Method for continuous preparation of pentamethyldiethylenetriamine and catalyst system for the method

Abstract

The invention discloses a method for continuously preparing pentamethyldiethylenetriamine and a catalyst system used in the method. The method comprises: mixing diethylenetriamine, a solvent, hydrogen, and formaldehyde at a certain reaction temperature, pressure, Pass through two-stage fixed-bed reactors under space velocity conditions to obtain pentamethyldiethylenetriamine reaction liquid. The first-stage reactor is filled with supported copper-based catalyst, and the reaction temperature is controlled at 60-100°C; the second-stage reactor is filled with supported palladium-based catalyst, and the reaction temperature is controlled at 100-130°C. By adopting two-stage reactions with different catalysts and different reaction conditions, the generation of by-products of amides can be effectively reduced, thereby increasing the yield of pentamethyldiethylenetriamine. In addition, the present invention adopts a fixed bed continuous process, which can avoid a series of problems caused by catalyst crushing into the reaction liquid post-treatment system. This process has the advantages of high degree of automation, low labor intensity, safe process operation, and low production cost. It is suitable for Industrialized mass production.

Description

technical field

[0001] The present invention relates to a kind of preparation method of polyurethane catalyst, more specifically relate to a kind of method for continuously preparing pentamethyldiethylenetriamine and the catalyst system for this method. Background technique

[0002] Pentamethyldiethylenetriamine is a colorless to pale yellow clear liquid, easily soluble in water. It is a highly active catalyst for polyurethane reaction. It mainly catalyzes foaming reaction and is also used to balance overall foaming and gelling reactions. It is widely used in various polyurethane rigid foams, including polyisocyanurate sheet rigid foams. Due to its strong foaming effect, it can improve the foam flow, thus improving the production process and improving the quality of the product. It is often shared with N,N-dimethylcyclohexylamine, etc. The production methods of pentamethyldiethylenetriamine include formaldehyde formic acid method and formaldehyde hydrogenation method. ...

Examples

Embodiment 1

[0047] Preparation of 1# supported copper-based catalyst precursor:

[0048] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Calcined at 450°C for 4h. Prepare a nitrate dipping solution containing 10g copper, 0.1g hafnium and 0.5g zinc with 100ml deionized water, heat to 80°C to form a homogeneous solution, then add 89.4g γ-Al 2 o 3 Carrier, impregnated at 80°C for 12 hours, then baked in an oven at 120°C for 12 hours; finally moved to a muffle furnace, heated at 2-3°C / min to 450°C for 8 hours in an air atmosphere, and cooled naturally The 1# supported copper-based catalyst precursor was obtained. The composition of the catalyst is: copper is 10wt%, hafnium is 0.1wt%, zinc is 0.5wt%, and the rest is γ-Al 2 o 3 , calculated by the corresponding metal element in the total mass of the catalyst.

[0049] Preparation of 1# supported palladium-based catalyst precursor:

[0050] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m ...

Embodiment 2

[0054] Preparation of 2# supported copper-based catalyst precursor:

[0055] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Calcined at 450°C for 4h. Prepare a nitrate dipping solution containing 5g copper, 0.2g hafnium and 1g zinc with 100ml deionized water, heat to 80°C to form a homogeneous solution, then add 93.8gγ-Al 2 o 3 Carrier, impregnated at 80°C for 12 hours, then baked in an oven at 120°C for 12 hours; finally moved to a muffle furnace, heated at 2-3°C / min to 400°C for 6 hours in an air atmosphere, and cooled naturally The 2# supported copper-based catalyst precursor was obtained. The composition of the catalyst is: copper is 5wt%, hafnium is 0.2wt%, zinc is 1wt%, and the rest is γ-Al 2 o 3 , calculated by the corresponding metal element in the total mass of the catalyst.

[0056] Preparation of 2# supported palladium-based catalyst precursor:

[0057] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Ca...

technical field

[0001] The present invention relates to a kind of preparation method of polyurethane catalyst, more specifically relate to a kind of method for continuously preparing pentamethyldiethylenetriamine and the catalyst system for this method. Background technique

[0002] Pentamethyldiethylenetriamine is a colorless to pale yellow clear liquid, easily soluble in water. It is a highly active catalyst for polyurethane reaction. It mainly catalyzes foaming reaction and is also used to balance overall foaming and gelling reactions. It is widely used in various polyurethane rigid foams, including polyisocyanurate sheet rigid foams. Due to its strong foaming effect, it can improve the foam flow, thus improving the production process and improving the quality of the product. It is often shared with N,N-dimethylcyclohexylamine, etc. The production methods of pentamethyldiethylenetriamine include formaldehyde formic acid method and formaldehyde hydrogenation method. ...

Examples

Embodiment 1

[0047] Preparation of 1# supported copper-based catalyst precursor:

[0048] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Calcined at 450°C for 4h. Prepare a nitrate dipping solution containing 10g copper, 0.1g hafnium and 0.5g zinc with 100ml deionized water, heat to 80°C to form a homogeneous solution, then add 89.4g γ-Al 2 o 3 Carrier, impregnated at 80°C for 12 hours, then baked in an oven at 120°C for 12 hours; finally moved to a muffle furnace, heated at 2-3°C / min to 450°C for 8 hours in an air atmosphere, and cooled naturally The 1# supported copper-based catalyst precursor was obtained. The composition of the catalyst is: copper is 10wt%, hafnium is 0.1wt%, zinc is 0.5wt%, and the rest is γ-Al 2 o 3 , calculated by the corresponding metal element in the total mass of the catalyst.

[0049] Preparation of 1# supported palladium-based catalyst precursor:

[0050] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m ...

Embodiment 2

[0054] Preparation of 2# supported copper-based catalyst precursor:

[0055] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Calcined at 450°C for 4h. Prepare a nitrate dipping solution containing 5g copper, 0.2g hafnium and 1g zinc with 100ml deionized water, heat to 80°C to form a homogeneous solution, then add 93.8gγ-Al 2 o 3 Carrier, impregnated at 80°C for 12 hours, then baked in an oven at 120°C for 12 hours; finally moved to a muffle furnace, heated at 2-3°C / min to 400°C for 6 hours in an air atmosphere, and cooled naturally The 2# supported copper-based catalyst precursor was obtained. The composition of the catalyst is: copper is 5wt%, hafnium is 0.2wt%, zinc is 1wt%, and the rest is γ-Al 2 o 3 , calculated by the corresponding metal element in the total mass of the catalyst.

[0056] Preparation of 2# supported palladium-based catalyst precursor:

[0057] Spherical γ-Al 2 o 3 (particle size 3mm, specific surface area 280m 2 / g) Ca...

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