Catalytic process for the production of propylene glycol from glycerol, a copper and cerium catalyst, and a process to produce such catalyst

Patent metadata

Field	Value
Publication number	US-10857522-B2
Application number	US-201515537265-A
Country	US
Kind code	B2
Filing date	Dec 16, 2015
Priority date	Dec 17, 2014
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

A process for producing propylene glycol from glycerol including a catalyst of Cu and Ce at concentrations of up to 15% of each metal. In addition, it is described a catalyst of Cu and Ce to perform the selective reduction of glycerol and the process of production of such catalyst.

First claim

Once described and established the nature of the invention and its embodiment, it is hereby claimed as follows:

1. A process for producing a catalyst; comprising the following steps:
a. grinding an alumina support to produce alumina particles and sieving to a particle size ranging between 35 and 80 mesh;
b. conditioning the alumina particles at 110° C. for one hour and then burning them in air stream at 500° C. for 3 hours;
c. adding drop by drop the solution of the precursor of a first metal on the alumina particles support to damp the whole mass of alumina particles, with ongoing stirring, until wet particles remain united despite the stirring; then, continue adding 5% more solution than the equivalent to the volume of pores belonging to the support;
d. maintaining the impregnated support in a desiccator between 4 and 6 hours;
e. drying in oven at 110° C. for at least 8 hours;
f. burning the dried impregnated support in air stream at a temperature of up to 3000 C for at least 1.5 hours, remaining the metal oxide on the support;
g. cooling in a stream of nitrogen;
h. adding drop by drop the solution of precursor of a second metal on the alumina particles support until damping the whole mass of alumina particles, with ongoing stirring, until the wet particles remain united despite the stirring; then, continue adding 5% more of solution than the equivalent to the volume of the pores belonging to the support;
i. maintaining the impregnated support in a desiccator between 4 and 6 hours;
j. drying in oven at 110° C. for at least 8 hours;
k. burning the dried impregnated support in air stream at a temperature of up to 3000 C for at least 1.5 hours, remaining the metal oxide on the support; and
l. cooling in a stream of nitrogen;

wherein x-ray diffraction of said catalyst shows peaks at 43°, 28° and 56°.

2. The process of claim 1 wherein the first metal of step c) is copper and the second metal of step h) is cerium.

3. The process of claim 1 wherein the first metal of step c) is cerium and the second metal of step h) is copper.

4. The process of claim 1 wherein the catalyst obtained comprises a concentration of cerium of up to 15% by weight and a concentration of copper of up to 15% by weight.

5. The process of claim 1 wherein the catalyst obtained comprises a concentration of cerium of up to 7% by weight and a concentration of copper of up to 7% by weight.

6. A catalyst made by the process of claim 1 and comprising copper and cerium supported on alumina, wherein the concentration of Cu is up to 10% by weight, the concentration of Ce is up to 10% by weight.

7. The catalyst of claim 6 wherein the concentration of Cu is up to 7% by weight and the concentration of Ce is up to 7% by weight.

8. The catalyst of claim 6 comprising: an alumina support with specific surface ranging between 150 and 250 m 2 g −1 and pore volume ranging between 0.1 and 1.0 cm 3 g −1 ; copper oxide; and cerium oxide.

9. A catalytic process for producing propylene glycol by the selective reduction of glycerol comprising the following steps:
a. providing a stream of glycerol and H 2 ;
b. contacting the stream of step with the catalyst of claim 3 ; and
c. obtaining a stream of propylene glycol.

10. The catalytic process of claim 9 wherein the operating conditions of step b comprise the following: a temperature between 170 and 200° C.; a total pressure of 1 atm; a partial pressure of H 2 ranging between 0.3 and 1 atm; a relation of helium/hydrogen ranging between 0 and 3/2; a concentration of glycerol ranging between 20 and 50% in weight; a liquid hourly space velocity ranging between 0.05 and 15.00 h −1 ; and a contact time ranging between 0.03 and 5.00 minutes.

Assignees

• Consejo Nacional De Investigaciones Cientificas Y Tecn Conicet
• Univ Nacional Del Litoral
• Inis Biotech Llc

Inventors

• Comelli Raul Alberto
• Ferrari Lisandro Roberto

Classifications

• B01J2235/10

  Infrared [IR] · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J23/002

  Mixed oxides other than spinels, e.g. perovskite · CPC title