JPH0472817B2 - - Google Patents
Info
- Publication number
- JPH0472817B2 JPH0472817B2 JP59026090A JP2609084A JPH0472817B2 JP H0472817 B2 JPH0472817 B2 JP H0472817B2 JP 59026090 A JP59026090 A JP 59026090A JP 2609084 A JP2609084 A JP 2609084A JP H0472817 B2 JPH0472817 B2 JP H0472817B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- water
- amount
- dinitrotoluene
- tolylene diamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 29
- DYSXLQBUUOPLBB-UHFFFAOYSA-N 2,3-dinitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1[N+]([O-])=O DYSXLQBUUOPLBB-UHFFFAOYSA-N 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000011437 continuous method Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 description 21
- 150000002828 nitro derivatives Chemical class 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 1
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 1
- GAKLFAZBKQGUBO-UHFFFAOYSA-N 2-methyl-3-nitrophenol Chemical class CC1=C(O)C=CC=C1[N+]([O-])=O GAKLFAZBKQGUBO-UHFFFAOYSA-N 0.000 description 1
- INYDMNPNDHRJQJ-UHFFFAOYSA-N 3,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1 INYDMNPNDHRJQJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 150000004982 aromatic amines Chemical class 0.000 description 1
- -1 aromatic nitro compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
Description
【発明の詳細な説明】
本発明はジニトロトルエンの接触的水素添加に
よる未反応ニトロ化合物や不揮発性残渣分をほと
んど含まないトリレンジアミンの工業的に有利な
連続的製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an industrially advantageous continuous process for producing tolylene diamine containing almost no unreacted nitro compounds or non-volatile residues by catalytic hydrogenation of dinitrotoluene.
近年トリレンジアミンは、ポリウレタン樹脂の
原料である対応のトリレンジイソシアナート製造
の中間体として大量に生産されるようになつた。 In recent years, tolylene diamine has come to be produced in large quantities as an intermediate for the production of the corresponding tolylene diisocyanate, which is a raw material for polyurethane resins.
トリレンジイソシアナートの製造は、トルエン
のニトロ化によりジニトロトルエンとし、それを
接触的水素添加によりトリレンジアミンとなし、
さらにホスゲン化によりジイソシアナートとする
のが一般的方法であり、大量生産を行なうには連
続プロセスが適している。したがつてわずかの収
率改善、ユーテイリテイーの改善により、大きな
省資源、省エネルギー効果があらわれる。 Tolylene diisocyanate is produced by nitration of toluene to dinitrotoluene, which is then catalytically hydrogenated to tolylene diamine.
Further, it is a common method to obtain a diisocyanate by phosgenation, and a continuous process is suitable for mass production. Therefore, a slight improvement in yield and utility results in large resource and energy saving effects.
従来より多数、ジニトロトルエンなどの芳香族
ニトロ化合物の接触的水素添加反応により芳香族
アミンを製造するための方法が提供されている。 A number of methods have been provided in the past for producing aromatic amines by catalytic hydrogenation of aromatic nitro compounds such as dinitrotoluene.
これらの方法は一般に溶媒または希釈剤の存在
下にジニトロトルエンを水素添加することを特徴
としていて、この方法は大きな発熱反応の温度制
御のため多量の溶媒を使用し、蒸発潜熱で反応熱
を制御するという利点を有するが、容積効率が低
く、溶媒の回収を伴なうことで大規模、大量生産
には不利な方法である。 These methods are generally characterized by the hydrogenation of dinitrotoluene in the presence of a solvent or diluent; the method uses a large amount of solvent to control the temperature of a highly exothermic reaction, and the latent heat of vaporization controls the heat of reaction. However, this method is disadvantageous for large-scale, mass production because it has low volumetric efficiency and involves recovery of solvent.
これに対して米国特許2292879号明細書にはニ
トロベンゼンなどの芳香族モノニトロ化合物を液
相で水素添加して対応するアニリンなどの芳香族
モノアミンを製造する方法において、反応で生成
する水を連続的に系外に抜き出す条件下で行なう
ことにより触媒の活性が高く保持されること、さ
らに生成するアミンが反応溶媒となり、そのアミ
ン濃度を比較的高くして反応させることにより触
媒の活性度が増大されることが記載されている。 On the other hand, U.S. Patent No. 2,292,879 describes a method for producing an aromatic mononitro compound such as nitrobenzene in a liquid phase to produce a corresponding aromatic monoamine such as aniline, in which the water produced in the reaction is continuously removed. The activity of the catalyst is maintained at a high level by performing the reaction under conditions where it is extracted from the system, and the amine produced becomes a reaction solvent, and the activity of the catalyst is increased by conducting the reaction at a relatively high amine concentration. It is stated that.
このような観点からみればトリレンジアミンの
製造法においても反応液中のアミン濃度はできる
限り100％に近く保ち、生成する水を系外に除去
している方が有利なように思われる。 From this point of view, it seems to be advantageous to maintain the amine concentration in the reaction solution as close to 100% as possible and remove the produced water from the system in the method for producing tolylenediamine.
しかしながら、上記のアニリンなどのモノアミ
ンの製造においては、反応温度が比較的高く、ア
ミンの沸点も低いので反応生成物と一緒に反応生
成水は容易に除去できるがトリレンジアミンの場
合は沸点も高く、また比較的低い温度で実施され
るので生成水の除外は容易ではない。 However, in the production of monoamines such as aniline mentioned above, the reaction temperature is relatively high and the boiling point of the amine is low, so the reaction product water can be easily removed along with the reaction product, but in the case of tolylene diamine, the boiling point is also high. Also, since the process is carried out at a relatively low temperature, it is not easy to exclude the produced water.
また特許公報昭35−5763号明細書には触媒毒と
なるニトロフエノール類やニトロクレゾール類を
制御してジニトロトルエンを溶融状態の無溶媒で
接触的水素添加を行ない、反応により生成する水
を除去しながら反応させる方法が提案されてい
る。 Furthermore, Patent Publication No. 5763/1984 discloses that catalytic hydrogenation of dinitrotoluene is carried out in a molten state without a solvent by controlling nitrophenols and nitrocresols, which act as catalyst poisons, and the water produced by the reaction is removed. A method has been proposed in which the reaction is performed while
しかしながらこの方法では、水素添加反応時間
（滞留時間）が20時間以上と長いこと、したがつ
て単位時間当りの生産量が低いこと、生成する水
を除去するために大過剰の水素ガスを供給する必
要があること、ジニトロトルエンに対する触媒の
使用量が貴金属成分として多いこと、反応時間が
長いにもかかわらず未反応ニトロ化合物の残存量
が100ppm程度もあること、回分操作で行なうた
め、ユーテイリテイー使用の面で大量生産には不
向きであることなどの欠点を有する。 However, with this method, the hydrogenation reaction time (residence time) is long, over 20 hours, and therefore the production amount per unit time is low, and a large excess of hydrogen gas is supplied to remove the produced water. The amount of catalyst used for dinitrotoluene is large as a precious metal component, the amount of unreacted nitro compounds remaining is about 100 ppm despite the long reaction time, and the utility is low because it is a batch operation. In terms of usage, it has drawbacks such as being unsuitable for mass production.
本発明者らは未反応ニトロ化合物をほとんど含
まず、かつタール状の不揮発性残渣分の生成を抑
制し、大量生産に適した経済性のあるトリレンジ
アミンの連続的製造法を鋭意検討した結果本発明
方法を完成させたものである。 The inventors of the present invention have conducted extensive research into a continuous method for producing tolylenediamine that contains almost no unreacted nitro compounds, suppresses the formation of tar-like nonvolatile residues, and is economical and suitable for mass production. This is a completed version of the method of the present invention.
すなわち本発明方法はジニトロトルエンの接触
的水素添加反応によるトリレンジアミンの連続的
製造法において、10Kg／cm2Ｇ以下の加圧下で撹拌
機付槽型反応器を用いて、０〜20重量％の水を含
有するトリレンジアミンを溶媒とし、ジニトロト
ルエン供給量に対する滞留時間を４時間以上とし
て90〜150℃の温度で反応を行ない、その反応生
成物から連続的に反応生成水を蒸気として留去さ
せ、反応液は連続的に過により系外へ抜き出す
ことにより、得られた反応液には未反応ニトロ化
合物および不揮発性残渣分をほとんど含まれな
い、トリレンジアミンの連続的製造方法である。 That is, the method of the present invention is a continuous production method of tolylenediamine by catalytic hydrogenation reaction of dinitrotoluene, using a tank reactor equipped with a stirrer under a pressure of 10 Kg/cm 2 G or less, to produce 0 to 20% by weight. Using tolylene diamine containing water as a solvent, the reaction is carried out at a temperature of 90 to 150°C with a residence time of 4 hours or more for the amount of dinitrotoluene supplied, and the water produced by the reaction is continuously distilled from the reaction product as steam. This is a continuous method for producing tolylene diamine, in which the reaction solution is continuously extracted from the system by filtration, and the resulting reaction solution contains almost no unreacted nitro compounds and nonvolatile residues. .
通常、トリレンジアミン製造において得られた
粗トリレンジアミン反応液は、対応のジイソシア
ネートに転換した場合満足なスペツクの高品質を
得るため、精製工程に付されるが、本発明方法に
おいては反応液中の未反応ニトロ化合物の濃度を
30ppm以下及び、不揮発性残渣含量を極めて微量
に抑制できるので、必ずしも精製の必要はない。 Normally, the crude tolylene diamine reaction solution obtained in the production of tolylene diamine is subjected to a purification step in order to obtain a high quality with satisfactory specs when converted to the corresponding diisocyanate, but in the method of the present invention, the reaction solution is The concentration of unreacted nitro compounds in
Since the content of nonvolatile residues can be kept to an extremely small amount of 30 ppm or less, purification is not necessarily necessary.
反応液中の未反応ニトロ化合物の濃度を30ppm
以下に抑制させる、すなわちジニトロトルエンを
ほとんど完全に水素添加反応させる因子として、
圧力−滞留時間−撹拌実所要動力（撹拌速度）の
三者に相互関係があることがわかり、その関係を
図−１に示した。 Reduce the concentration of unreacted nitro compounds in the reaction solution to 30ppm
As a factor that suppresses the hydrogenation reaction of dinitrotoluene almost completely,
It was found that there is a mutual relationship among the three factors: pressure, residence time, and actual stirring power (stirring speed), and this relationship is shown in Figure 1.
図−１は反応温度110℃で実施した場合の未反
応ニトロ化合物が30ppm以下となる最低のポイン
トを滞留時間−圧力との相互関係でプロツトした
ものであり、パラメータは撹拌実所要動力（撹拌
速度）である。すなわち図中の実線で示した曲線
よりも上側の領域では未反応ニトロ化合物は
30ppm以下に抑制でき、下側の領域では30ppm以
上に上昇することを示している。未反応ニトロ化
合物が増大すればこれは次のホスゲン化により生
成するトリレンジイソシアナート中の不純物とな
るため何らかの精製工程を施さねばならない。 Figure 1 is a plot of the lowest point at which the unreacted nitro compound becomes 30 ppm or less when the reaction is carried out at a temperature of 110°C, as a function of residence time and pressure.The parameters are the actual power required for stirring (stirring speed ). In other words, in the region above the solid line in the figure, unreacted nitro compounds are
It shows that it can be suppressed to 30ppm or less, and increases to 30ppm or more in the lower region. If the unreacted nitro compound increases, it becomes an impurity in the tolylene diisocyanate produced by the subsequent phosgenation, so some purification step must be performed.
上記三者の関係で図中の実線の上側の領域であ
ればどこを選択してもよいのだが、大量生産およ
び経済性の面からみれば滞留時間を10時間以上に
もすればそれだけ大容量の反応器が必要となりそ
の点不利にはなるが、滞留時間を４時間以下とす
ると、圧力を10Kg／cm2Ｇ以上の高圧反応とする
か、撹拌実所要動力がm3当り4.0kw以上にせねば
ならない。そのために装置をより高圧化したり、
また本発明では反応生成水を連続的に蒸気として
除去しながら実施するため、そのための大容量の
ガス循環ブロワーが必要になつたり、また4.0kw
以上の強撹拌の実施においては膨大な電力消費を
伴い工業的に有利な方法とはなりえない。したが
つて本発明方法は、圧力10Kg／cm2Ｇ以下で滞留時
間４時間以上が必要であり、特に大量生産、経済
性の面からみると圧力５〜９Kg／cm2Ｇ、滞留時間
５〜７時間、撹拌実所要動力m3当り3.0〜3.5kwが
もつと望ましい。 In relation to the above three factors, any region above the solid line in the diagram may be selected, but from the standpoint of mass production and economic efficiency, increasing the residence time to 10 hours or more will increase the capacity. However, if the residence time is 4 hours or less, a high-pressure reaction with a pressure of 10 Kg/cm 2 G or more is required, or the actual stirring power required is 4.0 kW per m 3 or more. Must be. For this purpose, we have to increase the pressure of the equipment,
In addition, in the present invention, since the reaction product water is continuously removed as steam, a large-capacity gas circulation blower is required, and a 4.0kw
In carrying out the above-mentioned strong stirring, a huge amount of power is consumed and it cannot be an industrially advantageous method. Therefore, the method of the present invention requires a pressure of 10 Kg/cm 2 G or less and a residence time of 4 hours or more. In particular, from the viewpoint of mass production and economic efficiency, a pressure of 5 to 9 Kg/cm 2 G and a residence time of 5 to 5 hours are required. It is desirable that the actual stirring power required for 7 hours is 3.0 to 3.5 kw per m 3 .
本発明方法において反応中に生成する水の存在
は触媒活性を低下させるとともにタール状の不揮
発性残渣分が増加するのでできるだけ系外に除去
する必要がある。不揮発性残渣分の抑制をするた
めには反応系内の水の量は少くとも20重量％以下
に抑制し、トリレンジアミン濃度を80重量％以上
に上げる必要がある。したがつて本発明方法はワ
ンパスでジニトロトルエンを導入して反応を行な
い、反応器に導入されたジニトロトルエンは瞬時
にトリレンジアミンと水に転化され、水は蒸気と
して系外に除去する。これは90〜150℃の温度範
囲内で水素圧力との関連で適宜反応温度を選択
し、生成する反応熱の一部とともにオフガスを強
制的に循環させることで生成する水を蒸発させる
ことにより必要量の水の除去は容易に可能であ
る。そして蒸気は凝縮して水として系外へ除去
し、過剰の水素ガスはブロワーにより強制循環さ
れ再び反応器へ導入される。 In the method of the present invention, the presence of water produced during the reaction reduces the catalyst activity and increases the amount of tar-like nonvolatile residue, so it is necessary to remove it from the system as much as possible. In order to suppress the nonvolatile residue content, it is necessary to suppress the amount of water in the reaction system to at least 20% by weight or less, and to increase the tolylenediamine concentration to 80% by weight or more. Therefore, in the method of the present invention, dinitrotoluene is introduced in one pass to carry out the reaction, and the dinitrotoluene introduced into the reactor is instantaneously converted into tolylene diamine and water, and the water is removed from the system as steam. This is necessary by selecting an appropriate reaction temperature in relation to the hydrogen pressure within the temperature range of 90 to 150°C, and evaporating the water produced by forcibly circulating the off-gas together with a part of the reaction heat produced. Removal of quantities of water is easily possible. The steam is then condensed and removed from the system as water, and excess hydrogen gas is forcibly circulated by a blower and reintroduced into the reactor.
本発明においては反応温度は90〜150℃の範囲
であり、90℃未満では反応が遅く滞留時間を長く
する必要があり、また生成水を系外へ除去するた
めにはガスブロワーの循環量を非常に大きくする
必要があるために90℃以上の温度が必要である
が、150℃を越えるとタール状の不揮発性残渣分
が増大し、トリレンジアミン収量の低下をもたら
す。従つて反応圧力５〜８Kg／cm2Ｇの場合では
100〜130℃で実施するのが望ましい。 In the present invention, the reaction temperature is in the range of 90 to 150°C; below 90°C, the reaction is slow and it is necessary to increase the residence time, and in order to remove the produced water from the system, the circulation rate of the gas blower must be increased. Since the temperature needs to be very large, a temperature of 90°C or higher is required, but if the temperature exceeds 150°C, the amount of tar-like nonvolatile residue increases, resulting in a decrease in the tolylenediamine yield. Therefore, when the reaction pressure is 5 to 8 Kg/cm 2 G,
It is desirable to carry out at 100-130°C.
本発明方法において使用する触媒は、ニツケ
ル、パラジウム、および白金のような通常の水素
添加触媒の使用が望ましく、上記金属を単独で用
いてもよいし、また活性炭やアルミナに沈着、担
持されたものでもよい。さらに鉄、ニツケルなど
の金属の酸化物あるいは水酸化物を少量混合する
こともできる。反応混合物系中における触媒の濃
度は通常0.2〜２重量％が適当である。 The catalyst used in the method of the present invention is preferably a conventional hydrogenation catalyst such as nickel, palladium, or platinum, and the above metals may be used alone or deposited or supported on activated carbon or alumina. But that's fine. Furthermore, a small amount of oxide or hydroxide of metals such as iron and nickel may be mixed. The appropriate concentration of the catalyst in the reaction mixture system is usually 0.2 to 2% by weight.
以上のように本発明方法を実施することによ
り、未反応ニトロ化合物およびタール状の不揮発
性残渣分をほとんど含まない高純度のトリレンジ
アミンを連続的に得ることができ、大規模大量生
産および経済性の面で極めて効果は大きいといえ
る。 By carrying out the method of the present invention as described above, it is possible to continuously obtain high-purity tolylenediamine containing almost no unreacted nitro compounds and tar-like nonvolatile residues, which makes it possible to achieve large-scale mass production and economical production. It can be said that the effect is extremely large in terms of sex.
次に本発明の実施方法の一例を図−２に示した
反応装置により説明する。 Next, an example of the method of carrying out the present invention will be explained using the reaction apparatus shown in FIG.
図−２において槽型水添反応器１は、撹拌機、
水素分散管、ジニトロトルエン供給管および冷却
するためのジヤケツトを備え付けた鉄製の200
耐圧反応槽である。 In Figure 2, the tank type hydrogenation reactor 1 includes a stirrer,
Steel 200 with hydrogen dispersion tube, dinitrotoluene supply tube and jacket for cooling.
It is a pressure-resistant reaction tank.
ジニトロトルエンはラインＡより連続的に反応
器１へ供給される。反応に使用される水素ガスは
ラインＢを通り圧縮機６により圧縮されたのち反
応器１へ供給される。過剰のオフガスはライン１
１より排出され、冷却器７で生成水蒸気を凝縮
し、凝縮水は貯槽８に分離される。過剰のガスは
ガス循環ブロワー１０により強制的に循環され、
このときオフガス中水素純度を一定に保つために
ライン１２より一部のオフガスが系外へパージさ
れる。さらに循環ガスはフレツシユの水素ガスと
ともに混合され反応器１へ循環される。 Dinitrotoluene is continuously supplied to reactor 1 from line A. Hydrogen gas used in the reaction passes through line B, is compressed by compressor 6, and then supplied to reactor 1. Excess off-gas goes to line 1
1, the generated steam is condensed in a cooler 7, and the condensed water is separated into a storage tank 8. Excess gas is forcibly circulated by a gas circulation blower 10,
At this time, a part of the off-gas is purged out of the system through the line 12 in order to keep the hydrogen purity in the off-gas constant. Further, the circulating gas is mixed with fresh hydrogen gas and circulated to the reactor 1.
所定濃度に調整された触媒−水スラリー液は貯
槽５より連続的に反応器１へ導入され、同時に添
加触媒スラリーと同量の反応液スラリーがライン
１３より連続的に系外へ排出され、系内の触媒濃
度は実質的に一定に保持される。 The catalyst-water slurry liquid adjusted to a predetermined concentration is continuously introduced into the reactor 1 from the storage tank 5, and at the same time, the same amount of reaction liquid slurry as the added catalyst slurry is continuously discharged out of the system from the line 13. The catalyst concentration within is held substantially constant.
反応熱を除熱するために所定温度に調整された
温水がライン１４より反応器１のジヤケツトおよ
び冷却器４へ導入され、反応温度は一定に保持さ
れる。反応液は連続過器３および冷却器４を備
え付けた循環ライン中を循環ポンプ２により循環
され反応器１へもどる。この間反応器１の液面を
一定に保つように連続的にトリレンジアミン水溶
液は貯槽９へ排出して得られる。 Hot water adjusted to a predetermined temperature is introduced from line 14 into the jacket of reactor 1 and cooler 4 to remove reaction heat, and the reaction temperature is maintained constant. The reaction liquid is circulated by a circulation pump 2 through a circulation line equipped with a continuous filter 3 and a cooler 4, and then returned to the reactor 1. During this time, the tolylene diamine aqueous solution is continuously discharged to the storage tank 9 while keeping the liquid level in the reactor 1 constant.
次に実施例によりさらに詳しく本発明を説明す
る。％は他に指示されていない限り重量％であ
る。 Next, the present invention will be explained in more detail with reference to Examples. Percentages are by weight unless otherwise indicated.
実施例 １
水素添加槽型反応器１へトリレンジアミン170
Kg、純水27Kgおよびカーボン粉末にパラジウム
0.8％、白金0.1％および鉄0.8％を沈着させて得ら
れた水素添加触媒３Kgを仕込み、撹拌を開始して
撹拌速度を300ppmとした。さらに循環ポンプ２
を駆動させ毎時2.5m3の速度で循環させた。内温
を90℃に上げ、全圧力を7.0Kg／cm2Ｇに保ちつつ、
約80〜90℃に溶融されたジニトロトルエン（２，
４−ジニトロトルエン78.1％、２，６−ジニトロ
トルエン19.2％、２，３−ジニトロトルエン1.1
％、３，４−ジニトロトルエン1.4％、及び水0.2
％の組成）を毎時30Kg、水素ガスを毎時26Nm3の
速度および1.5％の濃度に調整した前記触媒−水
−スラリーを触媒槽５より毎時0.33Kgの速度で供
給した。そのとき内温を11℃まで上昇させ、過剰
の反応熱は反応器１のジヤケツトおよび冷却器４
へ約80℃の温水を循環させることで除熱し、その
温度に保持した。過剰の水素ガスおよび蒸気をガ
スブロワー１０を駆動させて循環し、途中冷却器
７で蒸気を水に凝縮させ貯槽８へ分離した。分離
水の量は毎時８Kgの速度であつた。ガスブロワー
１０より循環されるオフガスの水素ガス量は毎時
91Nm3であり、そのうち毎時約4Nm3の速度ライ
ン１２よりパージガスとして外系で排出し、循環
ガス中の水素純度は96容量％に保持された。循環
ガスは新たに供給されるフレツシユの水素ガスと
混合され反応器１へ導入された。Example 1 Tolylenediamine 170 to hydrogenation tank reactor 1
Kg, pure water 27Kg and palladium in carbon powder
3 kg of hydrogenation catalyst obtained by depositing 0.8% platinum, 0.1% platinum, and 0.8% iron were charged, and stirring was started at a stirring speed of 300 ppm. Furthermore, circulation pump 2
was driven to circulate at a speed of 2.5 m3 /hour. While raising the internal temperature to 90℃ and keeping the total pressure at 7.0Kg/cm 2 G,
Dinitrotoluene (2,
4-dinitrotoluene 78.1%, 2,6-dinitrotoluene 19.2%, 2,3-dinitrotoluene 1.1
%, 3,4-dinitrotoluene 1.4%, and water 0.2
% composition) at 30 kg per hour, hydrogen gas at a rate of 26 Nm 3 per hour, and the catalyst-water slurry adjusted to a concentration of 1.5% were supplied from the catalyst tank 5 at a rate of 0.33 kg per hour. At that time, the internal temperature was raised to 11℃, and the excess reaction heat was discharged from the jacket of reactor 1 and cooler 4.
Heat was removed by circulating hot water at approximately 80°C, and the temperature was maintained. Excess hydrogen gas and steam were circulated by driving a gas blower 10, and the steam was condensed into water by an intermediate cooler 7 and separated into a storage tank 8. The amount of separated water was at a rate of 8 kg/hour. The amount of off-gas hydrogen gas circulated by the gas blower 10 is per hour.
Of this, about 4 Nm 3 per hour was discharged externally as purge gas from the speed line 12, and the hydrogen purity in the circulating gas was maintained at 96% by volume. The circulating gas was mixed with newly supplied fresh hydrogen gas and introduced into the reactor 1.
この間反応器１の液面を一定に保つように過
器３により毎時23.68Kgの速度でトリレンジアミ
ン水溶液が貯槽９へ連続的に排出された。またラ
イン１３より反応混合物スラリーが毎時0.33Kgの
速度で系外へ排出され反応系内の触媒濃度は1.5
％に保持された。 During this period, the tolylene diamine aqueous solution was continuously discharged to the storage tank 9 at a rate of 23.68 kg/hour so as to keep the liquid level in the reactor 1 constant. In addition, the reaction mixture slurry is discharged from line 13 at a rate of 0.33 kg/hour, and the catalyst concentration in the reaction system is 1.5.
% was retained.
反応器１の撹拌機の撹拌速度は300ppmであり、
定常状態での撹拌実所要動力はm3当たり3.0kwに
相当した。さらに反応液の全ホールドアツプは
200Kgであり、そのうち160Kgが反応器１内にあ
り、40Kgが循環ライン中にあつた。ジニトロトル
エン供給量に対する滞留時間は6.7時間であつた。
このようにして連続的に貯槽９へ排出されたトリ
レンジアミン水溶液の濃度は85％、残り15％が水
であり、未反応ニトロ化合物は20ppmであつた。 The stirring speed of the stirrer in reactor 1 is 300 ppm,
The actual power required for stirring in steady state was equivalent to 3.0kw per m3 . Furthermore, the total hold-up of the reaction solution is
200Kg, of which 160Kg was in reactor 1 and 40Kg was in the circulation line. The residence time for the amount of dinitrotoluene fed was 6.7 hours.
The concentration of the tolylene diamine aqueous solution continuously discharged into the storage tank 9 in this manner was 85%, the remaining 15% was water, and the unreacted nitro compound was 20 ppm.
これを所定の方法で蒸留すると得られたトリレ
ンジアミンは理論量の99.1％であり、残り0.9％
がタール状の不揮発性残渣であつた。 When this is distilled using a prescribed method, the tolylenediamine obtained is 99.1% of the theoretical amount, with the remaining 0.9%.
was a tar-like nonvolatile residue.
実施例 ２
圧力5.0Kg／cm2Ｇ、撹拌速度350rpm（撹拌実所
要動力m3当たり3.5kwに相当）、温度130℃、ガス
ブロワーよりのオフガス循環量毎時88Nm3、パー
ジ水素ガス量毎時3Nm3（オフガス中の水素純度
94容量％）、1.5触媒−水スラリー添加量毎時0.67
Kgとした以外は実施例１と同様な方法で実施し
た。滞留時間は実施例１と同様6.7時間であつた。
貯槽８に分離される水は毎時10.8Kg、貯槽９へ排
出されるトリレンジアミン水溶液は毎時21.19Kg
の速度であり、トリレンジアミン濃度は95％、未
反応ニトロ化合物25ppmであつた。蒸留により得
られたトリレンジアミンは理論量の98.9％であ
り、残り1.1％がタール状不揮発性残渣であつた。Example 2 Pressure: 5.0 Kg/cm 2 G, stirring speed: 350 rpm (equivalent to 3.5 kw per stirring actual power required for m 3 ), temperature: 130°C, off-gas circulation amount from the gas blower: 88 Nm 3 /hour, purge hydrogen gas amount: 3 Nm 3 /hour (Hydrogen purity in off-gas
94% by volume), 1.5 catalyst-water slurry addition rate 0.67 per hour
It was carried out in the same manner as in Example 1 except that the weight was set to Kg. The residence time was 6.7 hours as in Example 1.
The amount of water separated into storage tank 8 is 10.8 kg per hour, and the amount of tolylene diamine aqueous solution discharged into storage tank 9 is 21.19 kg per hour.
The tolylene diamine concentration was 95% and the unreacted nitro compound was 25 ppm. The tolylene diamine obtained by distillation was 98.9% of the theoretical amount, and the remaining 1.1% was a tar-like nonvolatile residue.
実施例 ３
圧力4.0Kg／cm2Ｇ、ジニトロトルエン供給量毎
時２Kg、水素供給量毎時17Nm3、オフガス循環量
毎時32Nm3、パージ水素量毎時3Nm3（オフガス
中の水素純度96容量％）とした以外は実施例１と
同様な方法で実施した。ジニトロトルエン供給量
に対する滞留時間は10時間であつた。Example 3 The pressure was 4.0 Kg/cm 2 G, the amount of dinitrotoluene supplied was 2 Kg/hour, the amount of hydrogen supplied was 17 Nm 3 per hour, the amount of off gas circulation was 32 Nm 3 per hour, and the amount of purge hydrogen was 3 Nm 3 per hour (hydrogen purity in off gas was 96% by volume). The procedure was the same as in Example 1 except for this. The residence time for the amount of dinitrotoluene fed was 10 hours.
貯槽８に分離される水は毎時5.5Kg、貯槽９に
排出されるトリレンジアミン水溶液は毎時15.7Kg
であり、トリレンジアミンの濃度は85％、未反応
ニトロ化合物は20ppmであつた。さらに蒸留によ
り得られたトリレンジアミンは理論量の98.8％で
あり、残り1.2％がタール状の不揮発性残渣であ
つた。 The amount of water separated into storage tank 8 is 5.5 kg per hour, and the amount of tolylene diamine aqueous solution discharged into storage tank 9 is 15.7 kg per hour.
The concentration of tolylene diamine was 85%, and the unreacted nitro compound was 20 ppm. Further, the tolylene diamine obtained by distillation was 98.8% of the theoretical amount, and the remaining 1.2% was a tar-like nonvolatile residue.
実施例 ４
圧力2.0Kg／cm2Ｇ、ジニトロトルエン供給量毎
時10Kg、1.5％触媒−水スラリー供給量毎時0.27
Kg、水素供給量毎時8.5Nm3、オフガス循環量毎
時11Nm3、パージ水素量毎時1Nm3（オフガス中
の水素純度95容量％）とした以外は実施例１と同
様な方法で実施した。ジニトロトルエン供給量に
対する滞留時間は20時間であつた。Example 4 Pressure 2.0 Kg/cm 2 G, dinitrotoluene feed rate 10 Kg/hour, 1.5% catalyst-water slurry feed rate 0.27/hour
The same method as in Example 1 was carried out except that the hydrogen supply amount was 8.5 Nm 3 per hour, the off gas circulation amount was 11 Nm 3 per hour, and the purge hydrogen amount was 1 Nm 3 per hour (hydrogen purity in off gas was 95% by volume). The residence time for the amount of dinitrotoluene fed was 20 hours.
貯槽８に分離される水は毎時3.2Kg、貯槽９に
排出されるトリレンジアミン水溶液は毎時7.46Kg
であり、トリレンジアミンの濃度は90％、未反応
ニトロ化合物は18ppmであつた。さらに蒸留によ
り得られたトリレンジアミンは理論量の98.3％で
あり、残り1.7％がタール状の不揮発性残渣であ
つた。 The amount of water separated into storage tank 8 is 3.2Kg per hour, and the amount of tolylene diamine aqueous solution discharged into storage tank 9 is 7.46Kg per hour.
The concentration of tolylene diamine was 90% and the unreacted nitro compound was 18 ppm. Furthermore, the tolylene diamine obtained by distillation was 98.3% of the theoretical amount, and the remaining 1.7% was a tar-like nonvolatile residue.
実施例 ５
圧力9.0Kg／cm2Ｇ、温度440℃、撹拌速度
400rpm（撹拌実所要動力m3当たり4.0kwに相当す
る）、ジニトロトルエン供給量毎時40Kg、1.5触媒
−水スラリー供給量毎時0.44Kg、水素供給量毎時
33.5Nm3、オフガス循環量毎時100Nm3、パージ
水素ガス量毎時4Nm3（オフガス中水素純度94容
量％）とした以外は実施例１と同様な方法で実施
した。ジニトロトルエン供給量に対する滞留時間
は５時間であつた。Example 5 Pressure 9.0Kg/cm 2 G, temperature 440℃, stirring speed
400 rpm (equivalent to 4.0 kw per m3 of stirring actual power required), dinitrotoluene supply rate 40 kg/hour, 1.5 catalyst-water slurry supply rate 0.44 kg/hour, hydrogen supply rate/hour
The experiment was carried out in the same manner as in Example 1 except that the off-gas circulation amount was 100 Nm 3 per hour, and the purge hydrogen gas amount was 4 Nm 3 per hour (hydrogen purity in off-gas 94% by volume). The residence time for the amount of dinitrotoluene fed was 5 hours.
貯槽８に分離される水は毎時11Kg、貯槽９に排
出されるトリレンジアミン水溶液は毎時31.58Kg
であり、トリレンジアミンの濃度は85％、未反応
ニトロ化合物は27ppmであつた。さらに蒸留によ
り得られたトリレンジアミンは理論量の99％であ
り、残り１％がタール状の不揮発性残渣であつ
た。 The amount of water separated into storage tank 8 is 11 kg per hour, and the amount of tolylene diamine aqueous solution discharged into storage tank 9 is 31.58 kg per hour.
The concentration of tolylene diamine was 85% and the unreacted nitro compound was 27 ppm. Further, the tolylene diamine obtained by distillation was 99% of the theoretical amount, and the remaining 1% was a tar-like nonvolatile residue.
比較例 １
圧力を2.0Kg／cm2Ｇとした以外は実施例１と同
様な方法で実施した。ジニトロトルエン供給開始
後約１時間で貯槽９に排出されたトリレンジアミ
ン水溶液は黒色不透明液となり、未反応ニトロ化
合物は300ppmに上昇した。Comparative Example 1 The same method as in Example 1 was carried out except that the pressure was 2.0 Kg/cm 2 G. Approximately 1 hour after the start of dinitrotoluene supply, the tolylene diamine aqueous solution discharged into the storage tank 9 became a black opaque liquid, and the amount of unreacted nitro compounds increased to 300 ppm.
また蒸留により得られたトリレンジアミンは理
論量の97％であり、残り３％がタール状の不揮発
性残渣であつた。 Further, the tolylene diamine obtained by distillation was 97% of the theoretical amount, and the remaining 3% was a tar-like nonvolatile residue.
比較例 ２
圧力3.0Kg／cm2Ｇとした以外は実施例５と同様
なの件で実施した。ジニトロトルエンの供給開始
後約0.5時間で貯槽９に排出されたトリレンジア
ミン水溶液は黒色不透明液となり、未反応ニトロ
化合物は500ppmに上昇した。Comparative Example 2 The same procedure as in Example 5 was carried out except that the pressure was 3.0 Kg/cm 2 G. About 0.5 hours after the start of supply of dinitrotoluene, the aqueous tolylene diamine solution discharged into the storage tank 9 became a black opaque liquid, and the amount of unreacted nitro compounds increased to 500 ppm.
また蒸留により得られたトリレンジアミンは理
論量の95％であり、残り５％がタール状の不揮発
性残渣であつた。 Further, the tolylene diamine obtained by distillation was 95% of the theoretical amount, and the remaining 5% was a tar-like nonvolatile residue.
比較例 ３
ガスブロワーより循環されるオフガス循環量を
毎時10Nm3とした以外は実施例１と同様の条件で
実施した。Comparative Example 3 A test was carried out under the same conditions as in Example 1 except that the amount of off gas circulated from the gas blower was 10 Nm 3 per hour.
貯槽８に回収される水は毎時１Kg、貯槽９に排
出されるトリレンジアミン水溶液は毎時30.9Kgで
あり、トリレンジアミンの濃度は65％、未反応ニ
トロ化合物は28ppmであつた。 The amount of water collected into storage tank 8 was 1 kg per hour, and the amount of tolylene diamine aqueous solution discharged into storage tank 9 was 30.9 kg per hour, and the concentration of tolylene diamine was 65% and the unreacted nitro compound was 28 ppm.
さらに蒸留により得られたトリレンジアミンは
理論量の98％であり、残り２％がタール状の不揮
発性残渣であつた。 Further, the tolylene diamine obtained by distillation was 98% of the theoretical amount, and the remaining 2% was a tar-like nonvolatile residue.
図−１は、110℃における反応液中の未反応ニ
トロ化合物が30ppm以下となる最低のポイント
を、滞留時間−圧力との相関関係で示したもので
あり、パラメータの曲線は夫々のm3当たりの撹拌
実所要動力である。図−２は、本発明方法を実施
する場合の好ましい１例のフローシートであり、
１……撹拌機付槽型反応器、２……反応液循環
ポンプ、３……過器、４……冷却器、５……触
媒貯槽、６……水素ガス圧縮機、７……冷却器、
８……分離水貯槽、９……反応液貯槽、１０……
ガス循環ブロワー、Ａ……ジニトロトルエン供給
ライン、Ｂ……水素供給ラインである。
Figure 1 shows the lowest point at which the unreacted nitro compound in the reaction solution becomes 30 ppm or less at 110°C, as a correlation between residence time and pressure. This is the actual power required for stirring. FIG. 2 is a flow sheet of a preferred example of carrying out the method of the present invention, and includes the following: 1...tank reactor with stirrer, 2... reaction liquid circulation pump, 3... filter, 4... Cooler, 5...Catalyst storage tank, 6...Hydrogen gas compressor, 7...Cooler,
8...Separated water storage tank, 9...Reaction liquid storage tank, 10...
Gas circulation blower, A... dinitrotoluene supply line, B... hydrogen supply line.
Claims (1)
るトリレンジアミンの連続的製造法において、10
Kg／cm2Ｇ以下の加圧下、撹拌機付槽型反応器を用
いて、０〜20重量％の水を含有するトリレンジア
ミンを溶媒とし、供給されるジニトロトルエンの
滞留時間を４時間以上として、反応生成物から連
続的に反応生成水を蒸気として留去させながら90
〜150℃の温度で撹拌、反応を行ない、得られた
反応後は連続的に過して系外へ抜き出すことを
特徴とするトリレンジアミンの連続的製造方法。 ２ 圧力、５〜９Kg／cm2Ｇで反応させる特許請求
の範囲第１項記載の方法。 ３ 滞留時間、５〜７時間で反応させる特許請求
の範囲第１項記載の方法。 ４ 反応温度が、100〜130℃である特許請求の範
囲第１項記載の方法。 ５ 槽型反応器内の撹拌に要する撹拌実所要動力
が、m3当り3.0〜3.5kwである特許請求の範囲第１
項記載の方法。 ６ 接触的水素添加反応をニツケル、パラジウム
または白金触媒と接触させながら反応させる特許
請求の範囲第１項記載の方法。 ７ 過剰の水素ガス、および反応で生成する水を
蒸気として、オフガスラインに装備されたガスブ
ロワーにより強制循環させ、ライン中より蒸気を
水として分離し、過剰の水素ガスは反応機へ循環
回収させる特許請求の範囲第１項記載の方法。[Claims] 1. A continuous method for producing tolylene diamine by catalytic hydrogenation reaction of dinitrotoluene,
Using a tank reactor equipped with a stirrer under a pressure of Kg/cm 2 G or less, using tolylene diamine containing 0 to 20% by weight of water as a solvent, the residence time of dinitrotoluene to be supplied is 4 hours or more. 90% while continuously distilling off the reaction product water as steam from the reaction product.
A continuous method for producing tolylene diamine, which is characterized in that stirring and reaction are carried out at a temperature of ~150°C, and the resulting reaction is continuously filtered and extracted from the system. 2. The method according to claim 1, wherein the reaction is carried out at a pressure of 5 to 9 Kg/cm 2 G. 3. The method according to claim 1, wherein the reaction is carried out for a residence time of 5 to 7 hours. 4. The method according to claim 1, wherein the reaction temperature is 100 to 130°C. 5. Claim 1, in which the actual stirring power required for stirring in the tank reactor is 3.0 to 3.5 kw per m 3
The method described in section. 6. The method according to claim 1, wherein the catalytic hydrogenation reaction is carried out in contact with a nickel, palladium or platinum catalyst. 7 Excess hydrogen gas and water produced by the reaction are forced to circulate as steam using a gas blower installed in the off-gas line, the steam is separated from the line as water, and the excess hydrogen gas is circulated and recovered to the reactor. A method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59026090A JPS60172947A (en) | 1984-02-16 | 1984-02-16 | Continuous preparation of tolylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59026090A JPS60172947A (en) | 1984-02-16 | 1984-02-16 | Continuous preparation of tolylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60172947A JPS60172947A (en) | 1985-09-06 |
| JPH0472817B2 true JPH0472817B2 (en) | 1992-11-19 |
Family
ID=12183903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59026090A Granted JPS60172947A (en) | 1984-02-16 | 1984-02-16 | Continuous preparation of tolylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60172947A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH062718B2 (en) * | 1985-08-20 | 1994-01-12 | 三井東圧化学株式会社 | Continuous production of tolylenediamine |
| IT1318602B1 (en) * | 2000-06-29 | 2003-08-27 | Enichem Spa | PROCEDURE FOR THE PRODUCTION OF AROMATIC AMINES. |
| BR112012027954A2 (en) * | 2010-05-17 | 2017-07-25 | Basf Se | process for the continuous preparation of toluenediamine. |
| CN102151525B (en) * | 2011-01-27 | 2013-07-31 | 甘肃银光聚银化工有限公司 | Hydrogenation reaction device |
-
1984
- 1984-02-16 JP JP59026090A patent/JPS60172947A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60172947A (en) | 1985-09-06 |
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| Date | Code | Title | Description |
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| EXPY | Cancellation because of completion of term |