DE1112238B - Process for the production of reforming catalysts consisting of ceramic carrier and precious metal - Google Patents
Process for the production of reforming catalysts consisting of ceramic carrier and precious metalInfo
- Publication number
- DE1112238B DE1112238B DED28131A DED0028131A DE1112238B DE 1112238 B DE1112238 B DE 1112238B DE D28131 A DED28131 A DE D28131A DE D0028131 A DED0028131 A DE D0028131A DE 1112238 B DE1112238 B DE 1112238B
- Authority
- DE
- Germany
- Prior art keywords
- production
- ceramic carrier
- reforming catalysts
- precious metal
- catalyst
- 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 19
- 238000000034 method Methods 0.000 title claims description 10
- 238000002407 reforming Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000000919 ceramic Substances 0.000 title claims description 4
- 239000010970 precious metal Substances 0.000 title description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- SSVFCHUBLIJAMI-UHFFFAOYSA-N platinum;hydrochloride Chemical compound Cl.[Pt] SSVFCHUBLIJAMI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Description
DEUTSCHESGERMAN
PATENTAMT C 10 g; B 01 jPATENT OFFICE C 10 g; B 01 j
D28131IVc/23bD28131IVc / 23b
BEKANNTMACHUNG DER ANMELDUNG UND AUS GABE DER AUSLEGESCHRIFT:NOTICE THE REGISTRATION AND FROM ISSUE OF EDITORIAL:
3. AUGUST 1961AUGUST 3, 1961
Die Erfindung bezieht sich auf ein Verfahren zur Herstellung von Platinmetallkatalysatoren für die Reformierung. Der Katalysator besteht aus einer keramischen Trägermasse, auf oder in der Platinmetalle durch Imprägnierung auf- oder eingebracht sind.The invention relates to a process for the production of platinum metal catalysts for Reforming. The catalyst consists of a ceramic carrier mass on or in the platinum metals are applied or introduced by impregnation.
Bei Katalysatoren, die bei der Reformierung zur Treibstoffverarbeitung eingesetzt werden, kommt es neben der Aktivität vor allem auf eine möglichst hohe Lebensdauer und eine leichte und vollständige Regenerierbarkeit an. Kleine oder geringe Änderungen und Verbesserungen dieser Eigenschaften wirken sich erfahrungsgemäß auf den Wert des Katalysators erheblich aus und können somit einen wesentlichen technischen Fortschritt erbringen.In the case of catalysts that are used in reforming for fuel processing, it happens In addition to the activity, above all, the longest possible lifespan and a light and complete one Regenerability on. Small or minor changes and improvements in these properties Experience has shown that they have a considerable effect on the value of the catalytic converter and can therefore have a make significant technical progress.
Für die Herstellung eines Katalysators für die vorgenannten Zwecke bedarf es einer Reihe von Verfahrensschritten, mit denen die Imprägnierung des Trägers mit Metall, die Entwässerung und Trocknung sowie die Reduktion des Metalls auf dem Katalysator bewirkt wird. Es ist bekannt, daß schon geringe Abweichungen bei der Behandlung solcher Katalysatoren Änderungen der Eigenschaften hervorrufen können.The production of a catalyst for the aforementioned purposes requires a number of process steps, with which the impregnation of the carrier with metal, the drainage and drying as well as effecting the reduction of the metal on the catalyst. It is known that even small deviations cause changes in properties when treating such catalysts can.
Erfindungsgemäß wird der Katalysator im Anschluß an die Reduktion der Metallverbindung zum Metall bei Temperaturen zwischen 110 und 1800C mit überhitztem Wasserdampf behandelt. Nach einer vorteilhaften Ausführungsform der Erfindung vermeidet man zweckmäßigerweise jede Kondensation von flüssigem Wasser auf dem Katalysator oder in dessen Poren dadurch, daß der Katalysator ohne nennenswerte Abkühlung nach Abschluß der Wasserdampfbehandlung zur Verdrängung des Wasserdampfes einer Behandlung mit inerten Gasen, wie Luft, Wasserstoff oder Stickstoff, oder Gasgemischen unterworfen wird.According to the invention, following the reduction of the metal compound to the metal, the catalyst is treated with superheated steam at temperatures between 110 and 180 ° C. According to an advantageous embodiment of the invention, it is expedient to avoid any condensation of liquid water on the catalyst or in its pores by treating the catalyst with inert gases, such as air, hydrogen or nitrogen, without significant cooling after the steam treatment has ended, to displace the steam. or gas mixtures.
Aus der französischen Patentschrift 1154 552 ist ferner die Herstellung von monofunktionellen Hydrierungs- oder Dehydrierungskontakten bekanntgeworden, bei denen aktive j'-Aluminiumoxydteilchen mit wäßrigen Lösungen von Platinchlorwasserstoffsäure imprägniert und mit Wasserstoff reduziert werden. Anschließend werden diese Teilchen mit Wasserdampf enthaltenden Gasen bei Temperaturen von 375 bis 535° C zur Verminderung des Chlorgehaltes mehrere Stunden nachbehandelt. Zur Herstellung dieser Kontakte kann man nach einer Variante des Verfahrens auch von Reformierungskontakten ausgehen und diese durch eine scharfe Nachbehandlung mit Wasserdampf in monofunktionelle Hydrierungs-Dehydrierungs-Katalysatoren über-Verf ahren zur HerstellungFrom French patent specification 1154 552 is also the production of monofunctional hydrogenation or dehydrogenation contacts became known, where active j'-alumina particles impregnated with aqueous solutions of platinum hydrochloric acid and reduced with hydrogen will. These particles are then treated with gases containing water vapor at temperatures Treated for several hours from 375 to 535 ° C to reduce the chlorine content. For the production According to a variant of the process, these contacts can also be called reforming contacts go out and this by a sharp aftertreatment with steam in monofunctional Hydrogenation-Dehydrogenation Catalysts on Process for Production
von aus keramischem Trägerstofffrom ceramic carrier
und Edelmetall bestehenden Reformierungs-and precious metal existing reforming
katalysatorencatalysts
Anmelder: Deutsche Gold- und Silber-ScheideanstaltApplicant: German gold and silver refinery
vormals Roessler, Frankfurt/M., Weißfrauenstr. 9formerly Roessler, Frankfurt / M., Weißfrauenstr. 9
Dr. Edgar Koberstein, Konstanz, ist als Erfinder genannt wordenDr. Edgar Koberstein, Constance, has been named as the inventor
führen. Die Katalysatoren verlieren durch die Wasserdampfbehandlung ihre reformierende Funktion. Demgegenüber muß es als überraschend angesehen werden, daß nach dem erfindungsgemäßen Verfahren durch eine milde Wasserdampfbehandlung ein Reformierungskatalysator in seiner Wirkung verbessert werden kann.to lead. The catalysts lose their reforming function as a result of the steam treatment. In contrast, it must be regarded as surprising that according to the invention Process improves the effectiveness of a reforming catalyst by means of a mild steam treatment can be.
Das Verfahren der vorliegenden Erfindung wird in nachstehendem Beispiel erläutert.The method of the present invention is illustrated in the following example.
Eine Trägermasse aus Aluminiumoxyd wird mit einer Lösung von Platinfluorwasserstoffsäure in der Weise imprägniert, daß der fertige Kontakt etwa 0,5% Platin enthält. Nach der Imprägnierung wird an Luft bei 120° C getrocknet und sodann die Metallverbindung durch lstündiges Behandeln im Wasserstoffstrom reduziert. Die Katalysatormenge wird in zwei Proben A und B geteilt. Während A anschließend an die Reduktion noch 1 Stunde bei 170° C in einem Strom mit überhitztem Wasserdampf behandelt wird, wird die Probe B ohne diese Nachbehandlung entsprechend der Probe A auf ihre Oktanzahl getestet. Zu diesem Zweck wird in einer Druckapparatur ein Schwerbenzin mit Siedegrenzen zwischen 80 bis 190° C und einer Oktanzahl von 36 (bestimmt nach der Fj-Methode gemäß DIN-Blatt 51756) bei 480° C und 30 Atm. Wasserstoffdruck über die Katalysatorproben geleitet. Es zeigt sich, daß die Probe A bereits bei einer um 20° C tieferA carrier mass of aluminum oxide is mixed with a solution of platinum fluoric acid in the Impregnated way that the finished contact contains about 0.5% platinum. After the impregnation dried in air at 120 ° C and then the metal compound by treatment in a hydrogen stream for 1 hour reduced. The amount of catalyst is divided into two samples A and B. While A subsequently treated after the reduction for 1 hour at 170 ° C in a stream with superheated steam sample B is tested for its octane rating in accordance with sample A without this post-treatment. For this purpose, a heavy gasoline with boiling points between 80 and 190 ° C and an octane number of 36 is used in a pressure apparatus (determined by the Fj method in accordance with the DIN sheet 51756) at 480 ° C and 30 Atm. Hydrogen pressure passed over the catalyst samples. It appears, that sample A is already 20 ° C lower
109 650/380109 650/380
liegenden Temperatur die gleiche Oktanzahl ergibt als die Probe B, so daß der Probe A eine wesentlich höhere Aktivität zugesprochen werden muß. Die Probe B läßt sich im Gegensatz zur Probe A nicht ■ mehr regenerieren; im Gegenteil nimmt ihre Aktivitat durch den Versuch einer Regenerierung erheblich ab.lying temperature gives the same octane number as the sample B, so that the sample A a substantial higher activity must be attributed. In contrast to sample A, sample B cannot be regenerate more; on the contrary, the attempt at regeneration decreases their activity considerably away.
Claims (2)
Französische Patentschrift Nr. 1154 552.Considered publications:
French Patent No. 1154 552.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED28131A DE1112238B (en) | 1958-05-17 | 1958-05-17 | Process for the production of reforming catalysts consisting of ceramic carrier and precious metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED28131A DE1112238B (en) | 1958-05-17 | 1958-05-17 | Process for the production of reforming catalysts consisting of ceramic carrier and precious metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1112238B true DE1112238B (en) | 1961-08-03 |
Family
ID=7039539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED28131A Pending DE1112238B (en) | 1958-05-17 | 1958-05-17 | Process for the production of reforming catalysts consisting of ceramic carrier and precious metal |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1112238B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1154552A (en) * | 1955-07-13 | 1958-04-11 | Cie Francaise Procedes Houdry | Dehydrogenation catalyst |
-
1958
- 1958-05-17 DE DED28131A patent/DE1112238B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1154552A (en) * | 1955-07-13 | 1958-04-11 | Cie Francaise Procedes Houdry | Dehydrogenation catalyst |
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