Method for intermittently producing 4,4′-diaminodicyclohexylmethane with a low amount of the trans-trans isomer
The present invention discloses a method for intermittently producing 4,4′-diaminodicyclohexyl methane (H 12 MDA) with a low amount of the trans-trans isomer thereof, which comprises: controlling the reaction process by stopping the reaction when, except for a solvent, the reaction solution comprises MDA of 0-5 wt % and H 6 MDA of 1-20 wt %; and b) separating the reaction solution obtained from step a) by conventional means to obtain H 12 MDA product with desired purity, and allowing the un-reacted material and intermediate product to be recycled to the reactor after being accumulated. The method of the present invention decreases the amount of the trans-trans isomer in H 12 MDA, increases the yield of the reaction, and reduces the production cost. The present invention also provides a post treatment process of the reaction mixture.
1. A method for intermittently producing 4,4′-diaminodicyclohexylmethane with a low amount of the trans-trans isomer, wherein the method comprises:
a) subjecting MDA to a hydrogenation reaction in an organic solvent at a reaction temperature of 120-190° C., and under a hydrogen pressure of 50-150 bar in the presence of a catalyst to generate H 12 MDA, wherein the hydrogenation reaction is stopped when the hydrogen consumption reaches 92-98 volume % of the theoretical hydrogen consumption required for complete hydrogenation of the MDA in order to obtain a reaction solution comprising 0-5 wt % MDA and 1-20 wt % H 6 MDA, except for the solvent; and
b) separating the reaction solution obtained from step a) by conventional means to obtain H 12 MDA with desired purity and recycle accumulated un-reacted MDA and intermediate product to the hydrogenation reaction.
2. A method according to claim 1 , wherein the hydrogenation reaction is stopped in order to obtain a reaction solution comprising 0-4 wt % of MDA and 2-10 wt % of H 6 MDA.
3. A method according to claim 2 , wherein the hydrogenation reaction is stopped in order to obtain a reaction solution comprising 0-2 wt % of MDA and 3-8 wt % of H 6 MDA.
4. A method according to claim 1 , wherein the catalyst in step a) is a rhodium- or ruthenium-supported catalyst, and based on the weight of a carrier, rhodium or ruthenium has an amount of 0.5-8 wt %.
5. A method according to claim 4 , wherein the amount of the rhodium-supported catalyst is 0.1-10 wt %, or the ruthenium-supported catalyst is 0.1-20 wt %, based on the amount of MDA.
6. A method according to claim 1 , wherein the conventional means of separation in step b) comprises the steps of:
i) subjecting the reaction mixture containing H 12 MDA produced in step a) to a filtration to separate the catalyst to recycle to the hydrogenation reaction for reuse;
ii) introducing the filtrate produced in step i) to a first distillation column to obtain a crude H 12 MDA stream from the bottom of the column and recover the solvent from the top of the column for reuse;
iii) introducing the crude H 12 MDA stream to a second distillation column to obtain the deaminated products as light components from the top of the column and a bottom stream from the bottom of the column;
iv) introducing the bottom stream from the second distillation column to a third distillation column to obtain relatively pure H 12 MDA from the top of the column, collect a stream mainly containing H 6 MDA and MDA from the lateral of the column and collect heavy components from the bottom of the column.
7. A method according to claim 6 , wherein in step i) the filter is a conventional filter in the related field, and optionally the filtration is performed under protection of an inert gas.
8. A method according to claim 6 , wherein the first, second and third distillation columns are filled by sheet metal fillers or sieve fillers respectively.
9. A method according to claim 6 , wherein re-introducing the accumulated stream mainly containing H 6 MDA and MDA collected from the lateral in step iv) into the hydrogenation reaction.
10. A method according to claim 6 , wherein in step ii), a temperature of the bottom of the first distillation column is 100-240° C., a temperature of the top of the column is the boiling temperature of the solvent under standard conditions plus or minus 0-30° C., a column pressure is 200-10000 mbar, and a theoretical plate number is 2-60.
11. A method according to claim 6 , wherein in step iii), a temperature of the bottom of the second distillation column is 130-250° C., a temperature of the top of the column is 120-200° C., a column pressure is 1-30 mbar, and a theoretical plate number is 2-60.
12. A method according to claim 6 , wherein in step iv), a temperature of the bottom of the third distillation column is 200-270° C., a temperature of the lateral of the column is 190-240° C., a temperature of the top of the column is 140-210° C., a column pressure is 1-30 mbar, and a theoretical plate number is 2-60.