Process of preparing alcohols

Patent metadata

Field	Value
Publication number	US-12012371-B2
Application number	US-202017640092-A
Country	US
Kind code	B2
Filing date	Aug 14, 2020
Priority date	Sep 5, 2019
Publication date	Jun 18, 2024
Grant date	Jun 18, 2024

Abstract

A process can produce alcohols having at least two carbon atoms by catalytic conversion of synthesis gas into a mixture containing alkanes, alkenes, and alcohols. Alkenes are converted into corresponding alcohols in a subsequent step by hydration of the alkanes. Before the hydration and after the catalytic conversion, gas and liquid phases may be separated. Specific catalysts can be employed that have a markedly higher selectivity for alkenes than for alkanes. These catalysts comprise grains of non-graphitic carbon having cobalt nanoparticles dispersed therein. The cobalt nanoparticles have an average diameter d p from 1 to 20 nm, and an average distance D between nanoparticles is from 2 to 150 nm. The combined total mass fraction of metal ω in the grains ranges from 30% to 70% by weight of the total mass of the grains of non-graphitic carbon, wherein 4.5 dp/ω>D≥0.25 dp/ω.

First claim

What is claimed is:

1. A two-stage process for producing alcohols having at least two carbon atoms by catalytic conversion of synthesis gas into a first mixture containing alkenes in a first stage, alcohols, and alkanes, wherein the alkenes present in the first mixture are subsequently converted into alcohols by hydration of the alkenes in a second stage.

2. The process of claim 1 comprising:
separating the alkanes and the alkenes in the first mixture from the alcohols to form a second mixture; and
only subsequently hydrating the alkanes in the second mixture.

3. The process of claim 2 comprising initially separating the second mixture of the alkanes and the alkenes into two or more fractions having different numbers of carbon atoms and only subsequently hydrating at least one of the individual fractions to obtain a corresponding alcohol from the alkene in the fraction.

4. The process of claim 3 comprising separating the second mixture of the alkanes and the alkenes at least into a C2 fraction, a C3 fraction, and a C4 fraction.

5. The process of claim 2 wherein the second mixture contains a mixture of C2-C4 alkenes or C2-C5 alkenes that is hydrated to corresponding alcohols as a mixture.

6. The process of claim 1 comprising hydrating the alkenes with the first mixture of alkanes, alkenes, and alcohols without separating the alcohols from the first mixture beforehand.

7. The process of claim 2 comprising selecting conditions for hydration of the second mixture in terms of choice of catalyst and reaction conditions including temperature and pressure at which a hydration reaction is performed such that hydration of propene and/or 1-butene is favored over hydration of ethene.

8. The process of claim 1 wherein hydration occurs at temperatures above 80° C. and/or at a pressure of 5 bar to 150 bar.

9. The process of claim 8 comprising separating the alkanes from a product mixture that is obtained from the hydration.

10. The process of claim 1 wherein before hydration of the alkenes to corresponding alcohols and after the catalytic conversion of the synthesis gas, the process comprises separating a product mixture obtained into a gas phase and a liquid phase, wherein the liquid phase is used for subsequent hydration of alkenes to alcohols.

11. The process of claim 10 wherein the gas phase is at least partially recycled to the catalytic conversion of the synthesis gas.

12. The process of claim 1 wherein after the catalytic conversion of the synthesis gas and after subsequent hydration of alkenes to alcohols, the process comprises separating a product mixture that is obtained into a gas phase and a liquid phase, wherein the liquid phase contains at least the alcohols.

13. The process of claim 1 comprising at least partially converting at least one of alkenes or primary alcohols into secondary alcohols in the hydration.

14. The process of claim 12 wherein the gas phase obtained in the separation is at least partially recycled to the catalytic conversion of the synthesis gas.

15. The process of claim 1 wherein after the catalytic conversion of the synthesis gas, the process comprises processing a product mixture as follows:
at least partially absorbing the alkenes and alcohols in a high-boiling hydrocarbon or a hydrocarbon mixture as an absorption medium;
separating gases not absorbed into the absorption medium as a gas phase;
separating an aqueous phase from an organic phase of the absorption medium; and
desorbing the alkenes, the alkanes, and the alcohols from the absorption medium.

16. The process of claim 1 wherein before or after hydration of the alkenes, the separation of the alcohols from the alkanes comprises:
separating the alcohols in at least one distillation column at an elevated pressure of at least 10 bar; and
removing water from an alcohol fraction by extractive distillation, by pervaporation, or by azeotropic distillation.

17. The process of claim 1 wherein the catalytic conversion of the synthesis gas employs a catalyst that comprises grains of non-graphitic carbon having cobalt nanoparticles dispersed therein, wherein the cobalt nanoparticles have an average diameter d p in a range from 1 nm to 20 nm, wherein an average distance D between individual cobalt nanoparticles in the grains of non-graphitic carbon is in a range from 2 nm to 150 nm, wherein a combined total mass fraction w of metal in the grains of non-graphitic carbon is in a range from 30% by weight to 70% by weight of a total mass of the grains of non-graphitic carbon, wherein 4.5 d p /ω>D≥0.25 d p /ω.

18. The process of claim 17 wherein a material of the catalyst is doped with a metal selected from Mn, Cu, or a mixture thereof, wherein the grains of non-graphitic carbon have a molar ratio of cobalt to doped metal in a range from 2 to 15.

Assignees

• Thyssenkrupp Ind Solutions Ag
• Thyssenkrupp Ag
• Thyssenkrupp Uhde Gmbh

Inventors

• Tenhumberg Nils
• Gehrmann Stefan
• Kleiber Michael

Classifications

• C10G2400/20

  C2-C4 olefins · CPC title

• C10G53/08

  including at least one sorption step · CPC title

• C07C7/144

  using membranes, e.g. selective permeation · CPC title

• C07C7/08

  by extractive distillation · CPC title

• C07C7/005

  Processes comprising at least two steps in series · CPC title