Method for partially regenerating methanol to olefin catalyst and methanol to olefin process

Abstract

The present application discloses a method for partially regenerating a methanol to olefin catalyst, comprising: placing a deactivated methanol to olefin catalyst in a regenerator to carry out a partial regeneration reaction to obtain a regenerated catalyst; at least a portion of the regenerated catalyst has a coke amount of more than 1%. The present application discloses a methanol to olefin process, the methanol to olefin reaction is carried out in a fluidized bed with the use of a methanol to olefin catalyst, wherein at least a portion of the regenerated catalyst has a coke amount of more than 1%.

Claims

1. A methanol to olefin process comprising: placing a deactivated methanol to olefin catalyst in a regenerator; partially regenerating the deactivated methanol to olefin catalyst by gasifying coke deposited on the deactivated methanol to olefin catalyst with regeneration gas which consists of steam, to obtain a regenerated catalyst, wherein at least a portion of the regenerated catalyst has a coke amount in a range from 3.89 wt % to 6 wt % and wherein the regeneration gas does not include oxygen; and carrying out a methanol to olefin reaction in a fluidized bed reactor comprising the regenerated catalyst.

2. The methanol to olefin process according to claim 1, wherein the partial regeneration reaction is carried out at a temperature in a range of 710° C. to 750° C.

3. The methanol to olefin process according to claim 1, wherein a contact time between the steam and the deactivated methanol to olefin catalyst is in a range of 10 min to 40 min.

4. The methanol to olefin process according to claim 3, wherein the steam is introduced into the regenerator with a space velocity in a range of 4 h.sup.−1 to 8 h.sup.−1.

5. The methanol to olefin process according to claim 1, wherein the partial regeneration reaction is carried out at a temperature in a range of 600° C. to 750° C.

6. The methanol to olefin process according to claim 1, wherein the deactivated methanol to olefin catalyst has a coke amount in a range of 7 wt % to 12 wt %.

7. The methanol to olefin process according to claim 1, wherein an inert gas is also introduced into the regenerator and the inert gas is at least one selected from nitrogen, helium, argon, and neon.

8. The methanol to olefin process according to claim 1 further comprising: carrying out a methanol to olefin reaction in a fluidized bed reactor comprising a methanol to olefin catalyst which contains a silicoaluminophosphate molecular sieve, wherein the reaction produces the deactivated methanol to olefin catalyst, and recycling the regenerated catalyst to the fluidized bed reactor.

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

(2) FIG. 2 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

(3) FIG. 3 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

(4) FIG. 4 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

(5) FIG. 5 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

(6) FIG. 6 is a schematic view showing the performance test results of a partially regenerated catalyst in an embodiment of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENT

(7) The present application is described in detail below with reference to the examples, but the application is not limited to the examples.

(8) The methanol to olefin catalyst SAPO-34 used commercially in the present application is purchased from Zhengda Energy Materials (Dalian) Co., Ltd.

(9) The coke amount of the catalyst is measured as follows:

(10) The catalyst is heated to 250° C. in air, and the mass of the catalyst is recorded as m.sub.250° C.; the catalyst is further heated to 900° C. in air, and the mass of the catalyst is recorded as m.sub.900° C.; the coke amount of the catalyst is determined by the following formula I:
The coke amount ω==(m.sub.250° C.−m.sub.900° C.)/m.sub.250° C.×100%  Formula I

Example 1

(11) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 9.18%.

(12) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 700° C., the nitrogen gas is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 15 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 5.95%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 1. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

Example 2

(13) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 11.88%.

(14) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 700° C., the nitrogen gas is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 30 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 4.82%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 2. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

Example 3

(15) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 7.08%.

(16) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 750° C., the nitrogen is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 10 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 5.16%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 3. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

Example 4

(17) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 9.18%.

(18) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 750° C., the nitrogen gas is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 20 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 3.89%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 4. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

Example 5

(19) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 9.18%.

(20) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 750° C., the nitrogen gas is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 30 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 2.94%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 5. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

Example 6

(21) 4 g of commercial methanol to olefin catalyst SAPO-34 is charged into a fixed-fluidized bed reactor to carry out a methanol to olefin reaction. The reaction raw material is a methanol aqueous solution with a concentration of 80 wt %, the reaction temperature is 490° C., the pressure is 0.1 MPa and the space velocity is 2.1 h.sup.−1. After the catalyst is deactivated, the coke amount of the deactivated catalyst is measured to be 9.18%.

(22) After the catalyst is deactivated, a nitrogen gas with a flow rate of 100 mL/min is introduced into the reactor for sweeping, the temperature of the reactor heating furnace is set. When the temperature is raised to 750° C., the nitrogen gas is continuously swept for 10 minutes, and then steam is introduced with a mass space velocity of 6 h.sup.−1, and the temperature is kept for 40 min. When the gasification of the steam is finished, a small amount of catalyst is taken to measure the coke amount. The coke amount is 1.76%. The regeneration is stopped after the temperature programming is over, the regeneration gas is switched to nitrogen gas. When the temperature of the heating furnace drops to 490° C., keep it for 20 min. A methanol aqueous solution with a concentration of 80 wt % is introduced after the temperature is stabilized, the space velocity is 2.1 h.sup.−1, the pressure is 0.1 MPa, and an evaluation of methanol to olefin reaction is carried out. The conversion of methanol and the selectivity to olefin with the regenerated catalyst are shown in FIG. 6. In the figure, “fresh agent” means a methanol to olefin catalyst which has not been used in the examples, that is, which is used as a methanol to olefin catalyst for the first time.

(23) The above are only a few examples of the present application, and are not intended to limit the present application in any way. Although the present application is disclosed in the above with preferred example, it is not intended to limit the present application. Any one skilled in the art can understand that other changes and modifications by using the above technical content without departing from the scope of the technical solution of the present application are equivalent to equivalent embodiments and belong to the scope of the technical solution.