Process for producing light olefins by using a ZSM-5-based catalyst

Patent metadata

Field	Value
Publication number	US-9314780-B2
Application number	US-201113882946-A
Country	US
Kind code	B2
Filing date	Oct 25, 2011
Priority date	Nov 2, 2010
Publication date	Apr 19, 2016
Grant date	Apr 19, 2016

Abstract

The present invention relates to a catalyst composition useful in a process for producing lower olefins from a oxygenate feedstream, a process for producing said catalyst composition and a process for producing lower olefins comprising contacting a oxygenate feedstream with the catalyst composition M 1 -M 2 -P/ZSM-5 with an oxygenate-comprising feedstream, wherein M 1 is one or more basic species, M 2 is one or more redox elements selected from Groups 6-8 of the Periodic Table of Elements and Sn and P is phosphorus, wherein said basic species is a molecular entity forming a weak Lewis base and/or a weak Bronsted base in the catalyst composition. In addition thereto, the present invention relates to an integrated process for producing lower olefins from a feedstream comprising hydrocarbons.

First claim

The invention claimed is:

1. A process for producing lower olefins comprising:
contacting a catalyst composition with an oxygenate-comprising feedstream to produce the lower olefin, wherein the catalyst composition comprises
M 1 , M 2 , P, and ZSM-5 zeolite,
wherein
M 1 comprises one or more basic species selected from the group consisting of alkaline earth metals, rare earth elements, and elements forming amphoteric oxide or hydroxide;
M 2 comprises at least 0.5 wt-% of one or more redox elements selected from the group consisting of Fe, Cr, W, and Sn or Mn not forming an amphoteric oxide or hydroxide; and
P is phosphorus.

2. The process according to claim 1 , wherein the basic species is an element selected from the group consisting of Mg, Ca, Sr, La and Zr; or an amphoteric oxide or hydroxide of Mn.

3. The process according to claim 1 , wherein the catalyst further comprises a binder.

4. The process according to claim 1 , wherein the basic species is Ca and the redox element is Mn not forming an amphoteric oxide or hydroxide; or wherein the basic element is Mg and the redox element is Cr.

5. The process according to claim 1 , wherein the oxygenate is selected from the group consisting of dimethyl ether (DME), diethyl ether, methanol (MeOH), and ethanol (EtOH).

6. The process according to claim 1 , further comprising:
(i) a syngas producing step, wherein a syngas composition is produced by contacting a syngas producing catalyst with a hydrocarbon feedstream comprising hydrocarbons (HC), oxygen (O 2 ) and carbon-dioxide (CO 2 ); and
(ii) an oxygenate synthesis step, wherein dimethyl ether (DME), methanol (MeOH) or a mixture thereof is produced by contacting an oxygenate synthesis catalyst with the syngas composition of step (i)
to produce the oxygenate-comprising feedstream prior to contacting the catalyst composition with the oxygenate-comprising feedstream.

7. The process according to claim 6 , wherein the process is an integrated process wherein:
the CO 2 comprised in the syngas composition produced in step (i) and the CO 2 comprised in the oxygenate stream produced in step (ii) is separated and recycled to the hydrocarbon feedstream;
the carbon-monoxide (CO) and hydrogen (H 2 ) comprised in the product stream produced in the olefin synthesis step are separated and recycled to the oxygenate synthesis feedstream; and
the reaction products other than the lower olefins, carbon-monoxide (CO) and hydrogen (H 2 ) comprised in the product stream produced in the olefin synthesis step are separated and are recycled to the hydrocarbon feedstream.

8. The process according to claim 6 , wherein the syngas producing catalyst is a Ni-comprising supported catalyst.

9. The process according to claim 6 , wherein the oxygenate synthesis catalyst is a Cu-comprising supported catalyst.

10. The process according to claim 1 , further comprising:
contacting the ZSM-5 zeolite with one or more solutions comprising soluble salts of M 1 , soluble salts of M 2 and phosphoric acid to modify said ZSM-5 zeolite with M 1 , M 2 , and P; and
drying and calcining the modified ZSM-5 zeolite in an oxygen-comprising atmosphere to prepare the catalyst composition prior to contacting the catalyst composition with the oxygenate-comprising feedstream.

11. The process according to claim 10 , wherein the ZSM-5 zeolite is mixed with a binder prior to contacting the ZSM-5 zeolite with one or more solutions comprising soluble salts of M 1 , M 2 , and phosphoric acid.

12. The process according to claim 3 , wherein the binder comprises silica.

13. The process according to claim 1 , wherein the basic species is selected from the group consisting of Ca, La, and Sr, and the redox element is Cr.

14. The process according to claim 1 , wherein the basic species is selected from the group consisting of an amphoteric oxide or hydroxide of Mn, and the redox element is Fe.

15. The process according to claim 1 , wherein the catalyst composition comprises:
0.5 wt-% to 12 wt-% of the basic species,
0.5 wt-% to 12 wt-% of the redox element, and
0.5 wt-% to 12 wt-% of the phosphorus.

Assignees

• Mammadov Aghaddin Kh
• Saudi Basic Ind Corp

Inventors

• Mammadov Aghaddin Kh

Classifications

• C07C2521/08

  Silica · CPC title

• B01J2229/40

  Special temperature treatment, i.e. other than just for template removal · CPC title

• B01J37/0207

  Pretreatment of the support · CPC title

• C07C1/20 Primary

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title

• C07C2529/48

  containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium · CPC title