Method for preparing acrolein from glycerol or glycerine

a technology of glycerol or glycerine, which is applied in the direction of catalyst regeneration/reactivation, physical/chemical process catalysts, metal/metal-oxide/metal-hydroxide catalysts, etc., can solve the problems of not being able to absorb such a surplus, applications that are clearly insufficient for absorbing, etc., to avoid parasitic reactions and easy to adjust the concentration of glycerol in the solution

Inactive Publication Date: 2011-11-24
AVEATIS ANIMAL NUTRITION SA +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0047]Another advantage of the method of the invention lies in the form of the starting glycerol or glycerine which may be in pure or partly purified form or in solution, notably an aqueous solution. Advantageously, an aqueous solution of glycerol is used. In an aqueous solution, the concentration of the glycerol is preferably of at least 1%, at best it varies from 10 to 50% by weight and preferably between 15 and 30% by weight in the reactor. The glycerol concentration should not be too high for the purpose of avoiding parasitic reactions which burden the acrolein yield, like the formation of glycerol ethers or acetalization reactions between the produced acrolein and the non-converted glycerol. Moreover, the glycerol solution should not be too diluted, because of a redhibitory energy cost induced by the evaporation of the glycerol. In every case, it is easy to adjust the glycerol concentration of the solution by partly or totally recycling the water produced by the relevant reaction. Energy optimization at the bounds of the synthesis tends to recover heat at the reaction output in order to vaporize the flow of glycerol supplied to the reactor.

Problems solved by technology

These applications will prove to be clearly insufficient for absorbing the amounts of glycerol which will be co-produced with biodiesels and although in progress, the conventional glycerol market (soaps, pharmacy, .
. . ) will not be able either to absorb such a surplus.

Method used

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  • Method for preparing acrolein from glycerol or glycerine
  • Method for preparing acrolein from glycerol or glycerine
  • Method for preparing acrolein from glycerol or glycerine

Examples

Experimental program
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example 1

Preparation and Characterization of the Catalyst A

[0076]A catalyst according to the invention of the zirconium and niobium oxide type prepared from zirconium oxide hydrate and ammonium oxalate-niobiate, (NH4)(C2O4)2NbO.xH2O (Aldrich, 99.99%). The zirconium oxide hydrate is prepared by co-precipitation of a solution of zirconium oxonitrate ZrO(NO3)2.xH2O (Aldrich, 99%) and a 28% ammonia solution at pH=8.8.

[0077]The ammonium oxalate-niobiate is dissolved in permuted water acidified with concentrated HNO3 at pH˜0.5 and heated to 45° C. After returning to room temperature, the zirconium hydroxide hydrate is added in a ZrO2 / Nb2O5 molar ratio of 3:1, the hydration degree of the zirconium oxide hydrate is determined beforehand by thermogravimetric analysis (TGA). After 24 h with stirring, the mixture is filtered and the solid is calcined under air flow at 600° C. The specific surface area of this catalyst is 40 m2 / g. The specific surface areas of the solids were measured with the BET (Brun...

example 2

Preparation and Characterization of the Catalyst A′

[0078]A catalyst according to the invention of the zirconium and niobium oxide type is prepared according to the procedure described by Kantcheva. et. Al, Catalysis Communications (2009), 9(5), p 874-879, by impregnation of zirconium oxide hydrate.

[0079]The zirconium oxide hydrate was prepared by co-precipitation of a solution of zirconium oxonitrate ZrO(NO3)2.xH2O (Aldrich, 99%) and of a 28% ammonia solution. The precursor of Nb(V), (NH4)(C2O4)2NbO.xH2O (Aldrich, 99.99%) is added with stirring to a 35% hydrogen peroxide solution (Sigma Aldrich) acidified to pH≈0.5 with concentrated HNO3 and heated to 50° C. The H2O2 / oxalate molar ratio is 13 / 1. The solution is heated for 1 h at 50° C. before being cooled down to room temperature. Next, the zirconium oxide hydrate is again added while ensuring a ZrO2:Nb2O5 ratio of 6:1, the hydration degree of the zirconium oxide hydrate being determined by thermogravimetric analysis (TGA). The mixt...

example 3

Preparation and Characterization of the Catalyst E

[0081]A catalyst according to the invention of the zirconium and niobium oxide type is prepared according to the procedure described by Kantcheva. et. Al, (Catalysis Communications 9(5), (2008) p 874-879), by impregnation of zirconium oxide hydrate with a solution containing a mixed ammonium and niobium oxalate.

[0082]The precursor of Nb(V), (NH4)(C2O4)2NbO.xH2O (Aldrich, 99.99%) is added with stirring to a 35% hydrogen peroxide solution (Sigma Aldrich) acidified to pH˜0.5 with concentrated HNO3 and heated to 50° C. The H2O2 / oxalate molar ratio is 13 / 1. The solution is heated for 1 h at 50° C. before being cooled down to room temperature. Next, the zirconium oxide hydrate prepared beforehand by co-precipitation of a solution of zirconium oxonitrate (ZrO(NO3)s.xH2O (Aldrich, 99%) and of a 28% ammonia solution, is added while ensuring a ZrO2:Nb2O5 ratio of 6:1. The mixture is maintained with stirring at room temperature for 24 hrs and t...

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Abstract

The invention relates to a method for preparing acrolein from glycerol or glycerine, comprising dehydrating glycerol or glycerine in the presence of a catalyst consisting of at least a) a mixed oxide of zirconium and at least one metal, said metal being selected from niobium, tantalum and vanadium, b) a zirconium oxide and at least one metal oxide, the metal being selected from niobium, tantalum and vanadium, c) a silicon oxide and a mixed oxide of zirconium and at least one metal, the metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon, d) a silicon oxide and a mixed oxide of zirconium and at least one metal, the metal being selected from tungsten, cerium, manganese, niobium, tantalum, vanadium and titanium, e) a titanium oxide and a mixed oxide of zirconium and at least one metal, said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon, f) a titanium oxide and a mixed oxide or zirconium and at least one metal, said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon. The method can be used for producing -3-(methylthio)propionic (MMP) aldehyde, 2-hydroxy-4-methylthiobutyronitrile (HMTBN), methionine and analogues thereof from acrolein.

Description

TECHNICAL FIELD[0001]The present invention relates to a catalytic method for making acrolein by dehydration of glycerol or glycerine and to the application of such a method.BRIEF SUMMARY[0002]By glycerol is meant a glycerol either purified or not, preferably stemming from biomass and notably a highly purified or partly purified glycerol. A purified glycerol has a purity greater than or equal to 98%, obtained by distillation of glycerine. A non-purified or only partly purified glycerol may be in solution in methanol when it for example stems from transesterification of triglycerides, as described hereafter. By glycerine is notably meant glycerine of natural origin, stemming from hydrolysis of vegetable oils and / or animal fats, or more or less purified or refined or else raw glycerine of synthetic origin stemming from petroleum. As an example, raw glycerine has a titer comprised between 80 and 85%. Thus, subsequently in the description, reference is mainly made to the conversion of a ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C45/29C07C253/00C07C51/235C07C381/00
CPCB01J23/20B01J23/92B01J38/12C07C45/52C07C319/18C07C45/66C07C47/22C07C323/22C07C323/52C07C323/58Y02P20/584
Inventor BELLIERE-BACA, VIRGINIELORIDANT, STEPHANEMILLET, JEAN-MARCLAURIOL-GARBEY, PASCALINE
Owner AVEATIS ANIMAL NUTRITION SA
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