Copper-iron-based catalytic composition comprising zeolites, method for producing such catalytic composition and process using such catalytic composition for the conversion of syngas to higher alcohols

Patent metadata

Field	Value
Publication number	US-11607673-B2
Application number	US-202017425932-A
Country	US
Kind code	B2
Filing date	Jan 28, 2020
Priority date	Feb 1, 2019
Publication date	Mar 21, 2023
Grant date	Mar 21, 2023

Abstract

The present disclosure relates to a catalyst composition comprising copper and iron on a support for use in a process for the synthesis of higher alcohols from a syngas feed stream comprising hydrogen and carbon monoxide, the catalyst composition being remarkable in that the support is one or more zeolite, in that the total content of iron and copper is ranging from 1 to 10 wt. % based on the total weight of the catalyst composition and as determined by inductively coupled plasma optical emission spectroscopy, in that the Cu/Fe bulk molar ratio is ranging from 1.1:1.0 to 5.0:1.0 as determined by XRF spectroscopy.

First claim

The invention claimed is:

1. A catalyst composition comprising an active phase comprising copper and iron on a support for use in a process for the synthesis of higher alcohols from a syngas feed stream comprising hydrogen and carbon monoxide, the catalyst composition being characterized in that the support is one or more zeolites having a Si/Al molar ratio ranging from 10 to 200 as determined by inductively coupled plasma optical emission spectroscopy (ICP-OES), in that the total content of iron and copper is ranging from 3.0 to 10 wt. % based on the total weight of the catalyst composition and as determined by X-ray fluorescence spectroscopy, in that the Cu/Fe bulk molar ratio is ranging from 1.1:1.0 to 5.0:1.0 as determined by X-ray fluorescence spectroscopy and, wherein said catalyst composition is a reduced catalyst composition as determined by X-ray diffraction, wherein the catalyst composition is devoid of iron oxide wherein iron oxide is Fe 2 O 3 , and wherein the total content of iron and copper of the catalyst composition ranges of the from 3.0 to 8.0 wt. % based on the total weight of the catalyst composition and as determined by X-ray fluorescence spectroscopy.

2. The catalyst composition according to claim 1 , characterized in that the one or more zeolites are selected from MFI, FAU, MOR, FER, BEA, TON, MTT, OFF families, or any mixture thereof.

3. The catalyst composition according to claim 1 , characterized in that the one or more zeolites are or comprises ZSM-5.

4. The catalyst composition according to claim 1 , characterized in that said catalyst composition includes one or more zeolites having a pore volume ranging between 0.15 cm 3 g −1 and 1.00 cm 3 g −1 , as determined by nitrogen adsorption measurement.

5. The catalyst composition according to claim 1 , characterized in that the one or more zeolites have a Si/Al molar ratio ranging from 11 to 190 as determined by inductively coupled plasma optical emission spectroscopy (ICP-OES).

6. The catalyst composition according to claim 1 , characterized in that the one or more zeolites have a density of Brønsted acid sites ranging from 5 μmol g −1 to 500 μmol g −1 as determined by Fourier transform infrared spectroscopy of adsorbed pyridine.

7. The catalyst composition according to claim 1 , characterized in that the catalyst composition further comprises at least one promoter.

8. The catalyst composition according to claim 7 , characterised in that the bulk molar ratio of said at least one promoter to the total content of the copper and iron is ranging from 0.001/1 to 0.5/1 as determined by inductively coupled plasma optical emission spectroscopy.

9. The catalyst composition to claim 1 , characterized in that Cu/Fe bulk molar ratio is ranging from 1.2/1.0 to 4.0/1.0.

10. The catalyst composition according to claim 1 , characterized in that the one or more zeolites have a mesoporous surface area comprised between 10 m 2 g −1 and 600 m 2 g −1 as determined by Brunauer-Emmett-Teller (BET) method.

11. The catalyst composition according to claim 1 , characterized in that the Cu particle size is at least 7 nm as determined from the (111) reflection in an X-ray diffraction pattern using the Scherrer equation; and/or the Cu particle size is at most 35 nm as determined from the (111) reflection in an X-ray diffraction pattern using the Scherrer equation.

12. A method to produce a catalyst composition according to claim 1 characterised in that the method comprises the following steps:
i. Dry impregnation of the copper and iron, and optionally at least one promoter, on the support being one or more zeolites to obtain a catalyst composition;
ii. Optionally calcining the catalyst composition to obtain a calcined catalyst;
iii. Activating the catalyst composition through a reduction to obtain a reduced catalyst composition.

13. A process for the synthesis of higher alcohols from a syngas feed stream comprising hydrogen and carbon monoxide, characterized in that the process comprises the following steps:
a) Providing a syngas feed stream comprising hydrogen and carbon monoxide;
b) Providing a catalyst composition according to claim 1 ;
c) Putting the syngas feed stream in contact with the catalyst composition at a reaction pressure ranging from 1 to 10 MPa and a reaction temperature ranging from 443 K (169.85° C.) to 653 K (379.85° C.); and
d) Recovering the effluent containing higher alcohols.

Assignees

• Total Se
• Eth Zuerich

Inventors

• Curulla-Ferre Daniel
• Stewart Joseph
• Perez-Ramirez Javier
• Mondelli Cecilia
• Luk Ho Ting

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J35/70

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

• B01J35/393

  Metal or metal oxide crystallite size · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title