CH667598A5 - METHOD AND DEVICE FOR REMOVING ORGANIC AND / OR COLLOID DISPERSIVE INGREDIENTS FROM WATER FREE FROM UNDESOLVED SOLIDS. - Google Patents
METHOD AND DEVICE FOR REMOVING ORGANIC AND / OR COLLOID DISPERSIVE INGREDIENTS FROM WATER FREE FROM UNDESOLVED SOLIDS. Download PDFInfo
- Publication number
- CH667598A5 CH667598A5 CH3333/86A CH333386A CH667598A5 CH 667598 A5 CH667598 A5 CH 667598A5 CH 3333/86 A CH3333/86 A CH 3333/86A CH 333386 A CH333386 A CH 333386A CH 667598 A5 CH667598 A5 CH 667598A5
- Authority
- CH
- Switzerland
- Prior art keywords
- resin
- water
- cation resin
- solids
- removing organic
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 14
- 239000007787 solid Substances 0.000 title claims description 5
- 239000000084 colloidal system Substances 0.000 title description 2
- 239000004615 ingredient Substances 0.000 title 1
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 39
- 150000001768 cations Chemical class 0.000 claims description 23
- 150000001450 anions Chemical class 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012492 regenerant Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 230000008929 regeneration Effects 0.000 description 8
- 238000011069 regeneration method Methods 0.000 description 8
- 238000001223 reverse osmosis Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/04—Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Description
BESCHREIBUNG Die v orliegende Erfindung betrifft ein Verfahren zum Entfernen organischer und/oder kolloiddisperser Bestandteile aus von ungelösten Feststoffen befreitem Wasser mittels eines durch ein alkalisches Regeneriermittel regenerierbares stark basisches makroporöses Anionenharz. DESCRIPTION The present invention relates to a method for removing organic and / or colloidally dispersed constituents from water freed from undissolved solids by means of a strongly basic macroporous anion resin which can be regenerated by an alkaline regenerating agent.
Ein solches Verfahren ist im Prospekt der Anmelderin «Wassertechnik Umkehrosmose-Anlagen», Seite 4, angesprochen. Bei Behandlung von Wasser in einer Umkehrosmose wird das Uferfiltrat vor Eintritt in die Anlage entkarbonisiert und zweistufig filtriert. Die Filtration der ungelösten Feststoffe erfolgt über Kies, während organische Bestandteile und kolloiddisperse Stoffe über Adsorberharze aus dem Wasser entfernt werden. In der Beschreibung und in den Ansprüchen umfasst der Begriff «Wasser» auch wässrige Lösungen. Mit dieser Filtration wird der Kolloidindex verringert. Der Filter besteht im wesentlichen aus einem Druckbehälter und einer stark basischen Anionenharzfüllung, die in der Regel mittels einer alkalischen Kochsalzlösung regeneriert wird. Es hat sich nun herausgestellt, dass eine Reihe von Kationen, die bereits bei sehr geringen Ionenkonzentrationen zu erheblichen Störungen bei der Umkehrosmose führen, in den immer stärker verschmutzten und zu reinigenden Wässern vorhanden sind, so dass es schon nach relativ kurzen Betriebszeiten zu einer irreversiblen Verschmutzung der Umkehrosmoseeinrichtung, insbesondere durch Barium-und Strontiumsalze kam. Such a method is addressed in the prospectus of the applicant “Water technology reverse osmosis systems”, page 4. When treating water in reverse osmosis, the bank filtrate is decarbonized and filtered in two stages before entering the system. The undissolved solids are filtered through gravel, while organic constituents and colloid-dispersed substances are removed from the water via adsorber resins. In the description and in the claims, the term “water” also includes aqueous solutions. This filtration reduces the colloid index. The filter essentially consists of a pressure vessel and a strongly basic anion resin filling, which is generally regenerated using an alkaline saline solution. It has now been found that a number of cations, which lead to considerable disturbances in reverse osmosis even at very low ion concentrations, are present in the increasingly polluted and cleanable water, so that irreversible pollution occurs after relatively short operating times the reverse osmosis device, in particular due to barium and strontium salts.
Es wurde versucht, mit in das zu regenerierende Wasser eindosierten Konditionierungsmitteln eine Ausfällung in der Membran der Umkehrosmose zu verhindern. Diese Versuche veriefen jedoch wenig erfolgreich. " Attempts have been made to prevent precipitation in the membrane of the reverse osmosis with conditioning agents metered into the water to be regenerated. However, these attempts are unsuccessful. "
Die Erfindung bezweckt ein Verfahren zu schaffen, bei dem eine Entfernung von in nachfolgenden Schritten störenden Kationen möglich ist, insbesondere eine irreversible Verschmutzung von semipermeablen Membranen durch Kationen. insbesondere zweiwertigen Erdalkaliionen vermieden wird. The invention aims to provide a method in which it is possible to remove cations which interfere in subsequent steps, in particular irreversible contamination of semipermeable membranes by cations. especially divalent alkaline earth metal ions is avoided.
Das erfmdungsgemässe Verfahren ist dadurch gekennzeichnet. dass das Wasser zusätzlich über ein stark saures Kationenharz geführt wird, wobei sowohl das Anionenharz als auch das Kationenharz mit demselben Regeneriermittel regenerierbar sind. The method according to the invention is characterized in this. that the water is additionally passed over a strongly acidic cation resin, both the anion resin and the cation resin being regenerable with the same regenerant.
Weiter betrifft die Erfindung eine Vorrichtung zur Durchführung des Verfahrens, bei welcher sich in mindestens einem Filterbehälter ein stark basisches makroporöses Anionenharz und ein stark saures Kationenharz befinden. The invention further relates to a device for carrying out the method, in which a strongly basic macroporous anion resin and a strongly acidic cation resin are located in at least one filter container.
Das stark saure Kationenharz kann die Kationen im Zulaufwasser aufnehmen. The strongly acidic cation resin can absorb the cations in the feed water.
Nach Anspruch 2 wird das Wasser vorzugsweise zunächst über das Anionenharz geführt, um die organischen substanzen bzw. die kolloiddispersen Stoffe zu entfernen und danach über das Kationenharz. According to claim 2, the water is preferably first passed over the anion resin to remove the organic substances or the colloidally dispersed substances and then over the cation resin.
Der Anteil der beiden Harz-Typen an der erforderlichen Gesamtmenge richtet sich nach der organischen Belastung und dem Ionenangebot im Zulaufwasser unter Berücksichtigung der kinetischen und hydraulischen Eigenschaften der Harzprodukte. The share of the two resin types in the total amount required depends on the organic load and the ion supply in the feed water, taking into account the kinetic and hydraulic properties of the resin products.
Beim erfindungsgemässen Verfahren brauchen keine Konditionierungsmittel eingesetzt werden. Die beiden Harze können ohne Schwierigkeiten vorzugsweise in ein und demselben Filterbehälter eingebracht und somit von einer gemeinsamen Regeneriereinrichtung her regeneriert werden. No conditioning agents need be used in the method according to the invention. The two resins can preferably be introduced without difficulty into one and the same filter container and thus regenerated from a common regeneration device.
Es tritt kein Mehrverbrauch an Waschwasser und Regenerierchemikalien auf; auch ist keine Erhöhung der Regenerationszeit zu erwarten. There is no additional consumption of washing water and regeneration chemicals; nor is an increase in the regeneration time to be expected.
Nachfolgend wird anhand einer Zeichnungsfigur ein Ausführungsbeispiel des erfindungsgemässen Verfahrens beschrieben, und zwar die Reinigung von Uferfiltrat. An exemplary embodiment of the method according to the invention is described below with the aid of a drawing figure, namely the cleaning of bank filtrate.
Das Uferfiltrat UF wird unter Zugabe von Ca(OH)2 in einem Behälter 1 entkarbonisiert. In einem dem Behälter 1 nachgeschalteten ersten Filter 2 werden über ein Kiesbett 2a ungelöste Feststoffe entfernt. Danach tritt das Wasser in einen Filterbehälter 3 ein, in dem sich eine obere Schicht von stark basischem makroporösem Anionenharz 3a und eine untere Schicht von stark saurem Kationenharz 3b befindet. Das Ablaufwasser wird unter Zugabe von HCLCb und Poly-phosphat über einen Feinfilter 4 einer Umkehrosmosestufe 5 zugeleitet und gelangt schliesslich über eine Ionenaustauscherstufe 6 in den Prozess. Durch die gestrichelte Linie 7 ist angedeutet, dass dem Filterbehälter 3 eine Regeneriereinrichtung zugeordnet ist, die als Regeneriermittel NaCl + NaOH zuführt. Das stark basische Anionenharz liegt im Betriebszustand des Filters in der Cl-Form vor. Das Harz reduziert die organischen Substanzen und die kolloiddispersen Stoffe adsorptiv. Das stark saure Kationenharz 3b ist vorzugsweise ein Kationenharz in der Na+-Form, der NH4-Form oder in der K+-Form und wiederum bevorzugt ein Kationenharz in der Na+-Form. Das stark saure Kationenharz kann gemäss der folgenden Reaktionsvergleichung, die zu einer Verschmutzung der Membran führenden Kationen im Zulaufwasser aufnehmen: The bank filtrate UF is decarbonized in a container 1 with the addition of Ca (OH) 2. In a first filter 2 arranged downstream of the container 1, undissolved solids are removed via a gravel bed 2a. The water then enters a filter container 3 in which there is an upper layer of strongly basic macroporous anion resin 3a and a lower layer of strongly acidic cation resin 3b. With the addition of HCLCb and poly-phosphate, the waste water is fed through a fine filter 4 to a reverse osmosis stage 5 and finally reaches the process via an ion exchanger stage 6. The dashed line 7 indicates that the filter container 3 is assigned a regeneration device which supplies NaCl + NaOH as the regeneration agent. The strongly basic anion resin is in the Cl form in the operating state of the filter. The resin reduces the organic substances and the colloidally dispersed substances by adsorption. The strongly acidic cation resin 3b is preferably a cation resin in the Na + form, the NH4 form or in the K + form and again preferably a cation resin in the Na + form. According to the following reaction comparison, the strongly acidic cation resin can absorb the cations in the feed water that lead to contamination of the membrane:
Harz-2Na+ + (Ca++/Mg++/Ba++/Sr++)-> Harz-(Ca++/Mg++/Ba++/Sr++) + 2Na+. Resin-2Na + + (Ca ++ / Mg ++ / Ba ++ / Sr ++) -> Resin- (Ca ++ / Mg ++ / Ba ++ / Sr ++) + 2Na +.
Es hat sich dabei herausgestellt, dass die Bindungsfestigkeit von Ba++ und Sr++ an das Harz (Kationenaustauscher) nahe der Bindungsfestigkeit von Ca++ und Mg++ liegt, so dass in allen Fällen ein guter Wirkungsgrad des Ionenaustausches gegen Na++ gewährleistet ist. It was found that the bond strength of Ba ++ and Sr ++ to the resin (cation exchanger) is close to the bond strength of Ca ++ and Mg ++, so that a good efficiency of the ion exchange against Na ++ is guaranteed in all cases.
Für die Regeneration des stark basischen makroporösen Anionenharzes wurde bisher eine alkalische NaCl-Lösung eingesetzt. Eine Wiederbelebung des stark sauren Kationenharzes ist mit demselben Regeneriermittel, z.B. NaCl, KCl, NH4CI, möglich. Als Regeneriermittel wird Natriumchlorid bevorzugt, während als alkalischer Partner im Regeneriermittel Natriumhydroxid bevorzugt wird. Hier wäre z.B. der Einsatz von Kaliumhydroxid ebenfalls denkbar. Desweiteren können Lösungen von Natriumsulfat und Meerwasser zum Einsatz kommen. So far, an alkaline NaCl solution has been used for the regeneration of the strongly basic macroporous anion resin. The strong acid cation resin can be revived with the same regenerant, e.g. NaCl, KCl, NH4CI possible. Sodium chloride is preferred as the regenerant, while sodium hydroxide is preferred as the alkaline partner in the regenerant. Here would be e.g. the use of potassium hydroxide is also conceivable. Furthermore, solutions of sodium sulfate and sea water can be used.
Die Regeneration des erschöpften Kationenharzes läuft nach folgender Reaktionsgleichung ab: The regeneration of the exhausted cation resin proceeds according to the following reaction equation:
2 2nd
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667 598 667 598
Harz-(Ca^+/Mg++/Ba++/Sr++) + 2NaCl-> Harz-2Na+ + (Ca + + /Mg+-7Ba+-7Sr+-'-). Resin- (Ca ^ + / Mg ++ / Ba ++ / Sr ++) + 2NaCl-> Resin-2Na + + (Ca + + / Mg + -7Ba + -7Sr + -'-).
Somit werden beide Harze mit demselben Regeneriermittel regeneriert. Thus both resins are regenerated with the same regenerant.
Es soll abschliessend daraufhingewiesen werden, dass diese Kombination, das heisst zwei verschiedene Harze mit einem Regeneriermittel, insbesondere zwei verschiedene Harze in einem Filterbehälter, sowohl in einem Schichtbettverfahren, Zwei- oder Mehrkammersystem bei Regeneration im Gleichstrom oder Gegenstrom betrieben werden kann. In conclusion, it should be pointed out that this combination, that is to say two different resins with one regenerating agent, in particular two different resins in a filter container, can be operated in a stratified bed process, two- or multi-chamber system during regeneration in cocurrent or countercurrent.
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1 Blatt Zeichnungen 1 sheet of drawings
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853531404 DE3531404A1 (en) | 1985-09-03 | 1985-09-03 | Process for removing organic constituents from water to be fed to reversed osmosis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH667598A5 true CH667598A5 (en) | 1988-10-31 |
Family
ID=6280010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH3333/86A CH667598A5 (en) | 1985-09-03 | 1986-08-20 | METHOD AND DEVICE FOR REMOVING ORGANIC AND / OR COLLOID DISPERSIVE INGREDIENTS FROM WATER FREE FROM UNDESOLVED SOLIDS. |
Country Status (4)
| Country | Link |
|---|---|
| CH (1) | CH667598A5 (en) |
| DE (1) | DE3531404A1 (en) |
| FR (1) | FR2586671A1 (en) |
| ZA (1) | ZA866622B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1204691B (en) * | 1987-06-05 | 1989-03-10 | Snia Fibre | Treatment of effluents from olive oil industry |
| JP2902511B2 (en) * | 1991-12-24 | 1999-06-07 | 三菱電機株式会社 | Ultrapure water production apparatus, production method, and production apparatus control method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1285956B (en) * | 1954-07-01 | 1968-12-19 | Corte | Process for the desilification of water |
| GB906243A (en) * | 1960-05-20 | 1962-09-19 | Permutit Co Ltd | Improvements relating to processes for the treatment of water |
| GB914511A (en) * | 1960-09-06 | 1963-01-02 | Permutit Co Ltd | Improvements relating to the purification of water |
| NL282900A (en) * | 1961-09-22 | 1900-01-01 |
-
1985
- 1985-09-03 DE DE19853531404 patent/DE3531404A1/en active Granted
-
1986
- 1986-08-20 CH CH3333/86A patent/CH667598A5/en not_active IP Right Cessation
- 1986-08-25 FR FR8612019A patent/FR2586671A1/en active Pending
- 1986-09-01 ZA ZA866622A patent/ZA866622B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA866622B (en) | 1987-04-29 |
| DE3531404A1 (en) | 1987-03-05 |
| DE3531404C2 (en) | 1988-08-25 |
| FR2586671A1 (en) | 1987-03-06 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |