Fischer-Tropsch synthesis process comprising a catalyst prepared by addition of an organic compound in gas phase

Patent metadata

Field	Value
Publication number	US-11111442-B2
Application number	US-201916662643-A
Country	US
Kind code	B2
Filing date	Oct 24, 2019
Priority date	Oct 25, 2018
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A Fischer-Tropsch process for synthesizing hydrocarbons, by bringing a catalyst comprising a support and an active phase comprising a Group VIII metal into contact with a feedstock comprising synthesis gas, said catalyst being prepared according to the following steps:a) a porous support is provided;b) an organic compound containing oxygen and/or nitrogen is added to the porous support;c) a step of bringing said porous support into contact with a solution containing a salt of a precursor of the phase comprising a Group VIII metal is carried out;d) the porous support obtained at the end of step c) is dried;characterized in that step b) is carried out by bringing together said porous support and said organic compound under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred in the gaseous state to the porous support.

First claim

The invention claimed is:

1. A Fischer-Tropsch process for preparing a catalyst and synthesizing hydrocarbons using the catalyst, which comprises:
preparing the catalyst by the following steps:
a) providing a porous support containing silica, alumina, and at least one partial or non-partial single spinel phase MAl 2 O 4 or mixed spinel phase M x M′ (1-x) Al 2 O 4 in which M and M′ are distinct metals selected from the group consisting of magnesium (Mg), copper (Cu), cobalt (Co); nickel (Ni), tin (Sn), zinc (Zn), lithium (Li), calcium (Ca), caesium (Cs), sodium (Na), potassium (K), iron (Fe), and manganese (Mn) and in which x is between 0 and 1, the values of 0 and 1 themselves being excluded;
b) adding at least one organic compound containing oxygen and/or nitrogen and comprising one or more chemical functions selected from the group consisting of carboxylic, alcohol, ester, amine, amide, ether, dilactone, carboxyanhydride, aldehyde, ketone, nitrile, imide, oxime and urea functions, but not comprising sulfur, to the porous support;
c) bringing said porous support into contact with at least one solution containing at least one salt of a precursor of the phase comprising at least one Group VIII metal selected from the group consisting of iron (Fe) and cobalt (Co);
d) drying the porous support obtained at the end of step c);
wherein step b) is carried out before or after steps c) and d) and is carried out by bringing together said porous support with a porous solid comprising said at least one organic compound containing oxygen and/or nitrogen under conditions of temperature, pressure and duration such that a fraction of said organic compound is transferred in the gaseous state from said porous solid to the porous support; and
using the catalyst obtained from the above steps to prepare hydrocarbons by bringing the catalyst into contact with a feedstock comprising synthesis gas under a total pressure of between 0.1 and 15 MPa, under a temperature of between 150 and 350° C., at an hourly space velocity of between 100 and 20,000 volumes of synthesis gas per volume of catalyst per hour and with an H 2 /CO molar ratio of the synthesis gas of between 0.5 and 4.

2. The process according to claim 1 , wherein step b) is carried out by bringing said porous support together with said porous solid comprising said organic compound, without physical contact.

3. The process according to claim 1 , wherein, in step b), the porous support and the porous solid comprising said organic compound are of different porosity and/or chemical nature.

4. The process according to claim 1 , wherein, at the end of step b), the porous solid containing the organic compound is separated from said porous support and is returned to step b).

5. The process according to claim 1 , wherein said organic compound comprises at least one carboxylic function selected from the group consisting of ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), 4-oxopentanoic acid (levulinic acid) and 3-carboxy-3-hydroxypentanedioic acid (citric acid).

6. The process according to claim 1 , wherein said organic compound comprises at least one alcohol function selected from the group consisting of methanol, ethanol, phenol, ethylene glycol, propane-1,3-diol, glycerol, sorbitol, diethylene glycol, polyethylene glycols having an average molar mass of less than 600 g/mol, glucose, fructose and sucrose in any of the isomeric forms thereof.

7. The process according to claim 1 , wherein said organic compound comprises at least one ester function selected from the group consisting of a γ-lactone or a δ-lactone containing between 4 and 8 carbon atoms, γ-butyrolactone, γ-valerolactone, methyl laurate, dimethyl malonate, dimethyl succinate and propylene carbonate.

8. The process according to claim 1 , wherein said organic compound comprises at least one amine function selected from the group consisting of aniline, ethylenediamine, diaminohexane, tetramethylenediamine, hexamethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine, diethylenetriamine and triethylenetetramine.

9. The process according to claim 1 , wherein said organic compound comprises at least one amide function selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, gamma-valerolactam and N,N′-dimethylurea.

10. The process according to claim 1 , wherein said organic compound comprises at least one carboxyanhydride function selected from the group consisting of the O-carboxyanhydrides consisting of 5-methyl-1,3-dioxolane-2,4-dione and 2,5-dioxo-1,3-dioxolane-4-propanoic acid, and the N-carboxyanhydrides consisting of 2,5-oxazolidinedione and 3,4-dimethyl-2,5-oxazolidinedione.

11. The process according to claim 1 , wherein said organic compound comprises at least one dilactone function selected from the group consisting of the cyclic dilactones having 4 ring members consisting of 1,2-dioxetanedione, the cyclic dilactones having 5 ring members consisting of 1,3-dioxolane-4,5-dione, 1,5-dioxolane-2,4-dione, and 2,2-dibutyl-1,5-dioxolane-2,4-dione, the cyclic dilactones having 6 ring members consisting of 1,3-dioxane-4,6-dione, 2,2-dimethyl-1,3-dioxane-4,6-dione, 2,2,5-trimethyl-1,3-dioxane-4,6-dione, 1,4-dioxane-2,5-dione, 3,6-dimethyl-1,4-dioxane-2,5-dione, 3,6-diisopropyl-1,4-dioxane-2,5-dione, and 3,3-ditoluyl-6,6-diphenyl-1,4-dioxane-2,5-dione, and the cyclic dilactones having 7 ring members consisting of 1,2-dioxepane-3,7-dione, 1,4-dioxepane-5,7-dione, 1,3-dioxepane-4,7-dione and 5-hydroxy-2,2-dimethyl-1,3-dioxepane-4,7-dione.

12. The process according to claim 1 , wherein said organic compound comprises at least one ether function comprising at most two ether functions and not comprising any hydroxyl groups, selected from the group consisting of the linear ethers consisting of diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether, diisopropyl ether, di-tert-butyl ether, methoxybenzene, phenyl vinyl ether, isopropyl vinyl ether and isobutyl vinyl ether, and the cyclic ethers consisting of tetrahydrofuran, 1,4-dioxane and morpholine.

Assignees

• Ifp Energies Now
• Total Res & Technology Feluy

Inventors

• Guillou Florent
• Carrette P-Louis
• Guichard Bertrand
• Delcroix Damien

Classifications

• C10G2/331

  containing group VIII-metals · CPC title

• B01J37/0203

  the impregnation liquid containing organic compounds · CPC title

• C10G2/332 Primary

  of the iron-group · CPC title

• B01J21/08

  Silica · CPC title

• B01J23/75

  Cobalt · CPC title