Process for direct synthesis of (meth)acrolein from ethers and/or acetals

Patent metadata

Field	Value
Publication number	US-9714205-B2
Application number	US-201515300444-A
Country	US
Kind code	B2
Filing date	Mar 26, 2015
Priority date	Apr 4, 2014
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

The subject matter of the present invention is a process for direct synthesis of (meth)acrolein from a reactive mixture comprising at least one compound chosen from ethers, acetals or hemiacetals derived from linear alcohols comprising from 1 to 3 carbon atoms. Examples of compounds are dimethyl ether, diethyl ether, methyl ethyl ether, dimethoxymethane, diethoxymethane, dipropoxymethane, 1,1-dimethoxyethane or 1,1-diethoxyethane. The process of the invention comprises two successive phases: oxidation then aldol condensation, which can be carried out in the presence of a solid oxidation catalyst chosen from molybdenum-based catalysts and optionally of an aldol condensation catalyst. These two phases are carried out in a reaction system comprising a single reactor or optionally two reactors in cascade.

First claim

The invention claimed is:

1. A process for direct synthesis of (meth)acrolein comprising i) reacting a reactive mixture comprising at least one reactive compound, oxygen and a non-reactive diluent gas, in a reaction assembly operated in the gas phase at a temperature of between 200° C. and 400° C. and at a pressure of between 1 and 10 bar, in the presence of a solid oxidation catalyst chosen from molybdenum-based catalysts and optionally of an aldol condensation catalyst, and then ii) recovering gas effluent comprising the (meth)acrolein formed in the presence of water coproduced by the reaction,
wherein the at least one reactive compound comprises a compound of formula (I) R 1 —O—R 2 wherein,

R 1 is H or a methyl, ethyl or propyl radical, and
R 2 is a methyl, ethyl or propyl radical or a radical of formula CH 2 —O—R 3 , CH(CH 3 )—O—R 3 or CH(CH 2 —CH 3 )—O—R 3 , with R 3 being a methyl, ethyl or propyl radical,
wherein R 1 and R 2 are identical or different, or R 1 and R 3 are identical or different, and
wherein, when R 1 is H, R 2 is other than a methyl, ethyl or propyl radical, failing which the reactive mixture comprises an additional reactive compound of formula (I), having R 1 other than H, and
wherein the at least one reactive compound is chosen such that the R 1 , R 2 and R 3 radicals present in its structure are capable of forming (meth)acrolein by an oxidation reaction coupled to an aldol condensation reaction.

2. The process as claimed in claim 1 , wherein the reactive mixture is reacted in the presence of a solid oxidation catalyst chosen from molybdenum-based catalysts and the presence of an aldol condensation catalyst.

3. The process as claimed in claim 1 , wherein the at least one reactive compound comprises dimethyl ether, diethyl ether, methyl ethyl ether, dimethoxymethane, diethoxymethane, dipropoxymethane, 1,1-dimethoxyethane or 1,1-diethoxyethane.

4. The process as claimed in claim 1 , wherein when acrolein is synthesized, the at least one reactive compound comprises dimethyl ether/diethyl ether; methyl ethyl ether; dimethyl ether/diethoxymethane; diethyl ether/dimethoxymethane; dimethoxymethane/diethoxymethane; dimethoxymethane/diethoxyethane; dimethyl ether/ethanol; diethyl ether/methanol; or dimethoxymethane/ethanol.

5. The process as claimed in claim 1 , wherein when methacrolein is synthesized, the at least one reactive compound comprises dipropoxymethane; dipropyl ether/methanol; or dipropyl ether/dimethyl ether.

6. The process as claimed in claim 1 , wherein the flow rate for introduction of the at least one reactive compound into the reaction assembly is such that a total content of the at least one reactive compound in the reactive mixture is between 1% and 15% by volume.

7. The process as claimed in claim 1 , wherein the oxygen introduction flow rate is such that an oxygen content of the reactive mixture is not greater than 15% by volume.

8. The process as claimed in claim 1 , wherein the reaction is carried out with an hourly space velocity of between 2000 and 40,000 h −1 .

9. The process as claimed in claim 1 , wherein the oxidation catalyst is represented by the following general formula:
A a X b Mo c Z d O e   (I)

in which
A is at least one cation selected from the group consisting of the elements of groups 1 to 16 of the Periodic Table of Elements and lanthanides,
X is P or Si,
Z is at least one element selected from the group consisting of W, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn, Ag, As, Ge, B, Bi, La, Ba, Sb, Te, Ce and Pb,
O is oxygen,
a, b, c and d are indices comprising whole or decimal numbers which satisfy the following ranges
0≦a≦9
0≦b≦2
0<c≦12
0≦d≦12
such that a+b+d>0
and e is a number determined by the total degree of oxidation of the elements.

10. The process as claimed in claim 1 , wherein the reaction is carried out in a single reactor with a catalytic bed comprising a single molybdenum-based oxidation catalyst or optionally a physical mixture of a molybdenum-based oxidation catalyst with a condensation catalyst.

11. The process as claimed in claim 10 , wherein the reaction is carried out in a single reactor with a catalytic bed comprising a physical mixture of a molybdenum-based oxidation catalyst with a condensation catalyst.

12. The process as claimed in claim 1 , wherein the reaction is carried out in a single reactor with two superimposed catalytic beds, the oxidation catalytic bed being placed upstream of the condensation catalytic bed.

Assignees

• Arkema France

Inventors

• Dubois Jean-Luc

Classifications

• B01J35/023

  Operations & Transport · mapped topic

• B01J23/002

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

• B01J35/1061

  Operations & Transport · mapped topic

• B01J23/04

  Alkali metals · CPC title

• C07C45/38 Primary

  being a primary hydroxyl group · CPC title