JPS6372675A - Production of hetero aromatic nitrile - Google Patents
Production of hetero aromatic nitrileInfo
- Publication number
- JPS6372675A JPS6372675A JP61218485A JP21848586A JPS6372675A JP S6372675 A JPS6372675 A JP S6372675A JP 61218485 A JP61218485 A JP 61218485A JP 21848586 A JP21848586 A JP 21848586A JP S6372675 A JPS6372675 A JP S6372675A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- catalyst
- alkyl
- ammonia
- antimony
- 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 hetero aromatic nitrile Chemical class 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002390 heteroarenes Chemical class 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 239000001301 oxygen Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 150000001463 antimony compounds Chemical class 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000003682 vanadium compounds Chemical class 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 2
- 238000007254 oxidation reaction Methods 0.000 abstract 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- CAWHJQAVHZEVTJ-UHFFFAOYSA-N methylpyrazine Chemical compound CC1=CN=CC=N1 CAWHJQAVHZEVTJ-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- PMSVVUSIPKHUMT-UHFFFAOYSA-N cyanopyrazine Chemical compound N#CC1=CN=CC=N1 PMSVVUSIPKHUMT-UHFFFAOYSA-N 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- OXQOBQJCDNLAPO-UHFFFAOYSA-N 2,3-Dimethylpyrazine Chemical compound CC1=NC=CN=C1C OXQOBQJCDNLAPO-UHFFFAOYSA-N 0.000 description 2
- LCZUOKDVTBMCMX-UHFFFAOYSA-N 2,5-Dimethylpyrazine Chemical compound CC1=CN=C(C)C=N1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 239000001934 2,5-dimethylpyrazine Substances 0.000 description 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012002 vanadium phosphate 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】
〈産業上の利用分身〉
本発明はアルキル置換へテロ芳香族化合物をアンモニア
及び分子状酸素の存在下に気相アンモ酸化し、ヘテロ芳
香族ニトリル類を製造する方法に関する。[Detailed Description of the Invention] <Industrial Application> The present invention relates to a method for producing heteroaromatic nitriles by gas-phase ammoxidation of an alkyl-substituted heteroaromatic compound in the presence of ammonia and molecular oxygen. .
〈従来技術および本発明が解決しようとする問題点〉ア
ルキル置換芳香族化合物を原料として対応するニトリル
類を合成するアンモ酸化触媒として、酸化バナジウムを
主体とする触媒がよく知られている。しかし、これらの
触媒は、アルキル置換へテロ芳香族のアンモ酸化の場合
活性が強すぎて、脱アルキル化反応、あるいは、ヘテロ
芳香族環の開裂などの異常反応が起こり、目的生成物で
あるニトリル類の選択率及び収率が低下するという欠点
があった。<Prior Art and Problems to be Solved by the Present Invention> Catalysts based on vanadium oxide are well known as ammoxidation catalysts for synthesizing corresponding nitriles using alkyl-substituted aromatic compounds as raw materials. However, these catalysts are too active for the ammoxidation of alkyl-substituted heteroaromatics, resulting in abnormal reactions such as dealkylation or cleavage of the heteroaromatic ring, resulting in the production of the desired nitrile. There was a drawback that the selectivity and yield of 2.
アルキル置換へテロ芳香族化合物のアンモ酸化触媒とし
ては、特公昭５７−１９７０６号公報に、アンチモン、
バナジウムの酸化物と鉄、銅、チタン、コバルト、マン
ガン及びニッケルカラする群から選ばれる少なくとも１
種の元素の酸化物からなる触媒が開示されている。これ
は比較的高い選択性を示すが、アンモニアの還元を受け
て、活性が低下しやすいという欠点がある。As ammoxidation catalysts for alkyl-substituted heteroaromatic compounds, antimony,
Vanadium oxide and at least one member selected from the group consisting of iron, copper, titanium, cobalt, manganese and nickel.
Catalysts comprising oxides of certain elements are disclosed. Although this shows relatively high selectivity, it has the disadvantage that it is susceptible to reduction of ammonia and its activity tends to decrease.
本発明者らは鋭意検討を重ねた結果、アルキル置換へテ
ロ芳香族化合物をアンモニア及び分子状酸素の存在下に
気相アンモ酸化し、対応するニトリル類を合成するに際
し、異常反応が起こりにくく、収率及び選択率が高い上
に、耐熱、耐還元性を備え、操業上の安全性の高い触媒
を見い出し、本発明を完成するに到った。As a result of extensive studies, the present inventors found that abnormal reactions are less likely to occur when alkyl-substituted heteroaromatic compounds are subjected to gas phase ammoxidation in the presence of ammonia and molecular oxygen to synthesize corresponding nitriles. The present invention has been completed by discovering a catalyst that not only has high yield and selectivity but also has heat resistance and reduction resistance, and is highly operationally safe.
〈問題点を解決するための手段〉
本発明は、アルキル置換へテロ芳香族化合物をアンモニ
ア及び分子状酸素の存在下に、気相アンモ酸化するに際
し、式
％式％（１）
で表わされる化学式を有する触媒を使用することを特徴
とするヘテロ芳香族ニトリル類の製造法テある。<Means for Solving the Problems> The present invention provides a method for ammoxidizing an alkyl-substituted heteroaromatic compound in the gas phase in the presence of ammonia and molecular oxygen. There is a method for producing heteroaromatic nitriles characterized by using a catalyst having the following.
本発明において特に好ましい触媒は、式（１）において
ａが２Ｓ−４、ｂが０．２〜１．５の値をとるものであ
る。（但しＣは、他の元素の原子価から求まる値である
。）
本発明における触媒の調製方法としては、一般に広く知
られている調製方法が適用できる。例えば水にバナジウ
ム化合物、アンチモン化合物及びリン化合物を加え、更
に必要があれば、担体を加え蒸発乾固し、それを焼成す
ることにより得られる。焼成温度は４６０〜８００°Ｃ
で空気あるいは、不活性ガス存在下、数時間〜２０時間
焼成を行う。Particularly preferred catalysts in the present invention are those in formula (1) in which a has a value of 2S-4 and b has a value of 0.2 to 1.5. (However, C is a value determined from the valences of other elements.) As a method for preparing the catalyst in the present invention, generally widely known preparation methods can be applied. For example, it can be obtained by adding a vanadium compound, an antimony compound, and a phosphorus compound to water, and if necessary, adding a carrier and evaporating to dryness, followed by firing. Firing temperature is 460-800°C
Firing is performed for several hours to 20 hours in air or in the presence of an inert gas.
触媒をＷＩｌする際に用いる各踵元素の化合物は、特殊
なものに限らず、通常用いる化合物は、いずれも使用す
ることができる。バナジウム化合物としては、メタパナ
、ジン酸アンモニウム、五酸化バナジウム、リン酸バナ
ジウム等。アンチモン化合物としては、金属アンチモン
、三二酸化アンチモン、三二酸化アンチモン、三塩化ア
ンチモン等。The compound of each heel element used in WIl of the catalyst is not limited to a special one, and any commonly used compound can be used. Vanadium compounds include metapana, ammonium zinate, vanadium pentoxide, vanadium phosphate, etc. Antimony compounds include antimony metal, antimony sesquioxide, antimony sesquioxide, and antimony trichloride.
リン化合物としては、リン酸、メタリン酸、亜リン酸、
リン酸塩等が使、用できる。Phosphorus compounds include phosphoric acid, metaphosphoric acid, phosphorous acid,
Phosphates etc. can be used.
本発明における触媒は、担体を用いてもよいが、特にシ
リカ、ケイソウ土、シリコーンカーバイド等が好ましい
。Although a carrier may be used as the catalyst in the present invention, silica, diatomaceous earth, silicone carbide, etc. are particularly preferred.
本発明におけるアルキル置換へテロ芳香族化合物として
は、例えば２−メチルピリジン、８−メチルピリジン等
のピコリン類；２，３−ジメチルル
ピリジン、３，４−ジメチルピリジン等の号チジン類；
２−メチルー５−エチルピリジン： ２ 、４゜６−ト
リメチルピリジン、２，８．４−トリメチルピリジン等
のコリジン類；メチルピラジン、２゜８−ジメチルピラ
ジン、２．５−ジメチルピラジン、２，６−ジメチルピ
ラジン等のピラジン類があげられる。Examples of the alkyl-substituted heteroaromatic compound in the present invention include picolines such as 2-methylpyridine and 8-methylpyridine; thidines such as 2,3-dimethyllpyridine and 3,4-dimethylpyridine;
2-Methyl-5-ethylpyridine: Collidines such as 2,4゜6-trimethylpyridine, 2,8.4-trimethylpyridine; methylpyrazine, 2゜8-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6 -Pyrazines such as dimethylpyrazine are mentioned.
反応供給ガス中のアルキル置換へテロ芳香族化合物の濃
度は、０．５〜７モル％が好ましい。反応供給ガス中の
アルキル置換へテロ芳香族化合物、アンモニア及び分子
状酸素の好ましいモル比は、１：５〜４０：１〜５であ
る。この他、不活性気亀
体、例えば水蒸気あるいは、窒素等で希釈することがで
きる。The concentration of the alkyl-substituted heteroaromatic compound in the reaction feed gas is preferably 0.5 to 7 mol%. The preferred molar ratio of alkyl-substituted heteroaromatic compound, ammonia and molecular oxygen in the reaction feed gas is 1:5 to 40:1 to 5. In addition, it can be diluted with an inert gas such as water vapor or nitrogen.
本発明における反応温度は、２８０〜６００°Ｃであり
、好ましくは、８００〜５００″Ｃである。The reaction temperature in the present invention is 280 to 600°C, preferably 800 to 500''C.
空間速度は７００〜８，５００ Ｈｒ−’である。反応
は通常常圧で行われるが、減圧あるいは、加圧下におい
ても実施することができる。The space velocity is 700-8,500 Hr-'. The reaction is usually carried out at normal pressure, but it can also be carried out under reduced pressure or increased pressure.
反応器は、通常の固定床で行えるが流動床を用いること
もできる。The reactor can be a normal fixed bed, but a fluidized bed can also be used.
〈発明の効果〉
本発明の方法とリンを含まない触媒を用いた本発明以外
の方法（比較例）を比較すると、前者では例えば（実施
例８）収率９６％のとき５００時間後の収率は９１８％
、後者では収率８６％のとき５００時間後の収率は５２
．７％である。即ち本発明の触媒は耐熱性、耐還元性を
備え、触媒活性の低下が非常に少ない優れたものである
。<Effects of the Invention> Comparing the method of the present invention and a method other than the present invention (comparative example) using a catalyst that does not contain phosphorus, it is found that in the former case, for example (Example 8), the yield after 500 hours was 96%. The rate is 918%
In the latter case, when the yield is 86%, the yield after 500 hours is 52
．． It is 7%. That is, the catalyst of the present invention has excellent heat resistance and reduction resistance, and exhibits very little decrease in catalytic activity.
以下、実施例により説明する。Examples will be explained below.
なお反応率及び収率は、次の定義に従って計算した。Note that the reaction rate and yield were calculated according to the following definitions.
実施例１
メタバナジン酸アンモニウム２４１１三酸化アンチモン
６０ｇを０．５１の水に懸濁させる。この懸濁液に８５
％リン酸２８．８ｆを加えて加熱し、担体としてシリカ
７４１を加え、更に加熱濃縮し、ペースト状にし蒸発乾
固したのち、７５０℃で８時間空気存在下で焼成した。Example 1 60 g of ammonium metavanadate 2411 antimony trioxide are suspended in 0.51 g of water. 85 to this suspension
% phosphoric acid was added and heated, silica 741 was added as a carrier, and the mixture was further heated and concentrated to form a paste, evaporated to dryness, and then calcined at 750° C. for 8 hours in the presence of air.
このようにして得られた触媒の組成は、Ｖ Ｓｂｓ Ｐ
ｏ、ｓｓ ｏ７Ｊ２ であツタ。The composition of the catalyst thus obtained is V Sbs P
o, ss o7J2 and ivy.
得られた触媒を砕いて、１０〜１６メツシユにそろえ、
２５−を固定床反応器に充填した。反応器を電気炉で加
熱し４２０″Ｃに保った。Crush the obtained catalyst and arrange it into 10 to 16 mesh pieces.
25- was charged into a fixed bed reactor. The reactor was heated in an electric furnace and maintained at 420''C.
２−メチルピラジン３モル％、アンモニア５７モル％、
空気２６モル％、水蒸気１４モル％を含む混合ガスを反
応器に供給し、空間速度８５０Ｈｒ ’ で反応を行
った。反応率９９％、２−シアノピラジン収率８６％で
あった。2-methylpyrazine 3 mol%, ammonia 57 mol%,
A mixed gas containing 26 mol % of air and 14 mol % of water vapor was supplied to the reactor, and the reaction was carried out at a space velocity of 850 Hr'. The reaction rate was 99% and the yield of 2-cyanopyrazine was 86%.
実施例２
実施例１の触媒を用いて、２−メチルピリジンのアンモ
酸化を行った。Example 2 Using the catalyst of Example 1, 2-methylpyridine was ammoxidized.
２−メチルビリジン２．４モル％、アンモニア２４．４
モル％、空気８６．６モル％及び水蒸気８６．６モル％
を含む混合ガスを反応器に供給し反応器温度を４２０″
Ｃに保ち、空間速度８，０００Ｈｒ’で反応を行った。2-methylpyridine 2.4 mol%, ammonia 24.4
mol%, air 86.6 mol% and water vapor 86.6 mol%
A mixed gas containing
The reaction was carried out at a space velocity of 8,000 Hr'.
′ 反応率９９％、２−シアノピリジン収率７８％であ
った。' The reaction rate was 99%, and the yield of 2-cyanopyridine was 78%.
実施例８
実施例１の触媒を用いて４−メチルピリジンのアンモ酸
化を行った。Example 8 Using the catalyst of Example 1, 4-methylpyridine was ammoxidized.
４−メチルビリジン４．０モル％、アンモニア２０モル
％、空気４０モル％及び水蒸気８６モル％を含む混合ガ
スを反応器に供給し、反応器温度を８４０ ’Ｃに保ち
、空間速度８，０００Ｈｒ’で反応を行った。A mixed gas containing 4.0 mol% of 4-methylpyridine, 20 mol% of ammonia, 40 mol% of air, and 86 mol% of water vapor was supplied to the reactor, the reactor temperature was maintained at 840'C, and the space velocity was 8,000 Hr. 'The reaction was performed.
反応率９９％、４−シアノピリジン収率９６％であった
。又、５００時間後の収率は９２．８％であった。The reaction rate was 99% and the yield of 4-cyanopyridine was 96%. Moreover, the yield after 500 hours was 92.8%.
実施例４〜６
メタバナジン酸アンモニウム１６ｆ１三酸化アンチモン
４０ｇを０，４ｔの水に懸濁させる。この懸濁液に、８
５％リン酸５．４ｇ及び濃硝酸８２Ｎを加えて加熱し、
担体としそ、ベントナイト４９．５ｆを加え、更に加熱
し蒸発乾固したのち７５０°Ｃで８時間空気存在下で焼
成した。このようにして得られた触媒の組成はＶ Ｓｂ
２ ｐ ０−８４０ｓ、ａｓ ｉ’ ｊ） うた。Examples 4-6 40 g of ammonium metavanadate 16f1 antimony trioxide are suspended in 0.4 t of water. To this suspension, add 8
Add 5.4 g of 5% phosphoric acid and 82 N of concentrated nitric acid and heat.
The carrier, soybean, and 49.5 f of bentonite were added, and the mixture was further heated and evaporated to dryness, and then calcined at 750°C for 8 hours in the presence of air. The composition of the catalyst thus obtained was V Sb
2 p 0-840s, as i' j) Song.
実施例１〜８と同様の反応を行い、第１表の結果を得た
。The same reactions as in Examples 1 to 8 were carried out, and the results shown in Table 1 were obtained.
比較例
メタバナジン酸アンモニウム１６ｇ、三酸化アンチモン
８０ｇを０．４ｔの水に懸濁させ、加熱濃縮し、蒸発乾
固したのち、７５０℃で８時間空気存在下で焼成した。Comparative Example 16 g of ammonium metavanadate and 80 g of antimony trioxide were suspended in 0.4 t of water, concentrated by heating, evaporated to dryness, and then calcined at 750° C. for 8 hours in the presence of air.
このようにして得られた触媒の組成はＶ Ｓｂ４０１１
．５ であった。The composition of the catalyst thus obtained was V Sb4011
．． It was 5.
実施例１と同様の反応を行った。反応率８７％、２−シ
アノピラジン収率８６％であった。５００時間後反応器
温度４５０″Ｃで反応率７１，４％、２−シアノピラジ
ン収率５２．７％になった。The same reaction as in Example 1 was carried out. The reaction rate was 87% and the yield of 2-cyanopyrazine was 86%. After 500 hours, the reaction rate was 71.4% and the yield of 2-cyanopyrazine was 52.7% at a reactor temperature of 450''C.
Claims (1)
状酸素の存在下に、気相アンモ酸化するに際し、式 ＶＳｂ＿ａＰ＿ｂＯ＿ｃ（ I ） 式中ａ、ｂ及びｃは、それぞれアンチモン、リン及び酸
素の原子数を示し、ａは０．１〜８、ｂは０．１〜５、
ｃは他の元素の原子価から求まる値である。 で表わされる化学式を有する触媒を使用することを特徴
とするヘテロ芳香族ニトリル類の製造法。[Claims] When alkyl-substituted heteroaromatic compounds are subjected to gas-phase ammoxidation in the presence of ammonia and molecular oxygen, the formula VSb_aP_bO_c (I) where a, b and c are antimony, phosphorus and oxygen, respectively Indicates the number of atoms, a is 0.1 to 8, b is 0.1 to 5,
c is a value determined from the valences of other elements. 1. A method for producing heteroaromatic nitriles, the method comprising using a catalyst having the chemical formula represented by:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61218485A JPS6372675A (en) | 1986-09-16 | 1986-09-16 | Production of hetero aromatic nitrile |
| EP19870110158 EP0253360B1 (en) | 1986-07-15 | 1987-07-14 | Process for preparing nitriles |
| DE19873788308 DE3788308T2 (en) | 1986-07-15 | 1987-07-14 | Process for the production of nitriles. |
| US07/075,037 US4778890A (en) | 1986-08-04 | 1987-07-16 | Process for preparing nitriles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61218485A JPS6372675A (en) | 1986-09-16 | 1986-09-16 | Production of hetero aromatic nitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6372675A true JPS6372675A (en) | 1988-04-02 |
Family
ID=16720662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61218485A Pending JPS6372675A (en) | 1986-07-15 | 1986-09-16 | Production of hetero aromatic nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6372675A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001187783A (en) * | 1999-12-28 | 2001-07-10 | Koei Chem Co Ltd | Method for producing cyanoisoquinolines |
-
1986
- 1986-09-16 JP JP61218485A patent/JPS6372675A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001187783A (en) * | 1999-12-28 | 2001-07-10 | Koei Chem Co Ltd | Method for producing cyanoisoquinolines |
| JP4686001B2 (en) * | 1999-12-28 | 2011-05-18 | 広栄化学工業株式会社 | Method for producing cyanoisoquinolines |
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