JPH0514703B2 - - Google Patents
Info
- Publication number
- JPH0514703B2 JPH0514703B2 JP59155936A JP15593684A JPH0514703B2 JP H0514703 B2 JPH0514703 B2 JP H0514703B2 JP 59155936 A JP59155936 A JP 59155936A JP 15593684 A JP15593684 A JP 15593684A JP H0514703 B2 JPH0514703 B2 JP H0514703B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- aniline
- reaction
- nitrobenzene
- palladium
- 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.)
- Expired - Lifetime
Links
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はニトロベンゼンを接触還元して、アニ
リンを製造する方法に関する。更に詳細にはアニ
リンの接触還元に用いる触媒の使用方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing aniline by catalytic reduction of nitrobenzene. More specifically, the present invention relates to a method of using a catalyst for catalytic reduction of aniline.
従来の技術
芳香族ニトロ化合物から芳香族アミン、例えば
ニトロベンゼンからアニリンを得るには還元触媒
の存在下に液相で水素添加反応を行つている。こ
の反応において使用する触媒は、反応が長期に亘
る場合、反応装置に仕込まれ、反応期間中、使用
した触媒を１部取除き、この分に相応する新触媒
を追加しながら継続的に反応も行なつている。し
かし、所定期間反応を継続した後、各種装置の点
検設備のため反応を停止しなければならない。Prior Art To obtain aromatic amines from aromatic nitro compounds, such as aniline from nitrobenzene, a hydrogenation reaction is carried out in the liquid phase in the presence of a reduction catalyst. If the reaction is to last for a long time, the catalyst used in this reaction is charged into a reactor, and during the reaction period, one part of the used catalyst is removed and a corresponding amount of new catalyst is added to continue the reaction. I am doing it. However, after continuing the reaction for a predetermined period of time, the reaction must be stopped due to inspection equipment for various devices.
従来、このような反応のシヤツトダウン（定
修）時反応機中の使用済触媒は反応機より抜き出
し、再生処理を行なつていた。 Conventionally, during shutdown (regular maintenance) of such a reaction, the spent catalyst in the reactor was extracted from the reactor and subjected to regeneration treatment.
一方、反応を再開するときは、スタートアツプ
（運転再開）時新しい触媒を用いていた。 On the other hand, when restarting the reaction, a new catalyst was used at start-up (resumption of operation).
発明が解決しようとする問題点
上記のような、使用触媒の再生処理では、どう
しても処理による触媒の損失は避けられず、高価
な触媒であるためコスト的に問題があつた。Problems to be Solved by the Invention In the regeneration treatment of the used catalyst as described above, loss of the catalyst due to the treatment cannot be avoided, and since the catalyst is expensive, there is a cost problem.
また、反応スタートアツプ時に新触媒を用いる
と活性が強すぎて、スタート直後から不純物の発
生が多く、初期の製品からはこれらの不純物の除
去のため、蒸留操作が余分に必要である等の問題
があつた。 In addition, when a new catalyst is used at the start of a reaction, its activity is too strong and many impurities are generated immediately after the start, and early products require an extra distillation operation to remove these impurities. It was hot.
問題点を解決するための手段
本発明者らは、前記の問題点を解決するために
種々検討した結果、スタートアツプ時に使用する
触媒として、新触媒を用いることなく、シヤツト
ダウン時に回収した触媒を不活性ガスの雰囲気に
保存して、これをスタートアツプ時の触媒として
使用することにより、スタートアツプの当初から
品質の安定した目的物が得られることを見出し、
本発明を完成した。Means for Solving the Problems As a result of various studies to solve the above problems, the inventors of the present invention decided to use the catalyst recovered at the time of shutdown instead of using a new catalyst as the catalyst used at startup. It was discovered that by storing it in an active gas atmosphere and using it as a catalyst during startup, a target product with stable quality can be obtained from the beginning of startup.
The invention has been completed.
すなわち、本発明はニトロベンゼンをパラジウ
ムまたはパラジウム−白金触媒の存在下、接触還
元してアニリンを製造する方法において、スター
トアツプ時に使用する該触媒がシヤツトダウン時
に回収され窒素雰囲気下に保存された該触媒を含
有することを特徴とするアニリンの製造法であ
る。 That is, the present invention provides a method for producing aniline by catalytic reduction of nitrobenzene in the presence of a palladium or palladium-platinum catalyst, in which the catalyst used at startup is recovered at shutdown and stored under a nitrogen atmosphere. This is a method for producing aniline characterized by containing.
本発明の方法では、ニトロベンゼンをアニリン
を溶媒として水添触媒の存在下に水素を添加して
連続的に反応を行なう。 In the method of the present invention, the reaction is carried out continuously by adding hydrogen to nitrobenzene using aniline as a solvent in the presence of a hydrogenation catalyst.
使用する触媒はパラジウム、またはパラジウム
−白金触媒であり、通常、パラジウムおよび／ま
たは白金触媒として市販されている活性炭やアル
ミナに担持させて使用する。一般に、親油性炭素
担体の水分散液中で、パラジウム、白金化合物の
沈澱法などの普通の方法で調製したものが好まし
い。白金やパラジウムの担体への担持量は0.1〜
５重量％程度に担持したものである。パラジウム
は単独でもよいが、白金と併用したものが活性お
よび選択性の面で特に効果が大きい。このような
併用の場合、パラジウムに対して約５〜20重量％
の白金が併用される。 The catalyst used is palladium or palladium-platinum catalyst, and is usually supported on activated carbon or alumina, which are commercially available as palladium and/or platinum catalysts. Generally, those prepared by conventional methods such as precipitation of palladium or platinum compounds in an aqueous dispersion of a lipophilic carbon carrier are preferred. The amount of platinum or palladium supported on the carrier is 0.1~
It is supported at about 5% by weight. Although palladium may be used alone, its use in combination with platinum is particularly effective in terms of activity and selectivity. In such a combination, approximately 5 to 20% by weight relative to palladium
platinum is used in combination.
反応混合物系中における触媒の濃度は、通常、
0.2〜2.0重量％程度である。 The concentration of catalyst in the reaction mixture system is usually
It is about 0.2 to 2.0% by weight.
反応はアニリン溶媒中に反応液中のニトロベン
ゼン濃度が0.5重量％以下であるように、ニトロ
ベンゼンをアニリンへの転化にほゞ見合う量を供
給しなから行う。 The reaction is carried out by supplying nitrobenzene to the aniline solvent in an amount approximately commensurate with the conversion to aniline so that the concentration of nitrobenzene in the reaction solution is 0.5% by weight or less.
供給されたニトロベンゼンはアニリンと水に転
化され蒸気として系外に除去される。 The supplied nitrobenzene is converted into aniline and water and removed from the system as steam.
水素の添加は大気圧下でも実施できるが、通常
1.5〜10気圧の圧力で実施する。 Hydrogen addition can also be carried out at atmospheric pressure, but usually
Perform at a pressure of 1.5 to 10 atmospheres.
反応温度150〜250℃の範囲である。 The reaction temperature is in the range of 150-250°C.
反応液中の液量はニトロベンゼンの供給量、す
なわちアニリンへの転化量に見合うアニリンの量
を反応系から蒸気として取出すか、留去されたア
ニリンを水と分離後一部反応系へ戻して調節す
る。 The amount of liquid in the reaction solution is adjusted by taking out the amount of aniline corresponding to the amount of nitrobenzene supplied, that is, the amount of aniline converted to aniline, from the reaction system as vapor, or by returning a portion of the distilled aniline to the reaction system after separating it from water. do.
以上の方法により、ニトロベンゼンの液相にお
ける水添反応を連続的に実施できる。この場合、
触媒の反応系中の触媒を所定時間後に新触媒と入
れ替えながら使用される。 By the above method, the hydrogenation reaction of nitrobenzene in the liquid phase can be carried out continuously. in this case,
The catalyst in the catalyst reaction system is replaced with a new catalyst after a predetermined period of time.
以上の反応をシヤツトダウンした場合、使用触
媒は、反応器よりアニリンとともに触媒貯蔵槽に
アニリンと触媒と混合物として移し、これを不活
性ガス、通常は窒素雰囲気下に密封貯蔵する。 When the above reaction is shut down, the catalyst used is transferred from the reactor together with aniline to a catalyst storage tank as a mixture of aniline and catalyst, and the mixture is sealed and stored under an inert gas, usually nitrogen atmosphere.
前記の反応を再び新規にスタートアツプすると
きは、密封貯蔵されたアニリンと触媒をそのま
ま、又は一部のアニリン、または触媒を新しいも
のと入れ替えて使用する。 When starting up the above reaction anew, the hermetically stored aniline and catalyst are used as they are, or some of the aniline or catalyst is replaced with new ones.
作用および効果
従来、ニトロベンゼンの水添反応のスタートア
ツプ時に新触媒を使用すると、活性が高いために
副反応を起し、品質安定までかなりの時間を必要
とし、この間生成する目的物は副生物を含むため
に特定な用途への高純度品を得るには蒸留精製が
必要であつた。しかし、本発明の方法によれば、
スタートアツプ時の触媒活性が適度で、初期の生
成物から品質が安定し不純物がなく、蒸留精製の
必要もなく使用出来る。Actions and Effects Conventionally, when a new catalyst is used at the start-up of the hydrogenation reaction of nitrobenzene, its high activity causes side reactions, and it takes a considerable amount of time for the quality to stabilize. Therefore, distillation purification was necessary to obtain high purity products for specific uses. However, according to the method of the present invention,
The catalytic activity at startup is moderate, the quality of the product is stable from the initial stage, there are no impurities, and it can be used without the need for distillation.
以下、本発明を実施例により説明する。 The present invention will be explained below using examples.
反応器に溶媒としてアニリン14m3を装入し、白
金、パラジウム、及び鉄を親油性炭素にそれぞれ
0.1％、0.8％、及び0.8重量鵜％を沈着させた触媒
を水中約4.5％のスリラー濃度になるように懸濁
させた液を140加えた。
The reactor was charged with 14 m3 of aniline as a solvent, and platinum, palladium, and iron were each added to the lipophilic carbon.
140 ml of a suspension of 0.1%, 0.8%, and 0.8% by weight of catalyst deposited in water to a thriller concentration of about 4.5% was added.
温度を200℃に保ち、毎時3200Kgのニトロベン
ゼンを連続的に供給した。同時に６Kg／cm2に圧縮
された水素ガスを反応器圧力が5.5Kg／cm2に常時
保持されるように供給した。ニトロベンゼンは水
添され、反応器より水とともに毎時約2400Kgのア
ニリンとして得られる。留出物は２相に分離しア
ニリンを得た。 The temperature was maintained at 200°C and 3200 kg of nitrobenzene was continuously fed per hour. At the same time, hydrogen gas compressed to 6 kg/cm 2 was supplied so that the reactor pressure was constantly maintained at 5.5 kg/cm 2 . Nitrobenzene is hydrogenated and obtained from the reactor together with water as approximately 2400 kg of aniline per hour. The distillate was separated into two phases to obtain aniline.
この反応をシヤツトダウン時まで続け、反応を
停止した。この間、触媒を含むアニリン液を１日
に約30抜き出す。抜き出した触媒量及びアニリ
ンの見合う新触媒及びアニリンの補充を行なつ
た。 This reaction was continued until shutdown, when the reaction was stopped. During this time, about 30 times a day the aniline liquid containing the catalyst is extracted. New catalyst and aniline were replenished to match the amount of catalyst and aniline removed.
シヤツトダウン前に得られたアニストは無色な
いし淡黄色のもので、水分を５％含有し、クロマ
トグラフイーで分析の結果、シクロヘキサノール
trace、シクロヘキサノン9.5ppm、シクロヘキシ
リデンアニリン3.9ppm未反応ニトロベンゼン
traceであつた。 The aniste obtained before shutdown was colorless to pale yellow, containing 5% water, and chromatographic analysis revealed that cyclohexanol
trace, cyclohexanone 9.5ppm, cyclohexylideneaniline 3.9ppm unreacted nitrobenzene
It was trace.
反応停止時、反応器中の触媒とアニリンの混合
液を別の貯槽に移した。その後、空気を窒素ガス
で置換し密封した。 When the reaction stopped, the mixed solution of catalyst and aniline in the reactor was transferred to another storage tank. Thereafter, the air was replaced with nitrogen gas and the container was sealed.
反応を再開する際し、前記と同一の反応器に貯
蔵していた触媒のアニリンの混合液を戻した。 When restarting the reaction, the catalytic aniline mixture that had been stored in the same reactor as above was returned.
この液を200℃に保ち、毎時3200Kgのニトロベ
ンゼンと６Kg／cm2に圧縮された水素ガスを反応器
圧力が5.5Kg／cm2に常時保持されるように供給し
た。 This liquid was maintained at 200° C., and 3200 kg of nitrobenzene and hydrogen gas compressed to 6 kg/cm 2 were supplied per hour so that the reactor pressure was constantly maintained at 5.5 kg/cm 2 .
アニリンが生成水と留出するので、これを２相
に分離し、無色ないし淡黄色のアニリンを得た。 Since aniline was distilled out from the produced water, this was separated into two phases to obtain colorless to pale yellow aniline.
このアニリン中には若干量の水分を含有し、ガ
スクロマトグラフイーで分析したところ、シクロ
ヘキサール、シクロヘキサノン、シクロヘキシリ
デンアニリンおよびニトロベンゼンがそれぞれ
trce、9.4ppm、4.1ppm、およびtraceであり、こ
れは先のアニリンと品質的に差が殆んどない。 This aniline contains a small amount of water, and analysis by gas chromatography revealed that cyclohexal, cyclohexanone, cyclohexylideneaniline, and nitrobenzene were detected, respectively.
trce, 9.4ppm, 4.1ppm, and trace, which have almost no difference in quality from the above aniline.
一方、反応のスタートアツプ時に新触媒を用い
た場合、生成するアニリン中に含まれるのは水分
4.5％、シクロヘキサノール48ppm、シクロヘキ
サノン301ppm、シクロヘキシリデンアニリン
52ppmおよびニトロベンゼンがtraceであり、新
触媒の活性が強すぎるために不純物の生成が多
い。 On the other hand, when a new catalyst is used at the start-up of the reaction, the aniline produced contains water.
4.5%, cyclohexanol 48ppm, cyclohexanone 301ppm, cyclohexylideneaniline
The trace was 52ppm and nitrobenzene, and the activity of the new catalyst was too strong, resulting in the production of many impurities.
Claims (1)
ム−白金触媒の存在下、接触還元してアニリンを
製造する方法において、スタートアツプ時に使用
する該触媒がシヤツトダウン時に回収され窒素雰
囲気下に保存された該触媒を含有することを特徴
とするアニリンの製造法。1 In a method for producing aniline by catalytic reduction of nitrobenzene in the presence of a palladium or palladium-platinum catalyst, the catalyst used at startup contains the catalyst recovered at shutdown and stored under a nitrogen atmosphere. Characteristic method for producing aniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59155936A JPS6136248A (en) | 1984-07-26 | 1984-07-26 | Production of aniline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59155936A JPS6136248A (en) | 1984-07-26 | 1984-07-26 | Production of aniline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6136248A JPS6136248A (en) | 1986-02-20 |
| JPH0514703B2 true JPH0514703B2 (en) | 1993-02-25 |
Family
ID=15616750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59155936A Granted JPS6136248A (en) | 1984-07-26 | 1984-07-26 | Production of aniline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6136248A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5105012A (en) * | 1989-03-24 | 1992-04-14 | Fmc Corporation | Catalytic reduction of dinitrobenzenes using a noble metal catalyst and iron or iron salts |
| JP6327607B2 (en) * | 2014-03-11 | 2018-05-23 | 公立大学法人首都大学東京 | Composites in which palladium particles are supported on organic polymer compounds |
-
1984
- 1984-07-26 JP JP59155936A patent/JPS6136248A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6136248A (en) | 1986-02-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |