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

Abstract

The application discloses a modified ZMQ-1 molecular sieve for catalytic cracking and a catalyst composition thereof, and belongs to the technical field of molecular sieves. The preparation steps of the modified ZMQ-1 molecular sieve are as follows: first, a CH3COONa solution is prepared, CeO2 is added, and the mixture is uniformly mixed at a stirring speed of 150-200 r / min to obtain a modified liquid A; the ZMQ-1 molecular sieve is put into the modified liquid A, and is stirred and treated under water bath conditions and calcined to obtain a modified ZMQ-1 molecular sieve intermediate material; (NH4)2Fe(SO4)2.6H2O, ZnSO4.7H2O, (NH4)2C2O4 and Ce(NO3)4 are taken and uniformly mixed in water to obtain a modified liquid B; the modified ZMQ-1 molecular sieve intermediate material is put into the preheated modified liquid B at 88-95 DEG C by using an equal-volume impregnation method, is dried after impregnation is completed, and is calcined to obtain the modified ZMQ-1 molecular sieve. The catalyst composition has the advantages that the yield of dry gas, liquefied gas, gasoline and diesel oil is high, the yield of coke and heavy oil is low, and the yield of low-carbon olefins (ethylene and propylene) is high.

Description

TECHNICAL FIELD

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

[0002] Ethylene and propylene are important chemical raw materials, and the demand is very strong. The heavy oil catalytic cracking process for producing 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 the heavy oil raw material gradually becomes heavy and inferior, the catalytic cracking performance of the catalyst is increasingly required.

[0003] CN 118515294 A discloses a new silicate zeolite molecular sieve ZMQ-1 and its application. The anhydrous chemical composition of the ZMQ-1 molecular sieve silicate zeolite molecular sieve precursor is SiO2·1 / xXO 1.5 ·mMO 0.5 ·qQ, the anhydrous chemical composition of the silicate zeolite molecular sieve precursor is SiO2·1 / xXO 1.5 ·mMO 0.5 ·qQ, wherein X is a framework trivalent element, the Si / X molar ratio x is greater than or equal to 5, M is a framework balancing cation, the M / Si molar ratio 0

[0004] At present, there is little research on the modification of ZMQ-1 molecular sieves and their application in the production of ethylene and propylene by heavy oil catalytic cracking.

[0005] Therefore, the present application provides a modified ZMQ-1 molecular sieve for catalytic cracking and a catalyst composition thereof to solve the above problems. SUMMARY

[0006] In view of the above-mentioned shortcomings of the prior art, the present application provides a modified ZMQ-1 molecular sieve for catalytic cracking and a catalyst composition thereof.

[0007] To achieve the above purpose, the present application is realized by the following technical scheme:

[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, CH3COONa solution is prepared, CeO2 is added, and the mixture is uniformly mixed at a stirring speed of 150-200 r / min to obtain modified liquid A; ZMQ-1 molecular sieve is put into the modified liquid A, stirred at a water bath temperature of 35-40 ℃ for 10-15 min, and calcined at 250-300 ℃ for 0.5-1 h to obtain modified ZMQ-1 molecular sieve intermediate material.

[0010] (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 are added to water and uniformly mixed to obtain modified liquid B; the modified ZMQ-1 molecular sieve intermediate material is put into the preheated modified liquid B at 88-95 ℃ by using an equal-volume impregnation method, dried at 65-70 ℃ for 5-7 h after impregnation is completed, then calcined at 500-520 ℃ for 1-2 h, then heated to 688-700 ℃ for 0.5-1 h, and then cooled to 450-500 ℃ for 1-2 h to obtain modified ZMQ-1 molecular sieve.

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

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

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

[0014] Further, the amount-of-substance 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 application, the present application further provides a catalyst composition containing modified ZMQ-1 molecular sieve, which comprises the following raw materials in parts by weight: 15-55 parts of modified ZMQ-1 molecular sieve, 5-20 parts of USY type molecular sieve and / or 5-10 parts of ZSM-5 molecular sieve, 5-30 parts of an aluminum source, 15-30 parts of clay, and 12-20 parts of a binder.

[0016] Further, the aluminum source is selected from one of pseudoboehmite, boehmite and alumina.

[0017] Further, 2*m(USY type molecular sieve) + 2*m(ZSM-5 molecular sieve) < m(modified ZMQ-1 molecular sieve). That is, 2 times the mass of the USY type molecular sieve + 2 times the mass of the ZSM-5 molecular sieve < the mass of the modified ZMQ-1 molecular sieve.

[0018] Further, the binder is aluminum sol.

[0019] In order to better achieve the purpose of the present application, the present application also provides an application of the catalyst composition in the production of ethylene and propylene by catalytic cracking of heavy oil.

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

[0021] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0022] Embodiment 1: In some embodiments, a catalyst composition containing a modified ZMQ-1 molecular sieve includes the following raw materials in parts by weight: 15 parts of modified ZMQ-1 molecular sieve, 5 parts of USY type molecular sieve, 5 parts of aluminum source, 15 parts of clay, and 12 parts of binder. The aluminum source is pseudo-boehmite. The binder is aluminum sol. The raw materials are mixed and beaten at room temperature, and then are sprayed to form a catalyst composition after solidification, washing, and drying.

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

[0024] Step one, first prepare a CH3COONa solution (0.35 mol·L -1), CeO2(CeO2: CH3COONa = 0.05:1, mass ratio) was added, and the mixture was stirred at 150 r / min to obtain modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared according to the disclosure of 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), and stirring treatment was carried out under the condition of a 35℃ water bath for 10 min, and calcination was carried out at 250℃ for 0.5 h to obtain modified ZMQ-1 molecular sieve intermediate material;

[0025] Step two, (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) were added into 2 times the volume of water and mixed uniformly to obtain modified liquid B;

[0026] Step three, the modified ZMQ-1 molecular sieve intermediate material was put into the preheated 88℃ modified liquid B by using the equal volume impregnation method, and after impregnation was completed, it was placed in an oven for drying at 65℃ for 5 h, and then calcination was carried out at 500℃ for 1 h, and then the temperature was increased to 688℃ for calcination for 0.5 h, and then the temperature was decreased to 450℃ for calcination for 1 h to obtain the modified ZMQ-1 molecular sieve;

[0027] The modified ZMQ-1 molecular sieve intermediate material is obtained by modifying the ZMQ-1 molecular sieve by CH3COONa and CeO2, and then ZnFe2O4 and CeO2 are loaded on the ZMQ-1 molecular sieve by using the equal volume impregnation method.

[0028] In some embodiments, a catalyst composition containing modified ZMQ-1 molecular sieve includes the following raw materials in parts by weight: modified ZMQ-1 molecular sieve 55 parts, USY type molecular sieve 20 parts, ZSM-5 molecular sieve 5 parts, aluminum source 30 parts, clay 30 parts, and binder 20 parts. The aluminum source is boehmite. The binder is aluminum sol. The raw materials are mixed and beaten at room temperature, and then spray formed, and then solidified, washed, and dried to obtain the catalyst composition.

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

[0030] Step one, CH3COONa solution (0.4 mol·L -1), CeO2(CeO2: CH3COONa = 0.13:1, mass ratio) was added, and the mixture was stirred at 200 r / min to obtain modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared according to the disclosure of 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), and stirring treatment was carried out under the condition of a 40℃ water bath for 15 min, and calcination was carried out at 300℃ for 1h to obtain modified ZMQ-1 molecular sieve intermediate material;

[0031] Step two, (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) were mixed uniformly in 4 times the volume of water to obtain modified liquid B;

[0032] Step three, the modified ZMQ-1 molecular sieve intermediate material was put into the preheated 95℃ modified liquid B by using the equal volume impregnation method, and after impregnation was completed, it was placed in an oven at 70℃ for 7h, and then calcination was carried out at 520℃ for 2h, and then the temperature was increased to 700℃ for 1h, and then the temperature was decreased to 500℃ for 2h to obtain the modified ZMQ-1 molecular sieve;

[0033] The CH3COONa and CeO2 are used to modify the ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve intermediate material, and then the ZnFe2O4 and CeO2 are loaded on the ZMQ-1 molecular sieve by using the equal volume impregnation method.

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

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

[0036] Step one, CH3COONa solution (0.37 mol·L -1), CeO2(CeO2: CH3COONa = 0.1:1, mass ratio) was added, and the mixture was stirred at 180 r / min to obtain modified liquid A; ZMQ-1 molecular sieve (ZMQ-1 molecular sieve was prepared according to the disclosure of 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), and stirring treatment was carried out under the condition of a 37℃ water bath for 13 min, and calcination was carried out at 260℃ for 0.7 h to obtain modified ZMQ-1 molecular sieve intermediate material;

[0037] Step two, (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) were mixed uniformly in 3 times the volume of water to obtain modified liquid B;

[0038] Step three, using the equal volume impregnation method, the modified ZMQ-1 molecular sieve intermediate material was put into the modified liquid B preheated to 90℃, and after impregnation, it was placed in an oven for drying at 68℃ for 6 h, then it was calcined at 512℃ for 1.1 h, then it was heated to 695℃ for calcination for 0.6 h, and then it was cooled to 470℃ for calcination for 1.2 h to obtain the modified ZMQ-1 molecular sieve;

[0039] The CH3COONa and CeO2 are used to modify the ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve intermediate material, and then the equal volume impregnation method is used to load ZnFe2O4 and CeO2 on the ZMQ-1 molecular sieve.

[0040] In some embodiments, a catalyst composition containing modified ZMQ-1 molecular sieve includes the following raw materials in parts by weight: 50 parts of modified ZMQ-1 molecular sieve, 10 parts of USY type molecular sieve and / or 10 parts of 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 pseudoboehmite, boehmite, and alumina. The binder is aluminum sol. After stirring and mixing the raw materials at room temperature, the slurry is formed by spraying, and then the catalyst composition is obtained after solidification, washing, and drying.

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

[0042] Step one, CH3COONa solution (0.39 mol·L -1), CeO2 (CeO2: CH3COONa = 0.12:1, mass ratio) was added, and uniform mixing was carried out under the condition of 190 r / min stirring speed, to prepare modified liquid A; the ZMQ-1 molecular sieve (the ZMQ-1 molecular sieve was prepared according to the content 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), and stirring treatment was carried out under the condition of 36℃ water bath for 14 min, and calcination was carried out at 295℃ for 0.8 h, to obtain a modified ZMQ-1 molecular sieve intermediate material;

[0043] Step two, (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) were mixed uniformly in 3.5 times the volume of water to prepare modified liquid B;

[0044] Step three, using an equal volume impregnation method, the modified ZMQ-1 molecular sieve intermediate material was put into the modified liquid B preheated to 93℃, and after impregnation, it was placed in an oven at 69℃ for 5.5 h, then calcined at 515℃ for 1 h, then the temperature was increased to 692℃ for 0.5 h, and then the temperature was decreased to 485℃ for 1 h, to obtain the modified ZMQ-1 molecular sieve;

[0045] The CH3COONa and CeO2 are used to modify the ZMQ-1 molecular sieve to obtain the modified ZMQ-1 molecular sieve intermediate material, and then the ZnFe2O4 and CeO2 are loaded on the ZMQ-1 molecular sieve using the equal volume impregnation method.

[0046] Comparative example 1: different from example 3, the preparation method of the modified ZMQ-1 molecular sieve is different.

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

[0048] Step one, first prepare a CH3COONa solution (0.39 mol·L -1 ), CeO2 (CeO2: CH3COONa = 0.12:1, mass ratio) was added, and uniform mixing was carried out under the condition of 190 r / min stirring speed, to prepare modified liquid A;

[0049] Step two, 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 uniformly to prepare modified liquid B;

[0050] Step three, mix modified liquid A and modified liquid B to obtain a mixed modified liquid, put ZMQ-1 molecular sieve (ZMQ-1 molecular sieve is prepared according to the disclosure of Chinese invention patent CN 118515294 A) into the mixed modified liquid (ZMQ-1 molecular sieve: mixed modified liquid = 1:1.6, volume ratio), stir under 36℃ water bath condition for 14 min, and calcine at 295℃ for 0.8h to obtain modified ZMQ-1 molecular sieve.

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

[0052] The preparation method of modified ZMQ-1 molecular sieve is as follows:

[0053] Step one, first prepare CH3COONa solution (0.39mol·L -1 ), add CeO2 (CeO2:CH3COONa=0.12:1, mass ratio), mix uniformly at 190r / min stirring speed, and prepare modified liquid A;

[0054] Step two, 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 uniformly to prepare modified liquid B;

[0055] Step three, mix modified liquid A and modified liquid B to obtain a mixed modified liquid, and take ZMQ-1 molecular sieve (ZMQ-1 molecular sieve is prepared according to the disclosure of Chinese invention patent CN 118515294 A) into the mixed modified liquid preheated to 93℃, and after impregnation, place it in an oven at 69℃ for 5.5h, then heat it to 515℃ for 1h, then heat it to 692℃ for 0.5h, and then heat it to 485℃ for 1h to obtain modified ZMQ-1 molecular sieve.

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

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

[0058] Table 1 Basic properties of raw oil

[0059] Item Value 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 application has the advantages of high dry gas, liquefied gas, gasoline and diesel yield, low coke and heavy oil yield, and high yield of low carbon olefins (ethylene and propylene) in catalytic cracking of heavy oil.

[0065] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it; although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that the technical solutions recorded in the foregoing examples can be modified, or some technical features can be replaced by equivalents; and these modifications or replacements will not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A modified ZMQ-1 molecular sieve for catalytic cracking, characterized in that, The modified ZMQ-1 molecular sieve is obtained by modification treatment, 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 150-200 r / min to obtain modified liquid A; the ZMQ-1 molecular sieve is placed in the modified liquid A, stirred at 35-40 DEG C for 10-15 min in a water bath, and calcined at 250-300 DEG C for 0.5-1 h to obtain a modified ZMQ-1 molecular sieve intermediate material; (NH4)2Fe(SO4)2·6H2O, ZnSO4·7H2O, (NH4)2C2O4 and Ce(NO3)4 are taken, mixed uniformly in water to obtain modified liquid B; the modified ZMQ-1 molecular sieve intermediate material is placed in the preheated 88-95 DEG C modified liquid B by equal volume impregnation method, dried at 65-70 DEG C for 5-7 h after impregnation is completed, then calcined at 500-520 DEG C for 1-2 h, then heated to 688-700 DEG C for 0.5-1 h, and then cooled to 450-500 DEG C for 1-2 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 0.35-0.4 mol·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 of claim 4, wherein, The amount-of-substance 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 comprising the modified ZMQ-1 molecular sieve for catalytic cracking of claim 5, characterized in that, The catalyst composition comprises the following raw materials in parts by weight: 15-55 parts of the modified ZMQ-1 molecular sieve, 5-20 parts of the USY type molecular sieve and / or 5-10 parts of the ZSM-5 molecular sieve, 5-30 parts of an aluminum source, 15-30 parts of clay, and 12-20 parts of a binder.

7. The catalyst composition of claim 6, wherein, The aluminum source is selected from one of pseudoboehmite, boehmite and alumina.

8. The catalyst composition of claim 7, wherein, 2 times the mass of the USY type molecular sieve + 2 times the mass of the ZSM-5 molecular sieve < the mass of the modified ZMQ-1 molecular sieve.

9. The catalyst composition of claim 8, wherein, The binder is aluminum sol.

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

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