DE1953970A1 - Fluoride ion recovery from solutions with - anion exchange resin - Google Patents
Fluoride ion recovery from solutions with - anion exchange resinInfo
- Publication number
- DE1953970A1 DE1953970A1 DE19691953970 DE1953970A DE1953970A1 DE 1953970 A1 DE1953970 A1 DE 1953970A1 DE 19691953970 DE19691953970 DE 19691953970 DE 1953970 A DE1953970 A DE 1953970A DE 1953970 A1 DE1953970 A1 DE 1953970A1
- Authority
- DE
- Germany
- Prior art keywords
- fluoride
- anion exchange
- solutions
- fluoride ion
- medium
- 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.)
- Granted
Links
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 11
- 239000003957 anion exchange resin Substances 0.000 title abstract description 3
- 238000011084 recovery Methods 0.000 title abstract 2
- 150000001450 anions Chemical class 0.000 claims abstract description 14
- -1 fluoride ions Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005349 anion exchange Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 102000016955 Erythrocyte Anion Exchange Protein 1 Human genes 0.000 description 1
- 108010014384 Erythrocyte Anion Exchange Protein 1 Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
- C01B7/197—Separation; Purification by adsorption
- C01B7/198—Separation; Purification by adsorption by solid ion-exchangers
-
- 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verfahren zur Entfernung von Fluoriden aus wässrigen Lösungen und zur Herstellung von Fluoriden und Flußsäure Es ist bekannt, daß stark saure Kationenaustauscher und stark basische Anionenaustauscher eine Kapazität für schwache organische Säuren haben können, die weit über ihre Austauschkapazität hinausgeht. Desgleichen ist die große Affinität vieler Austauscher für Phenol bekannt. Bekannt ist auch, daß stark båsische Anionenaustauscher und stark saure Kationenaustauscher eine Kapazität für organische Basen wie Pyridin und Piperidin haben können, die weit über ihre Austauschkapazität hinausgeht.Process for removing fluorides from aqueous solutions and for the production of fluorides and hydrofluoric acid It is known that strongly acidic cation exchangers and strongly basic anion exchangers have a capacity for weak organic acids that goes far beyond their exchange capacity. The same is known for the great affinity of many exchangers for phenol. It is also known that strongly basic anion exchangers and strongly acidic cation exchangers have one capacity for organic bases like pyridine and piperidine they can have well above their Exchange capacity.
Überraschenderweise wurde nunmehr gefunden, daß schwach-basische und mittel-basische Anionenaustauscher eine Kapazität gegenüber Fluoridionen haben, die die Austauschkapazität weit überschreitet.Surprisingly, it has now been found that weakly basic and medium-basic anion exchangers have a capacity for fluoride ions, which far exceeds the exchange capacity.
Insbesondere mittel-basische Anionenaustauscher können ein Mehrfaches ihrer Austauschkapazität an Fluoridionen aufnehmen.In particular, medium-basic anion exchangers can multiply absorb their exchange capacity of fluoride ions.
Es wurde gefunden, daß die von schwach-basischen und mittel-basischen Anionenaustauschern aus wässrigen Lösungen auf genommenen Fluoridionenr mengen mit zunehmender Konzentration der Fluoridionen zunehmen und einem Sättigungswert zustreben. Entgegen den nach den Kenndaten zu erwartenden Werten für die Fluoridionenkapazität vermag ein mittelbasisches Anionenaustauscherharz etwa die 5-fache Menge an Fluorid-Zonen auf zunehmen, wie aus der nachstehenden Tabelle hervorgeht, die zugleich zeigt, daß beim Überschreiten eines Optimums für die Konzentration der Fluoridionen in der Lösung eine weitere Aufkonzentration unwirtschaftlich wird: Kapazität für die Fluoridionen nach den Kenndaten des Harzes: 20 - 30 g F' pro Liter Harz Konzentration der Beladungslösung (g F'/1) 0,2 1 , o 2,o 5,o 10,25 15,55 53,0 Fluoridaufnahme pro Liter Harz 36,2 t4,1 47,3 60,0 73,3 81,0 128,o Kennzeichnend für die Erfindung ist insbesondere auch die nachstehende weitere Tabelle, in der die aus Lösungen mit optimaler Konzentration für die Fluoridionen für ein bestimmtes Harz, beispielsweise 15 g F'/Liter Harz, bei Verwendung verschiedener Harz sorten aus der Lösung aufgenommenen Mengen an Fluoridionen aufgetragen sind und die Harz sorte 1 die gleiche ist wie in der vorausgehenden Tabelle: Handelsprodukte Fluoridaufnahme pro Liter Harz Anionenaustauscher 1 80 g II II 36 g li III 9o g Iv in 62 g n V 6o g Die vorstehende Tabelle zeigt, daß die Wirtschaftlichkeit des Verfahrens von der Auswahl eines besonders geeigneten schwachbasischen oder mittel-basischen Anionenaustauschers wesentlich abhangt. Eine besonders hohe Kapazität für die Fluoridaufnahme haben beispielsweise mittel-basische Anionenaustauscher, die als aktive Gruppen die Gruppen -N(R)2 oder -N(R)30H oder beide Gruppen gemeinsam enthalten. Solcherart Anionenaustauscher nehmen bei der optimalen Konzentration der Fluoridionen in der Lösung bereits die 3 - 4 fache Menge der Austauschkapazität an Fluoridionen auf.It was found that those of weakly basic and medium basic Anion exchangers from aqueous solutions on absorbed fluoride ions with increasing concentration of fluoride ions and strive for a saturation value. Contrary to the values for the fluoride ion capacity to be expected according to the characteristic data A medium-based anion exchange resin is capable of about 5 times the amount of fluoride zones increase, as can be seen from the table below, which also shows that when an optimum for the concentration of fluoride ions is exceeded in the solution a further concentration becomes uneconomical: capacity for the Fluoride ions according to the characteristics of the resin: 20 - 30 g F 'per liter resin concentration of the loading solution (g F '/ 1) 0.2 1, o 2, o 5, o 10.25 15.55 53.0 fluoride uptake per liter of resin 36.2 t4.1 47.3 60.0 73.3 81.0 128, o Characteristic for the invention is in particular also the following further table in which those from solutions with optimal concentration for the fluoride ions for a given Resin, for example 15 g F '/ liter of resin, when using different types of resin The amounts of fluoride ions absorbed from the solution are applied and the resin Type 1 is the same as in the previous table: Commercial products fluoride intake per liter of resin anion exchanger 1 80 g II II 36 g li III 9o g Iv in 62 g n V 6o The table above shows that the economy of the process depends on the Selection of a particularly suitable weakly basic or medium-basic anion exchanger depends essentially. Have a particularly high capacity for fluoride uptake for example, medium-basic anion exchangers, which act as active groups, the groups -N (R) 2 or -N (R) 30H or both groups together. Such an anion exchanger take with the optimal concentration of fluoride ions in the solution 3 - 4 times the amount of the exchange capacity of fluoride ions.
Der besondere Vorteil des erfindungsgemäßen Verfahrens für die Entfernung von Fluoriden aus wässriger Lösung besteht darin, daß nach der Regeneration des Austauschmaterials die Eonzentration des Fluorids in der Lösung wesentlich höher ist als in der Ausgangslösung. Außerdem wird durch das erfindungsgemäße auswählende Vorgehen die notwendige Harzmenge stark verringert.The particular advantage of the method according to the invention for removal of fluorides from aqueous solution is that after the regeneration of the Exchange material, the concentration of fluoride in the solution is significantly higher is than in the initial solution. In addition, the inventive selection Procedure greatly reduced the amount of resin required.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691953970 DE1953970C (en) | 1969-10-27 | Process for removing fluorides from aqueous solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691953970 DE1953970C (en) | 1969-10-27 | Process for removing fluorides from aqueous solutions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1953970A1 true DE1953970A1 (en) | 1971-05-06 |
| DE1953970B2 DE1953970B2 (en) | 1973-01-04 |
| DE1953970C DE1953970C (en) | 1973-08-09 |
Family
ID=
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2348474A1 (en) * | 1972-09-29 | 1974-04-11 | Alusuisse | PROCESS FOR RECOVERY OF FLUORINE FROM AN AQUATIC SOLUTION |
| US4056605A (en) * | 1976-11-23 | 1977-11-01 | Alexandr Ilich Vulikh | Method for purification of hydrofluoric acid |
| JPS5310553A (en) * | 1976-07-15 | 1978-01-31 | Kurita Water Ind Ltd | Mehtod of treating waste water containing fluorine and boron |
| DE3102552A1 (en) * | 1981-01-27 | 1982-10-21 | Werner 2082 Tornesch Czepluch | Fully automatic device for packaging piece goods, especially easily bruised fruit and hollow chocolate pieces |
| DE8915286U1 (en) * | 1989-12-30 | 1990-03-29 | NIKO Nahrungsmittel-Maschinen GmbH & Co KG, 41334 Nettetal | Steep conveyor for vegetables, fruit, etc. |
| EP0593771A1 (en) * | 1992-03-13 | 1994-04-27 | Daikin Industries, Limited | Method of recovering volatile acids |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2348474A1 (en) * | 1972-09-29 | 1974-04-11 | Alusuisse | PROCESS FOR RECOVERY OF FLUORINE FROM AN AQUATIC SOLUTION |
| JPS5310553A (en) * | 1976-07-15 | 1978-01-31 | Kurita Water Ind Ltd | Mehtod of treating waste water containing fluorine and boron |
| JPS5633999B2 (en) * | 1976-07-15 | 1981-08-07 | ||
| US4056605A (en) * | 1976-11-23 | 1977-11-01 | Alexandr Ilich Vulikh | Method for purification of hydrofluoric acid |
| DE3102552A1 (en) * | 1981-01-27 | 1982-10-21 | Werner 2082 Tornesch Czepluch | Fully automatic device for packaging piece goods, especially easily bruised fruit and hollow chocolate pieces |
| DE8915286U1 (en) * | 1989-12-30 | 1990-03-29 | NIKO Nahrungsmittel-Maschinen GmbH & Co KG, 41334 Nettetal | Steep conveyor for vegetables, fruit, etc. |
| EP0593771A1 (en) * | 1992-03-13 | 1994-04-27 | Daikin Industries, Limited | Method of recovering volatile acids |
| EP0593771A4 (en) * | 1992-03-13 | 1994-08-17 | Daikin Ind Ltd | Method of recovering volatile acids |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1953970B2 (en) | 1973-01-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| EHJ | Ceased/non-payment of the annual fee |