EP0000902A1 - Procédé de préparation de sels d'hydroxylammonium - Google Patents

Procédé de préparation de sels d'hydroxylammonium Download PDF

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Publication number
EP0000902A1
EP0000902A1 EP78100631A EP78100631A EP0000902A1 EP 0000902 A1 EP0000902 A1 EP 0000902A1 EP 78100631 A EP78100631 A EP 78100631A EP 78100631 A EP78100631 A EP 78100631A EP 0000902 A1 EP0000902 A1 EP 0000902A1
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EP
European Patent Office
Prior art keywords
zone
reaction mixture
reaction
gas
circulation
Prior art date
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Granted
Application number
EP78100631A
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German (de)
English (en)
Other versions
EP0000902B1 (fr
Inventor
Guenther Dr. Rapp
Erwin Thomas
Dieter Dr. Wolf
Heribert Kuerten
Peter Dr. Zehner
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BASF SE
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BASF SE
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Application filed by BASF SE filed Critical BASF SE
Publication of EP0000902A1 publication Critical patent/EP0000902A1/fr
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    • 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
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
    • B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00777—Baffles attached to the reactor wall horizontal

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 platinum catalysts at elevated temperature, the reaction mixture being circulated.
  • the aim is therefore to achieve the highest possible space-time yield with a small reaction volume, if possible without using stirring devices.
  • DE-AS 11 93 923 describes a procedure in which the reaction is carried out in a sieve tray column, the reaction solution being pumped continuously.
  • a reaction method working according to the mammoth pump principle is used.
  • DE-OS 15 42 219 a method of operation is already known in which an intimate gas-liquid-solid mixture is brought about by nozzles and the dispersion is introduced tangentially into the reaction zone.
  • the procedures listed above are still in need of improvement with regard to the space-time yields of nitrogen oxide achieved.
  • the new process has the advantage that better space-time yields, based on nitrogen oxide, are achieved under the pressures used in each case. This means that higher throughputs can be achieved with devices of existing size, or smaller devices can be selected for a given throughput. Furthermore, the new method has the advantage that it can be easily transferred to a larger scale.
  • Strong mineral acids such as hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid, are generally used. 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 used and are left in the course of the reaction f the acid concentration does not fall below 0.2 normal. '
  • the reaction is preferably carried out at temperatures from 30 to 80 ° C. Temperatures of 40 to 60 ° C have proven particularly useful.
  • the reaction generally takes place at atmospheric pressure. However, it has proven advantageous to carry out the reaction under increased pressure, e.g. up to 300 bar.
  • Supported catalysts are advantageously used as platinum catalysts; Carbon carriers have proven particularly useful. Platinum-graphite supported catalysts have gained particular technical importance. Such a catalyst advantageously contains 0.3 to 5% by weight of platinum.
  • the supported catalysts are present in a fine distribution so that they are suspended in the reaction medium.
  • 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 production are described, for example, in DE-PS 10 88 037, DE-PS 920 963, 956 038, 945 752. 1 to 400 g of supported platinum catalyst are generally used per liter of aqueous mineral acid.
  • the gas mixture containing hydrogen and nitrogen oxide in the gas space above the reaction zone is separated by at least one liquid jet, directed downwards and emerging from an opening in the nozzle, of the circulating reaction mixture, which essentially consists of aqueous mineral acid, catalyst, optionally from already formed hydroxylammonium salts and any By-products as well as dissolved and / or finely divided gases exist in at least one circulation zone located in the reaction zone, which is open on both sides and extends completely and in the direction of the incoming liquid jet is covered by the aqueous reaction mixture.
  • the gas mixture can also contain gases which are formed as by-products, such as N 2 O and inerts.
  • the circulation zone is a tube inserted vertically centrally into the reaction zone.
  • the circulation zone or circulation zones are open on both sides and extend in the direction of the incoming liquid jet or jets.
  • the circulation zone is also completely covered by the reaction mixture.
  • the reaction zone generally has a height to diameter ratio of 2 to 30: 1, preferably 5 to 15: 1.
  • the diameter ratio of the circulation zone to the reaction zone is generally about 0.7 to 0.1 and is preferably around 0. 5.
  • the velocity of the liquid jet introduced is advantageously from 5 to 40 m / sec, preferably from 10 to 30 m / see.
  • the amount of recycled reaction solution is generally from 10 to 500, in particular 100 to 4 00 m 3 / m 3 of the reaction zone and hour.
  • the speed of the liquid in the circulation zone should advantageously be a factor of 1 to 6, preferably 2 to 4 times as large as in the annular zone surrounding the circulation zone. In this way, the gas content in the circulation zone and in the annular zone are approximately the same size and the density differences are small.
  • the nozzle opening is advantageously at a distance from the 'upper end of the circulation zone which is 0.1 to 3, preferably 0.3 to 0.9 times the diameter of the circulation zone.
  • the reaction mixture emerging from the bottom of the circulation zone and the gas mixture not used up to that point are redirected.
  • the deflection is brought about by a deflection plate arranged transversely below the circulation zone. This is advantageously at a distance from the lower end of the circulation zone which is 0.1 to 1.0 times, preferably 0.2 to 0.7 times the diameter of the circulation zone. Unused gas mixture and part of the liquid rise in the ring-shaped zone surrounding the circulation zone.
  • the liquid reaction mixture is moved down again in the circulation zone by the liquid jet entering from above, and at the same time the gas mixture located above the liquid level is introduced into the circulation zone and finely distributed by the liquid jet directed downwards.
  • the gas entry from the gas phase above the liquid level is regulated automatically by immersing the nozzle mouth of the nozzle opening in the liquid, ie if the liquid level is lower, more gas is introduced until the liquid level rises and vice versa if the liquid level is above the nozzle mouth, so less gas is introduced so that the liquid level drops.
  • the content of finely divided gas bubbles in the reaction mixture can also be regulated in a simple manner. This is expediently carried out in such a way that the amount of liquid in the reaction zone is lowered by draining off after the circulation has started. It is then entered until the liquid level has reached the nozzle opening.
  • the liquid level does not increase due to the increased supply of liquid reaction mixture, but rather through increased gas absorption, which is present in the liquid in a fine distribution.
  • a gas content (gas hold-up) of 5 to 50%, based on the liquid reaction mixture, is advantageously maintained in the liquid reaction mixture in the reaction zone.
  • the fresh gas supply can also advantageously take place under the deflection plate at the point where the reaction mixture is deflected.
  • a separation zone Immediately below the reaction zone is a separation zone, in which entrained gas bubbles separate from the liquid reaction mixture. The gas bubbles move upward against the liquid flow, while the liquid reaction mixture is drawn off and returned to the nozzle opening or openings.
  • a jet drive in which the nozzle works from top to bottom.
  • the driving jet brings energy for the circulation in the reactor. Since the nozzle mouth is on the surface of the liquid, the propellant jet introduces gas into the liquid, which is very finely dispersed in the circulation pipe. This makes the slip between liquid and gas very small and one high rotational speed generated.
  • the propellant jet therefore only introduces so much gas that the liquid level reaches the nozzle opening. This also limits the gas content in the liquid and can never become so great that the circulation of the gas-liquid flow in the reactor can be at risk of collapsing due to the formation of large bubbles.
  • the advantage of the process according to the invention is accordingly the uniform distribution of gas and also of the suspended catalyst in the entire reaction zone. When the reactor is switched off, the nozzle opening cannot become blocked by the deposited catalyst.
  • the process is suitable for continuous and discontinuous working methods.
  • the aqueous mineral acid to be reacted optionally in a mixture with hydroxylamine salts, is continuously introduced into the reaction zone.
  • the reaction product is continuously removed from the external liquid circulation. Amounts of catalyst removed with the reaction liquid are supplemented by appropriate additions of catalyst to the liquid feed.
  • the desired gas hold-up can be regulated by varying the liquid inflow or outflow. The gas hold-up can e.g. by determining the apparent density of the liquid-solid gas mixture or the amount of liquid in the reaction space.
  • Hydroxylammonium salts are used for the production of cyclohexanone oxime, a precursor for the production of caprolactam.
  • an immersion jet device consisting of a reactor vessel (1) with circulation pipe (2) and baffle plate (3) and an external liquid circulation (4) with pump (5) and heat exchanger (6) for removing the heat of reaction and immersion jet nozzle (7) ,
  • Gas supply (8, 9) and gas discharge (10) 4.3 n sulfuric acid and 40 g of a platinum-graphite catalyst with a content of 0.5 wt.% Pt are added per liter of sulfuric acid used.
  • a gas mixture consisting of 36% by volume NO and 63% by volume H2 (rest of intergas) is introduced into the reactor at 40 ° C.
  • the escaping exhaust gas is measured and analyzed.
  • the sulfuric acid in the reaction solution is almost used up, the reaction is terminated, the hydroxylamine solution is separated from the catalyst and the amount of hydroxylamine formed is determined.

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)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP78100631A 1977-08-16 1978-08-09 Procédé de préparation de sels d'hydroxylammonium Expired EP0000902B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2736872A DE2736872B2 (de) 1977-08-16 1977-08-16 Verfahren zur Herstellung von Hydroxylammoniumsalzen
DE2736872 1977-08-16

Publications (2)

Publication Number Publication Date
EP0000902A1 true EP0000902A1 (fr) 1979-03-07
EP0000902B1 EP0000902B1 (fr) 1980-07-23

Family

ID=6016499

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100631A Expired EP0000902B1 (fr) 1977-08-16 1978-08-09 Procédé de préparation de sels d'hydroxylammonium

Country Status (5)

Country Link
US (1) US4192856A (fr)
EP (1) EP0000902B1 (fr)
JP (1) JPS5448700A (fr)
DE (2) DE2736872B2 (fr)
IT (1) IT1097942B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048974A1 (fr) * 1980-09-29 1982-04-07 Kao Corporation Procédé pour la production d'oxydes de saccharides
EP0185868A3 (en) * 1984-12-15 1987-10-21 Dynamit Nobel Aktiengesellschaft Process and apparatus for carrying out heterogeneous mass transport limiting reactions
EP0452574A1 (fr) * 1988-08-24 1991-10-23 Exxon Research And Engineering Company Contact amélioré entre plusieurs phases de fluides distinctes dans un réacteur placé verticalement
WO2020014211A1 (fr) * 2018-07-09 2020-01-16 Blue Cube Ip Llc Buse d'éjecteur pour améliorer la rétention de gaz dans un réacteur gaz-liquide
US20200243991A1 (en) * 2017-03-10 2020-07-30 Rosenberger Hochfrequenztechnik Gmbh & Co. Kg Inner conductor element

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3107702A1 (de) * 1981-02-28 1982-09-16 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen herstellung von hydroxylammoniumsalzen
DE3130305A1 (de) * 1981-07-31 1983-02-17 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von hydroxylammoniumsalzen
DE4403479A1 (de) * 1994-02-04 1995-08-10 Basf Ag Verfahren zur Herstellung von Hydroxylammoniumsalzen
DE59905881D1 (de) 1998-12-12 2003-07-10 Basf Ag Verfahren zur herstellung von aminen
AT410406B (de) * 2001-09-17 2003-04-25 Andritz Ag Maschf Verfahren und vorrichtung zur belüftung einer flüssigkeit mit gas
CN101804317B (zh) 2010-04-02 2012-10-17 南京大学 一种多相催化塔式碰撞流反应器

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE803113C (de) * 1946-12-30 1951-03-01 Basf Ag Verfahren zur Herstellung von imidodisulfonsaurem Ammoniak
DE1956670A1 (de) * 1968-11-14 1970-05-21 Inventa Ag Verfahren zur Ausfuehrung von katalytischen Gasreaktionen im Mehrphasensystem
DE1767201A1 (de) * 1968-04-11 1971-09-16 Hoechst Ag Verfahren zur Herstellung von Amidosulfonsaeure
DE1542219B2 (de) * 1964-11-10 1973-01-11 Inventa AG für Forschung und Patentverwertung Zürich, Zürich (Schweiz) Verfahren und vorrichtung zur hydrierung von stickoxyd zu hydroxylamin
DE2151206A1 (de) * 1971-10-14 1973-04-19 Basf Ag Verfahren und vorrichtung zum vermischen von fluessigkeiten
FR2307574A1 (fr) * 1975-04-14 1976-11-12 Burgert Burdosa Reacteur a boucles pour reactions chimiques et similaires
DE2433967B2 (de) * 1973-07-17 1977-02-17 Inventa AG für Forschung und Patentverwertung, Zürich (Schweiz) Verfahren zur umsetzung von stickoxyd mit wasserstoff
FR2336174A1 (fr) * 1975-12-24 1977-07-22 Fisons Ltd Procede et appareil pour executer une reaction chimique faisant intervenir une phase gazeuse
FR2366868A1 (fr) * 1976-10-09 1978-05-05 Basf Ag Procede d'injection de gaz dans un liquide contenu dans un reacteur a circulation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2414142A (en) * 1944-01-17 1947-01-14 Bonard Claude Manufacture of hydroxylamine
DE956038C (de) * 1954-04-01 1957-01-10 Basf Ag Verfahren zur Herstellung von Hydroxylammoniumsalzen
BE634876A (fr) 1962-07-13
NL6908934A (en) 1969-06-12 1970-12-15 Hydroxylamine preparation without commin - ution of catalyst
CH583588A5 (fr) * 1973-10-10 1977-01-14 Inventa Ag
US3954946A (en) * 1974-07-18 1976-05-04 Inventa Ag Fur Forschung Und Patentverwertung, Zurich Process for reacting nitric oxide with hydrogen

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE803113C (de) * 1946-12-30 1951-03-01 Basf Ag Verfahren zur Herstellung von imidodisulfonsaurem Ammoniak
DE1542219B2 (de) * 1964-11-10 1973-01-11 Inventa AG für Forschung und Patentverwertung Zürich, Zürich (Schweiz) Verfahren und vorrichtung zur hydrierung von stickoxyd zu hydroxylamin
DE1767201A1 (de) * 1968-04-11 1971-09-16 Hoechst Ag Verfahren zur Herstellung von Amidosulfonsaeure
DE1956670A1 (de) * 1968-11-14 1970-05-21 Inventa Ag Verfahren zur Ausfuehrung von katalytischen Gasreaktionen im Mehrphasensystem
DE2151206A1 (de) * 1971-10-14 1973-04-19 Basf Ag Verfahren und vorrichtung zum vermischen von fluessigkeiten
DE2433967B2 (de) * 1973-07-17 1977-02-17 Inventa AG für Forschung und Patentverwertung, Zürich (Schweiz) Verfahren zur umsetzung von stickoxyd mit wasserstoff
FR2307574A1 (fr) * 1975-04-14 1976-11-12 Burgert Burdosa Reacteur a boucles pour reactions chimiques et similaires
FR2336174A1 (fr) * 1975-12-24 1977-07-22 Fisons Ltd Procede et appareil pour executer une reaction chimique faisant intervenir une phase gazeuse
FR2366868A1 (fr) * 1976-10-09 1978-05-05 Basf Ag Procede d'injection de gaz dans un liquide contenu dans un reacteur a circulation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMIE-INGENIEUR-TECHNIK, Jahrgang 46, August 1974, Weinheim; W. HIRNER & H. BLENKE: "Stoff}bergang in Gas/Fl}ssigkeits-Strahlreaktoren und Blasenkolonnen", Seite 353 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0048974A1 (fr) * 1980-09-29 1982-04-07 Kao Corporation Procédé pour la production d'oxydes de saccharides
EP0185868A3 (en) * 1984-12-15 1987-10-21 Dynamit Nobel Aktiengesellschaft Process and apparatus for carrying out heterogeneous mass transport limiting reactions
EP0452574A1 (fr) * 1988-08-24 1991-10-23 Exxon Research And Engineering Company Contact amélioré entre plusieurs phases de fluides distinctes dans un réacteur placé verticalement
US20200243991A1 (en) * 2017-03-10 2020-07-30 Rosenberger Hochfrequenztechnik Gmbh & Co. Kg Inner conductor element
WO2020014211A1 (fr) * 2018-07-09 2020-01-16 Blue Cube Ip Llc Buse d'éjecteur pour améliorer la rétention de gaz dans un réacteur gaz-liquide

Also Published As

Publication number Publication date
IT1097942B (it) 1985-08-31
EP0000902B1 (fr) 1980-07-23
JPS5448700A (en) 1979-04-17
DE2860073D1 (en) 1980-11-13
IT7826690A0 (it) 1978-08-10
US4192856A (en) 1980-03-11
DE2736872A1 (de) 1979-02-22
DE2736872B2 (de) 1979-07-19

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