Catalytic preparation of linear polyethylenepolyamines

Claim 2

In a method wherein monoethanolamine is reacted with ethylenediamine in a reaction zone in the presence of a phosphorus containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using, as a catalyst, a thermally activated pelleted group IVb metal oxide having about 0.5 to about 10 wt. % of phosphorus thermally chemically bonded to at least the surface thereof, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole of monoethanolamine with said pelleted catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

Claim 3

A method as claim 1, wherein the group IVb metal oxide is titania.

Claim 4

A method as in claim 2, wherein the source of phosphorus is phosphoric acid.

Claim 5

A method as in claim 2, wherein the titania pellets are initially treated with phosphoric acid and are thereafter treated with aluminum nitrate.

Claim 6

A method as in claim 1, wherein the reaction product is fractionated to obtain at least a fraction comprising diethylenetriamine and wherein at least a portion of said diethylenetriamine is recycled to the reaction zone.

Claim 7

In a method wherein monoethanolamine is reacted with ethylenediamine in a reaction zone in the presence of a phosphorus-containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using, as a catalyst, a composition prepared by treating pellets of a group IVb metal oxide with a liquid containing a liquid or liquefiable phosphorus compound at a temperature within the range of about 100° to about 150° C. for about 0.5 to about 5 hours to thermally chemically bond to at least the surface of said pellets from about 0.5 wt. % to about 10 wt. % of phosphorus and thereafter water washing, recovering and drying the thus treated pellets, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole of monoethanolamine with said pelleted catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

Claim 8

In a method wherein monoethanolamine is reacted with ethylenediamine in a reaction zone in the presence of a phosphorus-containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using, as a catalyst, a composition prepared by treating pellets of a group IVb metal oxide with a liquid containing a liquid or liquefiable phosphorus compound at a temperature within the range of about 100° to about 150° C. for about 0.5 to about 5 hours to thermally chemically bond to at least the surface of said pellets from about 0.5 wt. % to about 10 wt. % of phosphorus and thereafter water washing, recovering and drying the thus treated pellets, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 moles of ethylenediamine per mole of monoethanolamine with said pelleted catalyst at a temperature of about 250° to about 400° C. and a pressure of about 500 to about 3000 psig. to obtain an essentially noncyclic reaction product.

Claim 9

A method as in claim 6 wherein the group IVb metal oxide is titania and wherein the treated pellets contain titanium triphosphate.

Claim 10

A method as in claim 6 wherein the groop IVb metal oxide is zirconia and wherein the treated pellets contain an amorphous compound of zirconia and phosphorous.