DE1265132B - Process for the removal of anions of oxygen acids from a solution - Google Patents
Process for the removal of anions of oxygen acids from a solutionInfo
- Publication number
- DE1265132B DE1265132B DEC34893A DEC0034893A DE1265132B DE 1265132 B DE1265132 B DE 1265132B DE C34893 A DEC34893 A DE C34893A DE C0034893 A DEC0034893 A DE C0034893A DE 1265132 B DE1265132 B DE 1265132B
- Authority
- DE
- Germany
- Prior art keywords
- solution
- anions
- removal
- oxygen acids
- temperature
- 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.)
- Pending
Links
- 150000001450 anions Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 9
- 150000002926 oxygen Chemical class 0.000 title description 5
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000005349 anion exchange Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 150000004715 keto acids Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 5
- 229910052901 montmorillonite Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- CBOMKORDEVXTOW-UHFFFAOYSA-K [Si](=O)=O.[OH-].[Al+3].[OH-].[OH-] Chemical compound [Si](=O)=O.[OH-].[Al+3].[OH-].[OH-] CBOMKORDEVXTOW-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- 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
- B01J41/02—Processes using inorganic 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
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/10—Inorganic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/50—Zeolites wherein inorganic bases or salts occlude channels in the lattice framework, e.g. sodalite, cancrinite, nosean, hauynite
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. CL: Int. CL:
BOIdBOId
Deutsche Kl.: 12 d-1/03 German class: 12 d- 1/03
Nummer: 1 265 132Number: 1 265 132
Aktenzeichen: C 34893 IV a/12 dFile number: C 34893 IV a / 12 d
Anmeldetag: 19. Januar 1965Filing date: January 19, 1965
Auslegetag: 4. April 1968Open date: April 4, 1968
Die Erfindung betrifft ein Verfahren zum Anionenaustausch, wodurch man Anionen von Sauerstoffsauren aus einer wäßrigen neutralen oder schwach alkalischen Lösung bei Temperaturen nahe bei oder über 2000C und unter dem entsprechenden Wasserdampfdruck entfernen kann.The invention relates to a method for anion exchange, whereby anions of oxygen acids can be removed from an aqueous neutral or weakly alkaline solution at temperatures close to or above 200 ° C. and under the corresponding water vapor pressure.
Es sind eine Anzahl von Anionenaustauschern organischer Herkunft, insbesondere für Anionen von Sauerstoffsäuren, bekannt, die bis zu einer Temperatur von 1000C völlig befriedigen; oberhalb dieser Temperatur erleiden sie einen sehr raschen Abbau, der sie unbrauchbar macht. Für bestimmte Zwecke, insbesondere in der Atomenergietechnik, benötigt man Ionenaustauscher, die höheren Temperaturen über beispielsweise 200° C und Strahlungen widerstehen und dabei eine gute Ionenabtrennung aus der zu behandelnden Flüssigkeit gewährleisten. Das ist beispielsweise der Fall bei der Reinigung des Kühlmediums eines Kernreaktors, der mit Wasserdampf gekühlt wird. Damit ein Anionenaustauscher zur ao Reinigung von Wasser benutzt werden kann, muß er außerdem zwei weitere Bedingungen erfüllen, nämlich nur OH"-Ionen austauschen und einen leichten Durchgang der zu behandelnden Flüssigkeit gestatten.A number of anion exchangers of organic origin, in particular for anions of oxygen acids, are known which are completely satisfactory up to a temperature of 100 ° C .; Above this temperature they undergo very rapid degradation, which makes them unusable. For certain purposes, in particular in atomic energy technology, ion exchangers are required which can withstand higher temperatures above 200 ° C., for example, and radiation, while ensuring good ion separation from the liquid to be treated. This is the case, for example, when cleaning the cooling medium of a nuclear reactor, which is cooled with water vapor. In order for an anion exchanger to be used for purifying water, it must also meet two further conditions, namely only exchange OH "ions and allow easy passage of the liquid to be treated.
Man hat sehr bald das Augenmerk auf mineralische Ionenaustauscher gerichtet, die aus natürlichen Mineralien vom Typ Montmorillonit oder synthetischen Mineralien (Salzen sehr geringer Löslichkeit, Phosphate und Hydroxide von Zirkonium und Thorium) bestehen.Very soon attention was drawn to mineral ion exchangers, which are made from natural minerals of the montmorillonite type or synthetic minerals (salts of very low solubility, phosphates and hydroxides of zirconium and thorium).
Der Montmorillonit ist kein Anionenaustauscher, kann jedoch unter bestimmten Bedingungen zu einem solchen werden, so daß beispielsweise ein mit Ba2+- Kationen gesättigter Montmorillonit das Anion SOfin einer Menge bis 0,8 mäq/g Montmorillonit austauscht. The montmorillonite is not an anion exchanger, but can become one under certain conditions, so that, for example, a montmorillonite saturated with Ba 2+ cations exchanges the SOfin anion in an amount of up to 0.8 meq / g montmorillonite.
Die Verwendung von Montmorillonit als Anionenaustauscher ist jedoch auf bestimmte Fälle beschränkt, und er verliert außerdem seine Wirksamkeit mit der Temperatur.However, the use of montmorillonite as an anion exchanger is limited to certain cases, and it also loses its effectiveness with temperature.
Man hat auch als Anionenaustauscher mit einer sehr guten Beständigkeit bei erhöhten Temperaturen Thoriumhydroxid und eine Mischung von Zirkoniumhydroxid und Zirkoniumphosphat verwendet. Diese Austauscher eignen sich besonders gut, wenn das auszutauschende Anion in sehr geringer Konzentration gelöst vorliegt. Solche Austauscher haben jedoch eine sehr viel geringere Extraktionskapazität als ein organischer Anionenaustauscher.One also has an anion exchanger with a very good resistance at elevated temperatures Thorium hydroxide and a mixture of zirconium hydroxide and zirconium phosphate are used. These Exchangers are particularly suitable when the anion to be exchanged is in a very low concentration solved. However, such exchangers have a much lower extraction capacity than one organic anion exchanger.
Die Erfindung betrifft ein Verfahren zum Anionenaustausch, wodurch man mit guter Ausbeute und
einem gleichen Wirkungsgrad die Anionen von Sauer-Verfahren zur Entfernung von Anionen
von Sauerstoffsäuren aus einer LösungThe invention relates to a process for anion exchange, whereby the anions of Sauer processes for removing anions can be obtained with good yield and the same degree of efficiency
of oxo acids from a solution
Anmelder:Applicant:
Commissariat ä !'Energie Atomique, ParisCommissariat ä! 'Energie Atomique, Paris
Vertreter:Representative:
Dr. H. U. May, Patentanwalt,
8000 München 2, Ottostr. 1 aDr. HU May, patent attorney,
8000 Munich 2, Ottostr. 1 a
Als Erfinder benannt:Named as inventor:
Jean Louis Guth,Jean Louis Guth,
Raymond Wey,Raymond Wey,
Mulhouse, Haut-Rhin (Frankreich)Mulhouse, Haut-Rhin (France)
Beanspruchte Priorität:Claimed priority:
Frankreich vom 27. Januar 1964 (961 690,
961 691)France of January 27, 1964 (961 690,
961 691)
stoffsäuren aus einer wäßrigen alkalischen Lösung bei höheren Temperaturen unter dem entsprechenden Wasserdampfdruck entfernen kann.material acids from an aqueous alkaline solution at higher temperatures below the corresponding Can remove water vapor pressure.
Das erfindungsgemäße Verfahren besteht darin, daß man eine die Anionen von Sauerstoffsäuren enthaltende Lösung bei einer Temperatur nahe bei oder über 0C mit einem Anionenaustauscher in Berührung bringt, der aus Hydroxyparacancrinit besteht.The process according to the invention consists in bringing a solution containing the anions of oxygen acids into contact at a temperature close to or above 0 ° C. with an anion exchanger which consists of hydroxyparacancrinite.
Es wurde gefunden, daß Hydroxyparacancrinit, ein synthetischer Stoff mit der chemischen FormelIt has been found that hydroxyparacancrinite, a synthetic substance with the chemical formula
3 (Al2O3, 2 SiO2, Na2O) 2 NaOH3 (Al 2 O 3 , 2 SiO 2 , Na 2 O) 2 NaOH
in wäßriger Lösung unter Erhaltung seiner Struktur die OH~-Ionen gegen Ionen von Sauerstoffsäuren, wie SOl~-Ionen, austauscht. Dieser Austausch geschieht bei einer Temperatur nahe bei oder über 2000C in neutralem oder basischem Milieu und unter dem entsprechenden Wasserdampfdruck, wobei die OH - Ionenkonzentration vorteilhafterweise unter 0,lnormal liegt.in aqueous solution, while maintaining its structure, exchanges the OH ~ ions for ions of oxygen acids, such as SOl ~ ions. This exchange takes place at a temperature close to or above 200 ° C. in a neutral or basic medium and under the corresponding water vapor pressure, the OH ion concentration advantageously being below 0.1 normal.
Die Behälter, in denen sich der Austausch vollzieht, müssen der alkalischen Korrosion und dem Druck widerstehen. Man verwendet zu diesem Zweck geschlossene Kupferrohre, die sich in einem Autoklav befinden.The containers in which the exchange takes place must be exposed to alkaline corrosion and pressure resist. For this purpose, closed copper pipes are used, which are located in an autoclave are located.
809 557/494809 557/494
In einem Ausführungsbeispiel des Verfahrens geht man von einer Sulfationen enthaltenden Lösung aus, wobei die Anfangskonzentration dieser Lösung an OH--Ionen auf l,6n/100 eingestellt ist. Die Versuche wurden in einem Autoklav bei 250° C durchgeführt, wobei man bei jedem Versuch die Sulfationenkonzentration veränderte.In one embodiment of the method, a solution containing sulfate ions is assumed, The initial concentration of OH ions in this solution is set to 1.6n / 100. The trials were carried out in an autoclave at 250 ° C., the sulfate ion concentration being used for each experiment changed.
Proben von 500 mg Hydroxyparacancrinit wurden mit 6 cm3 der die SOf-- und OH~-Ionen enthaltenden Lösung in Berührung gebracht. Der Gehalt der Lösung an SOf~-Ionen wurde vor und nach dem Austausch bestimmt. Die Ergebnisse sind in der folgenden Tabelle aufgeführt, die die Bindung der SO|~-Anionen durch den Hydroxyparacancrinit zeigtSamples of 500 mg hydroxyparacancrinite were brought into contact with 6 cm 3 of the solution containing the SOf-- and OH ~ ions. The SOf ~ ion content of the solution was determined before and after the exchange. The results are shown in the following table, which shows the binding of the SO | ~ anions by the hydroxyparacancrinite
Der Hydroxyparacancrinit wird entsprechend den ao Angaben von B a r r e r und White in »Journal of the Chemical Society«, London, 1952, S. 1566 und 1567, aus einer Mischung von Siliciumdioxid, Aluminiumhydroxid, Ätznatron und Wasser hergestellt, in der das Atomverhältnis Silicium zu Aluminium über 1, das Atomverhältnis Natrium zu Aluminium über 5, das Molverhältnis Wasser zu Ätznatron über 6 liegt, indem man diese Mischung auf eine über 200° C liegende Temperatur bei dem dieser Temperatur entsprechenden Sättigungswasserdampfdruck erhitzt. Bei einer Erhitzungstemperatur über 200° C stellt sich das Gleichgewicht rasch ein; diese Temperatur liegt vorteilhafterweise zwischen 200 und 370° C, wobei der Druck stets der Sättigungswasserdampfdruck bei der entsprechenden Temperatur ist.The Hydroxyparacancrinit is according to the ao information from B a r r e r and White in »Journal of the Chemical Society ", London, 1952, pp. 1566 and 1567, from a mixture of silicon dioxide, aluminum hydroxide, Caustic soda and water are produced in which the atomic ratio of silicon to aluminum is about 1, the atomic ratio of sodium to aluminum is over 5, the molar ratio of water to caustic soda is over 6, by bringing this mixture to a temperature above 200 ° C at the temperature corresponding to this temperature Saturated water vapor pressure heated. This occurs at a heating temperature of over 200 ° C Balance quickly; this temperature is advantageously between 200 and 370 ° C, the Pressure is always the saturation water vapor pressure at the corresponding temperature.
Es wurden eine Reihe von Versuchen durchgeführt, wobei man die Molverhältnisse der verschiedenen Verbindungen in der Ausgangsmischung und die Erhitzungstemperatur veränderte. Die besten Ergebnisse wurden bei einer Erhitzungstemperatur zwischen 300 und 325° C und bei den folgenden Molverhältnissen der Ausgangsprodukte erzielt: Siliciumdioxid—Aluminiumhydroxid nahezu 2, Ätznatron—Aluminiumhydroxid zwischen 6 und 7, Wasser—Ätznatron nahezu 8.A number of experiments were carried out keeping the molar ratios of the various compounds in the starting mixture and the heating temperature changed. The best results were at a heating temperature between 300 and 325 ° C and at the following molar ratios of the raw materials obtained: silicon dioxide — aluminum hydroxide nearly 2, caustic soda — aluminum hydroxide between 6 and 7, water — caustic soda almost 8.
Bei Beachtung der angegebenen Grenzen der Verfahrensbedingungen erhält man stets Hydroxyparacancrinit in ausgezeichneten Ausbeuten, die über 95°/o> bezogen auf das Gewicht des eingesetzten Aluminiumhydroxids, betragen können. Das Produkt wird in Form von hexagonalen Kristallen erhalten; für seine Herstellung wird kein Schutz beansprucht.If the stated limits of the process conditions are observed, hydroxyparacancrinite is always obtained in excellent yields that are over 95% based on the weight of the aluminum hydroxide used, can be. The product is obtained in the form of hexagonal crystals; for his No protection is claimed during manufacture.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR961690A FR1393381A (en) | 1964-01-27 | 1964-01-27 | Process for removing anions derived from oxacids from a solution |
| FR961691A FR1393382A (en) | 1964-01-27 | 1964-01-27 | Process for preparing hydroxyparacancrinite and product obtained |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1265132B true DE1265132B (en) | 1968-04-04 |
Family
ID=26205575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC34893A Pending DE1265132B (en) | 1964-01-27 | 1965-01-19 | Process for the removal of anions of oxygen acids from a solution |
Country Status (6)
| Country | Link |
|---|---|
| CH (1) | CH431469A (en) |
| DE (1) | DE1265132B (en) |
| ES (1) | ES308615A1 (en) |
| GB (1) | GB1102554A (en) |
| LU (1) | LU47850A1 (en) |
| NL (1) | NL6501020A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1271016B (en) * | 1963-02-14 | 1968-06-20 | Diamond Int Corp | Paper stock container |
-
1965
- 1965-01-18 CH CH65065A patent/CH431469A/en unknown
- 1965-01-18 GB GB2192/65A patent/GB1102554A/en not_active Expired
- 1965-01-19 DE DEC34893A patent/DE1265132B/en active Pending
- 1965-01-25 LU LU47850A patent/LU47850A1/xx unknown
- 1965-01-27 NL NL6501020A patent/NL6501020A/xx unknown
- 1965-01-27 ES ES0308615A patent/ES308615A1/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1271016B (en) * | 1963-02-14 | 1968-06-20 | Diamond Int Corp | Paper stock container |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1102554A (en) | 1968-02-07 |
| ES308615A1 (en) | 1967-01-01 |
| CH431469A (en) | 1967-03-15 |
| LU47850A1 (en) | 1965-03-26 |
| NL6501020A (en) | 1965-07-28 |
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