Modified ZMQ-1 molecular sieve for catalytic cracking and catalyst composition thereof

Abstract

The invention discloses a modified ZMQ-1 molecular sieve for catalytic cracking and a catalyst composition thereof, and belongs to the technical field of molecular sieves, and the modified ZMQ-1 molecular sieve is prepared by the following steps: firstly preparing a CH3COONa solution, adding CeO2, and uniformly mixing at a stirring speed of 150-200r / min to prepare a modified liquid A; putting a ZMQ-1 molecular sieve into the modified liquid A, stirring under a water bath condition, and calcining to obtain a modified ZMQ-1 molecular sieve intermediate material; (NH4) 2Fe (SO4) 2.6 H2O, ZnSO4. 7H2O, (NH4) 2C2O4 and Ce (NO3) 4 are taken and added into water to be evenly mixed, and modified liquid B is prepared; and putting the modified ZMQ-1 molecular sieve intermediate material into a modified liquid B which is preheated to 88-95 DEG C by adopting an equivalent-volume impregnation method, drying after impregnation is completed, and calcining to obtain the modified ZMQ-1 molecular sieve. The catalyst composition for catalytic cracking of heavy oil has the advantages of high yields of dry gas, liquefied gas, gasoline and diesel oil, low yields of coke and heavy oil, high yields of low-carbon olefins (ethylene and propylene) and the like.

Description

Technical Field

[0001] The invention relates to the technical field of molecular sieves, and in particular to a modified ZMQ-1 molecular sieve for catalytic cracking and a catalyst composition thereof. Background Art

[0002] Ethylene and propylene are important chemical raw materials, and the demand for them is very strong. Heavy oil catalytic cracking to produce low-carbon olefins is an important way to produce ethylene and propylene, but it has problems such as low ethylene yield and high coke yield. At the same time, as heavy oil raw materials gradually become heavier and worse, the requirements for the catalytic cracking performance of catalysts are increasing.

[0003] CN 118515294 A discloses a novel silicate zeolite molecular sieve ZMQ-1 and its use. The anhydrous chemical composition of the precursor of the ZMQ-1 molecular sieve silicate zeolite molecular sieve is SiO2·1 / xXO 1.5 mMO 0.5 qQ, silicate zeolite molecular sieve precursor anhydrous chemical composition is SiO2·1 / xXO 1.5 mMO 0.5 qQ, wherein X is a framework trivalent element, Si / X molar ratio x≥5, M is a framework balancing cation, M / Si molar ratio 0≤m≤1, Q is a diquaternary ammonium or diquaternary phosphorus organic structure directing agent, Q / Si molar ratio q≥0.01. The molecular sieve can be further applied to energy storage, sensing, loading, adsorption, separation or catalysis processes due to its novel topological structure, unique pore system, and high thermal and hydrothermal stability, and may exhibit unique properties.

[0004] At present, there is little research on the application of ZMQ-1 molecular sieve modification and its use in catalytic cracking of heavy oil to produce ethylene and propylene.

[0005] Based on this, the present invention designs a modified ZMQ-1 molecular sieve and a catalyst composition thereof for catalytic cracking 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 modified ZMQ-1 molecular sieve and a catalyst composition thereof for catalytic cracking.

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

[0008] A modified ZMQ-1 molecular sieve for catalytic cracking is obtained by modifying the ZMQ-1 molecular sieve, and the specific steps are as follows:

[0009] First, a CH3COONa solution is prepared, CeO2 is added, and the mixture is uniformly mixed at a stirring speed of 150 to 200 r / min to prepare a modified liquid A; a ZMQ-1 molecular sieve is placed in the modified liquid A, stirred for 10 to 15 minutes at a temperature of 35 to 40° C. in a water bath, and calcined at 250 to 300° C. for 0.5 to 1 hour to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0010] Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4, add them into water and mix them evenly to prepare modified liquid B; adopt the equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated to 88-95°C, after the impregnation is completed, place it at 65-70°C for drying for 5-7h, then place it at 500-520°C for calcination for 1-2h, then heat it to 688-700°C for calcination for 0.5-1h, then cool it to 450-500°C for calcination for 1-2h, and then obtain the modified ZMQ-1 molecular sieve.

[0011] Furthermore, the concentration of CH3COONa solution is 0.35-0.4 mol·L -1 .

[0012] Furthermore, the mass ratio of CeO2 to CH3COONa solution is 0.05-0.13:1.

[0013] Furthermore, the volume ratio of ZMQ-1 molecular sieve to modified liquid A is 1:1.4-1.6.

[0014] Furthermore, the molar ratio of (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 is 1:(1.1~1.2):(1.3~1.6):(1.2~1.7).

[0015] In order to better achieve the purpose of the present invention, the present invention also provides a catalyst composition containing a modified ZMQ-1 molecular sieve, comprising the following raw materials in parts by weight: 15 to 55 parts of modified ZMQ-1 molecular sieve, 5 to 20 parts of USY molecular sieve and / or 5 to 10 parts of ZSM-5 molecular sieve, 5 to 30 parts of aluminum source, 15 to 30 parts of clay, and 12 to 20 parts of binder.

[0016] Furthermore, the aluminum source is selected from one of pseudo-boehmite, boehmite, and alumina.

[0017] Furthermore, 2×m (USY molecular sieve) + 2×m (ZSM-5 molecular sieve) < m (modified ZMQ-1 molecular sieve), that is, twice the mass of USY molecular sieve + twice the mass of ZSM-5 molecular sieve < the mass of modified ZMQ-1 molecular sieve.

[0018] Furthermore, the binder is aluminum sol.

[0019] In order to better achieve the purpose of the present invention, the present invention also provides the use of the catalyst composition in the catalytic cracking of heavy oil to produce ethylene and propylene.

[0020] Compared with the prior art, the present invention has the following beneficial effects: the present invention first modifies the ZMQ-1 molecular sieve by CH3COONa and CeO2 to obtain a modified ZMQ-1 molecular sieve intermediate material, and then uses the ZMQ-1 molecular sieve as a carrier and adopts an equal volume impregnation method to load ZnFe2O4 and CeO2 onto the ZMQ-1 molecular sieve. Then, the modified ZMQ-1 molecular sieve, USY type molecular sieve and / or ZSM-5 molecular sieve, aluminum source, clay, and binder are stirred and mixed at room temperature, and spray-formed after beating, and the catalyst composition is obtained after solidification, washing, and drying. The catalyst composition of the present invention is used to catalyze and crack heavy oil, which has the advantages of high yield of dry gas, liquefied gas, gasoline, and diesel, low yield of coke and heavy oil, and high yield of low-carbon olefins (ethylene and propylene). DETAILED DESCRIPTION

[0021] 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.

[0022] Embodiment 1: In some embodiments, a catalyst composition containing a modified ZMQ-1 molecular sieve comprises the following raw materials in parts by weight: 15 parts of a modified ZMQ-1 molecular sieve, 5 parts of a USY molecular sieve, 5 parts of an aluminum source, 15 parts of clay, and 12 parts of a binder. The aluminum source is pseudo-boehmite. The binder is aluminum sol. The raw materials are stirred and mixed at room temperature, slurried, and then sprayed to form, and then cured, washed, and dried to obtain a catalyst composition.

[0023] The preparation method of the modified ZMQ-1 molecular sieve comprises the following specific steps:

[0024] Step 1: Prepare CH3COONa solution (0.35 mol·L -1), CeO2 (CeO2:CH3COONa=0.05:1, mass ratio) was added, and the mixture was uniformly mixed at a stirring speed of 150r / min to prepare a modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A) was put into the modified liquid A (ZMQ-1 molecular sieve: modified liquid A=1:1.4, volume ratio), stirred for 10min in a water bath at 35°C, and calcined at 250°C for 0.5h to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0025] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.1:1.3:1.2, molar ratio), add to 2 times the volume of water and mix well to prepare modified liquid B;

[0026] Step 3: adopt an equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated at 88°C, place it at 65°C for drying for 5h after impregnation, then place it at 500°C for calcination for 1h, then heat it to 688°C for calcination for 0.5h, then cool it to 450°C for calcination for 1h to obtain the modified ZMQ-1 molecular sieve;

[0027] The present invention first modifies the ZMQ-1 molecular sieve by CH3COONa and CeO2 to obtain a modified ZMQ-1 molecular sieve intermediate material, and then uses the ZMQ-1 molecular sieve as a carrier to load ZnFe2O4 and CeO2 onto the ZMQ-1 molecular sieve by an equal volume impregnation method.

[0028] Embodiment 2: In some embodiments, a catalyst composition containing a modified ZMQ-1 molecular sieve includes the following raw materials in parts by weight: 55 parts of a modified ZMQ-1 molecular sieve, 20 parts of a USY molecular sieve, 5 parts of a ZSM-5 molecular sieve, 30 parts of an aluminum source, 30 parts of clay, and 20 parts of a binder. The aluminum source is boehmite. The binder is aluminum sol. The raw materials are stirred and mixed at room temperature, slurried, and then sprayed to form, and then cured, washed, and dried to obtain a catalyst composition.

[0029] The preparation method of the modified ZMQ-1 molecular sieve comprises the following specific steps:

[0030] Step 1: Prepare CH3COONa solution (0.4 mol·L -1), CeO2 (CeO2:CH3COONa=0.13:1, mass ratio) was added, and the mixture was uniformly mixed at a stirring speed of 200 r / min to prepare a modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A) was put into the modified liquid A (ZMQ-1 molecular sieve: modified liquid A=1:1.6, volume ratio), stirred for 15 min in a 40°C water bath, and calcined at 300°C for 1 h to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0031] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.2:1.6:1.7, molar ratio), add to 4 times the volume of water and mix well to prepare modified liquid B;

[0032] Step 3: adopt an equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated at 95°C, after impregnation, place it at 70°C for drying for 7h, then place it at 520°C for calcination for 2h, then heat it to 700°C for calcination for 1h, then cool it to 500°C for calcination for 2h, and obtain the modified ZMQ-1 molecular sieve;

[0033] The present invention first modifies the ZMQ-1 molecular sieve by CH3COONa and CeO2 to obtain a modified ZMQ-1 molecular sieve intermediate material, and then uses the ZMQ-1 molecular sieve as a carrier to load ZnFe2O4 and CeO2 onto the ZMQ-1 molecular sieve by an equal volume impregnation method.

[0034] Embodiment 3: In some embodiments, a catalyst composition containing a modified ZMQ-1 molecular sieve includes the following raw materials in parts by weight: 40 parts of a modified ZMQ-1 molecular sieve, 10 parts of a ZSM-5 molecular sieve, 20 parts of an aluminum source, 20 parts of clay, and 15 parts of a binder. The aluminum source is alumina. The binder is aluminum sol. The raw materials are stirred and mixed at room temperature, slurried, and then sprayed to form, and then cured, washed, and dried to obtain a catalyst composition.

[0035] The preparation method of the modified ZMQ-1 molecular sieve comprises the following specific steps:

[0036] Step 1: Prepare CH3COONa solution (0.37 mol·L -1), CeO2 (CeO2:CH3COONa=0.1:1, mass ratio) was added, and the mixture was uniformly mixed at a stirring speed of 180r / min to prepare a modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A) was put into the modified liquid A (ZMQ-1 molecular sieve: modified liquid A=1:1.5, volume ratio), stirred for 13min in a water bath at 37°C, and calcined at 260°C for 0.7h to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0037] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.1:1.4:1.5, molar ratio), add 3 times the volume of water and mix well to prepare modified liquid B;

[0038] Step 3: Using an equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated at 90°C. After impregnation, place it at 68°C for drying for 6 hours, then place it at 512°C for calcination for 1.1 hours, then heat it to 695°C for calcination for 0.6 hours, and then cool it to 470°C for calcination for 1.2 hours to obtain a modified ZMQ-1 molecular sieve;

[0039] The present invention first modifies the ZMQ-1 molecular sieve by CH3COONa and CeO2 to obtain a modified ZMQ-1 molecular sieve intermediate material, and then uses the ZMQ-1 molecular sieve as a carrier to load ZnFe2O4 and CeO2 onto the ZMQ-1 molecular sieve by an equal volume impregnation method.

[0040] Embodiment 4: In some embodiments, a catalyst composition containing a modified ZMQ-1 molecular sieve comprises the following raw materials in parts by weight: 50 parts of a modified ZMQ-1 molecular sieve, 10 parts of a USY molecular sieve and / or 10 parts of a ZSM-5 molecular sieve, 15 parts of an aluminum source, 18 parts of clay, and 16 parts of a binder. The aluminum source is selected from one or more of pseudo-boehmite, boehmite, and alumina. The binder is aluminum sol. The raw materials are stirred and mixed at room temperature, slurried, and then sprayed to form, and then cured, washed, and dried to obtain a catalyst composition.

[0041] The preparation method of the modified ZMQ-1 molecular sieve comprises the following specific steps:

[0042] Step 1: Prepare CH3COONa solution (0.39 mol·L -1), CeO2 (CeO2:CH3COONa=0.12:1, mass ratio) was added, and the mixture was uniformly mixed at a stirring speed of 190 r / min to prepare a modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A) was put into the modified liquid A (ZMQ-1 molecular sieve: modified liquid A=1:1.6, volume ratio), stirred for 14 min in a 36°C water bath, and calcined at 295°C for 0.8 h to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0043] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.2:1.5:1.3, molar ratio), add 3.5 times the volume of water and mix well to prepare modified liquid B;

[0044] Step 3: Using an equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated at 93°C. After impregnation, place it at 69°C for drying for 5.5h, then place it at 515°C for calcination for 1h, then heat it to 692°C for calcination for 0.5h, and then cool it to 485°C for calcination for 1h to obtain the modified ZMQ-1 molecular sieve;

[0045] The present invention first modifies the ZMQ-1 molecular sieve by CH3COONa and CeO2 to obtain a modified ZMQ-1 molecular sieve intermediate material, and then uses the ZMQ-1 molecular sieve as a carrier to load ZnFe2O4 and CeO2 onto the ZMQ-1 molecular sieve by an equal volume impregnation method.

[0046] Comparative Example 1: The difference from Example 3 is that the preparation method of the modified ZMQ-1 molecular sieve is different.

[0047] The preparation method of modified ZMQ-1 molecular sieve comprises the following specific steps:

[0048] Step 1: Prepare CH3COONa solution (0.39 mol·L -1 ), adding CeO2 (CeO2:CH3COONa=0.12:1, mass ratio), and mixing evenly at a stirring speed of 190r / min to prepare a modified liquid A;

[0049] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.2:1.5:1.3, molar ratio), add 3.5 times the volume of water and mix well to prepare modified liquid B;

[0050] Step 3: Mix the modified liquid A and the modified liquid B to obtain a mixed modified liquid, put the ZMQ-1 molecular sieve (ZMQ-1 molecular sieve is prepared according to the contents disclosed in Chinese invention patent CN 118515294 A) into the mixed modified liquid (ZMQ-1 molecular sieve: mixed modified liquid = 1:1.6, volume ratio), stir for 14 min in a 36°C water bath, and calcine at 295°C for 0.8 h to obtain a modified ZMQ-1 molecular sieve.

[0051] Comparative Example 2: The difference from Example 3 is that the preparation method of the modified ZMQ-1 molecular sieve is different.

[0052] The preparation method of modified ZMQ-1 molecular sieve comprises the following specific steps:

[0053] Step 1: Prepare CH3COONa solution (0.39 mol·L -1 ), adding CeO2 (CeO2:CH3COONa=0.12:1, mass ratio), and mixing evenly at a stirring speed of 190r / min to prepare a modified liquid A;

[0054] Step 2: Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 ((NH4)2Fe(SO4)2·6H2O: ZnSO4·7H2O: (NH4)2C2O4: Ce(NO3)4=1:1.2:1.5:1.3, molar ratio), add 3.5 times the volume of water and mix well to prepare modified liquid B;

[0055] Step 3: Mix the modified liquid A and the modified liquid B to obtain a mixed modified liquid. Using an equal volume impregnation method, take a ZMQ-1 molecular sieve (ZMQ-1 molecular sieve is prepared with reference to the contents disclosed in Chinese invention patent CN 118515294 A) and put it into the mixed modified liquid preheated to 93°C. After the impregnation is completed, place it at 69°C for drying for 5.5h, then place it at 515°C for calcination for 1h, then heat it to 692°C for calcination for 0.5h, and then cool it to 485°C for calcination for 1h to obtain a modified ZMQ-1 molecular sieve.

[0056] Test Example: The performance of the catalyst compositions containing the modified ZMQ-1 molecular sieve prepared in Examples 1 to 3 and Comparative Examples 1 to 2 was tested.

[0057] Test conditions: FFB small fixed fluidized bed, catalytic cracking reaction temperature 625℃, catalyst-oil weight ratio 15. The basic properties of the feedstock oil are shown in Table 1.

[0058] Table 1 Basic properties of crude oil

[0059] project Numeric <![CDATA[Density (20 °C) kg / m 3 > 921.6 Residual carbon m% 8.7 Hydrogen m% 14.39 Sulfur m% 0.15 Fe ppm 7.5 Ni ppm 5.8 V ppm 0.3 Na ppm 1.6

[0060] The test results are shown in Table 2:

[0061] Table 2 Test results

[0062]

[0063]

[0064] The catalyst composition of the present invention is used to catalytically crack heavy oil, which has the advantages of high yield of dry gas, liquefied gas, gasoline and diesel, low yield of coke and heavy oil, high yield of light olefins (ethylene and propylene), etc.

[0065] 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 modified ZMQ-1 molecular sieve for catalytic cracking, characterized in that: It is obtained by modifying ZMQ-1 molecular sieve, and the specific steps are as follows: First, a CH3COONa solution is prepared, CeO2 is added, and the mixture is uniformly mixed at a stirring speed of 150 to 200 r / min to prepare a modified liquid A; a ZMQ-1 molecular sieve is placed in the modified liquid A, stirred for 10 to 15 minutes at a temperature of 35 to 40° C. in a water bath, and calcined at 250 to 300° C. for 0.5 to 1 hour to obtain a modified ZMQ-1 molecular sieve intermediate material; Take (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4, add them into water and mix them evenly to prepare modified liquid B; adopt the equal volume impregnation method, take the modified ZMQ-1 molecular sieve intermediate material and put it into the modified liquid B preheated to 88-95°C, after the impregnation is completed, place it at 65-70°C for drying for 5-7h, then place it at 500-520°C for calcination for 1-2h, then heat it to 688-700°C for calcination for 0.5-1h, then cool it to 450-500°C for calcination for 1-h to obtain the modified ZMQ-1 molecular sieve.

2. The modified ZMQ-1 molecular sieve for catalytic cracking according to claim 1, characterized in that: The concentration of CH3COONa solution is 0.35~0.4mol·L -1 .

3. The modified ZMQ-1 molecular sieve for catalytic cracking according to claim 2, characterized in that: The mass ratio of CeO2 to CH3COONa solution is 0.05-0.13:

1.

4. The modified ZMQ-1 molecular sieve for catalytic cracking according to claim 3, characterized in that: The volume ratio of ZMQ-1 molecular sieve to modified liquid A is 1:1.4-1.

6.

5. The modified ZMQ-1 molecular sieve for catalytic cracking according to claim 4, characterized in that: The molar ratio of (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 is 1:(1.1~1.2):(1.3~1.6):(1.2~1.7).

6. A catalyst composition containing the modified ZMQ-1 molecular sieve for catalytic cracking according to claim 5, characterized in that: The invention comprises the following raw materials in parts by weight: 15 to 55 parts of modified ZMQ-1 molecular sieve, 5 to 20 parts of USY molecular sieve and / or 5 to 10 parts of ZSM-5 molecular sieve, 5 to 30 parts of aluminum source, 15 to 30 parts of clay and 12 to 20 parts of binder.

7. The catalyst composition according to claim 6, characterized in that The aluminum source is selected from one of pseudo-boehmite, boehmite and alumina.

8. The catalyst composition according to claim 7, characterized in that 2×m (USY type molecular sieve) + 2×m (ZSM-5 molecular sieve) < m (modified ZMQ-1 molecular sieve).

9. The catalyst composition according to claim 8, characterized in that The binder is aluminum sol.

10. Use of the catalyst composition according to claim 9 in catalytic cracking of heavy oil to produce ethylene and propylene.

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