JPH03246269A - Method for increasing yield of acetonitrile - Google Patents
Method for increasing yield of acetonitrileInfo
- Publication number
- JPH03246269A JPH03246269A JP2038333A JP3833390A JPH03246269A JP H03246269 A JPH03246269 A JP H03246269A JP 2038333 A JP2038333 A JP 2038333A JP 3833390 A JP3833390 A JP 3833390A JP H03246269 A JPH03246269 A JP H03246269A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acetonitrile
- acetone
- yield
- ethyl alcohol
- 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 235000019441 ethanol Nutrition 0.000 claims abstract description 20
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- -1 nitrogen- containing hydrocarbon Chemical class 0.000 claims abstract description 9
- 150000002825 nitriles Chemical class 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はアセトニトリルの増収方法に関するものである
。さらに詳しくいえば、本発明は、アンモオキシデーシ
ョン反応により不飽和ニトリルを製造する際に副生する
アセトニトリルを効率よく増収する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for increasing the yield of acetonitrile. More specifically, the present invention relates to a method for efficiently increasing the yield of acetonitrile, which is a by-product when producing unsaturated nitriles by an ammoxidation reaction.
従来の技術
アセトニトリルは医薬、香料、各種有機薬品の合成原料
として、あるいはブチレン−ブタンの抽出溶剤、合成繊
維用溶剤、その他溶剤などとして用いられる工業的価値
の高い化合物である。BACKGROUND OF THE INVENTION Acetonitrile is a compound of high industrial value that is used as a synthetic raw material for medicines, fragrances, and various organic chemicals, as an extraction solvent for butylene-butane, a solvent for synthetic fibers, and other solvents.
このアセトニトリルは主としてプロピレンのアンモオキ
シデーション反応によってアクリロニトリルを製造する
際に副生物として得られているが、近年、アンモオキシ
デーション反応触媒の改良Ｉこよりアセトニトリルの副
反応生成率が低下する一方、アセトニトリルの産業上の
有用性から需要が拡大し供給不足に落ちていっているの
が実情である。This acetonitrile is mainly obtained as a by-product when producing acrylonitrile through the ammoxidation reaction of propylene, but in recent years, the production rate of acetonitrile by side reactions has decreased due to improved ammoxidation reaction catalysts. The reality is that demand has increased due to its industrial utility, leading to a shortage of supply.
しかしながら、該アンモオキシデーション反応において
アセトニトリルを増収する方法については、これまで全
く技術開示がなされておらず、アセトニトリルの増収方
法の開発が強く望まれていＩこ。However, no technical disclosure has been made so far regarding a method for increasing the yield of acetonitrile in the ammoxidation reaction, and there is a strong desire to develop a method for increasing the yield of acetonitrile.
発明が解決しようとする課題
本発明はこのような事情のもとで、アンモオキシデーシ
ョン反応において、主反応生成物の収量を減少させるこ
となく、アセトニトリルを効率よく増収する方法を提供
することを目的としてなされたものである。Problems to be Solved by the Invention Under these circumstances, an object of the present invention is to provide a method for efficiently increasing the yield of acetonitrile in an ammoxidation reaction without reducing the yield of the main reaction product. This was done as a.
課題を解決するための手段
本発明者は、前記目的を達成するために鋭意研究を重ね
た結果、アンモオキシデーション反応において、反応系
にアセトンやエチルアルコールを共存させることにより
、その目的を達成しうろことを見い出し、この知見に基
づいて本発明を完成するに至った。Means for Solving the Problems As a result of extensive research in order to achieve the above object, the present inventor has achieved the object by allowing acetone and ethyl alcohol to coexist in the reaction system in the ammoxidation reaction. They discovered scales and completed the present invention based on this knowledge.
すなわち、本発明は、 炭化水素、含酸素炭化水素又は
含窒素炭化水素にアンモニアと酸素とを反応させ、アン
モオキシデーションにより不飽和ニトリル及びアセトニ
トリルを製造するに当り、反応系にアセトン又はエチル
アルコール若しくはその両方を共存させることを特徴と
するアセトニトリルの増収方法を提供するものである。That is, the present invention involves reacting hydrocarbons, oxygen-containing hydrocarbons, or nitrogen-containing hydrocarbons with ammonia and oxygen to produce unsaturated nitriles and acetonitrile by ammoxidation, and in which acetone, ethyl alcohol, or acetone is added to the reaction system. The present invention provides a method for increasing the yield of acetonitrile, which is characterized by allowing both of them to coexist.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法においては、原料として炭化水素、含酸素炭
化水素又は含窒素炭化水素が用いられる。In the method of the present invention, hydrocarbons, oxygen-containing hydrocarbons, or nitrogen-containing hydrocarbons are used as raw materials.
該炭化水素としては、例えばプロピレン、インブチレン
、トルエン、キシレン、プロパン、インブタンなどが挙
げられ、含酸素炭化水素としては、例えばメチルアルコ
ール、プロピルアルコーノ呟第三ブチルアルコール、イ
ソブチルアルコールなどが挙げられる。また、含窒素炭
化水素としては、例えばピコリンなどが挙げられる。こ
れらの化合物は、いずれもアンモオキシデーション反応
によってニトリル化合物を生成する原料のものであるが
、もちろんこれらに限定されるものではない。Examples of the hydrocarbon include propylene, imbutylene, toluene, xylene, propane, imbutane, etc., and examples of the oxygen-containing hydrocarbon include methyl alcohol, propyl alcohol, tertiary butyl alcohol, isobutyl alcohol, etc. . Further, examples of nitrogen-containing hydrocarbons include picoline and the like. All of these compounds are raw materials that produce nitrile compounds through an ammoxidation reaction, but are of course not limited to these.
アンモオキシデーション反応において用いられるアンモ
ニアとしては、アンモニアガスやアンモニア水で代表さ
れるアンモニア前駆物質が挙げられる。一方、使用する
酸素の濃度については特に制限はなく、通常空気が用い
られるが、酸素富化空気も用いることができる。また、
アンモニア供給量については、アンモオキシデーション
反応によって消費される量に見合った量であればよく、
特に制限はない。Examples of ammonia used in the ammoxidation reaction include ammonia precursors such as ammonia gas and aqueous ammonia. On the other hand, there is no particular restriction on the concentration of oxygen used, and normal air is used, but oxygen-enriched air can also be used. Also,
Regarding the amount of ammonia supplied, it is sufficient that the amount is commensurate with the amount consumed by the ammoxidation reaction.
There are no particular restrictions.
本発明方法においては、反応系にアセトン又はエチルア
ルコール若しくはその両方を共存させることが必要であ
る。その量については特に制限はないが、通常アセトニ
トリル必要量に見合った量を供給すればよい。In the method of the present invention, it is necessary to coexist acetone, ethyl alcohol, or both in the reaction system. Although there is no particular restriction on the amount, it is sufficient to supply an amount corresponding to the required amount of acetonitrile.
反応器の形式については、アセトンやエチルアルコール
を供給する設備があればよく、特に制限されず、流動床
反応器、固定床反応器のいずれも用いることができる。The type of reactor is not particularly limited as long as it has equipment for supplying acetone or ethyl alcohol, and either a fluidized bed reactor or a fixed bed reactor can be used.
また、アセトンやエチルアルコールの供給方法について
も特に制限はなく、原料の炭化水素類とアンモニアとの
混合物と混合して供給してもよいし、該混合物供給口よ
り後部から供給してもよい。さらに、使用する酸素の量
については反応量に見合った量であればよく、特に制限
はない。Furthermore, there are no particular restrictions on the method of supplying acetone or ethyl alcohol, and they may be supplied after being mixed with a mixture of raw material hydrocarbons and ammonia, or may be supplied from the rear of the mixture supply port. Furthermore, the amount of oxygen used is not particularly limited as long as it is appropriate for the amount of reaction.
本発明方法においては、従来アンモオキシデーション反
応において慣用されている触媒を用いることができる。In the method of the present invention, catalysts conventionally used in ammoxidation reactions can be used.
このような触媒として、例えばリン・モリブデン酸ビス
マスを主成分とする触媒（特公昭３６−５８７０号公報
）、リン・モリブデン酸ビスマスに鉄、コバルト、ニッ
ケルなどの種々の添加物を加えｔ；触媒（特開昭４８−
４９７１９号公報）やその改良触媒（特開昭５０−２５
５２８号公報、特開昭５１−４０３９１号公報）、アン
チモン、鉄を含有する触媒（特開昭５１−１７１９４号
公報）やその改良触媒（特開昭５７−２６５９２号公報
、特開平１−２２４３５４号公報、特開平１−２６５０
６８号公報）、リン・モリブデン酸ビスマスにナトリウ
ムが添加された触媒（特開昭５０−１２９５１９号公報
）やその改良触媒（特開昭５４−９５５１３号公報、特
開昭５８−６７３４９号公報、特開昭５８−７２５５０
号公報、特公昭６１−５８４２６号公報）などを挙げる
ことができる。Such catalysts include, for example, a catalyst containing bismuth phosphomolybdate as a main component (Japanese Patent Publication No. 36-5870), a catalyst containing various additives such as iron, cobalt, and nickel to bismuth phosphomolybdate; (Unexamined Japanese Patent Publication 1973-
49719) and its improved catalyst (Japanese Unexamined Patent Publication No. 50-25
528, JP-A-51-40391), catalysts containing antimony and iron (JP-A-51-17194) and improved catalysts thereof (JP-A-57-26592, JP-A-1-224354) Publication No. 1-2650
68 Publication), a catalyst in which sodium is added to bismuth phosphomolybdate (Japanese Unexamined Patent Publication No. 50-129519) and its improved catalyst (Japanese Unexamined Patent Publication No. 54-95513, Unexamined Japanese Patent Application No. 58-67349, Japanese Patent Publication No. 58-72550
(Japanese Patent Publication No. 61-58426).
これらの触媒には優劣はあるが、いずれの触媒を用いて
も、反応系にアセトンやエチルアルコールを共存させる
ことにより、アセトニトリルを増収することができる。Although these catalysts have advantages and disadvantages, no matter which catalyst is used, the yield of acetonitrile can be increased by allowing acetone or ethyl alcohol to coexist in the reaction system.
本発明におけるアンモオキシデーション反応における反
応温度、反応圧力などの反応条件は、通常のアンモオキ
シデーション反応において慣用されている範囲内で選ば
れる。Reaction conditions such as reaction temperature and reaction pressure in the ammoxidation reaction in the present invention are selected within the range commonly used in normal ammoxidation reactions.
次に添付図面に従って本発明の好適な実施態様を説明す
る。Next, preferred embodiments of the present invention will be described with reference to the accompanying drawings.
区は、本発明を実施するのに好適な反応装置の１例を示
す説明図であって、焼結フィルター２を配設し、電気ヒ
ーター３，３により外部から所定温度に加熱された触媒
充填反応器ｌの中へ、管路４を経て炭化水素類とアンモ
ニアと空気の混合物を、また管路５よりアセトンとエチ
ルアルコールと空気の混合物をそれぞれ導入し反応させ
る。得られた反応混合物は管路６を経て回収され、それ
ぞれ別に設けた分離器において分離される。図中のし□
は炭化水素類供給口と触媒層上端との距離、Ｌ２はアセ
トンやエチルアルコールと空気との混合物の供給口と触
媒層上端との距離である。1 is an explanatory diagram showing one example of a reaction apparatus suitable for carrying out the present invention, in which a sintered filter 2 is disposed and a catalyst filling is heated to a predetermined temperature from the outside by electric heaters 3. A mixture of hydrocarbons, ammonia and air is introduced into the reactor 1 through line 4, and a mixture of acetone, ethyl alcohol and air is introduced through line 5 and reacted. The resulting reaction mixture is recovered via line 6 and separated in separate separators. Noshi in the diagram □
is the distance between the hydrocarbon supply port and the top of the catalyst layer, and L2 is the distance between the supply port of the mixture of acetone or ethyl alcohol and air and the top of the catalyst layer.
発明の効果
本発明によると、アンモオキシデーション反応によりニ
トリル化合物を製造する際に、反応系にアセトンやエチ
ルアルコールを共存させることにより、主反応生成物の
収量を減少させることなく効率よくアセトニトリルを増
収することができる。Effects of the Invention According to the present invention, when a nitrile compound is produced by an ammoxidation reaction, acetone or ethyl alcohol is allowed to coexist in the reaction system, thereby efficiently increasing the yield of acetonitrile without reducing the yield of the main reaction product. can do.
実施例
次に実施例により本発明をさらに詳細に説明するが本発
明はこれらの例によってなんら限定されるものではない
。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
なお、実施例及び比較例中において反応成績を表わすた
めに用いたプロピレン反応率（％）、インブチレン反応
率（％）、アクリロニトリル収率（％）、メタクリロニ
トリル収率（％）、アセトニトリル収率（％）及びアセ
トニトリル収量増加率（％）は次式で定義される。In addition, propylene reaction rate (%), inbutylene reaction rate (%), acrylonitrile yield (%), methacrylonitrile yield (%), acetonitrile yield used to express reaction results in Examples and Comparative Examples. The rate (%) and the acetonitrile yield increase rate (%) are defined by the following formula.
プロピレン反応率（％）−
インブチレン反応率（％）−
アクリロニトリル収率（％）
供給したインブチレンのモル族
アセトニトリル収率（％）
アセトニトリル収量増加率（％）＝
ただし、
Ａ：アセトン及び／又はエチルアルコールを供給した時
のアセトニトリル収率
Ｂ：アセトン及び／又はエチルアルコールを供給しない
時のアセトニトリル収率
また、実施例及び比較例におけるアンモオキシデーショ
ン反応には、触媒流動部の内径が２インチで内部に１６
メツシユのステンレス鋼製金鋼を内蔵した図に示すよう
な流動床反応器を用いた。Propylene reaction rate (%) - Inbutylene reaction rate (%) - Acrylonitrile yield (%) Mole group acetonitrile yield (%) of supplied imbutylene Acetonitrile yield increase rate (%) = However, A: Acetone and/or Acetonitrile yield B when ethyl alcohol is supplied: Acetonitrile yield when acetone and/or ethyl alcohol are not supplied.Also, for the ammoxidation reactions in Examples and Comparative Examples, the inner diameter of the catalyst flow section was 2 inches. 16 inside
A fluidized bed reactor as shown in the figure containing mesh stainless steel gold steel was used.
反応器に充填した触媒は３〜４日間反応を行い活性が安
定したのちに、アセトンやエチルアルコールを供給しア
セトニトリル増収試験を行つた。After the catalyst filled in the reactor reacted for 3 to 4 days and its activity stabilized, acetone and ethyl alcohol were supplied to perform an acetonitrile yield increase test.
反応条件は目的に反応して、適宜変化させ、反応生成物
はガスクロマトグラフにより分析定量を行った。ただし
、アンモニアと青酸については滴定法により分析定量し
た。The reaction conditions were changed as appropriate depending on the desired reaction, and the reaction products were analyzed and quantified using gas chromatography. However, ammonia and hydrocyanic acid were analyzed and determined by titration.
さらに、実施例及び比較例における接触時間は下記の定
義による。Further, the contact time in Examples and Comparative Examples is defined as below.
プロピレン又はインブチレンの見掛接触時間（θ１）及
びアセトン及び／又はエチルアルコールの見掛接触時間
（θ２）は次式で与えられる。The apparent contact time (θ1) of propylene or imbutylene and the apparent contact time (θ2) of acetone and/or ethyl alcohol are given by the following equations.
ただし
Ｑｌ：反応器底部より供給されるプロピレン又はインブ
チレン、アンモニア及び空
気のガス流量〔ｍＱ／ＳｅＣ〕（反応条件換算）Ｑ２：
反応器へ供給されるアセトン及び／又はエチルアルコー
ルと空気とのガス流
量〔ＩＩＩＱ／ｓｅｃ〕（反応条件換算）Ｌｌ：プロピ
レン又はインブチレン供給口と触媒層上端との距離（ｃ
ｍ）
Ｌ、：アセトン及び／又はエチルアルコールの供給口と
触媒層上端との距離（ｃｍ）Ａ ：反応器の断面積Ｃｃ
ｍ２）
θ１．θ２の単位はＣ５ｅｃ）で表示される。However, Ql: Gas flow rate of propylene or imbutylene, ammonia and air supplied from the bottom of the reactor [mQ/SeC] (converted to reaction conditions) Q2:
Gas flow rate of acetone and/or ethyl alcohol and air supplied to the reactor [IIIQ/sec] (converted to reaction conditions) Ll: distance between propylene or imbutylene supply port and the top of the catalyst layer (c
m) L: Distance between the acetone and/or ethyl alcohol supply port and the top of the catalyst layer (cm) A: Cross-sectional area of the reactor Cc
m2) θ1. The unit of θ2 is expressed in C5ec).
調製例１ 触媒（Ｉ）の調製
５０重量％のシリカに担持された金属成分の原子比組成
が、ＭＯＢＩＯ，８２６Ｆｅｅ、 ｓ７ｓ Ｌ、’ｏｏ
ａＮａ、 Ｏ５Ｐｏ。１゜で示される酸化物触媒を次の
ようにして調製した。Preparation Example 1 Preparation of Catalyst (I) The atomic ratio composition of the metal component supported on 50% by weight of silica is MOBIO, 826Fee, s7s L,'oo
aNa, O5Po. An oxide catalyst having an angle of 1° was prepared as follows.
３０重量％の５ｉＯｚを含むシリカゾル（日産化学製の
スノーテックスＮ）５００ｈに、かきまぜながら８５重
量％のリン酸２８．８９を加え、次いで水１１００ｇに
ｔ・モリブデン酸アンモニウム〔（ＮＨＪ）ａＭｏｔｏ
□・４ＨｚＯ）４４ｈを溶解した液を加え、最後にあら
かじめ１５重量％の硝酸１０００ｇに、硝酸ビスマス［
Ｂｉ（ＮＯｘ）ｓ・５ＨｚＯ） １０１０９、硝酸第二
鉄ＣＦｅＣＮ０ｘ）ｓ ” ９Ｈ２０） ６９６１？、
硝酸ナトリウム１０．６ｇ及び硝酸カリウム１．５２ｇ
を溶解した混合液を加えた。ここで得られた原料スラリ
ーを並流式噴霧乾燥器に送り約２００℃で乾燥した。To 500 hours of silica sol (Snowtex N manufactured by Nissan Chemical) containing 30% by weight of 5iOz, 85% by weight of phosphoric acid (28.89 g) was added with stirring, and then t-ammonium molybdate [(NHJ)aMoto] was added to 1100 g of water.
□・4HzO) 44h was added, and finally, bismuth nitrate [
Bi(NOx)s・5HzO) 10109, ferric nitrate CFeCN0x)s” 9H20) 6961?,
Sodium nitrate 10.6g and potassium nitrate 1.52g
A mixed solution containing dissolved was added. The raw material slurry obtained here was sent to a co-current spray dryer and dried at about 200°C.
得られた乾燥粉体をマツフル炉で４００℃、１時間、次
いで６９０℃で２時間焼成して触媒（１）を得た。The obtained dry powder was calcined in a Matsufuru furnace at 400°C for 1 hour and then at 690°C for 2 hours to obtain catalyst (1).
調製例２ 触媒（Ｉ［）の調製
５０重量％のシリカに担持された金属成分の原子組成が
、Ｐｄｏ、 ０２ ＭＯ＋ｔ Ｂｊａ１Ｆｅ７．２Ｐ＋
ＫＯ，＋１７で示される酸化物触媒を調製例１と同様
の方法で噴霧造粒し、次いで４００°Ｃで１時間、６９
０°Ｃで２時間焼成して触媒（ＩＩ）を得た。Preparation Example 2 Preparation of Catalyst (I[) The atomic composition of the metal component supported on 50% by weight of silica is Pdo, 02 MO+t Bja1Fe7.2P+
The oxide catalyst represented by KO, +17 was spray-granulated in the same manner as in Preparation Example 1, and then heated at 400°C for 1 hour at 69°C.
The catalyst (II) was obtained by calcining at 0°C for 2 hours.
調製例３ 触媒（Ｉ［［）の調製
５０重量％のシリカに担持された金属成分の原子比組成
が、ｐｄｏｏ６ Ｍｏ＋ｚ Ｂ１０． ＠ Ｆｅａ、
ｓＰ＋Ｋｌ ３で示される酸化物触媒を調製例１と同様
の方法で噴霧造粒し、次いで４００℃で１時間、６９０
℃で２時間焼成して触媒（ｎ［）を得た。Preparation Example 3 Preparation of Catalyst (I[[) The atomic ratio composition of the metal component supported on 50% by weight of silica is pdoo6 Mo+z B10. @ Fea,
The oxide catalyst represented by sP+Kl 3 was spray-granulated in the same manner as in Preparation Example 1, and then heated at 400°C for 1 hour at 690 °C.
The catalyst (n[) was obtained by calcining at ℃ for 2 hours.
実施例１〜１６、比較例１〜３
調製例で得た触媒（Ｉ）〜（ＩＩＩ）を用いて、図に示
す反応器に９５０ｇ充填し反応を行った。Examples 1 to 16, Comparative Examples 1 to 3 Using the catalysts (I) to (III) obtained in Preparation Examples, 950 g of the catalysts were charged into the reactor shown in the figure and reacted.
酸素源としては空気を用い、反応圧力は０．５ｋｇ／ｃ
が・Ｇ一定に保ったが、反応温度及び触媒時間は適宜調
整した。Air was used as the oxygen source, and the reaction pressure was 0.5 kg/c.
Although G was kept constant, the reaction temperature and catalyst time were adjusted as appropriate.
プロピレンを用いたときの反応結果を反応条件と共に第
１表に、またイソブチレンを用いたときの反応結果を反
応条件と共に第２表にそれぞれ示す。The reaction results when propylene was used are shown in Table 1 together with the reaction conditions, and the reaction results when isobutylene was used are shown in Table 2 together with the reaction conditions.
本発明方法は比較例の結果と比ベアクリロニトリルやメ
タクリロニトリルの収率を減少させることなく、大巾に
アクリロニトリルの収量が増加していることは明らかで
ある。It is clear that the method of the present invention greatly increases the yield of acrylonitrile without reducing the yield of bare acrylonitrile or methacrylonitrile compared to the results of the comparative examples.
図は本発明方法を実施するために用いられる反応装置の
１例の説明図であり、図中符号ｌは反応器、２は焼結フ
ィルター、３は電気ヒーター、４は炭化水素類とアンモ
ニアと空気との混合物の導入管路、５はアセトンやエチ
ルアルコールと空気との混合物の導入管路、６反応生成
物の回収管路である。The figure is an explanatory view of one example of a reaction apparatus used to carry out the method of the present invention. In the figure, reference numeral l is a reactor, 2 is a sintered filter, 3 is an electric heater, and 4 is a reactor for hydrocarbons and ammonia. 5 is a conduit for introducing a mixture with air, 5 is a conduit for introducing a mixture of acetone or ethyl alcohol and air, and 6 is a conduit for recovering reaction products.
Claims (1)
ンモニアと酸素とを反応させ、アンモオキシデーション
により不飽和ニトリル及びアセトニトリルを製造するに
当り、反応系にアセトン又はエチルアルコール若しくは
その両方を共存させることを特徴とするアセトニトリル
の増収方法。1. When producing unsaturated nitriles and acetonitrile by ammoxidation by reacting hydrocarbons, oxygen-containing hydrocarbons, or nitrogen-containing hydrocarbons with ammonia and oxygen, acetone or ethyl alcohol, or both, are allowed to coexist in the reaction system. A method for increasing the yield of acetonitrile, characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2038333A JPH03246269A (en) | 1990-02-21 | 1990-02-21 | Method for increasing yield of acetonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2038333A JPH03246269A (en) | 1990-02-21 | 1990-02-21 | Method for increasing yield of acetonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03246269A true JPH03246269A (en) | 1991-11-01 |
Family
ID=12522356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2038333A Pending JPH03246269A (en) | 1990-02-21 | 1990-02-21 | Method for increasing yield of acetonitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03246269A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073261A1 (en) * | 1999-05-27 | 2000-12-07 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and hydrogen cyanide |
| JP2003002870A (en) * | 2001-06-21 | 2003-01-08 | Asahi Kasei Corp | Method for coproducing prussic acid in production of unsaturated nitrile |
| JP2003064041A (en) * | 2001-08-29 | 2003-03-05 | Asahi Kasei Corp | Method for stably increasing production of acetonitrile and hydrocyanic acid |
| JP2003064042A (en) * | 2001-08-29 | 2003-03-05 | Asahi Kasei Corp | Method for stably increasing production of acetonitrile |
| JP2004525913A (en) * | 2001-03-05 | 2004-08-26 | ザ・スタンダード・オイル・カンパニー | Ammoxidation of alcohol mixtures to nitrile mixtures, acetonitrile and HCN mixtures |
| CN102452954A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for increasing yield of acetonitrile in acrylonitrile production |
| CN102452956A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for increasing production of acetonitrile by hydrocarbon and alcohol mixed ammoxidation |
| KR20140112522A (en) | 2012-03-26 | 2014-09-23 | 아사히 가세이 케미칼즈 가부시키가이샤 | Method for purifying acetonitrile |
-
1990
- 1990-02-21 JP JP2038333A patent/JPH03246269A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073261A1 (en) * | 1999-05-27 | 2000-12-07 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and hydrogen cyanide |
| BG65744B1 (en) * | 1999-05-27 | 2009-09-30 | The Standard Oil Company | Ammonium oxidation of a ketones mixture to acetonitrile and hydrocyanogen |
| JP2004525913A (en) * | 2001-03-05 | 2004-08-26 | ザ・スタンダード・オイル・カンパニー | Ammoxidation of alcohol mixtures to nitrile mixtures, acetonitrile and HCN mixtures |
| JP4716643B2 (en) * | 2001-03-05 | 2011-07-06 | イネオス・ユーエスエイ・エルエルシー | Ammoxidation of alcohol mixtures to nitrile mixtures, acetonitrile and HCN mixtures |
| JP2003002870A (en) * | 2001-06-21 | 2003-01-08 | Asahi Kasei Corp | Method for coproducing prussic acid in production of unsaturated nitrile |
| JP2003064041A (en) * | 2001-08-29 | 2003-03-05 | Asahi Kasei Corp | Method for stably increasing production of acetonitrile and hydrocyanic acid |
| JP2003064042A (en) * | 2001-08-29 | 2003-03-05 | Asahi Kasei Corp | Method for stably increasing production of acetonitrile |
| CN102452954A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for increasing yield of acetonitrile in acrylonitrile production |
| CN102452956A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for increasing production of acetonitrile by hydrocarbon and alcohol mixed ammoxidation |
| KR20140112522A (en) | 2012-03-26 | 2014-09-23 | 아사히 가세이 케미칼즈 가부시키가이샤 | Method for purifying acetonitrile |
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