Catalytic cracking catalyst and its preparation method and application

Abstract

The present invention provides a catalytic cracking catalyst, a preparation method, and an application thereof. The preparation method comprises: subjecting a NaY molecular sieve containing the metal element Mn in its framework and having a molar ratio of MnO2 to Al2O3 of 0.01-10.0 to an isomorphous substitution reaction at 200-600°C with gaseous SiCl4 at a mass ratio of 0.1-20:1, followed by calcination to obtain a high silicon-aluminum ratio Y molecular sieve containing the metal element Mn in its framework; and then utilizing the Y molecular sieve in combination with a ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder to prepare a catalytic cracking catalyst; based on the total dry weight of the raw materials used to prepare the catalytic cracking catalyst being 100%, the Y molecular sieve accounts for 15-35%, the ZSM-5 molecular sieve accounts for 0-20%, the natural clay accounts for 40-50%, and the inorganic oxide binder accounts for 10-45% as an inorganic oxide.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to a catalytic cracking catalyst and a preparation method and application thereof. Background Art

[0002] Currently, the contradiction between overcapacity in refining, an irrational oil product mix, and insufficient production capacity for light olefins like ethylene and propylene, along with the ever-changing fuel and petrochemical markets, presents both opportunities and challenges for the petrochemical industry. Demand for light olefins like ethylene and propylene has maintained a high growth rate, gradually becoming one of the primary drivers of crude oil demand growth. Producing these light olefins from crude oil is a promising option for addressing this capacity shortfall.

[0003] The direct catalytic cracking of crude oil to produce light olefins is the primary method for producing ethylene, propylene, and other light olefins from crude oil, with catalytic cracking catalysts being the core of the process. Currently, the refining industry is facing the challenge of increasingly heavier crude oil, which places higher demands on the performance of catalytic cracking catalysts used in the direct catalytic cracking of crude oil to produce light olefins.

[0004] One of the main active components of the catalytic cracking catalyst used in the process of direct catalytic cracking of crude oil to produce light olefins is Y-type zeolite. The framework atomic composition, silicon-aluminum ratio, acid properties and pore structure of Y-type molecular sieve all affect the catalytic performance of the catalytic cracking catalyst in catalyzing the direct cracking of crude oil to produce light olefins.

[0005] At present, the industry usually uses the hydrothermal method to synthesize Y-type molecular sieves. However, due to the constraints of the hydrothermal synthesis mechanism, the silicon-aluminum ratio of Y-type molecular sieves synthesized by conventional hydrothermal methods is difficult to be greater than 6, which is far from meeting the high thermal stability and hydrothermal stability required in actual industrial applications. In order to improve the silicon-aluminum ratio of the Y-type molecular sieve framework, the industry usually uses the hydrothermal ultra-stabilization method to treat Y-type molecular sieves. However, this method has limited ability to improve the silicon-aluminum ratio of Y-type molecular sieves; and it often requires two or even multiple ammonium ion exchange treatments and harsh hydrothermal conditions (600℃-700℃), resulting in a long production process, high water consumption, high energy consumption, and a large amount of ammonium salt (ammonia nitrogen wastewater treatment has great environmental pressure, and its cost accounts for more than half of the production cost of USY), resulting in high production costs and difficulty in clean production; in addition, it also causes the collapse of part of the zeolite crystal structure, a large decrease in crystallinity (nearly 40%), severe acidity loss, and reduced activity.

[0006] To increase the Si / Al ratio of Y-type zeolites, industry researchers have proposed alternative treatment methods, distinct from the hydrothermal ultrastabilization method. However, these methods generally suffer from limited Si / Al ratio enhancement, complex processing, significant reduction in crystallinity, and severe acid loss. Consequently, it has been difficult to effectively improve the performance of catalytic cracking catalysts using Y-type zeolite as the primary active component in the direct catalytic cracking of crude oil to produce light olefins.

[0007] Based on this, at present, there is still a need to study a simple and easy-to-implement technical solution that can significantly increase the silicon-aluminum ratio of Y-type molecular sieves while ensuring crystallinity and acidity, so as to achieve the improvement of the catalytic performance of catalytic cracking catalysts with Y-type zeolite as the main active component in catalyzing the direct cracking of crude oil to produce light olefins. Summary of the Invention

[0008] The object of the present invention is to provide a technical solution that can effectively improve the catalytic performance of a catalytic cracking catalyst using Y-type zeolite as the main active component in the direct cracking of crude oil to produce light olefins.

[0009] In order to achieve the above objectives, the present invention provides the following three technical solutions.

[0010] In a first aspect, the present invention provides a method for preparing a catalytic cracking catalyst, wherein the method comprises:

[0011] A NaY molecular sieve containing the metal element Mn in its framework is subjected to an isomorphous substitution reaction with gaseous SiCl4 at a mass ratio of 0.1-20:1, and then calcined to obtain a high silicon-aluminum ratio Y molecular sieve containing the metal element Mn in its framework; wherein the reaction temperature of the isomorphous substitution reaction is 200-600° C.; wherein the molar ratio of MnO2 to Al2O3 in the NaY molecular sieve containing the metal element Mn in its framework is 0.01-10.0;

[0012] A catalytic cracking catalyst is prepared by using the Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn in the framework, and optionally adding a ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder (i.e., the catalytic cracking catalyst is prepared by using the Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn in the framework, the ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder, or the catalytic cracking catalyst is prepared by using the Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn in the framework, natural clay, and an inorganic oxide binder); wherein, based on the total dry weight of the raw material components used to prepare the catalytic cracking catalyst being 100%, the Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn accounts for 15-35wt.%, the ZSM-5 molecular sieve accounts for 0-20wt.%, the natural clay accounts for 40-50wt.%, and the inorganic oxide binder accounts for 10-45wt.% in terms of inorganic oxide.

[0013] The catalytic cracking catalyst prepared by the technical solution provided by the present invention is a catalyst for the direct catalytic cracking of crude oil to produce light olefins, capable of effectively catalyzing the cracking of crude oil to produce light olefins. The technical solution provided by the present invention achieves a significant increase in the silicon-to-aluminum ratio of the Y-type molecular sieve while still retaining a high degree of crystallinity by first doping manganese into the NaY-type molecular sieve framework and then reacting with gas-phase SiCl4 to undergo an isomorphous substitution reaction, thereby obtaining a high silicon-to-aluminum ratio Y-type molecular sieve containing the metallic element Mn in the framework. The catalytic cracking catalyst prepared by combining this special Y-type molecular sieve with an optional ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder exhibits high crude oil catalytic cracking activity and high yields of ethylene, propylene, and butene when used in a crude oil catalytic cracking reaction. In the technical solution provided by the present invention, manganese Mn atoms are first doped into the NaY type molecular sieve framework to replace the positions of a small part of the Al atoms in the NaY molecular sieve framework, and then an isomorphous substitution reaction is carried out with gas-phase SiCl4. The gas-phase SiCl4 further synergizes with the heteroatom Mn in the NaY molecular sieve framework, and a large number of Al atoms are isomorphously replaced, thereby achieving a significant increase in the framework silicon-aluminum ratio without the need for hydrothermal dealumination, and the prepared Y molecular sieve has high relative crystallinity; and then the strong acidic cracking function and strong dehydrogenation function of this special Y-type molecular sieve are combined with the selectivity function of ZSM-5 molecular sieve, so that it has high crude oil catalytic cracking activity and high ethylene, propylene and butene selectivity in the crude oil catalytic cracking reaction.

[0014] According to a preferred embodiment of the first aspect, the method further comprises the step of preparing a NaY molecular sieve containing the metal element Mn in the framework, specifically comprising:

[0015] Sodium hydroxide, an aluminum source, a silicon source, and water are mixed in a molar ratio of (10-30)Na2O:Al2O3:(10-30)SiO2:(180-400)H2O, and aged at 0-80°C to obtain a directing agent;

[0016] A directing agent, sodium hydroxide, a silicon source, an aluminum source, a manganese source, and water are mixed in a molar ratio of (1-10)Na2O:Al2O3:(0.01-10.0)MnO2:(5-20)SiO2:(120-360)H2O to obtain a reaction system to be crystallized, and the reaction system to be crystallized at 60-120°C to obtain a NaY molecular sieve containing the metallic element Mn in its framework; wherein, based on the mass of Al2O3 in the reaction system to be crystallized being 100%, the mass of Al2O3 provided by the directing agent accounts for 3-25% of the mass of Al2O3 in the reaction system to be crystallized;

[0017] The preferred technical solution is to introduce Mn heteroatoms into the framework of the molecular sieve by a direct synthesis method, and then carry out an isomorphous substitution reaction between the obtained NaY type molecular sieve containing Mn heteroatoms and gas-phase SiCl4 at a certain temperature, and then calcine to obtain a high silicon-to-aluminum ratio Y type molecular sieve with a framework containing Mn heteroatoms; the Y type molecular sieve prepared by this method not only has a high silicon-to-aluminum ratio but also has a high crystallinity, and does not require multiple ammonium ion exchange and hydrothermal treatment processes to reduce the sodium oxide content of the molecular sieve to below 1.0wt%; the Y type molecular sieve prepared by this preferred technical solution has a higher silicon-to-aluminum ratio, higher crystallinity, and suitable acidity compared to the Y type molecular sieve prepared by traditional metal impregnation and hydrothermal ultra-stabilization technology, and shortens the production process, reduces production costs, and reduces ammonia nitrogen wastewater discharge;

[0018] This preferred technical solution is to introduce Mn heteroatoms into the molecular sieve framework by a direct synthesis method, which has significant advantages over the traditional impregnation method or ion exchange method: the impregnation method usually introduces metal heteroatoms into the molecular sieve surface, but it is difficult to introduce them into the molecular sieve framework, and the metal heteroatoms introduced by the impregnation method easily clog the molecular sieve pores; the ion exchange method can only introduce a very small amount of metal heteroatoms into the molecular sieve, and the introduced metal heteroatoms are mostly present on the outer surface and pore surface of the molecular sieve and are difficult to enter the molecular sieve framework; the metal heteroatom introduction by the direct synthesis method is to directly add part of the metal source into the synthesis gel during the molecular sieve synthesis process, gradually form crystal nuclei under the action of a directing agent, and then crystallize to introduce part of the metal into the molecular sieve framework;

[0019] Furthermore, in the process of preparing the directing agent, sodium hydroxide, an aluminum source, a silicon source and water are mixed according to a molar ratio of (10-20)Na2O:Al2O3:(10-20)SiO2:(240-360)H2O;

[0020] Furthermore, in the process of preparing the reaction system to be crystallized, a directing agent, sodium hydroxide, a silicon source, an aluminum source, a manganese source, and water are mixed according to a molar ratio of (1-5) Na2O:Al2O3:(0.01-5.0)MnO2:(5-15)SiO2:(150-300)H2O to obtain the reaction system to be crystallized;

[0021] Further, aging is carried out at 10-60°C;

[0022] Furthermore, the aging time is 1-60 hours; furthermore, the aging time is 2-50 hours;

[0023] Further, crystallization is carried out at 70-110°C;

[0024] Further, the crystallization time is 0.5-72h; further, the crystallization time is 12-48h;

[0025] Further, the crystallized sample is filtered, washed, dried, and calcined; further, the drying is performed at 120° C. for 24 hours; further, the calcination temperature is 500-600° C.; further, the calcination time is 2-6 hours;

[0026] Furthermore, the silicon source includes but is not limited to at least one of ethyl silicate, water glass and silica sol.

[0027] Further, the aluminum source includes but is not limited to at least one of sodium metaaluminate, aluminum sulfate, aluminum isopropoxide, tert-butyl aluminum and aluminum oxide;

[0028] Furthermore, the manganese source includes but is not limited to at least one of manganese chloride and manganese sulfate.

[0029] According to a preferred embodiment of the first aspect, when the isomorphous substitution reaction is carried out, the mass ratio of the NaY type molecular sieve containing the metal element Mn in the framework to the gas phase SiCl4 is 0.5-15:1.

[0030] According to a preferred embodiment of the first aspect, the molar ratio of MnO2 to Al2O3 in the NaY type molecular sieve containing the metal element Mn in the framework is 0.01-5.0.

[0031] According to a preferred embodiment of the first aspect, the reaction temperature of the isomorphous substitution reaction is 280-580°C; further, the reaction temperature of the isomorphous substitution reaction is 300-500°C.

[0032] According to a preferred embodiment of the first aspect, the reaction time of the isomorphous substitution reaction is 10 minutes to 5 hours.

[0033] According to a preferred embodiment of the first aspect, the method further comprises cooling, washing, filtering, and drying the isomorphous substitution reaction product after the isomorphous substitution reaction and before calcination;

[0034] Furthermore, the cooling is performed under N2 purge.

[0035] According to a preferred embodiment of the first aspect, the calcination temperature after the isomorphous substitution reaction is 500-600°C.

[0036] According to a preferred embodiment of the first aspect, the calcination time after the isomorphous substitution reaction is 2-6 hours.

[0037] According to a preferred embodiment of the first aspect, the framework silicon-aluminum molar ratio n(SiO2) / n(Al2O3) of the high silicon-aluminum ratio Y-type molecular sieve using the metal element Mn in the framework is 9 or more.

[0038] According to a preferred embodiment of the first aspect, the relative crystallinity of the high silicon-aluminum ratio Y-type molecular sieve using the metal element Mn contained in the framework is above 80%.

[0039] According to a preferred embodiment of the first aspect, the preparation of the catalytic cracking catalyst using a high silicon-aluminum ratio Y-type molecular sieve containing the metal element Mn in the framework, a ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder is achieved by the following method:

[0040] The high silicon-aluminum ratio Y-type molecular sieve containing the metal element Mn in the framework, ZSM-5 molecular sieve, natural clay, inorganic oxide binder and water are mixed and slurried, and the obtained slurry is spray-dried to obtain spray-dried microspheres; the obtained spray-dried microspheres are calcined to obtain the catalytic cracking catalyst;

[0041] Furthermore, the spray-dried microspheres are calcined at a temperature of 500-600°C.

[0042] Furthermore, the spray-dried microspheres are calcined for 2-6 hours.

[0043] According to a preferred embodiment of the first aspect, the ZSM-5 molecular sieve accounts for 5-15 wt.%, based on the total dry weight of the raw material components used to prepare the catalytic cracking catalyst being 100%.

[0044] According to a preferred embodiment of the first aspect, the silicon-aluminum molar ratio n(SiO2) / n(Al2O3) of the ZSM-5 molecular sieve is 30-300.

[0045] According to a preferred embodiment of the first aspect, the natural clay may be, but is not limited to, kaolin, such as tertiaclase.

[0046] According to a preferred embodiment of the first aspect, the inorganic oxide binder may be, but is not limited to, aluminum sol.

[0047] In a second aspect, the present invention provides a catalytic cracking catalyst prepared by the method for preparing the catalytic cracking catalyst provided in the first aspect.

[0048] In a third aspect, the present invention provides use of the catalytic cracking catalyst provided in the second aspect as a catalyst in the catalytic cracking of crude oil and / or hydrocarbon oil to produce light olefins;

[0049] Wherein, the olefin is ethylene and / or propylene and / or butene.

[0050] According to a preferred embodiment of the third aspect, the hydrocarbon oil includes but is not limited to atmospheric residue oil, vacuum residue oil, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, solvent deasphalted oil and hydrotreated oil obtained by hydrotreating the above hydrocarbon oils, or a combination of two or more thereof.

[0051] According to a preferred embodiment of the third aspect, in the above application, crude oil and / or hydrocarbon oil are contacted with the catalytic cracking catalyst provided by the second aspect of the present invention to carry out catalytic cracking of crude oil and / or hydrocarbon oil to produce light olefins.

[0052] Since metal heteroatoms are different from Si and Al atoms in the molecular sieve framework in terms of ionic radius, electronegativity and complexing ability, the introduction of metal heteroatoms will regulate the acidity and surface properties of the molecular sieve catalyst. However, due to the diversity of heteroatom types and the diversity of molecular sieve pores, the effects of different heteroatoms on the performance of different molecular sieves are different. Therefore, it has always been a research difficulty in the field of molecular sieves to determine what kind of heteroatom to introduce into what kind of molecular sieve and what kind of performance impact it will bring. The present invention achieves a significant improvement in Y-type molecular sieves by introducing Mn atoms into the NaY-type molecular sieve framework and then performing an isomorphous substitution reaction with SiCl4, and then cooperates with ZSM-5 molecular sieves to achieve an improvement in the catalytic performance of catalytic cracking catalysts catalyzing crude oil direct cracking to produce light olefins using Y-type zeolite as the main active component. Compared with the prior art, it has the following beneficial effects:

[0053] 1. In the technical solution provided by the present invention, a substantial improvement in the framework silicon-aluminum ratio of the Y-type molecular sieve is achieved by isomorphously replacing a NaY-type molecular sieve containing the metal element Mn in its framework with gas-phase SiCl4 and then calcining the NaY-type molecular sieve. The framework silicon-aluminum molar ratio n(SiO2) / n(Al2O3) of the prepared Y-type molecular sieve is above 9.

[0054] In the technical solution provided by the present invention, Y-type molecular sieves with different silicon-aluminum ratios can be obtained by regulating the reaction conditions of NaY-type molecular sieves containing the metal element Mn in the framework and gas-phase SiCl4. In the preferred technical solution, the framework silicon-aluminum molar ratio n(SiO2) / n(Al2O3) of the Y-type molecular sieve can reach more than 18 or even more than 20.

[0055] In the technical solution provided by the present invention, the framework of the NaY molecular sieve contains the metal element Mn, and the aluminum element of the framework is replaced by the Mn element. The silicon-aluminum ratio of the framework is improved compared with the conventional NaY. When the framework of the NaY molecular sieve containing Mn undergoes an isomorphous substitution reaction with the gas phase SiCl4, the SiCl4 vapor contacts the NaY molecular sieve, and under the influence of the Mn element, the NaY molecular sieve is effectively exchanged. + Produces NaCl and SiCl3+ ions and adsorbed on the molecular sieve surface, and then SiCl3 + The ions replace the framework aluminum at high temperature and produce AlCl3, so that the framework silicon-aluminum ratio is significantly improved.

[0056] 2. The technical solution provided by the present invention performs special pretreatment on the Y-type molecular sieve used in the catalytic cracking catalyst:

[0057] (1) The treated Y-type molecular sieve has a high silicon-aluminum ratio and a high crystallinity, wherein the crystallinity is above 80% (far exceeding the crystallinity of the Y-type molecular sieve obtained by conventional hydrothermal treatment and the crystallinity of the Y-type molecular sieve obtained by gas-phase SiCl4 treatment without Mn skeleton doping).

[0058] (2) The treated Y-type molecular sieve is a high silicon-aluminum ratio Y-type molecular sieve containing the metal element Mn in its framework. It has excellent dehydrogenation function, which further enhances its ability to increase propylene production. It is used in the catalytic cracking reaction of petroleum hydrocarbons to significantly improve the selectivity of light olefins.

[0059] (3) The technical solution provided by the present invention is to pre-treat the Y-type molecular sieve used in the catalytic cracking catalyst by isomorphously replacing the NaY-type molecular sieve containing the metal element Mn in the framework with gas-phase SiCl4 and then calcining it. There is no need to perform multiple ammonium ion exchanges and harsh hydrothermal treatments (600°C-700°C) to reduce the sodium oxide content of the Y-type molecular sieve to below 1.0wt%. The production process is simple, the production cost is low, and the discharge of ammonia nitrogen wastewater is reduced.

[0060] 3. The catalytic cracking catalyst prepared in the technical solution provided by the present invention has a strong acidic cracking function due to the high silicon-aluminum ratio Y molecular sieve, which cooperates with the strong dehydrogenation function of the heteroatom Mn metal element in the Y molecular sieve framework and the selectivity function of the ZSM-5 molecular sieve, so that when it is applied to the catalytic cracking reaction of crude oil, it shows high crude oil cracking activity and high ethylene, propylene and butene yields. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1 The XRD spectra of the Y-type molecular sieve used in the catalytic cracking catalyst provided in Examples 1 to 5 and Comparative Examples 2, 3 and 5 are shown. DETAILED DESCRIPTION

[0062] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0063] The relative crystallinity, unit cell parameters, and framework silicon-to-aluminum ratio (SiO2 / Al2O3 molar ratio) of the Y-type molecular sieve of the present invention were determined by X-ray diffraction (XRD), with spectra recorded at 2θ angles of 5 to 40 degrees. The metal element content and Na2O content of the Y-type molecular sieve were determined by X-ray fluorescence spectrometry, and the specific surface area and pore structure parameters were measured by low-temperature nitrogen adsorption-desorption measurements.

[0064] Description of the raw materials used in the embodiments of the present invention:

[0065] Sodium hydroxide: produced by Beijing Chemical Plant, purity 99%;

[0066] Sodium metaaluminate: produced by Tianjin Jinke Fine Chemical Research Institute, Al2O3 content is 45wt%, Na2O content is 41wt%, and the balance is water;

[0067] Water glass: produced by Beijing Red Star Soda Factory, with SiO2 content of 28.83wt%, Na2O content of 8.84wt%, and the balance being water;

[0068] Silica sol: produced by Tianjin Jinke Fine Chemical Research Institute, with SiO2 content of 28.88wt%, the balance being water;

[0069] Aluminum sulfate: produced by Nanzhao Huaxin Chemical Co., Ltd., with a purity of 99%;

[0070] Manganese sulfate: produced by Tianjin Suzhuang Chemical Reagent Factory, purity 99%.

[0071] Manganese chloride (MnCl2·H2O): produced by Tianjin Suzhuang Chemical Reagent Factory, purity 99%.

[0072] Aluminum isopropoxide: Shanghai MacLean Biochemical Technology Co., Ltd., purity 99.8%;

[0073] Alumina: Shanghai MacLean Biochemical Technology Co., Ltd., purity 99.99%;

[0074] Ethyl silicate: Shanghai MacLean Biochemical Technology Co., Ltd., SiO2 content is 28.83wt%, the balance is water.

[0075] Alumina sol: Qilu Catalyst Branch, alumina content is 22.5wt%.

[0076] Ammonium chloride: Produced by Beijing Chemical Plant, purity is 99%.

[0077] Kaolin: Suzhou China Kaolin Company, solid content 75wt%.

[0078] ZSM-5 molecular sieve: Nankai Catalyst Company, SiO2 / Al2O3 molar ratio 38.

[0079] Example 1

[0080] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0081] 1. Preparation steps of Y-type molecular sieve:

[0082] 8.51 g of sodium hydroxide was added to 38.62 g of distilled water, and after stirring for 30 minutes, 2.25 g of sodium aluminate and 30.66 g of water glass were added, and after stirring evenly, the mixture was aged at 35° C. for 5 hours to obtain a directing agent;

[0083] 41.0 g of directing agent was added to 225.6 g of silica sol, and the mixture was stirred for 1 h. Then, 13.78 g of sodium hydroxide, 3.75 g of sodium aluminate, and 141.92 g of distilled water were added and stirred for 1 h. Then, 159.80 g of aluminum sulfate solution (Al2O3 mass concentration is 7.6 wt%) was added and stirred for 1 h. Then, 1.72 g of manganese sulfate (MnSO4·H2O) was added and the mixture was stirred for another 1 h to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed, and subjected to dynamic crystallization in a rotary oven at 100°C for 28 hours, filtered, washed, and the filter cake was dried in an oven at 120°C for 24 hours; the dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to heat (4° / min) to 550°C, and calcined at 550°C in a nitrogen atmosphere for 44 hours to obtain a NaY molecular sieve containing the metal element Mn in the framework (the molar ratio of MnO2 to Al2O3 was 0.071).

[0084] Then, 7.64 g of gaseous SiCl4 was introduced into a rotary tube furnace quartz tube reactor containing 38.6 g of NaY type molecular sieve containing the metal element Mn in the framework to carry out isomorphous substitution reaction at 350°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C in a nitrogen atmosphere for 4 hours to obtain a high silicon-aluminum ratio Y type molecular sieve containing heteroatom Mn, named Mn-DY1. The physicochemical properties data of the sample are shown in Table 1, and the XRD spectrum is shown in Figure 1 .

[0085] 2. Catalyst preparation steps:

[0086] The Y-type molecular sieve prepared in step 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-A.

[0087] Catalytic Performance Evaluation: The catalytic cracking catalyst provided in this example was evaluated on an ACE reaction evaluation device. The feedstock oil was Daqing paraffin-based feedstock oil (parameter indicators are shown in Table 3). The evaluation conditions were: reaction temperature 650°C, regeneration temperature 700°C, and catalyst to feedstock mass ratio (abbreviated as catalyst to oil ratio, the same below) 7.0. The evaluation results are detailed in Table 2, and the XRD spectrum is shown in Table 2. Figure 1 .

[0088] Example 2

[0089] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0090] 1. Preparation steps of Y-type molecular sieve:

[0091] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent.

[0092] 97 g of a directing agent was added to 200 g of water glass and stirred for 1 h. 12.70 g of sodium hydroxide, 3.46 g of sodium aluminate, and 140.09 g of distilled water were added and stirred for 1 h. 136.20 g of an aluminum sulfate solution (with an Al2O3 mass concentration of 7.6 wt%) was added and stirred for 1 h. 4.16 g of manganese sulfate (MnSO4·H2O) was added and stirred for another 1 h to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed, and crystallized in a rotary oven at 105°C for 24 hours, filtered, washed, and the filter cake was dried in an oven at 120°C for 24 hours; the dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to heat (4° / min) to 550°C, and calcined at 550°C for 4 hours to obtain a NaY type molecular sieve containing the metal element Mn in the framework (the molar ratio of MnO2 to Al2O3 was 0.192).

[0093] Then, 7.78 g of gaseous SiCl4 was introduced into a quartz tube reactor of a rotary tube furnace containing 26 g of NaY type molecular sieve containing the metal element Mn in the framework to carry out isomorphous substitution reaction at 450°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C for 4 hours to obtain a high silicon-aluminum ratio Y type molecular sieve containing heteroatom Mn, named Mn-DY2. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Table 1. Figure 1 .

[0094] 2. Catalyst preparation steps:

[0095] The Y-type molecular sieve prepared in step 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-E.

[0096] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0097] Comparative Example 1

[0098] This comparative example provides a Y-type molecular sieve, which is prepared by the following method:

[0099] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent.

[0100] 97 g of directing agent was added to 200 g of water glass and stirred for 1 h. 12.70 g of sodium hydroxide, 3.46 g of sodium aluminate and 140.09 g of distilled water were added and stirred for 1 h. 136.20 g of aluminum sulfate solution (Al2O3 mass concentration of 7.6 wt%) was added and stirred for 1 h to form a gel mixture. Stirring was continued for 1 hour to obtain a reaction system to be crystallized. The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed and subjected to dynamic crystallization in a rotary oven at 105° C. for 24 h. The mixture was then filtered, washed and the filter cake was dried in an oven at 120° C. for 24 h. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to 550° C. at 4° / min. The mixture was calcined at 550° C. for 4 h to obtain a NaY type molecular sieve named NaY2. The physicochemical properties of the sample are shown in Table 1.

[0101] Comparative Example 2

[0102] This comparative example provides a catalytic cracking catalyst, which is prepared by the following method:

[0103] 1. Preparation steps of Y-type molecular sieve:

[0104] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent.

[0105] 97g of directing agent was added to 200g of water glass and stirred for 1h. 12.70g of sodium hydroxide, 3.46g of sodium aluminate and 140.09g of distilled water were added and stirred for 1h. 136.20g of aluminum sulfate solution (Al2O3 mass concentration of 7.6wt%) was added and stirred for 1h to form a gel mixture. Stirring was continued for 1h to obtain a reaction system to be crystallized. The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed and subjected to dynamic crystallization in a rotary oven at 105°C for 24h, filtered, washed, and the filter cake was dried in an oven at 120°C for 24h. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to rise in temperature (4° / min) to 550°C. It was calcined at 550°C for 4h to obtain a NaY molecular sieve.

[0106] NaY molecular sieve was mixed with 1 mol / L ammonium chloride solution at a mass ratio of 1:10 and ion exchange was carried out at 90°C for 1 hour. The mixture was filtered, washed repeatedly, and the filter cake was dried in an oven at 120°C for 24 hours. The mixture was then treated with 100% water vapor at 600°C for 2 hours. The above steps were repeated for another ion exchange and water vapor treatment to obtain a hydrothermal USY molecular sieve named USY-2. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Table 1. Figure 1 .

[0107] 2. Catalyst preparation steps:

[0108] The Y-type molecular sieve prepared in step 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-B.

[0109] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0110] Comparative Example 3

[0111] This comparative example provides a catalytic cracking catalyst, which is prepared by the following method:

[0112] 1. Preparation steps of Y-type molecular sieve:

[0113] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent.

[0114] 97 g of a directing agent was added to 200 g of water glass and stirred for 1 h. 12.70 g of sodium hydroxide, 3.46 g of sodium aluminate and 140.09 g of distilled water were added and stirred for 1 h. 136.20 g of an aluminum sulfate solution (with an Al2O3 mass concentration of 7.6 wt%) was added and stirred for 1 h. 4.16 g of manganese sulfate (MnSO4·H2O) was added and stirred for 1 h to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed, and subjected to dynamic crystallization in a rotary oven at 105° C. for 24 h. The mixture was then filtered, washed, and the filter cake was dried in an oven at 120° C. for 24 h. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to 550° C. at 4° / min. The product was calcined at 550° C. for 4 h to obtain a NaY molecular sieve containing the metal element Mn in its framework. The NaY molecular sieve containing the metal element Mn in the framework was mixed with a 1 mol / L ammonium chloride solution at a mass ratio of 1:10 and ion exchanged at 90°C for 1 hour. The mixture was filtered, washed repeatedly, and the filter cake was dried in an oven at 120°C for 24 hours. The mixture was then treated with 100% water vapor at 600°C for 2 hours. The above steps were repeated for another ion exchange and water vapor treatment to obtain a hydrothermal USY molecular sieve containing heteroatom Mn, named Mn-USY2. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Table 1. Figure 1 .

[0115] 2. Catalyst preparation steps:

[0116] The Y-type molecular sieve prepared in step 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-C.

[0117] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0118] Comparative Example 4

[0119] This comparative example provides a Y-type molecular sieve, which is prepared by the following method:

[0120] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent.

[0121] 97g of directing agent was added to 200g of water glass and stirred for 1h. 12.70g of sodium hydroxide, 3.46g of sodium aluminate and 140.09g of distilled water were added and stirred for 1h. 136.20g of aluminum sulfate solution (with an Al2O3 mass concentration of 7.6wt%) was added and stirred for 1h. 4.16g of manganese sulfate (MnSO4·H2O) was added and stirred for 1h to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallizer. The product was placed in a sealed autoclave and subjected to dynamic crystallization in a rotary oven at 105°C for 24 hours. The product was then filtered, washed, and the filter cake was dried in an oven at 120°C for 24 hours. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to heat (4° / min) to 550°C. The product was calcined at 550°C for 4 hours to obtain a NaY molecular sieve containing the metal element Mn in its framework, which was named Mn-NaY2. The physicochemical properties of the sample are shown in Table 1.

[0122] Comparative Example 5

[0123] This comparative example provides a catalytic cracking catalyst, which is prepared by the following method:

[0124] 1. Preparation steps of Y-type molecular sieve:

[0125] 9.02 g of sodium hydroxide was added to 40.52 g of distilled water, and after stirring for 30 minutes, 2.46 g of sodium aluminate and 45 g of water glass were added, and after stirring evenly, the mixture was aged at 30° C. for 6 hours to obtain a directing agent;

[0126] 97g of directing agent was added to 200g of water glass and stirred for 1h. 12.70g of sodium hydroxide, 3.46g of sodium metaaluminate and 140.09g of distilled water were added and stirred for 1h. 136.20g of aluminum sulfate solution (with an Al2O3 mass concentration of 7.6wt%) was added and stirred for 1h to form a gel mixture. Stirring was continued for 1h to obtain a reaction system to be crystallized. The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed and subjected to dynamic crystallization in a rotary oven at 105°C for 24h. The mixture was then filtered, washed and the filter cake was dried in a 120°C oven for 24h. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to 550°C at a temperature of 4° / min. The mixture was calcined at 550°C for 4h to obtain a NaY molecular sieve free of heteroatom Mn.

[0127] Then, 7.64 g of gaseous SiCl4 was introduced into a rotary tube furnace quartz tube reactor containing 38.6 g of NaY type molecular sieve without heteroatom Mn, and an isomorphous substitution reaction was carried out at 350°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C for 4 hours to obtain a high silicon-aluminum ratio Y type molecular sieve without heteroatom Mn, named DY2. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Figure 1 .

[0128] 2. Catalyst preparation steps:

[0129] The Y-type molecular sieve prepared in step 1 is used as an active component, and the ZSM-5 molecular sieve is used as an additive. Kaolin and an inorganic oxide binder aluminum sol are mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry is spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres are aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm are sieved to obtain a catalytic cracking catalyst, which is named CAT-D.

[0130] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0131] Comparative Example 6

[0132] This comparative example provides a Y-type molecular sieve, which is prepared by the following method:

[0133] 2.22 g of sodium aluminate, 8.21 g of sodium hydroxide, 35.62 g of distilled water, and 30.61 g of water glass were mixed in order, stirred evenly, and aged at 25° C. for 24 h to obtain a directing agent.

[0134] 188.7 g of water glass, 46.3 g of a 30 wt% sodium metaaluminate solution, 42.8 g of a 50 wt% aluminum sulfate solution, 1.30 g of manganese chloride (MnCl2·H2O), and 40.3 g of a directing agent were mixed and vigorously stirred until uniform to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallization kettle, sealed, and subjected to dynamic crystallization in a rotary oven at 100°C for 28 h. The mixture was then filtered, washed, and the filter cake was dried in an oven at 120°C for 24 h to obtain a NaY molecular sieve containing the metal element Mn in its framework, named Mn-D1-NaY. The physicochemical properties of the sample are shown in Table 1.

[0135] Comparative Example 7

[0136] This comparative example provides a Y-type molecular sieve, which is prepared by the following method:

[0137] The Y-type molecular sieve provided in Comparative Example 6 was rinsed three times with a 1.5 mol / L ammonium sulfate solution at 85°C, and then calcined at 540°C for 2 hours. The calcined molecular sieve was rinsed three times with a 0.5 mol / L ammonium sulfate solution. A 0.5 mol / L manganese sulfate solution was added to the wet filter cake, stirred evenly, and then transferred to a hydrothermal device and calcined at 600°C with steam for 4 hours to obtain an ultra-stable Y-type molecular sieve. The sample was named Mn-D1-USY. The physicochemical properties of the sample are listed in Table 1.

[0138] Example 3

[0139] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0140] 1. Preparation steps of Y-type molecular sieve:

[0141] 8.51 g of sodium hydroxide was added to 38.62 g of distilled water, and after stirring for 30 minutes, 2.25 g of sodium aluminate and 37.09 g of silica sol were added, and after stirring evenly, the mixture was aged at 60° C. for 2 hours to obtain a directing agent.

[0142] 40.3 g of directing agent was added to 132.47 g of silica sol, and after stirring for 1 hour, 23.27 g of NaOH and 160 g of distilled water and 1.58 g of sodium aluminate were added, and after stirring for 1 hour, 98.72 g of aluminum sulfate solution (Al2O3 mass concentration is 7.6 wt%) was added, and after stirring for 1 hour, 6.08 g of manganese chloride (MnCl2·H2O) was added, and stirring was continued for 1 hour to obtain a reaction system to be crystallized (gel mixture); the reaction system to be crystallized was placed in a non- The obtained product was placed in a stainless steel crystallization kettle, sealed, and subjected to dynamic crystallization in a rotary oven at 94°C for 28 hours. The product was then filtered, washed, and the filter cake was dried in an oven at 120°C for 24 hours. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to heat (4° / min) to 550°C. The product was calcined at 550°C for 4 hours to obtain a NaY molecular sieve containing the metal element Mn in its framework (the molar ratio of MnO2 to Al2O3 was 0.360).

[0143] Then, 8.61 g of gaseous SiCl4 was introduced into a quartz tube reactor of a rotary tube furnace containing 25 g of NaY molecular sieve containing the metal element Mn in its framework to carry out isomorphous substitution reaction at 410°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C for 4 hours to obtain a high silicon-aluminum ratio Y molecular sieve containing heteroatom Mn, named Mn-DY3. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Figure 1 .

[0144] 2. Catalyst preparation steps:

[0145] The Y-type molecular sieve prepared in step 1 is used as an active component, and the ZSM-5 molecular sieve is used as an additive. Kaolin and an inorganic oxide binder aluminum sol are mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry is spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres are aged at 800°C and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm are sieved to obtain a catalytic cracking catalyst, which is named CAT-F.

[0146] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0147] Example 4

[0148] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0149] 1. Preparation steps of Y-type molecular sieve:

[0150] 15.48 g of sodium hydroxide was added to 60 g of distilled water, and after stirring for 30 minutes, 3.06 g of sodium aluminate and 35.58 g of ethyl silicate were added, and after stirring evenly, the mixture was aged at 35° C. for 16 hours to obtain a directing agent.

[0151] 100 g of directing agent was added to 137.79 g of ethyl silicate, and stirred for 1 hour. Then, 23.27 g of NaOH and 282.43 g of distilled water were added, and stirred for 1 hour. Then, 1.58 g of sodium metaaluminate was added, and stirred for 1 hour. Then, 12.81 g of aluminum isopropoxide and 92 g of water were added, and stirred for 1 hour. Then, 2.30 g of manganese chloride (MnCl2·H2O) was added, and stirring was continued for 1 hour to obtain a reaction system to be crystallized (gel mixture). The reaction system to be crystallized was placed in a stainless steel crystallizer. The product was placed in a rotary oven at 100°C and sealed for dynamic crystallization for 28 hours. The product was then filtered, washed, and the filter cake was dried in a 120°C oven for 24 hours. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to heat (4° / min) to 550°C. The product was calcined at 550°C for 4 hours to obtain a NaY molecular sieve containing the metal element Mn in the framework (the molar ratio of MnO2 to Al2O3 is 0.234).

[0152] Then, 8.05 g of gaseous SiCl4 was introduced into a quartz tube reactor of a rotary tube furnace containing 26.8 g of NaY type molecular sieve containing the metal element Mn in the framework to carry out isomorphous substitution reaction at 380°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C for 4 hours to obtain a high silicon-aluminum ratio Y type molecular sieve containing heteroatom Mn, named Mn-DY4. The physicochemical properties data of the sample are shown in Table 1, and the XRD spectrum is shown in Figure 1 .

[0153] 2. Catalyst preparation steps:

[0154] The Y-type molecular sieve prepared in step 1 is used as an active component, and the ZSM-5 molecular sieve is used as an additive. Kaolin and an inorganic oxide binder aluminum sol are mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry is spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres are aged at 800° C. and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm are sieved to obtain a catalytic cracking catalyst, which is named CAT-G.

[0155] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0156] Example 5

[0157] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0158] 1. Preparation steps of Y-type molecular sieve:

[0159] 10.7 g of sodium hydroxide was added to 38.62 g of distilled water, and 1.2 g of aluminum oxide and 30.66 g of water glass were added, stirred evenly, and then aged at 50° C. for 3 h to obtain a directing agent.

[0160] 41.0 g of directing agent was added to 189.0 g of water glass, and after stirring for 1 hour, 12.65 g of sodium hydroxide, 1.20 g of aluminum oxide and 303.21 g of distilled water were added, and after stirring for 1 hour, 104 g of aluminum sulfate solution (aluminum oxide mass concentration is 7.6 wt%) was added, and after stirring for 1 hour, 15.31 g of manganese chloride (MnCl2·H2O) was added, and stirring was continued for 1 hour to obtain a reaction system to be crystallized (gel mixture); the reaction system to be crystallized was placed in a stainless steel container. The crystallization kettle was sealed and subjected to dynamic crystallization in a rotary oven at 100°C for 28 hours. The product was then filtered, washed, and dried in a 120°C oven for 24 hours. The dried product was transferred to a quartz tube reactor in a rotary tube furnace, purged with high-purity nitrogen, and programmed to 550°C at a temperature of 4°C / min. Calcination at 550°C for 4 hours yielded a NaY molecular sieve containing the metallic element Mn in its framework (the molar ratio of MnO2 to Al2O3 was 1.030).

[0161] Then, 8.55 g of gaseous SiCl4 was introduced into a quartz tube reactor of a rotary tube furnace containing 20 g of NaY type molecular sieve containing the metal element Mn in the framework to carry out isomorphous substitution reaction at 460°C for 1 hour. The product of the isomorphous substitution reaction was repeatedly washed with deionized water, filtered, dried, and calcined at 550°C for 4 hours to obtain a high silicon-aluminum ratio Y type molecular sieve containing heteroatom Mn, named Mn-DY5. The physicochemical properties of the sample are shown in Table 1, and the XRD spectrum is shown in Table 1. Figure 1 .

[0162] 2. Catalyst preparation steps:

[0163] The Y-type molecular sieve prepared in step 1 is used as an active component, and the ZSM-5 molecular sieve is used as an additive. Kaolin and an inorganic oxide binder aluminum sol are mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry is spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres are aged at 800°C and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm are sieved to obtain a catalytic cracking catalyst, which is named CAT-H.

[0164] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0165] Example 6

[0166] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0167] Catalyst preparation:

[0168] The Y-type molecular sieve prepared in Example 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800°C and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-I.

[0169] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0170] Example 7

[0171] This embodiment provides a catalytic cracking catalyst, which is prepared by the following method:

[0172] Catalyst preparation:

[0173] The Y-type molecular sieve prepared in Example 1 was used as an active component, and the ZSM-5 molecular sieve was used as an additive. Kaolin and an inorganic oxide binder aluminum sol were mixed with water according to the raw material ratio in Table 2 and slurried. The resulting slurry was spray-dried to obtain spray-dried microspheres. After the spray-dried microspheres were aged at 800°C and 100% water vapor for 17 hours in a fixed bed aging device, microsphere particles with a particle size of 38-212 μm were sieved to obtain a catalytic cracking catalyst, which was named CAT-J.

[0174] Catalytic performance evaluation: The catalytic performance evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0175] Table 1

[0176]

[0177]

[0178] Table 2

[0179]

[0180] Table 3

[0181] project crude oil <![CDATA[Density (20 °C), g / cm 3 > 0.8628 Freezing point, ℃ 34 Residual carbon, m% 3.07 Asphaltene, m% 0.08 Sulfur content, m% 0.103 Nitrogen content, m% 0.13 Metal content, mg / kg Ni 3.27 V 0.55 Naphtha yield, m% 9.38 Diesel yield, m% 21 Wax oil yield, m% 30.3 Slag reduction yield, m% 41.4

[0182] It can be seen from Table 1 that in the process of improving the silicon-to-aluminum ratio of the Y molecular sieve framework, there is a synergistic effect between the framework doping with Mn and the gas-phase SiCl4 isomorphous substitution reaction. With the cooperation of the framework doping with Mn and the gas-phase SiCl4 isomorphous substitution reaction, the silicon-to-aluminum ratio of the Y molecular sieve framework can be greatly improved, which is an effect that cannot be achieved by only doping with Mn in the framework, only performing the SiCl4 isomorphous substitution reaction, only performing the hydrothermal superstabilization, or performing both the framework doping with Mn and the SiCl4 isomorphous substitution reaction.

[0183] It can be seen from Table 2 that under the same preparation process and catalytic cracking reaction conditions, the Y molecular sieve prepared by the synergistic effect between the framework doping Mn and the gas-phase SiCl4 isomorphous substitution reaction as the active component has a catalytic activity and ethylene and propylene yields that are higher than those of conventional hydrothermal USY (Comparative Example 2), hydrothermal USY containing Mn (Comparative Example 2) and gas-phase ultra-stable Y without Mn (Comparative Example 5).

Claims

1. A method for preparing a catalytic cracking catalyst, wherein: The method includes: A NaY molecular sieve containing the metal element Mn in its framework is subjected to an isomorphous substitution reaction with gaseous SiCl4 at a mass ratio of 0.1-20:1, and then calcined to obtain a high silicon-to-aluminum ratio Y molecular sieve containing the metal element Mn in its framework; wherein the reaction temperature of the isomorphous substitution reaction is 200-600° C.; wherein the molar ratio of MnO2 to Al2O3 in the NaY molecular sieve containing the metal element Mn in its framework is 0.01-5.0, and the framework silicon-to-aluminum molar ratio n(SiO2) / n(Al2O3) of the Y molecular sieve containing the metal element Mn in its framework is greater than 9; A catalytic cracking catalyst is prepared by using a Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn in the framework, a ZSM-5 molecular sieve, natural clay, and an inorganic oxide binder, or a catalytic cracking catalyst is prepared by using a Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn in the framework, natural clay, and an inorganic oxide binder; wherein, based on the total dry basis weight of the raw material components used to prepare the catalytic cracking catalyst being 100%, the Y-type molecular sieve with a high silicon-aluminum ratio containing the metal element Mn accounts for 15-35wt.%, the ZSM-5 molecular sieve accounts for 0-20wt.%, the natural clay accounts for 40-50wt.%, and the inorganic oxide binder accounts for 10-45wt.% in terms of inorganic oxide.

2. The method according to claim 1, wherein The method also includes the step of preparing a NaY type molecular sieve containing the metal element Mn in the framework, specifically comprising: Sodium hydroxide, an aluminum source, a silicon source, and water are mixed in a molar ratio of (10-30)Na2O:Al2O3:(10-30)SiO2:(180-400)H2O, and aged at 0-80°C to obtain a directing agent; A directing agent, sodium hydroxide, a silicon source, an aluminum source, a manganese source and water are mixed according to a molar ratio of (1-10)Na2O:Al2O3:(0.01-10.0)MnO2:(5-20)SiO2:(120-360)H2O to obtain a reaction system to be crystallized. The reaction system to be crystallized is crystallized at 60-120°C to obtain a NaY type molecular sieve containing the metal element Mn in the framework; wherein the mass of Al2O3 provided by the directing agent accounts for 3-25% of the mass of Al2O3 in the reaction system to be crystallized.

3. The method according to claim 2, wherein In the process of preparing the directing agent, sodium hydroxide, an aluminum source, a silicon source and water are mixed according to the molar ratio of Na2O: Al2O3: SiO2: H2O of 10-20:1:10-20:240-360.

4. The method according to claim 2, wherein: In the process of preparing the reaction system to be crystallized, the directing agent, sodium hydroxide, silicon source, aluminum source, manganese source and water are mixed according to the molar ratio of Na2O:Al2O3:MnO2:SiO2:H2O of 1-5:1:0.01-5.0:5-15:150-300.

5. The method according to claim 2 or 3, wherein: Aging is carried out at 10-60°C.

6. The method according to claim 2 or 4, wherein: Crystallization is carried out at 70-110°C.

7. The method according to any one of claims 2, 3 and 4, wherein: The silicon source includes at least one of ethyl silicate, water glass and silica sol; The aluminum source includes at least one of sodium metaaluminate, aluminum sulfate, aluminum isopropoxide, tert-butyl aluminum and aluminum oxide; The manganese source includes at least one of manganese chloride and manganese sulfate.

8. The method according to claim 1, wherein When performing the isomorphous substitution reaction, the mass ratio of the NaY type molecular sieve containing the metal element Mn in the framework to the gas phase SiCl4 is 0.5-15:

1.

9. The method according to claim 1, wherein The reaction temperature of the isomorphous substitution reaction is 300-500°C.

10. The method according to claim 1, wherein The preparation of the catalytic cracking catalyst using the high silicon-aluminum ratio Y-type molecular sieve containing the metal element Mn in the framework, the ZSM-5 molecular sieve, natural clay, and the inorganic oxide binder is achieved by the following method: The high silicon-aluminum ratio Y-type molecular sieve containing the metal element Mn in the framework, ZSM-5 molecular sieve, natural clay, inorganic oxide binder and water are mixed and slurried, and then the obtained slurry is spray-dried to obtain spray-dried microspheres; the obtained spray-dried microspheres are calcined to obtain the catalytic cracking catalyst.

11. The method according to claim 1 or 10, wherein: Based on the total dry weight of the raw material components used to prepare the catalytic cracking catalyst being 100%, the ZSM-5 molecular sieve accounts for 5-15 wt.%.

12. The method according to claim 1 or 10, wherein: The silicon-aluminum molar ratio n(SiO2) / n(Al2O3) of the ZSM-5 molecular sieve is 30-300; The natural clay is kaolin; The inorganic oxide binder is aluminum sol.

13. The catalytic cracking catalyst prepared by the preparation method of the catalytic cracking catalyst according to any one of claims 1 to 12.

14. Use of the catalytic cracking catalyst according to claim 13 as a catalyst in the catalytic cracking of crude oil and / or hydrocarbon oil to produce light olefins; in, The light olefins are ethylene and / or propylene and / or butene.

Images