Preparation of linear polyethylenepolyamines with modified catalysts

Claim 2

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous 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 pelleted group IV b metal oxide having thermally chemically bonded thereto from about 0.5 wt. % to about 10 wt. % of phosphorous derived from phosphoryl chloride or phosphorous bromide, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 mols 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 in claim 1, wehrein the group IV b metal oxide is titania.

Claim 4

A method as in claim 1, wherein the source of phosphorus is phosphoryl chloride.

Claim 5

A method as in claim 1, wherein the source of phosphorus is phosphorus bromide.

Claim 6

A method as in claim 1, wherein the group IV b metal oxide is zirconia.

Claim 7

A method as in claim 5, wherein the source of phosphorus is phosphoryl chloride.

Claim 8

A method as in claim 5, wherein the source of phosphorus is phosphorus bromide.

Claim 9

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 together with the said feedstock.

Claim 10

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous 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 pelleted group IV b metal oxide having thermally chemically bonded thereto phosphorous derived from phosphoryl chloride or phosphorous bromide, said catalyst having been prepared by impregnating pellets of a group IV b metal oxide with a liquid containing, as a halide, phosphoryl chloride or phosphorous bromide, heating said impregnated pellets of about 100° C. to about reflux temperature for a period of time within the range of about 0.5 to 5 hours sufficient to thermally chemically bond from about 0.5 wt. % to about 10 wt. % of phosphorous to said pellets, and thereafter hydrolysing said halide and 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 mols 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 11

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous 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 pelleted group IV b metal oxide having thermally chemically bonded thereto phosphorous derived from phosphoryl chloride or phosphorous bromide, said catalyst having been prepared by impregnating pellets of a group IV b metal oxide with a liquid containing, as a halide, phosphoryl chloride or phosphorous bromide, heating said impregnated pellets of about 100° C. to about reflux temperature for a period of time within the range of about 0.5 to 5 hours sufficient to thermally chemically bond from about 0.5 wt. % to about 10 wt. % of phosphorous to said pellets, and thereafter hydrolysing said halide and 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 mols 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 12

A method as in claim 9, wherein the group IV b metal oxide is titania.

Claim 13

A method as in claim 9, wherein the group IV b metal oxide is zirconia.

Claim 14

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using a catalyst composition consisting essentially of a pelleted group IV b metal oxide having thermally, chemically bonded thereto from about 0.5 wt. % to about 10 wt. % of phosphorous derived from phosphoryl chloride or phosphorous bromide, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 mols 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 15

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using a catalyst composition consisting essentially of a pelleted group IV b metal oxide having thermally, chemically bonded thereto from about 0.5 wt. % to about 10 wt. % of phosphorous derived from phosphoryl chloride or phosphorous bromide, b. continuously contacting a mixture of ethylenediamine and monoethanolamine in a molar ratio of about 1 to 5 mols 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 16

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using a catalyst composition consisting essentially of a pelleted group IV b metal oxide having thermally chemically bonded thereto phosphorous derived from phosphoryl chloride or phosphorous bromide, said catalyst having been prepared by impregnating pellets of a group IV b metal oxide with a liquid containing, as a halide, phosphoryl chloride or phosphorous bromide, heating said impregnated pellets at a temperature of about 100° C. to about reflux temperature for a period of time within the range of about 0.5 to 5 hours sufficient to thermally chemically bond from about 0.5 wt. % to about 10 wt. % of phosphorous to said pellets, and thereafter hydrolysing said halide and 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 mols 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 17

In a method wherein monoethanolamine is reacted with ethylenediamine in the presence of a phosphorous containing catalyst to provide an essentially noncyclic product comprising polyethylenepolyamines, the improvement for conducting said process on a continuous basis which comprises: a. using a catalyst composition consisting essentially of a pelleted group IV b metal oxide having thermally chemically bonded thereto phosphorous derived from phosphoryl chloride or phosphorous bromide, said catalyst having been prepared by impregnating pellets of a group IV b metal oxide with a liquid containing, as a halide, phosphoryl chloride or phosphorous bromide, heating said impregnated pellets at a temperature of about 100° C. to about reflux temperature for a period of time within the range of about 0.5 to 5 hours sufficient to thermally chemically bond from about 0.5 wt. % to about 10 wt. % of phosphorous to said pellets, and thereafter hydrolysing said halide and 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 mols 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 18

A method as in claim 13, wherein the group IV b metal oxide is titania.

Claim 19

A method as in claim 13, wherein the group IV b metal oxide is zirconia.