AU2003300723B2 - Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst - Google Patents

Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst Download PDF

Info

Publication number
AU2003300723B2
AU2003300723B2 AU2003300723A AU2003300723A AU2003300723B2 AU 2003300723 B2 AU2003300723 B2 AU 2003300723B2 AU 2003300723 A AU2003300723 A AU 2003300723A AU 2003300723 A AU2003300723 A AU 2003300723A AU 2003300723 B2 AU2003300723 B2 AU 2003300723B2
Authority
AU
Australia
Prior art keywords
catalyst
range
acetaldehyde
ammonia
slurry
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.)
Ceased
Application number
AU2003300723A
Other versions
AU2003300723A1 (en
Inventor
Pashupati Dutta
Tarun Kanti Goswami
Shyam Kishor Roy
Subhash Chandra Roy
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.)
Council of Scientific and Industrial Research CSIR
Original Assignee
Council of Scientific and Industrial Research CSIR
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 Council of Scientific and Industrial Research CSIR filed Critical Council of Scientific and Industrial Research CSIR
Publication of AU2003300723A1 publication Critical patent/AU2003300723A1/en
Application granted granted Critical
Publication of AU2003300723B2 publication Critical patent/AU2003300723B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/08—Preparation by ring-closure
    • C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
    • C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Description

WO 2005/063389 PCT/IN2003/000467 CATALYST FOR SYNTHESIS OF 2- AND 4-PICOLINES, PROCESS FOR PREPARING 2- AND 4-PICOLINE AND PROCESS FOR PREPARING THE CATALYST Field of the invention The present invention provides a catalyst composite for the synthesis of 2- and 4 picolines. The present invention also provides a process for the preparation of a catalyst 5 useful for the synthesis of 2- and 4- Picolines. The present invention also provides a process for the preparation of 2- and 4- picolines using said, novel catalyst. The present invention finds its usage in preparation of various intermediates for pharmaceuticals and agrochemicals. 2-Picoline is one of the main components in manufacture of pesticides. Major outlet for 4 Picoline is for the synthesis of 4-VinylPyridine and Iso-Nicotinic Acid Hydrazide (INH), an 10 anti-tubercular drug. Background of the invention Commercially important sources of pyridine bases are tar and saturated liquor obtained by the carbonization of coal. However, the stringent specifications laid down for these products in pharmaceuticals and agricultural applications cannot be met from natural 15 sources, namely from coal carbonization byproducts. Amongst the various synthetic routes, the reaction between acetaldehyde and ammonia is the most common one known in the prior art for making pyridine bases. Acids have been used as catalysts or co-catalysts in a number of reactions. U.S. Patent 2,186,392 reveals that ethanolamines may be produced from ammonia or a primary amine 20 and ethylene oxide and a salt of a weak acid, such as ammonium carbonate, in the presence of an aliphatic radical which is positive with respect to hydrogen. German Patent 844,449 (CA 48:1429c) informs tertiary amines with hydroxyalkyl radicals may be made from ammonia, primary or secondary amines and an alkylene oxide at a temperature of from 30'C to 60'C, with improved yields being possible if water or a weak acid is also present. British Patent No. 25 497,093, (CA 36:4131-8) indicates that monoalkanolamines may be made from olefin oxides and ammonia in the presence of water and an acid. The reaction of acetaldehyde or certain other low molecular weight aldehydes and ammonia either in the absence or presence of methanol and/or formaldehyde to yield pyridine and alkyl derivatives thereof has heretofore been carried out in the presence of amorphous 30 silica-alumina composites containing various promoters. The yields of desired products using the latter catalysts have been poor. Alkylpyridines have also been synthesized, as reported in Advances in Catalysis, Volume 18, page 344 (1968) Academic Press, Inc., New York, N.Y., by passing gaseous acetaldehyde and ammonia over crystalline aluminosilicates, NaX and H mordenite. While initial conversion utilizing these materials as catalysts was high, catalyst 2 deactivation by coking was rapid, providing a commercially unattractive system, characterized by poor catalytic stability. US Patent 4,220,783 provides a method for synthesizing pyridine or alkylpyridines by reacting ammonia and a carbonyl reactant which is an aldehyde containing 2 to 4 carbon 5 atoms, a ketone containing 3 to 5 carbon atoms or mixtures of said aldehydes and/or ketones under effective conditions in the presence of a catalyst comprising a crystalline aluminosilicate zeolite having a silica to alumina ratio of at least about 12 and a constraint index within the approximate range of 1 to 12 and recovering from the resulting reaction mixture, a product containing at least one compound of pyridine or an alkylpyridine. 10 Addition of methanol and/or formaldehyde to the feed improves selectivity to unsubstituted pyridine. The yields of desired products have been poor. Manufacture of pyridine bases by employing the catalyst causes environmental pollution because these routes use toxic Th02 and CdO. The catalyst preparation involves tedious method for the preparation of silica alumina gel. 15 Objects of the invention The main object of the invention is to provide a catalyst suitable for the conversion of acetaldehyde and ammonia to 2-and 4-Picolines which obviates the drawbacks as detailed above. Another object of the invention is to provide a stable catalyst for the conversion of 20 acetaldehyde and ammonia. Still another object of the invention is to provide a catalyst which is highly selective and active. Summary of the invention Accordingly the present invention provides a process for synthesis of 2-and 4 25 Picolines which comprises providing a heteropoly acid catalyst selected from the group consisting of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid provided on a support, and reacting acetaldehyde and ammonia under heat in the presence of the catalyst being present in an amount in the range of 5 to 15 wt %, and separating the 2-and 4-picoline formed. 30 In one embodiment of the invention, the support is selected from the group consisting of silica gel, alumina, silica-alumina, clays and montmorillonite. The present invention also provides a process for the preparation of a catalyst useful for the synthesis of 2-and 4-picolines, the process comprising dissolving a heteropoly acid in distilled water; mixing the resulting mixture with desired amount of a support to obtain a 3 slurry; stirring the slurry till uniform impregnation is achieved; drying the slurry in air at 200 250'C for a time period in the range of 0.5 to 1.5 hours; further heating the slurry at a temperature in the range of 300 to 400*C for time period in the range of 0.5 to 1.5 hours and cooling the resultant product to room temperature in a desiccator to get the desired catalyst. 5 In one embodiment of the invention the heteropoly acid is selected from the group consisting of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid. In another embodiment of the invention the support is selected from the group consisting of silica, alumina, silica-alumina, clays and montmorillonite. 10 In another embodiment of the invention, the heteropoly acid is dissolved in distilled water in a ratio of 0.5 : 4.5 (w/w). In another embodiment of the invention, the support comprises silica gel of mesh size 6-14. In yet another embodiment of the invention, the slurry is stirred for a time period in 15 the range of 30-40 minutes. In one embodiment of the invention, the acetaldehyde and ammonia are taken in a ratio of 0.8 to 1.2 (w/w) and are reacted at a temperature in the range of 300 to 500 0 C. In another embodiment of the invention, the reaction is carried out in a glass reactor. In yet another embodiment of the invention, the weight hourly space velocity of the 20 acetaldehyde and ammonia is maintained in the range of 0.1 to 10 g/g of catalyst (preferably I to 3). In yet another embodiment of the invention, the 2-and 4-picolines are separated by fractional distillation. Detailed description of the invention 25 The present invention provides a catalyst useful for synthesis of 2-and 4-Picolines which is prepared by dissolution of a heteropoly acid in distilled water in a suitable proportion in the range of 0.5 : 4.5 (w/w). The resulting mixture is then mixed with desired amount of a binder such as silica gel (having mesh size 6-14) and the slurry obtained stirred for a time period in the range of 30-40 minutes to get a uniform impregnation. After uniform 30 impregnation is obtained, the slurry is first dried in air at a temperature in the range of 200 250'C for a time period in the range of 0.5 to 1.5 hours and then further heated at temperature 4 WO 2005/063389 PCT/IN2003/000467 in the range of 300 to 400'C for time period in the range of 0.5 to 1.5 hours. The resulting product is then cooled to room temperature in a desiccator to get the desired catalyst. The heteropoly acid is selected from silicotungstic acid, phosphotungstic acid, phosphomolybdic acid and vanadotungstic acid and the binder is from silica, alumina, silica 5 alumina, clays, montmorilonite. 'The catalyst obtained is useful for the synthesis of 2- and 4- picolines by heating acetaldehyde and ammonia in a ratio of 0.8 to 1.2 (w/w) at a temperature in the range of 300 to 500C. The amount of the catalyst is in the range of 5 to 15 wt % and the reaction is carried out preferably in a glass reactor. The reaction is carried out by maintaining weight hourly 10 space velocity of the feed, comprising of acetaldehyde and ammonia, between 0.1 to 10 g/g of catalyst (preferably 1 to 3). The pyridine bases and product obtained are analyzed by by known spectrochromatographic methods and the pyridine bases separated from the desired products by conventional fractional distillation. The novelty of the present invention lies in preparing the catalyst for the conversion 15 of acetaldehyde and ammonia to 2- and 4-picolines in an ecofriendly manner. This process avoids environmental pollution in comparison to prior art processes. The following examples are given by way of illustration of the present invention and should not be construed to limit the scope of the present invention. Example-i 20 Preparation of the Catalyst: Silica gel, mesh size 6-14, was used as the silica support. Phosphotungstic acid (10 g) was dissolved in water (25 ml) and the solution was mixed with silica gel (100 g). The slurry was stirred to get a uniform impregnation, dried in air at 200-250'C for one hr., then at 400'C for one hour, and finally cooled to room temperature in a desiccator. This catalyst was used for the reaction between acetaldehyde and 25 ammonia. The experiment was carried out in a downward flow glass reactor of internal diameter of 2 cm and of sufficient length which was kept in a furnace of length 32 cm. In the middle of the reactor was kept the catalyst (10 g) made and heated to 3 80"C with the help of a tubular electrical furnace. Acetaldehyde was fed at a rate of 9.5 ml/br and ammonia was fed at a rate 30 60 ml/min. The products formed in 2 hours were condensed in an ice cooled receiver, weighed and analyzed by gas chromatography (fitted with FID using 2 m x 3 mm SS column containing 30 % glycerol on chromosorb-p. The column temperature was maintained at 135'C and nitrogen flow was 30 ml/min.) Pure standard substances were-used for calibration. Conversion of acetaldehyde to picolines was found to be 50-60%. 5 WO 2005/063389 PCT/IN2003/000467 Example-2 Preparation of the Catalyst: Silica gel, mesh size 6-14, was used as the silica support. Silicotungstic acid (10 g) was dissolved in water (25 ml) and the solution was mixed with silica gel (100 g). The slurry was stirred to get a uniform impregnation, dried in air at 5 225'C for one hr., then at 400"C for one hour, and finally cooled to room temperature in a desiccator. This catalyst was used for the reaction between acetaldehyde and ammonia. The experiment was carried out in a downward flow glass reactor of internal diameter of 2 cm and of sufficient length which was kept in a furnace of length 32 cm. In the middle of the reactor was kept the catalyst (10 g) made and heated to 400*C with the help of a tubular 10 electrical furnace. Acetaldehyde was fed at a rate of 9.5 ml/hr and ammonia was fed at a rate 60 ml/min. The products formed in 2 hours were condensed in an ice cooled receiver, weighed and analyzed by gas chromatography (fitted with FID using 2 m x 3 mm stainless steel column containing 30 % glycerol on chromosorb-p. The column temperature was maintained at 135C and nitrogen flow was 30 ml/min.) Pure standard substances were used 15 for calibration. Conversion of acetaldehyde to picolines was found to be 55%. Example-3 Preparation of the Catalyst: Silica gel, mesh size 6-14, was used as the silica support. Vanadotungstic acid (10 g) was dissolved in water (25 ml) and the solution was mixed with silica gel (100 g). The slurry was stirred to get a uniform impregnation, dried in air at 20 210 0 C for one hr., then at 400'C for one hour, and finally cooled to room temperature in a desiccator. This catalyst was used for the reaction between acetaldehyde and ammonia. The experiment was carried out in a downward flow glass reactor of internal diameter of 2 cm and of sufficient length which was kept in a furnace of length 32 cm. In the middle of the reactor was kept the catalyst (10 g) made and heated to 370 0 C with the help of a tubular 25 electrical furnace. Acetaldehyde was fed at a rate of 9.5 ml/hr and ammonia was fed at a rate 60 ml/min. The products formed in 2 hours were condensed in an ice cooled receiver, weighed and analyzed by gas chromatography (fitted with FID using 2 m x 3 mm stainless steel column containing 30 % glycerol on chromosorb-p. The column temperature was maintained at 135 0 C and nitrogen flow was 30 ml/min.) Pure standard substances were used 30 for calibration. Conversion of acetaldehyde to picolines was found to be 70%. The main advantages of the present invention are: 1. The process is very simple and economic. 2. The catalyst preparation avoids tedious methods in comparison to prior art processes 6

Claims (12)

1. A process for the preparation of 2- and 4- Picolines which comprises providing a heteropoly acid catalyst selected from the group, consisting of a silicotungstic acids, phosphomolybdic acid and vanadotungstic acid provided on a support, and reacting 5 acetaldehyde and ammonia under heat in the presence of the catalyst being present in the range from 5 to 15 wt%, and separating the 2- and 4- picoline formed.
2. A process as claimed in claim 1 wherein the support is selected from the group consisting of silica gel, alumina, silica-alumina, clays and montmorillonite.
3. A process according to claim 1, further comprising dissolving the heteropoly acid 10 catalyst in distilled water; mixing the resulting mixture with desired amount of a support to obtain a slurry; stirring the slurry till uniform impregnation is achieved; drying the slurry in air at 200-250'C for a time period in the range of 0.5 to 1.5 hours; further heating the slurry at a temperature in the range of 300 to 400'C for a time period in the range of 0.5 to 1.5 hours and cooling the resultant product to room temperature in a 15 desiccator to get the desired catalyst.
4. A process as claimed in claim 3 wherein the support is selected from the group consisting of silica, alumina, silica-alumina, clays and montmorillonite.
5. A process as claimed in claim 3 wherein the heteropoly acid is dissolved in distilled water in a ratio of 0.5:4.5 (w/w). 20 6. A process as claimed in claim 3 wherein the support comprises silica gel of mesh size
6-14.
7. A process as claimed in claim 3 wherein the slurry is stirred for a time period in the range of 30-40 minutes.
8. A process as claimed in claim 1 wherein the acetaldehyde and ammonia are taken in a 25 ratio of 0.8 to 1,2 (w/w) and are reacted at a temperature in the range of 300 to 500'C.
9. A process as claimed in claim 1 wherein the reaction is carried out in a glass reactor. 7
10. A process as claimed in claim 1 wherein weight hourly space velocity of the acetaldehyde and ammonia is maintained in the range of 0.1 to 10 g/g of catalyst.
11. A process as claimed in claim 10 wherein the weight hourly space velocity of the acetaldehyde and ammonia is maintained in the range of 1 to 3 g/g of the catalyst. 5
12. A process as claimed in claim 1 wherein the 2- and 4-picolines are separated by fractional distillation. 8
AU2003300723A 2003-12-31 2003-12-31 Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst Ceased AU2003300723B2 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IN2003/000467 WO2005063389A1 (en) 2003-12-31 2003-12-31 Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst

Publications (2)

Publication Number Publication Date
AU2003300723A1 AU2003300723A1 (en) 2005-07-21
AU2003300723B2 true AU2003300723B2 (en) 2010-01-14

Family

ID=34717583

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2003300723A Ceased AU2003300723B2 (en) 2003-12-31 2003-12-31 Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst

Country Status (5)

Country Link
EP (1) EP1708811A1 (en)
CN (1) CN100448534C (en)
AU (1) AU2003300723B2 (en)
CA (1) CA2552158C (en)
WO (1) WO2005063389A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100446857C (en) * 2006-11-02 2008-12-31 武汉理工大学 Method for preparing heteropoly acid/ordered mesic porous silicon oxide catalyst, and its application
CN107983398B (en) * 2017-10-27 2020-07-17 苏州盖德精细材料有限公司 Production method of nano-attapulgite composite catalyst for preparing 3-methylpyridine
CN110586187B (en) * 2019-10-11 2022-05-13 沧州那瑞化学科技有限公司 Supported phosphotungstic acid catalyst, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463466A (en) * 1948-09-29 1949-03-01 Socony Vacuum Oil Co Inc Production of nitriles
WO1990003366A1 (en) * 1988-09-30 1990-04-05 Reilly Industries, Inc. Pyridine base synthesis process and catalyst for same
US5856575A (en) * 1997-01-22 1999-01-05 Council Of Scientific Industrial Research Process for the preparation of N-acetyl aminophenols

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9419387D0 (en) * 1994-09-26 1994-11-09 Bp Chem Int Ltd Olefin hydration process
CN1093000C (en) * 1996-12-27 2002-10-23 吉林化学工业公司研究院 Catalyst for ether pyrolysis isobutylene and applications
US5994550A (en) * 1998-12-30 1999-11-30 Mobil Oil Corporation Pyridine/picoline production process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2463466A (en) * 1948-09-29 1949-03-01 Socony Vacuum Oil Co Inc Production of nitriles
WO1990003366A1 (en) * 1988-09-30 1990-04-05 Reilly Industries, Inc. Pyridine base synthesis process and catalyst for same
US5856575A (en) * 1997-01-22 1999-01-05 Council Of Scientific Industrial Research Process for the preparation of N-acetyl aminophenols

Also Published As

Publication number Publication date
EP1708811A1 (en) 2006-10-11
CA2552158C (en) 2010-06-22
WO2005063389A1 (en) 2005-07-14
CA2552158A1 (en) 2005-07-14
AU2003300723A1 (en) 2005-07-21
CN100448534C (en) 2009-01-07
CN1886195A (en) 2006-12-27

Similar Documents

Publication Publication Date Title
JPS6325575B2 (en)
JP4426095B2 (en) Pyridine / picoline production method
EP0131887B1 (en) Improved process for preparing pyridine-type bases in a fluid bed using a crystalline aluminosilicate zeolite catalyst
AU2003300723B2 (en) Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst
US5780635A (en) Pyridine base synthesis
US7514559B2 (en) Catalyst for synthesis of 2- and 4-picolines
US6596872B2 (en) Process for preparing alkenyl-substituted heterocycles
JPS6048501B2 (en) Method for producing N-alkyl aromatic amine
RU2328343C2 (en) Catalyst for synthesising 2-and 4-picolines, method for producing 2-and 4-picolines and method for producing catalyst
NZ548652A (en) Catalyst for synthesis of 2-and 4-picolines, process for preparing 2- and 4-picoline and process for preparing the catalyst
US6118003A (en) Processes for producing 3-cyanopyridine from 2-methyl-1,5-pentanediamine
JP3132062B2 (en) Process for producing triethylenediamines and piperazines
US20040087799A1 (en) Process for the preparation of vinylpyridine from picoline over modified zeolites
US4395554A (en) Process for producing alpha-picoline
US5994562A (en) Preparation of N-alkenylcarboxamides
EP1347961B1 (en) A process for the preparation of a collidine and 2,3,5,6-tetramethyl pyridine
EP0371615B1 (en) High yield synthesis of pyridine and/or alkylpyridine(s) via condensation of ternary mixtures of aldehydes and/or ketones with ammonia
CN116063225A (en) Process for synthesizing 2-methylpyridine from aniline
US6492524B1 (en) Process for the synthesis of an aryl pyridine base using a zeolite catalyst
JPH0674254B2 (en) Process for producing pyrazine derivative
EP4149675A1 (en) Process and catalyst for the preparation of ethylene
SU761464A1 (en) Method of preparing alkylpyridines
JPH06157409A (en) Production of carbonic acid oxyethylmethyl ester
WO1998032737A1 (en) Processes for producing 3-cyanopyridine from 2-methyl-1,5-pentanediamine
EP1373209B1 (en) A process for the synthesis of an aryl pyridine base using a zeolite catalyst

Legal Events

Date Code Title Description
MK5 Application lapsed section 142(2)(e) - patent request and compl. specification not accepted
NA Applications received for extensions of time, section 223

Free format text: AN APPLICATION TO EXTEND THE TIME FROM 26 APR 2009 TO 26 JAN 2011 IN WHICH TO GAIN ACCEPTANCE HAS BEEN FILED .

NB Applications allowed - extensions of time section 223(2)

Free format text: THE TIME IN WHICH TO GAIN ACCEPTANCE HAS BEEN EXTENDED TO 26 JAN 2011.

FGA Letters patent sealed or granted (standard patent)
MK14 Patent ceased section 143(a) (annual fees not paid) or expired