DE1147922B - Process for the production of highly active metal catalysts - Google Patents
Process for the production of highly active metal catalystsInfo
- Publication number
- DE1147922B DE1147922B DEV21445A DEV0021445A DE1147922B DE 1147922 B DE1147922 B DE 1147922B DE V21445 A DEV21445 A DE V21445A DE V0021445 A DEV0021445 A DE V0021445A DE 1147922 B DE1147922 B DE 1147922B
- Authority
- DE
- Germany
- Prior art keywords
- heavy metal
- silicates
- production
- highly active
- active metal
- 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
- 239000003054 catalyst Substances 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 title claims description 6
- 239000002184 metal Substances 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 11
- 150000004760 silicates Chemical class 0.000 claims description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- -1 silver ions Chemical class 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 229910021527 natrosilite Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 229910000171 calcio olivine Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910019929 CrO2Cl2 Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 101710104662 Enterotoxin type C-3 Proteins 0.000 description 1
- 102100030844 Exocyst complex component 1 Human genes 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021333 Na2Si Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Description
Verfahren zur Herstellung hochaktiver Metallkatalysatoren In der Vergangenheit sind verschiedene Klassen von Silikaten und Alumosilikaten mit Ionenaustauschcharakter bekanntgeworden. Dabei können die Produkte sowohl natürlichen als auch synthetischen Ursprungs sein. Die Fähigkeit zum Ionenaustausch zeigen z. B. folgende Silikate bzw. Alumosilikate: Synthetische Gelzeolithe, die z.B. in derWasseraufbereitungstechnik Verwendung fanden; synthetische kristalline Zeolithe, die neuerdings unter dem Namen Molekularsiebe bekanntgeworden sind; natürliche kristalline Zeolithe, wie z. B. Montmorillonite; a-Na2Si2O5 oder BaSi2O5; diese Verbindungen stellen Schichtsilikate dar, die synthetisch erzeugt werden können. Process for the production of highly active metal catalysts In the Various classes of silicates and aluminosilicates with ion exchange character are a thing of the past known. The products can be natural as well as synthetic Be of origin. The ability to exchange ions show z. B. the following silicates or aluminosilicates: Synthetic gel zeolites that are used, for example, in water treatment technology Found use; synthetic crystalline zeolites, recently under the name Molecular sieves have become known; natural crystalline zeolites, such as. B. Montmorillonites; a-Na2Si2O5 or BaSi2O5; these compounds represent layered silicates that can be produced synthetically.
Weiterhin lassen sich auch beim Ca2SiO4 oder Na2SiO3 die Kationen durch andere austauschen. Furthermore, the cations can also be used with Ca2SiO4 or Na2SiO3 exchange with others.
Die Silikate und Alumosilikate mit austauschfähigen Kationen zeichnen sich im allgemeinen durch eine große Säureempfindlichkeit aus, so daß sie nicht in einem Wasserstoffionenaustauschzyklus benutzt werden können oder mit Lösungen von Salzen, die durch Hydrolyse sauer reagieren, in Berührung gebracht werden dürfen. Dies ist besonders ausgeprägt bei den Molekularsieben oder beim Na2Si2O5. Draw the silicates and aluminosilicates with exchangeable cations are generally characterized by a great sensitivity to acids, so that they are not can be used in a hydrogen ion exchange cycle or with solutions of salts, which react acidic through hydrolysis, may be brought into contact. This is particularly pronounced with molecular sieves or with Na2Si2O5.
Es besteht aber neuerdings an mit Schwermetallen beladenen synthetischen Silikaten und Alumosilikaten technisches Interesse im Hinblick auf den Einsatz dieser Produkte als Katalysatoren. Schwermetallsalzlösungen, wie z. B. die von FeCl3 oder All3, von Chromsalzen u. a., reagieren aber mehr oder minder sauer, so daß sie für die Zwecke eines Ionenaustausches nicht ohne weiteres in Frage kommen können. Außerdem treten eine Reihe von technisch interessierenden Schwermetallionen nicht über den Weg des Ionen au stausches aus Lösungen in die silikatischen Produkte ein. Beispielsweise lassen sich im a-Na2Si.2O oder BaSioOs die Natrium- bzw. Bariumionen nicht durch Silberionen aus wäßriger Lösung austauschen. Es ist dagegen möglich, nach einem bekannten Verfahren den Ionenaustausch über den Weg einer Salzschmelze durchzuführen. So gelingt beim a-Na2Sil05 oder BaSi2O5 der Ersatz der Natrium-oder Bariumionen durch Silberionen beim Einbringen des a-Na2Si2O5 bzw. BaSi2O5 in eine Silbernitratschmelze. Reduzierte Silbersilikate, wie reduziertes Ag,Si20s, sind z. B. vorzügliche Katalysatoren bei der Oxydation des Methanols zu Formaldehyd. Aber auch der Weg des Ionenaustausches vermittels einer Salzschmelze ist nur auf wenige Schwermetallionen, wie z. B. Silber, anwendbar. Es gelang bisher nicht, eine Reihe von technisch unter dem Gesichtspunkt der Katalyse interessierenden Schwermetallionen, wie z. B. Fe, Al, Ti u. a., in gewisse silikatische Träger, wie a-Na2Si2 05, BaSi2O5 oder verschiedene Molekularsiebtypen, einzuführen. Es ist bekannt, daß neben dem Schwermetallkation auch die Struktur des Trägers einen entscheidenden Einfluß auf die katalytische Wirksamkeit von Katalysatoren ausübt. Recently, however, there are synthetic ones loaded with heavy metals Silicates and aluminosilicates of technical interest with regard to the use of these Products as catalysts. Heavy metal salt solutions, such as. B. that of FeCl3 or All3, of chromium salts and others, react more or less acidic, so that they are used for the purposes of an ion exchange cannot easily come into question. aside from that a number of technically interesting heavy metal ions do not occur over the Way of the ion exchange from solutions into the silicate products. For example the sodium or barium ions cannot pass through in a-Na2Si.2O or BaSioOs Exchange silver ions from aqueous solution. It is, however, possible after a known methods to carry out the ion exchange via a molten salt route. In the case of a-Na2Sil05 or BaSi2O5, the sodium or barium ions can be replaced by silver ions when the a-Na2Si2O5 or BaSi2O5 is introduced into a silver nitrate melt. Reduced silver silicates, such as reduced Ag, Si20s, are e.g. B. excellent catalysts in the oxidation of methanol to formaldehyde. But also the way of ion exchange by means of a molten salt is only a few heavy metal ions such. B. silver, applicable. So far it has not succeeded a number of technically from the point of view heavy metal ions of interest in catalysis, such as. B. Fe, Al, Ti et al., In certain silicate carriers, such as a-Na2Si2 05, BaSi2O5 or various types of molecular sieves, to introduce. It is known that in addition to the heavy metal cation, the structure the carrier has a decisive influence on the catalytic effectiveness of catalysts exercises.
Es wurde nun gefunden, daß die Einführung von Schwermetallionen in Silikate oder Alumosilikate mit der Fähigkeit zum Ionenaustausch gelingt, wenn diese Träger mit den Dämpfen von Schwermetallverbindungen oder mit Gasen, die Dämpfe von Schwermetallverbindungen enthalten, in Berührung gebracht werden. Die schwermetallhaltigen Silikate werden anschließend mit einem Lösungsmittel, vorzugsweise Wasser, gewaschen und nach dem Trocknen in an sich bekannter Weise reduziert. It has now been found that the introduction of heavy metal ions in Silicates or aluminosilicates with the ability to exchange ions succeed if this Carrier with the vapors of heavy metal compounds or with gases that contain the vapors of Contain heavy metal compounds, are brought into contact. The heavy metals Silicates are then washed with a solvent, preferably water and reduced after drying in a manner known per se.
Diese Einführung der Schwermetallionen über den Weg der Dampfphase bringt eine Reihe vonVorteilen mit sich. Es gelingt auf diese Weise, in eine Reihe von Silikaten oder Alumosilikaten Schwermetallionen einzuführen, die bislang nach bekannten Verfahren (z. B. Ionenaustausch in Lösung oder in der Schmelze) einem Ionenaustausch nicht zugänglich waren. Das Verfahren des Austausches über den Weg der Dampfphase ist technisch einfach durchzuführen. This introduction of heavy metal ions via the vapor phase brings a number of advantages. It succeeds in this way, in a row of silicates or aluminosilicates to introduce heavy metal ions, which so far after known processes (e.g. ion exchange in solution or in the melt) Ion exchange were not accessible. The procedure of sharing over the way the vapor phase is technically easy to carry out.
Es ist auch möglich, Metalisalzdampfgemische zur Einwirkung zu bringen.It is also possible to bring metal salt vapor mixtures to act.
Durch das erfindungsgemäße Verfahren werden neue Schwermetallkatalysatoren mit einem kieselsäurehaltigen Träger zugänglich, die sich z. B. für folgende Reaktionen hervorragend eignen: Hydrierungen, Oxydationen, Dehydrierungen, Cyclisierungen, Alkylierungen und Entalkvlierungen, Isomerislerungen u. a. The process according to the invention creates new heavy metal catalysts accessible with a silica-containing carrier, which z. B. for the following reactions ideally suited: hydrogenations, Oxidations, dehydrations, Cyclizations, alkylations and deallocations, isomerizations and others.
Durch den Ausschluß von Wasser beim Ionenaustausch in der Dampfphase wird der schädigende Einfluß einer saueren Hydrolyse der Schwermetallsalze vermieden, so daß die silikatischen Produkte durch H+-Ionen nicht mehr angegriffen oder zerstört werden können. By excluding water during ion exchange in the vapor phase the damaging influence of acid hydrolysis of heavy metal salts is avoided, so that the silicate products are no longer attacked or destroyed by H + ions can be.
Folgende Kieselsäure und austauschfähige Kationen enthaltende Verbindungen eignen sich beispielsweise für das erfindungsgemäße Verfahren: a-Na2Si2Os, BaSi205, Ca2SiO4, Na2SiO3, synthetische Molekularsiebe. Als Metallsalzdämpfe dienen z. B. AlCl5,FeCl3, BiCI3, CuCl2, TiCl4, SnCl4, SEC3, CrO2Cl2 u. a., weiterhin die flüchtigen Metalljodide z. B. von Zr, Th, U u. a. Nach dem Ionenaustausch in der Dampfphase lassen- sich die Schwermetallionen in den kieselsäurehaltigen Produkten nach vorherigem Waschen und Trocknen der letzteren durch geeignete Reduktionsmittel, wie Wasserstoff, Formaldehyd, Hydrazin, Hydroxylamin u. a. in bekannter Weise zu den entsprechenden Metallen reduzieren. Diese so erzeugten Produkte dienen als hervorragende Katalysatoren für die oben angeführten katalytischen Reaktionen. Compounds containing the following silica and exchangeable cations are for example suitable for the process according to the invention: a-Na2Si2Os, BaSi205, Ca2SiO4, Na2SiO3, synthetic molecular sieves. As metal salt vapors z. B. AlCl5, FeCl3, BiCl3, CuCl2, TiCl4, SnCl4, SEC3, CrO2Cl2 and others, still the volatile ones Metal iodides e.g. B. from Zr, Th, U and others. After ion exchange in the vapor phase The heavy metal ions in the silicic acid-containing products can be removed after previous Washing and drying of the latter by suitable reducing agents, such as hydrogen, Formaldehyde, hydrazine, hydroxylamine and others. in a known manner to the corresponding Reduce metals. The products produced in this way serve as excellent catalysts for the catalytic reactions listed above.
Beispiel 1 a-Na2Si205 wird bei einem Druck von zur 600 Torr und einer Temperatur von 5000 C den Dämpfen von FeCl3 ausgesetzt. Die Dauer der Einwirkung ist durch den gewünschten Eisengehalt des Silikates bedingt. Example 1 a-Na2Si205 is at a pressure of 600 Torr and a Temperature of 5000 C to the vapors of Exposed to FeCl3. The duration of exposure is due to the desired iron content of the silicate.
Nach dem Abkühlen wird das Produkt mit destilliertem Wasser chloridfrei gewaschen, getrocknet und anschließend bei 400 bis 6000 C mit Wasserstoff behandelt.After cooling, the product becomes chloride-free with distilled water washed, dried and then treated with hydrogen at 400 to 6000 C.
Beispiel 2 Ba2Si2O5 wird bei 2500 C mit den Dämpfen von SnCl4 behandelt. Das Reaktionsprodukt wird nach dem Abkühlen mit Wasser gewaschen, getrocknet und anschließend in einem Wasserstoffstrom auf 5000 C erhitzt. Example 2 Ba2Si2O5 is treated with the vapors of SnCl4 at 2500 C. After cooling, the reaction product is washed with water, dried and then heated to 5000 C in a stream of hydrogen.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV21445A DE1147922B (en) | 1961-10-10 | 1961-10-10 | Process for the production of highly active metal catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV21445A DE1147922B (en) | 1961-10-10 | 1961-10-10 | Process for the production of highly active metal catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1147922B true DE1147922B (en) | 1963-05-02 |
Family
ID=7579181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEV21445A Pending DE1147922B (en) | 1961-10-10 | 1961-10-10 | Process for the production of highly active metal catalysts |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1147922B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1066192B (en) * | 1959-10-01 | Deutsche Akademie der Wissenschaften zu Berlin, Berlin-Adlcrshof | Process for the production of anhydrous silver silicates |
-
1961
- 1961-10-10 DE DEV21445A patent/DE1147922B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1066192B (en) * | 1959-10-01 | Deutsche Akademie der Wissenschaften zu Berlin, Berlin-Adlcrshof | Process for the production of anhydrous silver silicates |
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