are retained because of a high affinity for ~he ex-change sites and hydrophobic interactions with ~he po1ymer backbone ol~ the resin~
Since the diffusion rates of the organics within the res~n are usually slower than those of inorganic ions9 not all of the bonds linking the organic acids to the resin are broken during the regener-ation cycle. This situation results 1n only partial regeneration of the resin and excessive rinse times following regeneration. In severe cases, the resin may become "-irreversibly" fouled. To allevi ate these problems, out-of-service brine or brine/caustic cleaning 1, ~22~6~
has traditionally been performed. I~ has alsu been suggested that sodium hypochlorite may also be used as such a cleaning treatment.
However, resin degradation may o:cur with use of such a strong oxi-dizing agent. Other prior art cleansing compounds and methods are disclosed ln U.Sq Patent 3,536,637 (Noll et al) and U.S. Patent 3~748,285 (Wiltsey).
Another approach has been suggested in U.S. Patent 4,1539761 (Marsh). Specifically, Marsh teaches the use of aqueous solu~ions comprising hydrogen peroxide, ozone, or sodium peroxide.
To be sure9 ~he use of such compounds has proven ePfective insofar as the resin cleaning function is ccncerned. However, as is well known, hydrogen peroxide in aqueous solltion is extremely unstable~ More-over, when concentrated and in d~,rect contact ~ith impurities, explo-sion may occur. Simllar comment; can be made with respect to sodium peroxide and ozone itself.
Accordingly, there remLins a need in the art for the provi-sion of an effective anionic exc~ange resin cleaner ~hat ~s generally as effect1ve as hydrogen peroxidl! ln its cleaning function and is safe ~or commercial use and tran;port from manufacturer to customer ; 20 location.
Detailed Description I have surprisingly found that organic foulants are effec-tively cleansed from anionic exchange resins by the use of aqueous solutions compr~sing a water soluble inorganic peroxide salt having a peroxy containing anion selected from the group consisting of per-borate, persulfate and percarbonate an~ons. The cation of the perox-~de salt may be any cation which is non-oxidizable upon dilutlon of water and which renders the peroxide salt water soluble. Exemplary catlons include, but are not 11mited to, Na nd K.
~2~:6~
Preferred inorganic peroxide salts include sod~um per-borate, sod~um persulfate and sodium percarbonate. At present5 sodi-um perborate is most highly preferred for commercial use. Utiliza-tion of these compounds allows the manufacturer to provide a dry, stable product that is more safely transported to khe customer location, in contrast to the suggested use of hydrogen peroxide made by Marsh. Moreover, upon rece~pt of the dry product from the manu-facturer, the end-user may simply add water to the product on an as needed basis prior to cleansing of the fouled res~n thereby.
As the resln cleaning agents of the present ~nvention are ideally suited for use in combination with the tra~itional use of brine (NaCl), the brine may read~7y be incorporated into the dry, stable compos~tion of the water soluble inorganlc peroxide salt. The end user may then derive the benefit of improved anion resin cleans-lS ~ng simply by adding water to the dry composition an~ contacting the resin with the resulting aqueous composltion.
In many instances, it has been found desirable to mix the water soluble peroxide salt directly wlth an inorganic chela~ing agent such as tetrasodium pyrophosphate and pentasodium tripolyphos-phate for the purpose of complexing ~ron wh;ch normally accompaniesorganic foulants.
The presently preferred composition comprises sodium per-borate 90% (weight), tetrasodium pyrophospnate 5% (weight) and sodium tetraborate 5% (weight) an inert lnorganic salt.
Exemplary sompositions, in accordance with the invention, may comprise:
~2~2~
Compos~tion one: 5 - 99X (weight) sodium perborate, remainder ~norgan~c chelating agent Compos~ion ~wo: 80 - 95% sodium perborate
IMPROVED METHOD AND COMPOSITIONS FOR
CLEA~ING ORGANICALLY FOULED ANION
EXCHANGE RESINS
Field of The Invention:
The present invention pertains to an improved method and composltlons for cleaning organically fouled anionlc exchange resins.
Background: The fouling of anion resins-has posed a prob-lem that has confronted ion exchange applications since their incep-tion. Humic substances found in surface waters are high molecular weight polyfunctional organic ac~ds (both carbo~ylic and phenolic) formed ~rom the breakdo~n of plant and animal materials. In deminer~
alizer operations, the large organic molecules may coat the resin bead, block~ng and/or entering the pores of an an~on exchange resln.
These organics are retained because of a high affinity for ~he ex-change sites and hydrophobic interactions with ~he po1ymer backbone ol~ the resin~
Since the diffusion rates of the organics within the res~n are usually slower than those of inorganic ions9 not all of the bonds linking the organic acids to the resin are broken during the regener-ation cycle. This situation results 1n only partial regeneration of the resin and excessive rinse times following regeneration. In severe cases, the resin may become "-irreversibly" fouled. To allevi ate these problems, out-of-service brine or brine/caustic cleaning 1, ~22~6~
has traditionally been performed. I~ has alsu been suggested that sodium hypochlorite may also be used as such a cleaning treatment.
However, resin degradation may o:cur with use of such a strong oxi-dizing agent. Other prior art cleansing compounds and methods are disclosed ln U.Sq Patent 3,536,637 (Noll et al) and U.S. Patent 3~748,285 (Wiltsey).
Another approach has been suggested in U.S. Patent 4,1539761 (Marsh). Specifically, Marsh teaches the use of aqueous solu~ions comprising hydrogen peroxide, ozone, or sodium peroxide.
To be sure9 ~he use of such compounds has proven ePfective insofar as the resin cleaning function is ccncerned. However, as is well known, hydrogen peroxide in aqueous solltion is extremely unstable~ More-over, when concentrated and in d~,rect contact ~ith impurities, explo-sion may occur. Simllar comment; can be made with respect to sodium peroxide and ozone itself.
Accordingly, there remLins a need in the art for the provi-sion of an effective anionic exc~ange resin cleaner ~hat ~s generally as effect1ve as hydrogen peroxidl! ln its cleaning function and is safe ~or commercial use and tran;port from manufacturer to customer ; 20 location.
Detailed Description I have surprisingly found that organic foulants are effec-tively cleansed from anionic exchange resins by the use of aqueous solutions compr~sing a water soluble inorganic peroxide salt having a peroxy containing anion selected from the group consisting of per-borate, persulfate and percarbonate an~ons. The cation of the perox-~de salt may be any cation which is non-oxidizable upon dilutlon of water and which renders the peroxide salt water soluble. Exemplary catlons include, but are not 11mited to, Na nd K.
~2~:6~
Preferred inorganic peroxide salts include sod~um per-borate, sod~um persulfate and sodium percarbonate. At present5 sodi-um perborate is most highly preferred for commercial use. Utiliza-tion of these compounds allows the manufacturer to provide a dry, stable product that is more safely transported to khe customer location, in contrast to the suggested use of hydrogen peroxide made by Marsh. Moreover, upon rece~pt of the dry product from the manu-facturer, the end-user may simply add water to the product on an as needed basis prior to cleansing of the fouled res~n thereby.
As the resln cleaning agents of the present ~nvention are ideally suited for use in combination with the tra~itional use of brine (NaCl), the brine may read~7y be incorporated into the dry, stable compos~tion of the water soluble inorganlc peroxide salt. The end user may then derive the benefit of improved anion resin cleans-lS ~ng simply by adding water to the dry composition an~ contacting the resin with the resulting aqueous composltion.
In many instances, it has been found desirable to mix the water soluble peroxide salt directly wlth an inorganic chela~ing agent such as tetrasodium pyrophosphate and pentasodium tripolyphos-phate for the purpose of complexing ~ron wh;ch normally accompaniesorganic foulants.
The presently preferred composition comprises sodium per-borate 90% (weight), tetrasodium pyrophospnate 5% (weight) and sodium tetraborate 5% (weight) an inert lnorganic salt.
Exemplary sompositions, in accordance with the invention, may comprise:
~2~2~
Compos~tion one: 5 - 99X (weight) sodium perborate, remainder ~norgan~c chelating agent Compos~ion ~wo: 80 - 95% sodium perborate
2.5 - 10% inert organic salt, such as sodium tetraborate 2.5 - 10% inorganic chelating agent, with the fore~oing percentages adding up to 100%
Composi~ion three: 5 - 99% (weight) sodlum perborate, remainder NaC~.
Although the resin cleaning agents of the invention are preferred for use in the cleansing of strong base anionic res~nsJ
they may also be employed ln the cleansing of weak base anion exchange resins~
At the end user locat~on it is preferred to add water to the dry water soluble peroxide salt composition and to add brlne and/
or caus~c to the extent necessary so that the resulting aqueous com-position comprises abo~t 0.1 - abnu~. 30X (weigh~) peroxide salt, about 1 - 5% caustic and, 0 - 30% brine, rPmainder water.
. ~
The invention will now be further described w~th reference to a number of specific e~amples wh~ch are to be regarded solely as illustrative and not as restricting the scope of the invention~
In order to demonstrate the efficacy of the resin cleaning agents in accordance with the invention, effluent from a treated 6~
resin was analyzed to ascertain the Total Or~anic Carbon (TOC) con-tent thereof. Samples treated in accordanc~ with the invention were comparecl to control values. TOC content higher than control values ~ndicates efficacy of the cleaning agents.
TOC measurements were made by a ccmbustion/I.R.
spectroscopy method in which all of the organic carbon found in the effluent is first converted to C02 which is then detected by I.R~
analysis.
Table I hereinbelow gives ~he results for materi als evalua-~ed as cleaning agents ~n demineral k ed water three-hour static soak tests ~n combination with caustic and brine. In each instance in which a material in accordance with the invention was tested~ only a 1~ (weight) aqueous solution of each was used.
Table I
~ ~L~L_ts Under Static Soak Condition!, STRONG BASE RESIN
ProGedure - 50 grdms ~f a drainea~ fou7ed res~n were p7aced in a 600 ml beaker. Each tested cleaning solution comprised a 1%
(weight) concentration of the cleaning agent along with 10% NaOl and 1% Na~H In demineralized waterD The thus treated resins were agi-tated and then allowed to stand at room temperature over a three hour period. The TOC of ~he resulting effluents was then determined in accordance with the combustiontI.R. spectroscopy method outlined above.
~_f2d ~
Treatment TO
.
Brine C~ustic Control 3240 NaC10 NaB03 4H20 (perborate) 3780 Table II gives the test results for two different fouled strong base resins cleaned with sodium perborate in brine-caustic.
These data show an Increase in e~f~cacy with the sodium perborate over bline caustic alone. The use of sodium perborate in brine-caus-tic as an alternative to sodium hypochlorite was indicated by these test re!,ults.
TABLE II
__ EYPLUATION OF SODIUM PERBORATE IN STATIC SOAK TESTS
(BRINE-CAUSTIC) -% Increase Resin P~ (Same as resin tested in Table I).
1% NaCH 70 10% Na~l 2100 10% NaCl + 1% NaOH - Control 2521 lG% NaCl ~ 1% NaOH ~ 1% NaB03 4 H202950 17 lOg NaCl + 1% NaOH + 1% NaB03 4 H2032~C 29 10% NaCl ~ lX NaOH + 1% NaC10 3450 37 ~2~Z620 TABLE I I
(Cont~nued) X Increase Res~n B TOC (ppm) In Efficacy 10% NaCl ~ 1% NaOH - Control 663 lG% NaCl ~ 1% NaOH ~ 0.2% NaB03 4 H20 765 15 10% NaCl + l~ NaOH + Q~4% NaBO3 4 H20 867 31 10% NaCl ~ 1% NaOH ~ 0.6% NaB03 4 H20 765 15 10% NaCl ~ 1% NaOH + 0.~ NaB03 4 H20 714 8 10% NaCl ~ 1% NaOH ~ 1.0~ NaB03 4 H20 816 23 Test Conditions Par~ A - Three-hour stat1c soak test same as Table I.
Par~ B - Resin samples cleaned for one hour ln brine-caustic only9 drained and r~nsed two times with demineralized water.
Brlne-caustic or sodium perbora~e in brine caustic is then added to the precondit~oned resin. The length of the second static soak was one hour.
As Cleaning Agents for Weak Base Resin -Beaker Tests In accordance with the procedure reported above for Table I, 50 grams of a weak base resln was ~ested for TOC effluent content after wash~ng. Each of the noted clean~ng a~ents was present in a 1%
; aqueous solut~on. Results are repor~ed in Table III.
.iL-Cd;~2262(.) Table III
Evaluat~on of Inor~an~c Compounds As Cleaning A~qents For Weak Base Res~n - Beaker Tests % Increase Sample Test Conditions TOC (ppm) In Eff~ ac~
_. ~ .
Brine-Caustic Control Brine-Caustic 160 Na2B407 Soak-3 hrs 181 13 10 NaC10 480 200 3rine-Caustic Oontrol - 94 TSP
NaBO 4 H 0 198 111 NaF 146 55 ? 15 1% NaOH Control 1 hr. Gang Stirrer 219 NaBO 4 H O lX NaOH274 25 Room Temper~ture, Na2B407 = sodium tetraborate (borax).
TSP = Na3P04) trisodium phosphate NaC10 = sodium hypochlorite NaB03 4 H20 = sodium perborate NaF = sodium fluoride ~262~
g Resin Degradnt n Studies with Sodlum Perborate Sodium perborate is an oxidizing agent. Upon dilution with water, it forms hydrogen peroxide in situ. The potential for oxida-t1ve degradation of a strong base anion resin or boron or borate up-take on the resin due to the sodium perborate cleaning treatment was1nvestigated.
Fouled s~rong base resin was placed in the ~on exchange column. 0.3% sodium perborate (as NaB03) in brine-caustic was passed through the resin column at a flow rate of approxima~ely 22 lQ mls/min for 1.5 hour; at room temperature. Another resin sample was treated similarly, e~cept heat was applied ~o the column such that the effluent temper ture was maintained at 100F. These two sodium perborate cleaned samples plus an "as received" sample were then analyzed for absolu1e salt-splitting anion exchange capacity deter-minations. ~The ab~olute salt-splittlng anion exchange capacity is determ~ned followins an exhaustive cleaning procedure, and thus it measures the active sites which are available in the absence of fouling. Any permarent degradation of active exchange sites will be expressed as a reduction in absolute salt-splitting capacity.) No differences in the ~alt-splitting capacity were found for these samples. Sodium pe!borate cleaning did not affect the absolute salt-splitting anicn exchange capacity of the resin.
A fouled strong base resin sample was placed in the ion exchange column, cleaned with 200 mls brine-caustic plus 0.4~ of Formulation "A" ~as NaB03) (see Table IY), rinsed with demineral-~zed water, regenerated with 200 mls of 4% NaOH and rinsed again with dem~neral~zed water. The e~fluent solutions were sent for boron analyses by the ICP method (inductively coupled plasma emission spectroscopy). A materials balance utiliz~ng these data showed no ~2~ 6;~
-~o uptake o~ ~oron in the resin. The sodium perborate was not rPta~ned on the resin after regeneration.
Accordinglyg it appears tha~ there are no or only minimal detrimental effects (oxidative degradation) on the salt-spl~tting anion exchange capacity of a fouled strong base resln sample cleaned with sod~um perborate.
Evaluation of Sodium Perborate Formulat~on ~ .. .... ~ , .
A fonmulation consisting of 90~ (weight) NaB03 4 H20 (sod~um perborate), 5% Na4P207 (tetrasodium pyro-~O phosphate) and 5% Na2B407 ' 10 H20 (sod~um tetraborate), was tested to determine the TOC content of effluent from a treated res~n compared to the TOC content of a control standard in accordance w~th the procedures expla~ned here~nabove. Results are reported in Table IV.
3L~222626) TABLE IV
EYALUATION OF SODIUM PERBORATE_FORMULATION BRINE-CAUSTIC AND DEM.NERILIZED WATER STATIC AND GANG
STIRRER EEAKER TESTS
ROOM TEMPERATURE
% Increase Resin ~e * Tes~ Conditions ToC ( ~ In Efficacy 1 Control Br~ne-Caust~c 630 0.8~ A Sta~ic Soak-3 hrs 790 25 0.8% ~ 8~ 3~`
0.8% A 740 17 2 Control Brine-Caustlc 690 0.8X A Gang Stirrer-l hr 840 2"
0.8% A 790 1 o.a~ A 740 7'
Composi~ion three: 5 - 99% (weight) sodlum perborate, remainder NaC~.
Although the resin cleaning agents of the invention are preferred for use in the cleansing of strong base anionic res~nsJ
they may also be employed ln the cleansing of weak base anion exchange resins~
At the end user locat~on it is preferred to add water to the dry water soluble peroxide salt composition and to add brlne and/
or caus~c to the extent necessary so that the resulting aqueous com-position comprises abo~t 0.1 - abnu~. 30X (weigh~) peroxide salt, about 1 - 5% caustic and, 0 - 30% brine, rPmainder water.
. ~
The invention will now be further described w~th reference to a number of specific e~amples wh~ch are to be regarded solely as illustrative and not as restricting the scope of the invention~
In order to demonstrate the efficacy of the resin cleaning agents in accordance with the invention, effluent from a treated 6~
resin was analyzed to ascertain the Total Or~anic Carbon (TOC) con-tent thereof. Samples treated in accordanc~ with the invention were comparecl to control values. TOC content higher than control values ~ndicates efficacy of the cleaning agents.
TOC measurements were made by a ccmbustion/I.R.
spectroscopy method in which all of the organic carbon found in the effluent is first converted to C02 which is then detected by I.R~
analysis.
Table I hereinbelow gives ~he results for materi als evalua-~ed as cleaning agents ~n demineral k ed water three-hour static soak tests ~n combination with caustic and brine. In each instance in which a material in accordance with the invention was tested~ only a 1~ (weight) aqueous solution of each was used.
Table I
~ ~L~L_ts Under Static Soak Condition!, STRONG BASE RESIN
ProGedure - 50 grdms ~f a drainea~ fou7ed res~n were p7aced in a 600 ml beaker. Each tested cleaning solution comprised a 1%
(weight) concentration of the cleaning agent along with 10% NaOl and 1% Na~H In demineralized waterD The thus treated resins were agi-tated and then allowed to stand at room temperature over a three hour period. The TOC of ~he resulting effluents was then determined in accordance with the combustiontI.R. spectroscopy method outlined above.
~_f2d ~
Treatment TO
.
Brine C~ustic Control 3240 NaC10 NaB03 4H20 (perborate) 3780 Table II gives the test results for two different fouled strong base resins cleaned with sodium perborate in brine-caustic.
These data show an Increase in e~f~cacy with the sodium perborate over bline caustic alone. The use of sodium perborate in brine-caus-tic as an alternative to sodium hypochlorite was indicated by these test re!,ults.
TABLE II
__ EYPLUATION OF SODIUM PERBORATE IN STATIC SOAK TESTS
(BRINE-CAUSTIC) -% Increase Resin P~ (Same as resin tested in Table I).
1% NaCH 70 10% Na~l 2100 10% NaCl + 1% NaOH - Control 2521 lG% NaCl ~ 1% NaOH ~ 1% NaB03 4 H202950 17 lOg NaCl + 1% NaOH + 1% NaB03 4 H2032~C 29 10% NaCl ~ lX NaOH + 1% NaC10 3450 37 ~2~Z620 TABLE I I
(Cont~nued) X Increase Res~n B TOC (ppm) In Efficacy 10% NaCl ~ 1% NaOH - Control 663 lG% NaCl ~ 1% NaOH ~ 0.2% NaB03 4 H20 765 15 10% NaCl + l~ NaOH + Q~4% NaBO3 4 H20 867 31 10% NaCl ~ 1% NaOH ~ 0.6% NaB03 4 H20 765 15 10% NaCl ~ 1% NaOH + 0.~ NaB03 4 H20 714 8 10% NaCl ~ 1% NaOH ~ 1.0~ NaB03 4 H20 816 23 Test Conditions Par~ A - Three-hour stat1c soak test same as Table I.
Par~ B - Resin samples cleaned for one hour ln brine-caustic only9 drained and r~nsed two times with demineralized water.
Brlne-caustic or sodium perbora~e in brine caustic is then added to the precondit~oned resin. The length of the second static soak was one hour.
As Cleaning Agents for Weak Base Resin -Beaker Tests In accordance with the procedure reported above for Table I, 50 grams of a weak base resln was ~ested for TOC effluent content after wash~ng. Each of the noted clean~ng a~ents was present in a 1%
; aqueous solut~on. Results are repor~ed in Table III.
.iL-Cd;~2262(.) Table III
Evaluat~on of Inor~an~c Compounds As Cleaning A~qents For Weak Base Res~n - Beaker Tests % Increase Sample Test Conditions TOC (ppm) In Eff~ ac~
_. ~ .
Brine-Caustic Control Brine-Caustic 160 Na2B407 Soak-3 hrs 181 13 10 NaC10 480 200 3rine-Caustic Oontrol - 94 TSP
NaBO 4 H 0 198 111 NaF 146 55 ? 15 1% NaOH Control 1 hr. Gang Stirrer 219 NaBO 4 H O lX NaOH274 25 Room Temper~ture, Na2B407 = sodium tetraborate (borax).
TSP = Na3P04) trisodium phosphate NaC10 = sodium hypochlorite NaB03 4 H20 = sodium perborate NaF = sodium fluoride ~262~
g Resin Degradnt n Studies with Sodlum Perborate Sodium perborate is an oxidizing agent. Upon dilution with water, it forms hydrogen peroxide in situ. The potential for oxida-t1ve degradation of a strong base anion resin or boron or borate up-take on the resin due to the sodium perborate cleaning treatment was1nvestigated.
Fouled s~rong base resin was placed in the ~on exchange column. 0.3% sodium perborate (as NaB03) in brine-caustic was passed through the resin column at a flow rate of approxima~ely 22 lQ mls/min for 1.5 hour; at room temperature. Another resin sample was treated similarly, e~cept heat was applied ~o the column such that the effluent temper ture was maintained at 100F. These two sodium perborate cleaned samples plus an "as received" sample were then analyzed for absolu1e salt-splitting anion exchange capacity deter-minations. ~The ab~olute salt-splittlng anion exchange capacity is determ~ned followins an exhaustive cleaning procedure, and thus it measures the active sites which are available in the absence of fouling. Any permarent degradation of active exchange sites will be expressed as a reduction in absolute salt-splitting capacity.) No differences in the ~alt-splitting capacity were found for these samples. Sodium pe!borate cleaning did not affect the absolute salt-splitting anicn exchange capacity of the resin.
A fouled strong base resin sample was placed in the ion exchange column, cleaned with 200 mls brine-caustic plus 0.4~ of Formulation "A" ~as NaB03) (see Table IY), rinsed with demineral-~zed water, regenerated with 200 mls of 4% NaOH and rinsed again with dem~neral~zed water. The e~fluent solutions were sent for boron analyses by the ICP method (inductively coupled plasma emission spectroscopy). A materials balance utiliz~ng these data showed no ~2~ 6;~
-~o uptake o~ ~oron in the resin. The sodium perborate was not rPta~ned on the resin after regeneration.
Accordinglyg it appears tha~ there are no or only minimal detrimental effects (oxidative degradation) on the salt-spl~tting anion exchange capacity of a fouled strong base resln sample cleaned with sod~um perborate.
Evaluation of Sodium Perborate Formulat~on ~ .. .... ~ , .
A fonmulation consisting of 90~ (weight) NaB03 4 H20 (sod~um perborate), 5% Na4P207 (tetrasodium pyro-~O phosphate) and 5% Na2B407 ' 10 H20 (sod~um tetraborate), was tested to determine the TOC content of effluent from a treated res~n compared to the TOC content of a control standard in accordance w~th the procedures expla~ned here~nabove. Results are reported in Table IV.
3L~222626) TABLE IV
EYALUATION OF SODIUM PERBORATE_FORMULATION BRINE-CAUSTIC AND DEM.NERILIZED WATER STATIC AND GANG
STIRRER EEAKER TESTS
ROOM TEMPERATURE
% Increase Resin ~e * Tes~ Conditions ToC ( ~ In Efficacy 1 Control Br~ne-Caust~c 630 0.8~ A Sta~ic Soak-3 hrs 790 25 0.8% ~ 8~ 3~`
0.8% A 740 17 2 Control Brine-Caustlc 690 0.8X A Gang Stirrer-l hr 840 2"
0.8% A 790 1 o.a~ A 740 7'
3 Control Brf ne-Caustic 850 0.8% A Gang St~rrer 2 hrs 900 H
4 Contro~ Brine-Caust~c 350 O~g A Gang St~rrer-2 hrs 750 214 *TOC values dete~mined by Combust~on/IR Spectroscopy me~hod.
Formulation "A" equals 90 weight % NaB03 ' 4H20, 5%
Na4P207, and 5% Na2B407; in aqueous solution concen-trat~on 0.8X NaB03 4H20 as NaB03. This formulation is presently preferred for use.
3l2 D~scuss~on As Table I indicates, the sodium perborate cleaning agent is comparable to sodium hypochlor~te in efflcacy as measured by the TOC content of ~he ~ffluen~ ~rom washed resin samples.
Table II demonstrate~ that khe sodium perborate treatments lncrease the cleans~ng efficacy of br~ne and caustic washing.
Insofar as weak bas~ anion resins are concerned, Table III
lndicates that the sodium perborate cleansing compos~tions of the present invention are approxin.itely equal to sodium hypochlorite.
10 However, unlike those me~hods involving sodium hypochlorite, the sodium perborate containing c eans~ng compos~tions are not, in any significant amount retained on the resin, nor is there any s~gnlf~-cant resin degradation occasioned by use of the sodium perborate treatment of the invent~on.
Table IY indicates 1.ha~ the compositions presently pre-ferred for use (Formulation ~ herein) increases brine and caus~ic cleansing efficacy It can thus be seen that the disclosed inven~ion carries out ~he objects of the inven1.ion set forth above. In accord with the 20 patent statutes, the best mode has been set forth However, it will be apparent to those skilled ~n the art that many other modificat~ons can be made without departing from the invention herein disolosed and descrlbed, ~he scope of the lnventlon being limited only by the scope of the attaGhed claims.
Formulation "A" equals 90 weight % NaB03 ' 4H20, 5%
Na4P207, and 5% Na2B407; in aqueous solution concen-trat~on 0.8X NaB03 4H20 as NaB03. This formulation is presently preferred for use.
3l2 D~scuss~on As Table I indicates, the sodium perborate cleaning agent is comparable to sodium hypochlor~te in efflcacy as measured by the TOC content of ~he ~ffluen~ ~rom washed resin samples.
Table II demonstrate~ that khe sodium perborate treatments lncrease the cleans~ng efficacy of br~ne and caustic washing.
Insofar as weak bas~ anion resins are concerned, Table III
lndicates that the sodium perborate cleansing compos~tions of the present invention are approxin.itely equal to sodium hypochlorite.
10 However, unlike those me~hods involving sodium hypochlorite, the sodium perborate containing c eans~ng compos~tions are not, in any significant amount retained on the resin, nor is there any s~gnlf~-cant resin degradation occasioned by use of the sodium perborate treatment of the invent~on.
Table IY indicates 1.ha~ the compositions presently pre-ferred for use (Formulation ~ herein) increases brine and caus~ic cleansing efficacy It can thus be seen that the disclosed inven~ion carries out ~he objects of the inven1.ion set forth above. In accord with the 20 patent statutes, the best mode has been set forth However, it will be apparent to those skilled ~n the art that many other modificat~ons can be made without departing from the invention herein disolosed and descrlbed, ~he scope of the lnventlon being limited only by the scope of the attaGhed claims.
Claims (11)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. In a method of removing organic foulants from an anionic ex-change resin wherein said fouled resin is treated with a member or members selected from the group consisting of brine and caus-tic to aid in removal of said foulants, the improvement compris-ing also contacting said fouled resin with an aqueous composi-tion comprising a water soluble inorganic peroxide salt having a peroxy containing anion selected from the group consisting of perborate, persulfate and percarbonate anions and a cation which is non-oxidizable upon dilution with water. - 2. An improved method as defined in Claim 1 wherein said water soluble inorganic peroxide salt comprises a member or members selected from the group consisting of sodium perborate, sodium persulfate, and sodium percarbonate.
- 3. An improved method as defined in Claim 2 further comprising also contacting said fouled resin with an inorganic chelating agent.
- 4. An improved method as defined in Claim 3 wherein said inorganic chelatins agent is a member or members selected from the group consisting of tetrasodium pyrophosphate and pentasodium tripoly-phosphate.
- 5. An improved method as recited in Claim 1 wherein said anionic exchange resin is a strong base anionic exchange resin.
- 6. In a method of removing organic foulants from an anionic ex-change resin wherein said fouled resin is treated with a member or members selected from the group consisting of brine and caus-tic to aid in removal of said foulants, the improvement compris-ing also contacting said fouled resin with an aqueous solution comprising sodium perborate.
- 7. Dry, stable composition for cleaning organic foulants from an anionic exchange resin, said composition comprising:
a water soluble inorganic peroxide salt having a peroxy containing anion selected from the group consisting of perborate, persulfate and percar-bonate anions and a cation which is non-oxidizable upon dilution with water, and an inert inorganic salt. - 8. Dry stable composition as defined in Claim 7 further comprising an inorganic chelating agent.
- 9. Dry stable composition is defined in Claim 8 wherein said inert inorganic salt comprises sodium tetraborate.
- 10. Dry stable composition as defined in Claim 9 wherein said inor-ganic chelating agent comprises a member or members selected from the group consisting of tetrasodium pyrophosphate and pentasodium tripolyphosphate.
- 11. Dry stable composition as defined in Claim 7 wherein said water soluble peroxide salt comprises sodium perborate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52129783A | 1983-08-08 | 1983-08-08 | |
| US521,297 | 1983-08-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1222620A true CA1222620A (en) | 1987-06-09 |
Family
ID=24076189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000460186A Expired CA1222620A (en) | 1983-08-08 | 1984-08-01 | Method and compositions for cleaning organically fouled anion exchange resins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1222620A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2519563A1 (en) * | 1982-01-14 | 1983-07-18 | Azote & Prod Chim | Catalyst for converting synthesis gas to hydrocarbon(s) - comprises transition metals and de:aluminated mordenite |
| US4500646A (en) * | 1982-01-14 | 1985-02-19 | Societe Chimique De La Grande Paroisse, Azote Et Producits Chimiques | Conversion catalysts for synthesis gas |
-
1984
- 1984-08-01 CA CA000460186A patent/CA1222620A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2519563A1 (en) * | 1982-01-14 | 1983-07-18 | Azote & Prod Chim | Catalyst for converting synthesis gas to hydrocarbon(s) - comprises transition metals and de:aluminated mordenite |
| US4500646A (en) * | 1982-01-14 | 1985-02-19 | Societe Chimique De La Grande Paroisse, Azote Et Producits Chimiques | Conversion catalysts for synthesis gas |
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