Heavy oil catalytic cracking catalyst containing composite molecular sieve and preparation method thereof

Abstract

The invention discloses a heavy oil catalytic cracking catalyst containing a composite molecular sieve and a preparation method, and belongs to the technical field of heavy oil catalytic cracking catalysts. The catalyst carrier comprises 28-40% of a modified mesoporous-microporous molecular sieve, 20-29% of a microporous molecular sieve and the balance of a binder; wherein the mesoporous-microporous molecules are selected from a ZMQ-1 molecular sieve; the preparation method of the modified mesoporous-microporous molecular sieve comprises the following steps: activating a ZMQ-1 molecular sieve; putting the ZMQ-1 molecular sieve into a mixed solution of an active agent and a surfactant, stirring and drying; the preparation method comprises the following steps: putting a ZMQ-1 molecular sieve and chitosan into a citric acid solution, stirring, and drying to realize coating; performing chemical vapor deposition of tetraethoxysilane on the ZMQ-1 molecular sieve; and roasting in a muffle furnace, and reducing with H2 to obtain the modified mesoporous-microporous molecular sieve. The catalytic effect of the heavy oil catalytic cracking catalyst containing the composite molecular sieve is further improved, and the compressive strength of the catalyst is high and can reach 63.9 N / cm.

Description

Technical Field

[0001] The invention relates to the technical field of heavy oil catalytic cracking catalysts, and in particular to a heavy oil catalytic cracking catalyst containing a composite molecular sieve and a preparation method thereof. Background Art

[0002] Heavy oil is characterized by large molecules and complex molecular structure. Molecular sieves have a pore structure and can be used as a heavy oil catalytic cracking catalyst to catalytically crack large molecules of heavy oil.

[0003] CN 102744099 B discloses a heavy oil catalytic cracking catalyst and a preparation method, wherein the content of microporous molecular sieve is 10-40%, the content of modified meso-microporous molecular sieve is 1-40%, the content of binder is 1-30%, and the content of clay is 30-80%. The modified meso-microporous molecular sieve refers to dissolving a salt of rare earth and sulfuric acid, phosphoric acid, hydrochloric acid or a mixture thereof in deionized water, adding the meso-microporous molecular sieve into the above solution and impregnating it for 1-4 hours, drying the impregnated meso-microporous molecular sieve in an oven at 100-120° C. for 2-4 hours, and calcining it in a muffle furnace at 500-550° C. for 4-8 hours to obtain the modified meso-microporous molecular sieve.

[0004] However, its heavy oil yield, light oil yield and coke yield still need to be further improved. At the same time, the mechanical strength of the molecular sieve also needs to be further improved.

[0005] Based on this, the present invention designs a heavy oil catalytic cracking catalyst containing a composite molecular sieve and a preparation method to solve the above problems. Summary of the invention

[0006] In view of the above-mentioned shortcomings of the prior art, the present invention provides a heavy oil catalytic cracking catalyst containing a composite molecular sieve and a preparation method thereof.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0008] A heavy oil catalytic cracking catalyst containing a composite molecular sieve, comprising a catalyst carrier and an activator; the catalyst carrier comprises the following raw materials in weight percentage: 28-40% of a modified meso-microporous molecular sieve, 20-29% of a microporous molecular sieve, and the remainder being a binder; wherein the meso-microporous molecular sieve is selected from a ZMQ-1 molecular sieve;

[0009] The preparation method of the modified meso-microporous molecular sieve is:

[0010] (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere;

[0011] (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 1 to 2 minutes, and drying at 60 to 80° C.;

[0012] (3) placing ZMQ-1 molecular sieve and chitosan in a 55-65% citric acid solution, stirring for 2-5 minutes, and drying at 55-65° C. to achieve coating;

[0013] (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 85-96°C;

[0014] (5) The ZMQ-1 molecular sieve is then placed in a muffle furnace and calcined at 400-410°C for 3-4 hours, and then reduced with H2 to obtain a modified meso-microporous molecular sieve.

[0015] Furthermore, the modified meso-microporous molecular sieve has a particle size of 300-400 nm.

[0016] Furthermore, the particle size of the microporous molecular sieve is 200-300 nm.

[0017] Furthermore, the microporous molecular sieve is one or more of USY molecular sieve, HY molecular sieve, REUSY molecular sieve, REHSUY molecular sieve, HZSM-5 molecular sieve, REZSM-5 molecular sieve, and REHZSM-5 molecular sieve.

[0018] Furthermore, the binder is aluminum sol.

[0019] Furthermore, the active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.2-1.5:2.

[0020] Furthermore, the mass ratio of ZMQ-1 molecular sieve to chitosan is 100:1-3.

[0021] Furthermore, the volume ratio of ZMQ-1 molecular sieve to 55-65% citric acid solution is 1:2.2-5.

[0022] In order to better achieve the purpose of the present invention, the present invention also provides a method for preparing a heavy oil catalytic cracking catalyst containing a composite molecular sieve, wherein a microporous molecular sieve, a modified meso-microporous molecular sieve, a binder and an activator are mixed and extruded into strips, and then calcined at 400-450°C for 1-2h to obtain a heavy oil catalytic cracking catalyst containing a composite molecular sieve.

[0023] Furthermore, the surfactant is a nonionic surfactant.

[0024] Compared with the prior art, the present invention has the following beneficial effects: the catalytic effect of the heavy oil catalytic cracking catalyst containing the composite molecular sieve is further improved, the heavy oil yield is reduced, the light oil yield is increased, and the coke yield is reduced in the heavy oil catalytic cracking reaction product. The catalyst has a high compressive strength, which can reach 63.9N / cm.

[0025] The ZMQ-1 molecular sieve of the invention is modified and coated with chitosan and citric acid solution after being activated, and then subjected to chemical vapor deposition of tetraethyl orthosilicate to form a core-shell structure, and then subjected to calcination and H2 reduction to obtain a modified meso-microporous molecular sieve. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Embodiment 1: In some embodiments, a heavy oil catalytic cracking catalyst containing a composite molecular sieve includes a catalyst carrier and an activator; the catalyst carrier includes the following raw materials in weight percentage: 28% of modified meso-microporous molecular sieve, 29% of microporous molecular sieve, and the balance is a binder; wherein the meso-microporous molecular sieve is selected from ZMQ-1 molecular sieve;

[0028] The modified meso-microporous molecular sieve has a particle size of 300 nm;

[0029] The particle size of the microporous molecular sieve is 200 nm;

[0030] The ZMQ-1 molecular sieve is prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A.

[0031] The microporous molecular sieve is USY molecular sieve.

[0032] The binder is aluminum sol.

[0033] The active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.2:2.

[0034] The preparation method of the modified meso-microporous molecular sieve is:

[0035] (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere;

[0036] (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 1 min, and drying at 80°C;

[0037] The surfactant is a nonionic surfactant (TX series nonionic surfactant).

[0038] (3) placing ZMQ-1 molecular sieve and chitosan in a 55% citric acid solution, stirring for 5 min, and drying at 55° C. to achieve coating;

[0039] The mass ratio of ZMQ-1 molecular sieve to chitosan is 100:1;

[0040] The volume ratio of ZMQ-1 molecular sieve to 55% citric acid solution is 1:5;

[0041] (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 85°C;

[0042] (5) Then, the ZMQ-1 molecular sieve was placed in a muffle furnace and calcined at 400 °C for 4 h, and then reduced with H2 to obtain a modified meso-microporous molecular sieve;

[0043] The microporous molecular sieve, modified meso-microporous molecular sieve, binder and activator are mixed and extruded into strips, and then calcined at 400℃ for 2h to obtain a heavy oil catalytic cracking catalyst containing a composite molecular sieve. The specific surface area of ​​the catalyst is 850m 2 / g.

[0044] Embodiment 2: In some embodiments, a heavy oil catalytic cracking catalyst containing a composite molecular sieve includes a catalyst carrier and an activator; the catalyst carrier includes the following raw materials in weight percentage: 40% of modified meso-microporous molecular sieve, 20% of microporous molecular sieve, and the balance is a binder; wherein the meso-microporous molecular sieve is selected from ZMQ-1 molecular sieve;

[0045] The modified meso-microporous molecular sieve has a particle size of 400 nm;

[0046] The particle size of the microporous molecular sieve is 300 nm;

[0047] The ZMQ-1 molecular sieve is prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A.

[0048] The microporous molecular sieve is HY molecular sieve.

[0049] The binder is aluminum sol.

[0050] The active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.5:2.

[0051] The preparation method of the modified meso-microporous molecular sieve is:

[0052] (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere;

[0053] (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 2 min, and drying at 60°C;

[0054] The surfactant is a nonionic surfactant (NP series nonionic surfactant).

[0055] (3) placing ZMQ-1 molecular sieve and chitosan in a 65% citric acid solution, stirring for 2 min, and drying at 65° C. to achieve coating;

[0056] The mass ratio of ZMQ-1 molecular sieve to chitosan is 100:3;

[0057] The volume ratio of ZMQ-1 molecular sieve to 65% citric acid solution is 1:2.2;

[0058] (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 96°C;

[0059] (5) Then, the ZMQ-1 molecular sieve was placed in a muffle furnace and calcined at 410°C for 3 h, and then reduced with H2 to obtain a modified meso-microporous molecular sieve;

[0060] The microporous molecular sieve, modified meso-microporous molecular sieve, binder and activator are mixed and extruded into strips, and then calcined at 450℃ for 1h to obtain a heavy oil catalytic cracking catalyst containing a composite molecular sieve. The specific surface area of ​​the catalyst is 900m 2 / g.

[0061] Embodiment 3: In some embodiments, a heavy oil catalytic cracking catalyst containing a composite molecular sieve includes a catalyst carrier and an activator; the catalyst carrier includes the following raw materials in weight percentage: 35% of modified meso-microporous molecular sieve, 25% of microporous molecular sieve, and the balance is a binder; wherein the meso-microporous molecular sieve is selected from ZMQ-1 molecular sieve;

[0062] The modified meso-microporous molecular sieve has a particle size of 350 nm;

[0063] The particle size of the microporous molecular sieve is 220 nm;

[0064] The ZMQ-1 molecular sieve is prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A.

[0065] The microporous molecular sieves are USY molecular sieves and HY molecular sieves.

[0066] The binder is aluminum sol.

[0067] The active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.3:2.

[0068] The preparation method of the modified meso-microporous molecular sieve is:

[0069] (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere;

[0070] (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 1.6 min, and drying at 70°C;

[0071] The surfactant is a nonionic surfactant (TX series nonionic surfactant).

[0072] (3) placing ZMQ-1 molecular sieve and chitosan in a 58% citric acid solution, stirring for 3 min, and drying at 60° C. to achieve coating;

[0073] The mass ratio of ZMQ-1 molecular sieve to chitosan is 100:2;

[0074] The volume ratio of ZMQ-1 molecular sieve to 58% citric acid solution is 1:4;

[0075] (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 92°C;

[0076] (5) Then, the ZMQ-1 molecular sieve was placed in a muffle furnace and calcined at 405°C for 3.2 h, and then reduced with H2 to obtain a modified meso-microporous molecular sieve;

[0077] The microporous molecular sieve, modified meso-microporous molecular sieve, binder and activator are mixed and extruded into strips, and then calcined at 430℃ for 1.6h to obtain a heavy oil catalytic cracking catalyst containing a composite molecular sieve. The specific surface area of ​​the catalyst is 1000m 2 / g.

[0078] Embodiment 4: In some embodiments, a heavy oil catalytic cracking catalyst containing a composite molecular sieve includes a catalyst carrier and an activator; the catalyst carrier includes the following raw materials in weight percentage: 39% of modified meso-microporous molecular sieve, 22% of microporous molecular sieve, and the balance is a binder; wherein the meso-microporous molecular sieve is selected from ZMQ-1 molecular sieve;

[0079] The modified meso-microporous molecular sieve has a particle size of 320 nm;

[0080] The particle size of the microporous molecular sieve is 290 nm;

[0081] The ZMQ-1 molecular sieve is prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A.

[0082] The microporous molecular sieve is REUSY molecular sieve.

[0083] The binder is aluminum sol.

[0084] The active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.4:2.

[0085] The preparation method of the modified meso-microporous molecular sieve is:

[0086] (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere;

[0087] (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 1.7 min, and drying at 65°C;

[0088] The surfactant is a nonionic surfactant (NP series nonionic surfactant).

[0089] (3) placing ZMQ-1 molecular sieve and chitosan in a 62% citric acid solution, stirring for 4 min, and drying at 57° C. to achieve coating;

[0090] The mass ratio of ZMQ-1 molecular sieve to chitosan is 100:2.6;

[0091] The volume ratio of ZMQ-1 molecular sieve to 62% citric acid solution is 1:4.2;

[0092] (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 95°C;

[0093] (5) Then, the ZMQ-1 molecular sieve was placed in a muffle furnace and calcined at 408°C for 3.8 h, and then reduced with H2 to obtain a modified meso-microporous molecular sieve;

[0094] The microporous molecular sieve, modified meso-microporous molecular sieve, binder and activator are mixed and extruded into strips, and then calcined at 440℃ for 1.9h to obtain a heavy oil catalytic cracking catalyst containing a composite molecular sieve. The specific surface area of ​​the catalyst is 900m 2 / g.

[0095] Embodiment 5: The microporous molecular sieve is one or more of USY molecular sieve, HY molecular sieve, REUSY molecular sieve, REHSUY molecular sieve, HZSM-5 molecular sieve, REZSM-5 molecular sieve and REHZSM-5 molecular sieve. The surfactant is a combination of TX series nonionic surfactant and NP series nonionic surfactant.

[0096] Comparative Example 1: The difference from Example 3 is that in the preparation method of the modified meso-microporous molecular sieve, the process of step (3) is not performed: the ZMQ-1 molecular sieve is replaced by the commercially available meso-microporous ZSM-5 molecular sieve, the commercially available meso-microporous ZSM-5 molecular sieve and chitosan are placed in a 30% citric acid solution, stirred for 3 minutes, and dried at 60°C to achieve coating; the mass ratio of ZMQ-1 molecular sieve to chitosan is 100:5; the volume ratio of ZMQ-1 molecular sieve to citric acid solution is 1:4.

[0097] The catalysts prepared in Example 3 of the present invention and Comparative Example 1 were respectively used to participate in the catalytic cracking reaction of heavy oil. The catalytic cracking performance and mechanical strength of each catalyst were tested and shown in Table 1.

[0098] Table 1 Catalytic cracking performance and mechanical strength test results

[0099] name Example 3 Comparative Example 1 Dry gas Wt% 1.60 1.90 Liquefied gas Wt% 14.88 17.35 Light oil Wt% 71.87 62.31 Heavy oil Wt% 9.21 11.80 Coke Wt% 2.44 6.64 Compressive strength N / cm 63.9 56.3

[0100] The catalytic effect of the heavy oil catalytic cracking catalyst containing the composite molecular sieve of the present invention is further improved, and the heavy oil yield in the heavy oil catalytic cracking reaction product is further reduced, the light oil yield is further increased, and the coke yield is further reduced. The catalyst has a high compressive strength, which can reach 63.9N / cm.

[0101] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A heavy oil catalytic cracking catalyst containing a composite molecular sieve, characterized in that: It includes a catalyst carrier and an activator; the catalyst carrier includes the following raw materials in weight percentage: 28-40% of modified meso-microporous molecular sieve, 20-29% of microporous molecular sieve, and the balance is a binder; wherein the meso-microporous molecular sieve is selected from ZMQ-1 molecular sieve; The preparation method of the modified meso-microporous molecular sieve is: (1) activating the ZMQ-1 molecular sieve under an inert gas atmosphere; (2) placing the ZMQ-1 molecular sieve into a mixed solution of the active agent and the surfactant, stirring for 1 to 2 minutes, and drying at 60 to 80° C.; (3) placing ZMQ-1 molecular sieve and chitosan in a 55-65% citric acid solution, stirring for 2-5 minutes, and drying at 55-65° C. to achieve coating; (4) chemical vapor deposition of tetraethyl orthosilicate on ZMQ-1 molecular sieve at 85-96°C; (5) The ZMQ-1 molecular sieve is then placed in a muffle furnace and calcined at 400-410°C for 3-4 hours, and then reduced with H2 to obtain a modified meso-microporous molecular sieve.

2. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 1, characterized in that: The modified meso-microporous molecular sieve has a particle size of 300-400 nm.

3. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 2, characterized in that: The particle size of the microporous molecular sieve is 200-300 nm.

4. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 3, characterized in that: The microporous molecular sieve is one or more of USY molecular sieve, HY molecular sieve, REUSY molecular sieve, REHSUY molecular sieve, HZSM-5 molecular sieve, REZSM-5 molecular sieve and REHZSM-5 molecular sieve.

5. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 4, characterized in that: The binder is aluminum sol.

6. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 5, characterized in that: The active agent is tungsten carbide doped with titanium dioxide; the mass of tungsten carbide: the mass of titanium dioxide = 1.2-1.5:

2.

7. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 6, characterized in that: The mass ratio of ZMQ-1 molecular sieve to chitosan is 100:1-3.

8. The heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 7, characterized in that: The volume ratio of ZMQ-1 molecular sieve to 55-65% citric acid solution is 1:2.2-5.

9. A method for preparing a heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 8, characterized in that: The microporous molecular sieve, modified meso-microporous molecular sieve, binder and activator are mixed and extruded into strips, and then calcined at 400-450° C. for 1-2 hours to obtain a heavy oil catalytic cracking catalyst containing the composite molecular sieve.

10. The method for preparing a heavy oil catalytic cracking catalyst containing a composite molecular sieve according to claim 9, characterized in that: The surfactant is a nonionic surfactant.