EP0000901B1 - Process for the preparation of hydroxyl ammonium salts - Google Patents

Process for the preparation of hydroxyl ammonium salts 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
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EP
European Patent Office
Prior art keywords
catalyst
space
reaction
platinum
supported
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Expired
Application number
EP78100630A
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German (de)
French (fr)
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EP0000901A1 (en
Inventor
Guenther Dr. Rapp
Klaus Dr. Kartte
Erwin Thomas
Genya Matsumoto
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BASF SE
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BASF SE
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Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/082Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/14Hydroxylamine; Salts thereof
    • C01B21/1409Preparation
    • C01B21/1418Preparation by catalytic reduction of nitrogen oxides or nitrates with hydrogen

Description

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • The process according to the invention is illustrated by the following examples.
  • Examples 1 to 6
  • 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.
  • Further details can be found in the following table.
  • Example 7
  • 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.
  • (See table on page 4 f.)
  • Figure imgb0001

Claims (3)

1. A process for the manufacture of hydroxylammonium sulfate by catalytically reducing nitric oxide with hydrogen in a dilute aqueous solution of sulfuric acid or ammonium bisulfate in the presence of a suspended supported platinum catalyst at an elevated temperature, wherein from 40 to 700 g of supported platinum catalyst are used per liter of reaction solution.
2. A process as claimed in claim 1, wherein from 40 to 400 g of supported platinum catalyst are used per liter of reaction solution.
3. A process as claimed in claims 1 and 2, wherein a platinum/graphite supported catalyst is used.
EP78100630A 1977-08-16 1978-08-09 Process for the preparation of hydroxyl ammonium salts Expired EP0000901B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19772736906 DE2736906C2 (en) 1977-08-16 1977-08-16
DE2736906 1977-08-16

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)

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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 (1) DE2736906C2 (en)
IT (1) IT1097993B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE900213C (en) * 1951-10-20 1953-12-21 Basf Ag A process for the preparation of hydroxylamine
DE1117118B (en) * 1958-11-12 1961-11-16 Organon Nv A process for preparing 20-Monoenolacylaten of 11, 20-Diketosteroiden
DE1667045A1 (en) * 1967-05-13 1971-06-03 Bayer Ag A process for preparing a hydrogenation NO suitable especially for the hydroxylamine platinum catalyst
DE1667513B2 (en) * 1967-12-20 1976-01-02 Bayer Ag, 5090 Leverkusen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1047178B (en) * 1955-08-22 1958-12-24 Spencer Chem Co A process for the manufacture of hydroxylamine salts or hydroxylamine
NL126246C (en) * 1964-10-08
DE1806537A1 (en) * 1968-11-02 1970-05-21 Bayer Ag A process for the preparation of hydroxylammonium
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, De

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE900213C (en) * 1951-10-20 1953-12-21 Basf Ag A process for the preparation of hydroxylamine
DE1117118B (en) * 1958-11-12 1961-11-16 Organon Nv A process for preparing 20-Monoenolacylaten of 11, 20-Diketosteroiden
DE1667045A1 (en) * 1967-05-13 1971-06-03 Bayer Ag A process for preparing a hydrogenation NO suitable especially for the hydroxylamine platinum catalyst
DE1667513B2 (en) * 1967-12-20 1976-01-02 Bayer Ag, 5090 Leverkusen

Also Published As

Publication number Publication date
EP0000901A1 (en) 1979-03-07
JPS5846444B2 (en) 1983-10-17
DE2736906C2 (en) 1979-10-31
JPS5463000A (en) 1979-05-21
IT1097993B (en) 1985-08-31
DE2736906B1 (en) 1978-11-16
AR219119A1 (en) 1980-07-31
IT7826343D0 (en) 1978-07-31

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