BE510436A - - Google Patents
Info
- Publication number
- BE510436A BE510436A BE510436DA BE510436A BE 510436 A BE510436 A BE 510436A BE 510436D A BE510436D A BE 510436DA BE 510436 A BE510436 A BE 510436A
- Authority
- BE
- Belgium
- Prior art keywords
- catalyst
- dimethylhex
- alumina
- yne
- process according
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 235000011007 phosphoric acid Nutrition 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- -1 potassium alkoxide Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 3
- 229910003452 thorium oxide Inorganic materials 0.000 claims description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 239000012025 fluorinating agent Substances 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N Tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052790 beryllium Inorganic materials 0.000 claims 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium(0) Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims 1
- 239000012024 dehydrating agents Substances 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- ZSLUVFAKFWKJRC-UHFFFAOYSA-N thorium Chemical compound [Th] ZSLUVFAKFWKJRC-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 229920001098 polystyrene-block-poly(ethylene/propylene) Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N BeO Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N Boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N HF Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PDVFSPNIEOYOQL-UHFFFAOYSA-N (4-methylphenyl)sulfonyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OS(=O)(=O)C1=CC=C(C)C=C1 PDVFSPNIEOYOQL-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K Aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- OHORFAFFMDIQRR-UHFFFAOYSA-P Hexafluorosilicic acid Chemical compound [H+].[H+].F[Si-2](F)(F)(F)(F)F OHORFAFFMDIQRR-UHFFFAOYSA-P 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N M-Xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N Phosphorus trifluoride Chemical class FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N Silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JPJZHBHNQJPGSG-UHFFFAOYSA-N titanium;zirconium;tetrahydrate Chemical compound O.O.O.O.[Ti].[Zr] JPJZHBHNQJPGSG-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/31—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
- C07C2521/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/16—Clays or other mineral silicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/12—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/30—Tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
- C07C2527/054—Sulfuric acid or other acids with the formula H2Sn03n+1
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
- C07C2527/173—Phosphoric acid or other acids with the formula Hn+2PnO3n+1
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
IMPERIAL CHEMICAL INDUSTRIES LIMITED résidant à LONDRES.
PERFECTIONNEMENTS A LA PRODUCTION D HYDROCARBURES AROMATIQUES.
La présente invention est relative à la production des hydrocar- bures xylènes.
Suivant cette invention, dans un procédé de production d'un mélan- ge d'hydrocarbures contenant du p-xylène, on met en contact en phase vapeur et à température élevée du 2:5-diméthylhex-3-yne-l:5-diène avec un catalyseur d'isomérisation.
On peut utiliser toute une gamme de catalyseurs'dans le procédé de la présente invention. On peut par exemple utiliser de l'alumine, des gels d'alumine-silice, des argiles activées èt de l'alumine-oxyde chromique.
On peut préparer un catalyseur alumine-oxyde chromique convena- ble, par exemple par déshydratation de trihydrate d'alumine à une température de 400 C jusqu'à ce que sa teneur en eau soit de 9-11% en poids. On met en- suite l'alumine en comprimés,en utilisant un lubrifiant appropriée etsi c'est nécessaire, on peut alors calciner les comprimés à une température de 700 C pour éliminer le lubrifiant servant à la préparation des comprimés On les immerge finalement dans une solution diacide chromique, on les enlève et on les sèche. Il est désirable que la teneur en oxyde de chrome soit com- prise dans la gamme de 10 à 15% en poids.
L'incorporation de chromate de mag- nésium. en(quantité mineure,équivalente par exemple à 2% de MgO en poids, dans le catalyseur, augmente l'activité et tend à accroître la vie du cataly- seur. On peut également préparer un catalyseur alumine-oxyde chromique par pré- cipitation simultanée des oxydes et mise ultérieure du produit sous forme de comprimés.
On peut produire d'autres catalyseurs appropriés par contact d'a- lumine, soit seule soit avec des oxydes tels que l'oxyde de thorium, l'oxyde de béryllium, l'oxyde de zirconium et l'oxyde de titane, avec un agent de fluo- ration tel que le fluor, l'acide fluorhydrique, le tétrafluorure de silicium, le trifluorure de bore, des fluorures de phosphore, des composés interhalo- génés contenant du fluor et de l'acide fluosilicique. Dans la production de catalyseurs de ce genre, il est préférable d'utiliser comme matière de départ
<Desc/Clms Page number 2>
un oxyde substantiellement anhydre, et d'effectuer l'opération de fluoration à une température et,pendant une durée telles que la teneur en fluor du cata- lyseur final ne dépasse pas 5% en poids.
EMI2.1
On met de préférence le 2:5-diméthylhex-3-yne-1:sdiène au contact du catalyseur de façon continue. La température optimum à laquelle on effectue la réaction dépend du catalyseur utilisé, mais en général, des températures comprises dans la gamme de 311 C à 600 C conviennent.
On peut effectuer la réaction en opérant de façon continue en présence d'un gaz véhiculaire, tel que de l'hydrogène ou de l'azote, qu'on peut mélanger à l'hydrocarbure évaporé, et on porte le mélange au contact du catalyseur à la température désirée. Il est avantageux d'introduire le gaz véhiculaire à une vitesse similaire à la vitesse de passage de la vapeur d'hy- drocarbures à travers la zone de réaction.
On peut séparer les xylènes produits par le procédé de la présen- te invention, par exemple, par distillation fractionnée.
On peut produire le 2:5-diméthylhex-3-yne-l:5-diène utilisé dans le procédé de la présente invention par condensation d'acétone avec de l'acé- tylène en présence d'hydroxyde de potassium pour obtenir du 2:5-diméthylhex- 3-yne-2 :5-diol:
EMI2.2
et déshydratation subséquente de celui-ci par traitement au moyen d'agents déshydratants en phase liquide ou par traitement catalytique en phase vapeur.
Quant on opère en phase liquide, dès agents de déshydratation par- ticulièrement appropriés sont une solution aqueuse d'acide phosphorique con- tenant en poids 60% de H3PO4 et l'acide sulfurique contenant en poids 10% à 40% de H2SO4 D'autres agents de déshydratation qu'on peut utiliser comprennent 1'alumine, l'acide p-toluène sulfonique et l'anhydride acétique contenant de préférence une petite quantité d'acide sulfurique. Dans un procédé avanta- geux d'exécution de la déshydratation, on chauffe ensemble le diol et l'acide phosphorique à une température voisine de 100 C, en faisant passer un courant d'anhydride carbonique à travers le mélange pour séparer le 2:5-dimétbylhex- 3-yne-l:5-diène immédiatement après sa formation.
En opérant de cette manière,
EMI2.3
on obtient un mélange qui contient de l'eau et du 2:5-diméthylhex-3 yne-1:5- diène. On peut enlever ce dernier, qui se sépare sous forme d'une couche su- périeure, par décantation, et le purifier si on le désire, par distillation fractionnée.
Quand on effectue cette réaction de déshydratation par catalyse en phase vapeur, les catalyseurs préférés sont des terres silicieuses, telles que la nordénite et la bentonite, l'alumine, le gel de silice-alumine, l'o- xyde de thorium, l'oxyde de zinc, le phosphate d'aluminium basique, l'acide phosphorique supporté sur une matière inerte, telle que le kieselguhr, le co- ke ou le charbon de bois, et l'oxyde bleu de tungstène. On effectue la réac- tion de préférence à des températures comprises dans la gamme de 200 C à 450 C.
La déshydratation peut donner lieu à une quantité mineure de 2:5 diméthylhex-3-yne-l-ène-5-ol. On fait de préférence recirculer ce composé vers la zone de déshydratation en même temps qu'une nouvelle quantité de
EMI2.4
2:5-diméthylhex-3-yne-2:5-diol.
EXEMPLE.
EMI2.5
On chauffe 250 gr de 2:5-dn.éthyLhex 3-yne-2:5 iol et 2500 ml d'acide phosphorique contenant 60% de H3PO4en poids, dans un courant d'an-
<Desc/Clms Page number 3>
EMI3.1
iiydr!dB, carbonique. Au cours de la déshydratation, le 2:5:diméthylhex-3- ye-1:5-diène quitte le flacon par distillation avec'de la vapeur'd'eau. On condense le mélange, on sépare de façon continue l'eau de la couche.d'huile et on la réintroduit dans le flacon pour maintenir la concentration en acide phosphorique à une valeur constante. La couche d'huile donne, par distilla-
EMI3.2
tion, 127 gr. de 2:5-dimêthylhex 3-yne-1:5-diène (correspondant à une produc- tion de 68%) et 22,7 gr. de 2: 5-diméthylhex- 3-yne-l-èJ..1e -5-01.
(corre spondant à une production de 10,4%) , et on remet ce dernier en circulation en vue d' une déshydratation subséquente avec une nouvelle quantité de 2.5-diméthyl- 3-yne-2:5-diol.
EMI3.3
On fait passer 58,5 gro de 2:5-d-.éthylhe. 3 yne-15-diène à raison de 25 ml/heure sur 50 ml d'un catalyseur comprenant 13% en poids d'o- xydes de chrome, 85% en poids d'alumine activée et 2% en poids de magnésie, présente sous forme de chromate de magnésium. On maintient le catalyseur à une température de 450 C et on fait passer de l'oxygène à travers le conver- tisseur à raison de 5 litres/heure. On obtient 37,9 gr. de produit liquide.
On trouve par distillation et analyse ultraviolette et infrarouge que le pro- duit contient : -
EMI3.4
2:5-diznéthylhex 3-yne1:5-diène inchangé 14,1 gr
EMI3.5
<tb> p-xylène <SEP> 5,2 <SEP> gr
<tb>
<tb> m-xylène <SEP> 0,3 <SEP> gr
<tb>
<tb> Résidu <SEP> 16,0 <SEP> gr
<tb>
Le résidu consiste en hydrocarbures fortement non-.saturés, for- més par la polymérisation du diène acétylénique. Le rendement en p-xylène est de 8.9% et la production de 11,7%.
REVENDICATIONS.
1. - Procédé de production de mélanges d'hydrocarbures contenant
EMI3.6
du p-xylène, caractérisé en ce qu'on met du 2:5-diméthylhex-,3-yne-1:5-diène en contact avec un catalyseur d'isomérisation en phase vapeur et à tempéra- ture élevée.
<Desc / Clms Page number 1>
IMPERIAL CHEMICAL INDUSTRIES LIMITED resident in LONDON.
IMPROVEMENTS IN THE PRODUCTION OF AROMATIC HYDROCARBONS.
The present invention relates to the production of xylene hydrocarbons.
According to this invention, in a process for producing a mixture of hydrocarbons containing p-xylene, 2: 5-dimethylhex-3-yne-1: 5- is contacted in the vapor phase and at an elevated temperature. diene with an isomerization catalyst.
A variety of catalysts can be used in the process of the present invention. It is possible, for example, to use alumina, alumina-silica gels, activated clays and alumina-chromic oxide.
A suitable alumina-chromic oxide catalyst can be prepared, for example, by dehydrating alumina trihydrate at a temperature of 400 ° C until its water content is 9-11% by weight. The alumina is then compressed into tablets, using a suitable lubricant and, if necessary, the tablets can then be calcined at a temperature of 700 ° C. to remove the lubricant used in the preparation of the tablets. They are finally immersed in a chromic diacid solution, they are removed and dried. It is desirable that the content of chromium oxide be in the range of 10 to 15% by weight.
Incorporation of magnesium chromate. (a minor amount, for example equivalent to 2% MgO by weight, in the catalyst increases the activity and tends to increase the life of the catalyst. An alumina-chromic oxide catalyst can also be prepared by simultaneous precipitation. oxides and subsequent placing of the product in tablet form.
Other suitable catalysts can be produced by contacting alumina, either alone or with oxides such as thorium oxide, beryllium oxide, zirconium oxide and titanium oxide, with a. fluorinating agent such as fluorine, hydrofluoric acid, silicon tetrafluoride, boron trifluoride, phosphorus fluorides, halogen compounds containing fluorine and fluosilicic acid. In the production of such catalysts, it is preferable to use as a starting material
<Desc / Clms Page number 2>
a substantially anhydrous oxide, and to carry out the fluorination operation at a temperature and for a time such that the fluorine content of the final catalyst does not exceed 5% by weight.
EMI2.1
The 2: 5-dimethylhex-3-yne-1: sdiene is preferably brought into contact with the catalyst continuously. The optimum temperature at which the reaction is carried out depends on the catalyst used, but in general temperatures in the range of 311 C to 600 C are suitable.
The reaction can be carried out by operating continuously in the presence of a carrier gas, such as hydrogen or nitrogen, which can be mixed with the evaporated hydrocarbon, and the mixture is brought into contact with the catalyst. at the desired temperature. It is advantageous to introduce the carrier gas at a rate similar to the rate of passage of the hydrocarbon vapor through the reaction zone.
The xylenes produced by the process of the present invention can be separated, for example, by fractional distillation.
The 2: 5-dimethylhex-3-yne-1: 5-diene used in the process of the present invention can be produced by condensing acetone with acetylene in the presence of potassium hydroxide to obtain 2. : 5-dimethylhex-3-yne-2: 5-diol:
EMI2.2
and subsequent dehydration thereof by treatment with liquid phase dehydrating agents or by catalytic vapor phase treatment.
When operating in the liquid phase, particularly suitable dehydrating agents are an aqueous solution of phosphoric acid containing 60% by weight of H3PO4 and sulfuric acid containing by weight 10% to 40% of H2SO4. Dehydrating agents which can be used include alumina, p-toluene sulfonic acid and acetic anhydride preferably containing a small amount of sulfuric acid. In a preferred method of carrying out the dehydration, the diol and phosphoric acid are heated together to a temperature in the region of 100 ° C, passing a stream of carbon dioxide through the mixture to separate the 2: 5. -dimetbylhex-3-yne-1: 5-diene immediately after its formation.
By operating in this way,
EMI2.3
a mixture is obtained which contains water and 2: 5-dimethylhex-3-yne-1: 5-diene. The latter, which separates out as a top layer, can be removed by decantation, and if desired, purified by fractional distillation.
When carrying out this dehydration reaction by vapor phase catalysis, the preferred catalysts are siliceous earths, such as nordenite and bentonite, alumina, silica gel-alumina, thorium oxide, zinc oxide, basic aluminum phosphate, phosphoric acid supported on an inert material, such as kieselguhr, coke or charcoal, and blue tungsten oxide. The reaction is preferably carried out at temperatures in the range of 200 C to 450 C.
Dehydration can result in a minor amount of 2: 5 dimethylhex-3-yne-1-en-5-ol. This compound is preferably recirculated to the dehydration zone along with a new quantity of
EMI2.4
2: 5-dimethylhex-3-yne-2: 5-diol.
EXAMPLE.
EMI2.5
250 gr of 2: 5-dn.éthyLhex 3-yne-2: 5 iol and 2500 ml of phosphoric acid containing 60% of H3PO4 by weight are heated in a stream of an-
<Desc / Clms Page number 3>
EMI3.1
iiydr! dB, carbonic. During dehydration, the 2: 5: dimethylhex-3-ye-1: 5-diene leaves the flask by distillation with water vapor. The mixture is condensed, the water is continuously separated from the oil layer and returned to the flask to maintain the phosphoric acid concentration at a constant value. The oil layer gives, by distillation
EMI3.2
tion, 127 gr. of 2: 5-dimethylhex 3-yne-1: 5-diene (corresponding to a production of 68%) and 22.7 gr. of 2: 5-dimethylhex-3-yne-1-EJ..1e -5-01.
(corresponding to a production of 10.4%), and the latter is put back into circulation with a view to subsequent dehydration with a further quantity of 2.5-dimethyl-3-yne-2: 5-diol.
EMI3.3
Pass 58.5 gro of 2: 5-d-.ethylhe. 3 yne-15-diene at a rate of 25 ml / hour on 50 ml of a catalyst comprising 13% by weight of chromium oxides, 85% by weight of activated alumina and 2% by weight of magnesia, present in the form of magnesium chromate. The catalyst is maintained at a temperature of 450 ° C. and oxygen is passed through the converter at a rate of 5 liters / hour. 37.9 g are obtained. of liquid product.
We find by distillation and ultraviolet and infrared analysis that the product contains: -
EMI3.4
2: 5-diznethylhex 3-yne1: 5-diene unchanged 14.1 gr
EMI3.5
<tb> p-xylene <SEP> 5,2 <SEP> gr
<tb>
<tb> m-xylene <SEP> 0.3 <SEP> gr
<tb>
<tb> Residue <SEP> 16.0 <SEP> gr
<tb>
The residue is highly unsaturated hydrocarbons formed by the polymerization of acetylenic diene. The yield of p-xylene is 8.9% and the production is 11.7%.
CLAIMS.
1. - Process for the production of hydrocarbon mixtures containing
EMI3.6
p-xylene, characterized in that 2: 5-dimethylhex-, 3-yne-1: 5-diene is contacted with an isomerization catalyst in the vapor phase and at elevated temperature.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE510436A true BE510436A (en) |
Family
ID=149544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE510436D BE510436A (en) |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE510436A (en) |
-
0
- BE BE510436D patent/BE510436A/fr unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1115261A (en) | Catalyst based on silver for the production of ethylene oxide | |
| EP0434485B1 (en) | Method of production of phenol | |
| WO1996026914A1 (en) | Process for preparing 1,1,1,3,3-pentafluoropropane | |
| FR2552078A1 (en) | PROCESS FOR SELECTIVE HYDROGENATION OF ACETYLENE CONTAINED IN A MIXTURE OF ACETYLENE AND ETHYLENE | |
| JPH0357905B2 (en) | ||
| CH381215A (en) | Isoprene preparation process | |
| BE510436A (en) | ||
| US2737537A (en) | Production of aromatic hydrocarbons by catalytic isomerization of 2:5 dimethylhex-3-yne-1:5 diene | |
| US3994986A (en) | Method of producing cyclopentene | |
| JPS58126826A (en) | Manufacture of pure neohexanol | |
| US2277650A (en) | Process of producing n-butylene | |
| US4139569A (en) | Vapor phase cracking of dicyclopentadiene and synthesis of 2,3-dihydroxycyclopentadiene and cyclopentene | |
| JP2000063299A (en) | Production of indene | |
| BE514028A (en) | ||
| US3288853A (en) | Method for the preparation of dicyclohexyl ketone | |
| US1955050A (en) | Production of monocarboxylic acids | |
| US1982196A (en) | Manufacturing monocarboxylic acids | |
| FR2516504A1 (en) | PROCESS FOR THE PREPARATION OF 2-TRIFLUOROMETHYLPROPANOL BY VAPOR HYDROGENATION OF 2-TRIFLUOROMETHYLPROPANAL | |
| BE510437A (en) | ||
| BE569440A (en) | Method for the manufacture of isoprene | |
| JPH03236336A (en) | Preparation of cymenol by direct dehydro- genation | |
| US1982195A (en) | Preparation of monocarboxylic acids | |
| Donald et al. | The air oxidation of mixtures of benzene and cyclohexane to phenol | |
| EP0043631B1 (en) | Process for the preparation of a 6-alkyl-valerolactone | |
| CH346867A (en) | Process for preparing an aromatic mono- or polycarboxylic acid |