DE1286002B - Process for the production of aromatic nitriles - Google Patents
Process for the production of aromatic nitrilesInfo
- Publication number
- DE1286002B DE1286002B DEH56900A DEH0056900A DE1286002B DE 1286002 B DE1286002 B DE 1286002B DE H56900 A DEH56900 A DE H56900A DE H0056900 A DEH0056900 A DE H0056900A DE 1286002 B DE1286002 B DE 1286002B
- Authority
- DE
- Germany
- Prior art keywords
- percent
- catalyst
- antimony
- weight
- xylene
- 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
- -1 aromatic nitriles Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims description 23
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 239000012876 carrier material Substances 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical class CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- BOHCMQZJWOGWTA-UHFFFAOYSA-N 3-methylbenzonitrile Chemical compound CC1=CC=CC(C#N)=C1 BOHCMQZJWOGWTA-UHFFFAOYSA-N 0.000 description 1
- VCZNNAKNUVJVGX-UHFFFAOYSA-N 4-methylbenzonitrile Chemical compound CC1=CC=C(C#N)C=C1 VCZNNAKNUVJVGX-UHFFFAOYSA-N 0.000 description 1
- YFDJCWXBKWRDPW-UHFFFAOYSA-N 4-propan-2-ylbenzonitrile Chemical compound CC(C)C1=CC=C(C#N)C=C1 YFDJCWXBKWRDPW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 241001530455 Antigone Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- UKUJCSBWRBWNAV-UHFFFAOYSA-N [Sn].[V] Chemical compound [Sn].[V] UKUJCSBWRBWNAV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- RJAAXVMENUVEAN-UHFFFAOYSA-N antimony vanadium Chemical compound [V].[Sb] RJAAXVMENUVEAN-UHFFFAOYSA-N 0.000 description 1
- RPJGYLSSECYURW-UHFFFAOYSA-K antimony(3+);tribromide Chemical compound Br[Sb](Br)Br RPJGYLSSECYURW-UHFFFAOYSA-K 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- RSHKUZJQXPUUNQ-UHFFFAOYSA-N benzonitrile;1,2-xylene Chemical compound CC1=CC=CC=C1C.N#CC1=CC=CC=C1 RSHKUZJQXPUUNQ-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- YJMNOKOLADGBKA-UHFFFAOYSA-N naphthalene-1-carbonitrile Chemical compound C1=CC=C2C(C#N)=CC=CC2=C1 YJMNOKOLADGBKA-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/28—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing six-membered aromatic rings, e.g. styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
AlkenylaromatenAlkyl or
Alkenyl aromatics
phthalsäuredinitrilp-tolunitrile and tere
phthalic acid dinitrile
säuredinitrilm-tolunitrile and isophthalic
acid dinitrile
dinitril und Phthalimido-tolunitrile, phthalic acid
dinitrile and phthalimide
benzonitril und Tere
phthalsäuredinitrilp-tolunitrile, p-isopropyl
benzonitrile and tere
phthalic acid dinitrile
Phthalsäuredinitrilα-cyano-naphthalene and
Phthalic acid dinitrile
Gegenstand der Erfindung ist ein Verfahren zur Herstellung
von aromatischen Nitrilen durch Ammoydation
von alkyl- und alkenylaromatischen Verbindungen in
der Gasphase bei erhöhter Temperatur und in Gegenwart eines Katalysators auf Basis Vanadinpentoxid und 25
einem anderen Metalloxid auf einem inerten Trägermaterial, dadurch gekennzeichnet, daß man die Umsetzung
in Gegenwart eines 0,1 bis 20 Gewichtsprozent
Vanadin, berechnet als Vanadinpentoxid, und 0,5 bis
20 Gewichtsprozent Antimon, berechnet als Antimon- 30
trioxid, auf einem inerten Trägermaterial vorzugsweise
Aluminiumoxid, mit einer Oberfläche von weniger als Zu den zur Herstellung des" fertigen KatalysatorsThe invention relates to a process for the preparation of aromatic nitriles by ammoydation
of alkyl and alkenyl aromatic compounds in
the gas phase at elevated temperature and in the presence of a catalyst based on vanadium pentoxide and 25
another metal oxide on an inert support material, characterized in that the reaction is carried out in the presence of 0.1 to 20 percent by weight
Vanadium, calculated as vanadium pentoxide, and 0.5 to
20 percent by weight of antimony, calculated as antimony 30
trioxide, preferably on an inert support material
Alumina, with a surface area less than that used to make the "finished catalyst"
1 m2/g enthaltenden Katalysators.durchführt. .,·.-. verwendbaren Verbindungen gehören die folgenden:1 m 2 / g containing catalyst. Carried out. ., · .-. Usable compounds include the following:
Die als Ausgangsstoffe für das erfindungsgemäße Antimonhalogenide', z. B. Antimontrichlorid undThe starting materials for the antimony halides according to the invention ', for. B. antimony trichloride and
Verfahren verwendbaren aromatischen Verbindungen 35 Antimonbromid, und Antimonoxide, z. B. Antimonkönnen durch folgende allgemeine Formel wieder- trioxid und Antimonpentoxid, zur Lieferung der Antigegeben werden: monkomponente. Die Antimonverbindungen könnenProcess usable aromatic compounds 35 antimony bromide, and antimony oxides, e.g. B. Antimony can by the following general formula re-trioxide and antimony pentoxide, added to supply the antigone become: moncomponent. The antimony compounds can
„ in Wasser und konzentrierter Salzsäure gelöst werden."Can be dissolved in water and concentrated hydrochloric acid.
/ Die Vanadinkomponente läßt sich in zweckmäßiger/ The vanadium component can be more expedient
X — C;— R' 40 Weise als Vanadinpentoxid und Ammoniummeta-X - C; - R '40 way as vanadium pentoxide and ammonium meta-
\ π vanadat einführen. Die Vanadinverbindungen werdenIntroduce \ π vanadate. The vanadium compounds are
■"''■■'■■■ in Wasser oder konzentrierter Salzsäure mit Oxalsäure ■ "'' ■■ '■■■ in water or concentrated hydrochloric acid with oxalic acid
In dieser Formel bedeuten R Wasserstoff oder eine oder Schwefeldioxid in die V+4-Form reduziert, und Alkyl- oder Alkenylgruppe; R' und R" — H, — OH, man erhält eine homogene Lösung.In this formula, R denotes hydrogen or a sulfur dioxide or sulfur dioxide reduced to the V +4 form, and an alkyl or alkenyl group; R 'and R "- H, - OH, a homogeneous solution is obtained.
— O oder eine Alkyl- oder Alkenylgruppe und X einen- 45 Der Katalysatorträger ist vorzugsweise Aluminiumnichtsubstituierten oder in.beliebiger Stellung durch oxid mit einer Oberfläche von etwa 0,5 m2/g. Silicium-- O or an alkyl or alkenyl group and X a- 45 The catalyst support is preferably aluminum not substituted or in any position by oxide with a surface area of about 0.5 m 2 / g. Silicon
— F,—Cl,—Br oder den Rest . carbid, Bimsstein und Zirkondioxid können gleichfalls- F, —Cl, —Br or the rest. Carbide, pumice stone and zirconia can also be used
als Träger verwendet werden.can be used as a carrier.
,,R" Der Antimonbestandteil des - Katalysators: ist be-"R" The antimony component of the - catalyst: is
>__Q^-g> 50 rechnet als Äntimontrioxid in Mengen von 0,5 bis > __ Q ^ -g> 50 counts as antimony trioxide in amounts from 0.5 to
' ■ \ 20 Gewichtsprozent, vorzugsweise von 4 bis 10 Ge-20% by weight, preferably from 4 to 10
R- wichtsprozent zugegen. Die Vanadinverbindung, be-R- weight percent present. The vanadium compound,
■ ■■■·/■ · ■ ; . ■ .rechnet als Vanadinpentoxid, ist in Mengen von 0,1■ ■■■ · / ■ · ■ ; . ■. Calculated as vanadium pentoxide, is in amounts of 0.1
substituierten Phenylrest oder einen mit nicht mehr als bis 20 Gewichtsprozent, vorzugsweise von 0,5 bis einem Benzolring kondensierten Phenylrest. Wenn in 55 3 Gewichtsprozent zugegen.substituted phenyl radical or one with no more than to 20 percent by weight, preferably from 0.5 to a benzene ring condensed phenyl. If present in 55 3 percent by weight.
der angegebenen Formel R, R' und R" Wasserstoff Die Lösungen der Metallsalze werden miteinander oder einen Alkyl- oder Alkenylrest und X einen nicht- vermischt und mit. dem Träger in Berührung gebracht, substituierten Phenylrest oder einen mit nicht mehr als Dann wird der Katalysator getrocknet, vorzugsweise einem Benzolring kondensierten Phenylrest bedeuten, in einem Rotationsverdampfer, und schließlich bei dann handelt es sich bei den aromatischen Verbindun- 60 einer Temperatur von 300 bis 550° C kalziniert, gen um alkylsubstituierte oder alkenylsubstituierte Bei der Durchführung des erfindungsgemäßen VerBenzol- oder Naphthalinkohlenwasserstoffe. Alkohole, fahrens wird der Ausgangsstoff mit einem sauerstoff-Aldehyde oder Ketone, die als Zwischenprodukte bei haltigen Gas und Ammoniak oder einer Ammoniak der Oxydation solcher Kohlenwasserstoffe auftreten, liefernden Substanz vermischt. In den meisten Fällen enthalten den Sauerstoff in direkter Bindung an ein 65 verwendet man als sauerstoffhaltiges Gas Luft, dochof the given formula R, R 'and R "hydrogen The solutions of the metal salts are with one another or an alkyl or alkenyl radical and X one non-mixed and with. brought into contact with the wearer, substituted phenyl radical or one with not more than Then the catalyst is dried, preferably denote phenyl condensed to a benzene ring, in a rotary evaporator, and finally at then the aromatic compounds are calcined at a temperature of 300 to 550 ° C, gen to alkyl-substituted or alkenyl-substituted When carrying out the VerBenzol- or naphthalene hydrocarbons. Alcohols, the starting material is an oxygen aldehyde or ketones, which are used as intermediates when containing gas and ammonia or an ammonia the oxidation of such hydrocarbons occur, supplying substance mixed. In most cases contain the oxygen in direct bond to a 65 one uses air as the oxygen-containing gas, but
acyclisches Kohlenstoffatom, wobei kein Sauerstoffatom an mehr als eines der acyclischen Kohlenstoffatome und kein acyclisches Kohlenstoffatom über mehracyclic carbon atom, with no oxygen atom on more than one of the acyclic carbon atoms and no more acyclic carbon atom
kann man selbstverständlich auch reinen Sauerstoff einsetzen. Es ist in der Regel zweckmäßig, wenn die Beschickung 8 bis 20°/0 Sauerstoff enthält.you can of course also use pure oxygen. It is generally appropriate when the feed contains 8 to 20 ° / 0 oxygen.
Der Ammoniakgehalt der Beschickung kann ganz allgemein zwischen 2 und 20°/0 liegen und beträgt vorzugsweise 4 bis 8 °/0. Im allgemeinen wird Ammoniak selbst verwendet, doch kann man statt dessen auch Verbindungen einsetzen, die unter den Reaktionsbedingungen Ammoniak liefern, z. B. Ammoniumcarbonat.The ammonia content of the feed may in general / 0 are between 2 and 20 ° and is preferably 4 to 8 ° / 0th In general, ammonia itself is used, but you can instead use compounds which give ammonia under the reaction conditions, z. B. ammonium carbonate.
Die verwendete Menge an alkyl- oder alkenylaromatischer Verbindung kann in einem weiten Bereich schwanken und hängt von der im Einzelfall verwendeten Verbindung ab. Im allgemeinen werden weniger als 10% der aromatischen Verbindung, vorzugsweise 0,5 bis 5°/0, eingesetzt.The amount of alkyl or alkenyl aromatic compound used can vary within a wide range and depends on the compound used in the individual case. In general, the aromatic compound is less than 10%, preferably 0.5 to 5 ° / 0, are used.
Die Umsetzung wird vorzugsweise in Gegenwart von Wasserdampf durchgeführt. Mengen von bis zu 60 °/0 sind gut geeignet, doch verwendet man Vorzugsweise 5 bis 25°/0 Wasserdampf, bezogen auf das Beschickungsgas. Wasserdampf wirkt als Reaktionsmoderator, wodurch die Bildung von CO und CO2 gesenkt wird. Die gebildete Nitrilverbindung hat gleichfalls einen Einfluß auf die Reaktionsbedingungen. Die so Zahl der gebildeten Nitrile und die Flüchtigkeit der alkyl- oder alkenylaromatischen Bestandteile der Beschickung müssen berücksichtigt werden. Die angewandten Temperaturen liegen im Bereich von 200 bis 8000C, vorzugsweise von 325 bis 5000C. Im Fall der Herstellung von Terephthalsäurenitril liegen die bevorzugten Temperaturen zwischen 425 und 6000C.The reaction is preferably carried out in the presence of steam. Amounts of up to 60 ° / 0 are suitable, but there are preferably used 5 to 25 ° / 0 water vapor, based on the feed gas. Water vapor acts as a reaction moderator, which reduces the formation of CO and CO 2 . The nitrile compound formed also has an influence on the reaction conditions. The number of nitriles formed and the volatility of the alkyl or alkenyl aromatic constituents of the feed must be taken into account. The temperatures used are in the range from 200 to 800 ° C., preferably from 325 to 500 ° C. In the case of the production of terephthalic acid nitrile, the preferred temperatures are between 425 and 600 ° C.
Man kann mit gutem Erfolg bei Atmosphärendruck arbeiten, doch können auch Drücke von bis zu 100 at angewandt werden. Die Durchsatzgeschwindigkeiten in Volumteilen, bezogen auf das Vorrichtungsvolumen, liegen zwischen 500 und 4000 je Stunde, vorzugsweise zwischen 1000 und 2500 je Stunde.You can work at atmospheric pressure with good success, but pressures of up to 100 at can be applied. The throughput rates in parts by volume, based on the device volume, are between 500 and 4000 per hour, preferably between 1000 and 2500 per hour.
Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.
3535
Zum Nachweis der hervorragenden Ergebnisse, die durch Verwendung des erfindungsgemäßen Katalysators erhalten werden, werden Vergleichsversuche mit anderen Katalysatoren durchgeführt. In der Tabelle II ist die Katalysatorkomponente in Prozent, die Temperatur der Salzschmelze und die Ausbeute an Terephthalsäuredinitril aufgeführt.To demonstrate the excellent results obtained by using the catalyst according to the invention are obtained, comparative tests are carried out with other catalysts. In Table II is the catalyst component in percent, the temperature of the molten salt and the yield of terephthalic acid dinitrile listed.
Tempe
raturSalt-
Tempe
rature
MolTPN
Mole
Der erfindungsgemäße Katalysator war folgendermaßen hergestellt worden: 20,8 g Vanadinpentoxid werden zu 100 ml konzentrierter Salzsäure gegeben. Durch die erhaltene Lösung wird Schwefeldioxid geleitet, bis die Lösung klar blau und homogen geworden ist. Eine zweite Lösung wird aus 202 g Antimontrichlorid in 400 ml konzentrierter Salzsäure hergestellt. Die beiden Lösungen werden miteinander vermischt, zu 1440 g tafelförmigem Aluminiumoxid (»Alcoa T-71«, Produkt der »Aluminium Company of America«) mit einer Korngröße von 6,35 bis 2,38 mm gegeben und in einem Rotationsverdampfer getrocknet. Der Katalysator wird dann durch Erhitzen auf 4250C in einem Ofen kalziniert. Die Temperatur wird 2 Stunden aufrechterhalten. Der fertige Katalysator enthält 1,3 Gewichtsprozent Vanadinpentoxid und 8,1 Gewichtsprozent Antimontrioxid auf Aluminiumoxid. Der kaizinierte Katalysator wird in ein ummanteltes Stahlrohr (2,54 cm Außendurchmesser · 305 cm) bis zu einer Betthöhe von etwa 290 cm eingefüllt. Ein Gasgemisch, das bezogen auf das Volumen I0I0 p-Xylol, 10°/0 Wasserdampf, 6 °/0 Ammoniak und 83 % Luft enthält, wird mit einer auf das Volumen bezogenen Durchsatzgeschwindigkeit von 1500/Stunde durch den Katalysator geleitet. Das Rohr wird durch eine in dem Mantel im Gegenstrom zu der Beschickung umlaufende Salzschmelze auf etwa 3900C erhitzt.The catalyst according to the invention was prepared as follows: 20.8 g of vanadium pentoxide are added to 100 ml of concentrated hydrochloric acid. Sulfur dioxide is passed through the resulting solution until the solution has become clear blue and homogeneous. A second solution is made from 202 g of antimony trichloride in 400 ml of concentrated hydrochloric acid. The two solutions are mixed together, added to 1440 g of tabular aluminum oxide ("Alcoa T-71", product of the "Aluminum Company of America") with a particle size of 6.35 to 2.38 mm and dried in a rotary evaporator. The catalyst is then calcined by heating to 425 ° C. in an oven. The temperature is maintained for 2 hours. The finished catalyst contains 1.3 percent by weight vanadium pentoxide and 8.1 percent by weight antimony trioxide on alumina. The calcined catalyst is poured into a jacketed steel tube (2.54 cm outer diameter x 305 cm) up to a bed height of about 290 cm. A gas mixture which, based on the volume, contains I 0 I 0 p-xylene, 10 ° / 0 water vapor, 6 ° / 0 ammonia and 83% air is passed through the catalyst at a throughput rate of 1500 / hour based on the volume. The tube is heated to about 390 ° C. by a molten salt circulating in the jacket in countercurrent to the charge.
Bei praktisch vollständiger Umwandlung wird Terephthalsäuredinitril in einer Ausbeute von 82,5 Molprozent erhalten.When the conversion is practically complete, terephthalic acid dinitrile is obtained in a yield of 82.5 mole percent obtained.
Beim Versuch Nr. 2 wird das Zinn als wäßrige Zinn(II)-chloridlösung in den Katalysator eingeführt.In experiment no. 2, the tin is introduced into the catalyst as an aqueous tin (II) chloride solution.
In Versuch Nr. 3 wird das Chrom als wäßrige Chromtrioxidlösung eingeführt.In experiment no. 3, the chromium is introduced as an aqueous chromium trioxide solution.
Aus der Tabelle II geht hervor, daß der im Beispiel 1 beschriebene Vanadin-Antimon-Katalysator den vergleichsweise angewandten Katalysatoren überlegen ist. Der nächstbeste Katalysator, der Vanadin-Zinn-Katalysator, hat eine Selektivität, die um mehr als 10 Teile unter der durch das erfindungsgemäße Verfahren erreichten liegt. Überraschenderweise ist der Antimonkatalysator für sich allein völlig unwirksam, und erst in Verbindung mit dem Vanadin, das für sich allein gleichfalls kein guter Katalysator ist, werden die besonders hohen Ausbeuten erhalten.From Table II it can be seen that the vanadium-antimony catalyst described in Example 1 is the comparative applied catalysts is superior. The next best catalyst, the vanadium tin catalyst, has a selectivity which is more than 10 parts below that achieved by the process of the invention lies. Surprisingly, the antimony catalyst is completely ineffective on its own, and only in combination with vanadium, which is also not a good catalyst on its own, they become special obtained high yields.
Der Versuch Nr. 1 wurde wiederholt, mit der Ausnahme, daß m-Xylol als Ausgangsstoff verwendet wurde. Isophthalsäuredinitril wurde in einer Ausbeute von 65 °/0 erhalten.Experiment No. 1 was repeated with the exception that m-xylene was used as the starting material. Isophthalonitrile was obtained in a yield of 65 ° / 0th
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39020664A | 1964-08-17 | 1964-08-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1286002B true DE1286002B (en) | 1969-01-02 |
Family
ID=23541548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH56900A Pending DE1286002B (en) | 1964-08-17 | 1965-08-17 | Process for the production of aromatic nitriles |
Country Status (7)
| Country | Link |
|---|---|
| BE (1) | BE668043A (en) |
| CH (1) | CH448989A (en) |
| DE (1) | DE1286002B (en) |
| ES (1) | ES316568A1 (en) |
| GB (1) | GB1114898A (en) |
| IL (1) | IL24162A (en) |
| LU (1) | LU49318A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2082930A5 (en) * | 1969-09-26 | 1971-12-10 | Degussa | |
| DE2711332A1 (en) * | 1977-01-14 | 1978-07-20 | Nippon Kayaku Kk | PROCESS FOR PRODUCING AROMATIC NITRILE |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56139444A (en) | 1980-04-01 | 1981-10-30 | Takeda Chem Ind Ltd | Production of aromatic nitrile |
| US6413485B2 (en) * | 1999-05-27 | 2002-07-02 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and HCN |
| EP2428267A1 (en) * | 2010-09-08 | 2012-03-14 | Leibniz-Institut für Katalyse e.V. an der Universität Rostock | Catalyst, its preparation and use for the preparation of nitriles from alkyl aromatic or heteroaromatic compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1071690B (en) * | 1959-12-24 | The Dis'ftilliens Coimpany Limided, Edinburgh (Großbritannien) | Process for the production of nitriles and / or imiiiden of bienzo carboxylic acids | |
| US3041363A (en) * | 1959-08-14 | 1962-06-26 | Dow Corning | Silethylenesiloxane copolymers |
| DE1141274B (en) * | 1960-08-20 | 1962-12-20 | Bayer Ag | Process for the production of aromatic nitriles |
-
1965
- 1965-08-04 GB GB33386/65A patent/GB1114898A/en not_active Expired
- 1965-08-09 BE BE668043D patent/BE668043A/xx unknown
- 1965-08-13 LU LU49318D patent/LU49318A1/xx unknown
- 1965-08-16 CH CH1148865A patent/CH448989A/en unknown
- 1965-08-16 IL IL24162A patent/IL24162A/en unknown
- 1965-08-17 ES ES0316568A patent/ES316568A1/en not_active Expired
- 1965-08-17 DE DEH56900A patent/DE1286002B/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1071690B (en) * | 1959-12-24 | The Dis'ftilliens Coimpany Limided, Edinburgh (Großbritannien) | Process for the production of nitriles and / or imiiiden of bienzo carboxylic acids | |
| US3041363A (en) * | 1959-08-14 | 1962-06-26 | Dow Corning | Silethylenesiloxane copolymers |
| DE1141274B (en) * | 1960-08-20 | 1962-12-20 | Bayer Ag | Process for the production of aromatic nitriles |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2082930A5 (en) * | 1969-09-26 | 1971-12-10 | Degussa | |
| DE2711332A1 (en) * | 1977-01-14 | 1978-07-20 | Nippon Kayaku Kk | PROCESS FOR PRODUCING AROMATIC NITRILE |
Also Published As
| Publication number | Publication date |
|---|---|
| CH448989A (en) | 1967-12-31 |
| GB1114898A (en) | 1968-05-22 |
| BE668043A (en) | 1966-02-09 |
| IL24162A (en) | 1969-07-30 |
| ES316568A1 (en) | 1965-11-16 |
| LU49318A1 (en) | 1967-02-13 |
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