Heterogeneous synthesis of methylene dianiline
The present invention relates to a catalytic material for the preparation of one or more of 4,4′-methylenedianiline, 2,2′-methylenedianiline, 2,4′-methylenedianiline, and oligomers of two or more thereof, the catalytic material comprising an oxidic support, wherein the oxidic support comprises an element E OS1 selected from the group consisting of Ti, Zr, Al, Si, and mixtures of two or more thereof, and further comprising a supported material supported on the oxidic support, wherein the supported material comprises an element ESM1 selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, W, Ge, Sn, Sc, Y, La, Ce, Nd, Pr, Hf, Cr, Fe, Co, Ni, Cu, Zn, Pb and mixtures of two or more thereof. Further, the present invention relates in particular to a process for the preparation of a catalytic material and to a process for the preparation of one or more of 4,4′-methylenedianiline, 2,2′-methylenedianiline, 2,4′-methylenedianiline and oligomers of two or more thereof.
1 . A catalytic material for use in the preparation of one or more of 4,4′-methylenedianiline, 2,2′-methylenedianiline, 2,4′-methylenedianiline, and oligomers of two or more thereof, the catalytic material comprising an oxidic support, wherein the oxidic support comprises titania, zirconia, alumina, or silica, and further comprising a supported material supported on the oxidic support, wherein the supported material comprises an element E SM1 selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, W, Ge, Sn, Sc, Y, La, Ce, Nd, Pr, Hf, Cr, Fe, Co, Ni, Cu, Zn, Pb, and mixtures of two or more thereof, the catalytic material exhibiting a Brønsted acid site density of equal or less than 100 μmol/g, wherein the Brønsted acid site density is determined by pyridine adsorption using FTIR spectroscopy.
2 . The catalytic material of claim 1 , wherein E SM1 is selected from the group consisting of Sc, Y, La, Ce, Nd, Pr, Hf, Cr, Fe, Co, Ni, Cu, Zn, Pb, Zr, and mixtures of two or more thereof.
3 . The catalytic material of claim 1 , wherein the catalytic material comprises E SM1 , calculated as element, in an amount in the range of from 0.1 to 10 weight-%, based on the total weight of the oxidic support.
4 . The catalytic material of claim 1 , wherein the supported material further comprises an element E SM2 selected from groups 3-14 of the periodic system of elements, rare earth metals, and mixtures of two or more thereof, wherein E SM2 is different to E SM1 .
5 . The catalytic material of claim 4 , wherein E SM2 is selected from groups 3, 4, 5, 6, 8, 10, 11, 12, 14, rare earth metals, and mixtures of two or more thereof.
6 . The catalytic material of claim 4 , wherein the catalytic material comprises E SM2 , calculated as element, in an amount in the range of from 0.1 to 3 weight-%, based on the total weight of the oxidic support.
7 . The catalytic material of claim 1 , wherein from 95 to 100 weight-% of the catalytic material consists of the oxidic support and the supported material, based on the total weight of the catalytic material.
8 . The catalytic material of claim 1 , having a mesopore volume V meso in the range of from 0.50 to 1.30 cm 3 /g, wherein the mesopore volume is determined according to the Barrett-Joyner-Halenda (BJH) method.
9 . The catalytic material of claim 1 , exhibiting an acid site density in the range of from 0.050 to 1.000 mmol/g, as determined by temperature-programmed-desorption of NH 3 (NH 3 -TPD).
10 . A process for the preparation of the catalytic material of claim 1 , the process comprising:
(i) preparing a mixture comprising a liquid solvent system, a source of an oxidic support comprising titania, zirconia, alumina, or silica, a source of an element E SM1 selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, W, Ge, Sn, Sc, Y, La, Ce, Nd, Pr, Hf, Cr, Fe, Co, Ni, Cu, Zn, Pb, and mixtures of two or more thereof, and optionally a source of an element E SM2 selected from groups 3-14 of the periodic system of elements, rare earth metals, and mixtures of two or more thereof, wherein the optional E SM2 is different to E SM1 , obtaining a precursor of the catalytic material; and
(ii) calcining the precursor of the catalytic material in a gas atmosphere, obtaining the catalytic material.
11 . A catalytic material obtainable and/or obtained by the process of claim 10 .
12 . A process for the preparation of one or more of 4,4′-methylenedianiline, 2,2′-methylenedianiline, 2,4′-methylenedianiline, and oligomers of two or more thereof, the process comprising:
(1) providing a reactor comprising a reaction zone, wherein the reaction zone comprises a catalytic material according to claim 1 ;
(2) providing a feed into the reaction zone according to (1), wherein the feed comprises one or more of aniline, formaldehyde, and N,N′-diphenylmethylenediamine;
(3) converting the feed under reaction conditions in the reaction zone; obtaining a product mixture comprising one or more of 4,4′-methylenedianiline, 2,2′-methylenedianiline, 2,4′-methylenedianiline, and oligomers of two or more thereof; and
(4) separating the product mixture from the reaction zone.
13 . The catalytic material of claim 1 , having a BET specific surface area S BET in a range from 100 to 310 m 2 /g, wherein the BET specific surface area S BET is determined according to BET method.