EP0000901B1 - Process for the preparation of hydroxyl ammonium salts - Google Patents
Process for the preparation of hydroxyl ammonium salts Download PDFInfo
- Publication number
- EP0000901B1 EP0000901B1 EP78100630A EP78100630A EP0000901B1 EP 0000901 B1 EP0000901 B1 EP 0000901B1 EP 78100630 A EP78100630 A EP 78100630A EP 78100630 A EP78100630 A EP 78100630A EP 0000901 B1 EP0000901 B1 EP 0000901B1
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- European Patent Office
- Prior art keywords
- catalyst
- platinum
- supported
- reaction
- space
- Prior art date
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- Expired
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- 238000000034 method Methods 0.000 title claims description 14
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 title description 10
- 238000002360 preparation method Methods 0.000 title description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 28
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 ammonium bisulfate Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003756 stirring 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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1418—Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen
Definitions
- the invention relates to a process for the preparation of hydroxylammonium salts by catalytic reduction of nitrogen monoxide with hydrogen in dilute aqueous solutions of mineral acids in the presence of suspended supported platinum catalysts at elevated temperature.
- the technical task was therefore to increase the space-time yield in the production of hydroxylammonium salts by catalytic reduction of nitrogen monoxide under the pressures used in each case.
- This object is achieved in a process for the preparation of hydroxylammonium salts by catalytic reduction of nitrogen monoxide with hydrogen in dilute aqueous solutions of mineral acids in the presence of suspended supported platinum catalysts at elevated temperature, 40 to 700 g of supported platinum catalyst being used per liter of reaction solution.
- the new process has the advantage that, with unchanged high yields under the pressures used in each case, significantly higher space-time yields, based on nitrogen monoxide, are achieved. As a result, smaller devices are required for the production of the same production quantities, on the other hand it is possible to achieve larger throughputs with the existing devices.
- Strong mineral acids such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, are advantageously used as acids.
- Their acidic salts such as ammonium bisulfate, are also suitable.
- Sulfuric acid is particularly preferably used. As a rule, 4 to 6 normal aqueous acids are assumed and the acid concentration is not allowed to drop below 0.2 normal in the course of the reaction.
- reaction solution is understood to mean the above-mentioned solution of acids, which may additionally contain hydroxylammonium salts, by-products and dissolved gases.
- the reaction is advantageously carried out at temperatures from 30 to 80 ° C. Temperatures of 40 to 60 ° C have proven particularly useful.
- the reaction is carried out at atmospheric pressure or elevated pressure, e.g. B. up to 30 bar. However, it is also possible to use significantly higher pressures, e.g. B. up to 300 bar. to apply.
- the reaction is carried out in the presence of supported platinum catalysts.
- Platinum on carbon supports, in particular on graphite, have proven particularly useful.
- Such a supported catalyst preferably has a content of 0.2 to 5% by weight of platinum.
- the catalysts additionally contain one or more elements of the 5th and / or 6th main group of the periodic system with an atomic weight> 31, also lead and / or mercury as poisoning agents.
- Suitable catalysts and their preparation are described, for example, in DE-PS 920 963, 956 038, 945 752 or 1 088 037.
- the supported catalyst is present as a suspension in the reaction solution.
- An essential feature of the invention is that 40 to 700 g of supported platinum catalyst are used per liter of reaction solution.
- the upper limit of the catalyst concentration is only through limits the criterion of sufficient fluidity and filterability of the suspension.
- Preferably 40 to 400 g of supported platinum catalyst are used. If activated carbon is used as the carrier, amounts of 40 to 250 g have been found, and if graphite has been used as the carrier, amounts of 40 to 350 g of supported catalyst per liter of reaction solution have proven particularly useful.
- the process according to the invention can be carried out batchwise or continuously.
- a suitable continuous process is described for example in DE-PS 1 113 448.
- Hydroxylammonium salts produced according to the invention are used on a large scale for the production of cyclohexanone oxime, a precursor for caprolactam.
- Measured quantities of a platinum-graphite catalyst with a platinum content of 0.5% by weight are suspended in 5 liters of 4.1N sulfuric acid in a pressure vessel with a stirrer. At a pressure of 1 or 9 bar abs. is introduced with stirring amounts of NO and H 2 in a volume ratio of 37: 63 into the reactor, which is kept at 40 ° C. by cooling. Unconverted gases that escape freely or via a pressure control valve are measured and analyzed. When the sulfuric acid is almost used up, the reaction is terminated, the pressure is released, the hydroxylamine solution is separated from the catalyst and the amount of hydroxylamine formed is determined.
- Example 2 The procedure is as described in Example 1, but the catalyst has a platinum content of 5.0% by weight.
- the results according to the table show that only by increasing the amount of platinum with the same amount of carrier does not achieve any additional improvement in the space-time yield.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Hydroxylammoniumsalzen durch katalytische Reduktion von Stickstoffmonoxid mit Wasserstoff in verdünnten wäßrigen Lösungen von Mineralsäuren in Gegenwart von suspendierten Platinträgerkatalysatoren bei erhöhter Temperatur.The invention relates to a process for the preparation of hydroxylammonium salts by catalytic reduction of nitrogen monoxide with hydrogen in dilute aqueous solutions of mineral acids in the presence of suspended supported platinum catalysts at elevated temperature.
Es ist bekannt, Hydroxylammoniumsalze durch Reduktion von Stickstoffmonoxid mit Wasserstoff in verdünnter wäßriger Mineralsäure, z. B. Schwefelsäure, in Gegenwart von Katalysatoren herzustellen. Als Katalysatoren verwendet man insbesondere Platin oder Platin mit Zusätzen, wobei das Katalysatormetall auf Trägerstoff niedergeschlagen ist. Solche Verfahren werden beispielsweise beschrieben in der DE-PS 956 038 und 945 752 oder den DE-AS 15 67 513 und 24 47 972. Der Platinträgerkatalysator wird in Mengen von 1 bis 33,4 g (vgl. DE-OS 1219453 und 2100 036) je Liter Lösung angewandt. Die dabei erreichten Raum-Zeit-Ausbeuten betragen bis zu 0,45 Mol umgesetztes Stickstoffmonoxid pro Stunde und Liter Reaktionsflüssigkeit im Reaktionsraum. Die erzielten Hydroxylaminausbeuten, bezogen auf umgesetztes Stickstoffmonoxid, liegen bei 78 bis 92 % der Theorie. Da man bestrebt ist, möglichst hohe Raum-Zeit-Ausbeuten bei dem jeweils angewandten Druck zu erzielen, bestand weiterhin das Bedürfnis, das Verfahren zu verbessern.It is known to remove hydroxylammonium salts by reducing nitrogen monoxide with hydrogen in dilute aqueous mineral acid, e.g. B. sulfuric acid, in the presence of catalysts. Platinum or platinum with additives is used in particular as catalysts, the catalyst metal being deposited on the support. Such processes are described, for example, in DE-PS 956 038 and 945 752 or DE-AS 15 67 513 and 24 47 972. The supported platinum catalyst is used in amounts of 1 to 33.4 g (cf. DE-OS 1219453 and 2100 036 ) applied per liter of solution. The space-time yields achieved are up to 0.45 mol of reacted nitrogen monoxide per hour and liter of reaction liquid in the reaction space. The hydroxylamine yields achieved, based on converted nitrogen monoxide, are 78 to 92% of theory. Since efforts are being made to achieve the highest possible space-time yields at the pressure used in each case, there was still a need to improve the process.
Es war deshalb die technische Aufgabe gestellt, bei der Herstellung von Hydroxylammoniumsalzen durch katalytische Reduktion von Stickstoffmonoxid unter den jeweils angewandten Drücken die Raum-Zeit-Ausbeute zu erhöhen.The technical task was therefore to increase the space-time yield in the production of hydroxylammonium salts by catalytic reduction of nitrogen monoxide under the pressures used in each case.
Diese Aufgabe wird gelöst in einem Verfahren zur Herstellung von Hydroxylammoniumsalzen durch katalytische Reduktion von Stickstoffmonoxid mit Wasserstoff in verdünnten wäßrigen Lösungen von Mineralsäuren in Gegenwart von suspendierten Platinträgerkatalysatoren bei erhöhter Temperatur, wobei man je Liter Reaktionslösung 40 bis 700 g Platinträgerkatalysator anwendet.This object is achieved in a process for the preparation of hydroxylammonium salts by catalytic reduction of nitrogen monoxide with hydrogen in dilute aqueous solutions of mineral acids in the presence of suspended supported platinum catalysts at elevated temperature, 40 to 700 g of supported platinum catalyst being used per liter of reaction solution.
Das neue Verfahren hat den Vorteil, daß man bei unverändert hohen Ausbeuten unter den jeweils angewandten Drücken wesentlich höhere Raum-Zeit-Ausbeuten, bezogen auf Stickstoffmonoxid, erzielt. Hierdurch benötigt man bei der Herstellung gleicher Produktionsmengen kleinere Vorrichtungen, andererseits gelingt es mit den vorhandenen Vorrichtungen, größere Durchsätze zu erzielen.The new process has the advantage that, with unchanged high yields under the pressures used in each case, significantly higher space-time yields, based on nitrogen monoxide, are achieved. As a result, smaller devices are required for the production of the same production quantities, on the other hand it is possible to achieve larger throughputs with the existing devices.
Das neue Verfahren ist insofern bemerkenswert, als ein Zusammenhang zwischen erhöhter Katalysatormenge und steigender Raum-Zeit-Ausbeute aus dem Stand der Technik bislang nicht zu entnehmen war. So wurde beispielsweise nach dem in der DE-OS 21 00 036 beschriebenen Verfahren bei Verwendung von 33,4 g Katalysator pro Liter Lösung eine Raum-Zeit-Ausbeute von 0,24, gemäß DE-OS 1806537 bei Verwendung von 30,0 g Katalysator eine Raum-Zeit-Ausbeute von 0,40 Mol umgesetztes Stickstoffmonoxid pro Stunde und Liter Flüssigkeit im Reaktionsraum erzielt. Es war daher nicht abzusehen, daß man durch eine wesentliche Erhöhung der Katalysatormenge die Raum-Zeit-Ausbeute bei einer Arbeitsweise unter Atmosphärendruck fast auf das Doppelte des bisher Bekannten steigern kann. Insbesondere war nicht vorherzusagen, daß bei einer Arbeitsweise unter erhöhtem Druck die für sich schon zu höheren Raum-Zeit-Ausbeuten führt (vgl. DE-PS 900213), trotzdem eine ebenso deutliche weitere Steigerung der Raum-Zeit-Ausbeute durch die Erhöhung der Katalysatormenge möglich ist. Dies gilt umsomehr, als lediglich die Erhöhung der Menge an Platin bei gleichbleibenden Trägermengen nicht zur Lösung der gestellten Aufgabe führt.The new process is remarkable in that a connection between the increased amount of catalyst and the increasing space-time yield has so far not been found in the prior art. For example, according to the process described in DE-OS 21 00 036, when using 33.4 g of catalyst per liter of solution, a space-time yield of 0.24 was obtained, according to DE-OS 1806537, when using 30.0 g of catalyst achieved a space-time yield of 0.40 mol of reacted nitrogen monoxide per hour and liter of liquid in the reaction space. It was therefore not foreseeable that a substantial increase in the amount of catalyst could almost double the space-time yield when working under atmospheric pressure. In particular, it could not be predicted that operating under increased pressure would in itself lead to higher space-time yields (cf. DE-PS 900213), nevertheless an equally significant further increase in the space-time yield by increasing the amount of catalyst is possible. This is all the more true since only the increase in the amount of platinum with the same amounts of carrier does not lead to the solution of the task.
In der Regel hält man ein Molverhältnis von Wasserstoff zu Stickstoffmonoxid von mehr als 1, vorzugsweise von 1,5 : 1 bis 6 : 1 ein. Besonders gute Ergebnisse erhält man, wenn man darauf achtet, daß in der Reaktionszone ein Molverhältnis von Wasserstoff zu Stickstoff monoxid von 3,5 bis 5 : 1 aufrechterhalten wird.As a rule, a molar ratio of hydrogen to nitrogen monoxide of more than 1, preferably from 1.5: 1 to 6: 1, is maintained. Particularly good results are obtained if care is taken to ensure that a molar ratio of hydrogen to nitrogen monoxide of 3.5 to 5: 1 is maintained in the reaction zone.
Vorteilhaft verwendet man als Säuren starke Mineralsäuren, wie Chlorwasserstoffsäure, Salpetersäure, Schwefelsäure oder Phosphorsäure. Geeignet sind auch deren saure Salze, wie Ammoniumbisulfat. Besonders bevorzugt wird Schwefelsäure verwendet. In der Regel geht man von 4 bis 6 normalen wäßrigen Säuren aus und läßt im Verlauf der Reaktion die Säurekonzentration nicht unter 0,2 normal fallen.Strong mineral acids, such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, are advantageously used as acids. Their acidic salts, such as ammonium bisulfate, are also suitable. Sulfuric acid is particularly preferably used. As a rule, 4 to 6 normal aqueous acids are assumed and the acid concentration is not allowed to drop below 0.2 normal in the course of the reaction.
Unter Reaktionslösung versteht man erfindungsgemäß die oben genannte Lösung von Säuren, die zusätzlich Hydroxylammoniumsalze, Nebenprodukte sowie gelöste Gase enthalten können. Die Umsetzung führt man vorteilhaft bei Temperaturen von 30 bis 80 °C durch. Besonders bewährt haben sich Temperaturen von 40 bis 60 °C. In der Regel führt man die Umsetzung bei Atmosphärendruck oder erhöhtem Druck, z. B. bis zu 30 bar durch. Es ist jedoch auch möglich, wesentlich höhere Drücke, z. B. bis zu 300 bar. anzuwenden.According to the invention, reaction solution is understood to mean the above-mentioned solution of acids, which may additionally contain hydroxylammonium salts, by-products and dissolved gases. The reaction is advantageously carried out at temperatures from 30 to 80 ° C. Temperatures of 40 to 60 ° C have proven particularly useful. As a rule, the reaction is carried out at atmospheric pressure or elevated pressure, e.g. B. up to 30 bar. However, it is also possible to use significantly higher pressures, e.g. B. up to 300 bar. to apply.
Die Umsetzung wird in Gegenwart von Platinträgerkatalysatoren durchgeführt. Besonders bewährt haben-sich Platin auf Kohleträger, insbesondere auf Graphit. Vorzugsweise hat ein solcher Trägerkatalysator einen Gehalt von 0,2 bis 5 Gew.% Platin. Vorteilhaft enthalten die Katalysatoren zusätzlich ein oder mehrere Elemente der 5. und/oder 6. Hauptgruppe des periodischen Systems mit einem Atomgewicht >31, ferner Blei und/oder Quecksilber als vergiftende Mittel. Geeignete Katalysatoren und deren Herstellung werden beispielsweise beschrieben in der DE-PS 920 963, 956 038, 945 752 oder 1 088 037. Während der Reaktion liegt der Trägerkatalysator als Suspension in der Reaktionslösung vor.The reaction is carried out in the presence of supported platinum catalysts. Platinum on carbon supports, in particular on graphite, have proven particularly useful. Such a supported catalyst preferably has a content of 0.2 to 5% by weight of platinum. Advantageously, the catalysts additionally contain one or more elements of the 5th and / or 6th main group of the periodic system with an atomic weight> 31, also lead and / or mercury as poisoning agents. Suitable catalysts and their preparation are described, for example, in DE-PS 920 963, 956 038, 945 752 or 1 088 037. During the reaction, the supported catalyst is present as a suspension in the reaction solution.
Wesentliches Merkmal der Erfindung ist es, daß man je Liter Reaktionslösung 40 bis 700 g Platinträgerkatalysator anwendet. Die obere Grenze der Katalysatorkonzentration wird lediglich durch das Kriterium der ausreichenden Fließfähigkeit und Filtrierbarkeit der Suspension begrenzt. Vorzugsweise wendet man 40 bis 400 g Platinträgerkatalysator an. Falls man Aktivkohle als Träger verwendet, haben sich Mengen von 40 bis 250 g und falls man Graphit als Träger verwendet, haben sich Mengen von 40 bis 350 g Trägerkatalysator je Liter Reaktionslösung besonders bewährt.An essential feature of the invention is that 40 to 700 g of supported platinum catalyst are used per liter of reaction solution. The upper limit of the catalyst concentration is only through limits the criterion of sufficient fluidity and filterability of the suspension. Preferably 40 to 400 g of supported platinum catalyst are used. If activated carbon is used as the carrier, amounts of 40 to 250 g have been found, and if graphite has been used as the carrier, amounts of 40 to 350 g of supported catalyst per liter of reaction solution have proven particularly useful.
Das Verfahren nach der Erfindung läßt sich diskontinuierlich oder kontinuierlich durchführen. Ein geeignetes kontinuierliches Verfahren wird beispielsweise in der DE-PS 1 113 448 beschrieben.The process according to the invention can be carried out batchwise or continuously. A suitable continuous process is described for example in DE-PS 1 113 448.
Erfindungsgemäß hergestellte Hydroxylammoniumsalze werden in großem Maßstab zur Herstellung von Cyclohexanonoxim, einem Vorprodukt für Caprolactam, verwendet.Hydroxylammonium salts produced according to the invention are used on a large scale for the production of cyclohexanone oxime, a precursor for caprolactam.
Das Verfahren nach der Erfindung sei an folgenden Beispielen veranschaulicht.The process according to the invention is illustrated by the following examples.
In einem Druckgefäß mit Rührer werden gemessene Mengen eines Platin-Graphit-Katalysators mit einem Platingehalt von 0,5 Gew.% in 5 Liter 4,1 n-Schwefelsäure suspendiert. Bei einem Druck von 1 bzw. 9 bar abs. leitet man unter Rühren gemessene Mengen NO und H2 im Volumen-Verhältnis 37 : 63 in den Reaktor ein, den man durch Kühlen auf einer Temperatur von 40 °C hält. Nicht umgesetzte Gase, die frei bzw. über ein Druckhalteventil entweichen, werden gemessen und analysiert. Wenn die Schwefelsäure nahezu aufgebraucht ist, beendet man die Reaktion, entspannt, trennt die Hydroxylaminlösung vom Katalysator ab und bestimmt die gebildete Menge Hydroxylamin.Measured quantities of a platinum-graphite catalyst with a platinum content of 0.5% by weight are suspended in 5 liters of 4.1N sulfuric acid in a pressure vessel with a stirrer. At a pressure of 1 or 9 bar abs. is introduced with stirring amounts of NO and H 2 in a volume ratio of 37: 63 into the reactor, which is kept at 40 ° C. by cooling. Unconverted gases that escape freely or via a pressure control valve are measured and analyzed. When the sulfuric acid is almost used up, the reaction is terminated, the pressure is released, the hydroxylamine solution is separated from the catalyst and the amount of hydroxylamine formed is determined.
Die näheren Einzelheiten sind aus folgender Tabelle zu entnehmen.Further details can be found in the following table.
Man verfährt wie in Beispiel 1 beschrieben, jedoch hat der Katalysator einen Platingehalt von 5,0 Gew.%. Die Ergebnisse entsprechend Tabelle zeigen, daß lediglich durch Erhöhung der Platinmenge bei gleichbleibender Trägermenge keine zusätzliche Verbesserung der Raum-Zeit-Ausbeute erreicht wird.The procedure is as described in Example 1, but the catalyst has a platinum content of 5.0% by weight. The results according to the table show that only by increasing the amount of platinum with the same amount of carrier does not achieve any additional improvement in the space-time yield.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2736906 | 1977-08-16 | ||
| DE2736906A DE2736906C2 (en) | 1977-08-16 | 1977-08-16 | Process for the preparation of hydroxylammonium salts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000901A1 EP0000901A1 (en) | 1979-03-07 |
| EP0000901B1 true EP0000901B1 (en) | 1984-05-23 |
Family
ID=6016512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100630A Expired EP0000901B1 (en) | 1977-08-16 | 1978-08-09 | Process for the preparation of hydroxyl ammonium salts |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0000901B1 (en) |
| JP (1) | JPS5846444B2 (en) |
| AR (1) | AR219119A1 (en) |
| DE (2) | DE2736906C2 (en) |
| IT (1) | IT1097993B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3713733A1 (en) * | 1987-04-24 | 1988-11-17 | Basf Ag | METHOD FOR PRODUCING HYDROXYLAMMONIUM SALTS |
| NL9201176A (en) * | 1992-07-02 | 1994-02-01 | Dsm Nv | PROCESS FOR PREPARING AND PURIFYING A HYDROXYLAMMONIUM SALT SOLUTION. |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE900213C (en) * | 1951-10-20 | 1953-12-21 | Basf Ag | Process for the production of hydroxylamine |
| DE1117118B (en) * | 1958-11-12 | 1961-11-16 | Organon Nv | Process for the preparation of 20-monoenol acylates of 11, 20-diketosteroids |
| DE1667045A1 (en) * | 1967-05-13 | 1971-06-03 | Bayer Ag | Process for the production of a platinum catalyst particularly suitable for the hydrogenation of NO to hydroxylamine |
| DE1667513B2 (en) * | 1967-12-20 | 1976-01-02 | Bayer Ag, 5090 Leverkusen | Process for the production of hydroxylamine-O-sulfo-acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1047178B (en) * | 1955-08-22 | 1958-12-24 | Spencer Chem Co | Process for the preparation of hydroxylamine salts or hydroxylamine |
| NL126246C (en) * | 1964-10-08 | |||
| DE1806537A1 (en) * | 1968-11-02 | 1970-05-21 | Bayer Ag | Process for the preparation of hydroxylammonium salts |
| NL6908934A (en) * | 1969-06-12 | 1970-12-15 | Hydroxylamine preparation without commin - ution of catalyst | |
| DE2100036C2 (en) * | 1971-01-02 | 1983-07-14 | Basf Ag, 6700 Ludwigshafen | Process for the production of hydroxylammonium nitrate |
-
1977
- 1977-08-16 DE DE2736906A patent/DE2736906C2/en not_active Expired
-
1978
- 1978-07-31 IT IT26343/78A patent/IT1097993B/en active
- 1978-07-31 AR AR273144A patent/AR219119A1/en active
- 1978-08-09 EP EP78100630A patent/EP0000901B1/en not_active Expired
- 1978-08-09 DE DE7878100630T patent/DE2862408D1/en not_active Expired
- 1978-08-16 JP JP53099154A patent/JPS5846444B2/en not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE900213C (en) * | 1951-10-20 | 1953-12-21 | Basf Ag | Process for the production of hydroxylamine |
| DE1117118B (en) * | 1958-11-12 | 1961-11-16 | Organon Nv | Process for the preparation of 20-monoenol acylates of 11, 20-diketosteroids |
| DE1667045A1 (en) * | 1967-05-13 | 1971-06-03 | Bayer Ag | Process for the production of a platinum catalyst particularly suitable for the hydrogenation of NO to hydroxylamine |
| DE1667513B2 (en) * | 1967-12-20 | 1976-01-02 | Bayer Ag, 5090 Leverkusen | Process for the production of hydroxylamine-O-sulfo-acid |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2862408D1 (en) | 1984-06-28 |
| IT7826343A0 (en) | 1978-07-31 |
| EP0000901A1 (en) | 1979-03-07 |
| DE2736906C2 (en) | 1979-10-31 |
| JPS5846444B2 (en) | 1983-10-17 |
| DE2736906B1 (en) | 1978-11-16 |
| JPS5463000A (en) | 1979-05-21 |
| IT1097993B (en) | 1985-08-31 |
| AR219119A1 (en) | 1980-07-31 |
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