| 94% |
With hydrogen In 1,2,4-Trimethylbenzene; ammonia at 100℃; for 50h; |
4
The procedure of Example 16 was repeated except for omitting the pretreatment. After 50 h of the hydrogenation, the conversion of isophthalonitrile was 100 mol %, the yield of m-xylylenediamine was 94.0 mol %, and the yield of high-boiling condensation products was 6.0 mol %. |
| 93% |
With hydrogen In ammonia; m-xylene at 90℃; |
1
EXAMPLE 1; In accordance with the process flow shown in Fig. 1, the ammoxidation, the extraction of dicyanobenzene, the distillation of extract, the hydrogenation and the purification of xylylenediamine were conducted. From the obtained xylylenediamine, a polyamide resin was produced and then made into a film. (1) Ammoxidation Step A silica-supported catalyst for fluidized bed ammoxidation was prepared according to the method described in JP 6-23158B. The content of silica was 50% by weight and the other components were composed of V, Cr, Mo and B in a ratio of 1:1:0.1:0.2. Into a fluidized bed ammoxidation reactor 1, was packed 6 kg of the catalyst. The ammoxidation was conducted while supplying a raw material gas composed of 3 % of m-xylene, 21% of ammonia and 76% of air, each based on volume, under the conditions of a reaction temperature of 400°C, a space velocity of 700 h-1, and a pressure of 0.05 MPaG. The yields were 80.2 mol% for isophthalonitrile and 3.7 mol% for 3-methylbenzonitrile, each based on m-xylene fed into the reaction system. (2) Extraction Step The ammoxidation gas from the ammoxidation reactor 1 was introduced into the extraction column 2 from its bottom portion. The extraction column 2 was a tower-shaped vessel made of SUS 304. The inner diameter of the cylindrical body portion was 100 mm and the height was 800 mm. At its bottom portion, an inlet for the ammoxidation gas and an outlet for the dicyanobenzene-containing solution were provided. At its vertically central portion, a dumped packing made of metal was packed. From the upper portion of the extraction column, 3-methylbenzonitrile (solvent for extraction) was supplied at a rate of 1 kg/h, to bring the ammoxidation gas into continuous contact with the solvent. The temperature of the liquid at its bottom portion was kept at 160°C. The chemical composition of the solution taken out of the bottom was 24.9% by weight of isophthalonitrile, 74.5% by weight of 3-methylbenzonitrile and 0.6% by weight of other high-boiling point components. (3) Distillation Step The extract from the extraction column was introduced into the distillation column 5 for distilling the extract from its middle portion. The distillation was conducted continuously at a column top temperature of 120°C and a column bottom temperature of 180°C under reduced pressure of 6 kPa. (4) Hydrogenation Step Into isophthalonitrile recovered from the bottom of the distillation column, a hydrogenation solvent (mixture of m-xylene and liquid ammonia) were added to prepare a hydrogenation raw material, the chemical composition of which was isophthalonitrile/m-xylene/ammonia = 6/10/84 by weight. Into the 4-L fixed bed hydrogenation reactor 6, was packed 5 kg of a Ni/diatomaceous earth catalyst (Ni content: 50% by weight). The hydrogenation raw material was supplied into the reactor from its upper portion at a rate of 5.6 kg/h. The hydrogenation was conducted at 90°C under 12 MPa while flowing hydrogen (purity: 99% or more) in parallel from the upper portion of the reactor. The yield of m-xylylenediamine of the hydrogenation was 93% based on isophthalonitrile. (5) Purification Step The solution containing m-xylylenediamine was fed into the purification apparatus 7 where the hydrogenation product solution was distilled to be separated into low-boiling point components (ammonia, m-xylene, methylbenzylamine by-produced in the hydrogenation, etc.) and high-boiling point components. The hydrogenation product solution was first distilled in a distillation column for separating ammonia under 0.5 MPa at a bottom temperature of 150°C to separate out ammonia. The remaining bottom liquid was then distilled in a distillation column for separating low-boiling point components under 6 kPa at a bottom temperature of 182°C to separate out the low-boiling point components such as m-xylylene and methylbenzylamine. The obtained bottom liquid was then distilled in a distillation column for separating high-boiling point components under 2.6 kPa at a bottom temperature of 173°C to separate out the high-boiling point components, thereby recovering the purified m-xylylenediamine from the top of the column. The chemical composition of the purified product was 99.98% by weight of m-xylylenediamine, 0.01% by weight of 3-methylbenzylamine and 0.01% by weight of other components. (6) Production of Polyamide Resin A polyamide resin was produced from m-xylylenediamine obtained above, which was then continuously extruded into a non-stretched film. The polyamide resin was evaluated by the following methods. (i) Relative viscosity of polyamide resin Accurately weighed one gram of polyamide resin was dissolved in 100 cc of 96% sulfuric acid at 20 to 30°C under stirring. Immediately after complete dissolution, 5 cc of the resulting solution was placed in a Canon Fenske viscometer, and the viscometer was allowed to stand in a thermostatic chamber maintained at 25 +/- 0.03°C for 10 min. Then, a dropping time (t) of the solution was measured. Also, a dropping time (to) of the 96% sulfuric acid was measured. The relative viscosity was calculated from the measured t and to according to the following formula: [Show Image] (ii) Yellowness index (YI) of non-stretched film The tristimulus values X, Y and Z of XYZ colorimetric system of reflected light were measured according to JIS-K7103 using a color difference meter Σ80 model available from Nippon Denshoku Co., Ltd., and the yellowness index (YI) was calculated from the following formula: [Show Image] (i) Relative viscosity of polyamide resin Accurately weighed one gram of polyamide resin was dissolved in 100 cc of 96% sulfuric acid at 20 to 30°C under stirring. Immediately after complete dissolution, 5 cc of the resulting solution was placed in a Canon Fenske viscometer, and the viscometer was allowed to stand in a thermostatic chamber maintained at 25 +/- 0.03°C for 10 min. Then, a dropping time (t) of the solution was measured. Also, a dropping time (to) of the 96% sulfuric acid was measured. The relative viscosity was calculated from the measured t and to according to the following formula: [Show Image] (ii) Yellowness index (YI) of non-stretched film The tristimulus values X, Y and Z of XYZ colorimetric system of reflected light were measured according to JIS-K7103 using a color difference meter Σ80 model available from Nippon Denshoku Co., Ltd., and the yellowness index (YI) was calculated from the following formula: [Show Image] To a molten adipic acid heated to 180°C in a reactor equipped with a stirrer and a partial condenser, m-xylylenediamine obtained above was added dropwise under atmospheric pressure while raising the temperature. The dropwise addition of m-xylylenediamine was stopped when the inner temperature reached 250°C. After reaching 255°C, the pressure was kept at 60 kPa and the temperature was raised to 260°C over 20 min. Thereafter, the reaction product was taken out, cooled, and granulated, to obtain poly(m-xylylene adipamide) (nylon MXD6) having a molar balance of 0.995 and a relative viscosity of 2.20. The molar balance is a molar ratio of the units derived from diamine monomer and the units derived from dicarboxylic acid monomer (diamine unit/dicarboxylic acid unit) each constituting the polyamide backbone inclusive of terminal ends. (7) Continuous extrusion of polyamide resin After vacuum-drying at 120°C for 6 h, the polyamide resin was extruded into a non-stretched film of 150 µm thick at 260°C from an extruder having a screw of 40 mm diameter. The extrusion into a 150 µm thick non-stretched film was continued for five days. During the continuous extrusion, serious problems which prevented the continuous operation, such as burning of die and the dirt of cooling roll, did not occur. During the continuous extrusion, the non-stretched film was sampled every 8 h to measure the yellowness index. Each sampled non-stretched film was fixed onto a flame and then kept in a thermostatic chamber at 150°C for one hour for crystallization and heat treatment. Thereafter, the yellowness index (YI) of reflected light was measured. The measured YI values fell within a range from 5.8 to 6.4, indicating the stable quality of non-stretched films. |
| 88% |
With C28H29Cl2CoNP2; hydrogen; sodium triethylborohydride In 1,4-dioxane at 80℃; for 6h; |
|
| 85% |
With sodium tetrahydroborate; copper ferrite In water for 0.416667h; Reflux; Green chemistry; chemoselective reaction; |
General procedure for the reduction of nitriles to primary amines
General procedure: As a representative example, in a round-bottom flask (15 mL) equipped with a magnetic stirrer, benzonitrile (1 mmol, 0.103 g) was dissolved in H2O (2 mL). Afterward, CuFe2O4 (0.2 mmol, 0.048 g) was added and the mixture was stirred. Then, NaBH4 (2 mmol, 0.076 g) was also added, and the resulting mixture continued to stir at reflux for 5 min. Upon completion of the reaction (monitored by TLC), the mixture was cooled to room temperature, and the catalyst was separated by an external magnet. The reaction mixture was extracted with ethyl acetate (EtOAc) (2 x 4 mL). The organic layers were combined together and dried over anhydrous sodium sulfate (Na2SO4). The solvent was evaporated under reduced pressure. The pure colorless liquid benzylamine was obtained in 95% yield. |
| 85% |
With sodium tetrahydroborate; nickel(II) acetate tetrahydrate In water at 50℃; for 0.2h; |
3.2. General procedure for the reduction of arynitriles to corresponding primary amines
General procedure: As a representative example, in a round-bottom flask (10 mL) equipped with a magnetic stirrer, benzonitrile (1 mmol) was dissolved in H2O (2 mL). Afterward, Ni(OAc)2•4H2O (50 mol%) was added, and the mixture was stirred. Then, NaBH4 (2 mmol) was added, and the resulting mixture was continued to stirring at 50 C for 12 min. Upon completion of the reaction (monitored by TLC), the mixture was cooled to room temperature, and then 5 mL of water was added to the reaction mixture and was stirred at room temperature for about 5-10 min. The reaction mixture was extracted with ethyl acetate (EtOAc) (2 × 4 mL). The organic layers were combined and dried over anhydrous sodium sulfate (Na2SO4). Next, the solvent was evaporated under reduced pressure, and subsequently, the pure colorless liquid benzylamine was obtained in 89% yield |
| 82% |
With hydrogen In ammonia; isopropyl alcohol at 170℃; for 1h; |
|
| 79% |
Stage #1: benzene-1,3-dicarbonitrile With cobalt(III) acetylacetonate; tris(2-(dicyclohexylphosphanyl)ethyl)phosphane In <i>tert</i>-butyl alcohol Sealed tube; Inert atmosphere;
Stage #2: With potassium <i>tert</i>-butylate In <i>tert</i>-butyl alcohol Sealed tube; Inert atmosphere;
Stage #3: With hydrogen In <i>tert</i>-butyl alcohol at 120℃; for 48h; Autoclave; |
|
| 70% |
With [DBUH(+)][C4H9COO(-)]; water; potassium formate at 70℃; for 10h; Ionic liquid; |
|
| 59% |
With borane-ammonia complex; C15H30Cl2CoN3P In hexane at 100℃; for 16h; Sealed tube; Inert atmosphere; chemoselective reaction; |
|
| 49.4% |
With hydrogen In ammonia; 1,3,5-trimethyl-benzene at 50℃; |
1 COMPARATIVE EXAMPLE 1 Hydrogenation of Isophthalonitrile
COMPARATIVE EXAMPLE 1 Hydrogenation of Isophthalonitrile Into a 100-ml autoclave, were charged 3.2 g of isophthalonitrile, 10.4 g of mesitylene, 10.0 g of liquid ammonia and 2.0 g of the catalyst A, and the inner pressure was raised to 4.9 MPa by hydrogen gas. Then, the autoclave was shaken at 50°C until the change of pressure was no longer appreciated. The analysis on the reaction product solution showed that the conversion of isophthalonitrile was 95.5 mol% and the yield of m-xylynenediamine was 49.4 mol%. |
| 28% |
With Ni-doped silica; ammonia; hydrogen In m-xylene at 80℃; for 2h; Autoclave; |
3% by mass of graphite was added to the calcined powder, which was then molded into 6 mmφ×6 mm by a tablet molding machine, and a reduced and stabilized product was produced in the same manner as described above. An activity (hydrogenation reaction) test was conducted as follows using the aforementioned reduced and stabilized product. In a 100 mL autoclave reaction vessel made of SUS, 2 g of the reduced and stabilized product was placed, and then an inner temperature of a reaction tube was set at 250° C. and 50% hydrogen/50% nitrogen was introduced at 20 mL/min for 10 hours. Subsequently, the reaction vessel was filled with 10 g of meta-xylene (manufactured by Wako Pure Chemical Industries, Ltd.), 6.7 g of isophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 g of the liquid ammonia, and hydrogen was filled up to 10 MPaG. After hydrogen was filled, a resultant in the vessel was heated at 80° C. for 2 hours with stirring to allow the hydrogenation reaction to proceed in the vessel to produce meta-xylylenediamine (MXDA). |
|
With 1,4-dioxane; ammonia; nickel at 100℃; Hydrogenation; |
|
|
With ammonia; hydrogen at 90℃; |
|
|
With lithium hydroxide; hydrogen In tetrahydrofuran; water at 100℃; for 7h; |
|
|
With potassium hydroxide; hydrogen In tetrahydrofuran; water at 100℃; for 15h; |
|
|
Stage #1: benzene-1,3-dicarbonitrile With ammonia; hydrogen at 70℃; for 240h;
Stage #2: With hydrogen at 80 - 100℃; |
1; 2; 4
Example 1 Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, a liquid mixture of isophthalonitrile and liquid ammonia (isophthalonitrile:liquid ammonia = 8.5:91.5 (weight ratio)) was supplied from the top of the reactor at a rate of 170 g/h, and first catalytic hydrogenation treatment was conducted continuously at 70°C for 10 days while 30 NL/h ("N" represents standard conditions, the same applies below) of a hydrogen gas was introduced at a reaction pressure of 7.0 MPa, to thereby produce a reaction product (A). The reaction product (A) was passed through a gas-liquid separator, and a liquid phase part was extracted into a receiver intermittently. Ammonia was subjected to pressure reduction to a normal temperature and a normal pressure and removed from a gas phase part of the receiver. Then, a nitrogen gas was passed therethrough for an operation of removing residual ammonia, to thereby extract intermittently the reaction product (B). The extracted reaction product (B) was mixed completely, and then was analyzed by gas chromatography, and had metaxylylenediamine of 93.1 wt%, 3-cyanobenzylamine of 0.6 wt%, 3-methylbenzylamine of 0.02 wt%. No isophthalonitrile was detected. Remaining components were oligomers of metaxylylenediamine and polymers each having a high boiling point and not detected by gas chromatography. Note that the residual ammonia amount was about 500 ppm. Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, 1,800 g of the reaction product (B) obtained as described above was supplied from above top of the the reactor at a rate of 75 g/h, and second catalytic hydrogenation treatment was conducted at 80°C while 3 NL/h of a hydrogen gas was introduced at a reaction pressure of 2.0 MPa. A gas and a liquid were separated, and then the reaction product (C) was extracted. The reaction product (C) was analyzed by gas chromatography, and had a metaxylylenediamine concentration of 93.5 wt%, a 3-methylbenzylamine concentration of 0.04 wt%, and a 3-cyanobenzylamine concentration of 0.001 wt% or less. The obtained reaction product (C) was subjected to distillation under reduced pressure of 6 kPa by using a distillation column with a theoretical plate number of 10, to thereby obtain metaxylylenediamine purified to have a purity of 99.99%. Note that a 3-cyanobenzylamine content in the obtained metaxylylenediamine was 0.001 wt% or less.Example 2 Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction: Then, 1,500 g of the reaction product (B) obtained in Example 1 was supplied from the top of the reactor at a rate of 150 g/h, and the second catalytic hydrogenation treatment was conducted at 100°C while 3 NL/h of a hydrogen gas was introduced at a reaction pressure of 2.0 MPa. A gas and a liquid were separated, and then the reaction product (C) was extracted. The reaction product (C) was analyzed by gas chromatography, and had a metaxylylenediamine concentration of 93.4 wt%, a 3-methylbenzylamine concentration of 0.06 wt%, and a 3-cyanobenzylamine concentration of 0.001 wt% or less. Remaining components were oligomers of metaxylylenediamine and polymers each having a high boiling point and not detected by gas chromatography. The obtained reaction product (C) was subjected to distillation in the same manner as in Example 1, to thereby obtain metaxylylenediamine purified to have a purity of 99.99%. Note that the 3-cyanobenzylamine content in the obtained metaxylylenediamine was 0.001 wt% or less. Example 4 Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, a liquid mixture of isophthalonitrile and liquid ammonia (isophthalonitrile:liquid ammonia = 1:3 (weight ratio)) was supplied to the reactor at a rate of 57.8 g/h. Meanwhile, a part of a reaction liquid was extracted from a liquid pool provided on a lower part of the reactor, subjected to pressure increase with a gear pump, and circulated at 173.4 g/hr through a liquid mass flow meter, and supplied from the top of the reactor together with the newly charged raw material (unused liquid mixture) describe above. The first catalytic hydrogenation treatment was conducted continuously at 70°C for 10 days while 30 NL/h of a hydrogen gas was introduced at a reaction pressure of 7.0 MPa, to thereby produce a reaction product (A). An amount of liquid ammonia at an inlet of the reactor (57.8 g/h x 3/4 + 173.4 g/h x 3/4 = 173.4 g/h) was 92 wt% per the amount of the liquid mixture of liquid ammonia and isophthalonitrile (173.4 g/h + 57.8 g/h x 1/4 = 187.8 g/h). The reaction product (A) was passed through a gas-liquid separator, and a liquid phase part was extracted into a receiver intermittently. Ammonia was subjected to pressure reduction to a normal temperature and a normal pressure and was removed from a gas phase part of the receiver. Then, a nitrogen gas was passed therethrough for an operation to remove residual ammonia, to thereby extract intermittently the reaction product (B). The extracted reaction product (B) was mixed completely, and then was analyzed by gas chromatography. The reaction product (B) had metaxylylenediamine of 92.8 wt%, 3-cyanobenzylamine of 0.7 wt%, and 3-methylbenzylamine of 0.02 wt%. No isophthalonitrile was detected. Remaining components were oligomers of metaxylylenediamine and polymers each having a high boiling point and not detected by gas chromatography. Note that the residual ammonia amount was about 500 ppm. The reaction product (B) was subjected to the second catalytic hydrogenation treatment under the same conditions as those of Example 1. A gas and a liquid were separated, and then the reaction product (C) was extracted. The reaction product (C) was analyzed by gas chromatography, and had a metaxylylenediamine concentration of 93.2 wt%, a 3-methylbenzylamine concentration of 0.04 wt%, and a 3-cyanobenzylamine concentration of 0.001 wt% or less. The obtained reaction product (C) was subjected to distillation in the same manner as in Example 1, to thereby obtain metaxylylenediamine purified to have a purity of 99.99%. Note that the 3-cyanobenzylamine content in the obtained metaxylylenediamine was 0.001 wt% or less. |
|
Stage #1: benzene-1,3-dicarbonitrile With ammonia; hydrogen In water at 20 - 200℃;
Stage #2: With hydrogen at 80℃; |
5
An autoclave equipped with a jacket and having a volume of 5 L was subjected to nitrogen replacement. Then, 30 g of a commercially available supported nickel catalyst (Ni content of 50%) reduced in a stream of hydrogen at 200°C in advance and 1,500 g of a solution of liquid ammonia containing 8.5 wt% of isophthalonitrile was charged into the autoclave, and the autoclave was subjected to pressure increase to 6.0 MPa at room temperature with a hydrogen gas. Then, hot water was passed through the jacket under stirring, and a liquid temperature was increased to 80°C. An inner pressure of the autoclave was increased once with heating. Then, absorption of hydrogen began, and the pressure was reduced. Thus, a hydrogen gas was intermittently supplied. The liquid temperature was maintained at 80°C, and the inner pressure was maintained at 7.0 to 8.0 MPa for the first catalytic hydrogenation treatment. After observation of no pressure reduction in the autoclave, the reaction was continued at a liquid temperature of 80°C for an additional hour. Then, water was passed through the jacket to reduce the liquid temperature to room temperature, and the hydrogen gas and a part of ammonia were removed from a gas phase part of the autoclave to a normal pressure while water was passed through the jacket, to thereby obtain a reaction product (A). After leaving at stand for 2 hours, the reaction product (A) was transferred to another autoclave having a volume of 5 L through an in-line filter. After the transfer, ammonia was removed at normal pressure until no pressure increase was observed while a nitrogen gas was passed through the liquid. Then, the liquid in the autoclave was extracted, and 130 g of the reaction product (B) was obtained. The reaction product (B) was analyzed by gas chromatography, and had metaxylylenediamine of 91.2 wt%, 3-cyanobenzylamine of 0.5 wt%, and 3-methylbenzylamine of 0.05 wt%. No isophthalonitrile was detected. Remaining components were oligomers of metaxylylenediamine and polymers each having a high boiling point and not detected by gas chromatography. Note that the residual ammonia amount was about 300 ppm. Into a tubular vertical hydrogenation reactor having a volume of 30 ml, was packed 15 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, 100 g of the reaction product (B) obtained as described above was supplied from the top of the reactor at a rate of 7.5 g/h, and second catalytic hydrogenation treatment was conducted at 80°C while 3 NL/h of a hydrogen gas was introduced at a reaction pressure of 2.0 MPa. A gas and a liquid were separated, and then a liquid was extracted, to thereby obtain 80 g of the reaction product (C). The reaction product (C) was analyzed by gas chromatography, and had a metaxylylenediamine concentration of 91.3 wt%, a 3-methylbenzylamine concentration of 0.07 wt%, and a 3-cyanobenzylamine concentration of 0.001 wt% or less. The obtained reaction product (C) was subjected to distillation in the same manner as in Example 1, to thereby obtain metaxylylenediamine purified to have a purity of 99.99%. Note that the 3-cyanobenzylamine content in the obtained metaxylylenediamine was 0.001 wt% or less. |
|
Stage #1: benzene-1,3-dicarbonitrile With ammonia; hydrogen In m-xylene at 70℃; for 168h;
Stage #2: With hydrogen at 100℃; |
3
Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, a liquid mixture of isophthalonitrile, metaxylene, and liquid ammonia (isophthalonitrile:metaxylene:liquid ammonia = 6:10:84 (weight ratio)) was supplied from the top of the reactor at a rate of 240 g/h, and the first catalytic hydrogenation treatment was conducted continuously at 70°C for 7 days while 30 NL/h of a hydrogen gas was introduced at a reaction pressure of 7.0 MPa, to thereby produce a reaction product (A). The reaction product (A) was passed through a gas-liquid separator, and a liquid phase part was extracted into a receiver intermittently. Ammonia was subjected to pressure reduction to a normal temperature and a normal pressure and removed from a gas phase part of the receiver. Then, a nitrogen gas was passed therethrough for an operation of removing residual ammonia, to thereby extract intermittently the reaction product (B). The extracted reaction product (B) was mixed completely, and then metaxylylene was distilled off with a rotary evaporator. The reaction product (B) after distillation was analyzed by gas chromatography, and had metaxylylenediamine of 92.8 wt%, 3-cyanobenzylamine of 0.8 wt%, 3-methylbenzylamine of 0.01 wt%, and metaxylylene of 0.9 wt%. No isophthalonitrile was detected. Remaining components were oligomers of metaxylylenediamine and polymers each having a high boiling point and not detected by gas chromatography. Note that the residual ammonia amount was below the detection limit. Into a tubular vertical hydrogenation reactor having a volume of 400 ml, was packed 150 g of a commercially available supported nickel catalyst (Ni content of 50%), and this catalyst was subjected to hydrogen reduction. Then, 1,500 g of the reaction product (B) obtained as described above was supplied from the top of the reactor at a rate of 150 g/h, and second catalytic hydrogenation treatment was conducted at 100°C while 3 NL/h of a hydrogen gas was introduced at a reaction pressure of 4.0 MPa. A gas and a liquid were separated, and then the reaction product (C) was extracted. The reaction product (C) was analyzed by gas chromatography, and had a metaxylylenediamine concentration of 92.9 wt%, a 3-methylbenzylamine concentration of 0.09 wt%, and a 3-cyanobenzylamine concentration of 0.001 wt% or less. The obtained reaction product (C) was subjected to distillation in the same manner as in Example 1, to thereby obtain metaxylylenediamine purified to have a purity of 99.99%. Note that the 3-cyanobenzylamine content in the obtained metaxylylenediamine was 0.001 wt% or less. |
|
With ammonia; hydrogen at 60 - 100℃; |
1; 2
Example 1; A reactor having a reactor volume of 70 ml which is suitable for upflow mode operation was charged with an all-active cobalt catalyst, doped with Mn, P, Na) as 4, mm extrudates. A 15% strength solution (at 60° C.) of IPN in MXDA was fed in at the lower end of the reactor. Hydrogen, and ammonia were likewise fed in from the bottom. At an inflow of 126 g/h of nitrile/MXDA solution and 54 g/h of ammonia, a hydrogen flow of 20 l/h (volume under standard conditions) and a recycle stream of 3.5 ml/min. were set. The reactor pressure was 190 bar (abs.). After 150 g of IPN had been reacted at a selectivity of 88% (based on IPN used), 15% of the crude MXDA obtained was discharged. The remaining amount was used as solvent for a further 150 g of IPN. This procedure was repeated 10 times. In all cases, no IPN could be detected in the output. The purity of the crude MXDA obtained was 89% by weight after the 10th pass. This corresponds to a selectivity of 87% based on IPN used.; Example 2; Solutions of 15% by weight of IPN in MXDA were prepared batchwise in a stirred vessel at 60° C. and pumped to an intermediate vessel. At the beginning of the campaign, MXDA having a purity of >99% by weight was available. The solution was compressed to 200 bar by means of a high-pressure pump and admixed with liquid ammonia (50 mol of NH3 per mol of IPN). The mixture was heated to 70° C. and fed-together with hydrogen to a hydrogenation reactor. The reactor was operated adiabatically in a single pass in the downflow mode at a space velocity over the catalyst of 0.3 kg of IPN/I/h. As a result of the heart of reaction, the temperature in the reactor increased to about 100° C. at the outlet. The reaction product mixture was depressurized to about 14 bar and ammonia was distilled off at this pressure and was reused after condensation. The remaining bottom product (=crude MXDA) was used in its entirety without a further work-up-step for dissolving a further batch of IPN which was then hydrogenated. In this way, the crude MXDA was recirculated five times for dissolving IPN before it was finally passed to the purifying distillation. The selectivity based on IPN used was 93%. |
|
Stage #1: benzene-1,3-dicarbonitrile With ammonia at 30 - 60℃; Neat (no solvent);
Stage #2: With hydrogen at 90℃; Neat (no solvent); |
1; 2
Example 1; 90 g/h of molten IPN (commercial IPN flakes which had been molten by heating to approx. 170° C.) were mixed in a vessel at 60° C. with 178 g/h from circulation stream [13] and 94 g/h of fresh ammonia [2] and thus dissolved. This forms a solution comprising 25% by weight of IPN. At 60° C., the solubility of IPN in the mixture is about 30% by weight. The mixing temperature can be adjusted by virtue of the temperature and the flow rate of the circulation stream [4]. When ammonia is fed at 30° C., the circulation stream [13] at 50° C. and IPN at 170° C., stream [4] may, for example, be 470 g/h at 58° C. in order to come to the mixing temperature of 60° C., not taking into account heat losses. The boiling pressure in the mixing vessel is then 23.3 bar (abs.), i.e., above this pressure, the mixture remains liquid and no evaporation of ammonia takes place. The solution is conducted into a circulation stream (approx. 839 g/h) consisting of the liquid recycle stream of the reactor effluent. The IPN concentration at the reactor inlet is thus 7.5% by weight. 50 mol of NH3 are present at the reactor inlet per mole of IPN.The resulting reaction mixture was hydrogenated continuously in a tubular reactor over an unsupported cobalt catalyst at 90° C. and 200 bar. The portion of the reactor effluent drawn off was freed of the majority of the amount of ammonia in an ammonia column and analyzed by GC. At full conversion of the IPN used (i.e. conversion greater than 99.95%; no further reactant detectable by GC), the selectivity was 92%.In subsequent distillation steps, first residual ammonia and low-boiling secondary components were removed. After the high-boiling impurities had been removed via the bottom, MXDA was obtained as the top product of a distillation column in a purity of more than 99.9% by weight.; Example 2; 90 g/h of molten IPN (commercial IPN flakes which had been molten by heating to approx. 170° C.) were mixed in a vessel at 60° C. with 320 g/h from circulation stream [13] and 40 g/h of fresh ammonia [2] and thus dissolved. This forms a solution comprising 20% by weight of IPN. At 60° C., the solubility of IPN in the mixture is about 25% by weight. The mixing temperature can be adjusted by virtue of the temperature and the flow rate of the circulation stream [4]. When ammonia is fed at 30° C., the circulation stream [13] at 45° C. and IPN at 170° C., stream [4] may, for example, be 527 g/h at 58° C. in order to come to the mixing temperature of 60° C., not taking into account heat losses. The boiling pressure in the mixing vessel is then 20.2 bar (abs.), i.e., above this pressure, the mixture remains liquid and no evaporation of ammonia takes place. The solution is conducted into a circulation stream (approx. 750 g/h) consisting of the liquid recycle stream of the reactor effluent. The IPN concentration at the reactor inlet is thus 7.5% by weight. 30 mol of NH3 are present at the reactor inlet per mole of IPN.The resulting reaction mixture was hydrogenated continuously in a tubular reactor over an unsupported cobalt catalyst at 90° C. and 200 bar. The portion of the reactor effluent drawn off was freed of the majority of the amount of ammonia in an ammonia column and analyzed by GC. At full conversion of the IPN used (i.e. conversion greater than 99.95%; no further reactant detectable by GC), the selectivity was 88%. |
|
Stage #1: benzene-1,3-dicarbonitrile With ammonia at 25℃;
Stage #2: With hydrogen at 90℃; |
1.4-6
4) Dissolution StepThe obtained molten isophthalonitrile (residence time at bottom of distillation column: 60 min) was fed to a dissolution tank D (made of SUS304 having a volume of 1 L) from its side portion at a flow rate of 280 g/h and liquid ammonia was fed to the dissolution tank D from its upper portion at a flow rate of 5320 g/h, thereby dissolving isophthalonitrile in liquid ammonia at 2 MPa and 25° C.(5) Solid-Liquid Separation StepThen, a solution containing insolubles was drawn from the bottom of the dissolution tank D and filtered through a filter E (stainless strainer with a pore size of 40 μm) while transferring the solution by pressure difference. By removing 0.17 g of 2,4,6-tris(3-cyanophenyl)-1,3,5-triazine as part of the filtered-off product per one hour, a filtrate was obtained at a rate of 279.8 g/h. The composition of the crude isophthalonitrile obtained by removing liquid ammonia from the filtrate is shown in Table 2. Upon comparing with the results in Table 1, it can be found that the content of 2,4,6-tris(3-cyanophenyl)-1,3,5-triazine is drastically reduced.(6) Hydrogenation StepIn a tubular vertical hydrogenation reactor F (made of SUS304 having an inner diameter of 100 mm), 4 L of a commercially available nickel/diatomaceous earth supported catalyst with a nickel content of 50% by weight (columnar shape with a diameter of 5 mm and a height of 5 mm) was packed. Then, the catalyst was reduced under hydrogen flow at 200° C. for activation. After cooling, hydrogen gas was introduced into the reactor under pressure to maintain the pressure constant at 10 MPa, and the catalyst layer was maintained at 90° C. by external heating. The filtrate obtained in the solid-liquid separation step was continuously fed to the reactor from its upper portion at a rate of 5.60 kg/h while flowing hydrogen gas from the upper portion of the reactor at a flow rate of 265 NL/h. The amount of the 3-cyanobenzylamine (reaction intermediate) increased with time. The reaction results and the total feeding amount of isophthalonitrile to the reactor at the time when the amount of 3-cyanobenzylamine in the hydrogenation product solution reached 0.10% by weight of the amount of m-xylylenediamine are shown in Table 3.After removing liquid ammonia from the hydrogenation product solution by a simple distillation, the remaining ammonia was further removed by bubbling nitrogen gas. The reaction product solution after removing ammonia was catalytically hydrogenated again in the present of a commercially available nickel/diatomaceous earth supported catalyst with a nickel content of 50% by weight in a fixed bed manner (WHSV (weight hourly space velocity: 0.5 h-1, reaction temperature: 80° C., reaction pressure: 2 MPa), to obtain crude m-xylylenediamine. The crude m-xylylenediamine was distilled under reduced pressure of 6 kPa using a distillation column with 10 theoretical plates, to obtain a purified m-xylylenediamine with 99.99% purity. The content of 3-cyanobenzylamine in the obtained m-xylylenediamine was 0.001% by weight or less.Example 2The procedure of Example 1 was repeated up to the dissolution step except for using the molten isophthalonitrile (residence time at the bottom of distillation column: 180 min). By removing 0.20 g of 2,4,6-tris(3-cyanophenyl)-1,3,5-triazine as part of the filtered-off product per one hour, a filtrate was obtained at a rate of 279.7 g/h. The composition of the crude isophthalonitrile obtained by removing liquid ammonia from the filtrate is shown in Table 2.The obtained isophthalonitrile was hydrogenated in the same manner as in Example 1 except for using the filtrate obtained in the above filtration. The reaction results and the total feeding amount of isophthalonitrile to the reactor at the time when the amount of 3-cyanobenzylamine in the hydrogenation product solution reached 0.10% by weight of the amount of m-xylylenediamine are shown in Table 3.Comparative Examples 1A raw solution for hydrogenation was prepared by mixing 5.0% by weight of the molten isophthalonitrile (residence time at the bottom of distillation column: 60 min) obtained in Example 1 and 95% by weight of liquid ammonia. The hydrogenation was conducted in the same manner as in Example 1 except for using the obtained raw solution for hydrogenation in place of the filtrate obtained in the solid-liquid separation step. The composition of the crude isophthalonitrile obtained by removing liquid ammonia from the raw solution for hydrogenation is shown in Table 2. The reaction results and the total feeding amount of isophthalonitrile to the reactor at the time when the amount of 3-cyanobenzylamine in the hydrogenation product solution reached 0.10% by weight of the amount of m-xylylenediamine are shown in Table 3. The hydrogenation was further continued, and the reaction results at the time when the total feeding amount of isophthalonitrile reached 26.3 kg were isophthalonitrile conversion of 99.93%, m-xylylenediamine selectivity of 88.03 mol %, and 3-cyanobenzylamine selectivity of 2.34 mol %. |
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With hydrogen In ammonia at 70℃; |
1
(Hydrogenation) A nickel/diatomaceous earth (carrier) catalyst (nickel content: 50 mass%, columnar, diameter: 3 mmφ, height 3 mm) (120 mL) was charged into a reactor (inner diameter: 25 mmφ) made of SUS. The catalyst was reduced under a flow of hydrogen at 200°C for activation and then coaled. Hydrogen gas was fed with pressure into the reactor via pipes connected to the reactor to thereby maintain the inside of the reactor constantly at 8 MPa. The reactor was heated to thereby maintain the inside temperature at 70°C. Hydrogen gas was supplied through the inlet of the reactor at a flow rate of 13 L/h. While the flow conditions of hydrogen gas were maintained, a raw-material mixture liquid prepared from raw-material isophthalonitrile (product of Mitsubishi Gas Co., Inc., produced through ammoxidation of m-xylylene, purity: ≥94 mass%) (1 part by mass) and liquid ammonia (product of Mitsubishi Chemical Corp., purity 99.9 mass%) (9 parts by mass) were supplied through the inlet of the reactor at 139 g/h. Continuous hydrogenation was started at an inside temperature of the reactor of 70°C in the trickle-bed mode. The hydrogenation reaction mixture produced through hydrogenation was extracted through the outlet of the reactor. After start of reaction, the hydrogenation reaction mixture was sampled through the outlet of the reactor at appropriate timings, and the obtained liquid samples were analyzed through gas chromatography.(Stopping hydrogenation: operation (1)) Three hundred hours after the start of hydrogenation, only the supply of the raw-material liquid was stopped.(Washing of catalyst: operation (2)) The inside temperature of the reactor was maintained at 70°C. MXDA (product of Mitsubishi Gas Co., Inc, GC purity: 99.9 mass%, isophthalonitrile content: about ≤10 ppm by mass (below GC detection limit)) (800 g) serving as a washing liquid was supplied to the reactor through the inlet thereof at 139 g/h (washing time: about 6 hours, one-path flow mode). In the washing liquid which had been used in the washing of the catalyst, a high-boiling-point by-product precursor which was thought to be derived from MXDA was detected through liquid chromatography.(Resuming hydrogenation: operation (3)) After completion of washing, while the flow conditions of hydrogen gas were maintained, a raw-material mixture liquid prepared from raw-material isophthalonitrile (1 part by mass) and liquid ammonia (9 parts by mass) was supplied through the inlet of the reactor at 139 g/h. Continuous hydrogenation was resumed at an inside temperature of the reactor of 70°C. After resuming hydrogenation, the hydrogenation reaction mixture was sampled through the outlet of the reactor at appropriate timings, and the obtained liquid samples were analyzed through gas chromatography. Table 1 shows changes over time in selectivity to MXDA and to reaction intermediate CBA and differential pressure of the catalyst layer in the reactor. |
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With hydrogen In methanol; toluene at 70℃; for 1.5h; |
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| 87 %Chromat. |
With sodium n-propoxide In 1,2-dimethoxyethane at 69.84℃; for 8h; |
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With hydrogen; sodium hydroxide In methanol; toluene at 80℃; Autoclave; |
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With hydrogen; sodium hydroxide In methanol; toluene at 80℃; Autoclave; |
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| 598 g |
With ammonia; hydrogen at 70℃; Inert atmosphere; |
1 Example 1
To Contents tubular vertical hydrogenation reactor of 200ml, a commercial supported nickel catalyst (Ni content of 50%) and 50ml filling, was activated by reduction with hydrogen flow under 250 ° C. The catalyst was hydrogen reduction. Then, the liquid ammonia solution containing isophthalonitrile (manufactured by Tokyo Kasei Kogyo) 8.5wt% was supplied from the reaction tube upward at a rate of 40g / h, while press fitting the hydrogen gas of 70ml / min at the reaction pressure 8.0MPa It was subjected to hydrogenation treatment continuously at 70 ° C. Is through the hydrogenation solution in the gas-liquid separator, at normal temperature the ammonia from the gas phase portion, and and removed until the normal pressure, after the operation for removing the ammonia which remains is further flushed with nitrogen gas, the liquid extracted phase portion into a receiver to obtain a reaction solution. They were charged and the reaction mixture to a distillation bottoms to remove low-boiling components by simple distillation. Distillation apparatus is using the batch system, kept constant pressure 5.3kPa under reduced pressure by a vacuum pump, subjected to a heat of the bottom liquid by external heating, was the end of the distillation when it becomes a bottom temperature of 172 ° C. The composition of the product solution 598g is MXDA 92.0%, was 8.0% high-boiling component. |
| 59 %Chromat. |
With borane-ammonia complex; C15H30Cl2CoN3P In hexane at 100℃; for 16h; Inert atmosphere; Schlenk technique; |
8 Cobalt catalysts (complexes of formula 1) catalyze the transfer hydrogenation of cyano groups to the development of substrates for primary amines
General procedure: Under the protection of argon, the complex represented by the catalyst formula 1 (0.5-1 mol%), ammonia borane (0.6 _1.5 equiv), benzonitrile (0.5 mmol) and n-hexane (2 mL) were sequentially added to a 25 mL shrek bottle containing a magnetic stirrer and reacted at 25-50°C for 16 hours. After the reaction was completed, the reaction mixture was diluted with 5 mL of methanol. The reaction product was quantified by GC using biphenyl as an internal standard. |
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With hydrogen In 1,4-dioxane at 100℃; for 24h; Flow reactor; |
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