US2934537A - Process of preparing pyridine and 3-picoline - Google Patents
Process of preparing pyridine and 3-picoline Download PDFInfo
- Publication number
- US2934537A US2934537A US410044A US41004454A US2934537A US 2934537 A US2934537 A US 2934537A US 410044 A US410044 A US 410044A US 41004454 A US41004454 A US 41004454A US 2934537 A US2934537 A US 2934537A
- Authority
- US
- United States
- Prior art keywords
- pyridine
- picoline
- ammonia
- acetylene
- formaldehyde
- 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.)
- Expired - Lifetime
Links
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims description 110
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 30
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 title description 60
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 57
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 29
- 229910021529 ammonia Inorganic materials 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 7
- 239000011369 resultant mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 45
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 26
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 23
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- 239000008246 gaseous mixture Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 238000004508 fractional distillation Methods 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- -1 aliphatic aldehydes Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- PITMOJXAHYPVLG-UHFFFAOYSA-N 2-acetyloxybenzoic acid;n-(4-ethoxyphenyl)acetamide;1,3,7-trimethylpurine-2,6-dione Chemical compound CCOC1=CC=C(NC(C)=O)C=C1.CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C PITMOJXAHYPVLG-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- GLPMHULIKFGNIJ-UHFFFAOYSA-N cadmium(2+);dioxido(dioxo)chromium Chemical compound [Cd+2].[O-][Cr]([O-])(=O)=O GLPMHULIKFGNIJ-UHFFFAOYSA-N 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910000286 fullers earth Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
Definitions
- Pyridine is obtained commercially as a by-product of the coal-tar industry.
- the manufacture of coal-tar, coke, and related products starts with the placing of coal into a chamber and heating it out of contact with air.
- the coal is thereby decomposed into volatile products and into a non-volatile residue, coke.
- the volatile products composed of condensable materials and non-condensable gases, are removed from the carbonization chamber and cooled, thereby condensing water and tar.
- the remaining gas is passed through a preheater and then to a saturator. In the saturator the gas is contacted with dilute sulfuric acid.
- Ammonia and pyridine bases present in the gas are absorbed by the dilute sulfuric acid (about 6% H 80
- the pyridine bases continue being absorbed until their concentration in the saturator bath Pyridine 115 .8 2-picoline 129.5 3 -picoline cut 143.6 Denaturing pyridine Up to 165
- the 3-picoline cut is composed of about equal parts of 3-picoline (B.P. 143.9 C.), 4-picoline (B.P. 144.9 C.), and 2,6-lutidine (B.P. 143.7 C.). Because the boiling points of these three methylpyridines are so close together, it is not possible to separate them from each other by fractional distillation.
- the patent literature is replete with processes for isolating one or more of these compounds from the 3-picoline cut; all are complicated processes and with one exception are not commercially practicable.
- condensates which usually comprise two layers, the oily layer consisting mainly of heterocyclic bases which are difficultly soluble in water, such as collidines, lutidines, and quinolines, while the aqueous layer contains mainly water-soluble pyridine derivatives, in particular picoline, (page 3, column 2, lines 114-121).
- the reactor used may be of various types. We prefer the fluid catalyst type, similar to those normally used in carrying out cracking operations in the petroleum industry. Such reactors are of tubular form with suitable connections at entrance and exit. They are provided with means for supporting the fluid bed of catalyst, and are provided with any convenient means for heating them.
- Example 1 We prepared a gaseous mixture composed of about zinc fluoride, the catalyst was finely divided, and all of r picolines were recovered from the condensate by fractional distillation. The pyridine obtained amounted to about 0.25 pound for each pound of formaldehyde passed through the reactor.
- Example 2 We prepared a gaseous mixture composed of one mole of acetylene, one mole of ammonia, and three moles of formaldehyde.
- a fluid catalyst type of reactor containing a fluidized catalytic bed of activated alumina (Alorco H-41) which had been impregnated with 10% zinc fluoride.
- the temperature of the reactor was maintained at about 425 C.
- the gaseous mixture of acetylene, ammonia, and formaldehyde was passed through at a superficial velocity of 1.25 feet per second.
- a reaction occurred whereby pyridine and 3-picoline were produced.
- the vapors of the unchanged reactants and the reaction products were condensed as they emerged from the reactor, and the condensate was collected in a suitable receiver.
- the condensate was composed fy pyridine compounds and non-basic or neutral compounds. In order to separate these two groups of compounds, the condensate was acidified to a pH of, 1 with sulfuric acid.
- pyridine base compounds present dissolved in the dilute sulfuric acid solution.
- the non-basic compounds were insoluble and formed a layer on top of the sulfuric acid solution. These were'separated by decantation. The last traces of non-basic compounds were removed by steaming the sulfuric acid solution.
- the sulfuric acid solution freed of non-basic contaminants was made strongly alkaline (pH 12.0) by the addition of sodium hydroxide.
- Pyridine bases separated from this strongly alkaline solution. They were removed by decantation. Any small amount of pyridines remaining in the alkaline solution were recovered by steam distillation and combined with the previously separated bases. After drying with flake caustic soda, the pyridine bases were fractionated to recover pyridine and 3-picoline.
- Example 3 The process of Example 2 was repeated with the exception that the gaseous mixture passed through the reactor was composed of one mole of acetylene, one mole of ammonia, and one mole of formaldehyde.
- the pyridine bases recovered were subjected to fractional distillation. The pyridine recovered amounted to about 20%.
- the 3-picoline fraction amounted to about 18%; as obtained from the fractionating column, the 3-picoline had a purity of about indicating that 4-picoline was formed to some extent.
- 2-picoline was recovered in an amount of about 9%
- Example 4 The process of Example 2 was repeated with the exception that the gaseousmixture passed through the reactor was composed of one mole of acetylene and one mole of ammonia; no formaldehyde was used.
- the pyrdine bases obtained were subjected to fractional distillation. No pyridine was recovered.
- 2-picoline was recovered in an amount of 32.0%.
- 4-picoline was recovered in an amount of 28.0%; the 4-picoline had a purity of 93%, clearly indicating that little if any 3-picoline was formed.
- Example 5 The process of Example 3 was repeated with the exception that the gaseous mixture passed through the reactor was composed of two moles acetylene, two moles ammonia, and one mole of formaldehyde.
- the pyridine bases recovered were subjected to fractional distillation.
- the pyridine recovered amounted to about 14%.
- the 3-picoline fraction amounted to about 17%; the 3-picoline as obtained from the fractionating column had a purity of about 50% indicating that as much 4-picoline was formed as there was of 3-picoline.
- the 2-picoline recovered amounted to about 16%.
- Example 6 A zinc zeolite catalyst was prepared in the following manner. A four-inch diameter porcelain tube eight feet long was mounted vertically and filled with distilled water. Then 21.75 pounds of Decalso Permutit was slowly added to form an ion exchange bed approximately inches long.- A zinc chloride solution (3.5 pounds of zinc chloride and pounds of water) was flowed downward over the Permutit in order to replace zeolitic sodium by zinc ion. The zeolite'waswashed with 20 pounds of distilled water, drained, and placed in a drying oven. The zinc zeolite was dried for about 72 hours at 85 C. 7 It was then ground to 65 mesh and finer. (Decalso Permutit is a synthetic sodium-alumino-silicate used for water softening.)
- Example 2 The process of Example 2 was repeated with the following exceptions.
- the zinc zeolite catalyst prepared above was used.
- the temperature of the reactor was maintained at 425 C.
- the gaseous mixture passed through the reactor was composed of two moles of acetylene, two moles of ammonia, and one mole of formaldehyde.
- the pyridine content of the water-free reaction product was about 29%.
- the 3 picoline fraction amounted to about 24%; as obtained from the fractionating column, the 3-picoline had a purity of about 50% indicating that 4-picoline was also formed.
- Example 7 A gaseous mixture composed of one mole of acetylene, one mole of ammonia, and three moles of formaldehyde was passed through a suitable reactor containing a fluidized catalytic bed of activated alumina which had been impregnated with cadmium fluoride, the catalyst was finely divided, and all of it passed through 65 mesh. The reactor was maintained at a temperature of about 425 435 C. As the mixture of reactants passed through the reactor, a reaction occurred producing pyridine and 3-.picoline. The vapors of the unchanged reactants and the reaction products were condensed as they emerged from the reactor; the condensate was collected in a suitable receiver. The pyridine and the picolines were isolated from the condensate by fractional distillation. The pyridine content of the reaction product was about 20.9%. The 3-picoline amounted to about it was about 95% pure.
- Example 8 The process of Example 7 was repeated with the exception that the catalyst used was a silica-magnesia catalyst impregnated with 10% zinc fluoride.
- the pyridine in the reaction product amounted to 19%.
- the yield of reaction product was about 0.50 to 0.60 pound per pound of acetylene passed through the reactor.
- Example 9 A zinc Filtrol catalyst was prepared as follows:
- Filtrol 58 which is a grade of montmorillonite clay having an amorphous or gel structure
- a zinc chloride solution (227 grams of anhydrous zinc chloride was dissolved in 17 pounds of distilled water) was poured over the Filtrol.
- a slurry was made by stirring for about one hour. The solids were removed from the slurry by filtration. The residue was removed from the filter and returned to the glass container. It was treated again with a zinc chloride solution prepared as mentioned above. The resulting slurry was filtered again. This process of slurrying the Filtrol and removing the aqueous solution was repeated fifteen times.
- the zinc Filtrol was thoroughly washed with distilled water. It was then dried in an oven and ground. Analyses on the thus-prepared catalyst showed it to contain about 2.5% zinc.
- Example 7 The process of Example 7 was repeated with the exception that the above prepared zinc Filtrol was used as catalyst.
- the condensate obtained was subjected to fractional distillation through an efiicient fractionating column to recover pyridine and 3-picoline.
- the pyridine recovered amounted to about 7.9%.
- the 3-picoline recovered amounted to about 11%; as recovered from the fractionating column, the purity of the 3-picoline was more than 95%.
- Example 10 The process of Example 6 was repeated with the exception that the catalyst used was alumina impregnated with 10% cupric chloride.
- the pyridine content of the condensate was about 14.8%.
- the condensate amounted to about 0.35 to 0.40 pound per pound of acetylene used.
- Example 11 instead of using acetylene, we can use the hydrated form of acetylene, i.e. acetaldehyde.
- acetaldehyde i.e. acetaldehyde.
- the yields of pyridine, 3-picoline, and of 2-picolirie were as indicated in Example 2.
- the silica magnesia, the Filtrol, and the zeolite as catalyst supports, we may use other catalyst supports, such as fullers earth, pumice, silica, and the like.
- the cupric chloride, and the cadmium fluoride we may utilize other catalysts, such as zinc chloride, cadmium chromate, cadmium molybdenate, lead chromate, zinc phosphate, and the like.
- other catalysts such as zinc chloride, cadmium chromate, cadmium molybdenate, lead chromate, zinc phosphate, and the like.
- acetylene, ammonia, and formaldehyde we may use the catalysts that have been found useful in the preparation of picolines from acetylene and ammonia.
- the proportions of the reactants may be varied widely. It is important, however, to have all three reactants present if pyridine is to be formed in any appreciable amount.
- the temperature at which the reaction is conducted may be varied widely. In general, we prefer to have the reaction temperature above about 400 C. and below about 500 C. It has been our experience that at temperatures below about 400 C., we have too large a proportion of the reactants passing through without reacting. At temperatures above about 500 C., we find that our catalyst becomes inactivated more rapidly and we obtain too many side reactions.
- the process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising an activated alumina impregnated with Zinc fluoride maintained at a temperature between about 400 C. and about 500 C. and recovering pyridine from the reaction product.
- the process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 400 C. and about 500 C. and recovering pyridine from the reaction product.
- the process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 470 C. and 480 C., and recovering pyridine from the reaction product.
- the process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 415 C. and 425 C., and recovering pyridine from the reaction product.
- the process of preparing pyridine which comprises preparing a gaseous mixture composed of about two parts of acetylene, of about four and one-half parts of ammonia, and of about one part of formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 470 C. and 480 C., and recovering pyridine from the reaction product.
- the process of preparing pyridine which comprises preparing a gaseous mixture composed of about two parts of acetylene, of about four and one-half parts of ammonia, and of about one part of formaldehyde, passing 7 the resultant rlnixturecthrough a reactor containing a i FOREIGN PATENTS catalyst comprlsmg actlvated alumma impregnated wlth 525,652 V'G "In"- June 9, 1931 10% Zinc fluoride maintained at a temperature between abbut'415 C. and 425 C. and recovering pyridine from 3 Great Brltam July 1930 the reaction product. 5 534,494 Great Britain Mar.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
PROCESS OF PREPARING PYRIDINE AND 3-PICOLINE Francis Cislak and William R. Wheeler,
Indianapolis, Ind.
N Drawing. Application February 12, 1954 Serial No. 410,044
6 Claims. (Cl. 260-290) Our present invention, which is a continuation in part of our co-pending application Serial No. 198,233, filed November 29, 1950, now abandoned, relates to a process of preparing pyridine and 3-picoline. More specifically, it relates to a process of preparing pyridine and 3-picoline by the interaction of acetylene, ammonia, and formaldehyde.
Pyridine is obtained commercially as a by-product of the coal-tar industry. The manufacture of coal-tar, coke, and related products starts with the placing of coal into a chamber and heating it out of contact with air. The coal is thereby decomposed into volatile products and into a non-volatile residue, coke. The volatile products, composed of condensable materials and non-condensable gases, are removed from the carbonization chamber and cooled, thereby condensing water and tar. After the complete removal of the water and tar, the remaining gas is passed through a preheater and then to a saturator. In the saturator the gas is contacted with dilute sulfuric acid. Ammonia and pyridine bases present in the gas are absorbed by the dilute sulfuric acid (about 6% H 80 The pyridine bases continue being absorbed until their concentration in the saturator bath Pyridine 115 .8 2-picoline 129.5 3 -picoline cut 143.6 Denaturing pyridine Up to 165 The 3-picoline cut is composed of about equal parts of 3-picoline (B.P. 143.9 C.), 4-picoline (B.P. 144.9 C.), and 2,6-lutidine (B.P. 143.7 C.). Because the boiling points of these three methylpyridines are so close together, it is not possible to separate them from each other by fractional distillation. The patent literature is replete with processes for isolating one or more of these compounds from the 3-picoline cut; all are complicated processes and with one exception are not commercially practicable.
The amount of pyridines that is normally obtainable as a by-product of coal carbonization is limited. At the present time, the amount is further curtailed because of economic considerations. The recovery of pyridine bases is incidental to the manufacture of ammonium sulfate. Unless there is a market. for the ammonium sulfate, it is unprofitable to recover pyridine bases from coke oven gases. Today, some of the largest producers of coal tar have discontinued recovering pyridine bases. The mar- 2,934,537 Patented Apr. 26, 1960 ket for ammonium sulfate has gradually shrunk, until now it is difficult to sell more than a small amount of that which is potentially available. With the steady increase in the use of anhydrous ammonia as a fertilizer, it is expected that the demand for ammonium sulfate will continue to decline.
For a number of years the demand for pyridines has exceeded the supply. If this demand is to be satisfied, it is imperative that a new source of pyridine be found. Many attempts have been made to synthesize pyridine bases. Some of the prior art describes processes for the synthesis of various alkylpyridines. Thus, British Patent 332,623, dated October 4, 1929, describes a process of catalytically condensing unsaturated hydrocarbons such as ethylene, butadiene, or in particular acetylene, or mixtures containing these substances, with ammonia (page 3, column 1, lines 19-23). By this process condensates are obtained which usually comprise two layers, the oily layer consisting mainly of heterocyclic bases which are difficultly soluble in water, such as collidines, lutidines, and quinolines, while the aqueous layer contains mainly water-soluble pyridine derivatives, in particular picoline, (page 3, column 2, lines 114-121).
British Patent 534,494, dated August 26, 1940, in discussing the process of the above mentioned British Patent 332,623 states that the process is not industrially useful as the yields of the bases obtained have been low and, large amounts of resins and other industrial by-products have been invariably formed. (page 2, column 1, lines 32-37.) Then the British Patent 534,- 494 goes on to describe a process for the manufacture of Z-methyl-S-ethylpyridine which consists in reacting in the liquid phase at temperatures between and 250 C. aliphatic aldehydes and ammonia or aliphatic amines Sufficient pressure must be used to maintain the reactants in the liquid phase at the temperature employed. (Page 2, column 1, lines 44-54).
US. Patent 1,882,518, dated October 11, 1932, describes a process of reacting acetylene with ammonia to prepare 2- and 4-methylpyridines as well as polymethylpyridines.
In spite of the years of research that have been devoted to the study of pyridine synthesis, no one has heretofore developed a commercial process for the simultaneous preparation of pyridine and 3-picoline.
We have found that we can react formaldehyde, acetylene, and ammonia to form pyridine and 3-picoline. Furthermore, we have found that we can so control the reaction that practically no Z-picoline or 4-picoline is formed. In other words, we can make 3-picoline which is uncontaminated by 4-picoline.
Our discovery is contrary to almost a century of prior art teaching. Formaldehyde and ammonia react to form hexamethylenetetramine in quantitative yield. This reaction which was first observed by Butlerov (1860) was later studied by Duden and Scharf, Eschweiler, and many other investigators. Its formation and structure are indicated in the equation shown below:
on, t
HEC CH methylene tetramine and obtain good yields of pyridine and 3-picoline.
The prior art teaches that acetylene reacts with ammonia to give mainly Z-picoline and 4-picoline.
We found that if we admix formaldehyde with the acetylene and ammonia, we suppress the formation of 4-picoline and cause the formation of pyridine and 3- picoline.
By our process we can prepare pyridine and 3-pico1ine economically and in commercial quantities with very good yields.
In carrying out our invention we mix the vapors of formaldehyde with acetylene and ammonia and pass the resultant mixture through a suitable reactor containing a catalyst. The temperature of the reactor is maintained preferably between about 400 C. and about 500 C. We prefer to carry out our process in a continuous manner although that is not necessary.
The reactor used may be of various types. We prefer the fluid catalyst type, similar to those normally used in carrying out cracking operations in the petroleum industry. Such reactors are of tubular form with suitable connections at entrance and exit. They are provided with means for supporting the fluid bed of catalyst, and are provided with any convenient means for heating them.
A highly satisfactory way of carrying out our invention is described more fully by means of the following specific examples:
Example 1 We prepared a gaseous mixture composed of about zinc fluoride, the catalyst was finely divided, and all of r picolines were recovered from the condensate by fractional distillation. The pyridine obtained amounted to about 0.25 pound for each pound of formaldehyde passed through the reactor.
Example 2 We prepared a gaseous mixture composed of one mole of acetylene, one mole of ammonia, and three moles of formaldehyde. We passed the mixture of vapors through a fluid catalyst type of reactor containing a fluidized catalytic bed of activated alumina (Alorco H-41) which had been impregnated with 10% zinc fluoride. The temperature of the reactor was maintained at about 425 C. The gaseous mixture of acetylene, ammonia, and formaldehyde was passed through at a superficial velocity of 1.25 feet per second. As this mixture of acetylene, ammonia, and formaldehyde passed through the reactor, a reaction occurred whereby pyridine and 3-picoline were produced. The vapors of the unchanged reactants and the reaction products were condensed as they emerged from the reactor, and the condensate was collected in a suitable receiver.
The condensate was composed fy pyridine compounds and non-basic or neutral compounds. In order to separate these two groups of compounds, the condensate was acidified to a pH of, 1 with sulfuric acid. The
pyridine base compounds present dissolved in the dilute sulfuric acid solution. The non-basic compounds were insoluble and formed a layer on top of the sulfuric acid solution. These were'separated by decantation. The last traces of non-basic compounds were removed by steaming the sulfuric acid solution. The sulfuric acid solution freed of non-basic contaminants was made strongly alkaline (pH 12.0) by the addition of sodium hydroxide. Pyridine bases separated from this strongly alkaline solution. They were removed by decantation. Any small amount of pyridines remaining in the alkaline solution were recovered by steam distillation and combined with the previously separated bases. After drying with flake caustic soda, the pyridine bases were fractionated to recover pyridine and 3-picoline. The pyridine recovered amounted to about 15%. The 3-picoline amounted to about 20%; as obtained from the fractionating column, the 3-picoline had a purity of more than 95%, clearly indicating that little if any 4-picoline was formed. 2-picoline was also recovered, but only in an amount of less than about 2% 7 Example 3 The process of Example 2 was repeated with the exception that the gaseous mixture passed through the reactor was composed of one mole of acetylene, one mole of ammonia, and one mole of formaldehyde. The pyridine bases recovered were subjected to fractional distillation. The pyridine recovered amounted to about 20%. The 3-picoline fraction amounted to about 18%; as obtained from the fractionating column, the 3-picoline had a purity of about indicating that 4-picoline was formed to some extent. 2-picoline was recovered in an amount of about 9% Example 4 The process of Example 2 was repeated with the exception that the gaseousmixture passed through the reactor was composed of one mole of acetylene and one mole of ammonia; no formaldehyde was used. The pyrdine bases obtained were subjected to fractional distillation. No pyridine was recovered. 2-picoline was recovered in an amount of 32.0%. 4-picoline was recovered in an amount of 28.0%; the 4-picoline had a purity of 93%, clearly indicating that little if any 3-picoline was formed.
Example 5 The process of Example 3 was repeated with the exception that the gaseous mixture passed through the reactor was composed of two moles acetylene, two moles ammonia, and one mole of formaldehyde. The pyridine bases recovered were subjected to fractional distillation. The pyridine recovered amounted to about 14%. The 3-picoline fraction amounted to about 17%; the 3-picoline as obtained from the fractionating column had a purity of about 50% indicating that as much 4-picoline was formed as there was of 3-picoline. The 2-picoline recovered amounted to about 16%.
Example 6 A zinc zeolite catalyst was prepared in the following manner. A four-inch diameter porcelain tube eight feet long was mounted vertically and filled with distilled water. Then 21.75 pounds of Decalso Permutit was slowly added to form an ion exchange bed approximately inches long.- A zinc chloride solution (3.5 pounds of zinc chloride and pounds of water) was flowed downward over the Permutit in order to replace zeolitic sodium by zinc ion. The zeolite'waswashed with 20 pounds of distilled water, drained, and placed in a drying oven. The zinc zeolite was dried for about 72 hours at 85 C. 7 It was then ground to 65 mesh and finer. (Decalso Permutit is a synthetic sodium-alumino-silicate used for water softening.)
,The process of Example 2 was repeated with the following exceptions. The zinc zeolite catalyst prepared above was used. The temperature of the reactor was maintained at 425 C. The gaseous mixture passed through the reactor was composed of two moles of acetylene, two moles of ammonia, and one mole of formaldehyde. The pyridine content of the water-free reaction product was about 29%. The 3 picoline fraction amounted to about 24%; as obtained from the fractionating column, the 3-picoline had a purity of about 50% indicating that 4-picoline was also formed.
Example 7 A gaseous mixture composed of one mole of acetylene, one mole of ammonia, and three moles of formaldehyde was passed through a suitable reactor containing a fluidized catalytic bed of activated alumina which had been impregnated with cadmium fluoride, the catalyst was finely divided, and all of it passed through 65 mesh. The reactor was maintained at a temperature of about 425 435 C. As the mixture of reactants passed through the reactor, a reaction occurred producing pyridine and 3-.picoline. The vapors of the unchanged reactants and the reaction products were condensed as they emerged from the reactor; the condensate was collected in a suitable receiver. The pyridine and the picolines were isolated from the condensate by fractional distillation. The pyridine content of the reaction product was about 20.9%. The 3-picoline amounted to about it was about 95% pure.
Example 8 The process of Example 7 was repeated with the exception that the catalyst used was a silica-magnesia catalyst impregnated with 10% zinc fluoride. The pyridine in the reaction product amounted to 19%. The yield of reaction product was about 0.50 to 0.60 pound per pound of acetylene passed through the reactor.
Example 9 A zinc Filtrol catalyst was prepared as follows:
2,500 grams of Filtrol 58 (which is a grade of montmorillonite clay having an amorphous or gel structure) was placed in a five-gallon glass container and a zinc chloride solution (227 grams of anhydrous zinc chloride was dissolved in 17 pounds of distilled water) was poured over the Filtrol. After this solution was poured over the Filtrol, a slurry was made by stirring for about one hour. The solids were removed from the slurry by filtration. The residue was removed from the filter and returned to the glass container. It was treated again with a zinc chloride solution prepared as mentioned above. The resulting slurry was filtered again. This process of slurrying the Filtrol and removing the aqueous solution was repeated fifteen times. Finally, the zinc Filtrol was thoroughly washed with distilled water. It was then dried in an oven and ground. Analyses on the thus-prepared catalyst showed it to contain about 2.5% zinc.
The process of Example 7 was repeated with the exception that the above prepared zinc Filtrol was used as catalyst. The condensate obtained was subjected to fractional distillation through an efiicient fractionating column to recover pyridine and 3-picoline. The pyridine recovered amounted to about 7.9%. The 3-picoline recovered amounted to about 11%; as recovered from the fractionating column, the purity of the 3-picoline was more than 95%.
Example 10 The process of Example 6 was repeated with the exception that the catalyst used was alumina impregnated with 10% cupric chloride. The pyridine content of the condensate was about 14.8%. The condensate amounted to about 0.35 to 0.40 pound per pound of acetylene used.
Example 11 Instead of using acetylene, we can use the hydrated form of acetylene, i.e. acetaldehyde. We prepared a gaseous mixture of one mole of acetaldehyde, one mole of ammonia, and two moles of formaldehyde. This mixture was reacted as was the mixture used in Example 2. The yields of pyridine, 3-picoline, and of 2-picolirie were as indicated in Example 2.
In place of the activated alumina, the silica magnesia, the Filtrol, and the zeolite as catalyst supports, we may use other catalyst supports, such as fullers earth, pumice, silica, and the like.
In place of the zinc fluoride, the cupric chloride, and the cadmium fluoride, we may utilize other catalysts, such as zinc chloride, cadmium chromate, cadmium molybdenate, lead chromate, zinc phosphate, and the like. As a matter of fact, we may cause acetylene, ammonia, and formaldehyde to react by passing the mixture of vapors over alumina itself. In other words, we may use the catalysts that have been found useful in the preparation of picolines from acetylene and ammonia.
As is evident from the specific examples given above, the proportions of the reactants may be varied widely. It is important, however, to have all three reactants present if pyridine is to be formed in any appreciable amount.
The temperature at which the reaction is conducted may be varied widely. In general, we prefer to have the reaction temperature above about 400 C. and below about 500 C. It has been our experience that at temperatures below about 400 C., we have too large a proportion of the reactants passing through without reacting. At temperatures above about 500 C., we find that our catalyst becomes inactivated more rapidly and we obtain too many side reactions.
We claim as our invention:
1. The process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising an activated alumina impregnated with Zinc fluoride maintained at a temperature between about 400 C. and about 500 C. and recovering pyridine from the reaction product.
2. The process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 400 C. and about 500 C. and recovering pyridine from the reaction product.
3. The process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 470 C. and 480 C., and recovering pyridine from the reaction product.
4. The process of preparing pyridine which comprises mixing the vapors of acetylene, ammonia, and formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 415 C. and 425 C., and recovering pyridine from the reaction product.
5. The process of preparing pyridine which comprises preparing a gaseous mixture composed of about two parts of acetylene, of about four and one-half parts of ammonia, and of about one part of formaldehyde, passing the resultant mixture through a reactor containing a catalyst comprising activated alumina impregnated with 10% zinc fluoride maintained at a temperature between about 470 C. and 480 C., and recovering pyridine from the reaction product.
6. The process of preparing pyridine which comprises preparing a gaseous mixture composed of about two parts of acetylene, of about four and one-half parts of ammonia, and of about one part of formaldehyde, passing 7 the resultant rlnixturecthrough a reactor containing a i FOREIGN PATENTS catalyst comprlsmg actlvated alumma impregnated wlth 525,652 V'G "In"- June 9, 1931 10% Zinc fluoride maintained at a temperature between abbut'415 C. and 425 C. and recovering pyridine from 3 Great Brltam July 1930 the reaction product. 5 534,494 Great Britain Mar. 7, 1941 References Cited in the file of this patent I O ER REFERENCES 0 UNITED STATES PATENTS Ser. No. 387,106, Stitz (A.P.C.), published July 13, 1,882,518 Nicodemus Oct. 11, 1932 1943' 2,700,042 Aries Jan. 18, 1955
Claims (1)
1. THE PROCESS OF PREPARING PYRIDINE WHICH COMPRISES MIXING THE VAPORS OF ACETYLENE, AMMONIA, AND FORMALDEHYDE, PASSING THE RESULTANT MIXTURE THROUGH A REACTOR CONTAINING A CATALYST COMPRISING AN ACTIVATED ALUMINA IMPREGNATED WITH ZINC FLUORIDE MAINTAINED AT A TEMPERATURE BETWEEN ABOUT 400*C. AND ABOUT 500*C. AND RECOVERING PYRIDINE FROM THE REACTION PRODUCT.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US410044A US2934537A (en) | 1954-02-12 | 1954-02-12 | Process of preparing pyridine and 3-picoline |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US410044A US2934537A (en) | 1954-02-12 | 1954-02-12 | Process of preparing pyridine and 3-picoline |
Publications (1)
Publication Number | Publication Date |
---|---|
US2934537A true US2934537A (en) | 1960-04-26 |
Family
ID=23622979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US410044A Expired - Lifetime US2934537A (en) | 1954-02-12 | 1954-02-12 | Process of preparing pyridine and 3-picoline |
Country Status (1)
Country | Link |
---|---|
US (1) | US2934537A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3264307A (en) * | 1963-04-09 | 1966-08-02 | Mobil Oil Corp | Production of pyridines |
US4990286A (en) * | 1989-03-17 | 1991-02-05 | President And Fellows Of Harvard College | Zinc oxyfluoride transparent conductor |
US20140056803A1 (en) * | 2012-08-21 | 2014-02-27 | Uop Llc | Production of nitrogen compounds from a methane conversion process |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB332623A (en) * | 1929-02-22 | 1930-07-22 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of condensation products containing nitrogen |
DE525652C (en) * | 1928-11-15 | 1931-06-09 | I G Farbenindustrie Akt Ges | Process for obtaining pyridine |
US1882518A (en) * | 1927-01-05 | 1932-10-11 | I G Farbenindustriie Ag | The process of preparing organic bases |
GB534494A (en) * | 1939-10-06 | 1941-03-07 | Distillers Co Yeast Ltd | Improvements in or relating to the manufacture of heterocyclic bases |
US2700042A (en) * | 1952-08-30 | 1955-01-18 | Robert S Aries | Production of pyridine and beta picoline |
-
1954
- 1954-02-12 US US410044A patent/US2934537A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1882518A (en) * | 1927-01-05 | 1932-10-11 | I G Farbenindustriie Ag | The process of preparing organic bases |
DE525652C (en) * | 1928-11-15 | 1931-06-09 | I G Farbenindustrie Akt Ges | Process for obtaining pyridine |
GB332623A (en) * | 1929-02-22 | 1930-07-22 | Ig Farbenindustrie Ag | Improvements in the manufacture and production of condensation products containing nitrogen |
GB534494A (en) * | 1939-10-06 | 1941-03-07 | Distillers Co Yeast Ltd | Improvements in or relating to the manufacture of heterocyclic bases |
US2700042A (en) * | 1952-08-30 | 1955-01-18 | Robert S Aries | Production of pyridine and beta picoline |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3264307A (en) * | 1963-04-09 | 1966-08-02 | Mobil Oil Corp | Production of pyridines |
US4990286A (en) * | 1989-03-17 | 1991-02-05 | President And Fellows Of Harvard College | Zinc oxyfluoride transparent conductor |
US20140056803A1 (en) * | 2012-08-21 | 2014-02-27 | Uop Llc | Production of nitrogen compounds from a methane conversion process |
US9023255B2 (en) * | 2012-08-21 | 2015-05-05 | Uop Llc | Production of nitrogen compounds from a methane conversion process |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1330666C (en) | Production of ethanolamine by amination of ethylene oxide over acid activated clays | |
US2512660A (en) | Production of pyridine derivative | |
US2516625A (en) | Derivatives of dihydropyridine | |
JPH0321009B2 (en) | ||
SU607553A3 (en) | Method of obtaining 3-methylpyridine | |
US3903079A (en) | Production of polymethylenimines by cycloammonolysis | |
JPH01132587A (en) | Production of 1, 4-diazabicyclo (2, 2, 2)-octane from piperadine | |
US2934537A (en) | Process of preparing pyridine and 3-picoline | |
US2760961A (en) | Preparation of melamine | |
US2523580A (en) | Production of alkyl pyridines | |
US2744904A (en) | Process of preparing pyridine and 3-picoline | |
US2807618A (en) | Synthesis of pyridine and 3-picoline | |
CH631705A5 (en) | METHOD FOR PRODUCING SUBSTITUTED PYRIDINE. | |
US2820791A (en) | Chemical manufacture | |
US2534285A (en) | Production of pyridine derivatives | |
US3020282A (en) | Process of preparing quinoline | |
US2698848A (en) | Making pyridine derivatives | |
US2854457A (en) | Process of preparing dipyridyls | |
US3829428A (en) | Process for the catalytic vapor-phase synthesis of alkylpyridines | |
US2716143A (en) | Preparation of vinyl fluoride and 1, 1-difluoroethane and catalyst therefor | |
EP0246349B1 (en) | Method of selectively chlorinating 2-chloro-5-(trichloromethyl) pyridine in the 3-position | |
US4369322A (en) | Process for the production of substituted acetonitriles | |
JP2764058B2 (en) | Propylene production method | |
US3020281A (en) | Method of preparing quinoline | |
US3065270A (en) | Preparation of dimethylnitrosoamine |