Regenerative process for the preparation of linear polyethylenepolyamines using a supported catalyst

Claim 2

In a method wherein monoethanolamine is continuously reacted with ethylenediamine in a reaction zone in the presence of a pelleted catalyst under conversion conditions including a temperature of from about 250° C. to about 400° C. and a pressure of from about 500 to about 3000 psig. to provide an essentially noncyclic reaction product comprising polyethylenepolyamines, wherein the catalyst comprises a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally chemically bonded to at least the surface thereof and wherein said pelleted catalyst becomes at least partially deactivated with the passage of time: The improvement which comprises: (a) regenerating said catalyst for further use in said continuous process at a catalyst activating temperature of from about 450° C. to about 700° C. with an oxygen-containing gas for a period of time within the range of about 2 to 12 hours sufficient to regenerate said catalyst; and (b) thereafter again initiating the continuous reaction of monoethanolamine with ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst under said conversion conditions to provide an essentially noncyclic product comprising polyethylenepolyamines.

Claim 3

A method as in claim 1 wherein said group IVb metal oxide support is titania.

Claim 4

A method as in claim 1 wherein said group IVb metal oxide support is zirconia.

Claim 5

In a continuous process for the manufacture of an essentially noncyclic reaction product comprising polyethylenepolyamines by continuously contacting monoethanolamine with ethylenediamine in a reaction zone in the presense of a pelleted catalyst comprising a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally, chemically bonded to at least the surface thereof under conversion conditions comprising a temperature within the range of about 250° to about 400° C., a pressure of about 500 to about 3000 psig and wherein the mol ratio of ethylenediamine to monoethanolamine is in the range of about 1 to about 5 mols of ethylenediamine per mol of monoethanolamine, whereby, with the passage of time, said catalyst becomes at least partially deactivated: The improvement which comprises: (a) passing an inert gas through said catalyst bed to purge said reaction bed of unreacted feedstock and reaction products; (b) contacting said catalyst bed at a temperature of from about 450° C. to about 550° C. with a mixture of oxygen and an inert gas containing from about 1 to about 20 mol percent of oxygen for a period of time within the range of about 0.5 to about 10 hours; and (c) thereafter again bringing monoethanolamine and ethylenediamine into contact with said catalyst under said reaction conditions to again provide an essentially noncyclic product comprising polyethylenepolyamines.

Claim 6

In a continuous process for the manufacture of an essentially noncyclic reaction product comprising polyethylenepolyamines by continuously contacting monoethanolamine with ethylenediamine in a reaction zone in the presense of a pelleted catalyst comprising a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally, chemically bonded to at least the surface thereof under conversion conditions comprising a temperature within the range of about 250° to about 400° C., a pressure of about 500 to about 3000 psig and wherein the mol ratio of ethylenediamine to monoethanolamine is in the range of about 1 to about 5 mols of ethylenediamine per mol of monoethanolamine, whereby, with the passage of time, said catalyst becomes at least partially deactivated: The improvement which comprises: (a) passing an inert gas through said catalyst bed to purge said reaction bed of unreacted feedstock and reaction products; (b) contacting said catalyst bed at a temperature of from about 450° C. to about 550° C. with a mixture of oxygen and an inert gas containing from about 1 to about 20 mol percent of oxygen for a period of time within the range of about 0.5 to about 10 hours; and (c) thereafter again bringing monoethanolamine and ethylenediamine into contact with said catalyst under said reaction conditions to again provide an essentially noncyclic product comprising polyethylenepolyamines.

Claim 7

A method as in claim 4 wherein said group IVb metal oxide support is titania.

Claim 8

A method as in claim 4 wherein said group IVb metal oxide is zirconia.

Claim 9

A method as in claim 4 wherein the inert gas is nitrogen.

Claim 10

In a method wherein monoethanolamine is continuously catalytically reacted with ethylenediamine in a reaction zone under conversion conditions including a temperature of from about 250° C. to about 400° C. and a pressure of about 500 to about 3000 psig. in the mol ratio of about 1 to 5 mols of ethylenediamine per mol of monoethanolamine to thereby provide an essentially noncyclic reaction product comprising polyethyleneopolyamines and wherein the pelleted catalyst comprises a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally chemically bonded to at least the surface thereof, whereby with the passage of time said catalyst will become at least partially deactivated: The improvement which comprises: (a) discontinuing the passage of feedstock over said catalyst bed; (b) passing a stream of nitrogen through said bed to purge said bed of unreacted feedstock and reaction products; (c) next charging a lean regeneration gas composed of a mixture of air and nitrogen containing from about 1 to about 3 mol percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400° to about 450° C.; (d) next charging a mixture of air and nitrogen containing about 4 to about 20 mol percent of oxygen over said catalyst bed for about 2 to 10 hours at a temperature of about 450° to 550° C.; (e) next charging air over said catalyst bed at a temperature of about 450° to about 550° C. for about 2 to 3 hours; and (f) again contacting said catalyst with a mixture of monoethanolamine and ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst under said conversion conditions to again provide an essentially linear product comprising polyethyleneopolyamines.

Claim 11

In a method wherein monoethanolamine is continuously catalytically reacted with ethylenediamine in a reaction zone under conversion conditions including a temperature of from about 250° C. to about 400° C. and a pressure of about 500 to about 3000 psig. in the mol ratio of about 1 to 5 mols of ethylenediamine per mol of monoethanolamine to thereby provide an essentially noncyclic reaction product comprising polyethyleneopolyamines and wherein the pelleted catalyst comprises a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally chemically bonded to at least the surface thereof, whereby with the passage of time said catalyst will become at least partially deactivated: The improvement which comprises: (a) discontinuing the passage of feedstock over said catalyst bed; (b) passing a stream of nitrogen through said bed to purge said bed of unreacted feedstock and reaction products; (c) next charging a lean regeneration gas composed of a mixture of air and nitrogen containing from about 1 to about 3 mol percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400° to about 450° C.; (d) next charging a mixture of air and nitrogen containing about 4 to about 20 mol percent of oxygen over said catalyst bed for about 2 to 10 hours at a temperature of about 450° to 550° C.; (e) next charging air over said catalyst bed at a temperature of about 450° to about 550° C. for about 2 to 3 hours; and (f) again contacting said catalyst with a mixture of monoethanolamine and ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst under said conversion conditions to again provide an essentially linear product comprising polyethyleneopolyamines.

Claim 12

In a method wherein monoethanolamine is continuously catalytically reacted with ethylenediamine in a reaction zone under conversion conditions including a temperature of from about 250° C. to about 400° C. and a pressure of about 500 to about 3000 psig. in the mol ratio of about 1 to 5 mols of ethylenediamine per mol of monoethanolamine to thereby provide an essentially noncyclic reaction product comprising polyethylenepolyamines and wherein the pelleted catalyst consists essentially of a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally chemically bonded to at least the surface thereof; whereby with the passage of time said catalyst will become at least partially deactivated: The improvement which consists essentially of the steps of: (a) discontinuing the passage of feedstock over said catalyst bed; (b) passing a stream of nitrogen through said bed to purge said bed of unreacted feedstock and reaction products; (c) next charging a lean regeneration gas composed of a mixture of air and inert gas containing from about 1 to about 3 mol percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400° to about 450° C.; (d) next charging a mixture of air and inert gas containing about 4 to about 20 mol percent of oxygen over said catalyst bed for about 2 to 10 hours at a temperature of about 450° to 550° C.; (e) next charging air over said catalyst bed at a temperature of about 450° to about 550° C. for about 2 to 3 hours; (f) next flushing said catalyst bed with an inert gas; and (g) again contacting said catalyst with a mixture of monoethanolamine and ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst under said conversion conditions to again provide an essentially linear product comprising polyethylenepolyamines.

Claim 13

In a method wherein monoethanolamine is continuously catalytically reacted with ethylenediamine in a reaction zone under conversion conditions including a temperature of from about 250° C. to about 400° C. and a pressure of about 500 to about 3000 psig. in the mol ratio of about 1 to 5 mols of ethylenediamine per mol of monoethanolamine to thereby provide an essentially noncyclic reaction product comprising polyethylenepolyamines and wherein the pelleted catalyst consists essentially of a group IVb metal oxide support having from about 0.5 to about 10 wt. % of phosphorous thermally chemically bonded to at least the surface thereof; whereby with the passage of time said catalyst will become at least partially deactivated: The improvement which consists essentially of the steps of: (a) discontinuing the passage of feedstock over said catalyst bed; (b) passing a stream of nitrogen through said bed to purge said bed of unreacted feedstock and reaction products; (c) next charging a lean regeneration gas composed of a mixture of air and inert gas containing from about 1 to about 3 mol percent of oxygen over said catalyst for a period of time within the range of about 1 to 2 hours at a temperature of about 400° to about 450° C.; (d) next charging a mixture of air and inert gas containing about 4 to about 20 mol percent of oxygen over said catalyst bed for about 2 to 10 hours at a temperature of about 450° to 550° C.; (e) next charging air over said catalyst bed at a temperature of about 450° to about 550° C. for about 2 to 3 hours; (f) next flushing said catalyst bed with an inert gas; and (g) again contacting said catalyst with a mixture of monoethanolamine and ethylenediamine in said reaction zone in the presence of said thus regenerated catalyst under said conversion conditions to again provide an essentially linear product comprising polyethylenepolyamines.

Claim 14

A method as in claim 9 wherein the group IVb metal oxide support is titania.

Claim 15

A method as in claim 9 wherein the group IVb metal oxide support is zirconia.