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EP0000901B1 - Procédé de préparation de sels d'hydroxylammonium - Google Patents

Procédé de préparation de sels d'hydroxylammonium Download PDF

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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
Authority
EP
European Patent Office
Prior art keywords
catalyst
platinum
supported
reaction
space
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.)
Expired
Application number
EP78100630A
Other languages
German (de)
English (en)
Other versions
EP0000901A1 (fr
Inventor
Guenther Dr. Rapp
Klaus Dr. Kartte
Erwin Thomas
Genya Matsumoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6016512&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0000901(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000901A1 publication Critical patent/EP0000901A1/fr
Application granted granted Critical
Publication of EP0000901B1 publication Critical patent/EP0000901B1/fr
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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.

Landscapes

  • 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)

Claims (3)

1. Procédé de préparation de sulfate d'hydroxylammonium par réduction catalytique d'oxyde azotique avec de l'hydrogène en solutions aqueuses diluées d'acide sulfurique ou de bisulfate d'ammonium, en présence de catalyseur sur support de platine, à températures élevées, caractérisé par le fait que l'on utilise, par litre de solution de réaction, 40 à 700 g de catalyseur sur support de platine.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on utilise, par litre de solution de réaction, 40 à 400 g de catalyseur sur support de platine.
3. Procédé selon les revendications 1 et 2, caractérisé par le fait que l'on utilise des catalyseurs sur support platine-graphite.
EP78100630A 1977-08-16 1978-08-09 Procédé de préparation de sels d'hydroxylammonium Expired EP0000901B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2736906 1977-08-16
DE2736906A DE2736906C2 (de) 1977-08-16 1977-08-16 Verfahren zur Herstellung von Hydroxylammoniumsalzen

Publications (2)

Publication Number Publication Date
EP0000901A1 EP0000901A1 (fr) 1979-03-07
EP0000901B1 true EP0000901B1 (fr) 1984-05-23

Family

ID=6016512

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100630A Expired EP0000901B1 (fr) 1977-08-16 1978-08-09 Procédé de préparation de sels d'hydroxylammonium

Country Status (5)

Country Link
EP (1) EP0000901B1 (fr)
JP (1) JPS5846444B2 (fr)
AR (1) AR219119A1 (fr)
DE (2) DE2736906C2 (fr)
IT (1) IT1097993B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3713733A1 (de) * 1987-04-24 1988-11-17 Basf Ag Verfahren zur herstellung von hydroxylammoniumsalzen
NL9201176A (nl) * 1992-07-02 1994-02-01 Dsm Nv Werkwijze voor het bereiden en zuiveren van een hydroxylammoniumzoutoplossing.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE900213C (de) * 1951-10-20 1953-12-21 Basf Ag Verfahren zur Herstellung von Hydroxylamin
DE1117118B (de) * 1958-11-12 1961-11-16 Organon Nv Verfahren zur Herstellung von 20-Monoenolacylaten von 11, 20-Diketosteroiden
DE1667045A1 (de) * 1967-05-13 1971-06-03 Bayer Ag Verfahren zur Herstellung eines besonders fuer die NO-Hydrierung zu Hydroxylamin geeigneten Platinkatalysators
DE1667513B2 (de) * 1967-12-20 1976-01-02 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Hydroxyl-amin-O-sulfo-säure

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047178B (de) * 1955-08-22 1958-12-24 Spencer Chem Co Verfahren zur Herstellung von Hydroxylaminsalzen oder Hydroxylamin
NL126246C (fr) * 1964-10-08
DE1806537A1 (de) * 1968-11-02 1970-05-21 Bayer Ag Verfahren zur Herstellung von Hydroxylammoniumsalzen
NL6908934A (en) * 1969-06-12 1970-12-15 Hydroxylamine preparation without commin - ution of catalyst
DE2100036C2 (de) * 1971-01-02 1983-07-14 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Hydroxylammoniumnitrat

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE900213C (de) * 1951-10-20 1953-12-21 Basf Ag Verfahren zur Herstellung von Hydroxylamin
DE1117118B (de) * 1958-11-12 1961-11-16 Organon Nv Verfahren zur Herstellung von 20-Monoenolacylaten von 11, 20-Diketosteroiden
DE1667045A1 (de) * 1967-05-13 1971-06-03 Bayer Ag Verfahren zur Herstellung eines besonders fuer die NO-Hydrierung zu Hydroxylamin geeigneten Platinkatalysators
DE1667513B2 (de) * 1967-12-20 1976-01-02 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Hydroxyl-amin-O-sulfo-säure

Also Published As

Publication number Publication date
DE2736906C2 (de) 1979-10-31
JPS5463000A (en) 1979-05-21
IT7826343A0 (it) 1978-07-31
DE2736906B1 (de) 1978-11-16
EP0000901A1 (fr) 1979-03-07
AR219119A1 (es) 1980-07-31
IT1097993B (it) 1985-08-31
JPS5846444B2 (ja) 1983-10-17
DE2862408D1 (en) 1984-06-28

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