Process to make olefins and aromatics from organics

Patent metadata

Field	Value
Publication number	US-8957274-B2
Application number	US-200913000401-A
Country	US
Kind code	B2
Filing date	Jun 24, 2009
Priority date	Jun 25, 2008
Publication date	Feb 17, 2015
Grant date	Feb 17, 2015

Abstract

The present invention relates to a process to make light olefins and aromatics, in a combined XTO-OC process, from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising:
a0) providing a first portion and a second portion of said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock, a) providing a catalyst comprising zeolitic molecular sieves containing at least 10 membered ring pore openings or larger in their microporous structure, b) providing an XTO reaction zone, an OC reaction zone and a catalyst regeneration zone, said catalyst circulating in the three zones, such that at least a portion of the regenerated catalyst is passed to the OC reaction zone, at least a portion of the catalyst in the OC reaction zone is passed to the XTO reaction zone and at least a portion of the catalyst in the XTO reaction zone is passed to the regeneration zone; c) contacting the first portion of said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the XTO reactor with the catalyst at conditions effective to convert at least a portion of the feedstock to form a XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction; d) separating said light olefins from said heavy hydrocarbon fraction; e) contacting said heavy hydrocarbon fraction and the second portion of said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the OC reactor with the catalyst at conditions effective to convert at least a portion of said heavy hydrocarbon fraction and oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to light olefins and aromatics.

First claim

The invention claimed is:

1. A process of making light olefins and aromatics, in a combined organics to olefins (XTO)-olefins conversion (OC) process, from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising:
selecting a zeolite having an Si/Al ratio between 4 and 30 from an H + or NH 4 + form of MFI, MEL, FER, MOR, or clinoptilolite;
steaming the zeolite at a temperature ranging from 400 to 870° C. for 0.01-200 h:
leaching the zeolite with an aqueous acid solution at conditions effective to remove at least 10% of Al from the zeolite;
contacting the zeolite with an aqueous solution containing a source of P at conditions effective to introduce at least 0.05 wt % of P to form a solid zeolite in liquid;
separating the solid zeolite from the liquid; and
calcining the solid zeolite to form a P-modified zeolite composite;
providing a first portion and a second portion of an oxygen-containing, halogenide-containing, or sulphur-containing organic feedstock;
providing an XTO reaction zone, an OC reaction zone and a catalyst regeneration zone, wherein one or more catalysts are in the XTO reaction zone and the same one or more catalysts are in the OC reaction zone and wherein each of the one or more catalysts is a zeolitic molecular sieve containing at least 10 membered rings pore opening in their microporous structure, wherein at least one of the catalysts is comprises the P-modified zeolite composite;
wherein each of the one or more catalysts circulates in the three zones, such that at least a portion of the regenerated one or more catalysts are passed to the OC reaction zone, at least a portion of the one or more catalysts in the OC reaction zone are passed to the XTO reaction zone and at least a portion of the one or more catalysts in the XTO reaction zone are passed to the regeneration zone;
contacting the first portion of the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the XTO reactor with the one or more catalysts at conditions effective to convert at least a portion of the feedstock to form a XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction;
separating the light olefins from the heavy hydrocarbon fraction; and
contacting the heavy hydrocarbon fraction and the second portion of the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the OC reactor with the one or more catalysts at conditions effective to convert at least a portion of the heavy hydrocarbon fraction and the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to light olefins and aromatics.

2. The process of claim 1 , further comprising washing and drying the solid zeolite before calcining.

3. The process of claim 1 , further comprising washing, drying, or drying followed by washing the solid zeolite before calcining.

4. The process according to claim 1 , further comprising: contacting the zeolite with a metal silicate comprising at least one alkaline earth metal, such that the composite comprises at least 0.1 wt % of silicate.

5. The process of claim 1 , further comprising: contacting of the zeolite with an alkaline earth metal or rare earth metal containing compound to introduce at least 0.05 wt % of the alkaline earth metal or the rare earth metal (M) during or after introducing P to the zeolite.

6. The process of claim 1 , wherein all of the one or more catalysts from the catalyst regeneration zone is sent to the OC reaction zone, then further sent to the XTO reaction zone and finally all the catalyst of the XTO reaction zone is sent to the catalyst regeneration zone.

7. The process of claim 1 , wherein all of the one or more catalysts from the catalyst regeneration zone is sent to the OC reaction zone, then further sent to the XTO reaction zone and finally at least a portion of the one or more catalysts of the XTO reaction zone is sent to the catalyst regeneration zone and the remaining portion of the one or more catalysts is sent to the OC reaction zone.

8. The process of claim 1 , wherein all of the one or more catalysts from the catalyst regeneration zone is sent to the OC reaction zone, at least part of the one or more catalysts from the OC reaction zone is further sent to the XTO reaction zone and the remaining part of the one or more catalysts is sent to the catalyst regeneration zone and all of the one or more catalysts from the XTO reaction zone is sent to the OC reaction zone.

9. The process of claim 1 , wherein OC reactor effluent is sent to a separation section and the light olefins are recovered, and wherein the hydrocarbons having 4 carbon atoms or more are recycled at an inlet of the OC reaction zone.

10. The process of claim 9 , further comprising mixing the hydrocarbons having 4 carbon atoms or more recycled at the inlet of the OC reaction zone with the hydrocarbons having 4 carbon atoms or more recovered from the effluent of the XTO reaction zone.

11. The process of claim 10 , wherein before recycling the hydrocarbons having 4 carbon atoms or more at the inlet of the OC reaction zone, the hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge aromatics and other heavy hydrocarbons.

12. The process of claim 1 , wherein an OC reaction zone effluent and the XTO reaction zone effluent are mixed and sent to a fractionator, or separately sent to the same fractionator, where the light olefins are recovered and at least a portion of the hydrocarbons having 4 carbon atoms or more are recycled at an inlet of the OC reaction zone.

13. The process of claim 12 , wherein before recycling the hydrocarbons having 4 carbon atoms or more at the inlet of the OC reaction zone, the hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge aromatics and heavies.

14. The process of claim 1 , wherein ethylene is recycled over the OC reaction zone and wherein the ethylene can either come from a separation section of the XTO reaction zone, from a separation section of the OC reaction zone, from both the separation section of the XTO reaction zone and the separation section of the OC reaction zone, or from a common recovery section.

15. The process of claim 1 , wherein ethylene is recycled over the XTO reaction zone and wherein the ethylene can either come from a separation section of the XTO reaction zone, from a separation section of the OC reaction zone, from both the separation section of the XTO reaction zone and the separation section of the OC reaction zone, or from a common recovery section.

16. The process of claim 1 , wherein the light olefins comprises ethylene, which is further polymerized.

17. The process of claim 16 , wherein the ethylene is further polymerized with one or more comonomers.

18. The process of claim 1 , wherein the light olefins comprises propylene, which is further polymerized.

19. The process of claim 18 , wherein the propylene is further polymerized with one or more comonomers.

20. The process of claim 1 , wherein the one or more catalysts leaving the OC reaction zone and flowing to the XTO reaction zone contains at least 0.1% carbon.

21. The process of claim 11 , wherein the purge of aromatics and other heavy hydrocarbons is further subjected to fractionation and wherein toluene is obtained from the fractionation and recycled to the OC reaction zone.

22. The process of claim 21 , wherein aromatics having at least 9 carbon atoms are further obtained from the

Assignees

• Nesterenko Nikolai
• Vermeiren Walter
• Grasso Giacomo
• Van Donk Sander
• Garcia Wolfgang
• Total Res & Technology Feluy

Inventors

• Nesterenko Nikolai
• Vermeiren Walter
• Grasso Giacomo
• Van Donk Sander
• Garcia Wolfgang

Classifications

• B01J27/14

  Phosphorus; Compounds thereof · CPC title

• B01J29/18

  of the mordenite type · CPC title

• B01J21/08

  Silica · CPC title

• B01J29/65

  of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively · CPC title

• C07C2/864

  the non-hydrocarbon is an alcohol · CPC title