Process for obtaining modified molecular sieves

Patent metadata

Field	Value
Publication number	US-9771307-B2
Application number	US-201514670277-A
Country	US
Kind code	B2
Filing date	Mar 26, 2015
Priority date	Jan 25, 2008
Publication date	Sep 26, 2017
Grant date	Sep 26, 2017

Abstract

A process may include contacting an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in an XTO reactor with a catalyst composite under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to olefin products. The catalyst composite may include at least 10 weight percent of a modified molecular sieve. The modified molecular sieve may include at least 0.05 weight percent of an alkaline earth metal or a rare earth metal based on a weight of the modified molecular sieve. The modified molecular sieve may include at least 0.3 weight percent of P based on the weight of the modified molecular sieve.

First claim

The invention claimed is:

1. A process-comprising:
contacting an oxygen-containing organic feedstock in an XTO reactor with a catalyst composite under conditions effective to convert the oxygen-containing organic feedstock to olefin products, wherein an XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction is sent to a fractionation section to separate said light olefins from said heavy hydrocarbon fraction and wherein the heavy hydrocarbon fraction is sent in an OCP reactor at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins, wherein a catalyst in the OCP reactor comprises the catalyst composite, wherein the catalyst composite comprises at least 10 weight percent of a modified molecular sieve, wherein the modified molecular sieve comprises:
at least 0.05 weight percent of an alkaline earth metal or a rare earth metal based on a weight of the modified molecular sieve; and
at least 0.3 weight percent of P based on the weight of the modified molecular sieve; and,

wherein the modified molecular sieve is made by a process comprising:
contacting a molecular sieve with a metal-containing compound in aqueous solution form in the presence of excess phosphorus such that the metal atoms located on an external surface of the molecular sieve are saturated with the phosphorus to introduce at least 0.05 wt % of the metal to the molecular sieve;
wherein the metal is an alkaline earth metal or a rare earth metal;
wherein the molecular sieve is selected from a group consisting of MFI, MOR, MEL, clinoptilolite, FER, FAU, MWW, BETA, MCM-41, ZSM-21, ZSM-22, ZSM-23, ZSM-42, ZSM-57, LTL and combinations thereof; and
wherein the molecular sieve that is contacted with the metal-containing compound is a P-modified molecular sieve comprising at least 0.3 wt % of P, and is modified with P by:

steaming the molecular sieve at a temperature ranging from 400 to 870° C. for 0.01-200 hours; and
leaching the molecular sieve with an acid solution comprising a source of P at conditions effective to remove a substantial part of Al from the molecular sieve and to introduce at least 0.3 wt % of P.

2. The process according to claim 1 , wherein an XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction is sent to a fractionation section to separate said light olefins from said heavy hydrocarbon fraction and recycling the heavy hydrocarbon fraction to the XTO reactor at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to olefin products.

3. The process according to claim 1 , wherein the olefin products are fractionated to form a stream comprising essentially ethylene, and wherein at least a part of said stream is recycled in the XTO reactor to increase propylene production.

4. The process according to claim 1 wherein OCP reactor effluent is sent to a fractionator and the light olefins are recovered, wherein hydrocarbons having 4 carbon atoms or more of the OCP reactor effluent are recycled at an inlet of the OCP reactor, optionally mixed with heavy hydrocarbon recovered from the XTO reactor effluent.

5. The process according to claim 4 , wherein, before recycling said hydrocarbons having 4 carbon atoms or more at the inlet of the OCP reactor, said hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge heavies.

6. The process according to claim 1 ethylene in whole or in part is recycled over the OCP reactor wherein said ethylene is from a fractionation section of the XTO reactor a fractionation section of the OCP reactor a fractionation section of the XTO reactor and a fraction section of the OCP reactor, or a common recovery section.

7. The process according to claim 1 , wherein ethylene in whole or in part is recycled over the XTO reactor, wherein said ethylene comes from a fractionation section of the XTO reactor, a fractionation section of the OCP reactor, a fractionation section of the XTO reactor and a fraction section of the OCP reactor, or a common recovery section.

8. The process according to claim 1 , wherein ethylene is further polymerized optionally with one or more comonomers.

9. The process according to claim 1 wherein propylene is further polymerized optionally with one or more comonomers.

10. The process according to claim 1 , wherein the catalyst composite comprises metal phosphate.

11. The process according to claim 1 , wherein the catalyst composite comprises matrix material.

12. The process according to claim 1 , wherein the catalyst composite comprises binder.

13. The process according to claim 1 , wherein a molar ratio of the alkaline earth metal or the rare earth metal to the P (M/P ratio) in the modified molecular sieve is less than 1.

14. The process according to claim 1 , wherein an average pores size of the modified molecular sieve is at least 0.5 nm.

15. The process according to claim 1 , wherein a crystal size of the modified molecular sieve is less than about 10 μm.

16. The process according to claim 1 , wherein the modified molecular sieve was modified with P prior to the introduction of the alkaline earth metal or rare earth metal to the molecular sieve.

17. The process according to claim 1 , wherein the alkaline earth metal or rare earth metal comprises one or more of the following metals: Mg, Sr, Ba, Ga, Al, Ce, In, Cs, Sc, Sn, Li, Zn, Co, Mo, Mn, Ni, Fe, Cu, Cr, Ti and V.

18. The process according to claim 1 , wherein the modified molecular sieve comprises MFI.

19. The process according to claim 1 , wherein the modified molecular sieve comprises ZSM-5.

20. The process according to claim 1 , wherein the modified molecular sieve was modified with P by dealuminating the molecular sieve in a steaming step, followed by a leaching step using an acid solution containing a source of P.

21. The process according to claim 1 , wherein the modified molecular sieve was modified with P according to the following steps in the order provided:
a) steaming at a temperature ranging from 400 to 870 ° C. for 0.01-200 hours;
b) leaching with an aqueous acid solution containing a source of P at conditions effective to remove a substantial part of Al from the molecular sieve and to introduce at least 0.3 wt % of P.

22. The process according to claim 21 , wherein the modified molecular sieve was further modified according to the following steps in the order provided:
c) separation of solid from liquid;
d) an optional washing step or an optional drying step or an optional washing step followed by a drying step; and
e) a calcination step.

23. The process according to claim 1 , further comprising:
contacting a molecular sieve with a metal-containing compound in aqueous solution form in the presence of excess phosphorus such that the metal atoms located on an external surface of the molecular sieve are saturated with the phosphorus to introduce the metal to the molecular sieve to obtain the modified molecular sieve;
wherein the metal is the alkaline earth metal or the rare earth metal, wherein the molecular sieve comprises MFI.

Assignees

• Total Res & Technology Feluy

Inventors

• Nesterenko Nikolai
• Vermeiren Walter
• Van Donk Sander
• Minoux Delphine

Classifications

• C07C4/06

  Catalytic processes {(C07C4/025 takes precedence)} · CPC title

• B01J29/405

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• B01J37/0207

  Pretreatment of the support · CPC title

• B01J29/06

  Crystalline aluminosilicate zeolites; Isomorphous compounds thereof · CPC title

• C07C2529/40

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