Process for preparing olefins by dehydrating alcohols with less side effects comprising addition of sulfur containing compounds

Patent metadata

Field	Value
Publication number	US-10472300-B2
Application number	US-201515540327-A
Country	US
Kind code	B2
Filing date	Dec 18, 2015
Priority date	Dec 31, 2014
Publication date	Nov 12, 2019
Grant date	Nov 12, 2019

Abstract

The component introduced at step (a) can be chosen from the group consisting of thiols, sulfides, disulfides.

First claim

The invention claimed is:

1. A process for dehydrating an alcohol to prepare one or more corresponding olefins, the process comprising:
(a) forming an acidic catalyst selected from modified crystalline aluminosilicates of the Framework Type FER having Si/Al framework molar ratio greater than 20 and a ratio between strong acid sites and weak acid sites, S/W, lower than 1.0, the ratio S/W being measured by temperature-programmed desorption of ammonia and being determined by the ratio of the peak area of ammonia desorbed above 340° C. to that desorbed below 340° by:
(1) providing a crystalline aluminosilicate of the Framework Type FER having an Si/AI framework molar ratio of greater than or equal to 20, and
(2) treating said crystalline aluminosilicate of (1) to form the modified crystalline aluminosilicate of the Framework Type FER having the Si/Al framework molar ratio greater than 20 and the ratio between strong acid sites and weak acid sites, S/W, lower than 1.0 by at least one treatment step selected from: (i) contacting said crystalline aluminosilicate of the Framework Type FER with a solution containing one or more organic compounds, wherein each of the one or more organic compounds comprises one or more —CO 2 H, —SO 3 H, or —SO 4 H groups or salts thereof, and wherein a concentration of each of the one or more organic compounds in the solution containing the one or more organic compounds is in a range of from 1×10 −4 Molar (M) to 10 M; (ii) applying partial ion exchange to said crystalline aluminosilicate of the Framework Type FER (iii) selectively poisoning strong acid sites of the crystalline aluminosilicate of the Framework Type FER: or (iv) a combination thereof:

(b) introducing into a dehydration unit containing metallic sites a feed (A) comprising one or more alcohols having at least 2 carbon atoms, optionally water, and optionally an inert component, and one or more sulfur containing compounds in an amount of from 0.5 wt ppm to 20 wt ppm of the total content of the feed (A),
(c) contacting the feed (A) with the acidic catalyst in a reaction zone of the dehydration unit at conditions effective to dehydrate at least a portion of the alcohol to make a corresponding olefin or mixture of olefins,
(d) recovering from the dehydration unit an effluent (B) comprising an olefin or mixture of olefins, water, undesired by-products including aldehydes, H 2 , CO, CO 2 , and CH 4 , optionally one or more unconverted alcohols, and optionally the inert component, and
(e) determining the amount of the one or more sulfur containing compounds in the feed (A) introduced into the dehydration unit at (b) by: performing (c) with a feed (A) not comprising said one or more sulfur containing compounds, measuring an amount of the undesired by-products in the effluent (B) recovered at (d), and increasing the amount of said one or more sulfur containing compounds until the amount of the undesired by-products in the effluent (B) recovered at (d) is less than 4 wt %.

2. The process according to claim 1 , wherein the dehydration unit comprises at least one metallic internal wall.

3. The process according to claim 1 , wherein the introducing step (b) comprises adding one or more sulfur-containing compounds to the feed (A) or directly in the dehydration unit.

4. The process according to claim 1 , wherein the one or more sulfur-containing compounds is at least one compound selected from the group consisting of thiols, sulfides and disulfides.

5. The process according to claim 1 , wherein:
the recovery step (d) comprises recovering one or more unconverted alcohols, the process further comprising, subsequent to recovery step (d), a step of:
(f) recycling the unconverted alcohol to the introducing step (b), in the dehydration unit.

6. The process according to claim 1 , wherein the recovering step (d) comprises recovering the one or more olefins and the one or more unconverted alcohols, as well as each compound contained in the effluent (B), by fractionation.

7. The process according to claim 1 , wherein the one or more alcohols provided in step (b) comprise one or more alcohols derived from edible or non-edible biomass.

8. The process according to claim 1 , wherein the one or more alcohols provided in step (b) comprise one or more alcohols obtained via syn-gas route or synthesized via partial oxidation of paraffin.

9. The process according to claim 1 , wherein the one or more alcohols provided in step (b) comprise one or more alcohols produced via hydrogenation of corresponding aldehydes, ketones or acids derived from the edible or non-edible biomass.

10. The process according to claim 1 , where the one or more olefins recovered in step (d) are used for production of polymers and elastomers.

11. The process according to claim 1 , where the one or more olefins recovered in step (d) are used for production of fuel.

12. The process according to claim 1 , wherein the dehydration unit is operated at a pressure ranging from 0.5 to 30 bars absolute (50 kPa to 3 MPa).

13. The process according to claim 1 , wherein the dehydration unit is operated at a temperature of from 220° C. to at most 500° C.

14. The process of claim 1 , further comprising subjecting the acidic catalyst to a preliminary pre-coking step.

15. The process of claim 1 , wherein the one or more treatment steps include at least two of treatment steps (i), (ii), or (iii); repetition of at least one of treatment steps (i), (ii), or (iii); or a combination thereof.

16. The process of claim 15 , wherein the one or more treatment steps include (i) or (iii) subsequently combined with (ii).

17. The process of claim 1 , wherein (ii) comprises contacting said crystalline aluminosilicate of the Framework Type FER with a solution containing one or more inorganic salts, wherein a concentration of the one or more inorganic salts in the solution containing the one or more inorganic salts is in a range of from 1×10 −4 Molar (M) to 10 M.

18. The process of claim 1 , wherein (iii) comprises impregnating said crystalline aluminosilicate of the Framework Type FER with an aqueous solution containing alkali ions, alkaline earth ions, or mixtures thereof.

19. The process of claim 1 , wherein the ratio between the strong acid sites and the weak acid sites, S/W, is greater than 0.1.

Assignees

• Total Res & Technology Feluy
• Ifp Energies Now

Inventors

• Minoux Delphine
• Nesterenko Nikolai
• Adam Cindy
• Vermeiren Walter
• De Smedt Philip
• Dath Jean-Pierre
• Coupard Vincent
• Maury Sylvie
• Aribert Nicolas

Classifications

• B01J2229/34

  Reaction with organic or organometallic compounds · CPC title

• B01J2229/123

  in order to deactivate outer surface · CPC title

• B01J29/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• B01J2229/20

  to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title