WO1996016039A1 - Procede de production d'amide d'acide nicotinique par hydratation catalytique de 3-cyanopyridine - Google Patents

Procede de production d'amide d'acide nicotinique par hydratation catalytique de 3-cyanopyridine Download PDF

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Publication number
WO1996016039A1
WO1996016039A1 PCT/EP1995/004409 EP9504409W WO9616039A1 WO 1996016039 A1 WO1996016039 A1 WO 1996016039A1 EP 9504409 W EP9504409 W EP 9504409W WO 9616039 A1 WO9616039 A1 WO 9616039A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
manganese dioxide
cyano
pyridine
weight
Prior art date
Application number
PCT/EP1995/004409
Other languages
German (de)
English (en)
Inventor
Karsten Eller
Hans Christoph Horn
Christof Herion
Original Assignee
Basf Aktiengesellschaft
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
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU38717/95A priority Critical patent/AU3871795A/en
Publication of WO1996016039A1 publication Critical patent/WO1996016039A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/116—Heterocyclic compounds
    • A23K20/132—Heterocyclic compounds containing only one nitrogen as hetero atom
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese

Definitions

  • the invention relates to an improved process for the preparation of nicotinamide by catalytic hydration of 3-cyano-pyridine over manganese dioxide catalysts.
  • Nicotinamide (also called vrffamin PP, niacin or niacinamide) has become particularly important as an additive to the feed of chickens and pigs.
  • 3-Cyano-pyridine can be hydrated, for example, enzymatically with the aid of nitrile hydratases (cf. for example CA 114 (13): 11 75 15k; CA 110 (21): 18 83 31a and EP 243 967 A2).
  • nitrile hydratases cf. for example CA 114 (13): 11 75 15k; CA 110 (21): 18 83 31a and EP 243 967 A2
  • a disadvantage of biotechnical processes is that the service life is unsatisfactory compared to hydration in the presence of heterogeneous catalysts.
  • JP-B2 16 092/82 describes the hydration of 3-cyano-pyridine under high pressure in the presence of ammonia and / or methanol.
  • a disadvantage of this method is the necessity to work at very high pressures.
  • Manganese dioxide catalysts can be described as particularly efficient the.
  • a disadvantage of the known manganese dioxide catalysts is their inadequate mechanical stability.
  • brown stone powder has recently been used in suspension reactors (cf. EP 461 85A1 and EP 545 697A1).
  • a disadvantage of these processes is the complex removal of the suspended, finely divided catalyst.
  • the invention accordingly relates to a process for the hydration of 3-cyano-pyridine to nicotinamide by passing a mixture of water and 3-cyano-pyidine and optionally an organic solubilizer over a manganese dioxide catalyst fixed bed, which is characterized in that that a manganese dioxide catalyst is used which is in the form of mechanically stable strands, tablets or in splintered form and
  • the process according to the invention is particularly successful if a manganese dioxide catalyst is used which contains 0.5 to 20, preferably 1 to 5% by weight of A10 3 or if a manganese dioxide catalyst is used which contains 0.1 to 10, preferably 0, 5 to 5 wt .-% K 2 0 contains.
  • Mudstone catalysts can be manufactured using many different methods; Glemser and co-workers in Z. Anorg, for example, provide an overview. Chem. 309, (1961), pages 1-19, 20-36 and 121-150. However, not all manufacturing processes lead to equally active materials in nitrile hydration. Depending on the design, defined phases, mixtures of different phases or even X-ray amorphous materials can arise which contain both water and foreign ions, in particular alkali metals. The oxidation level of the manganese can vary within certain limits.
  • manganese dioxide should be understood to mean the various modifications without precise specification and not only refer to the pure Mn (IV) present in its ideal formula as Mn0 2 , but have a composition of approximately MnO ⁇ to Mn0 2 .
  • the hydration of 3-cyano-pyridine can advantageously be carried out using catalysts in the form of strands, tablets or other larger particles which have been produced in accordance with the present invention in such a way that a fixed bed contact in a tubular reactor is removed from the aqueous solution of 3- Cyano-pyridine is flowed through.
  • the reaction temperature is advantageously 40 to 100 ° C., preferably 50 to 100 ° C. If one wishes to work at a higher temperature, a reaction procedure under pressure must be selected. Higher temperatures accelerate the course of the reaction, but can also lead to undesirable by-products at very high temperatures.
  • the reaction can also be carried out in the presence of an inert gas such as nitrogen, argon or carbon dioxide.
  • the starting material mixture advantageously consists of a solution of 3-cyano-pyridine in water.
  • a solubilizer can also be added. Its polarity should lie between water and the nitrile.
  • acetone in particular has proven useful. It is expedient to start from a prefabricated mixture which is removed from a storage container by means of a pump. However, separate feeding of the individual components to the reactor is also possible. After the reactor, the products and unreacted starting materials are collected using a cooler.
  • the solubilizers are generally used in amounts of 1 to 30% by weight, based on the total mixture fed to the reactor.
  • the catalyst Since the process according to the invention is one in which a liquid flows around the fixed-bed catalyst, the catalyst must have a particularly high mechanical stability, ie high hardness, since otherwise fine particles that have been blasted off separate the spaces in the catalyst bed Block the reaction vessel and the pressure becomes too high, which means that the catalyst has to be replaced too often.
  • the catalyst active composition which essentially consists of manganese dioxide or at least partially hydrated phases of the manganese dioxide or mixed oxides of alkali metals and manganese (III ) - or manganese (IV) oxides, in a kneader
  • Aluminum oxide (A1 2 0 3 ), silicon dioxide (Si0 2 ), titanium dioxide (Ti0 2 ) or zirconium dioxide (Zr0 2 ) are essentially suitable as binders. They can also be introduced in the form of compounds which only convert into the oxides mentioned when calcined.
  • AIO OH
  • Pural ® SB from Condea (approx. 75% A1 2 0 3 ) or as Versal ® from Firmal La-Roche Chemicals Inc. (formerly Kaiser Chemicals).
  • Finely divided silicon dioxide is, for example,
  • colloidal dispersion for example under the name Ludox ® from Du Pont (for example HS-40 containing 40% Si0 2 ) or Levasit ® (30% Si0 2 ) from Bayer AG or as a fine powder commercially.
  • TiO 2 is available in the form of fine powders, for example from Degussa AG (Ti0 2 P25) or Sachtleben (Ti0 2 VKR 611). Geei
  • 35 gnet is also zirconium hydroxide (for example from Magnesium Elektron Ltd.).
  • Aluminum oxide is particularly preferably used as the binder, since it leads to mechanically very stable strands or tablets even in very small amounts.
  • the binders are generally used in amounts of 0.5 to 70, preferably 1 to
  • Starch or other organic compounds can be used as so-called pore formers, which are decomposed without residue during the calcination. It is particularly advantageous to use organic compounds or preparations thereof which, due to their sticky nature, give the manganese dioxide binder mixture the consistency suitable for kneading and shaping.
  • organic compounds or preparations thereof which, due to their sticky nature, give the manganese dioxide binder mixture the consistency suitable for kneading and shaping.
  • numerous thickeners and adhesives are suitable, such as those used for textile printing and related fields of work (cf. special print of the Bayer color review by Helmut Dahm, Bayer AG, September 1981). Examples include carboxymethyl cellulose, hydroxyethyl cellulose and methyl hydroxyalkyl cellulose preparations which are commercially available under the name Walocel ® types from Wolff Walsrode.
  • Other suitable pore formers are, for example, polyacrylates such as the Sokalan types from BASF Aktiengesellschaft and polystyrene, polymethyl me
  • the pore formers are generally used in amounts of 0.1 to 40, preferably 5 to 10 wt .-%, based on the total mass of the shaped catalyst body before the calcination.
  • Alkali or alkaline earth oxides can be introduced into the catalyst used according to the invention by using alkali or alkaline earth manganese mixed oxides, such as K 2 Mn ⁇ O ⁇ o or KMn0 4 .
  • alkali or alkaline earth manganese mixed oxides such as K 2 Mn ⁇ O ⁇ o or KMn0 4 .
  • it can also be carried out in a manner known per se by metering precipitated manganese dioxide, for example by suspending the same in an aqueous solution of an alkali metal or alkaline earth metal salt, adding strong mineral acids and heating for a prolonged period.
  • the catalysts In order to be suitable for the process according to the invention, the catalysts must have a cutting hardness of at least 5 to 30 N.
  • the nicotinamide which is sought after as an animal feed additive can also be produced on an industrial scale in very good yields and purities.
  • the manganese dioxide powder doped in this way was separated off using a suction filter and washed three times with 0.5 l of water each time. After drying at 110 ° C., 100 g thereof were kneaded with 5 g Walocel (Wolff Walsrode AG), 5 g Ludox AS 40 (Du Pont, 40% Si0 2 ) and 80 g water and added at 50 to 60 bar 2 mm strands deformed. These were dried at 110 ° C. and then calcined at 500 ° C. for 5 hours.
  • the cut hardness of the strands thus produced was less than 1 N.
  • the composition of the catalyst was: 91.8% by weight Mn0 2 6.1% by weight Rb 2 0 0.3% by weight Si0 2 1.1% by weight K 2 0
  • This example shows that sufficient amounts of cutting hardness are not achieved with amounts of less than 1% by weight of SiO 2 .
  • a sodium sulfate-doped manganese dioxide powder was produced analogously to comparative example 1a. 90 g of it were kneaded with 5 g of Walocel, 10 g of Ludox AS 40 and 60 ml of water and shaped into 5 mm strands at 45 bar. The cutting hardness of the strands produced in this way was 8.3 N.
  • the composition of the catalyst was: 91.8% by weight Mn0 2 3.2% by weight Si0 2 0.2% by weight Na 2 0 4.2% by weight K 2 0
  • a calcium nitrate-doped manganese dioxide powder was produced analogously to comparative example 1a. 90 g of which were included
  • the cut hardness of the strands produced in this way was 7.9 N.
  • the composition of the catalyst was: 91.8% by weight of MnO 2
  • a manganese dioxide catalyst was produced analogously to comparative example 1c, but calcined at 250 ° C. According to X-ray diffraction analysis, it consisted of Mn (0, OH) 2 (Nsutite) and Mn (0H) 4 (Vernadite) as well as amorphous components. 7 g of the catalyst were installed in a splintered form in a glass reactor provided with a heating jacket (16 mm inner diameter). The reactor was brought to 60 ° C. by heating water in a thermostat and passing it through the heating jacket.
  • the feed was carried out in an ascending manner and consisted of a mixture of 1 part by weight of 3-cyano-pyridine, 9 parts by weight of water and 2 parts by weight of acetone, which was pumped to a storage container at 2.5 gh " 1
  • the discharges were analyzed at regular intervals After 19 hours the yield of nikotinamide was 96.6%, after 32 hours 99.1%, after 48 hours 96.4%, after 148 hours 95.9 % and after 203 h 93.5%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Animal Husbandry (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'amide d'acide nicotinique par hydratation catalytique de 3-cyanopyridine. Ledit procédé consiste à faire passer un mélange constitué d'eau et de 3-cyanopyridine et le cas échéant d'un agent de solubilisation organique, sur un lit fixe de catalyseur au bioxyde de manganèse. Ce procédé est caractérisé en ce que l'on utilise un catalyseur sous forme de boudins stables mécaniquement, de pastilles ou sous forme finement divisée, contenant outre du bioxyde de manganèse, Al2O3, SiO2, TiO2 et/ou ZrO2 et un oxyde alcalin ou alcalino-terreux.
PCT/EP1995/004409 1994-11-17 1995-11-09 Procede de production d'amide d'acide nicotinique par hydratation catalytique de 3-cyanopyridine WO1996016039A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38717/95A AU3871795A (en) 1994-11-17 1995-11-09 Process for producing nicotinic acid amide by the catalytic hydratation of 3-cyano pyridine

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4440927A DE4440927A1 (de) 1994-11-17 1994-11-17 Verfahren zur Herstellung von Nikotinsäureamid durch katalytische Hydratisierung von 3-Cyano-pyridin
DEP4440927.3 1994-11-17

Publications (1)

Publication Number Publication Date
WO1996016039A1 true WO1996016039A1 (fr) 1996-05-30

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PCT/EP1995/004409 WO1996016039A1 (fr) 1994-11-17 1995-11-09 Procede de production d'amide d'acide nicotinique par hydratation catalytique de 3-cyanopyridine

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Country Link
AU (1) AU3871795A (fr)
DE (1) DE4440927A1 (fr)
WO (1) WO1996016039A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996036592A2 (fr) * 1995-05-19 1996-11-21 Basf Aktiengesellschaft Procede de preparation de derives d'acide carboxylique
WO2004056776A1 (fr) * 2002-12-23 2004-07-08 Council Of Scientific And Industrial Research Procede de conversion de cyanopyridines en nicotinamides et catalyseur associe, et procede pour la preparation dudit catalyseur
US7455827B2 (en) 2003-03-20 2008-11-25 Council Of Scientific And Industrial Research Process for preparing a catalyst for conversion of cyanopyridines to nicotinamides
CN104496894A (zh) * 2014-11-22 2015-04-08 安徽国星生物化学有限公司 一种高纯度烟酰胺及烟酸的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115093366B (zh) * 2022-06-24 2024-07-30 佳化化学科技发展（上海）有限公司 一种合成烟酰胺的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2131813A1 (de) * 1970-08-24 1972-03-02 Reynolds Tobacco Co R Verfahren zur UEberfuehrung von Nitrilen in Amide
US4096149A (en) * 1974-11-05 1978-06-20 National Distillers And Chemical Corporation Hydrolysis of nitriles
EP0545697A1 (fr) * 1991-12-03 1993-06-09 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation de l'alpha-hydroxy-isobutyramide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2131813A1 (de) * 1970-08-24 1972-03-02 Reynolds Tobacco Co R Verfahren zur UEberfuehrung von Nitrilen in Amide
US4096149A (en) * 1974-11-05 1978-06-20 National Distillers And Chemical Corporation Hydrolysis of nitriles
EP0545697A1 (fr) * 1991-12-03 1993-06-09 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation de l'alpha-hydroxy-isobutyramide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K.-T. LIU ET AL.: "Catalytic hydrogenation of nitriles to amides with manganese dioxide on silica gel.", SYNTHESIS, no. 9, STUTTGART DE, pages 715 - 717 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996036592A2 (fr) * 1995-05-19 1996-11-21 Basf Aktiengesellschaft Procede de preparation de derives d'acide carboxylique
WO1996036592A3 (fr) * 1995-05-19 1997-01-09 Basf Ag Procede de preparation de derives d'acide carboxylique
AU713436B2 (en) * 1995-05-19 1999-12-02 Basf Aktiengesellschaft The preparation of carboxylic acid derivatives
US6002010A (en) * 1995-05-19 1999-12-14 Basf Aktiengesellschaft Carboxylic acid derivative preparation process
EA000799B1 (ru) * 1995-05-19 2000-04-24 Басф Аг Способ получения производных карбоновой кислоты
WO2004056776A1 (fr) * 2002-12-23 2004-07-08 Council Of Scientific And Industrial Research Procede de conversion de cyanopyridines en nicotinamides et catalyseur associe, et procede pour la preparation dudit catalyseur
US7345176B2 (en) 2002-12-23 2008-03-18 Council Of Scientific And Industrial Research Process for conversion of cyanopyridines to nicotinamides and catalyst therefor, process for preparing said catalyst
US7455827B2 (en) 2003-03-20 2008-11-25 Council Of Scientific And Industrial Research Process for preparing a catalyst for conversion of cyanopyridines to nicotinamides
CN104496894A (zh) * 2014-11-22 2015-04-08 安徽国星生物化学有限公司 一种高纯度烟酰胺及烟酸的制备方法

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Publication number Publication date
DE4440927A1 (de) 1996-05-23
AU3871795A (en) 1996-06-17

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