Process using catalytic composition for the conversion of syngas to higher alcohols

Patent metadata

Field	Value
Publication number	US-11306049-B2
Application number	US-202017424352-A
Country	US
Kind code	B2
Filing date	Jan 28, 2020
Priority date	Feb 1, 2019
Publication date	Apr 19, 2022
Grant date	Apr 19, 2022

Abstract

The present disclosure relates to a process for converting syngas to C2+ alcohols, said process comprising the steps of providing a reactor, of providing a catalyst composition and one or more acidic materials within said reactor, of providing a feed stream comprising a mixture of H2 and CO; and of contacting said feed stream with said catalyst composition and said one or more acidic materials under reaction conditions to provide product stream. Said process is remarkable in that said catalyst composition comprises an active phase comprising CuFe deposited on a carbon-containing support, and the one or more acidic materials are one or more zeolites having a Si/Al molar ratio ranging between 2 and 200.

First claim

The invention claimed is:

1. Process for converting syngas to C2+ alcohols said process comprising the following steps:
a) providing an installation comprising at least one reactor having one or more catalytic beds;
b) providing a catalyst composition and one or more acidic materials within said at least one reactor;
c) providing a feed stream comprising a mixture of H 2 and CO;
d) contacting said feed stream with said catalyst composition and said one or more acidic materials under reaction conditions to provide product stream;
characterized in that
said catalyst composition comprises an active phase comprising CuFe deposited on a carbon-containing support, the total content of iron and copper 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, and the one or more acidic materials being one or more zeolites having a Si/Al molar ratio ranging between 2 and 200 as determined by inductively coupled plasma-optical emission spectroscopy.

2. The process according to claim 1 , wherein said at least one reactor comprises a first reactive bed and one or more subsequent reactive beds, one or more subsequent reactive beds being arranged downstream of the first reactive bed, the process is characterized in that the catalyst composition and the one or more acidic materials are provided in different reactive beds, and in that the catalyst composition is provided in the first reactive bed and the one or more acidic materials are provided in the one or more subsequent reactive beds.

3. The process according to claim 1 , wherein said at least one reactor comprises a first reactive bed and one or more optional subsequent reactive beds, wherein the one or more subsequent reactive beds, when present, are arranged downstream of the first reactive bed, the process is characterized in that during step (b) a mixture of the catalyst composition and of the one or more acidic materials is provided in the first reactive bed.

4. The process according to claim 1 , characterized in that the carbon-containing support of the catalyst composition is selected from carbon nanofibers and/or carbon nanotubes.

5. The process according to claim 4 , characterized in that said carbon-containing support has a hollow-core structure with an inner diameter of at least 17 nm as determined according to N 2 sorption analysis; and/or, in that the carbon-containing support is or comprises carbon nanofibers selected from platelet-type carbon nanofibers and conical platelet-type carbon nanofibers.

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

7. The process according to claim 1 , characterized in that the catalyst composition has a Cu/Fe bulk molar ratio is ranging from 0.5/1 to 5/1; and/or in that the catalyst composition is reduced over hydrogen gas before step (c).

8. The process according to claim 1 , characterized in that the Cu particle size in the catalyst composition is at least 7 nm as determined from the (111) reflection in an XRD pattern using the Scherrer equation; or the Cu particle size in the catalyst composition is at most 35 nm as determined from the (111) reflection in a XRD pattern using the Scherrer equation.

9. The process according to claim 1 , characterized in that the one or more acidic materials are one or more zeolites are selected from MFI, FAU, MOR, FER, BEA, TON, MTT, or OFF families.

10. The process according to claim 1 , characterized in that the one or more acidic materials are one or more zeolites partially ion-exchanged with an alkali metal-based ion.

11. The process according to claim 1 , characterized in that the one or more acidic materials are one or more zeolites having a surface area comprised between 10 m 2 g −1 and 1000 m 2 g −1 , as determined by the Brunauer-Emmett-Teller (BET) method; and/or in that the one or more acidic materials are one or more zeolites having a pore volume comprised between 0.15 cm 3 g −1 and 1.25 cm 3 g −1 , as determined by N 2 sorption analysis.

12. The process according to claim 1 , characterized in that the one or more acidic materials are one or more zeolites having a density of Brønsted-acid sites ranging from 5 μmol g −1 to 700 μmol g −1 as determined by Fourier transform infrared spectroscopy of adsorbed pyridine; and/or in that the one or more acidic materials are one or more zeolites having a density of Lewis-acid sites ranging from 4 μmol g −1 to 250 μmol g −1 as determined by Fourier transform infrared spectroscopy of adsorbed pyridine.

13. The process according to claim 2 , wherein said at least one reactor comprises a first reactive bed, the process is characterized in that the reaction conditions in the first reactive bed comprise:
a reaction temperature ranging from 443 K (169.85° C.) to 653 K (379.85° C.), and/or
a reaction pressure range ranging from 1 MPa to 10 MPa, and/or
a weight hourly space velocity ranging from 500 cm 3 g cat −1 h −1 to 48,000 cm 3 g cat −1 h −1 .

14. The process according to claim 2 , wherein said at least one reactor comprises one or more subsequent reactive beds being arranged downstream of the first reactive bed, the process is characterized in that the reaction conditions in the one or more subsequent reactive beds comprise one or more of:
a reaction temperature ranging from 373 K (99.85° C.) to 773 K (499.85° C.), and/or
a reaction pressure range ranging from 0.1 MPa to 10.0 MPa; and/or
a weight hourly space velocity ranging from 500 cm 3 g cat −1 h −1 to 50,000 cm 3 g cat −1 h −1 .

Assignees

• Total Se
• Eth Zuerich

Inventors

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

Classifications

• B01J23/70

  of the iron group metals or copper · CPC title

• B01J23/745

  Iron · CPC title

• C07C29/153

  characterised by the catalyst used · CPC title

• C07C29/156 Primary

  containing iron group metals, platinum group metals or compounds thereof · CPC title

• B01J21/14

  Silica and magnesia · CPC title