JPS62901B2 - - Google Patents
Info
- Publication number
- JPS62901B2 JPS62901B2 JP53081201A JP8120178A JPS62901B2 JP S62901 B2 JPS62901 B2 JP S62901B2 JP 53081201 A JP53081201 A JP 53081201A JP 8120178 A JP8120178 A JP 8120178A JP S62901 B2 JPS62901 B2 JP S62901B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hydrogen
- amine
- ammonia
- nitrile
- 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
Links
- 238000006243 chemical reaction Methods 0.000 claims description 58
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- -1 aliphatic nitrile Chemical class 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 description 18
- 150000003512 tertiary amines Chemical class 0.000 description 12
- 150000003141 primary amines Chemical class 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 150000002825 nitriles Chemical class 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 239000003760 tallow Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- UIAMCVSNZQYIQS-KTKRTIGZSA-N oleonitrile Chemical compound CCCCCCCC\C=C/CCCCCCCC#N UIAMCVSNZQYIQS-KTKRTIGZSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- RHSBIGNQEIPSCT-UHFFFAOYSA-N stearonitrile Chemical compound CCCCCCCCCCCCCCCCCC#N RHSBIGNQEIPSCT-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction 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)
Description
【発明の詳細な説明】
本発明は長鎖脂肪族ニトリルを低圧で水素還元
して、対応する第２級長鎖脂肪族アミンを製造す
る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for reducing long-chain aliphatic nitriles with hydrogen at low pressure to produce corresponding secondary long-chain aliphatic amines.
従来、長鎖アルキル基を有するアミン類は、天
然油脂類から誘導された脂肪族ニトリルを水素還
元して製造されている。この長鎖アミン類におい
て、第３級アミンは実用性に乏しく、第１級及び
第２級アミンが汎用されている。長鎖脂肪族ニト
リルを水素還元する場合、第１級〜第２級アミン
の混合物が得られるが、これらの中、第２級アミ
ンは最も製造困難で、利用価値も高いことから、
このものを選択性よく製造することが望まれてい
る。このような第２級アミンを選択的に製造する
ために、特殊な触媒を選択する、反応を湿気の不
存在下で行なう、反応を２段階で行なうなどの工
夫が提案されているが、これらはいずれも、高い
水素圧の使用を不可欠にしたり、複雑な操作を必
要とするなどの難点を包含した。また、第１級ア
ミンの生成を抑制するためには、反応平衡上、生
成アンモニアの反応系からの除去が有効である
が、この場合には、第２級アミンとともに、第３
級アミンの収量をも必然的に増大する結果とな
り、第３級アミンの生成をいかにして抑制するか
に大きな問題がある。 Conventionally, amines having long-chain alkyl groups have been produced by hydrogen reduction of aliphatic nitriles derived from natural oils and fats. Among these long-chain amines, tertiary amines are of poor practical use, and primary and secondary amines are widely used. When a long-chain aliphatic nitrile is reduced with hydrogen, a mixture of primary to secondary amines is obtained, but among these, secondary amines are the most difficult to produce and have high utility value, so
It is desired to produce this product with good selectivity. In order to selectively produce such secondary amines, methods have been proposed such as selecting special catalysts, conducting the reaction in the absence of moisture, and conducting the reaction in two steps. All of these methods included drawbacks such as requiring the use of high hydrogen pressure and complicated operations. In addition, in order to suppress the production of primary amines, it is effective to remove the produced ammonia from the reaction system from the reaction equilibrium; however, in this case, along with secondary amines, tertiary amines
This inevitably results in an increase in the yield of tertiary amines, and there is a major problem in how to suppress the production of tertiary amines.
本発明者らは、反応操作を容易にするために高
水素圧の使用や２段階反応の使用を必要とせず、
しかも第１級及び第３級アミンの生成を抑制し
て、第２級アミンを選択性よくかつ高収率で得る
ことのできる長鎖脂肪族ニトリルの水素還元法を
開発すべく鋭意研究を重ねた結果、触媒としてニ
ツケル系水素化触媒を用いるとともに、反応温度
を特定範囲に保持し、さらに反応系におけるアン
モニア理論生成量の特定割合を特定時間内で系外
へ放出するようにして、脂肪族ニトリルの水素還
元反応を行なうことにより、その目的を達成し得
ることを見出し、本発明を完成するに到つた。 The inventors do not require the use of high hydrogen pressure or the use of a two-step reaction to facilitate reaction operation;
In addition, we have conducted extensive research to develop a hydrogen reduction method for long-chain aliphatic nitriles that can suppress the production of primary and tertiary amines and obtain secondary amines with good selectivity and high yields. As a result, a nickel-based hydrogenation catalyst was used as a catalyst, the reaction temperature was maintained within a specific range, and a specific proportion of the theoretical amount of ammonia produced in the reaction system was released outside the system within a specific time. The inventors have discovered that the objective can be achieved by carrying out a hydrogen reduction reaction of nitrile, and have completed the present invention.
すなわち、本発明は、ニツケル系水素化触媒の
存在下、200℃以上で230℃を越えない反応温度を
保持し、水素を流通させかつ生成アンモニアを系
外へ除去しながら、炭素数８〜22の脂肪族ニトリ
ルを、反応時間２時間以内に、アンモニア理論生
成量の85％以上を系外へ除去するようにして、水
素還元反応させることを特徴とする第２級長鎖脂
肪族アミンの製造方法を要旨とするものである。 That is, in the present invention, in the presence of a nickel-based hydrogenation catalyst, the reaction temperature is maintained at 200°C or higher and does not exceed 230°C, hydrogen is circulated, and produced ammonia is removed from the system, while hydrogenation with a carbon number of 8 to 22 A method for producing a secondary long-chain aliphatic amine, which comprises subjecting an aliphatic nitrile to a hydrogen reduction reaction in such a way that 85% or more of the theoretical amount of ammonia produced is removed from the system within a reaction time of 2 hours. The main points are as follows.
本発明において原料として使用する長鎖脂肪族
ニトリルは、炭素数８〜22の飽和脂肪族ニトリル
又は不飽和ニトリルあるいは両者の混合物が任意
に適用される。また、この長鎖脂肪族ニトリルに
は、不純物として炭素数８〜22の脂肪族第１級ア
ミンが含まれていてもよい。このニトリルの具体
例として、たとえば、オレオニトリル、ステアロ
ニトリル、ラウロニトリル、牛脂脂肪酸ニトリ
ル、ヤシ脂肪酸ニトリルなどが挙げられる。 The long-chain aliphatic nitrile used as a raw material in the present invention may be a saturated aliphatic nitrile having 8 to 22 carbon atoms, an unsaturated nitrile, or a mixture of the two. Further, this long-chain aliphatic nitrile may contain an aliphatic primary amine having 8 to 22 carbon atoms as an impurity. Specific examples of the nitrile include oleonitrile, stearonitrile, lauronitrile, tallow fatty acid nitrile, coconut fatty acid nitrile, and the like.
本発明において、第２級アミンを高収率かつ高
選択率で得るためには、後記する反応条件の特定
化と関連し、触媒として、高活性のニツケル系水
素化触媒、殊に、担体に担持されたニツケル系水
素化触媒、たとえば、ケイ藻士や、アルミナ、シ
リカアルミナ、その他の不活性担体に担持された
ニツケル触媒の使用を必要とする。触媒使用量
は、原料ニトリル100重量部に対し、0.1〜0.5重
量部が適当である。 In the present invention, in order to obtain a secondary amine in high yield and high selectivity, it is necessary to specify the reaction conditions described later, and a highly active nickel-based hydrogenation catalyst, especially a carrier, is used as the catalyst. It requires the use of supported nickel-based hydrogenation catalysts, such as nickel catalysts supported on diatoms, alumina, silica-alumina, or other inert supports. The appropriate amount of catalyst to be used is 0.1 to 0.5 parts by weight based on 100 parts by weight of the raw material nitrile.
本発明の方法は、反応容器に前記した原料ニト
リル及び触媒を装入し、内容物をかきまぜなが
ら、水素を反応容器内に流通させることによつて
実施される。この場合、水素圧はゲージ圧で０〜
10、殊に、０〜６Kg／cm2Gに選定する。 The method of the present invention is carried out by charging the above-mentioned raw material nitrile and catalyst into a reaction vessel, and flowing hydrogen into the reaction vessel while stirring the contents. In this case, the hydrogen pressure is 0 to 0 in gauge pressure.
10, in particular 0 to 6 kg/cm 2 G.
本発明においては、一段反応により、ニトリル
反応率100％で目的の第２級アミンを高選択率で
得るには、反応強度を200〜230℃という限定され
た範囲に選定し、かつ反応時間２時間以内に、ア
ンモニア理論生成量の85％以上を系外へ放出除去
するように反応を行なうことが必要である。本発
明の反応条件下で、反応温度230℃以下では第３
級アミンの生成割合は小さいが、反応温度が230
℃を越えるようになると第３級アミンの生成量が
急激に増大するようになるので好ましくない。ニ
トリルの水素還元反応は発熱反応であることか
ら、反応温度は230℃を越えるようになるが、こ
のような場合には外部冷却を行なつて、反応温度
を前記範囲に保持することが必要である。また、
本発明においては、その実質的反応が200℃以上
で行なわれるように留意する。反応温度がこれよ
り低いと、反応速度が遅く、長い反応時間を必要
とし、その結果、第３級アミンの生成を増加させ
る。しかしながら、本発明においては、内容物を
加熱し、所定反応温度に上昇させる場合、触媒の
活性化と急激な還元反応を避けるために、200℃
以下の温度、たとえば、150℃程度の温度からの
水素の流通反応を除外するものではない。本発明
においては、その実質的還元反応が230℃を越え
ないように、かつ200℃以上の温度で実施されれ
ばよい。 In the present invention, in order to obtain the desired secondary amine with a nitrile conversion rate of 100% and high selectivity through a one-step reaction, the reaction intensity is selected within a limited range of 200 to 230°C, and the reaction time is 2. It is necessary to carry out the reaction so that 85% or more of the theoretical amount of ammonia produced is removed from the system within a certain amount of time. Under the reaction conditions of the present invention, if the reaction temperature is 230°C or lower, the tertiary
The production rate of grade amines is small, but the reaction temperature is 230℃.
If the temperature exceeds .degree. C., the amount of tertiary amine produced will rapidly increase, which is not preferable. Since the hydrogen reduction reaction of nitrile is an exothermic reaction, the reaction temperature will exceed 230°C, but in such cases it is necessary to perform external cooling to maintain the reaction temperature within the above range. be. Also,
In the present invention, care is taken to ensure that the substantial reaction is carried out at 200°C or higher. If the reaction temperature is lower than this, the reaction rate is slow and requires a long reaction time, resulting in increased formation of tertiary amines. However, in the present invention, when heating the contents to raise the predetermined reaction temperature, in order to avoid activation of the catalyst and rapid reduction reaction,
This does not exclude hydrogen flow reactions at temperatures below, for example, temperatures of about 150°C. In the present invention, the substantial reduction reaction may be carried out at a temperature not exceeding 230°C and at a temperature of 200°C or higher.
本発明において、第２級アミンを選択性よく得
る上で殊に重要な要件は、反応時間以内に、反応
系におけるアンモニア理論生成量の85％以上を系
外に除去するように反応を行なうことである。こ
の場合、アンモニア理論生成量は、原料ニトリル
が全て第２級アミンに転換した場合に生成される
アンモニア生成量と定義され、また、反応時間
は、内容物の温度が200℃に達した時点を反応開
始時点とする。すなわち、本発明では、初期反応
をできる限り高反応速度でかつ生成アンモニアを
迅速に系外に除去するようにして反応を行なう。
このような目的を達成するには、前記したような
高活性の触媒及び限定された反応温度の条件の採
用が必須であり、また、流通させる水素ガスの流
速及び水素圧を適当に選定することが必要であ
る。反応時間が２時間を越えても、アンモニア理
論生成量が85％に達しないような低い反応速度や
低いアンモニア除去率では、目的の第２級アミン
の収率が著しく損なわれ、所期の目的を達成する
ことができない。 In the present invention, a particularly important requirement for obtaining secondary amines with good selectivity is to conduct the reaction so that 85% or more of the theoretical amount of ammonia produced in the reaction system is removed from the reaction system within the reaction time. It is. In this case, the theoretical amount of ammonia produced is defined as the amount of ammonia produced when all of the raw material nitrile is converted to secondary amine, and the reaction time is defined as the amount of ammonia produced when the temperature of the contents reaches 200°C. This is the start point of the reaction. That is, in the present invention, the initial reaction is carried out at the highest possible reaction rate and the ammonia produced is quickly removed from the system.
To achieve this purpose, it is essential to use a highly active catalyst and limited reaction temperature conditions as described above, and to appropriately select the flow rate and hydrogen pressure of the hydrogen gas to be circulated. is necessary. Even if the reaction time exceeds 2 hours, if the reaction rate is so low that the theoretical amount of ammonia produced does not reach 85% or the ammonia removal rate is low, the yield of the desired secondary amine will be significantly impaired, and the desired goal will not be achieved. cannot be achieved.
本発明においては、前記したような特定の反応
条件を採用したことにより、反応は、通常３〜６
時間という短時間で完結し、その第２級アミン収
率は90％以上という高い値を示す。また、本発明
では反応水素圧は低く、しかも一段の反応である
ので、その反応の実施には格別の困難はなく、そ
の産業的意義は大きい。 In the present invention, by employing the specific reaction conditions as described above, the reaction is usually carried out for 3 to 6 hours.
The process is completed in a short period of time, and the secondary amine yield is as high as 90% or more. Furthermore, in the present invention, the reaction hydrogen pressure is low and the reaction is a one-stage reaction, so there is no particular difficulty in carrying out the reaction, and its industrial significance is great.
次に本発明を実施例によりさらに詳細に説明す
る。 Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
0.5の誘導回転式オートクレーブに牛脂脂肪
酸ニトリル250ｇおよびニツケル―ケイソウ士触
媒0.5ｇを充填し、水素圧を５Kg／cm2（ゲージ
圧）に維持しながら水素を流通させ、撹拌下加熱
し、温度が200℃に達した時点を反応開始時点と
し、この時点から３時間、温度を220℃、水素圧
を５Kg／cm2（ゲージ圧）に維持して、水素を流通
させながら撹拌を続けた。反応の進行にともな
い、アンモニアが生成し、流通する水素といつし
よにガス状でオートクレーブ外に排出されるが、
このアンモニアガスを50％硫酸に吸収させ、その
量を測定したところ、反応開始時点から２時間の
あいだに、アンモニア理論生成量（ニトリルがす
べて第２級アミンに転換した場合のアンモニア生
成量をいう。以下の実施例および比較例において
同じ）の93％がオートクレーブ外に排出されたこ
とがわかつた。Example 1 A 0.5 mm induction rotary autoclave was filled with 250 g of beef tallow fatty acid nitrile and 0.5 g of Nickel-diatomite catalyst, and while maintaining the hydrogen pressure at 5 Kg/cm 2 (gauge pressure), hydrogen was passed through the autoclave, and the autoclave was heated with stirring. The reaction was started when the temperature reached 200°C, and from this point on, stirring was continued for 3 hours while maintaining the temperature at 220°C and the hydrogen pressure at 5 kg/cm 2 (gauge pressure) while flowing hydrogen. Ta. As the reaction progresses, ammonia is produced and is discharged out of the autoclave in gaseous form along with the circulating hydrogen.
When this ammonia gas was absorbed into 50% sulfuric acid and its amount was measured, it was found that the theoretical amount of ammonia produced (the amount of ammonia produced when all the nitrile was converted to secondary amines) within 2 hours from the start of the reaction. It was found that 93% of the sample (same in the following Examples and Comparative Examples) was discharged outside the autoclave.
反応終了後100℃に冷却し、触媒をロ別して、
第１級アミン3.1％、第２級アミン91.1％、第３
級アミン4.3％からなるアミン混合物を240ｇの収
量で得た。 After the reaction was completed, it was cooled to 100℃, the catalyst was filtered out,
Primary amine 3.1%, secondary amine 91.1%, tertiary amine
A yield of 240 g of an amine mixture consisting of 4.3% primary amine was obtained.
比較例 １
0.5オートクレーブに牛脂脂肪酸ニトリル250
ｇおよびニツケル―ケイソウ士触媒0.5ｇを充填
し、水素圧を20Kg／cm２（ゲージ圧）にした以外
は、実施例１と同様の方法で反応を行なつたとこ
ろ、反応開始時点から２時間のあいだに、アンモ
ニア理論生成量の82％のアンモニアガスがオート
クレーブ外に排出された。３時間反応後、実施例
１と同様にして触媒を除去し、241ｇの収量でア
ミン混合物を得たが、この混合物中の第１級、第
２級、第３級アミンの割合はそれぞれ、9.0％、
86.4％、3.9％であつた。Comparative example 1 Beef tallow fatty acid nitrile 250 in 0.5 autoclave
The reaction was carried out in the same manner as in Example 1, except that the hydrogen pressure was 20 Kg/cm 2 (gauge pressure) and 0.5 g of the Nickel-diamond catalyst was charged. During this period, 82% of the theoretical ammonia production amount of ammonia gas was discharged outside the autoclave. After 3 hours of reaction, the catalyst was removed in the same manner as in Example 1 to obtain an amine mixture with a yield of 241 g, but the proportions of primary, secondary, and tertiary amines in this mixture were each 9.0. %,
The percentages were 86.4% and 3.9%.
実施例 ２
0.5オートクレーブに牛脂脂肪酸ニトリル250
ｇおよびニツケル―ケイソウ士触媒0.5ｇを充填
し、水素圧を10Kg／cm２（ゲージ圧）にした以外
は実施例１と同様の方法で反応を行なつたとこ
ろ、反応開始時点から２時間のあいだに、アンモ
ニア理論生成量の90％のアンモニアガスがオート
クレーブ外に排出された。3.5時間反応後、実施
例１と同様にして触媒を除去し、第１級アミン
4.3％、第２級アミン90.4％、第３級アミン4.5％
からなるアミン混合物を243ｇの収量で得た。Example 2 0.5 Beef tallow fatty acid nitrile in autoclave 250
The reaction was carried out in the same manner as in Example 1, except that the hydrogen pressure was 10 Kg/cm 2 (gauge pressure) and 0.5 g of the Nickel-diamond catalyst was charged. During this time, 90% of the theoretical ammonia production amount of ammonia gas was discharged outside the autoclave. After 3.5 hours of reaction, the catalyst was removed in the same manner as in Example 1, and the primary amine
4.3%, secondary amine 90.4%, tertiary amine 4.5%
A yield of 243 g of an amine mixture was obtained.
実施例 ３
0.5オートクレーブに蒸留した牛脂脂肪酸ニ
トリル250ｇおよびニツケル―アルミナ触媒0.5ｇ
を充填し、水素圧を３Kg／cm２（ゲージ圧）にし
た以外は実施例１と同様の方法で反応を行なつた
ところ、反応開始時点から２時間のあいだに、ア
ンモニア理論生成量の91％のアンモニアガスがオ
ートクレーブ外に排出された。４時間反応後、実
施例１と同様にして触媒を除去し、第１級アミン
3.4％、第２級アミン91.3％、第３級アミン4.6％
からなるアミン混合物を240ｇの収量で得た。Example 3 250 g of tallow fatty acid nitrile distilled in a 0.5 autoclave and 0.5 g of nickel-alumina catalyst
The reaction was carried out in the same manner as in Example 1, except that the hydrogen pressure was changed to 3 kg/cm 2 (gauge pressure). Within 2 hours from the start of the reaction, 91% of the theoretical amount of ammonia was produced. % of ammonia gas was discharged outside the autoclave. After 4 hours of reaction, the catalyst was removed in the same manner as in Example 1, and the primary amine
3.4%, secondary amine 91.3%, tertiary amine 4.6%
A yield of 240 g of an amine mixture was obtained.
実施例 ４
0.5オートクレーブに蒸留した牛脂脂肪酸ニ
トリル250ｇおよびニツケル―アルミナ触媒0.5ｇ
を充填し、水素圧を0.5Kg／cm２（ゲージ圧）に
した以外は実施例１と同様の方法で反応を行なつ
たところ、反応開始時点から２時間のあいだに、
アンモニア理論生成量の86％のアンモニアガスが
オートクレーブ外に排出された。４時間反応後、
第１級アミン3.7％、第２級アミン92.2％、第３
級アミン2.7％からなるアミン混合物を239ｇの収
量で得た。Example 4 250 g of tallow fatty acid nitrile distilled in a 0.5 autoclave and 0.5 g of nickel-alumina catalyst
The reaction was carried out in the same manner as in Example 1 except that the hydrogen pressure was 0.5 Kg/cm 2 (gauge pressure). Within 2 hours from the start of the reaction,
Ammonia gas equivalent to 86% of the theoretical amount of ammonia produced was discharged outside the autoclave. After 4 hours of reaction,
Primary amine 3.7%, secondary amine 92.2%, tertiary amine
A yield of 239 g of an amine mixture consisting of 2.7% primary amine was obtained.
比較例 ２
0.5オートクレーブに蒸留した牛脂脂肪酸ニ
トリル250ｇおよびニツケル―アルミナ触媒0.5ｇ
を充填し、比較例１と同様の方法で反応を行なつ
たところ、反応開始時点から２時間のあいだに、
アンモニア理論生成量の78％のアンモニアガスが
オートクレーブ外に排出された。４時間反応後、
実施例１と同様にして触媒を除去し、243ｇの収
量でアミン混合物を得たが、混合物中の第１級、
第２級、第３級のアミンの割合は10.1％、85.2
％、4.7％であつた。Comparative Example 2 250 g of tallow fatty acid nitrile distilled in a 0.5 autoclave and 0.5 g of nickel-alumina catalyst
When the reaction was carried out in the same manner as in Comparative Example 1, within 2 hours from the start of the reaction,
Ammonia gas equivalent to 78% of the theoretical amount of ammonia produced was discharged outside the autoclave. After 4 hours of reaction,
The catalyst was removed in the same manner as in Example 1 to obtain an amine mixture in a yield of 243 g, but the primary,
The proportion of secondary and tertiary amines is 10.1% and 85.2
%, 4.7%.
Claims (1)
で230℃を越えない反応温度を保持し、水素を流
通させかつ生成アンモニアを系外へ除去しなが
ら、炭素数８〜22の脂肪族ニトリルを、反応時間
２時間以内に、アンモニア理論生成量の85％以上
を系外へ除去するようにして、水素還元反応させ
ることを特徴とする第２級長鎖脂肪族アミンの製
造方法。 ２ 反応系における水素圧が０〜６Kg／cm2Gで
ある特許請求の範囲第１項の方法。[Claims] 1. In the presence of a nickel-based hydrogenation catalyst, the reaction temperature is maintained at 200°C or higher and does not exceed 230°C, while hydrogen is flowing and ammonia produced is removed from the system. Production of a secondary long-chain aliphatic amine characterized by subjecting aliphatic nitrile No. 22 to a hydrogen reduction reaction in such a manner that 85% or more of the theoretical amount of ammonia produced is removed from the system within a reaction time of 2 hours. Method. 2. The method according to claim 1, wherein the hydrogen pressure in the reaction system is 0 to 6 Kg/cm 2 G.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8120178A JPS559018A (en) | 1978-07-04 | 1978-07-04 | Preparation of secondary long-chain aliphatic amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8120178A JPS559018A (en) | 1978-07-04 | 1978-07-04 | Preparation of secondary long-chain aliphatic amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS559018A JPS559018A (en) | 1980-01-22 |
| JPS62901B2 true JPS62901B2 (en) | 1987-01-10 |
Family
ID=13739854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8120178A Granted JPS559018A (en) | 1978-07-04 | 1978-07-04 | Preparation of secondary long-chain aliphatic amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS559018A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5848571A (en) * | 1981-09-17 | 1983-03-22 | Matsushita Graphic Commun Syst Inc | Picture signal compensating system |
| JPS62175445A (en) * | 1986-01-27 | 1987-08-01 | Lion Akzo Kk | Production of long-chain saturated aliphatic secondary amine |
-
1978
- 1978-07-04 JP JP8120178A patent/JPS559018A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS559018A (en) | 1980-01-22 |
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