JP2001172230A - Method for producing diarylamines - Google Patents
Method for producing diarylaminesInfo
- Publication number
- JP2001172230A JP2001172230A JP36072899A JP36072899A JP2001172230A JP 2001172230 A JP2001172230 A JP 2001172230A JP 36072899 A JP36072899 A JP 36072899A JP 36072899 A JP36072899 A JP 36072899A JP 2001172230 A JP2001172230 A JP 2001172230A
- Authority
- JP
- Japan
- Prior art keywords
- type
- arylamine
- arylamines
- producing
- weight
- 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.)
- Granted
Links
- 125000005266 diarylamine group Chemical group 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 150000003222 pyridines Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 239000010457 zeolite Substances 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- -1 hydroxy, amino Chemical group 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 2
- 241000269350 Anura Species 0.000 claims 1
- 229910052680 mordenite Inorganic materials 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 34
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 3
- 150000004992 toluidines Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VSHTWPWTCXQLQN-UHFFFAOYSA-N n-butylaniline Chemical compound CCCCNC1=CC=CC=C1 VSHTWPWTCXQLQN-UHFFFAOYSA-N 0.000 description 2
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- RGDQRXPEZUNWHX-UHFFFAOYSA-N 3-methylpyridin-2-amine Chemical compound CC1=CC=CN=C1N RGDQRXPEZUNWHX-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】
【課題】 原料アリールアミン類を固体酸触媒存在下、
加圧液相下で反応させてジアリールアミン類を工業的に
製造する方法において、アリールアミン類のジアリール
アミン類への転化率の高い製造方法を提供する。
【解決手段】 原料アリールアミン類を固体酸触媒存在
下、加圧液相下で反応させてジアリールアミン類を製造
するにあたり、原料アリールアミン類中のピリジン類含
有量を０．８重量％以下とすることを特徴とするジアリ
ールアミン類の製造方法。(57) [Problem] To provide a raw material arylamine in the presence of a solid acid catalyst.
In a method for industrially producing diarylamines by reacting under a pressurized liquid phase, there is provided a production method having a high conversion rate of arylamines to diarylamines. SOLUTION: In producing diarylamines by reacting raw arylamines in the presence of a solid acid catalyst under a pressurized liquid phase, the content of pyridines in the raw arylamines is set to 0.8% by weight or less. A process for producing diarylamines.
Description
【0001】[0001]
【発明の属する技術分野】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方法に関す
る。更に詳しくは、アニリン等のアリールアミン類を原
料にして固体酸触媒存在下、加圧液相下で反応させてジ
アリールアミン類を製造する方法に関する。The present invention relates to a method for producing diarylamines, which are raw materials for rubber drugs, medicines, dyes and the like. More specifically, the present invention relates to a method for producing a diarylamine by reacting an arylamine such as aniline as a raw material in the presence of a solid acid catalyst under a pressurized liquid phase.
【0002】[0002]
【従来の技術】従来、ジアリールアミン類を製造する方
法としては、固体酸触媒存在下、加圧液相下で反応させ
る方法（例えば特公昭５２−１５５８５号、５４−１３
５７２８号公報）が知られている。2. Description of the Related Art Conventionally, as a method for producing diarylamines, a method of reacting in the presence of a solid acid catalyst under a pressurized liquid phase (for example, Japanese Patent Publication No. 52-15585, 54-13).
No. 5728) is known.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、前記方
法を、反応後の未反応アリールアミン類を回収・リサイ
クルする工業的な製造プロセスに適用する場合には、ア
リールアミン類のジアリールアミン類への転化率が十分
でなく、反応後の未反応アリールアミン類の回収・リサ
イクル量が増加し、生産性の低下を余儀なくされてい
た。However, when the above method is applied to an industrial production process for recovering and recycling unreacted arylamines after the reaction, conversion of the arylamines to diarylamines is required. The rate was not sufficient, and the amount of unreacted arylamines after the reaction was recovered and recycled, and the productivity had to be reduced.
【0004】本発明の課題は、原料アリールアミン類を固体
酸触媒存在下、加圧液相下で反応させてジアリールアミ
ン類を工業的に製造する方法において、アリールアミン
類のジアリールアミン類への転化率の高い製造方法を提
供することにある。[0004] An object of the present invention is to provide a method for industrially producing diarylamines by reacting raw arylamines in the presence of a solid acid catalyst under a pressurized liquid phase. An object of the present invention is to provide a production method having a high conversion.
【0005】本発明者らは、かかる状況下において、アリー
ルアミン類のジアリールアミン類への転化率を向上させ
ることを目的として鋭意検討を行った結果、ピリジン類
含有量が特定量以下であるアリールアミン類を原料とし
て用いる場合には前記転化率を著しく向上し得ることを
見出し、本発明を完成するに至った。[0005] Under such circumstances, the present inventors have conducted intensive studies for the purpose of improving the conversion of arylamines to diarylamines. As a result, aryls having a pyridine content of not more than a specific amount have been studied. It has been found that when amines are used as a raw material, the conversion can be significantly improved, and the present invention has been completed.
【0006】[0006]
【課題を解決するための手段】すなわち本発明は、
（Ｉ）原料アリールアミン類を固体酸触媒存在下、加圧
液相下で反応させてジアリールアミン類を製造するにあ
たり、原料アリールアミン類中のピリジン類含有量を
０．８重量％以下とすることを特徴とするジアリールア
ミン類の製造方法であり、That is, the present invention provides:
(I) In producing diarylamines by reacting raw arylamines in the presence of a solid acid catalyst under a pressurized liquid phase, the content of pyridines in the raw arylamines is set to 0.8% by weight or less. A method for producing diarylamines, characterized in that:
【0007】（ＩＩ）原料アリールアミン類として、反応後
に回収されるアリールアミン類より該アリールアミン中
のピリジン類を除去して得られるアリールアミン類を用
いることを特徴とする（Ｉ）記載のジアリールアミン類
の製造方法であり、(II) The diaryl according to (I), wherein the starting arylamine is an arylamine obtained by removing pyridines in the arylamine from the arylamine recovered after the reaction. A method for producing amines,
【0008】（ＩＩＩ）固体酸触媒がβ型、Ｙ型およびＵＳ
Ｙ型から選ばれた少なくとも１種のゼオライトであるこ
とを特徴とする（Ｉ）又は（ＩＩ）記載のジアリールア
ミン類の製造方法であり、(III) The solid acid catalysts are β-type, Y-type and US
A method for producing diarylamines according to (I) or (II), wherein the method is at least one zeolite selected from the Y type.
【0009】（ＩＶ）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と
を反応させて下記一般式（３）で示されるジアリールア
ミンを製造することを特徴とする（Ｉ）〜（ＩＩＩ）の
いずれか一つに記載のジアリールアミン類の製造方法で
あり、 （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、ニトロまたは炭素数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。）(IV) reacting an arylamine represented by the following general formula (1) with an arylamine represented by the following general formula (2) to produce a diarylamine represented by the following general formula (3): A method for producing a diarylamine according to any one of (I) to (III), (In the formula, R 1 to R 10 may be the same or different, and each represents hydrogen, alkyl having 1 to 12 carbons, alkoxy, phenyl, hydroxy, amino, nitro or carbon having 1 to 12 carbons. 1 carbon atom substituted by alkoxy, hydroxy or phenyl having 1 to 12 carbon atoms
Selected from the group consisting of ~ 12 alkyls. )
【0010】（Ｖ）原料アリールアミン類中のピリジン類含
有量を０．４重量％以下とすることを特徴とする（Ｉ）
〜（ＩＶ）のいずれか一つに記載のジアリールアミン類
の製造方法である。(V) The content of pyridines in the starting arylamines is set to 0.4% by weight or less (I).
It is a manufacturing method of the diarylamine as described in any one of-(IV).
【0011】[0011]
【発明の実施の形態】以下、本発明について詳細に説明
する。本発明において、原料アリールアミン類は、下記
一般式（１）および（２）（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、ニトロまたは
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）で示されるものであり、これら原料アリ
ールアミン類を固体酸触媒存在下、加圧液相下で反応さ
せることにより下記一般式（３）〔式中の記号および条
件は上記一般式（１）および（２）と同じ〕で示される
ジアリールアミンを得ることができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, the starting arylamines represented by the following general formulas (1) and (2) (wherein R 1 to R 10 may be the same or different; Selected from the group consisting of alkyl having 1 to 12 carbons, alkoxy, phenyl, hydroxy, amino, nitro or alkyl having 1 to 12 carbons substituted with alkoxy, hydroxy or phenyl having 1 to 12 carbons) By reacting these starting arylamines in the presence of a solid acid catalyst under a pressurized liquid phase, the following general formula (3) [wherein the symbols and conditions in the formulas are those of the above general formulas (1) and (2) The same as the above) can be obtained.
【0012】 上記一般式（１）および（２）で示される原料アリール
アミンとしては、例えばアニリン、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
ニシジン等、好ましくはアニリン、トルイジン、クミジ
ン、キシリジン等が挙げられる。反応に際し一般式
（１）および（２）は勿論同一物、例えばアニリンのみ
であってもよい。[0012] Examples of the raw material arylamine represented by the above general formulas (1) and (2) include, for example, aniline, toluidine, ethylaniline, cumidine, xylidine, butylaniline, anisidine and the like, preferably aniline, toluidine, cumidine, xylidine and the like. . In the reaction, general formulas (1) and (2) may of course be the same, for example, only aniline.
【0013】本発明は、原料アリールアミン類中のピリジン
類含有量を０．８重量％以下、好ましくは０．４重量％
以下、さらに好ましくは０．０５重量％以上０．４重量
％以下とすることを特徴とする。原料アリールアミン類
中のピリジン類含有量を前記範囲内にすることにより、
アリールアミン類のジアリールアミン類への転化率を高
くすることができる。前記ピリジン類としては、例え
ば、２−メチルピリジン、２−アミノ−３−メチルピリ
ジン、又は本発明の反応に際してアニリン、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、アニシジン等のアリールアミンから生成し得る
各種ピリジン等が挙げられる。また、ピリジン類含有量
を０．０５重量％以上０．４重量％以下とする場合には
前記転化率を高くすることができ、かつ精留工程等のピ
リジン類除去工程の負荷を低減できる。尚、本発明にお
いて、原料アリールアミン類中のピリジン類含有量はガ
スクロマトグラフを用いて測定した。According to the present invention, the content of pyridines in the starting arylamine is 0.8% by weight or less, preferably 0.4% by weight.
Hereafter, the content is more preferably 0.05% by weight or more and 0.4% by weight or less. By setting the pyridine content in the raw material arylamines within the above range,
The conversion rate of arylamines to diarylamines can be increased. Examples of the pyridines include 2-methylpyridine, 2-amino-3-methylpyridine, or an arylamine such as aniline, toluidine, ethylaniline, cumidine, xylidine, butylaniline, or anisidine in the reaction of the present invention. And various pyridines to be obtained. When the pyridine content is 0.05% by weight or more and 0.4% by weight or less, the conversion can be increased and the load of the pyridine removal step such as the rectification step can be reduced. In the present invention, the content of pyridines in the starting arylamines was measured using a gas chromatograph.
【0014】反応後に回収される未反応アリールアミン類等
のピリジン類を含む粗アリールアミン類を原料の全部又
は一部として用いる場合は、例えば、前記粗アリールア
ミン類を用いて得られる原料アリールアミンのピリジン
類含有量が０．８重量％以下となるように、前記粗アリ
ールアミン類に含まれるピリジン類を予め除去する。ア
リールアミン類からアリールアミン類中のピリジン類を
除去する方法としては、例えば、りん酸、硫酸等を用い
る酸洗浄処理、イオン交換膜、イオン交換樹脂若しくは
活性白土等の固体酸物質等を用いる吸着除去処理又は蒸
留等が挙げられ、好ましくは蒸留による方法が挙げられ
る。When crude arylamines containing pyridines such as unreacted arylamines recovered after the reaction are used as all or a part of the raw material, for example, the raw arylamine obtained using the crude arylamines may be used. The pyridines contained in the crude arylamines are removed in advance so that the content of the pyridines becomes 0.8% by weight or less. Methods for removing pyridines in arylamines from arylamines include, for example, acid washing treatment using phosphoric acid, sulfuric acid, etc., adsorption using ion exchange membranes, ion exchange resins or solid acid substances such as activated clay. A removal treatment or distillation may be mentioned, and a distillation method is preferred.
【0015】本発明を行うに際しては、アリールアミン類の
ジアリールアミン類への転化率を更に向上させることが
できることから、使用する原料アリールアミン類はその
水分量が好ましくは約０．９重量％未満、さらに好まし
くは０．７重量％未満である。In carrying out the present invention, since the conversion of arylamines to diarylamines can be further improved, the starting arylamines used preferably have a water content of less than about 0.9% by weight. , More preferably less than 0.7% by weight.
【0016】本発明に用いる固体酸触媒としては、例えばβ
型、Ｙ型、ＵＳＹ型、Ｌ型、ＭＦＩ型、ＳＡＰＯ型、モ
ルデナイト型のゼオライト、又はゼオライト構成成分で
あるＡｌあるいはＳｉ等の一部が他の各種金属で置換さ
れたゼオライト等が挙げられ、就中β型、Ｙ型およびＵ
ＳＹ型から選ばれた少なくとも１種のゼオライトの使用
が推奨される。The solid acid catalyst used in the present invention includes, for example, β
Type, Y-type, USY-type, L-type, MFI-type, SAPO-type, mordenite-type zeolite, or a zeolite in which a part of zeolite component Al or Si is substituted with other various metals, and the like. Above all β-type, Y-type and U
It is recommended to use at least one zeolite selected from the SY type.
【0017】固体酸触媒としてゼオライトを用いる場合、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。アリールアミン類の転化
率の低下をまねかない範囲内でＮａ型、Ｋ型のゼオライ
トを併用しても良い。これらのゼオライトとしてβ型、
Ｙ型、ＵＳＹ型、Ｌ型、ＭＦＩ型、ＳＡＰＯ型、モルデ
ナイト型等として各種ゼオライトが市販されているの
で、これらの中から選択し使用してもよい。使用に際し
てのゼオライト触媒の形状は、例えば粉末状、粒状、タ
ブレット状等が挙げられ、取り扱い易さの観点より粒状
又はタブレット状が好ましい。ゼオライトを粒状等へ成
形するに際して、バインダーを使用することが好まし
い。バインダーとしては各種材料を使用可能であるが、
例えばアルミナ、シリカ、珪藻土等が挙げられる。When zeolite is used as the solid acid catalyst, acid points are present in the zeolite, and these acid points are preferably H-type or NH 4 -type. Na-type and K-type zeolites may be used together as long as the conversion of arylamines is not reduced. Β-type as these zeolites,
Various zeolites are commercially available as Y-type, USY-type, L-type, MFI-type, SAPO-type, mordenite-type, etc., and may be selected from these and used. The shape of the zeolite catalyst at the time of use includes, for example, powder, granules, tablets and the like, and is preferably granules or tablets from the viewpoint of easy handling. When forming the zeolite into granules or the like, it is preferable to use a binder. Various materials can be used as the binder,
For example, alumina, silica, diatomaceous earth and the like can be mentioned.
【0018】本発明を行うに際して、反応温度は例えば約３
００℃〜４００℃、好ましくは約３３０℃〜３６０℃で
ある。約３００℃より低いと反応の進行が遅く、また約
４００℃を越えると副成物の生成が多く、且つ原料にア
ニリンのような低沸点原料を使用するような場合、液体
として保持するために高い圧力を要する。In carrying out the present invention, the reaction temperature is, for example, about 3
The temperature is from 00C to 400C, preferably from about 330C to 360C. If the temperature is lower than about 300 ° C., the reaction progresses slowly. If the temperature exceeds about 400 ° C., a large amount of by-products is generated. Requires high pressure.
【0019】反応圧力は、発生するアンモニアを放出でき、
且つ反応相を前記反応温度にて液体の状態を保持できう
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
常前記反応温度では約１ＭＰａ〜約４ＭＰａの範囲とな
る。[0019] The reaction pressure can release the generated ammonia,
The reaction phase may be any one that can maintain 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. In addition, this pressure may generally correspond to the saturated vapor pressure of arylamines at the reaction temperature. For example, in the case of aniline, the reaction temperature is usually in the range of about 1 MPa to about 4 MPa.
【0020】本発明においては、反応後、単に反応物から未
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。この際、回収される
未反応アリールアミン類は原料アリールアミン類として
用いることができる。In the present invention, the desired diarylamine can be easily obtained by simply distilling the unreacted arylamine from the reaction product after the reaction and then separating the high-boiling by-product as a residue. . At this time, the unreacted arylamines recovered can be used as raw material arylamines.
【0021】本発明は回分法、連続法いずれによっても行う
ことができる。工業的には原料アリールアミン類を連続
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。連続法
で行う場合には、反応器への原料アリールアミン類の供
給速度〔アリールアミン類供給量（ｍｌ／ｈ）／触媒充
填量（ｍｌ）〕ＬＨＳＶは例えば約０．０１〜約１０、
好ましくは約０．１〜約１である。The present invention can be carried out by either a batch method or a continuous method. Industrially, a continuous method of continuously supplying the starting material arylamines and continuously extracting the reactants while controlling the pressure is advantageous in terms of work efficiency. When the continuous method is used, the feed rate of the raw material arylamines to the reactor [arylamines supply amount (ml / h) / catalyst charge amount (ml)] LHSV is, for example, about 0.01 to about 10,
Preferably it is from about 0.1 to about 1.
【0022】[0022]
【実施例】以下、実施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。EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【0023】実施例１ 外部加熱炉に設置されたステンレス製反応管(直径２８
ｍｍ×長さ４００ｍｍ)の下部に原料仕込み口、上部に
圧力計および調圧弁を取り付けた反応器に直径１．６ｍ
ｍ円柱状Ｈ−βゼオライト触媒（Ｓｉ／Ａｌ＝２５．
０、日揮ユニバーサル株式会社製、商品名ＢＥＴＡ）を
１７９．８ｍｌを充填し、アニリン（２−メチルピリジ
ン含有量０．０１重量％未満、水分濃度０重量％）を８
７．４ｍｌ／ｈ（ＬＨＳＶ＝０．４８）の速度で連続的
に供給した。その際、外部加熱炉の温度は３２５℃、圧
力は２．１ＭＰａに保って反応を行ない、連続的に反応
管上部から抜き出された反応液を冷却後回収した。前記
の連続反応評価での反応液中のジフェニルアミン濃度及
びアニリン転化率を表１に示す。Example 1 A stainless steel reaction tube (diameter 28) installed in an external heating furnace
1.6 mm in diameter in a reactor equipped with a raw material inlet at the bottom of
m columnar H-β zeolite catalyst (Si / Al = 25.
0, filled with 179.8 ml of BETA (trade name, manufactured by JGC Universal Co., Ltd.), and 8% of aniline (2-methylpyridine content less than 0.01% by weight and water concentration of 0% by weight).
It was fed continuously at a rate of 7.4 ml / h (LHSV = 0.48). At that time, the reaction was carried out while maintaining the temperature of the external heating furnace at 325 ° C. and the pressure at 2.1 MPa, and the reaction solution continuously withdrawn from the upper portion of the reaction tube was cooled and collected. Table 1 shows the diphenylamine concentration in the reaction solution and the aniline conversion rate in the continuous reaction evaluation.
【0024】実施例２ 実施例１において、アニリン（２−メチルピリジン含有
量０．０１重量％未満、水分濃度０重量％）に変えてア
ニリン（２−メチルピリジン含有量０．０８重量％、水
分濃度０重量％）を用いた以外は、実施例１と同様にし
て行った。前記の連続反応評価での反応液中のジフェニ
ルアミン濃度及びアニリン転化率を表１に示す。また、
冷却後回収された反応液を蒸留することにより、２−メ
チルピリジン含有量が０．０８重量％であるアニリンを
得ることができた。Example 2 In Example 1, aniline (2-methylpyridine content: less than 0.01% by weight, water concentration: 0% by weight) was replaced with aniline (2-methylpyridine content: 0.08% by weight, water content: (Concentration: 0% by weight), except that the procedure was the same as in Example 1. Table 1 shows the diphenylamine concentration in the reaction solution and the aniline conversion rate in the continuous reaction evaluation. Also,
By distilling the reaction solution collected after cooling, aniline having a 2-methylpyridine content of 0.08% by weight could be obtained.
【0025】実施例３ 実施例１において、アニリン（２−メチルピリジン含有
量０．０１重量％未満、水分濃度０重量％）に変えてア
ニリン（２−メチルピリジン含有量０．４４重量％、水
分濃度０重量％）を用いた以外は、実施例１と同様にし
て行った。前記の連続反応評価での反応液中のジフェニ
ルアミン濃度及びアニリン転化率を表１に示す。Example 3 In Example 1, aniline (2-methylpyridine content: less than 0.01% by weight, water concentration: 0% by weight) was replaced with aniline (2-methylpyridine content: 0.44% by weight, water content: (Concentration: 0% by weight), except that the procedure was the same as in Example 1. Table 1 shows the diphenylamine concentration in the reaction solution and the aniline conversion rate in the continuous reaction evaluation.
【0026】比較例１ 実施例１において、アニリン（２−メチルピリジン含有
量０．０１重量％未満、水分濃度０重量％）に変えてア
ニリン（２−メチルピリジン含有量０．８７重量％、水
分濃度０重量％）を用いた以外は、実施例１と同様にし
て行った。前記の連続反応評価での反応液中のジフェニ
ルアミン濃度及びアニリン転化率を表１に示す。Comparative Example 1 In Example 1, aniline (2-methylpyridine content: 0.87% by weight, water content: less than 0.01% by weight, water concentration: 0% by weight) was replaced by aniline (2-methylpyridine content: less than 0.01% by weight). (Concentration: 0% by weight), except that the procedure was the same as in Example 1. Table 1 shows the diphenylamine concentration in the reaction solution and the aniline conversion rate in the continuous reaction evaluation.
【0027】[0027]
【表1】 【table 1】
【0028】[0028]
【発明の効果】本発明は、原料アリールアミン類を固体
酸触媒存在下、加圧液相下で反応させてジアリールアミ
ン類を製造するに際し、アリールアミン類のジアリール
アミン類への転化率を著しく向上させることができ、そ
の産業上の利用価値は極めて大きいものである。Industrial Applicability According to the present invention, the conversion of arylamines to diarylamines is remarkably improved when diarylamines are produced by reacting raw arylamines in the presence of a solid acid catalyst under a pressurized liquid phase. It can be improved and its industrial utility value is extremely large.
Claims (5)
下、加圧液相下で反応させてジアリールアミン類を製造
するにあたり、原料アリールアミン類中のピリジン類含
有量を０．８重量％以下とすることを特徴とするジアリ
ールアミン類の製造方法。When producing a diarylamine by reacting a starting arylamine in the presence of a solid acid catalyst under a pressurized liquid phase, the content of pyridine in the starting arylamine is 0.8% by weight or less. A method for producing diarylamines, characterized in that:
回収されるアリールアミン類より該アリールアミン中の
ピリジン類を除去して得られるアリールアミン類を用い
ることを特徴とする請求項１記載のジアリールアミン類
の製造方法。2. The diarylamine according to claim 1, wherein an arylamine obtained by removing a pyridine in the arylamine from the arylamine recovered after the reaction is used as a raw material arylamine. Manufacturing methods.
型、ＭＦＩ型、ＳＡＰＯ型及びモルデナイト型からなる
群より選ばれた少なくとも１種のゼオライトであること
を特徴とする請求項１又は２記載のジアリールアミン類
の製造方法。3. The solid acid catalyst is β-type, Y-type, USY-type, and L-type.
The method for producing a diarylamine according to claim 1 or 2, wherein the zeolite is at least one zeolite selected from the group consisting of a type, an MFI type, a SAPO type, and a mordenite type.
ミンと下記一般式（２）で示されるアリールアミンとを
反応させて下記一般式（３）で示されるジアリールアミ
ンを製造することを特徴とする請求項１〜３のいずれか
一つに記載のジアリールアミン類の製造方法。 （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、ニトロまたは炭素数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。）4. A method of reacting an arylamine represented by the following general formula (1) with an arylamine represented by the following general formula (2) to produce a diarylamine represented by the following general formula (3). The method for producing a diarylamine according to any one of claims 1 to 3. (In the formula, R 1 to R 10 may be the same or different, and each represents hydrogen, alkyl having 1 to 12 carbons, alkoxy, phenyl, hydroxy, amino, nitro or carbon having 1 to 12 carbons. 1 carbon atom substituted by alkoxy, hydroxy or phenyl having 1 to 12 carbon atoms
Selected from the group consisting of ~ 12 alkyls. )
有量を０．４重量％以下とすることを特徴とする請求項
１〜４のいずれか一つに記載のジアリールアミン類の製
造方法。5. The method for producing diarylamines according to claim 1, wherein the content of pyridines in the starting arylamines is 0.4% by weight or less.
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|---|---|---|---|
| JP36072899A JP4505911B2 (en) | 1999-12-20 | 1999-12-20 | Method for producing diarylamine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36072899A JP4505911B2 (en) | 1999-12-20 | 1999-12-20 | Method for producing diarylamine |
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| JP4505911B2 JP4505911B2 (en) | 2010-07-21 |
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|---|---|---|---|
| JP36072899A Expired - Fee Related JP4505911B2 (en) | 1999-12-20 | 1999-12-20 | Method for producing diarylamine |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685362A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Separation method of 2-methylpyridine |
| WO2023071891A1 (en) * | 2021-10-31 | 2023-05-04 | 中国石油化工股份有限公司 | Method for selectively and continuously producing 2-methylpyridine and diphenylamine from aniline |
| CN116063189A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Method for improving selectivity of synthesizing diphenylamine from phenylamine |
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|---|---|---|---|---|
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| JPH11217358A (en) * | 1998-01-30 | 1999-08-10 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11222466A (en) * | 1998-02-04 | 1999-08-17 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11222467A (en) * | 1998-02-04 | 1999-08-17 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11310554A (en) * | 1998-04-28 | 1999-11-09 | Sumitomo Chem Co Ltd | Continuous production method of diarylamines |
-
1999
- 1999-12-20 JP JP36072899A patent/JP4505911B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54135728A (en) * | 1978-04-13 | 1979-10-22 | New Japan Chem Co Ltd | Preparation of diphenylamine |
| JPH11217358A (en) * | 1998-01-30 | 1999-08-10 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11222466A (en) * | 1998-02-04 | 1999-08-17 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11222467A (en) * | 1998-02-04 | 1999-08-17 | Sumitomo Chem Co Ltd | Method for producing diarylamines |
| JPH11310554A (en) * | 1998-04-28 | 1999-11-09 | Sumitomo Chem Co Ltd | Continuous production method of diarylamines |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685362A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Separation method of 2-methylpyridine |
| CN114685362B (en) * | 2020-12-31 | 2024-05-03 | 中国石油化工股份有限公司 | Separation method of 2-methylpyridine |
| WO2023071891A1 (en) * | 2021-10-31 | 2023-05-04 | 中国石油化工股份有限公司 | Method for selectively and continuously producing 2-methylpyridine and diphenylamine from aniline |
| CN116063189A (en) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | Method for improving selectivity of synthesizing diphenylamine from phenylamine |
| TWI831434B (en) * | 2021-10-31 | 2024-02-01 | 大陸商中國石油化工科技開發有限公司 | A method for selectively and continuously producing 2-methylpyridine and diphenylamine from aniline |
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|---|---|
| JP4505911B2 (en) | 2010-07-21 |
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