JPS6310753A - Production of aromatic nitrile or hetero aromatic nitrile - Google Patents
Production of aromatic nitrile or hetero aromatic nitrileInfo
- Publication number
- JPS6310753A JPS6310753A JP61154741A JP15474186A JPS6310753A JP S6310753 A JPS6310753 A JP S6310753A JP 61154741 A JP61154741 A JP 61154741A JP 15474186 A JP15474186 A JP 15474186A JP S6310753 A JPS6310753 A JP S6310753A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- catalyst
- antimony
- tin
- ammonia
- 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 nitrile Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 9
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 9
- 150000002390 heteroarenes Chemical class 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 239000004408 titanium dioxide Substances 0.000 abstract description 5
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 239000012495 reaction gas Substances 0.000 abstract description 2
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003118 aryl group Chemical class 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 6
- 229910052718 tin Inorganic materials 0.000 description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 description 2
- MFEIKQPHQINPRI-UHFFFAOYSA-N 3-Ethylpyridine Chemical compound CCC1=CC=CN=C1 MFEIKQPHQINPRI-UHFFFAOYSA-N 0.000 description 2
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 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
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PMSVVUSIPKHUMT-UHFFFAOYSA-N cyanopyrazine Chemical compound N#CC1=CN=CC=N1 PMSVVUSIPKHUMT-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 description 1
- NJQZTGGQYUUYKS-UHFFFAOYSA-N 4-ethyl-3-methylpyridine Chemical compound CCC1=CC=NC=C1C NJQZTGGQYUUYKS-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はアルキル置換芳香族化合物又はアルキル置換ヘ
テロ芳香族化合物とアンモニアおよび分子状酸素を触媒
の存在下気相接触反応させることにより、対応する芳香
族ニトリル又はヘテロ芳香族ニトリルを製造する方法に
関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the reaction of an alkyl-substituted aromatic compound or an alkyl-substituted heteroaromatic compound with ammonia and molecular oxygen by gas phase contact reaction in the presence of a catalyst. The present invention relates to a method for producing an aromatic nitrile or a heteroaromatic nitrile.
〈従来技術および本発明が解決しようとする問題点〉す
でに、適当な触媒を用いてアルキル置換された芳香族又
は、ヘテロ芳香族化合物類をアンモニアおよび酸素を含
むガスと接触反応させることにより、対応するニトリル
類を得る方法は公知である（特公昭４５−１９２８５号
公報、特公昭５７−４９７０６号公報、特公昭５８−４
１７号公報）、。<Prior art and problems to be solved by the present invention> Problems to be solved by the present invention have already been solved by catalytically reacting alkyl-substituted aromatic or heteroaromatic compounds with a gas containing ammonia and oxygen using an appropriate catalyst. Methods for obtaining nitrites are known (Japanese Patent Publication No. 45-19285, Japanese Patent Publication No. 57-49706, Japanese Patent Publication No. 58-4).
Publication No. 17),.
即ち、その際有効な触媒として特にアンチモン、バナジ
ウム、モリブデン、タングステン、クロム、錫およびマ
ンガン等の酸化物又はそれらの複合酸化物が用いられて
いる。また、これらはシリカ、アルミナ、二酸化チタン
、珪藻土、シリコンカーバイド、カオリン、ベントナイ
トおよびこれらの複合酸化物等を担体として使用してい
る。しかし、公知の方法および触媒では、過度の酸化に
よる副反応が起こりやすく又空気の割合が非常に過剰で
あったり、大量の不活性ガスの共存により空時収率が低
くかつ捕集が困難になる傾向があった。しかも選択率等
未だ充分に満足し得るものではなかった。That is, oxides of antimony, vanadium, molybdenum, tungsten, chromium, tin, manganese, etc. or composite oxides thereof are used as effective catalysts in this case. Furthermore, these use silica, alumina, titanium dioxide, diatomaceous earth, silicon carbide, kaolin, bentonite, composite oxides of these, and the like as carriers. However, with known methods and catalysts, side reactions are likely to occur due to excessive oxidation, and the space-time yield is low and collection is difficult due to the extremely excessive proportion of air or the coexistence of a large amount of inert gas. There was a tendency to Moreover, the selectivity was still not fully satisfactory.
本発明者らは、鋭意研究した結果、アンチモンおよび錫
の酸化物を含有する触媒を用いることにより、従来に見
られない性能即ち触媒層の局所での過度の発熱および過
度の酸化による副反応を抑制し、かつ空気の割合が比較
的小さい範囲でも又不活性ガスの割合が小さくても反応
を行うことができ、空時収率がとがり、捕集も容易にな
り、しかも高選択率で目的物が得られることを見い出し
た。これにより、工業的製造における安全性が大きく改
善されると共に、生産性が上がりより安価に芳香族ニト
リルまたはヘテロ芳香族ニトリルを製造できるようにな
った。As a result of extensive research, the present inventors have found that by using a catalyst containing antimony and tin oxides, they have achieved unprecedented performance, that is, excessive heat generation locally in the catalyst layer and side reactions caused by excessive oxidation. The reaction can be carried out even if the proportion of air is relatively small or the proportion of inert gas is small, the space-time yield is high, collection is easy, and the target can be achieved with high selectivity. I discovered that things can be obtained. As a result, safety in industrial production has been greatly improved, productivity has increased, and aromatic nitriles or heteroaromatic nitriles can now be produced at lower cost.
く問題点を解決するための手段〉
本発明は、アルキル置換芳香族化合物又はアルキル置換
ヘテロ芳香族化合物とアンモニアおよび分子状酸素を触
媒の存在下気相接触反応させることにより、対応する芳
香族ニトリル又はヘテロ芳香族ニトリルを製造する方法
において触媒としてアンチモンおよび錫の酸化物を含有
する触媒を用いることを特徴とする芳香族ニトリル又は
ヘテロ芳香族ニトリルの製造方法である。本発明の融媒
に使用されるアンチモンおよび錫の酸化物は、酸化物に
変じることのできる任意の化合物から出発合成すること
ができる。たとえば、金属アンチモン、水酸化アンチモ
ン、ハロゲン化アンチモンなどのアンチモン化合物およ
び金属錫、ハロゲン化錫、水酸化錫、シュウ酸錫、酢酸
錫、硫酸錫などの錫化合物等を用い、空気中で加熱焼成
するなどの方法を用いることができる。アンチモンと錫
の原子比は特に制限はないが、好ましい比率は、１：０
．０５〜１０、特に好ましい比率は、１：０，２〜５で
ある。触媒は、公知の方法を広く適用して製造すること
ができる。また触媒は単独でも用い得るがアルミナ、シ
リカ、二酸化チタン、珪藻土、シリコンカーバイド、カ
オリン、ベントナイトなどの適当な担体と共に用いるこ
とができる。たとえば、水酸化第２錫、三酸化アンチモ
ンを適当な担体と共に混合する。しかしながら、水を添
加し、場合によっては１種以上の混合すべき物質を水溶
液または水中の懸濁液として導入し、この水含有混合物
を蒸発乾固させても良い。これらの混合物を徐々に加熱
し、最終的には４００−１０００°Ｃまで昇温焼成し、
触媒を調製する。Means for Solving the Problems> The present invention provides a solution to a corresponding aromatic nitrile by subjecting an alkyl-substituted aromatic compound or an alkyl-substituted heteroaromatic compound to a gas phase contact reaction with ammonia and molecular oxygen in the presence of a catalyst. Alternatively, a method for producing an aromatic nitrile or a heteroaromatic nitrile is characterized in that a catalyst containing an oxide of antimony and tin is used as a catalyst in the method for producing a heteroaromatic nitrile. The antimony and tin oxides used in the melting medium of the present invention can be synthesized starting from any compound that can be converted into an oxide. For example, antimony compounds such as antimony metal, antimony hydroxide, and antimony halides, and tin compounds such as tin metal, tin halides, tin hydroxide, tin oxalate, tin acetate, and tin sulfate are used and fired in air. Methods such as doing this can be used. The atomic ratio of antimony and tin is not particularly limited, but the preferred ratio is 1:0.
．． 05-10, particularly preferred ratios are 1:0, 2-5. The catalyst can be manufactured by widely applying known methods. Although the catalyst can be used alone, it can also be used in conjunction with a suitable carrier such as alumina, silica, titanium dioxide, diatomaceous earth, silicon carbide, kaolin, bentonite, or the like. For example, stannic hydroxide and antimony trioxide are mixed with a suitable carrier. However, it is also possible to add water and optionally introduce one or more substances to be mixed as an aqueous solution or suspension in water and evaporate this water-containing mixture to dryness. These mixtures are gradually heated and finally fired at a temperature of 400-1000°C.
Prepare the catalyst.
アルキル置換芳香族化合物又は、アルキル置換ヘテロ芳
香族化合物とはトルエン、エチルベンゼン、キシレン、
メシチレン、ジイソプロピルベンゼン、サイメン、メチ
ルナフタ、ジン、α−ピコリン、β−ピコリン、ｒ−ピ
コリン、２．８−ルチジン、２．４−ルチジン、２．５
−ルチジン、２゜６−ルチジン、３．４−ルチジン、３
，５−ルチジン、２．８．４−コリジン、２，８．５−
コリ、ジン、２，８．６−コリジン、２，４．５−コリ
ジン、２，４．６−コリジン、３，４．５−コリジン、
２−エチルピリジン、３−エチルピリジン、４−エチル
ピリジン、２−メチル−５−エチルピリジン、３−メチ
ル−４−エチルピリジン、メチルピラジン、２．３−ジ
メチルピラジン、２．５−ジメチルビラジン、２．６−
ジメチルピラジン、で゛
２．３．５−トリメチルピラジンなどＸある。Alkyl-substituted aromatic compounds or alkyl-substituted heteroaromatic compounds include toluene, ethylbenzene, xylene,
Mesitylene, diisopropylbenzene, cymene, methylnaphtha, zine, α-picoline, β-picoline, r-picoline, 2.8-lutidine, 2.4-lutidine, 2.5
-lutidine, 2゜6-lutidine, 3.4-lutidine, 3
, 5-lutidine, 2.8.4-collidine, 2,8.5-
coli, gin, 2,8.6-collidine, 2,4.5-collidine, 2,4.6-collidine, 3,4.5-collidine,
2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-methyl-5-ethylpyridine, 3-methyl-4-ethylpyridine, methylpyrazine, 2.3-dimethylpyridine, 2.5-dimethylvirazine , 2.6-
There are X such as dimethylpyrazine and 2.3.5-trimethylpyrazine.
反応ガス中のアルキル置換芳香族化合物又はアルキル置
換ヘテロ芳香族化合物の濃度は、爆発混合物を形成しな
い範囲で選ぶのが好ましく、アルキル置換芳香族化合物
又は、アルキル置換ヘテロ芳香族化合物：アンモニア：
空気＝ｌ：５〜４０：９〜１００が適当である。この他
不活性希釈剤として水蒸気、窒素、炭酸ガス等を使用す
ることも可能である。反応温度は３００〜６００’Ｏと
広い範囲で実施できるが好ましくは３５０〜５００°Ｃ
が適当である。反応は常圧で行われるが減圧あるいは加
圧下においても実施し得る。反応器は通常の固定床で触
媒層内の異状な温度分布もなく充分に行えるが、流動床
あるいは移動床を用いることも可能である。反応生成物
は適当な方法たとえば空冷冷却器、水冷冷却器、冷媒冷
却器により、凝縮あるいは凝固によってまたは適当な溶
媒に吸収することによって捕集される。The concentration of the alkyl-substituted aromatic compound or alkyl-substituted heteroaromatic compound in the reaction gas is preferably selected within a range that does not form an explosive mixture, and the alkyl-substituted aromatic compound or alkyl-substituted heteroaromatic compound: ammonia:
Air=1:5-40:9-100 is suitable. In addition, it is also possible to use water vapor, nitrogen, carbon dioxide, etc. as an inert diluent. The reaction temperature can be carried out in a wide range of 300 to 600°C, but preferably 350 to 500°C.
is appropriate. The reaction is carried out at normal pressure, but can also be carried out under reduced pressure or increased pressure. Although a conventional fixed bed reactor can be used satisfactorily without abnormal temperature distribution within the catalyst bed, it is also possible to use a fluidized bed or a moving bed. The reaction products are collected in any suitable manner, such as in an air-cooled condenser, water-cooled condenser, refrigerant condenser, by condensation or solidification, or by absorption in a suitable solvent.
次に本発明の実施例について具体的に説明する。Next, examples of the present invention will be specifically described.
実施例１
塩化第２錫７１．５ｆをあらかじめ水に溶解させ、アン
モニア水で中和、沖過、水洗して、ペースト状の水酸化
錫を得たつこの水酸化錫および二酸化アンチモン４０．
０ｙ、二酸化チタン２１．９ｙ、シリカａ ｏ、 ｏ
ｙ、水２４０ｙを混合し、２時間９０〜９５°Ｃで攪拌
加熱した後濃縮する。さらに１２０°Ｃで１０時間乾燥
した後、５時間かけて７５０°Ｃまで昇温し、７５０°
Ｃで３時間焼成した。Example 1 71.5 f of tin chloride was dissolved in water in advance, neutralized with aqueous ammonia, filtered, and washed with water to obtain paste-like tin hydroxide.
0y, titanium dioxide 21.9y, silica ao, o
y and 240 y of water are mixed, stirred and heated at 90-95°C for 2 hours, and then concentrated. After further drying at 120°C for 10 hours, the temperature was raised to 750°C over 5 hours.
It was baked at C for 3 hours.
このようにして調製した触媒１０−を内径１２．６簡φ
のパイレックス製反応管に充填した。トルエン、アンモ
ニア空気及び窒素をそれぞれ１：５：１０ ： １０（
モル比）の割合の混合ガスを５ＶＬＯＯＯＨｒ’であら
かじめ４６０°Ｃに保った反応管に通じた。反応生成物
は０°Ｃに冷却したアセトンに吸収させ、ＦＩＤ−ガス
クロマトグラフに祈
より、分メを行った。トルエンの反応率は９２ｏ、／。The catalyst 10- prepared in this way was
The mixture was filled into a Pyrex reaction tube. Toluene, ammonia air and nitrogen at a ratio of 1:5:10:10 (
A mixed gas having a molar ratio of 5V LOOOHr' was passed through a reaction tube previously maintained at 460°C. The reaction product was absorbed into acetone cooled to 0°C, and fractionated using an FID gas chromatograph. The reaction rate of toluene is 92o,/.
でベンゾニトリルの収率は８５％、選択率は９２％であ
った。The yield of benzonitrile was 85% and the selectivity was 92%.
実施例２
実施例１で調製した触媒を使用し、β−ピコリンＸ ７
ンモニア：空気：水を１：１０：１０：１０（モル比
）の割合の混合ガスを５Ｖ２５００Ｈｒ’であらかじめ
４２０°Ｃに保った反応管に通じた。Example 2 Using the catalyst prepared in Example 1, β-picoline
A mixed gas of ammonia:air:water in a ratio of 1:10:10:10 (molar ratio) was passed through a reaction tube previously maintained at 420°C at 5V, 2500Hr'.
−ピコリンの反応率は８９％でニコチノニトリルの収率
は７２％、選択率は８１％であった。- The reaction rate of picoline was 89%, the yield of nicotinonitrile was 72%, and the selectivity was 81%.
実施例３
実施例１で調製した触媒を使用し、メチルピラを
ジン：アンモニア：空気：水そ１：２０：９：３（モル
比）の割合の混合ガスを５Ｖ７５０Ｈｒ’であらかじめ
４５０°Ｃに保った反応管に通じた。Example 3 Using the catalyst prepared in Example 1, methylpyra was preliminarily maintained at 450°C at 5V750Hr' in a mixed gas of zine:ammonia:air:water in a ratio of 1:20:9:3 (molar ratio). This led to a reaction tube.
反応生成物は０°Ｃに冷却した水に吸収させ、ＦＩＤ４
７′Ｔ
−ガスクロマトグラフにより、分析を行った。メチルピ
ラジンの反応率は８０％でシアノピラジンの収率は７６
％、選択率は９５％であった。The reaction product was absorbed into water cooled to 0°C and FID4
Analysis was performed by 7'T-gas chromatography. The reaction rate of methylpyrazine is 80% and the yield of cyanopyrazine is 76%.
%, and the selectivity was 95%.
実施例４
塩化第２Ｑ１７．９ｙ、三酸化アンチモン４０．Ｏｆ二
酸化チタン２１．９ｙ、シリカ３０．０ノ、水２４０ノ
を用いて実施例１と同様の方法で、触媒を調製し、反応
管の温度を４８０°Ｃにして、実施例３と同様の反応を
行った。メチルピラジンの反応率は７９％でシアノピラ
ジンの収率は７３％、選択率は９２％であった。Example 4 2Q chloride 17.9y, antimony trioxide 40. A catalyst was prepared in the same manner as in Example 1 using 21.9 y of titanium dioxide, 30.0 y of silica, and 240 y of water. The reaction was carried out. The reaction rate of methylpyrazine was 79%, the yield of cyanopyrazine was 73%, and the selectivity was 92%.
Claims (1)
芳香族化合物とアンモニアおよび分子状酸素を触媒の存
在下、気相接触反応させることにより、対応する芳香族
ニトリル又はヘテロ芳香族ニトリルを製造する方法にお
いて触媒として、アンチモンおよび錫の酸化物を含有す
る触媒を用いることを特徴とする芳香族ニトリル又はヘ
テロ芳香族ニトリルの製造方法。 ２、触媒におけるアンチモンと錫の原子比が１：０．２
〜５である特許請求の範囲第１項記載の製造方法[Claims] 1. A corresponding aromatic nitrile or heteroaromatic nitrile is produced by subjecting an alkyl-substituted aromatic compound or an alkyl-substituted heteroaromatic compound to a gas phase catalytic reaction with ammonia and molecular oxygen in the presence of a catalyst. A method for producing an aromatic nitrile or a heteroaromatic nitrile, the method comprising using a catalyst containing an oxide of antimony and tin as a catalyst. 2. The atomic ratio of antimony and tin in the catalyst is 1:0.2
~5 The manufacturing method according to claim 1, which is
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61154741A JPS6310753A (en) | 1986-07-01 | 1986-07-01 | Production of aromatic nitrile or hetero aromatic nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61154741A JPS6310753A (en) | 1986-07-01 | 1986-07-01 | Production of aromatic nitrile or hetero aromatic nitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6310753A true JPS6310753A (en) | 1988-01-18 |
Family
ID=15590905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61154741A Pending JPS6310753A (en) | 1986-07-01 | 1986-07-01 | Production of aromatic nitrile or hetero aromatic nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6310753A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8008314B2 (en) | 2006-08-08 | 2011-08-30 | Dow Agrosciences Llc | Method of recovering cyanopyridines |
-
1986
- 1986-07-01 JP JP61154741A patent/JPS6310753A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8008314B2 (en) | 2006-08-08 | 2011-08-30 | Dow Agrosciences Llc | Method of recovering cyanopyridines |
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