Two-step process for converting cyclic alkylene ureas into their corresponding alkylene amines
A process is provided for converting cyclic alkyleneureas into their corresponding alkyleneamines. The process includes, in a first step, converting cyclic alkyleneureas into their corresponding alkyleneamines by reacting cyclic alkyleneureas in the liquid phase with water with removal of CO2, so as to convert from about 5 mole % to about 95 mole % of alkyleneurea moieties in the feedstock to the corresponding amines. The process further includes, in a second step, adding an inorganic base and reacting cyclic alkylene ureas remaining from the first step with the inorganic base to convert them partially or completely into their corresponding alkyleneamines. Certain embodiments of the two-step process obtain a high conversion of cyclic alkyleneureas, while using substantially less strong inorganic base. Certain embodiments of the process process also show a higher selectivity to amines than prior art processes.
1. A process for converting cyclic alkyleneureas into their corresponding alkyleneamines, comprising:
in a first step, converting cyclic alkyleneureas into their corresponding alkyleneamines by reacting cyclic alkyleneureas in the liquid phase with water with removal of CO 2 , so as to convert from about 5 mole % to about 95 mole % of alkyleneurea moieties in a feedstock to corresponding amines, wherein the corresponding alkyleneamines are triethylenetetramine, aminoethylethanolamine, and ethylenediamine, and
in a second step, adding an inorganic base and reacting cyclic alkylene ureas remaining from the first step with the inorganic base to convert the cyclic alkylene ureas completely or partially into corresponding alkyleneamines.
2. The process of claim 1 , wherein the inorganic base has a pKb of less than 1.
3. The process of claim 1 , wherein the feedstock comprises at least about 10 mole % of cyclic urea derivatives of alkyleneamine compounds comprising a —NH—R 3 —NH—R 3 —NH—R 3 —NH— moiety, calculated on the total of cyclic urea compounds present in the mixture.
4. The process of claim 1 , wherein the first step is carried out at a temperature of from about 150° C. to about 400° C.
5. The process of claim 1 , wherein the first step is carried by reacting cyclic alkyleneureas in the liquid phase with water in an amount of from about 0.1 to about 20 mole water per mole urea moiety, at a temperature of at least about 230° C.
6. The process of claim 1 , wherein the first step is carried out in the presence of an amine compound selected from the group of primary amines, cyclic secondary amines, and bicyclic tertiary amines.
7. The process of claim 1 , wherein inorganic base is added in the second step in an amount of at least about 0.2:1 mole inorganic base per mole cyclic alkyleneurea moiety.
8. The process of claim 1 , wherein in the second step the molar amount of cyclic ethylene urea moieties in the product provided to the treatment with the inorganic base is at most about 20:1.
9. The process of claim 1 , wherein the second step is carried out at a temperature of from about 100° C. to about 350° C.
10. The process of claim 1 , further comprising removing salt formed in the second step.
11. The process of claim 1 , wherein the second step is carried out at a temperature of from about 170° C. to about 280° C.
12. The process of claim 1 , wherein in the second step the molar amount of cyclic ethylene urea moieties in the product provided to the treatment with the inorganic base is at most about 5.5:1.
13. The process of claim 1 , wherein in the second step the molar amount of cyclic ethylene urea moieties in the product provided to the treatment with the inorganic base is at most about 4:1.
14. The process of claim 1 , wherein in the second step the molar amount of cyclic ethylene urea moieties in the product provided to the treatment with the inorganic base is at most about 3:1.
15. The process of claim 1 , wherein inorganic base is added in the second step in an amount of at least about 2:1 mole inorganic base per mole cyclic alkyleneurea moiety.
16. The process of claim 1 , wherein the first step is carried out at a temperature of from about 250° C. to about 320° C.
17. The process of claim 1 , wherein the feedstock comprises at least about 20 mole % of cyclic urea derivatives of alkyleneamine compounds comprising a —NH—R 3 —NH—R 3 —NH—R 3 —NH— moiety, calculated on the total of cyclic urea compounds present in the mixture.