DE1903878A1 - Process for the production of pyridine and ss-picoline - Google Patents
Process for the production of pyridine and ss-picolineInfo
- Publication number
- DE1903878A1 DE1903878A1 DE19691903878 DE1903878A DE1903878A1 DE 1903878 A1 DE1903878 A1 DE 1903878A1 DE 19691903878 DE19691903878 DE 19691903878 DE 1903878 A DE1903878 A DE 1903878A DE 1903878 A1 DE1903878 A1 DE 1903878A1
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- alumina
- silica
- pyridine
- reaction
- 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.)
- Pending
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 9
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 20
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 150000001661 cadmium Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C07D213/06—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
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
dr. v. Schmied-Ko wARzi κ · dr.p. Wein hold 1 9 Q 3878dr. v. Schmied-Ko wARzi κ · dr.p. Wein hold 1 9 Q 3878
CH 2497 · 25. Januar ,1969CH 2497 January 25, 1969
Wd/BeWd / Be
BP CHMICALS (U.K.) LIMITED,BP CHMICALS (U.K.) LIMITED,
Britannic House, Moor lane,Britannic House, Moor lane,
London. E.C. 2 / EnglandLondon. E.C. 2 / England
"Verfahren zur Herstellung von Pyridin und ß-Picolin"" Process for the production of pyridine and ß-picoline"
Die vorliegende Erfindung bezieht sich auf die Herstellung von Pyridinbasen, insbesondere Pyridin und ß-Picolin.The present invention relates to the preparation of pyridine bases, in particular pyridine and β-picoline.
Aus der britischen Patentschrift 742 643 ist bekannt, daß Formaldehyd, Acetaldehyd und Ammoniak in der Dampfphase bei erhöhter Temperatur über einen Kiesel- oder Tonerde-Katalysator zu Pyridin und ß-Picol'in umgesetzt werden können. Aus der britischen Patentschrift 1 070 664 ist ebenfalls bekannt, daß durch Zumischen von Sauerstoff in die Reaktionsmischung die Ausbeute an Pyridin auf Kosten von ß-Picolin erhöht wird.From British patent specification 742 643 it is known that formaldehyde, acetaldehyde and ammonia in the vapor phase elevated temperature can be converted to pyridine and ß-picol'in via a silica or alumina catalyst. From the British Patent 1,070,664 is also known to have by adding oxygen to the reaction mixture, the pyridine yield is increased at the expense of β-picoline.
Die vorliegende Erfindung betrifft ein Verfahren zur· Herstellung von. Pyridin und ß-Picolin durch Umsetzung von Form-, Acetaldehyd und Ammoniak in der Dampfphase bei erhöhter Temperatur über einen Wirbelbettkatalysator ohne Anwesenheit von Sauerstoff.The present invention relates to a method of manufacture from. Pyridine and ß-picoline by reaction of form, acetaldehyde and ammonia in the vapor phase at elevated temperature over a fluidized bed catalyst without the presence of oxygen.
Das Verfahren wird vorzugsweise durchgeführt, indem die Beschikkung aus Formaldehyd und Acetaldehyd getrennt oder als Mischung vorerhitzt wird, wobei die Mischung auf die erhöhte Reaktionsteta0eratur gehalten und das vorzugsweise vorerhitzte Ammoniak unmittelbar vor der Be^ührunK^mit dem Katalysatorbett zugegebenThe process is preferably carried out by the loading is separated from formaldehyde and acetaldehyde or preheated as a mixture, the mixture to the increased reaction temperature and the ammonia, which is preferably preheated, is added immediately prior to the contact with the catalyst bed
Eine sehr zweckmäßige Methode für die Zuführung von Formaldehyd ist, das Formaldehyd oder ein Polymerisat des Formaldehyds in einem geeigneten Lösungsmittel, z.B. in Alkohol, vorzugsweise Methanol oder Wasser, zu lösen. Die verwendete Menge des Lösungsmittels sollte auf ein Minimum gehalten werden, so daß das verdampfte Lösungsmittel auch - . den Reaktor passieren kann. Die Reaküon kann innerhalb eines großen Temperaturbereiches erfolgen, z.B. etwa bei 300 - 55O0C, vorzugsweise jedoch zwischen etwa 350 - 500°0.A very useful method for adding formaldehyde is to dissolve the formaldehyde or a polymer of formaldehyde in a suitable solvent, for example in alcohol, preferably methanol or water. The amount of solvent used should be kept to a minimum so that the evaporated solvent also -. can pass the reactor. The Reaküon can be carried out within a wide temperature range, eg about 300 - 55O 0 C, but preferably between about 350 - 500 ° 0th
Die Reaktion kann bei unteratmosphärischem oder überatmosphärischem Druck durchgeführt werden. Die Anwendung eines im wesentlichen atmosphärischen Drucks wird jedoch bevorzugt. The reaction can be subatmospheric or superatmospheric Printing can be carried out. However, the use of substantially atmospheric pressure is preferred.
Die Kontaktzeit des Verfahrens kann innerhalb weiter Grenzen variieren, aber es ist normalerweise nicht notwendig,'50 Sekunden bei normaler Temperatur und Druck auf der Grundlage des fesistehenden Volumens des Katalysatorbettes zu überschreiten.The contact time of the procedure can be within wide limits vary, but it is usually not necessary based on the '50 seconds at normal temperature and pressure Exceeding fixed volume of the catalyst bed.
Bin Bereich von etwa 0,5 Sek. bis 50 Sek. wird bevorzugt.A range of about 0.5 seconds to 50 seconds is preferred.
Das Molverhältnis von Acetaldehyd zu Formaldehyd kann z.B. zwischen etwa 5 : 1 und 1:2, vorzugsweise jedoch zwischen etwa 3 : 1 und 1 :_1»5 stark variieren. Das Molverhältnis der gesamten Aldehyde' zu Ammoniak kann auch sehr variieren, z.B. zwischen etwa 4 : 1 und 1:5, wobei ein Molverhältnis zwischen etwa 2 : 1 und 1 : 3 besonders bevorzugt wird.The molar ratio of acetaldehyde to formaldehyde can e.g. vary greatly between about 5: 1 and 1: 2, but preferably between about 3: 1 and 1: 1 »5. The molar ratio of total aldehydes to ammonia can also vary widely, e.g. between about 4: 1 and 1: 5, with a molar ratio between about 2: 1 and 1: 3 is particularly preferred.
Das Acetaldehyd und das Formaldehyd können teilweise oder ganz durch eine äquivalente Menge einer Verbindung, die Acetaldehyd oder Formaldehyd unter- den Reaktionsbedingungen" ■■bildet, ersetzt werden. Beispiele solcher Verbindungen.sind: ?araldehyd, das Acetaldehyd freisetzt und MethyIaI, Paraformaldehyd, Methanol atid Trioxan« welche zur Bildung vonThe acetaldehyde and the formaldehyde can be partially or entirely by an equivalent amount of a compound containing acetaldehyde or formaldehyde under the reaction conditions " ■■ forms, to be replaced. Examples of such connections are: araldehyde, which releases acetaldehyde, and methyIaI, paraformaldehyde, Methanol atide Trioxane «which leads to the formation of
909 83 7/1537909 83 7/1537
Formaldehyd führen. Die genannten Molverhältnisse sind auch in solchen Fällen anwendbar, müssen dann aber natürlich auf der Grundlage der Acetaldehyd- oder Formaldehyd-Äquivalente errechnet werden.Formaldehyde. The mentioned molar ratios can also be used in such cases, but then of course they must calculated on the basis of acetaldehyde or formaldehyde equivalents.
Die für das erfindungsgemäße Verfahren geeigneten Katalysatoren sind solche, die als Dehydratisierungs- und/oder Krackkatalysatoren angesehen werden. Zu geeigneten Katalysatoren dieser Gruppe zählen z.B. Tonerde, Kieselerde/Tonerde, Kieselerde/ Magnesia oder Kieselerde/TonerdeAiagnesia. Metalle oder Verbin- " düngen der Metalle oder Ammoniumsalze in Anwesenheit von Dehydratisierungs- oder Krackkatalysatoren, insbesondere in Anwesenheit von Tonerde oder Kieselerde/Tonerde, können sehr wirksam sein, wenn sie bei der Umsetzungstemperatur stabil sind. Geeignete Metalle sind z.B. Zink, Cadmium, Zinn, Blei, Wolfram, Nickel, Kobalt, Chrom, Molybdän, Eisen, Kupfer, Palladium und Silber. Bevorzugte Verbindungen sind Palladium und Silber und Zink-, Cadmium-, Zinn- und Bleioxyde und -fluoride sollen besonders erwähnt "werden. Geeignete Ammoniumsalze sind Ammoniumfluorid und Ammoniumhydrogenbifluorid.The catalysts suitable for the process according to the invention are what are considered to be dehydration and / or cracking catalysts. To suitable catalysts this Groups include e.g. alumina, silica / alumina, silica / magnesia or silica / alumina-alumina. Metals or compounds " fertilize the metals or ammonium salts in the presence of dehydration or cracking catalysts, especially in the presence of alumina or silica / alumina, can do a lot be effective if they are stable at the reaction temperature. Suitable metals are e.g. zinc, cadmium, tin, lead, tungsten, Nickel, cobalt, chromium, molybdenum, iron, copper, palladium and silver. Preferred compounds are palladium and silver and Zinc, cadmium, tin and lead oxides and fluorides should be specially mentioned. Suitable ammonium salts are ammonium fluoride and ammonium hydrogen bifluoride.
Ein bevorzugter Katalysator umfaßt Kieselerde/Tonerde allein Λ oder in Verbindung mit einem oder mehreren der erwähnten anderen Oxyde oder Salze. Die Menge an Tonerde kann etwa 5 bis 50 f> , vorzugsweise etwa 7 bis 2550, betragen, wobei der Rest Kieselerde ist. Der Katalysator kann dann gegebenenfalls weiter behandelt werden.A preferred catalyst comprises silica / alumina alone Λ or in conjunction with one or more of the said other oxides or salts. The amount of clay can be from about 5 to 50 % , preferably from about 7 to 2550, with the remainder being silica. The catalyst can then optionally be treated further.
Gegebenenfalls kann auch der geeignete Katalysator mit einer Verbindung oder Verbindungen von einem oder mehreren Elementen
imprägniert werden, die dann - falls dies gewünscht ist in die Oxyde oder in ein stabiles Salz zum Beispiel durch Behandlung
mit Ammoniumfluorid oder Ammoniumhydrogenbifluorid urajewandelt werden.
+) baw. Siliziumoxyd = "silica"If necessary, the suitable catalyst can also be impregnated with a compound or compounds of one or more elements which, if desired, are then ura-converted into the oxides or into a stable salt, for example by treatment with ammonium fluoride or ammonium hydrogen bifluoride.
+) baw. Silicon oxide = "silica"
909837/1537909837/1537
Katalysatoren können zum Beispiel hergestellt werden., indem. Tonerde oder Kieselerde/Tonerde mit einem Nitrat oder anderen löslichen Salz von einem der gewünschteA Metalle in wässriger Lösung imprägniert wird, worauf das Material getrocknet und "bei etwa 40O0C in einem Langsamluft st rom erhitzt wird. In geeigneten Fällen kann das getrocknete Material mit wässrigem Ammoniumfluorid oder Ammoniumhydrogenbifluorid behandelt, von löslichen Salzen freigewaschen, wieder getrocknet und bei Temperaturen von etwa 4OO - 500 C mehrere Stunden lang erhitzt werden. Katalysatoren können auch hergestellt werden, indem Tonerde oder Kieselerde/Tonerde mit Fluorwasserstoff, Ammoniumhydrogenbifluorid oder Ammoniumfluorid allein behandelt wird.Catalysts can be prepared, for example, by. Alumina or silica / alumina is impregnated with a nitrate or other soluble salt of one of the desired metals in aqueous solution, whereupon the material is dried and heated at about 40O 0 C in a slow air stream. In appropriate cases, the dried material can with treated with aqueous ammonium fluoride or ammonium hydrogen bifluoride, washed free of soluble salts, dried again and heated for several hours at temperatures of about 400-500 C. Catalysts can also be produced by treating alumina or silica / alumina with hydrogen fluoride, ammonium hydrogen bifluoride or ammonium fluoride alone.
Die Erfindung wird durch die folgenden Beispiele näher erläu*-The invention is explained in more detail by the following examples
tert:-tert: -
Beispiele 1 bis 7 , .· Examples 1 to 7 ,. ·
Formaldehyd, Acetaldehyd und Ammoniak wurden zusammen in ein Reaktionsgefäß, das von einem Bad aus geschmolzenem Salz umgeben ist, zur Reaktion gebracht. Der Katalysator bestand aus Kieselerde/Tonerde (Typ MS 13/68, J. Crosfield & Son Ltd) in Form eines Wirbelbetts. Für Yergleichszwecke wurde in den Beispielen 1, 3 und 5 ein Kieselerde/Tonerde Katalysator als Festbett (Typ HS 46, Houdry Process Corporation) verwendet. Die Reaktionsbedingungen und Ergebnisse sind in. der Tabelle angegeben.Formaldehyde, acetaldehyde, and ammonia have been brought together in a reaction vessel, which is surrounded by a bath of molten S a lz to the reaction. The catalyst consisted of silica / alumina (type MS 13/68, J. Crosfield & Son Ltd) in the form of a fluidized bed. For comparison purposes, a silica / alumina catalyst was used as a fixed bed (type HS 46, Houdry Process Corporation) in Examples 1, 3 and 5. The reaction conditions and results are given in the table.
9 0£837/159 0 £ 837/15
TABELlSTABLES
Pyridin Und ß-Picolia aus Pormaldehyd/Acetaldehyd/AmaoniakPyridine and ß-Picolia from formaldehyde / acetaldehyde / ammonia
O to
O
I0.46
I.
ml?* ω
ml? *
CD <O LO OOCD <O LO OO
Claims (7)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB437868A GB1188891A (en) | 1968-01-27 | 1968-01-27 | Picolines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1903878A1 true DE1903878A1 (en) | 1969-09-11 |
Family
ID=9776040
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691903878 Pending DE1903878A1 (en) | 1968-01-27 | 1969-01-27 | Process for the production of pyridine and ss-picoline |
| DE19691903879 Pending DE1903879A1 (en) | 1968-01-27 | 1969-01-27 | Process for the production of alpha and gamma picoline |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691903879 Pending DE1903879A1 (en) | 1968-01-27 | 1969-01-27 | Process for the production of alpha and gamma picoline |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE727469A (en) |
| DE (2) | DE1903878A1 (en) |
| FR (1) | FR2000862A1 (en) |
| GB (1) | GB1188891A (en) |
| NL (2) | NL6900935A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS491568A (en) * | 1972-05-02 | 1974-01-08 | ||
| EP0040698A1 (en) * | 1980-05-23 | 1981-12-02 | Lonza Ag | Process for the preparation of 3-picoline |
| EP0131887A1 (en) * | 1983-07-11 | 1985-01-23 | Nepera, Inc. | Improved process for preparing pyridine-type bases in a fluid bed using a crystalline aluminosilicate zeolite catalyst |
| US5218122A (en) * | 1988-09-30 | 1993-06-08 | Reilly Industries, Inc. | Pyridine base synthesis process and catalyst for same |
| WO2021086679A1 (en) | 2019-10-29 | 2021-05-06 | W.R. Grace & Co.-Conn. | Modified zeolite catalyst compositions and methods of use |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3946020A (en) * | 1970-12-28 | 1976-03-23 | Koei Chemical Co., Ltd. | Process for producing pyridine bases |
| DE3581244D1 (en) * | 1984-08-31 | 1991-02-14 | Toyota Motor Co Ltd | ROOF HATCH ARRANGEMENT FOR VEHICLES. |
| CA1333793C (en) * | 1988-09-30 | 1995-01-03 | Gerald L. Goe | Pyridine base synthesis process and catalyst for same |
-
1968
- 1968-01-27 GB GB437868A patent/GB1188891A/en not_active Expired
-
1969
- 1969-01-20 NL NL6900935A patent/NL6900935A/xx unknown
- 1969-01-21 NL NL6900997A patent/NL6900997A/xx unknown
- 1969-01-27 DE DE19691903878 patent/DE1903878A1/en active Pending
- 1969-01-27 DE DE19691903879 patent/DE1903879A1/en active Pending
- 1969-01-27 BE BE727469D patent/BE727469A/xx unknown
- 1969-01-27 FR FR6901494A patent/FR2000862A1/fr not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS491568A (en) * | 1972-05-02 | 1974-01-08 | ||
| JPS5347111B2 (en) * | 1972-05-02 | 1978-12-19 | ||
| EP0040698A1 (en) * | 1980-05-23 | 1981-12-02 | Lonza Ag | Process for the preparation of 3-picoline |
| US4337342A (en) * | 1980-05-23 | 1982-06-29 | Lonza Ltd. | Process for the preparation of 3-picoline |
| EP0131887A1 (en) * | 1983-07-11 | 1985-01-23 | Nepera, Inc. | Improved process for preparing pyridine-type bases in a fluid bed using a crystalline aluminosilicate zeolite catalyst |
| US5218122A (en) * | 1988-09-30 | 1993-06-08 | Reilly Industries, Inc. | Pyridine base synthesis process and catalyst for same |
| WO2021086679A1 (en) | 2019-10-29 | 2021-05-06 | W.R. Grace & Co.-Conn. | Modified zeolite catalyst compositions and methods of use |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1903879A1 (en) | 1969-10-30 |
| GB1188891A (en) | 1970-04-22 |
| BE727469A (en) | 1969-07-28 |
| NL6900997A (en) | 1969-07-29 |
| NL6900935A (en) | 1969-07-29 |
| FR2000862A1 (en) | 1969-09-12 |
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