Method for dehydrating and isomerising alcohols using a non-zeolite aluminosilicate solid

Patent metadata

Field	Value
Publication number	US-9758442-B2
Application number	US-201314388859-A
Country	US
Kind code	B2
Filing date	Mar 25, 2013
Priority date	Mar 29, 2012
Publication date	Sep 12, 2017
Grant date	Sep 12, 2017

Abstract

Process for simultaneous dehydration and skeletal isomerization of a feedstock that comprises at least one C 4 monoalcohol and that contains between 0.5 and 50% water, for the purpose of producing C 4 alkenes, with said process operating at a temperature of between 250 and 550° C., under a pressure of between 0.1 and 1 MPa, with an hourly volumetric flow rate of between 0.1 and 10 h −1 , characterized in that it uses a catalyst that comprises at least one non-zeolitic aluminosilicate-type solid.

First claim

The invention claimed is:

1. A process for simultaneous dehydration and skeletal isomerization of a feedstock comprising at least one C 4 monoalcohol and between 0.5% by weight and 50% by weight of water to produce C 4 alkenes, the process comprising contacting the feedstock with a catalyst at a temperature of between 250° C. and 550° C., under a pressure of between 0.1 MPa and 1 MPa, and with an hourly volumetric flow rate of between 0.1 h −1 and 10 h −1 ,
wherein the catalyst comprises at least one non-zeolitic aluminosilicate solid with a silica content of between 4% by weight and 95% by weight of said non-zeolitic aluminosilicate solid, said non-zeolitic aluminosilicate solid having the following further characteristics:
a total pore volume, measured by mercury intrusion porosimetry, of between 0.1 ml/g and 0.7 ml/g,
a total pore volume, measured by nitrogen adsorption isotherm, of between 0.1 ml/g and 0.7 ml/g,
a BET specific surface area of between 100 m 2 /g and 550 m 2 /g,
a pore volume, measured by mercury intrusion porosimetry, in pores with a diameter of greater than 140 Å, of less than 0.1 ml/g,
a pore volume, measured by mercury intrusion porosimetry, in pores with a diameter of greater than 500 Å, of less than 0.01 ml/g, and
a mean pore diameter of between 20 Å and 140 Å,

and wherein said non-zeolitic aluminosilicate solid is prepared according to a process comprising the following stages:
stage a) forming a reaction mixture by mixing at least one aluminum compound that is partially soluble in an acid medium with either (i) at least one silicic compound that is totally soluble in the reaction mixture or (ii) a combination comprising the at least one silicic compound and the at least one aluminum compound, and obtaining a precursor solid,
stage b) shaping said precursor solid, and
stage c) subjecting said precursor solid to heat treatment and/or hydrothermal treatment with said stage c) being carried out before or after said stage b).

2. The process according to claim 1 , wherein said feedstock has a mass ratio of isobutanol to all of the C 4 monoalcohols in the feedstock of greater than 50%.

3. The process according to claim 1 , wherein said at least one silicic compound used in said stage a) is selected from the group consisting of a silicic acid, a silicic acid sol, a water-soluble alkaline silicate, and a cationic salt of silicon, and mixtures thereof.

4. The process according to claim 1 , wherein said at least one aluminum compound used in said stage a) is selected from the group consisting of a boehmite, a pseudo-boehmite, and an amorphous or essential amorphous gel, and mixtures thereof.

5. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has a silica content of between 4% by weight and 25% by weight of said non-zeolitic aluminosilicate solid.

6. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has a silica content of between 4% by weight and 15% by weight of said non-zeolitic aluminosilicate solid.

7. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has a silica content of between 35% by weight and 95% by weight of said non-zeolitic aluminosilicate solid.

8. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has a silica content of between 35% by weight and 50% by weight of said non-zeolitic aluminosilicate solid.

9. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has a cationic impurities content of less than 0.1% by weight of the catalyst.

10. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid has an anionic impurities content of less than 1% by weight of the catalyst.

11. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid is homogenous on the micrometer scale.

12. The process according to claim 1 , wherein acid properties of said non-zeolitic type aluminosilicate solid are such that its catalytic activity in the m-xylene isomerization test is between 0.02 mmol·h −1 g solid −1 and 0.4 mmol·h −1 g solid −1 .

13. The process according to claim 1 , wherein said catalyst integrally consists of the non-zeolitic aluminosilicate solid.

14. The process according to claim 1 , wherein said non-zeolitic aluminosilicate solid is shaped in the form of spheres, spheroids, pellets or extrudates.

15. The process of claim 1 , wherein the C 4 alkenes produced comprise isobutene and 1-butene.

16. The process of claim 1 , wherein the feedstock is contacted with the catalyst at a temperature between 300° C. and 450° C., under a pressure of between 0.1 MPa and 0.5 MPa, and with an hourly volumetric flow rate of between 0.7 h −1 and 5 h −1 .

17. The process according to claim 1 , wherein the said non-zeolitic aluminosilicate solid has the following characteristics:
a total pore volume, measured by mercury intrusion porosimetry, of between 0.1 ml/g and 0.5 ml/g,
a total pore volume, measured by nitrogen adsorption isotherm, of between 0.1 ml/g and 0.5 ml/g,
a BET specific surface area of between 150 m 2 /g and 350 m 2 /g,
a pore volume, measured by mercury intrusion porosimetry, in pores with a diameter of greater than 140 Å, of less than 0.05 ml/g,
a pore volume, measured by mercury intrusion porosimetry, in pores with a diameter of greater than 500 Å, of less than 0.01 ml/g, and
a mean pore diameter of between 20 Å and 140 Å.

Assignees

• Ifp Energies Now

Inventors

• Chaumonnot Alexandra
• Coupard Vincent
• Maury Sylvie

Classifications

• C07C11/09

  Isobutene · CPC title

• C07C11/08

  with four carbon atoms · CPC title

• B01J35/108

  Operations & Transport · mapped topic

• B01J35/1061

  Operations & Transport · mapped topic

• C07C1/24 Primary

  by elimination of water · CPC title