Method of high pressure and high capacity oxygenate conversion with catalyst exposure cycle

Abstract

A gas-solids reaction system is provided for improving product recovery in a multiple reactor reaction system. An oxygenate feedstock, desirably of high concentration in oxygenate, is reacted with a catalyst having a low to modest acidity and a Si/Al2 ratio of from 0.10 to 0.32. The reaction occurs in a reaction zone of a fluidized bed reactor at an oxygenate partial pressure of at least 45 psia and a reactor gas superficial velocity of at least 10 ft/s, conveying catalyst through the reaction zone to a circulation zone. The catalyst undergoes displacement with an inert gas in the circulation zone at a displacement gas superficial velocity of at least 0.03 m/s, after which at least a portion, preferably a large portion is returned to the reaction zone. The catalyst has a residence time in the circulation zone of at least twice that of the residence time of catalyst in the reaction zone. Extraordinary catalyst activity at high olefin selectivity results despite insignificant changes in coke on catalyst and coke yield when compared to lower pressure operations.

Description

DESCRIPTION OF FIGURES

FIG. 1 schematically shows a reaction system according to an embodiment of the invention.

FIGS. 2A and 2B schematically show a portion of a reaction system according to an embodiment of the invention.

FIG. 3 is a schematic diagram of an embodiment of a reactor apparatus of the present invention.

FIG. 4 is a schematic diagram of an embodiment of a reactor apparatus of the present invention.

FIG. 5 is a pseudo first order plot of experiment results for a reaction system not of the method of the present invention.

FIG. 6 plots the sum of the selectivities of ethylene and propylene, called Prime Olefin Selectivity or POS, vs. Cumulative grams Methanol Converted Per gram of molecular Sieve or CMCPS, for a reaction system directionally representing the method of the present invention.

FIG. 7 plots the ratio of the selectivity of ethylene to that of propylene, called Prime Olefin Ratio or POR, vs. CMCPS, for a reaction system directionally representing the method of the present invention.

FIG. 8 plots the conversion of methanol according to the definition in Example 1, below, vs. CMCPS, for a reaction system directionally representing the method of the present invention.

FIG. 9 schematically shows a large pilot plant reactor used in Examples 1-3.

FIG. 10 plots catalyst activity as a function of reactor pressure and methanol conversion for a reaction system not of the method of the present invention.

FIG. 11 shows a large pilot plant oxygenate conversion system of the method of the present invention used in Example 5.

FIGS. 12-18 show plots of experimental results from Example 5 using the large pilot plant oxygenate conversion system of method of the present invention, as described more in detail below.

Claims

1. A method for conducting an oxygenate conversion reaction comprising: providing an oxygenate feedstock, and a reactor apparatus that includes a reaction zone in fluid communication with a circulation zone, wherein said reaction zone has an inlet and an outlet, and said circulation zone has an inlet, an outlet and a transition zone, said transition zone including one or more displacing gas inlets;contacting the oxygenate feedstock with a catalytically effective amount of a gas-displaced catalyst in the reaction zone under oxygenate conversion conditions to form a product containing light olefins and an oxygenate-exposed catalyst, wherein the gas-displaced catalyst incorporates a silicoaluminophosphate molecular sieve with a Si/Al2 ratio of at least 0.10 and no greater than 0.32, and the conditions include an oxygenate partial pressure in the reaction zone of at least 45 psi (310 kPa) and a reactor gas superficial velocity of at least 10 ft/s (3.0 m/s) at least one point in the reaction zone such that the oxygenate-exposed catalyst is conveyed through the reaction zone to the outlet of the reaction zone;providing at least a portion of the oxygenate-exposed catalyst from the outlet of the reaction zone to the inlet of the circulation zone, and passing the oxygenate-exposed catalyst through the transition zone while flowing a displacing gas from the one or more displacing gas inlets of the transition zone countercurrently through the oxygenate-exposed catalyst in the transition zone, the displacing gas having a superficial velocity of at least 0.1 ft/s (0.03 m/s) at least one point in the transition zone, to form the gas-displaced catalyst;providing at least a portion of the gas-displaced catalyst from the transition zone to the outlet of the circulation zone; andproviding at least of portion of the gas-displaced catalyst from the outlet of the circulation zone to the inlet of the reaction zone to be at least a portion of catalyst for the contacting.

2. The method of claim 1 wherein the catalyst in the transition zone has a transition zone residence time and the catalyst within the reaction zone has a reaction zone residence time, and the transition zone residence time is at least two times that of the reaction zone residence time.

3. The method of claim 2 wherein the transition zone residence time is at least three times longer than the reaction zone residence time.

4. The method of claim 1 wherein the Si/Al2 ratio is at least 0.12 and no greater than 0.30.

5. The method of claim 1 wherein the silicoaluminophosphate molecular sieve comprises SAPO-34, SAPO-18, or both.

6. The method of claim 1 wherein the silicoaluminophosphate molecular sieve is selected from the group consisting of SAPO-34, SAPO-18, or a combination thereof.

7. The method of claim 1 wherein the oxygenate partial pressure in the reaction zone is at least 50 psia (345 kPaa).

8. The method of claim 1 wherein the oxygenate partial pressure in the reaction zone is at least 45 psia (310 kPaa) and not greater than 200 psia (1380 kPaa).

9. The method of claim 1 wherein at least one point in the reaction zone has a total pressure in the range about 45 psia (310 kPaa) to 9 about 200 psia (1380 kPaa).

10. The method of claim 1 wherein the reactor gas superficial velocity is at least 20 ft/s (6.1 m/s) at least one point in the reaction zone.

11. The method of claim 1 wherein the displacing gas superficial velocity is at least 0.16 ft/s (0.05 m/s) at least one point in the transition zone.

12. The method of claim 1 wherein the displacing gas superficial velocity is at least 0.1 ft/s (0.03 m/s) at all points the transition zone.

13. The method of claim 1 wherein the displacing gas superficial velocity at all points in the transition zone ranges from about 0.1 ft/s (0.03 m/s) to about 1.3 ft/s (0.40 m/s).

14. The method of claim 1 further comprising conducting the light olefin product away from the reactor apparatus wherein no greater than 5% of the oxygenate-exposed catalyst flowing through the reactor outlet into the circulation zone are carried out of the reactor apparatus with the product including a light olefin.

15. The method of claim 1 wherein at least 80 wt % of the catalyst from the inlet of the circulation zone is passed through the transition zone to the outlet of the circulation zone.

16. The method of claim 1 wherein the conditions include an oxygenate conversion of at least 92 wt % as measured at the reactor outlet.

17. The method of claim 1 wherein the conditions include weight hourly space velocity based on the silicoaluminophosphate molecular sieve of at least 25 hr−1.

18. The method of claim 1 wherein the transition zone further comprises a plurality of baffle layers.

19. The method of claim 18 wherein an orientation of a first baffle layer is rotated by 90 degrees relative to an orientation of a second baffle layer.

20. The method of claim 1 wherein the reactor apparatus comprises a plurality of reaction zones, and the circulation zone comprises a single transition zone and a further includes a plurality of standpipes equal in number to the reaction zones, with each standpipe having a discrete circulation zone outlet in fluid communication with a reaction zone inlet.

21. The method of claim 1 wherein the reactor apparatus comprises a single reaction zone, and the circulation zone comprises a single transition zone and no more than two standpipes in fluid communication with the single reaction zone to return the catalyst to the single reaction zone.

22. The method of claim 1 wherein at least one of said light olefins is polymerized to form a polymer product.