Process to make olefins from oxygenates

Patent metadata

Field	Value
Publication number	US-9561990-B2
Application number	US-201414560144-A
Country	US
Kind code	B2
Filing date	Dec 4, 2014
Priority date	Jun 25, 2008
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

The present invention relates to a process to make light olefins, 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.

First claim

The invention claimed is:

1. A process of making light olefins, in a combined Oxygenate to Olefin (XTO)-Olefin Cracking (OC) process, from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising:
selecting a molecular sieve having pores of 10- or more-membered rings, wherein the molecular sieve is a zeolite;
contacting the molecular sieve with a metal silicate, different from said molecular sieve, comprising at least one alkaline earth metal to form a catalyst composite, wherein the catalyst composite comprises at least 10 wt % of the zeolite and at least 0.1 wt % of silicate based on a total weight of the catalyst composite;
providing a first portion and a second portion of a feedstock that is 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, wherein at least one of the one or more catalysts is the catalyst composite;
wherein the one or more catalysts circulate in the three zones, such that at least a portion of the one or more catalysts from the catalyst regeneration zone is passed to the OC reaction zone, at least a portion of the one or more catalysts in the OC reaction zone is passed to the XTO reaction zone and at least a portion of the one or more catalysts in the XTO reaction zone is passed to the catalyst regeneration zone;
contacting the first portion of the 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 an 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 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 feedstock to light olefins.

2. The process of claim 1 , wherein the catalyst composite comprises from 10 to 90 wt % of the molecular sieve.

3. The process of claim 1 , the molecular sieve is selected from a group consisting of MFI, MOR, MEL, clinoptilolite, FER, FAU, MWW, BETA, ZSM-21, ZSM-22, ZSM-23, ZSM-42, ZSM-57, LTL, and mixtures of thereof.

4. The process of claim 1 , wherein the molecular sieve is a ZSM-5 zeolite.

5. The process of claim 1 , wherein phosphorus is introduced to the zeolite before, simultaneously or after blending of the molecular sieve with the metal silicate.

6. The process of claim 1 , wherein the molecular sieve has an initial atomic ratio Si/A1 of at least 4 and not greater than 500.

7. The process of claim 1 , wherein the molecular sieve is dealuminated and then modified with phosphorous before or during contact with the metal silicate.

8. The process of claim 1 , wherein the catalyst composite further comprises metal phosphates.

9. The process of claim 1 , wherein the metal silicate further includes a metal that is Ga, Al, Ce, In, Cs, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti or V.

10. The process of claim 1 , wherein silicate anion is present in the metal silicate as SiO 3 2− , SiO 4 4− , Si 2 O 7 6− , or Si 3 O 10 8− .

11. The process of claim 1 , wherein the metal silicate is a calcium silicate.

12. The process of claim 1 , wherein all of the one or more catalysts from the regenerator is sent to the OC reaction zone, used one or more catalysts from the OC reaction zone is sent to the XTO reaction zone, and all used one or more catalysts of the XTO reaction zone is sent to the catalyst regeneration zone.

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

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

15. The process of claim 1 , wherein the proportion of the second portion of the feedstock is from 15 to 30% by weight based on a total weight of an OC feed to the OC reaction zone.

16. The process of claim 1 , wherein feed at an inlet in the OC reactor comprises a paraffins content of at least 20 wt % and not more than 80 wt % on a carbon basis.

17. 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.

18. The process of claim 1 , wherein the one or more catalysts in the OC reaction zone comprise fresh or regenerated catalysts, and wherein the one or more catalysts in the XTO reaction zone comprise used catalysts from the OC reaction zone.

19. The process of claim 1 , wherein, in the XTO reactor effluent, more than 50 weight percent of olefins having 4 carbon atoms are butenes.

Assignees

• Total Res & Technology Feluy
• Total Res Tech Feluy

Inventors

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

Classifications

• Y02P20/584

  Recycling of catalysts · CPC title

• B01J21/16

  Clays or other mineral silicates · CPC title

• B01J29/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively · CPC title

• B01J27/14

  Phosphorus; Compounds thereof · CPC title

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title