JPS63130567A - Continuous production of ortho-or para-phenylenediamine - Google Patents
Continuous production of ortho-or para-phenylenediamineInfo
- Publication number
- JPS63130567A JPS63130567A JP61272828A JP27282886A JPS63130567A JP S63130567 A JPS63130567 A JP S63130567A JP 61272828 A JP61272828 A JP 61272828A JP 27282886 A JP27282886 A JP 27282886A JP S63130567 A JPS63130567 A JP S63130567A
- Authority
- JP
- Japan
- Prior art keywords
- dichlorobenzene
- phenylenediamine
- reaction
- reactor
- ammonia
- 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 title claims description 24
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims description 11
- 238000010924 continuous production Methods 0.000 title claims description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 32
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- 239000005749 Copper compound Substances 0.000 claims abstract description 10
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 10
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000003277 amino group Chemical group 0.000 claims abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005751 Copper oxide Substances 0.000 abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 7
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 35
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 27
- 238000000605 extraction Methods 0.000 description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- -1 copper complex ion Chemical class 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 6
- 239000005750 Copper hydroxide Substances 0.000 description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- QZHXKQKKEBXYRG-UHFFFAOYSA-N 4-n-(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1=CC=C(N)C=C1 QZHXKQKKEBXYRG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は化成品の製造法に係る。更に詳しくは流通管型
反応器を用いた〇−又はｐ−フェニレンジアミンの連続
製造法に係る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing chemical products. More specifically, the present invention relates to a method for continuous production of 〇- or p-phenylenediamine using a flow tube reactor.
従来の技術 ｏ−又はｐ−フェニレンジアミンは染料、顔料。Conventional technology o- or p-phenylenediamine is a dye or pigment.
樹脂等の中間体として有用な化合物である。It is a compound useful as an intermediate for resins, etc.
ｏ−又はｐ−フェニレンジアミンは通常銅触媒の存在下
〇−又はｐ−ジクロルベンゼンにアミノ化反応を施すこ
とによって製造されている。O- or p-phenylenediamine is usually produced by subjecting o- or p-dichlorobenzene to an amination reaction in the presence of a copper catalyst.
製造方法としては通常回分式によるが連続製造法として
槽式連続法が特開昭６０−１９５９５１に示され又多孔
板挿入基式反応器による連続製法が特開昭５６−１６４
４９に紹介されている。反応装置として流通管式反応器
を使用した例は触媒を使用しないニトロクロルベンゼン
類のアンモノリシス反応における実験例が報告されてい
る。The production method is usually a batch method, but as a continuous production method, a continuous tank method is shown in JP-A-60-195951, and a continuous method using a perforated plate-inserted base reactor is shown in JP-A-56-164.
It is introduced in 49. An experimental example using a flow tube reactor as a reaction device has been reported in the ammonolysis reaction of nitrochlorobenzenes without using a catalyst.
（Ｂ、工、０．Ｓ、、１１４７）
発明が解決しようとする問題点
銅触媒を用いて〇−又はｐ−ジクロルベンゼンから対応
する〇−又はｐ−２二二レンジアミンを連続的に製造す
る方法については前記したような特開昭が知られている
にすぎないがそれらの方法はいずれも容積効率が悪いと
いう欠点がある。(B, Engineering, 0.S,, 1147) Problems to be Solved by the Invention Continuously converting the corresponding 〇- or p-2 dichlorobenzene from 〇- or p-dichlorobenzene using a copper catalyst. The only known manufacturing method is the one disclosed in Japanese Patent Application Laid-Open No. 2003-120002, as mentioned above, but all of these methods have the disadvantage of poor volumetric efficiency.
従って銅触媒を用いた〇−又はｐ−ジクロルベンゼンか
ら対応する〇−又はｐ−フェニレンジアミンを効率よく
連続生産する方法は未だ確立されていない。Therefore, a method for efficiently and continuously producing the corresponding 0- or p-phenylenediamine from 0- or p-dichlorobenzene using a copper catalyst has not yet been established.
本発明者らは前記したような状況に鑑み銅化合物触媒を
用いて〇−又はｐ−ジクロルベンゼンから〇−又はｐ−
フェニレンジアミンを効率よく連続的に製造する方法に
つき下記するような問題点を含め鋭意研究を行った。と
ころで銅化合物触媒を用いて〇−又はｐ−ジクロルベン
ゼンカＣ，ｏ−又１ｄｐ−フェニレンジアミンを連続的
に製造するにあたり解決されるべき問題点は
■ 効率のよい連続生産を行うに適した反応器の選択
■ 反応器中において目づまりを起すような不均一系反
応の防止
■ 連続生産に適した銅−アンモニア触媒の調製法及び
使用法
■ 反応生成物からの効率のよい目的物の分離法
■ その他（反応条件１反応器の材質等）等である。In view of the above-mentioned situation, the present inventors used a copper compound catalyst to convert 〇- or p-dichlorobenzene to 〇- or p-
We conducted extensive research on a method for efficiently and continuously producing phenylenediamine, including the following problems. By the way, the problems to be solved in continuously producing 〇- or p-dichlorobenzene, C, o- or 1dp-phenylenediamine using a copper compound catalyst are as follows. Selection of reactor ■ Prevention of heterogeneous reactions that would cause clogging in the reactor ■ Method for preparing and using a copper-ammonia catalyst suitable for continuous production ■ Efficient method for separating the target product from the reaction product ■ Others (reaction conditions 1, material of reactor, etc.).
問題点を解決する為の手段
本発明者らは前記したような問題点を一挙に解決する方
法として本発明の方法を提供する。Means for Solving the Problems The present inventors provide the method of the present invention as a method for solving the above-mentioned problems all at once.
即ち本発明は〇−又はｐ−ジクロルベンゼンから〇−又
はｐ−２エニレンジアミンを製造する方法において
（１） 流通管型反応器に銅化合物触媒を溶解したア
ンモニア水浴液及びその融点以上に加熱せられた〇−又
はｐ−クロルベンゼンを供給してそれらのクロル基をア
ミン基にかえる工程（２） 流通管型反応器から抜き
出された〇−又はｐ−フェニレンジアミンを含む反応生
成溶液に無機塩基を添加しアンモニア及び低沸留分を留
出せしめたのち残留物から不溶性物質を除去し次いでア
ミンを用いて〇−又はｐ−フェニレンジアミンを抽出す
る工程
を含むことを特徴とする〇−又はｐ−フェニレンジアミ
ンの連続製造法を提供する。That is, the present invention provides a method for producing 〇- or p-2 enylenediamine from 〇- or p-dichlorobenzene. Step (2) of supplying heated 〇- or p-chlorobenzene to convert the chloro groups into amine groups Reaction product solution containing 〇- or p-phenylenediamine extracted from the flow tube reactor 〇 characterized in that it includes a step of adding an inorganic base to distill ammonia and a low-boiling fraction, removing insoluble substances from the residue, and then extracting 〇- or p-phenylenediamine using an amine. - or p-phenylenediamine is provided.
本発明を具体的に説明する。The present invention will be specifically explained.
本発明においては反応器として流通管型反応器が用いら
れる。流通管式反応器の構造については単管のコイル状
又はＵチューブ状のものが容積効率が高いという理由で
好ましいが反応器の一部又は全部を多管式の反応器とす
ることもできる。In the present invention, a flow tube reactor is used as the reactor. Regarding the structure of the flow tube reactor, a single tube coiled or U tube type is preferred because of its high volumetric efficiency, but part or all of the reactor may be a multi-tube reactor.
多管式の反応器の場合は多孔ノズルや衝突板を設けて容
積効率が下るのを防ぐのが望ましい。In the case of a multi-tubular reactor, it is desirable to provide a porous nozzle or a collision plate to prevent the volumetric efficiency from decreasing.
流通管型反応器は高温高圧下、高い塩素イオン濃度にさ
らされたーるのでそれら、に十分耐えることが必要であ
り通常使用材質としてはＳσ５３０４＋５ＵＳ３１６等
のステンレス鋼又はチタンが使用される。殊にチタンが
望ましい材質である。Since the flow tube reactor is exposed to high temperatures and pressures and high chloride ion concentrations, it is necessary to sufficiently withstand these conditions, and the materials usually used are stainless steel such as Sσ5304+5US316 or titanium. Titanium is a particularly desirable material.
本発明の製造法においては不均一反応系を形成しないよ
うに原料の仕込み管、流通管型反応器等を含むすべての
反応経路において原料、触媒、生成物等が均一な液状を
呈していることが必要である。触−媒としては１価又は
２価の銅化合物をアンモニア水に溶解したものが用いら
れ銅化合物は反応系においては銅錯イオンとして存在し
ているものと考えられる。銅化合物としては酸化銅、水
酸化鋼あるいは塩化銅、臭化銅等のハロゲン化銅が用い
られる。金属鋼の使用も可能であるが金属銅の使用は溶
解速度の点から難がある。触媒は通常′５０〜５０％の
アンモニア水にＮａ ３／ｃ ｕ のモル比が２０〜２
００モルより好ましくは２０〜１００モル比となるよう
に銅化合物を溶解して調製される。なお銅化合物として
ハロゲン化第１銅を用いた場合は空気と接触することに
よって第１銅イオンが酸化をうけ第２銅イオンとなり反
応温度において沈澱を起すことがあるので、第２銅イオ
ンから第１銅イオンに還元するに十分なヒドラジン又は
ヒドラジンヒトラードをあらかじめ加えておくか又は少
なくとも銅の酸化数に等モルのハロゲンイオンが存在す
る様にＩ・ロゲン化アンモニウム（例えば塩化アンモニ
ウム、臭化アンモニウム）を添加しておくのがよい。本
発明の製法においては使用ずみの触媒は水酸化銅又は酸
化銅の形で回収されるがこれらの回収水酸化鋼、酸化鋼
あるいは新しい水酸化銅、酸化銅を用いる場合も少なく
とも鋼の酸化数に相当するＩ・ロゲンイオンが存在する
様に塩化アンモニウム、臭化アンモニウム等のハロゲン
化アンモニウムを加えるのが好ましい。In the production method of the present invention, in order to prevent the formation of a heterogeneous reaction system, the raw materials, catalyst, products, etc. must be in a uniform liquid state in all reaction routes including raw material charging tubes, flow pipe reactors, etc. is necessary. As the catalyst, a monovalent or divalent copper compound dissolved in aqueous ammonia is used, and the copper compound is thought to exist as a copper complex ion in the reaction system. As the copper compound, copper oxide, steel hydroxide, or copper halides such as copper chloride and copper bromide are used. Although it is possible to use metallic steel, the use of metallic copper is difficult in terms of dissolution rate. The catalyst is usually a mixture of 50-50% aqueous ammonia and a molar ratio of Na3/cu of 20-2.
The copper compound is prepared by dissolving the copper compound so that the molar ratio is more preferably 20 to 100 mol. In addition, when cuprous halide is used as a copper compound, cuprous ions may be oxidized by contact with air and become cupric ions, which may precipitate at the reaction temperature. Add enough hydrazine or hydrazine hydride to reduce copper ions in advance, or add ammonium halogenide (e.g. ammonium chloride, ammonium bromide) so that there are at least equimolar halogen ions to the oxidation number of copper. ) should be added. In the production method of the present invention, the used catalyst is recovered in the form of copper hydroxide or copper oxide, but when using recovered hydroxide steel, oxidized steel, or new copper hydroxide or copper oxide, at least the oxidation number of the steel is It is preferable to add ammonium halides such as ammonium chloride and ammonium bromide so that I.halogen ions corresponding to .
なお回収された水酸化鋼、酸化鋼を用いて触媒を調製し
た場合は触媒調製後に不浴解物が含まれることがあるの
でそのような時は使用前に濾過してそれらを除去してお
くことが必要である。If the catalyst is prepared using recovered hydroxide steel or oxidized steel, unbath decomposition products may be included after the catalyst is prepared, so in such cases, filter them to remove them before use. It is necessary.
ｏ−又はｐ−ジクロルベンゼンはそれらの融点以上に加
熱されて供給されるものでおる。O- or p-dichlorobenzene is heated above its melting point and supplied.
反応温度におけるアンモニア水に対する溶解度以上に〇
−又はｐ−ジクロルベンゼンが反応管に供給されると〇
−又はｐ−ジクロルベンゼンがオイル分離して均一反応
が損なわれるので反応温度におけるアンモニア水に対す
る溶解度以下の〇−又１ｄｐ−ジクロルベンゼンを供給
することが必要である。触媒を調製するに当り５０〜５
０％のアンモニア水を用いた場合ＮＨｔ、１０−又はｐ
−ジクロルベンゼンのモル比が１２〜５０になるように
〇−又はｐ−ジクロルベンゼンを供給するのが好ましい
。If 〇- or p-dichlorobenzene is supplied to the reaction tube in an amount higher than its solubility in ammonia water at the reaction temperature, 〇- or p-dichlorobenzene will separate into oil and the homogeneous reaction will be impaired. It is necessary to supply 0- or 1 dp-dichlorobenzene below the solubility. 50-5 in preparing the catalyst
When using 0% ammonia water, NHt, 10- or p
It is preferable to supply 0- or p-dichlorobenzene so that the molar ratio of -dichlorobenzene is 12 to 50.
反応温度は通常１８０〜２４０℃より好ましくは２００
〜２２０℃であり反応圧力は通常１００〜２００に／／
ｃｒｎ より好ましくは１２０〜１８０ＫＰ／ｃｒｎ２
である。又原料、触媒、アンモニア水等の流通管型
反応器における平均滞留時間（反応器容積（／、）を反
応生成溶１ （Ａ、４）で除したもの）が３０〜１２０
分程度になるように反応装置、原料の仕込み量等を設計
あるいは設定するのが操作上好都合である。The reaction temperature is usually 180 to 240°C, preferably 200°C.
~220℃ and the reaction pressure is usually 100~200℃//
crn More preferably 120-180KP/crn2
It is. In addition, the average residence time of raw materials, catalysts, ammonia water, etc. in a flow tube reactor (reactor volume (/,) divided by reaction product solution 1 (A, 4)) is 30 to 120.
It is convenient for operation to design or set the reactor, the amount of raw materials charged, etc. so that the reaction time is about 1 minute.
なお流通管型反応器における平均滞留時間他の反応条件
を変更することによって〇−又はｐ−ジクロルベンゼン
の２個のアミン化されるべき塩素。In addition, by changing the average residence time in the flow tube reactor and other reaction conditions, two chlorine atoms of 〇- or p-dichlorobenzene to be aminated.
のうちの１ケのみをアミン化した〇−又はｐ−クロルア
ニリンの生成量を増加せしめることも可能である。It is also possible to increase the amount of 0- or p-chloroaniline produced by aminating only one of them.
次に反応生成溶液から目的物のと９出し法につき説明す
る。Next, a method for extracting the target product from the reaction product solution will be explained.
流通管型反応器における反応を終えた目的物他を含有し
た反応生成溶液を連続的に抜出槽に抜出し１反応生成液
中に存在する銅錯イオン、塩化アンモニウムを分解する
に足りる量又はそれ以上の無機塩基（例えばカセイカリ
、カセイノーダ、水酸化マグネシウム等の水溶液が好ま
しい）を連続的に加えて加熱しアンモニア、水、未反応
の〇−又はｐ−ジクロルベンゼン、副生〇−又はｐ−ク
ロルアニリン、副生アニリン等を留出させる。抜出槽の
圧力は大気圧でよいが０．３〜１＋ ＯＭｙ ／ ｃｍ
に加圧することも出来る。加圧することはアンモニ
アの回収の為には不利であるが抜出槽の温度を上げるこ
とが出来るため前記のアンモニア、水、未反応の〇−又
はｐ−ジクロルベンゼン、副生物等の留去に要する時間
を短かくすることが出来る。After the reaction in the flow tube reactor, the reaction product solution containing the target product, etc. is continuously withdrawn to a withdrawal tank, and an amount sufficient to decompose the copper complex ions and ammonium chloride present in the reaction product solution, or the amount thereof The above inorganic bases (for example, aqueous solutions of caustic potash, caustic acid, magnesium hydroxide, etc. are preferable) are continuously added and heated to produce ammonia, water, unreacted 〇- or p-dichlorobenzene, and by-product 〇- or p- Chloraniline, by-product aniline, etc. are distilled out. The pressure in the extraction tank may be atmospheric pressure, but 0.3 to 1+ OMy/cm
It is also possible to pressurize. Pressurizing is disadvantageous for ammonia recovery, but it allows the temperature of the extraction tank to be raised, allowing for the distillation of ammonia, water, unreacted 〇- or p-dichlorobenzene, by-products, etc. The time required can be shortened.
通常は７０〜１０５℃で平均滞留時間がＳＯ〜１００分
になるように圧力、温度を調節するりが好ましい。Usually, it is preferable to adjust the pressure and temperature at 70 to 105° C. so that the average residence time is SO to 100 minutes.
次いで抜出槽より連続的に分離器（槽）に反応液を抜出
しｐ適法、沈降分離法等によって析出した酸化銅、水酸
化銅を除去して〇−又はｐ−フェニレンジアミンを含む
水溶液を得る。（なおここで分離されｆｃ酸化銅、水酸
化銅は次回の触媒調製に再使用される。）なお前記した
反応器から抜出し以降の工程については所望により回分
式に実施することも出来る。Next, the reaction solution is continuously extracted from the extraction tank to a separator (tank), and the precipitated copper oxide and copper hydroxide are removed by p-property method, sedimentation separation method, etc. to obtain an aqueous solution containing 〇- or p-phenylenediamine. . (Note that the fc copper oxide and copper hydroxide separated here are reused for the next catalyst preparation.) Note that the steps after extraction from the reactor can be carried out batchwise if desired.
次に〇−又はｐ−フェニレンジアミンを含む水溶液につ
き向流抽出器を用いて連続的に抽出するか１通常の槽で
回分式又は連続式に抽出を行って。Next, the aqueous solution containing 〇- or p-phenylenediamine is extracted continuously using a countercurrent extractor, or extracted batchwise or continuously in a conventional tank.
水、抽出剤を留去したのち通常の蒸留（減圧蒸留。After water and extractant are distilled off, regular distillation (vacuum distillation) is performed.
真空フレーカ−等を含む）を行って高純度の〇−又はｐ
−フェニレンジアミンをえる。(including vacuum flaker, etc.) to obtain high-purity 〇- or p
- Obtain phenylenediamine.
抽出剤としては０−トルイジン、０−クロルアニリン、
アニリン等のベンゼン系アミンが使用されうるがアニリ
ンの使用が殊によい結果を与える。Extractants include 0-toluidine, 0-chloroaniline,
Benzene-based amines such as aniline can be used, but the use of aniline gives particularly good results.
抽出液の使用量は通常被抽出液に対して１５〜７０％（
重量比）抽出温度は４０〜１００℃より好ましくは６０
〜８０℃である。The amount of extract liquid used is usually 15 to 70% (
Weight ratio) Extraction temperature is 40 to 100°C, preferably 60°C
~80°C.
このようにして９９．９９％の〇−又はｐ−フェニレン
ジアミンを得ることが出来る。なお前記した抽出液の留
去あるいはｐ−７二二レンジアミンの減圧蒸留の際には
硫化ナトリウムの様な還元剤の存在下に行うと目的物の
熱変質を抑えることができるので好都合である。又ｐ−
フ二二レしジアミンを製造した場合には抽出液の釜残（
蒸留残渣）に４，４′−ジアミノジフェニルアミンが含
まれるので必要によりこれを回収することも出来る。In this way, 99.99% of 0- or p-phenylenediamine can be obtained. In addition, when distilling off the above-mentioned extract or distilling p-7 22-diamine under reduced pressure, it is convenient to carry out the distillation in the presence of a reducing agent such as sodium sulfide, since thermal deterioration of the target product can be suppressed. . Also p-
When Fujinireshi diamine is produced, the residue of the extract (
Since 4,4'-diaminodiphenylamine is contained in the distillation residue (distillation residue), it can be recovered if necessary.
次に本発明の方法の実施態様をフロー図によって説明す
る。（第１図を参照）
１は〇−又はｐ−ジクロルベンゼンの貯蔵タンクであり
（これは〇−又はｐ−ジクロルベンゼンの融点以上に加
熱、保温されている）一定の流量で送液ポンプ５によっ
て予熱器６に送り込まれる。Next, embodiments of the method of the present invention will be explained using flow diagrams. (See Figure 1) 1 is a storage tank for 〇- or p-dichlorobenzene (this is heated and kept warm above the melting point of 〇- or p-dichlorobenzene), and the liquid is fed at a constant flow rate. It is sent to a preheater 6 by a pump 5.
融点以上２００℃前後に加熱された〇−又はｐ−ジクロ
ルベンゼンは混合器８を経て流通管型反応器９に供給さ
れる。一方２は触媒のアンモニア水溶液の貯蔵タンクで
あり触媒のアンモニア水溶液は送液ポンプ４によって一
定流量で予熱器７に送りこまれここで約り５０℃〜約２
００’Ｃに加熱されたあと混合器８を経て流通管型反応
器９に供給される。混合器としてはラインミキサー、ス
タティックミキサーあるいはパイプにチタン、ハステロ
イ製の玉や網を挿入したものであってもよく要は融解し
た〇−又はｐ−ジクロルベンゼンと触媒を溶解したアン
モニア水溶液が均一に混合されればよい。そして混合器
で均一に混合された原料等の溶液は１５０〜２０５℃に
保持されて反応器に送り込まれる。（混合器は反応温度
より５〜２０℃低目の温度に保つのが好ましい）
流通管型反応器で所定の平均滞留時間を経過したのち反
応生成物は抜出７Ｆ １ｏを経て抜出槽１１に排出せら
れる。流通管型反応器における平均滞留時間は送液ポン
１３％同４の供給量を調整することにより５０〜１２０
分にコントロールされる。The 〇- or p-dichlorobenzene heated to about 200° C. above its melting point is supplied to a flow tube reactor 9 via a mixer 8 . On the other hand, 2 is a storage tank for an ammonia aqueous solution as a catalyst, and the ammonia aqueous solution as a catalyst is sent at a constant flow rate to a preheater 7 by a liquid feed pump 4, where it is heated to about 50°C to about 2°C.
After being heated to 00'C, it is supplied to a flow tube reactor 9 via a mixer 8. The mixer may be a line mixer, a static mixer, or a pipe with titanium or Hastelloy balls or nets inserted into it.The key is to mix molten 〇- or p-dichlorobenzene and an ammonia aqueous solution in which the catalyst is dissolved uniformly. It should be mixed with The solution of raw materials, etc., uniformly mixed in the mixer is maintained at 150 to 205°C and sent to the reactor. (It is preferable to keep the mixer at a temperature 5 to 20 degrees Celsius lower than the reaction temperature.) After a predetermined average residence time in the flow tube reactor, the reaction product is extracted via extraction tank 11 from 7F to 1o. is discharged. The average residence time in the flow tube reactor can be adjusted from 50 to 120 by adjusting the feed rate of the liquid pump 13%.
controlled in minutes.
反応系に反応すべき原料等の溶液を送りこむと同時に圧
力調整タンク５に窒素ガスを加圧子封入しこの封入窒素
圧によって反応時の圧力が反応器内でのアンモニア水の
自生圧以上（通常１００〜２００Ｋｙ／ｃｍ）に制御さ
れる。又、圧力調整タンク５は急激な圧上昇を防ぐ働き
もする。原料液。At the same time as the solution of the raw materials to be reacted is fed into the reaction system, a pressurizer of nitrogen gas is sealed in the pressure adjustment tank 5, and the pressure during the reaction is raised to the autogenous pressure of ammonia water in the reactor or higher (usually 100 ~200Ky/cm). Moreover, the pressure adjustment tank 5 also functions to prevent sudden pressure rise. Raw material liquid.
反応生成溶液の均一な液流れを保証するには圧力調整タ
ンク５の液面制御により、抜出弁１０を調整するのが好
ましい。In order to ensure a uniform flow of the reaction product solution, it is preferable to adjust the extraction valve 10 by controlling the liquid level in the pressure adjustment tank 5.
抜出槽１１に導かれた反応生成溶液に無機塩基水炉液タ
ンク１２から所定量の無機塩基水汀液が送液ポンプ１３
を介して供給される。抜出槽を加熱してアンモニア、水
、低沸留分を留去する。A predetermined amount of inorganic base water from the inorganic base water reactor liquid tank 12 is added to the reaction product solution led to the extraction tank 11 by the liquid sending pump 13.
Supplied via. The extraction tank is heated to distill off ammonia, water, and low-boiling fractions.
留出分を凝縮器１４を導きアンモニアガス吸収塔１５で
アンモニアを回収する。一方アンモニア。The distillate is led to a condenser 14 and an ammonia gas absorption tower 15 recovers ammonia. On the other hand, ammonia.
水、低沸成分の除去された反応液は不溶物分離器１６に
導かれて沈澱した酸化銅、水酸化銅が回収せられる。不
溶物の除去された反応液は必要に応じジアミン貯蔵タン
ク１７にたくわえられ次いでポンプ１８を介して向流抽
出器１９に送り込まれる。抽出剤タンク２０から送液ポ
ンプ２１を介して所定量のアニリンのようなアミン抽出
剤が向流抽出器に送りこまれる。〇−又はｐ−フェニレ
ンジアミンを含有したアミン抽出液はアニリン分離器２
２に導かれ低沸留分、抽出剤が留去せられ次いで目的化
合物（〇−又はｐ−フェニレンジアミン）が減圧蒸留等
により留出せしめられる。The reaction liquid from which water and low-boiling components have been removed is led to an insoluble matter separator 16, where precipitated copper oxide and copper hydroxide are recovered. The reaction solution from which insoluble matter has been removed is stored in a diamine storage tank 17 as required, and then sent to a countercurrent extractor 19 via a pump 18. A predetermined amount of an amine extractant, such as aniline, is pumped from an extractant tank 20 via a liquid pump 21 into a countercurrent extractor. The amine extract containing 〇- or p-phenylenediamine is sent to aniline separator 2.
2, the low-boiling fraction and the extractant are distilled off, and then the target compound (〇- or p-phenylenediamine) is distilled off by vacuum distillation or the like.
本発明の製造法は反応のコントロールが容易なので目づ
まりあるいは反応の暴走による危険がない、触媒をリサ
イクルして使用するので触媒の使用効率がたかい、えら
れた〇−又はｐ−フェニレンジアミンの純度がたかい、
製品当りの廃液、廃菓物が少ない等の多くの利点があり
従来確立されていなかった〇−又はｐ−ジクロルベンゼ
ンから対応するフェニレンジアミンを効率よく連続製造
する技術を確立したものでその工業的価値は極めて大き
い。In the production method of the present invention, the reaction can be easily controlled, so there is no risk of clogging or runaway reaction.Since the catalyst is recycled, the catalyst usage efficiency is high, and the purity of the obtained 〇- or p-phenylenediamine is high. Bumpy,
The technology has been established to efficiently and continuously produce the corresponding phenylene diamine from 〇- or p-dichlorobenzene, which has many advantages such as fewer waste liquids and waste sweets per product, and has been developed in the industry. The value is extremely large.
実施例
以下実施例によって本発明の方法を更に詳細に説明する
。実施例中チはすべて重量％である。EXAMPLES The method of the present invention will be explained in more detail with the following examples. In the examples, all values are % by weight.
実施例１
本実施例は第１図に示される反応装置を用いて製造した
。Example 1 This example was produced using the reaction apparatus shown in FIG.
スタティックミキサー（第１図の８以下同じ）と内径１
０４や及び２０’″ｌφのコイルからなる直列に接続し
た流通管型反応器９（材質チタン、耐圧２５０ Ｋｐ／
ｃｍ 、内容積３０ｔ）に送液ポンプ３及び４により下
記の均一に溶解されたアンモニア溶液Ａ及び１００℃に
加熱されたｐ−ジクロルベンゼンを下記の仕込量で供給
し、抜出弁１０から反応生成溶液を抜出槽１１に抜へ出
した。反応系の圧力は１５０ＫＰ／需２であった。Static mixer (same as 8 and below in Figure 1) and inner diameter 1
Flow tube type reactor 9 (material: titanium, pressure resistant: 250 Kp/
cm, internal volume: 30 t), the following uniformly dissolved ammonia solution A and p-dichlorobenzene heated to 100°C were supplied in the following amounts using the liquid feed pumps 3 and 4, and The reaction product solution was discharged to a withdrawal tank 11. The pressure of the reaction system was 150 KP/demand 2.
ｐ−ジクロルベンゼン ｓ、１５ Ｋ７＋／ｈ
ｒなおそれぞれの送液ポンプの吐出側の予熱器６，７に
おいて予熱を行い、混合器８で混合した際２００〜２０
５℃になる様にした。又反応器は２２０℃に保った。全
反応液比重は０．７と推定され反応液の反・名器におけ
る平均滞留時間は６０分であった。p-dichlorobenzene s, 15 K7+/h
rNote that when preheating is performed in the preheaters 6 and 7 on the discharge side of each liquid pump, and the mixture is mixed in the mixer 8, the temperature is 200 to 20
The temperature was set to 5°C. The reactor was also maintained at 220°C. The specific gravity of the total reaction liquid was estimated to be 0.7, and the average residence time of the reaction liquid in the reactor was 60 minutes.
反応器出口での反応液中の生成物の組成は以下に示され
る。The composition of the products in the reaction liquid at the reactor outlet is shown below.
ｐ−ジクロルベンゼン ０．０２５ ＩＦ／ｈｒ
ｐ−クロルアニリン ０．１５８ｐ−７二二レ
ンジアミン １．８９５アニリン
ｏ、ｏｓａ４．４′−ジアミノジフェニルアミン
０．１２４ｐ−アミンフェノール他 ０．０６
５反応液を抜出槽１１に抜き出すと同時に２８％ＮａＯ
Ｈ水浴液１０．２５ Ｋ、ｐ ／ ｈｒ を加え１０
０℃に加熱し留出してくるアンモニ水他を除去した。缶
液は２１．７７与／ｈｒ（２，７％アンモニア水１５・
２７ＫＰ／ｈｒを含む）で抜出槽１１での平均滞留時間
約１時間であった。抜出槽に続く濾過器１６で水酸化銅
、酸化鋼を回収した後１反応Ｆ液を保温材の貯蔵タンク
１７に６５℃で１時ストックした。p-dichlorobenzene 0.025 IF/hr
p-Chloraniline 0.158 p-7 22 diamine 1.895 Aniline
o, osa4.4'-diaminodiphenylamine
0.124 p-amine phenol and others 0.06
5. At the same time, the reaction solution is extracted into the extraction tank 11, and 28% NaO
Add H water bath solution 10.25 K, p/hr 10
The ammonia water and other distilled water were removed by heating to 0°C. Bottle liquid was 21.77 times/hr (2.7% ammonia water 15.
(including 27 KP/hr), and the average residence time in the extraction tank 11 was about 1 hour. After recovering copper hydroxide and oxidized steel in a filter 16 following the extraction tank, the first reaction F solution was stocked at 65° C. in a heat insulating storage tank 17 for 1 hour.
全反応Ｆ液中のｐ−フェニレンジアミン濃度は８．９％
であった。次いでこの反応ｐ液を向流抽出器１９に導き
ｐ−フェニレンジアミン含有反応ｐ液とアニリンの比が
２：１になる様に上段から９４′Ｋｆ／ｈｒ の反応
Ｐ液、下段からアニリンを向流接触させた。向流抽出装
置は多孔板塔、塔径１００朋φ塔高５ｍである。抽出は
６０〜６５℃であった。抽出相には１４．４％のｐ−フ
ェニレンジアミン０．１４％のｐ−クロルアニリンが含
まれていた。又ｐ−ジクロルベンゼン及びｐ−アミノフ
ェノールは含まれていなかった。The concentration of p-phenylenediamine in the total reaction solution F was 8.9%.
Met. Next, this reaction P liquid was introduced into the countercurrent extractor 19, and the reaction P liquid was introduced at 94'Kf/hr from the upper stage and aniline from the lower stage so that the ratio of p-phenylenediamine-containing reaction p liquid and aniline was 2:1. I brought it into contact with the flow. The countercurrent extraction device was a perforated plate column with a column diameter of 100 mm and a column height of 5 m. Extraction was at 60-65°C. The extract phase contained 14.4% p-phenylenediamine and 0.14% p-chloroaniline. Furthermore, p-dichlorobenzene and p-aminophenol were not contained.
抽出液は更に公知の蒸留法によね低沸分としてのアニリ
ン、水、ｐ−クロルアニリンを回収除去した後減圧蒸留
して９９．９９％のｐ−フェニレンジアミンを得ること
が出来た。なお蒸留の際に硫化ナトリワムの様な還元剤
を加えると熱変質を抑える上で効果的であった。The extract was further subjected to a known distillation method to recover and remove low-boiling components such as aniline, water, and p-chloroaniline, and then distilled under reduced pressure to obtain 99.99% p-phenylenediamine. Adding a reducing agent such as sodium sulfide during distillation was effective in suppressing thermal deterioration.
なお抜出槽より留出したアンモニア水は６３％濃度であ
り水を追加して吸収し、軽留分を併せて次のｐ−７二二
レンジアミンの反応に使用した。The aqueous ammonia distilled from the extraction tank had a concentration of 63%, and water was added and absorbed, and the light distillate was combined and used in the next reaction of p-7 22-diamine.
又分離した回収鋼も同様に次回に使用した。The separated recovered steel was also used the next time.
実施例２
実施例１と同じ装置において下記の均一に溶解したアン
モニア水溶液Ｂ及びＯ−ジクロルベンゼンを供給し、１
８０ＫＰ／、、２２０℃にて反応させた。Example 2 In the same apparatus as in Example 1, the following uniformly dissolved ammonia aqueous solution B and O-dichlorobenzene were supplied, and 1
The reaction was carried out at 80 KP/, 220°C.
０−ジクロルベンゼン １．８４４ Ｋｐ／ｈｒ
全反応液比重は０．７と推定され平均滞留時間は１００
分であった。0-dichlorobenzene 1.844 Kp/hr
The total reaction liquid specific gravity is estimated to be 0.7, and the average residence time is 100.
It was a minute.
反応管出口での生成物の組成は以下に示される。The composition of the product at the outlet of the reaction tube is shown below.
０−ジクロルベンゼン ０．０４４ Ｋｆ／ｈｒＯ−り
ＤＡ／アニリ７０．２７５＃
０−フェニレンジアミン０．９５３＃
アニリン ０．１５０＃
クロルベンゼン ０．０１０＃
抜出槽に２３％力セイカリ水溶液１１．９５８ＫＰ／ｈ
ｒを加え１０５℃に加熱した。留出したアンモニア水及
び軽留分は併せて１２・１１７馳Δ「 であり３０％ア
ンモニア水とオイルが分離していた。0-dichlorobenzene 0.044 Kf/hr O-ri DA/aniline 70.275# 0-phenylenediamine 0.953# aniline 0.150# chlorobenzene 0.010# Add 23% aqueous potash solution to the extraction tank 11. 958KP/h
r was added and heated to 105°C. The total amount of distilled ammonia water and light distillate was 12.117% Δ', and 30% ammonia water and oil were separated.
オイルは０−１０ルアニリン６１％０−ジクロルベンゼ
ン２４％の組成でＯ，＋ ６６ Ｋ／／ ｈｒ 生成し
た。缶液はＩ Ｌ ４３ Ｋｐ ／ ｈｒ でアンモ
ニア濃度は１％であった。缶液を濾過して０．２５２
Ｋｐ／ｈｒの酸化第一銅を回収した。（涙液は淡黄色）
更にＦ液に１５％硫化ノーダ水溶液を０．１７４ Ｋｐ
／ ｈｒを添加し、残留銅を硫化物として沈澱させた。The oil was produced with a composition of 61% 0-10 aniline and 24% 0-dichlorobenzene at 0, + 66 K//hr. The bottle liquid had an I L 43 Kp/hr and an ammonia concentration of 1%. Filter the can liquid and get 0.252
Kp/hr of cuprous oxide was recovered. (Tear fluid is pale yellow)
Furthermore, 0.174 Kp of 15% sulfurized nodal aqueous solution was added to the F solution.
/hr was added to precipitate the residual copper as sulfide.
Ｆ液はジアミン貯蔵タンク１７に集めて窒素シール下保
温した。全戸液中００−フェニレンジアミンは８％であ
った。実施例１と同様に反応ｐ液１０８ＫＪＩ ／ ｈ
「に対し５５ Ｋｐ／ｈｒでアニｌＪンを供給し６０
℃にて向流抽出を行った。抽出相には１３・５％の０−
フェニレンジアミンが含まれていて、０−クロルアニリ
ンは検出できなかった。The F solution was collected in a diamine storage tank 17 and kept warm under a nitrogen seal. The total amount of 00-phenylenediamine in the liquid was 8%. Reaction p liquid 108KJI/h as in Example 1
``Supplying aniline at a rate of 55 Kp/hr to 60
Countercurrent extraction was performed at °C. The extraction phase contains 13.5% 0-
Contains phenylenediamine, and no 0-chloroaniline was detected.
アニリン抽出液に更に硫化ソーダを加えて公知の方法に
よりアニリンを留去し真空フレーキングすることによっ
て９９．９９％のＱ−フェニレンジアミンを得ることが
できた。By further adding sodium sulfide to the aniline extract and distilling off the aniline by a known method and vacuum flaking, 99.99% Q-phenylenediamine could be obtained.
実施例３
５０ＣＣのオートクレーブ（混合用オートクレーブＳ［
ｒＳ３１６耐圧２００ＫＰ／ｃｒｎ２）の出口から内径
３φの流通管型反応器（Ｓ［ＪＥ１３１６耐圧３００Ｋ
ｐ／１ｙｎ２．内容積２８７ ｍ／ ）につながる反応
器の出口に圧力放出弁を備えた反応装置に １０ ｏ
Ｋｐ／ａｒｔの圧力で定量ポンプを用いて室温で均一に
溶解されアンモニア水溶液Ｃと、１００℃に加熱溶解さ
れたｐ−ジクロルベンゼンを各々下記の仕込量でｐ−ジ
クロルベンゼン １９−１９ ？／ｈｒこの条件下
では１９５〜２００℃で均一になるので混合用オートク
レーブは２０Ｑ〜２０５℃に設定し流通管型反応器は２
２０℃に保った。全反応液の比重は０．７と推定され平
均滞留時間は約１００分であった。反応生成液は以下の
組成であった。Example 3 50CC autoclave (mixing autoclave S [
From the outlet of the rS316 withstand pressure 200KP/crn2) to the flow pipe reactor (S [JE1316 withstand pressure 300K
p/1yn2. 10 o in a reactor equipped with a pressure release valve at the outlet of the reactor leading to an internal volume of 287 m/
Using a metering pump at a pressure of Kp/art, ammonia aqueous solution C uniformly dissolved at room temperature and p-dichlorobenzene heated and dissolved at 100°C were charged in the amounts shown below. /hr Under these conditions, the temperature becomes uniform at 195-200℃, so the mixing autoclave is set at 20Q-205℃, and the flow tube reactor is set at 20Q-205℃.
It was kept at 20°C. The specific gravity of the entire reaction solution was estimated to be 0.7, and the average residence time was about 100 minutes. The reaction product liquid had the following composition.
ｐ−ジクロルベンゼン トレース （％）ｐ−クロルア
ニリン ０．７
ｐ−フェニレンジアミン ８６．１
アニリ７ ２．９
ジアミノジフェニル７ミン５．８
ｐ−アミンフェノール他 ４．５
この反応生成液につき実施例２と同様の処理を施して９
９．９９％のｐ−フェニレンジアミンヲ得た。p-dichlorobenzene trace (%) p-chloroaniline 0.7 p-phenylenediamine 86.1 Anili7 2.9 Diaminodiphenyl 7mine 5.8 p-aminephenol, etc. 4.5 Examples for this reaction product liquid Perform the same processing as in 2 to create 9.
9.99% p-phenylenediamine was obtained.
発明の効果
〇−又はｐ−ジクロルベンゼンから効率よく高純度のＱ
−又はｐ−フェニレンジアミンを連続的に製造すること
が可能になった。Effects of the invention 〇- or p-dichlorobenzene can be efficiently produced with high purity.
- or p-phenylenediamine can now be produced continuously.
第１図は本発明の製法によりて〇−又はｐ−ジクロルベ
ンゼンかうｏ −又はｐ−７二二レンジアミンを連続的
に製造する為の反応装置の一例である。第１図において
＝で示されるライン及び二重のワクで囲まれた部分は高
圧部であることを示す。
第１図において
１ ； ０− 又はｐ−ジクロルベンゼンタンク２；触
媒のアンモニア溶液タンク
Ｓ、４；送液ポンプ
５；圧力調整タンク ６，７；予熱器８；混合器
９；流通管を反応器１０；抜出弁 １
１；抜出槽
１２℃無機塩基水溶液タンク １３；送液ポンプ１４
；凝縮器 １５；アンモニアガス吸収器１６；不
溶物分離器
１７；ジアミン貯蔵夕／り（ストックタンク）１８；送
液ポンプ １９；向流抽出器２０；抽出剤タンク
２１；送液ポンプ２２；抽出剤分離用蒸留器
をそれぞれ示す、。FIG. 1 shows an example of a reaction apparatus for continuously producing o- or p-dichlorobenzene or o- or p-7 22-diamine by the production method of the present invention. In FIG. 1, the line indicated by = and the area surrounded by a double box indicate a high pressure section. In FIG. 1, 1; 0- or p-dichlorobenzene tank 2; catalyst ammonia solution tank S, 4; liquid feed pump 5; pressure adjustment tank 6, 7; preheater 8; mixer
9; Connect the flow pipe to the reactor 10; Extract valve 1
1; Extraction tank 12°C inorganic base aqueous solution tank 13; Liquid feed pump 14
; Condenser 15; Ammonia gas absorber 16; Insoluble matter separator 17; Diamine storage tank (stock tank) 18; Liquid pump 19; Countercurrent extractor 20; Extractant tank 21; Liquid pump 22; Extraction Each shows a distiller for agent separation.
Claims (1)
ェニレンジアミンを製造する方法において （１）流通管型反応器に銅化合物触媒を溶解したアンモ
ニア水溶液及びその融点以上に加熱せられたｏ−又はｐ
−ジクロルベンゼンを供給してそれらのクロル基をアミ
ノ基にかえる工程 （２）流通管型反応器から抜き出されたｏ−又はｐ−フ
ェニレンジアミンを含む反応生成溶液に無機塩基を添加
しアンモニア及び低沸留分を留出せしめたのち残留物か
ら不溶性物質を除去し次いでアミンを用いてｏ−又はｐ
−フェニレンジアミンを抽出する工程 を含むことを特徴とするｏ−又はｐ−フェニレンジアミ
ンの連続製造法[Scope of Claims] 1. A method for producing o- or p-phenylenediamine from o- or p-dichlorobenzene, in which (1) an ammonia aqueous solution in which a copper compound catalyst is dissolved in a flow tube reactor and its melting point or higher; o- or p heated to
- Step of supplying dichlorobenzene and converting their chloro groups into amino groups (2) Adding an inorganic base to the reaction product solution containing o- or p-phenylenediamine extracted from the flow tube reactor and adding ammonia After distilling off the low-boiling fraction and removing insoluble substances from the residue, o- or p-
- A continuous production method for o- or p-phenylenediamine, characterized by including a step of extracting phenylenediamine
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61272828A JPH0825968B2 (en) | 1986-11-18 | 1986-11-18 | Continuous process for producing ortho- or para-phenylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61272828A JPH0825968B2 (en) | 1986-11-18 | 1986-11-18 | Continuous process for producing ortho- or para-phenylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63130567A true JPS63130567A (en) | 1988-06-02 |
| JPH0825968B2 JPH0825968B2 (en) | 1996-03-13 |
Family
ID=17519331
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61272828A Expired - Lifetime JPH0825968B2 (en) | 1986-11-18 | 1986-11-18 | Continuous process for producing ortho- or para-phenylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0825968B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276479A (en) * | 2011-06-28 | 2011-12-14 | 江苏科圣化工机械有限公司 | Method and device for producing p-phenylenediamine by using liquid phase continuous hydrogenation method |
| JP2013515768A (en) * | 2009-12-29 | 2013-05-09 | コーロン インダストリーズ インク | Aromatic diamine and method for producing the same, aramid fiber and method for producing the same |
| CN103145563A (en) * | 2013-03-29 | 2013-06-12 | 中北大学 | Method for co-producing p-phenylenediamine and o-phenylenediamine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50100028A (en) * | 1973-07-31 | 1975-08-08 | ||
| JPS6094946A (en) * | 1983-10-31 | 1985-05-28 | Japan Synthetic Rubber Co Ltd | Production of aromatic amine |
-
1986
- 1986-11-18 JP JP61272828A patent/JPH0825968B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50100028A (en) * | 1973-07-31 | 1975-08-08 | ||
| JPS6094946A (en) * | 1983-10-31 | 1985-05-28 | Japan Synthetic Rubber Co Ltd | Production of aromatic amine |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013515768A (en) * | 2009-12-29 | 2013-05-09 | コーロン インダストリーズ インク | Aromatic diamine and method for producing the same, aramid fiber and method for producing the same |
| CN102276479A (en) * | 2011-06-28 | 2011-12-14 | 江苏科圣化工机械有限公司 | Method and device for producing p-phenylenediamine by using liquid phase continuous hydrogenation method |
| CN103145563A (en) * | 2013-03-29 | 2013-06-12 | 中北大学 | Method for co-producing p-phenylenediamine and o-phenylenediamine |
| CN103145563B (en) * | 2013-03-29 | 2014-06-18 | 中北大学 | Method for co-producing p-phenylenediamine and o-phenylenediamine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0825968B2 (en) | 1996-03-13 |
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