CATALYST PRE-HYDROCARBON POOLING METHOD AND DEVICE THEREFOR

Abstract

Disclosed are a catalyst pre-hydrocarbon-pooling method and a pre-hydrocarbon-pooling device, relating to the technical field of preparation of low carbon olefins. A regenerated catalyst enters a pre-hydrocarbon-pooling reactor, and a pre-hydrocarbon-pooling reaction occurs between the regenerated catalyst and an activation medium to form “hydrocarbon pool” active species. “Pre-hydrocarbon-pooling” treatment is performed on the regenerated catalyst by providing a pre-hydrocarbon-pooling device, so that the regenerated catalyst forms the “hydrocarbon pooled” active species and carbon deposition before entering into an oxygenate conversion reactor, by way of which “hydrocarbon pool” active species distribution and coke distribution of the catalyst in the conversion reactor are improved. This shortens or eliminates a reaction “induction period” and improves the catalytic activity and selectivity of the regenerated catalyst for a reaction of an oxygenate to low-carbon olefins.

Claims

1. A catalyst pre-hydrocarbon-pooling method, wherein a regenerated catalyst enters a pre-hydrocarbon-pooling reactor to undergo a pre-hydrocarbon pooling reaction with an activation medium to form “hydrocarbon pool” active species.

2. The method according to claim 1, wherein main operating conditions of the pre-hydrocarbon pooling reactor are a reaction temperature of 300-600° C. and contact time of less than 300 minutes.

3. The method according to claim 1, wherein main operating conditions of the pre-hydrocarbon-pooling reactor are a reaction temperature of 360-560° C. and contact time of 0.001-200 minutes.

4. The method according to claim 1, wherein main operating conditions of the pre-hydrocarbon-pooling reactor are a reaction temperature of 400-530° C. and contact time of 10-150 minutes.

5. The method according to any one of claims 1 to 4, wherein the pre-hydrocarbon-pooling reactor adopts a low-velocity dense-phase fluidized bed having a superficial gas velocity of less than 0.5 m/s.

6. The method according to any one of claims 1 to 4, wherein the pre-hydrocarbon-pooling reactor adopts a low-velocity dense-phase fluidized bed having a superficial gas velocity of 0.0001-0.3 m/s.

7. The method according to any one of claims 1 to 4, wherein the pre-hydrocarbon-pooling reactor adopts a low-velocity dense-phase fluidized bed having a superficial gas velocity of 0.001-0.2 m/s.

8. The method according to any one of claims 1 to 7, wherein the activation medium is any one, two or more of an oxygenate raw material, a reaction product, a hydrocarbon, and other oxygenates, or a mixture thereof, wherein: the oxygenate raw material is any one, two or more of methanol, ethanol, dimethyl ether, and methyl ethyl ether, or a mixture thereof the reaction product is a reaction gas that has not undergone a separation or has been removed of part or all entrained catalyst by a first-stage separator or multiple stages of separators, or a reaction gas that has undergone heat exchanging, quenching, or water washing, or a reaction gas pressurized by a reaction gas compressor from a downstream olefin product separation unit, or a stripping gas from a top of a sewage stripper, or any one, two or more of the foregoing, or a mixture thereof the hydrocarbon is any one, two or more of products from the downstream olefin product separation unit, including ethylene, propylene, ethane, propane, mixed C4, C5+ fractions, and fuel gases, or a mixture thereof, or is any one, two or more of olefins, aromatic hydrocarbons, alkanes, or a mixture thereof and the other oxygenates are any one, two or more of any organic oxygenates, or a mixture thereof.

9. The method according to any one of claims 1 to 8, wherein the pre-hydrocarbon-pooling reactor is provided with an internal heat extractor or/and an external heat extractor, and a reaction temperature of the pre-hydrocarbon-pooling reactor is controlled mainly by adjusting an amount of the regenerated catalyst returned to the pre-hydrocarbon-pooling reactor, or/and a flow rate of a heat extracting medium or/and a flow rate of a fluidizing medium, or/and other parameters.

10. A catalyst pre-hydrocarbon-pooling device, comprising a regenerated catalyst inlet, a regenerated catalyst outlet, an activation medium inlet, and an activation medium outlet.

11. The device according to claim 10, further comprising an internal heat extractor or/and an external heat extractor.

12. The device according to claim 10 or 11, adopting any one, two or more of industrially used reactors including fluidized bed reactors, or a combination thereof, wherein the fluidized bed reactors include bubbling bed reactors, turbulent bed reactors, fast bed reactors, or riser reactors, and the like, wherein the riser reactors may be any industrially used equal-diameter or variable-diameter riser reactors.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIGS. 1 to 2 each are a schematic diagram of catalyst pre-hydrocarbon pooling (or pre-activation) method and device therefor according to the present invention.

[0044] The present invention will be described in detail below with reference to the accompanying drawings. The accompanying drawings are drawn to illustrate the present invention and do not constitute limitations on any specific implementation of the inventive concept of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0045] FIG. 1 is a schematic diagram of a catalyst pre-hydrocarbon pooling (or pre-activation) method and its device according to the present invention (countercurrent contact).

[0046] As shown in FIG. 1, the catalyst pre-hydrocarbon pooling (or pre-activation) device of the present invention includes a regenerated catalyst inlet 101 (including a catalyst distributor 41), a regenerated catalyst outlet 102, an activation medium inlet 103 (including a distributor 42), an activation medium outlet 104, or/and a fluidizing medium inlet 105 (including a distributor 43).

[0047] A regenerated catalyst 30 from a regenerator enters an upper portion of a pre-hydrocarbon pooling reactor sequentially through a regenerated catalyst conveying pipe 35 (including a control valve and a catalyst distributor, not shown in the figure), the regenerated catalyst inlet 101, and the catalyst distributor 41, and flows downwardly meanwhile having a countercurrent contact with an activation medium 12 to undergo chemical reactions such as pre-hydrocarbon pooling to form “hydrocarbon pool” active species and a certain amount of carbon deposition, so as to shorten or eliminate an “induction period” of a reaction.

[0048] The activation medium 12 enters a bottom of the pre-hydrocarbon pooling reactor sequentially through the activation medium inlet 103 and the distributor 42, and passes through a regenerated catalyst bed from bottom to top. A pre-hydrocarbon pooled reaction gas 10 enters a downstream oxygenate conversion reactor (settling zone) through the activation medium outlet 104.

[0049] Alternatively, the pre-hydrocarbon pooling reactor may also be provided therein with a first-stage or second-stage cyclone separator. After the pre-hydrocarbon pooled reaction gas is removed of the catalyst entrained therein, the reaction gas enters an inlet of a third-stage cyclone separator.

[0050] A “pre-hydrocarbon pooled” regenerated catalyst 40 leaving the pre-hydrocarbon pooling reactor enters a conversion reactor through the “pre-hydrocarbon pooled” regenerated catalyst outlet 102 and a regenerated catalyst conveying pipe 33 (including a control valve and a catalyst distributor, not shown in the figure), for recycling.

[0051] In order to better control a reaction temperature of the pre-hydrocarbon pooling reactor, the pre-hydrocarbon pooling reactor may be provided at an interior or/and an exterior thereof with an internal heat extractor or/and an external heat extractor (not shown in the figure) to maintain thermal balance of the pre-hydrocarbon pooling reaction system.

[0052] The reaction temperature of the pre-hydrocarbon pooling reactor may be controlled by adjusting an amount of the catalyst returned to the pre-hydrocarbon pooling reactor, or/and a flow rate of a heat extracting medium, or/and a flow rate of a fluidizing medium, or/and other parameters.

[0053] The fluidizing medium 19 may be steam or other fluids (preferably steam). The activation medium 12 is preferably a reaction gas. The heat extracting medium may be water, steam or other fluids (preferably water).

[0054] The catalyst distributor may be any industrially used catalyst distributor, and the steam (gas) distributor may be any industrially used gas distributor (including a distribution plate, a distribution pipe, etc.).

[0055] Main operating conditions of the pre-hydrocarbon pooling reactor are as follows: a reaction temperature of 300-600° C. (preferably 360-560° C., more preferably 400-530° C.), and contact time of less than 300 minutes (preferably 0.001-200 minutes, more preferably 10-150 minutes).

[0056] The pre-hydrocarbon pooling reactor adopts a low-velocity dense-phase fluidized bed having a superficial gas velocity of less than 0.5 m/s (preferably 0.0001-0.3 m/s, more preferably 0.001-0.2 m/s).

[0057] FIG. 2 is a schematic diagram of a catalyst pre-hydrocarbon pooling (or pre-activation) method and its device according to the present invention (co-current contact).

[0058] As shown in FIG. 2, the catalyst pre-hydrocarbon pooling (or pre-activation) device of the present invention includes a regenerated catalyst inlet 101 (including a catalyst distributor 41), a regenerated catalyst outlet 102, an activation medium inlet 103 (including a distributor 42), an activation medium outlet 104, or/and a fluidizing medium inlet 105 (including a distributor 43).

[0059] A regenerated catalyst 30 from a regenerator enters a bottom of the pre-hydrocarbon pooling reactor sequentially through a regenerated catalyst conveying pipe 35 (including a control valve and a catalyst distributor, not shown in the figure), the regenerated catalyst inlet 101, and the catalyst distributor 41. An activation medium 12 enters the bottom of the pre-hydrocarbon pooling reactor sequentially through the activation medium inlet 103 and the distributor 42. The regenerated catalyst 30 and the activation medium 12 flow co-currently, from bottom to top, through a regenerated catalyst bed to undergo chemical reactions such as pre-hydrocarbon pooling to form “hydrocarbon pool” active species and a certain amount of carbon deposition, so as to shorten or eliminate an “induction period” of a reaction.

[0060] A pre-hydrocarbon pooled reaction gas enters a downstream oxygenate conversion reactor (settling zone) through the activation medium outlet 104.

[0061] A “pre-hydrocarbon pooled” regenerated catalyst 40 leaving the pre-hydrocarbon pooling reactor enters a conversion reactor through the “pre-hydrocarbon pooled” regenerated catalyst outlet 102 and the regenerated catalyst conveying pipe 33 (including a control valve and a catalyst distributor, not shown in the figure), for recycling.

[0062] In order to better control a reaction temperature of the pre-hydrocarbon pooling reactor, the pre-hydrocarbon pooling reactor may be provided at an interior or/and an exterior thereof with an internal heat extractor or/and an external heat extractor (not shown in the figure) to maintain thermal balance of the pre-hydrocarbon pooling reaction system.

[0063] The reaction temperature of the pre-hydrocarbon pooling reactor may be controlled by adjusting an amount of the catalyst returned to the pre-hydrocarbon pooling reactor, or/and a flow rate of a heat extracting medium, or/and a flow rate of a fluidizing medium, or/and other parameters.

[0064] The fluidizing medium 19 may be steam or other fluids (preferably steam). The activation medium 12 is preferably a reaction gas. The heat extracting medium may be water, steam, or other fluids (preferably water).

[0065] The catalyst distributor may be any industrially used catalyst distributor, and the steam (gas) distributor may be any industrially used gas distributor (including a distribution plate, a distribution pipe, etc.).

[0066] Main operating conditions of the pre-hydrocarbon pooling reactor are as follows: a reaction temperature of 300-600° C. (preferably 360-560° C., more preferably 400-530° C.), and contact time of less than 300 minutes (preferably 0.001-200 minutes, more preferably 10-150 minutes).

[0067] The pre-hydrocarbon pooling reactor adopts a low-velocity dense-phase fluidized bed having a superficial gas velocity of less than 0.5 m/s (preferably 0.0001-0.3 m/s, more preferably 0.001-0.2 m/s).

Example 1

[0068] In Example 1, methanol is used as the oxygenate raw material, and a structure shown in FIG. 1 is adopted. The methanol conversion reactor and the regenerator are both operated under conventional conditions. SAPO-34 is used as the catalyst. A reaction gas is used as the activation medium. Main operating conditions of the pre-hydrocarbon pooling reactor are as follows: a superficial linear velocity of 0.1-0.2 m/s, a reaction temperature of 460° C., and contact time of 60-80 minutes. Here, hydrocarbon pool active species on the regenerated catalyst after pre-hydrocarbon pooling are substantially recovered and a reasonable level of carbon deposition is formed.

[0069] Simulation calculation results show that compared with the existing MTO technology, the method and the device of the present invention improve the selectivity to low-carbon olefins (C.sub.2.sup.=+C.sub.3.sup.=) by 5.7 percentage points.

[0070] A comparison of main parameters and effects is shown in Table 1.

TABLE-US-00001 TABLE 1 Existing MTO Present Parameters technology invention Temperature of conversion reaction ° C. 480 480 Temperature of regeneration ° C. 680 680 Catalyst/methanol ratio weight/weight 0.23 0.23 Coke on regenerated catalyst % 2.3 2.3 Regenerated catalyst cooler No Yes Temperature of cooled regenerated catalyst ° C. Pre-hydrocarbon pooling device No Yes Temperature of pre-hydrocarbon pooling 460 reaction ° C. Selectivity to low-carbon olefins 79.8 85.5 (C.sub.2.sup.= + C.sub.3.sup.=) % indicates data missing or illegible when filed

Example 2

[0071] In Example 2, methanol is used as the oxygenate raw material, and a structure shown in FIG. 1 is adopted. SAPO-34 is used as the catalyst. The methanol conversion reactor and the regenerator are both operated under conventional conditions. A reaction gas is used as the activation medium. Main operating conditions of the pre-hydrocarbon pooling reactor are as follows: a superficial linear velocity of 0.1-0.2 m/s, a reaction temperature of 460° C., and contact time of 30-40 minutes.

[0072] Simulation calculation results show that compared with the existing MTO technology, the present invention, with the addition of the pre-hydrocarbon pooling device of the present invention, improves the selectivity to low-carbon olefins (C.sub.2.sup.=+C.sub.3.sup.=) by 3.1 percentage points.

[0073] A comparison of main parameters and effects is shown in Table 2.

TABLE-US-00002 TABLE 2 Existing MTO Present Parameters technology invention Temperature of conversion reaction ° C. 480 480 Temperature of regeneration ° C. 680 680 Catalyst/methanol ratio weight/weight 0.23 0.23 Coke on regenerated catalyst % 2.3 2.3 Regenerated catalyst cooler No Yes Temperature of cooled regenerated 460 catalyst ° C. Pre-hydrocarbon pooling device No Yes Temperature of pre-hydrocarbon pooling 460 reaction ° C. Selectivity to low-carbon olefins 79.8 82.9 (C.sub.2.sup.= + C.sub.3.sup.=) %