JP3972443B2 - Process for producing diarylamines - Google Patents
Process for producing diarylamines Download PDFInfo
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- JP3972443B2 JP3972443B2 JP02341798A JP2341798A JP3972443B2 JP 3972443 B2 JP3972443 B2 JP 3972443B2 JP 02341798 A JP02341798 A JP 02341798A JP 2341798 A JP2341798 A JP 2341798A JP 3972443 B2 JP3972443 B2 JP 3972443B2
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- Prior art keywords
- zeolite
- catalyst
- silica
- reaction
- solid acid
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- 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
Description
【０００１】
【発明が属する技術分野】
本発明は、ゴム薬、医薬、染料等の原料であるジアリールアミン類の製造法に関する。更に詳しくは、アリールアミン類を出発原料にして固体酸触媒の存在下、加圧液相下にジアリールアミン類を製造する方法に関する。
【０００２】
【従来の技術】
従来、アニリンを出発原料としてジフェニルアミンを製造する方法としては、塩酸、Ｐ2 Ｏ5 、ＰＣｌ3 、ＡｌＣｌ3 、ＢＦ3 、ＮＨ4 ＢＦ4 等を触媒とする加圧液相法（例えば、特開昭５１−１３８６２８号公報、特開昭５３−４０６９７号公報）や、 酸処理されたγ−アルミナを使用する固定床気相法（例えば、特開昭６１−１０３８５７号公報、特公平３−１６９４３号公報等）、シリカ−アルミナ系合成固体酸触媒を使用する固定床加圧液相法（例えば、特公昭５２−１５５８５号公報、特開昭５４−１３５７２８号公報）等が開示されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、加圧液相法では触媒が腐食性であるため高度の耐食性容器を必要とすること、更には触媒の分離、回収に難点を有するとの欠点がある。また、固定床気相法では、反応装置が大型になり設備費が増大するとともに、反応中に生成するタール性副生物が触媒表面に付着し触媒活性の低下が著しいという欠点がある。一方、固定床加圧液相法では、シリカ−アルミナ系触媒の場合、活性が低いため、転化率が低い。そのため、生産性が低く、原料アニリンを大量に回収・リサイクルする必要がある等の欠点を有する。
本発明者らは、かかる状況下に鑑み、固体酸触媒を用いる加圧液相法について鋭意検討を行った結果、β−ゼオライトとシリカにからなる固体酸触媒を使用することで、アリールアミンのジアリールアミンへの転化率が著しく改善されることを見出し、本発明を完成した。
【０００４】
【課題を解決するための手段】
すなわち、本発明は、アリールアミン類を原料とし、加圧液相下にジアリールアミン類を製造するに当たり、β−ゼオライトとシリカからなる固体酸触媒を使用することを特徴とするジアリールアミン類の製造方法を提供することにある。
【０００５】
【発明の実施の形態】
以下、本発明方法について具体的に説明する。
本発明の実施に際しては固体酸触媒としてβ−ゼオライト触媒を用いることを必須とする。固体酸触媒としてゼオライトには酸点を存在せしめるが、これら酸点としてはＨ型、ＮＨ4 型が望ましい。勿論適応するゼオライトが固体酸触媒としての機能を有する範囲で有るならば、Ｎａ型、Ｋ型を含量しても良い。
【０００６】
また、固体酸触媒として著しい転化率の低下を見ない範囲に於いて、ゼオライト構成成分であることは勿論可能である。本発明方法におけるβ型ゼオライトのＳｉＯ2 ／Ａｌ2 Ｏ3 モル比は好ましくは５〜１００の範囲であり、より好ましくは２０〜５０の範囲である。ＳｉＯ2 ／Ａｌ2 Ｏ3 モル比がこの範囲より低くなると反応活性は高くなるが、不純物の生成量が多くなり、逆にこの範囲より高くなると反応活性が低くなる。β型ゼオライト触媒は通常公知の製法で得られたものであれば良く、特にその製造方法は制限されない。
【０００７】
使用に際してのゼオライト触媒の形状は特に制限されるものではなく、粉末状、粒状、タブレット状等の各種形状で使用可能であるが、取り扱いの点より、粒状或いはタブレット状に成形したものが推奨される。また、ゼオライト触媒を成形する際には、通常バインダーとしてアルミナ、シリカ等各種材料を使用することが可能であるが、本発明方法に於いてはシリカが使用される。シリカの使用量は、好ましくは１０〜７０％、より好ましくは２０〜５０％の範囲から選択される。シリカ使用量がこの範囲より少ないと成形触媒の強度が不足し、この範囲より多いとβ−ゼオライト濃度が下がるため、単位成形触媒当たりの活性が低くなる。
【０００８】
本発明においては、下記一般式〔１〕で示されるアリールアミンと下記一般式〔２〕で示されるアリールアミン〔式中、Ｒ1 〜Ｒ10はそれぞれ同一でも異なったものであってもよく、それぞれ水素、炭素数１〜１２のアルキル、炭素数１〜１２のアルコキシ、フェニル、ヒドロキシ、アミノ、ニトロ又は炭素数１〜１２のアルコキシ、ヒドロキシもしくはフェニルで置換された炭素数１〜１２のアルキルからなる群から選ばれる〕とを上記β−ゼオライトとシリカからなる固体酸触媒の存在下に反応させて、下記一般式〔３〕〔式中の記号および条件は一般式〔１〕及び〔２〕と同じ〕で示されるジアリールアミンを製造する。
【０００９】
原料である上記一般式〔１〕および〔２〕で示されるアリールアミンの具体例としてはアニリン、トルイジン、エチルアニリン、クミジン、キシリジン、ブチルアニリン、アニシジン、フルオロジメチルアニリン等を例示できるが、就中、アニリン、トルイジン、クミジン、キシリジンが好ましい。一般式（Ｉ）及び（II）は勿論同一物、例えばアニリンのみであってもよい。
【００１１】
本反応方法の実施に際し原料アリールアミン類には、そのまま又は水を添加して反応を行うことができる。反応時における水の添加については、シリカ−アルミナ等の複合酸化物触媒使用時に転化率向上効果があることが特開昭５４−１３５７２８号公報で開示されているが、その効果の程度は別にして、固体酸触媒としてβ−ゼオライトを使用する本発明方法に於いても、水の存在下、原料アリールアミンを反応させてもよい。この場合の水の添加方法及び添加量については、特開昭５４−１３５７２８号公報に記載の方法と同様の処方が適応可能である。
【００１２】
本発明に於ける原料アリールアミン類のβ−ゼオライトとシリカからなる固体酸触媒存在下、加圧液相下での反応は、３００〜４００℃の温度範囲、望ましくは３３０℃〜３６０℃の温度条件下に実施される。３００℃未満では反応の進行が遅く、また４００℃を越える場合には副成物の生成が多く、且つ原料にアニリンのような低沸原料を使用する場合には、液体として保持するために高い圧力を要する。
【００１３】
本発明における圧力は、反応により発生するアンモニアを反応系内より放出でき且つ反応相を上記反応温度下に液体の状態を保持させ得るものであれば良い。この圧力は反応温度に比例して高くなり、又、反応の進行と共に反応相中のアリールアミン類のモル分率が低くなるにつれて低くなる。また、この圧力は一般には反応温度でのアリールアミン類の飽和蒸気圧に相当させれば良く、例えばアニリンの場合、通常上記反応温度では１０〜４０Ｋｇ／ｃｍ2 Ｇの範囲となる。
【００１４】
本発明方法においては、反応後、反応物から未反応アリールアミン類を分留し、次いで高沸点副生物を残渣として分離することにより容易に目的とするジアリールアミン類を得ることができる。水を反応時に添加した場合には、上記未反応アリールアミン類の分留時に水がアリールアミン類と同時に大部分回収されるので、分留されたアリールアミン類はその含水率を適宜調整して再使用することができる。
【００１５】
本発明方法は回分法、連続法いずれによっても実施できるが、工業的には原料アリールアミン類及び水を連続的に供給し、圧力コントロールを行いながら反応物を連続的に抜き出す連続法が作業能率上有利である。
【００１６】
【発明の効果】
以上、詳述した本発明方法によれば、アリールアミン類を原料とし、加圧液相下にジアリールアミン類を製造するに当たり、β−ゼオライトとシリカからなる固体酸触媒を使用することで、その製品品質を向上することを可能ならしめたもので、その産業上の価値は極めて大きいものである。
【００１７】
【実施例】
以下実施例、比較例によって本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００１８】
実施例１
５００ｍＬステンレス製オートクレーブに、２５ｇのＨ−βゼオライト（Ｓｉ／Ａｌ＝２５．０、シリカ２０％含有）、２００ｇのアニリンを入れ、オートクレーブ内の空気を窒素で置換した後、密封系で３５０℃で３時間加熱を行った。反応物を冷却後、オートクレーブから取り出し、触媒を濾過した後、反応液をガスクロマトグラフを用いて分析した。その結果、反応液中のジフェニルアミン濃度は２５．０％であった。
【００１９】
比較例１
実施例１の方法に於いて、触媒として下記に示すシリカアルミナ触媒（日揮化学株式会社製）を５０ｇ使用し、水を２ｇ添加した以外は、実施例１と同様の操作を行った。得られた反応物を冷却後、オートクレーブから取り出し、触媒を濾過した後、反応液をガスクロマトグラフを用いて分析した。その結果を表１に示す。
シリカアルミナ（Ｓｉ／Ａｌ＝６．５）：商品名Ｎ６３３Ｌ
シリカアルミナ（Ｓｉ／Ａｌ＝２．６）：商品名Ｎ６３２ＮＨ
【００２０】
【表１】
[Technical field to which the invention belongs]
The present invention relates to a process for producing diarylamines which are raw materials for rubber drugs, medicines, dyes and the like. More specifically, the present invention relates to a process for producing diarylamines in a pressurized liquid phase in the presence of a solid acid catalyst using arylamines as a starting material.
[0002]
[Prior art]
Conventionally, as a method for producing diphenylamine using aniline as a starting material, a pressurized liquid phase method using hydrochloric acid, P 2 O 5 , PCl 3 , AlCl 3 , BF 3 , NH 4 BF 4 or the like as a catalyst (for example, JP, A JP-A-51-138628, JP-A-53-40697), fixed bed gas phase method using acid-treated γ-alumina (for example, JP-A-61-103857, JP-B-3-16943). And a fixed bed pressurized liquid phase method using a silica-alumina based synthetic solid acid catalyst (for example, Japanese Patent Publication No. 52-15585, Japanese Patent Laid-Open No. 54-135728).
[0003]
[Problems to be solved by the invention]
However, the pressurized liquid phase method is disadvantageous in that the catalyst is corrosive, so that a highly corrosion-resistant container is required, and further, there is a difficulty in separation and recovery of the catalyst. In addition, the fixed bed gas phase method has the disadvantage that the reaction apparatus becomes large and equipment costs increase, and that tar-like by-products generated during the reaction adhere to the catalyst surface and the catalytic activity is significantly reduced. On the other hand, in the fixed bed pressurized liquid phase method, in the case of a silica-alumina-based catalyst, the activity is low, so the conversion rate is low. For this reason, the productivity is low, and a large amount of raw material aniline needs to be collected and recycled.
In view of such circumstances, the present inventors have intensively studied a pressurized liquid phase method using a solid acid catalyst. As a result, by using a solid acid catalyst composed of β-zeolite and silica, The inventors found that the conversion to diarylamine was significantly improved and completed the present invention.
[0004]
[Means for Solving the Problems]
That is, the present invention is a process for producing diarylamines characterized in that a solid acid catalyst comprising β-zeolite and silica is used for producing diarylamines under a pressurized liquid phase using arylamines as raw materials. To provide a method.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the method of the present invention will be specifically described.
In practicing the present invention, it is essential to use a β-zeolite catalyst as the solid acid catalyst. As a solid acid catalyst, zeolite has acid sites, and these acid sites are preferably H type and NH 4 type. Of course, if the applicable zeolite has a function as a solid acid catalyst, it may contain Na type and K type.
[0006]
Of course, it is possible to be a zeolitic component as long as the conversion rate of the solid acid catalyst is not significantly reduced. The SiO 2 / Al 2 O 3 molar ratio of the β-type zeolite in the method of the present invention is preferably in the range of 5 to 100, more preferably in the range of 20 to 50. When the SiO 2 / Al 2 O 3 molar ratio is lower than this range, the reaction activity increases. However, the amount of impurities generated increases, and conversely, when the SiO 2 / Al 2 O 3 molar ratio is higher than this range, the reaction activity decreases. The β-type zeolite catalyst is not particularly limited as long as it is usually obtained by a known production method.
[0007]
The shape of the zeolite catalyst in use is not particularly limited, and it can be used in various shapes such as powder, granule, tablet, etc., but from the viewpoint of handling, it is recommended that it is shaped into a granule or tablet. The In molding the zeolite catalyst, various materials such as alumina and silica can be usually used as a binder, but silica is used in the method of the present invention. The amount of silica used is preferably selected from the range of 10 to 70%, more preferably 20 to 50%. If the amount of silica used is less than this range, the strength of the formed catalyst will be insufficient, and if it is more than this range, the β-zeolite concentration will decrease, so the activity per unit molded catalyst will be low.
[0008]
In the present invention, an arylamine represented by the following general formula [1] and an arylamine represented by the following general formula [2] [wherein R 1 to R 10 may be the same or different, From hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, phenyl, hydroxy, amino, nitro, or alkyl having 1 to 12 carbons substituted with alkoxy having 1 to 12 carbons, hydroxy or phenyl, respectively. Is selected from the group consisting of the above-mentioned β-zeolite and silica in the presence of a solid acid catalyst, and the following general formula [3] [wherein the symbols and conditions in the general formulas [1] and [2] Diarylamine represented by the same formula as above.
[0009]
Specific examples of the arylamine represented by the general formulas [1] and [2] as raw materials include aniline, toluidine, ethylaniline, cumidine, xylidine, butylaniline, anisidine, fluorodimethylaniline, etc. Aniline, toluidine, cumidine and xylidine are preferred. The general formulas (I) and (II) may of course be the same, for example aniline only.
[0011]
In carrying out this reaction method, the raw material arylamines can be reacted as they are or with water added. Regarding the addition of water during the reaction, JP-A No. 54-135728 discloses that there is an effect of improving the conversion rate when a composite oxide catalyst such as silica-alumina is used. Even in the method of the present invention using β-zeolite as the solid acid catalyst, the raw material arylamine may be reacted in the presence of water. In this case, the same prescription as that described in JP-A No. 54-135728 can be applied to the water addition method and the addition amount.
[0012]
In the present invention, the reaction in the pressurized liquid phase in the presence of a solid acid catalyst composed of β-zeolite of raw material arylamines and silica and a pressurized liquid phase is a temperature range of 300 to 400 ° C, preferably a temperature of 330 ° C to 360 ° C. Performed under conditions. If the temperature is lower than 300 ° C., the progress of the reaction is slow, and if it exceeds 400 ° C., a by-product is often generated, and when a low-boiling raw material such as aniline is used as the raw material, it is high to keep it as a liquid. Requires pressure.
[0013]
The pressure in the present invention may be any pressure as long as ammonia generated by the reaction can be released from the reaction system and the reaction phase can be maintained in a liquid state at the reaction temperature. This pressure increases in proportion to the reaction temperature, and decreases as the mole fraction of arylamines in the reaction phase decreases as the reaction proceeds. This pressure may generally correspond to the saturated vapor pressure of arylamines at the reaction temperature. For example, in the case of aniline, the pressure is usually in the range of 10 to 40 Kg / cm 2 G at the above reaction temperature.
[0014]
In the method of the present invention, after the reaction, the unreacted arylamines are fractionated from the reaction product, and then the high-boiling by-products are separated as a residue, whereby the desired diarylamines can be easily obtained. When water is added during the reaction, most of the water is recovered at the same time as the arylamines during the fractional distillation of the unreacted arylamines. Therefore, the water content of the fractionated arylamines is adjusted appropriately. Can be reused.
[0015]
The method of the present invention can be carried out by either a batch method or a continuous method, but industrially, a continuous method in which raw material arylamines and water are continuously supplied and the reactants are continuously extracted while controlling the pressure is a work efficiency. This is advantageous.
[0016]
【The invention's effect】
As described above, according to the method of the present invention described in detail, when producing diarylamines under a pressurized liquid phase using arylamines as raw materials, a solid acid catalyst composed of β-zeolite and silica is used. It is possible to improve product quality, and its industrial value is extremely high.
[0017]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0018]
Example 1
In a 500 mL stainless steel autoclave, 25 g of H-β zeolite (Si / Al = 25.0, containing 20% silica) and 200 g of aniline were placed, and the air in the autoclave was replaced with nitrogen, and then at 350 ° C. in a sealed system. Heating was performed for 3 hours. After the reaction product was cooled, it was removed from the autoclave, the catalyst was filtered, and the reaction solution was analyzed using a gas chromatograph. As a result, the diphenylamine concentration in the reaction solution was 25.0%.
[0019]
Comparative Example 1
In the method of Example 1, the same operation as in Example 1 was performed except that 50 g of a silica alumina catalyst (manufactured by JGC Chemical Co., Ltd.) shown below was used as a catalyst and 2 g of water was added. The obtained reaction product was cooled and then removed from the autoclave, the catalyst was filtered off, and the reaction solution was analyzed using a gas chromatograph. The results are shown in Table 1.
Silica alumina (Si / Al = 6.5): trade name N633L
Silica alumina (Si / Al = 2.6): trade name N632NH
[0020]
[Table 1]
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02341798A JP3972443B2 (en) | 1998-02-04 | 1998-02-04 | Process for producing diarylamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02341798A JP3972443B2 (en) | 1998-02-04 | 1998-02-04 | Process for producing diarylamines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11222466A JPH11222466A (en) | 1999-08-17 |
| JP3972443B2 true JP3972443B2 (en) | 2007-09-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02341798A Expired - Fee Related JP3972443B2 (en) | 1998-02-04 | 1998-02-04 | Process for producing diarylamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3972443B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4505911B2 (en) * | 1999-12-20 | 2010-07-21 | 住友化学株式会社 | Method for producing diarylamine |
| CN106083609A (en) * | 2016-06-27 | 2016-11-09 | 南通新邦化工科技有限公司 | Aniline syntehsizing diphenylamine reaction preparation MEA and cumidine |
-
1998
- 1998-02-04 JP JP02341798A patent/JP3972443B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11222466A (en) | 1999-08-17 |
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