MOLECULAR SIEVE-BASED CATALYST MODIFICATION APPARATUS, AND METHOD

Abstract

The present application discloses a molecular sieve-based catalyst modification apparatus. The apparatus comprises a feed unit 1, a modification unit 2 and a cooling unit 3 connected in sequence; the feed unit comprises a catalyst feed unit 11 and a modifier feed unit 12, a catalyst and a modifier are introduced into the modification unit 2 respectively by the catalyst feed unit and the modifier feed unit and are discharged from the modification unit after sufficient reaction in modification unit, and then enter the cooling unit 3 for cooling. The present application further discloses a use method for the molecular sieve-based catalyst modification apparatus. The use method comprises: introducing a catalyst and a modifier into the modification unit 2 respectively through the feed unit 1; wherein the catalyst is modified by the modifier in the modification unit 2, and then discharged to the cooling unit 3 to cool until the temperature is lower than 50 C., and then the cooled modified catalyst is transferred to any storage device.

Claims

1. A molecular sieve-based catalyst modification apparatus, comprising: a feed unit (1), a modification unit (2) and a cooling unit (3) connected in sequence; wherein the feed unit comprises a catalyst feed unit (11) and a modifier feed unit (12), a catalyst and a modifier are introduced into the modification unit (2) respectively by the catalyst feed unit and the modifier feed unit and are discharged from the modification unit after sufficient reaction in modification unit, and then enter the cooling unit 3 for cooling.

2. The molecular sieve-based catalyst modification apparatus according to claim 1, wherein the catalyst feed unit (11) comprises a feed bin (111), a conveyor (112), and the conveyor (112) is connected to the modification unit inlet (22) of the modification unit (2); the modifier feed unit (12) includes a modifier metering pump (121) and a preheater (122), and an outlet of the preheater (122) is connected to the modification unit feed distributor (24) of the modification unit (2).

3. The molecular sieve-based catalyst modification apparatus according to claim 2, wherein an inert gas pipe (123) and an air pipe (124) are disposed between the modifier metering pump (121) and the preheater (122).

4. The molecular sieve-based catalyst modification apparatus according to claim 1, wherein the modification unit (2) comprises a modification unit reactor (21), a modification unit inlet (22), a modification unit outlet (23), a modification unit feed distributor (24), a heater (25) and a modification unit exhaust port 26; wherein the modification unit reactor (21) is a fluidized bed reactor, the modification unit inlet (22) is disposed at a middle portion of the modification unit reactor (21); and the modification unit outlet (23) is disposed at the bottom of the side wall of the modification unit reactor (21); the modification unit feed distributor (24) is disposed at the bottom of the modification unit reactor (21); the heater (25) is disposed inside the modification unit reactor (21), and located below the modification unit inlet (22); the exhaust port (26) is disposed at the top of the modification unit reactor (21).

5. The molecular sieve-based catalyst modification apparatus according to claim 4, wherein a modification unit gas-solid separation device (27) is disposed below the exhaust port (26) inside the reactor (21).

6. The molecular sieve-based catalyst modification apparatus according to claim 1, wherein the cooling unit (3) includes a cooling unit reactor (31), a cooling unit inlet (32), a cooling unit outlet (33), a cooling unit feed distributor (34), a heat extractor (35), and a cooling unit exhaust port (36); wherein the cooling unit reactor is a fluidized bed reactor, the cooling unit inlet (32) is disposed at a middle portion of the cooling unit reactor (31); and the cooling unit outlet (33) is disposed at the bottom of the side wall of the cooling unit reactor (31); the modification unit feed distributor (34) is disposed at a bottom of the cooling unit reactor (31); the heat extractor (35) is disposed inside the cooling unit reactor (31), and is located below the modification unit inlet (32); the cooling unit exhaust port (36) is disposed at the top of the cooling unit reactor (31).

7. The molecular sieve-based catalyst modification apparatus according to claim 6, wherein a cooling unit gas-solid separation device (37) is disposed below the cooling unit exhaust port (36) inside the cooling unit reactor (31).

8. The molecular sieve-based catalyst modification apparatus according to claim 4, wherein the modification unit feed distributor (24) is any one selected from a powder metallurgy sintered plate distributor, a multi-tube distributor, and a distributor with wind caps.

9. The molecular sieve-based catalyst modification apparatus according to claim 4, wherein the heater (25) is at least one selected from an electric heater and a high temperature gas heater.

10. The molecular sieve-based catalyst modification apparatus according to claim 5, wherein the modification unit gas-solid separator (27) is at least one selected from a cyclone separator and a filter.

11. The molecular sieve-based catalyst modification apparatus according to claim 6, wherein the cooling unit feed distributor (34) is any one selected from a powder metallurgy sintered plate distributor, a multi-tube distributor, and a distributor with wind caps.

12. (canceled)

13. The molecular sieve-based catalyst modification apparatus according to claim 7, wherein the modification unit gas-solid separator (37) is at least one selected from a cyclone separator and a filter.

14. A method for modifying molecular sieve-based catalyst, wherein at least one of the molecular sieve-based catalyst modification apparatuses according to claim 1 is used in the method; comprising: introducing a catalyst and a modifier into the modification unit (2) respectively through the feed unit (1), wherein the catalyst is modified by the modifier in the modification unit (2), and then discharged to the cooling unit (3) to cool until the temperature is lower than 50 C., and then the cooled modified catalyst is transferred to any storage device.

15. The method for modifying molecular sieve-based catalyst according to claim 14, wherein the introduced catalyst is subjected to an activation treatment in the modification unit (2) before the modification, and the activation treatment specifically comprises: a) introducing air into the modification unit through the modifier feed unit; b) heating the catalyst to an activation treatment temperature, wherein the activation treatment temperature is in a range of 400 C. to 650 C.; c) activating the catalyst for an activation time in a range of 0.5 h to 3 h at an activation treatment temperature.

16. The method for modifying molecular sieve-based catalyst according to claim 15, wherein the air in the modification unit (2) is replaced with an inert gas after finishing the activation, and the replacement time is greater than 5 min, when the gas phase oxygen concentration is less than 1 vol. %, the replacement is completed.

17. (canceled)

18. The method for modifying molecular sieve-based catalyst according to claim 14, wherein the modification is carried out under an inert gas atmosphere at a temperature in a range of 150 C. to 600 C. with a modification time in a range of 0 h to 10 h.

19. (canceled)

20. (canceled)

21. (canceled)

22. The method for modifying molecular sieve-based catalyst according to claim 14, wherein the modifier is at least one selected from a phosphorus reagent, a silylating reagent, and toluene.

23. (canceled)

24. (canceled)

25. The method for modifying molecular sieve-based catalyst according to claim 22, wherein the phosphorus reagent is at least one selected from trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine, and methyldiethoxyphosphine.

26. (canceled)

27. (canceled)

28. The method for modifying molecular sieve-based catalyst according to claim 22, wherein the silylating reagent is at least one selected from tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, and tetrabutyl silicate.

29. The method for modifying molecular sieve-based catalyst according to claim 22, wherein the modifier has a phosphorus reagent content in a range of 1% to 10% by weight based on the total mass of the mixture wherein the modifier has a silylating reagent content in a range of 1% to 40% by weight based on the total mass of the mixture.

30. (canceled)

Description

DESCRIPTION OF THE FIGURES

[0052] FIG. 1 is a schematic view showing the structure of the molecular sieve-based catalyst modification apparatus of the present application.

LIST OF PARTS AND REFERENCE NUMBERS

[0053] 1feed unit; [0054] 2modification unit; [0055] 3cooling unit; [0056] 11catalyst feed unit; [0057] 12modifier feed unit; [0058] 111feed bin; [0059] 112conveyor; [0060] 121metering pump [0061] 122preheater [0062] 123inert gas pipe [0063] 124air pipe [0064] 21modification unit reactor [0065] 22modification unit inlet [0066] 23modification unit outlet [0067] 24modification unit feed distributor [0068] 25heater [0069] 26modification unit exhaust port [0070] 27modification unit gas-solid separation device [0071] 31cooling unit reactor [0072] 32cooling unit inlet [0073] 33cooling unit outlet [0074] 34cooling unit feed distributor [0075] 35heat extractor [0076] 36cooling unit exhaust [0077] 37cooling unit gas-solid separation device

DETAILED DESCRIPTION OF THE EMBODIMENT

[0078] The present application is described in detail below with reference to the examples, but the application is not limited to the examples.

[0079] Unless otherwise stated, the materials and catalysts in the examples of the present application are commercially purchased, wherein:

[0080] HZSM-5 molecular sieve-based catalyst and HZSM-11 molecular sieve-based catalyst are purchased from Nankai University Catalyst Factory, and the product particle size distribution is in a range of 20-150 m, D.sub.50=100 m.

[0081] Toluene is purchased from Qilu branch of sinopec, a superior grade product.

[0082] Trimethoxy phosphine, triethoxy phosphine, tripropoxy phosphine, tributoxy phosphine and methyl diethoxy phosphine are purchased from Wuhan Zeshancheng Biomedical Technology Co., Ltd., purity: 99%.

[0083] Tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate are purchased from Shandong Wanda Silicone New Materials Co., Ltd., purity: 99%.

Example 1

[0084] The apparatus shown in FIG. 1 is employed.

[0085] In this example, the reactor feed distributor is a powder metallurgy sintered plate distributor, the reactor heater is an electric heater, and the reactor gas-solid separator is a cyclone separator.

[0086] In this example, the cooler gas distributor is a powder metallurgy sintered plate distributor, the cooler heat extractor is a cooling water heat extractor, and the cooler gas-solid separator is a cyclone separator.

[0087] In this example, the catalyst is a HZSM-5 molecular sieve-based catalyst.

[0088] In this example, the modifier is a mixture of a phosphorus reagent, a silylating reagent, and toluene.

[0089] In this example, the phosphorus reagent is trimethoxyphosphorus; and the silylating reagent is tetramethyl silicate.

[0090] In this example, the content of phosphorus reagent in the modifier is 2% of the total mass of the mixture, and the content of silylating reagent is 20% of the total mass of the mixture.

[0091] In this example, the activation temperature is 650 C., the activation time is 3 h, the modification temperature is 600 C., the modification time is 2 h, the calcination temperature is 700 C., and the calcination time is 1 h.

[0092] The modified catalyst prepared in this example is named CAT-1.

Example 2

[0093] The apparatus shown in FIG. 1 is employed.

[0094] In this example, the reactor feed distributor is a multi-tube distributor, the reactor heater is a high temperature gas heater, and the reactor gas-solid separator is a filter.

[0095] In this example, the cooler gas distributor is a multi-tube distributor, the cooler heat extractor is a cooling air heat extractor, and the cooler gas-solid separator is a filter.

[0096] In this example, the catalyst is a HZSM-11 molecular sieve-based catalyst.

[0097] In this example, the modifier is a mixture of a phosphorus reagent, a silylating reagent, and toluene.

[0098] In this example, the phosphorus reagent is trimethoxyphosphorus; and the silylating reagent is tetraethyl silicate.

[0099] In this example, the content of phosphorus reagent in the modifier is 5% of the total mass of the mixture, and the content of silylating reagent is 40% of the total mass of the mixture.

[0100] In this example, the activation temperature is 500 C., the activation time is 3 h, the modification temperature is 500 C., the modification time is 3 h, the calcination temperature is 600 C., and the calcination time is 2 h.

[0101] The modified catalyst prepared in this example is named CAT-2.

Example 3

[0102] The apparatus shown in FIG. 1 is employed.

[0103] In this example, the reactor feed distributor is a hood type distributor, the reactor heater is a high temperature gas heater, and the reactor gas-solid separator is a filter.

[0104] In this example, the cooler gas distributor is a hood type distributor, the cooler heat extractor is a cooling water heat extractor, and the cooler gas-solid separator is a filter.

[0105] In this example, the catalyst is a HZSM-5 molecular sieve-based catalyst.

[0106] In this example, the modifier is a mixture of a phosphorus reagent, a silylating reagent, and toluene.

[0107] In this example, the phosphorus reagent is trimethoxyphosphorus; and the silylating reagent is tetramethyl silicate.

[0108] In this example, the content of phosphorus reagent in the modifier is 5% of the total mass of the mixture, and the content of silylating reagent is 40% of the total mass of the mixture.

[0109] In this example, the activation temperature is 400 C., the activation time is 3 h, the modification temperature is 400 C., the modification time is 5 h, the calcination temperature is 400 C., and the calcination time is 6 h.

[0110] The modified catalyst prepared in this example is named CAT-3.

Example 4

[0111] The apparatus shown in FIG. 1 is employed.

[0112] In this example, the reactor feed distributor is a powder metallurgy sintered plate distributor, the reactor heater is an electric heater, and the reactor gas-solid separator is a cyclone separator.

[0113] In this example, the cooler gas distributor is a powder metallurgy sintered plate distributor. The cooler heat extractor is a cooling air heat extractor, and the cooler gas-solid separator is a cyclone separator.

[0114] In this example, the catalyst is a HZSM-11 molecular sieve-based catalyst.

[0115] In this example, the modifier is a mixture of a phosphorus reagent, a silylating reagent, and toluene.

[0116] In this example, the phosphorus reagent is trimethoxyphosphorus; and the silylating reagent is tetraethyl silicate.

[0117] In this example, the content of phosphorus reagent in the modifier is 1% of the total mass of the mixture, and the content of silylation reagent is 10% of the total mass of the mixture.

[0118] In this example, the activation temperature is 500 C., the activation time is 0.5 h, the modification temperature is 300 C., the modification time is 8 h, the calcination temperature is 600 C., and the calcination time is 2 h.

[0119] The modified catalyst prepared in this example is named CAT-4.

Example 5

[0120] The reaction for preparing p-xylene and olefin from methanol with benzene and/or toluene is catalyzed using the modified catalysts prepared in Examples 1-4.

[0121] In the present application, the methanol and benzene and/or toluene, including three kinds of raw materials:

[0122] Methanol reacts with benzene, methanol reacts with toluene, and methanol reacts with benzene and toluene.

[0123] The reaction results are tested under the following conditions: the raw materials are fed with a micro feed pump, the catalyst loading is 10 g, the reaction temperature is 500 C., and the reaction pressure is normal pressure. The reaction product is analyzed by on-line Agilent 7890 gas chromatography, and sample analysis is conducted when the reaction has carried out for 10 min. The reaction conditions and results are shown in Table 1.

Methanol conversion rate=(the mass of methanol in the raw materialthe mass of methanol in the reaction product)/the mass of methanol in the raw material

Benzene conversion rate=(the mass of benzene in the raw materialthe mass of benzene in the reaction product)/the mass of benzene in the raw material

Toluene conversion rate=(the mass of toluene in the raw materialthe mass of toluene in the reaction product)/the mass of toluene in the raw material

Total selectivity of (ethylene+propylene+butene+p-xylene)=sum of masses of ethylene, propylene, butene and p-xylene in the reaction product/(total mass of reaction productthe mass of methanol in reaction productthe mass of benzene in reaction productthe mass of toluene in the reaction productthe mass of water in the reaction product)

Selectivity to p-xylene in xylene isomer=the mass of p-xylene in the reaction product/the mass of xylene in the reaction product

TABLE-US-00001 TABLE 1 Sequence Number 1 2 3 4 5 6 7 8 catalyst CAT-1 CAT-1 CAT-2 CAT-2 CAT-3 CAT-3 CAT-4 CAT-4 mass space velocity of 1 1 2 2 1 1 1 1 methanol (h.sup.1) mass space velocity of benzene 0 1 0 0.5 0 1 0.5 0 (h.sup.1) mass space velocity of toluene 1 0 1 0.5 1 0 0.5 1 (h.sup.1) conversion rate of methanol 91 92 80 81 95 96 98 97 (wt. %) conversion rate of benzene 30 32 35 33 (wt. %) conversion rate of toluene 35 38 39 40 40 39 (wt. %) total selectivity of (ethylene + 81 80 79 78 76 77 76 75 propylene + butene + p-xylene) (wt. %) Selectivity to p-xylene in 98 97 94 93 94 95 90 91 xylene isomer (wt. %)

[0124] The above is only a few embodiments of the present invention, and does not. Although the present invention is disclosed in the above preferred embodiments, it is not intended to limit the present invention. Without departing from the scope of the technical solutions of the present invention, slight changes or modifications according to the technical solution disclosed above by anyone skilled in the art are equivalent to equivalent implementation cases and all fall within the scope of the technical solutions.