A heat-resistant and wear-resistant, high-propylene-yield catalytic cracking catalyst aid, a preparation method thereof, and a hydrocarbon oil catalytic cracking method

Abstract

The present disclosure relates to a heat-resistant and attrition-resistant catalytic cracking catalyst additive for producing more propylene, a preparation method thereof and a method for catalytic cracking of hydrocarbon oil. The content of MFI molecular sieve is 10-75 wt%, the content of phosphorus aluminum binder calculated based on P2O5 and Al2O3 is 3-35 wt%, the content of silicon aluminum inorganic binder calculated based on SiO2 and Al2O3 is 1-20 wt%, the content of the first aluminum-based binder calculated based on Al2O3 is 0-15 wt%, and the content of clay is 0-50 wt%, based on the dry basis weight of the catalytic cracking catalyst additive. The catalytic cracking catalyst additive of the present disclosure has high attrition resistance, especially heat attrition resistance, and has good catalytic activity, can effectively increase the yield of catalytic cracking liquefied gas and propylene, has high propylene selectivity, has high conversion rate, and reduces coke at the same time.

Description

TECHNICAL FIELD

[0001] The present application relates to a heat-resistant and attrition-resistant catalytic cracking catalyst additive for producing more propylene and a method for preparing the same and a method for catalytic cracking of hydrocarbon oil. BACKGROUND

[0002] As a very important basic organic chemical raw material, the demand for propylene is continuously increasing. Catalytic cracking equipment is more economical and more convenient for increasing propylene production based on a wider source of raw materials and lower operating costs. For most catalytic cracking units, adding an additive is an effective technical approach to increasing the yield of low-carbon olefins, and the acidity and shape-selective effect of the catalyst determine the yield of low-carbon olefins in the products.

[0003] The prior art discloses a five-membered ring high-silicon zeolite catalyst for light olefins in a fluid catalytic cracking unit, which comprises (a) a five-membered ring high-silicon zeolite, (b) 8-24% by weight of phosphorus, based on the five-membered ring high-silicon zeolite-containing particles, 1-10% by weight of iron oxide, based on Fe2O3, which is located outside the five-membered ring high-silicon zeolite framework. The catalyst is fluidizable and has an average particle size of about 20 to about 200 microns. The catalyst composition can increase the yield of light olefins such as propylene in a fluidizable catalytic cracking (FCC) process. The prior art discloses a cracking additive for increasing the concentration of propylene, which consists of 10-65% by dry weight of modified ZSM-5 molecular sieve, 0-60% by weight of clay, 15-60% by weight of inorganic oxide binder, 0.5-15% by weight of metal additive selected from one or more of Group VIIIB metals, and 2-25% by weight of phosphorus additive, wherein the modified ZSM-5 molecular sieve is modified by phosphorus and a metal selected from one of Fe, Co or Ni, and the anhydrous chemical formula thereof, calculated as an oxide, is (0-0.3)Na2O·(0.5-5)Al2O3·(1.3-10)P2O5·(0.7-15)M x O y ·(70-97)SiO2, x represents the number of atoms of M, and y represents a number required to satisfy the oxidation state of M. Both the metal additive and the phosphorus additive are calculated as an oxide. The cracking additive is applied in the catalytic cracking process of petroleum hydrocarbons, which can significantly increase the propylene concentration in liquefied gas while increasing the yield of catalytic cracking liquefied gas and improving the octane number of catalytic cracking gasoline. However, the heat attrition strength of the catalyst in the prior art has always been poor due to the content of phosphorus aluminum binder in the matrix. SUMMARY

[0004] The purpose of this disclosure is to provide a catalytic cracking catalyst additive and its preparation method, as well as a method for catalytic cracking of hydrocarbon oils. The catalytic cracking catalyst additive disclosed herein has high wear resistance, especially thermal grinding resistance, and can effectively increase the yield of catalytic cracking liquefied gas and propylene, improve propylene selectivity and conversion rate, and reduce coke production.

[0005] To achieve the above objectives, the first aspect of this disclosure provides a heat-resistant and wear-resistant propylene-producing catalytic cracking catalyst, wherein the catalytic cracking catalyst contains MFI molecular sieve, phosphorus aluminum binder, silicon aluminum inorganic binder, first aluminum-based binder, and clay;

[0006] Based on the dry weight of the catalytic cracking catalyst, the content of the MFI molecular sieve is 10-75% by weight, the content of the phosphorus aluminum binder (calculated as P2O5 and Al2O3) is 3-35% by weight, the content of the silicon aluminum inorganic binder (calculated as SiO2 and Al2O3) is 1-20% by weight, the content of the first aluminum-based binder (calculated as Al2O3) is 0-15% by weight, and the content of the clay is 0-50% by weight.

[0007] The phosphorus aluminum binder, based on its weight, contains 3-15% by weight Al₂O₃, 15-40% by weight P₂O₅, and 0.1-10% by weight stabilizer; the P / Al weight ratio of the phosphorus aluminum binder is 1.6-6, the pH value is 0.5-2.5, and the QPO is [not specified]. 2 / QP0 0 The range is 1-5, where QP0 2 Indicates by 31 P-NMR spectroscopy analysis of the phosphorus aluminum binder yielded a resonance signal peak area with a chemical shift of 12 ± 2 ppm, QP0. 0 The area of ​​the resonance signal peak with a chemical shift of 0±2ppm is indicated; the average particle size of the phosphorus aluminum binder is 10-30nm;

[0008] The silicon-aluminum inorganic binder is obtained by reacting a second aluminum-based binder and a silicon-based binder in a weight ratio of (1-50):1, wherein the second aluminum-based binder is calculated as Al2O3 and the silicon-based binder is calculated as SiO2.

[0009] Optionally, the straight pipe wear index of the catalytic cracking catalyst is 0-2% / h; the thermal wear index is 0-8% / h.

[0010] Optionally, based on the dry weight of the catalytic cracking catalyst, the content of the MFI molecular sieve is 15-65% by weight, the content of the phosphorus aluminum binder (calculated as P2O5 and Al2O3) is 8-32% by weight, the content of the first aluminum-based binder is 2-10% by weight, and the content of the clay is 1-20% by weight.

[0011] Optionally, the phosphorus-aluminum binder contains 3-12 wt% of Al2O3, 15-32 wt% of P2O5 and 0.5-5 wt% of stabilizer, the P / Al weight ratio of the phosphorus-aluminum binder is 1.7-5.8, the pH value is 0.5-2.5, and the QP0 2 / QP0 0 is 1.5-5.

[0012] Optionally, the first aluminum-based binder and the second aluminum-based binder are each independently selected from one or more of pseudoboehmite, acidified alumina and aluminum sol; and the silicon-based binder is an acidic silicon sol.

[0013] The clay is selected from one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite.

[0014] The MFI molecular sieve is selected from one or more of hydrogen-type MFI molecular sieve, phosphorus-containing MFI molecular sieve and transition metal-containing MFI molecular sieve.

[0015] The second aspect of the present disclosure provides a method for preparing the catalytic cracking catalyst aid provided by the first aspect of the present disclosure, the method comprising:

[0016] S1, mixing and beating the second aluminum-based binder and the silicon-based binder, aging at 50-90°C for 30-60 min to obtain a silicon-aluminum inorganic binder;

[0017] S2, mixing and beating the silicon-aluminum binder, the MFI molecular sieve, the optional first aluminum-based binder, the optional clay and water, and controlling the pH value of the obtained first slurry to be 2-5 to obtain a second mixture;

[0018] S3, mixing and beating the second mixture with the phosphorus-aluminum binder, and performing spray drying and calcination on the obtained second slurry to obtain the catalytic cracking catalyst aid.

[0019] Optionally, the phosphorus-aluminum binder is prepared by a method comprising the following steps:

[0020] (1) mixing an aluminum source, water and a stabilizer under stirring at a temperature of 50-95°C to obtain an alumina precursor solution with a solid content of 5-40 wt%;

[0021] (2) mixing and reacting the alumina precursor solution with a phosphate under stirring at a temperature of 25-70°C to obtain the phosphorus-aluminum binder.

[0022] Optionally, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.

[0023] The phosphate is dihydrogen phosphate and / or ammonium dihydrogen phosphate.

[0024] The stabilizer is selected from one or more of acetic acid, glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, preferably acetic acid or citric acid.

[0025] The third aspect of the present disclosure provides a method for catalytic cracking of hydrocarbon oil, the method comprising: contacting and reacting the hydrocarbon oil with a catalyst, wherein the catalyst contains the catalytic aid provided by the first aspect of the present disclosure.

[0026] Optionally, the conditions for the catalytic cracking reaction of the hydrocarbon oil include: a temperature of 400-600℃, a weight hourly space velocity of 8-120 hours -1 , and a catalyst to oil weight ratio of 1-20.

[0027] Through the above technical solution, the catalytic cracking catalyst aid of the present disclosure has high wear resistance, especially hot wear resistance, wherein the synergistic effect of the phosphorus-aluminum binder and the silicon-aluminum inorganic binder and the MFI molecular sieve enables the catalytic cracking catalyst aid to effectively increase the yield of catalytic cracking liquefied gas and propylene, and the propylene has high selectivity, high conversion rate and low coke.

[0028] Other features and advantages of the present disclosure will be described in detail in the following specific embodiment part. BRIEF DESCRIPTION OF DRAWINGS

[0029] The accompanying drawings are included to provide a further understanding of the present disclosure and constitute a part of the specification, and are used together with the following specific embodiments to explain the present disclosure, but do not constitute a limitation on the present disclosure. In the drawings:

[0030] Figure 1 NMR spectrum of the prepared phosphorus-aluminum binder and NMR spectrum of the phosphorus-aluminum binder prepared in Comparative Example 1. DETAILED DESCRIPTION

[0031] The specific embodiments of the present disclosure are described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present disclosure, and are not used to limit the present disclosure.

[0032] The first aspect of the present disclosure provides a hot-wear-resistant and high-propylene-yield catalytic cracking catalyst aid, which contains MFI molecular sieve, phosphorus-aluminum binder, first inorganic binder and clay.

[0033] Based on the dry weight of the catalytic cracking catalyst, the content of the MFI molecular sieve is 10-75% by weight, the content of the phosphorus aluminum binder (calculated as P2O5 and Al2O3) is 3-35% by weight, the content of the silicon aluminum inorganic binder (calculated as SiO2 and Al2O3) is 1-20% by weight, the content of the first aluminum-based binder (calculated as Al2O3) is 0-15% by weight, and the content of the clay is 0-50% by weight.

[0034] The phosphorus aluminum binder, based on its weight, contains 3-15% by weight Al₂O₃, 15-40% by weight P₂O₅, and 0.1-10% by weight stabilizer; the P / Al weight ratio of the phosphorus aluminum binder is 1.6-6, the pH value is 0.5-2.5, and the QPO is [not specified]. 2 / QP0 0 The range is 1-5, where QP0 2 Indicates by 31 P-NMR spectroscopy analysis of the phosphorus aluminum binder yielded a resonance signal peak area with a chemical shift of 12 ± 2 ppm, QP0. 0 The area of ​​the resonance signal peak with a chemical shift of 0±2ppm is indicated; the average particle size of the phosphorus aluminum binder is 10-30nm;

[0035] The silicon-aluminum inorganic binder is obtained by reacting a second aluminum-based binder and a silicon-based binder in a weight ratio of (1-50):1, wherein the second aluminum-based binder is calculated as Al2O3 and the silicon-based binder is calculated as SiO2.

[0036] In this disclosure, the first aluminum-based binder refers to an aluminum-based binder other than phosphorus aluminum binder and silicon aluminum inorganic binder, which is directly used to prepare the additives of this application. The second aluminum-based binder is directly used to prepare the silicon aluminum inorganic binder and indirectly used to prepare the additives of this application.

[0037] The catalytic cracking catalyst promoter disclosed herein contains a specific phosphorus-aluminum binder. This phosphorus-aluminum binder has fewer free phosphate groups and more polymerized phosphate groups, exhibiting good binding performance and a long service life. When used in combination with a silicon-aluminum inorganic binder, it significantly improves the catalyst's wear resistance, especially during thermal grinding. Furthermore, it reduces reactions with the matrix aluminum and the aluminum on the MFI molecular sieve, increasing the catalyst's strength while retaining more active centers within the molecular sieve. The synergistic effect among the phosphorus-aluminum binder, the silicon-aluminum inorganic binder, and the molecular sieve results in a catalytic cracking catalyst promoter with superior wear resistance, effectively increasing the yield of liquefied petroleum gas and propylene from catalytic cracking, improving propylene selectivity and conversion, and reducing coking.

[0038] According to the present disclosure, the average colloidal particle size of the phosphorus-aluminum binder is detected by a transmission electron microscope method. Specifically, the phosphorus-aluminum binder is subjected to transmission electron microscope analysis, 100 colloidal particles of the phosphorus-aluminum binder are randomly selected on a TEM photo and their maximum diameters are respectively measured as their colloidal particle sizes, and the average value of the colloidal particle sizes of the 100 colloidal particles of the phosphorus-aluminum binder is calculated, i.e., the average colloidal particle size.

[0039] In one specific embodiment of the present disclosure, the straight tube abrasion index of the catalytic cracking catalyst aid is 0-2% per hour, and the hot abrasion index is 0-8% per hour. In the present disclosure, the determination method of the straight tube abrasion index is described in SINOPEC Q / SH 361909-2018. Specifically, a certain amount of sample is placed in an abrasion index determination device, and is blown for five hours at a constant gas velocity. The sample blown out in the first hour is discarded, the sample blown out in the last four hours is collected, and the average abrasion percentage per hour (the weight of the sample less than 15 microns blown out per hour accounts for the percentage of the weight of the catalyst greater than 15 microns) is calculated, which is called the catalyst abrasion index. The smaller the abrasion index, the better the abrasion resistance of the catalyst. In the present disclosure, under the conditions of 700°C, a gas velocity of 10 L / min, and an abrasion time of 5 hours, the fine powder generated by the friction and collision between the catalyst particles and the wall of the device is carried by the gas flow into the collector, and the hot abrasion index of the catalyst is obtained by calculating the amount of solid lost per unit time.

[0040] In one specific embodiment of the present disclosure, the content of the MFI molecular sieve is 15-65% by weight based on the dry weight of the catalytic cracking catalyst aid, the content of the phosphorus-aluminum binder is 8-32% by weight based on P2O5 and Al2O3, the content of the silicon-aluminum inorganic binder is 2-20% by weight based on SiO2 and Al2O3, the content of the first aluminum-based binder is 2-10% by weight, and the content of the clay is 1-20% by weight. Preferably, the content of the MFI molecular sieve is 20-60% by weight based on the dry weight of the catalytic cracking catalyst aid, the content of the phosphorus-aluminum binder is 10-30% by weight based on P2O5 and Al2O3, the content of the silicon-aluminum inorganic binder is 10-18% by weight based on SiO2 and Al2O3, the content of the first aluminum-based binder is 2-10% by weight, and the content of the clay is 5-18% by weight.

[0041] In one specific embodiment of the present disclosure, the phosphorus-aluminum binder contains 3-12% by weight of Al2O3, 15-32% by weight of P2O5, and 0.5-5% by weight of a stabilizer, the P / Al weight ratio of the phosphorus-aluminum binder is 1.7-5.8, the pH value is 0.5-2.5, and the QP0 2 / QP0 0 is 1.5-5.

[0042] In an embodiment of the present disclosure, the first aluminum-based binder and the second aluminum-based binder are each independently selected from one or more of pseudoboehmite, acidified alumina, and aluminum sol; and the silicon-based binder is an acidic silicon sol.

[0043] According to the present disclosure, the clay can be one commonly used by those skilled in the art in preparing catalysts. In an embodiment of the present disclosure, the clay is selected from one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomite.

[0044] In an embodiment of the present disclosure, the MFI molecular sieve is selected from one or more of a hydrogen-type MFI molecular sieve, a phosphorus-containing MFI molecular sieve, and a transition metal-containing MFI molecular sieve.

[0045] The second aspect of the present disclosure provides a method for preparing the catalytic cracking catalyst aid provided by the first aspect of the present disclosure, which comprises: S1, mixing and beating a second aluminum-based binder and a silicon-based binder, aging at 50-90°C for 30-60 min to obtain a silicon-aluminum inorganic binder; S2, mixing and beating the silicon-aluminum inorganic binder, an MFI molecular sieve, an optional first aluminum-based binder, an optional clay, and water, and controlling the pH value of the obtained first slurry to be 2-5 to obtain a second mixture; S3, mixing and beating the second mixture with a phosphorus-aluminum binder, and spray drying and calcining the obtained second slurry to obtain the catalytic cracking catalyst aid.

[0046] The method of the present disclosure can prepare a catalytic cracking catalyst aid with relatively optimal catalytic performance, which has relatively optimal attrition performance, especially hot attrition performance, can effectively increase the yield of catalytic cracking liquefied gas and propylene, has high propylene selectivity, high conversion rate, and low coke.

[0047] In an embodiment of the present disclosure, in step S2, the MFI molecular sieve, the silicon-aluminum inorganic binder, the clay, and water are first mixed and beaten, and then the first aluminum-based binder is added to the obtained mixture for mixing and beating to obtain the first slurry, which is beneficial to further improving the activity and strength of the catalytic cracking catalyst aid.

[0048] According to the present disclosure, spray drying is a technical means known to those skilled in the art, and the specific method is not described here. In an embodiment, the inlet temperature of spray drying can be 300-700°C, and the outlet temperature can be 80-200°C.

[0049] In an embodiment of the present disclosure, the calcination temperature is 400-700°C, preferably 450-600°C, and the calcination time is 0.5-100 hours, preferably 0.5-10 hours.

[0050] In one embodiment of the present disclosure, the phosphorus-aluminum binder is prepared by a method comprising the following steps: (1) mixing an aluminum source, water and a stabilizer under stirring at a temperature of 50-95℃ to obtain an alumina precursor solution with a solid content of 5-40wt%; (2) mixing the alumina precursor solution with a phosphate under stirring at a temperature of 25-70℃ to obtain the phosphorus-aluminum binder.

[0051] The phosphorus-aluminum binder used in the method of the present disclosure is prepared from low-cost aluminum salt and phosphate, and has less free phosphate and more polymeric phosphate, and good binding performance. The stabilizer contained therein can effectively prolong the service life of the phosphorus-aluminum binder.

[0052] In one embodiment of the present disclosure, in step (1), the weight ratio of the aluminum salt, water and stabilizer is 100:(50-800):(5-40), preferably 100:(100-750):(6-35), the aluminum salt being calculated as alumina; in step (2), the weight ratio of the alumina precursor solution to the phosphate is 100:(50-200), preferably 100:(60-150), the phosphate being calculated as phosphorus oxide.

[0053] In one embodiment of the present disclosure, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; the phosphate is diammonium hydrogen phosphate and / or ammonium dihydrogen phosphate; the stabilizer is selected from one or more of acetic acid, glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, preferably acetic acid or citric acid.

[0054] The third aspect of the present disclosure provides a method for catalytic cracking of hydrocarbon oil, which comprises: contacting and reacting hydrocarbon oil with a catalyst containing the catalytic aid provided in the first aspect of the present disclosure.

[0055] In one embodiment of the present disclosure, the catalyst is a mixture of the catalytic aid provided in the first aspect of the present disclosure and an optional main catalyst, and the reaction is a catalytic cracking reaction of hydrocarbon oil. According to the present disclosure, the main catalyst can be selected as required, and in one embodiment of the present disclosure, the main catalyst can be selected from catalytic cracking catalyst and / or catalytic cracking catalyst, for example, can include but is not limited to one or more of RFCC catalyst, CGP catalyst, GOR olefin-reducing catalyst and DCC catalyst.

[0056] In one embodiment of the present disclosure, the conditions of the catalytic cracking reaction of hydrocarbon oil include a temperature of 400-600℃, preferably 450-550℃, and a weight hourly space velocity of 8-120 hours-1 , preferably 8-80 hours -1 , the weight ratio of the catalyst to the oil is 1-20, preferably 3-15. The catalytic cracking catalyst provided by the present disclosure can be used in various existing catalytic cracking reactors, such as in fixed bed reactors, fluidized bed reactors, riser reactors, multi-reaction zone reactors, etc.

[0057] The present disclosure will be further illustrated by examples, but the present disclosure is not limited in any way by the examples.

[0058] The catalytic cracking catalyst of the present disclosure is evaluated by using an ACE device when used for catalytic cracking reaction performance evaluation.

[0059] The RIPP standard method described in the present disclosure can be specifically referred to in “Analysis Methods for Petroleum and Chemical Industry”, edited by Yang Cuiding et al., 1990 edition.

[0060] The method for measuring the abrasion strength by straight pipe method can be referred to in Sinopec Q / SH 361 909-2018.

[0061] The hot abrasion index is detected by the following method: under the conditions of 700℃, gas velocity of 10 L / min, and abrasion time of 5 h, the fine powder generated by the friction and collision between the catalyst particles and the catalyst and the wall is taken to the collector by the gas flow, and the hot abrasion index of the catalyst is obtained by calculating the amount of solid lost per unit time.

[0062] The pore volume is measured by nitrogen adsorption method (RIPP 151-90).

[0063] The properties of some raw materials used in the examples and comparative examples are as follows:

[0064] The pseudo-boehmite is an industrial product produced by Shandong Aluminum Company, with a solid content of 60% by weight;

[0065] The aluminum sol is an industrial product produced by Sinopec Catalyst Qilu Branch Company, with an Al2O3 content of 21.5% by weight;

[0066] The kaolin is a special kaolin for catalytic cracking catalyst produced by Suzhou Kaolin Company, with a solid content of 78% by weight.

[0067] Hydrochloric acid: chemically pure, with a concentration of 36-38% by weight, produced by Beijing Chemical Plant.

[0068] ZSP molecular sieve: an industrial product produced by Sinopec Catalyst Qilu Branch Company, with a P2O5 content of 3.25% by weight, a Fe2O3 content of 1.85% by weight, and a crystallinity of 75%.

[0069] Silica sol: SiO2 solid content of 30% by weight, pH value of 2.

[0070] The average colloidal particle size of the phosphorus-aluminum binder in the present disclosure is detected by a transmission electron microscope method.

[0071] Preparation Example 1-4 is a preparation example of the phosphorus-aluminum binder of the present disclosure.

[0072] Preparation Example 1

[0073] (1) 0.56 kg of anhydrous aluminum sulfate was mixed with 0.25 kg of deionized water and 0.05 kg of oxalic acid, and was stirred and heated to 70°C for 30 minutes to obtain an alumina precursor with a solid content of 39% by weight;

[0074] (2) The temperature was controlled at 45°C, and 0.56 kg of ammonium dihydrogen phosphate was added to the alumina precursor prepared in step (1) under stirring, and then reacted at 45°C for 45 minutes until the mixture became a transparent colloid to obtain a phosphorus-aluminum binder P-1. The material ratio is shown in Table 1, and the nuclear magnetic resonance spectrum is shown in Figure 1 .

[0075] Preparation Example 2-4

[0076] The phosphorus-aluminum binder was prepared by the same method as Preparation Example 1, except that the raw materials and their amounts used were different. The specific material ratio is shown in Table 1.

[0077] Preparation Comparative Example 1

[0078] The inorganic binder containing a phosphorus-aluminum compound was prepared according to the method provided in the patent ZL201110180891.X. The specific method is as follows:

[0079] At room temperature (25°C), 0.98 kg of pseudo-boehmite (containing 0.6 kg of Al2O3), 0.26 kg of a rectorite (dry basis 0.16 kg) and 0.44 kg of deionized water were mixed and slurried for 30 minutes, and 2.01 kg of concentrated phosphoric acid (mass concentration 85%) was added to the slurry under stirring, the addition speed of the phosphoric acid was 0.03 kg of phosphoric acid per minute per kg of alumina source, and the temperature was increased to 70°C, and then reacted at this temperature for 45 minutes to obtain the inorganic binder containing a phosphorus-aluminum compound DPAL-1. The nuclear magnetic resonance spectrum is shown in Figure 1 .

[0080] From Figure 1 It can be seen that in the 31P nuclear magnetic resonance spectrum of the phosphorus-aluminum binder, the peak area of the resonance signal with a chemical shift of 12±2 ppm is defined as QP0 2 , and the peak area of the resonance signal with a chemical shift of 0±2 ppm is defined as QP0 0 . At the same phosphorus-aluminum ratio, the QP0 2 / QP0 0 of the phosphorus-aluminum binder prepared in Preparation Example 1 is higher than that of the phosphorus-aluminum binder prepared in Preparation Comparative Example 1. 2QP0 0 The higher, the higher its degree of polymerization.

[0081] Table 1

[0082]

[0083]

[0084] Examples 1-6 are preparation examples of catalytic cracking catalyst aids.

[0085] Example 1

[0086] S1, mix and beat the aluminum sol and the acidic silica sol, age at 75°C for 40 min, to obtain a silica-alumina inorganic binder;

[0087] S2, take ZSP molecular sieve, add deionized water and beat for 10 min, beat for 120 min to obtain a molecular sieve slurry; then sequentially add the molecular sieve slurry, the silica-alumina inorganic binder, the pseudo-boehmite and the kaolin, add hydrochloric acid to adjust the pH value of the slurry to 3.0, then continue to beat for 45 min to obtain a second mixture;

[0088] S3, mix and beat the second mixture with the phosphorus-aluminum binder for 5 min, spray dry the obtained slurry, and calcine the obtained microspheres at 500°C for 2 hours to obtain a catalytic cracking catalyst aid CAT-1, the specific ratio of which is shown in Table 3.

[0089] Examples 2-6

[0090] The catalytic cracking catalyst aid is prepared by the same method as in Example 1, except that the raw materials and their amounts used are different, and the specific ratio is shown in Table 2.

[0091] Comparative Example 1

[0092] Take MPZ molecular sieve, kaolin and aluminum stone, add deionized water and aluminum sol and beat for 120 min, add hydrochloric acid to adjust the pH value of the slurry to 3.0, then continue to beat for 45 min, then add the phosphorus-aluminum inorganic binder (DPAL-1), stir for 5 min, spray dry the obtained slurry to obtain microspheres, and calcine the microspheres at 500°C for 1 hour to obtain DCAT-1, the specific ratio of which is shown in Table 2.

[0093] Comparative Example 2

[0094] The catalytic cracking catalyst aid is prepared by the same method as in Example 2, except that the phosphorus-aluminum inorganic binder DPAL-1 is used instead of the phosphorus-aluminum binder P-1, and the material ratio is shown in Table 2.

[0095] Comparative Example 3

[0096] The same method as in Example 2 was used to prepare the catalytic cracking catalyst auxiliary, except that in step S1, instead of mixing and beating the alumina sol and silica sol as the other inorganic binder, the alumina sol was directly used as the other inorganic binder, and the material ratio was as shown in Table 2.

[0097] Table 2

[0098]

[0099] In Table 2, the ratio is parts by weight.

[0100] As can be seen from Table 2, the attrition index and hot attrition index of the catalytic cracking catalyst auxiliary provided by the present disclosure are better than those of the reference catalyst.

[0101] Test Example

[0102] The following examples use a fixed fluidized bed reactor to illustrate the cracking reaction effect of the cracking catalyst provided by the present disclosure.

[0103] The catalytic cracking catalyst SLA and 30 g of CAT-1 to 6 and DCAT 1 to 3 were respectively aged at 800°C under 100% steam atmosphere for 17 hours. Different amounts of the aged catalysts were mixed with an industrial equilibrium catalyst (main properties are shown in Table 3), and the catalyst mixture was loaded into the reactor of a small fixed fluidized bed reaction device to catalytically crack the feedstock oil shown in Table 4. The reaction conditions and results are shown in Table 5.

[0104] Table 3 Main properties of industrial equilibrium catalyst

[0105]

[0106]

[0107] Table 4 Properties of feedstock oil for evaluation

[0108] Density (20°C), g / cm 3 ]] 0.92 Carbon residue, % (mass fraction) 4.81 Initial boiling point, °C 228.00 500 °C distillation, % (volume fraction) 44.50 538 °C distillation, % (volume fraction) 54.50 Asphaltene content, % (mass fraction) 1.73 Saturates content, % (mass fraction) 58.17 Aromatics content, % (mass fraction) 29.01 Resins content, % (mass fraction) 11.10 Total nitrogen, mg / kg 594.30 Iron content, mg / kg 2.16 Sodium content, mg / kg 1.39 Nickel content, mg / kg, < 10 6.44 Vanadium content, mg / kg, < 10 8.91

[0109] Table 5 Evaluation results

[0110]

[0111]

[0112] As can be seen from Table 5, compared with the reference catalytic cracking catalyst, the catalytic cracking catalyst auxiliary provided by the present disclosure can effectively increase the yield of catalytic cracking liquefied gas and propylene, has high propylene selectivity, high conversion rate, and low coke.

[0113] The preferred embodiments of the present disclosure are described in detail above with reference to the drawings, but the present disclosure is not limited to the specific details in the above-described embodiments. Various simple modifications can be made to the technical solutions of the present disclosure within the technical concept of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0114] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present disclosure.

[0115] In addition, various different embodiments of the present disclosure can also be combined in any appropriate manner, as long as they do not deviate from the idea of the present disclosure, and they should also be considered as disclosed in the present disclosure.

Claims

1. A heat-resistant and attrition-resistant catalytic cracking catalyst additive for producing propylene, the catalytic cracking catalyst additive comprising MFI molecular sieve, phosphorus-aluminum binder, silicon-aluminum inorganic binder, first aluminum-based binder and clay; the content of the MFI molecular sieve is 10-75 wt%, the content of the phosphorus-aluminum binder is 3-35 wt%, the content of the silicon-aluminum inorganic binder is 1-20 wt%, the content of the first aluminum-based binder is 0.5-15 wt%, and the content of the clay is 0-50 wt%, all based on the dry weight of the catalytic cracking catalyst additive; the silicon-aluminum inorganic binder is obtained by reacting second aluminum-based binder and silicon-based binder in a weight ratio of (1-50) : 1; the second aluminum-based binder is calculated based on Al 2 O 3, and the silicon-based binder is calculated based on SiO 2; the stabilizer is selected from one or more of acetic acid, glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid; the straight tube attrition index of the catalytic cracking catalyst additive is 0-2% / h, and the hot attrition index is 0-8% / h. 2.The catalytic cracking catalyst additive according to claim 1, wherein the content of the MFI molecular sieve is 15-65 wt%, the content of the phosphorus-aluminum binder is 8-32 wt%, the content of the silicon-aluminum inorganic binder is 2-20 wt%, the content of the first aluminum-based binder is 2-10 wt%, and the content of the clay is 1-20 wt%, all based on the dry weight of the catalytic cracking catalyst additive. The phospho-aluminum binder contains 3-15 wt% of Al203, 15-40 wt% of P205, and 0.1-10 wt% of a stabilizer, and has a P / Al weight ratio of 1.6-6, a pH value of 0.5-2.5, and a QP0 2 QP0 0 1-5, wherein, QP0 2 representing the peak area of the resonance signal of the chemical shift of 12 ± 2 ppm detected by P nuclear magnetic resonance spectrum of the phosphorus-aluminum binder 31 QP0 0 representing the peak area of the resonance signal of the chemical shift of 0 ± 2 ppm; the average colloidal particle size of the phosphorus-aluminum binder is 10-30 nm; 3.The catalytic cracking catalyst additive according to claim 1 or 2, wherein the first aluminum-based binder and the second aluminum-based binder are each independently selected from one or more of pseudo-boehmite, acidified aluminum stone and aluminum sol, and the silicon-based binder comprises acidic silicon sol. 4.The catalytic cracking catalyst additive according to any one of claims 1-3, wherein the clay is selected from one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite.

2. The catalytic cracking catalyst adjunct of claim 1, wherein, 5.The catalytic cracking catalyst additive according to any one of claims 1-4, wherein the MFI molecular sieve is selected from one or more of hydrogen-type MFI molecular sieve, phosphorus-containing MFI molecular sieve and transition metal-containing MFI molecular sieve.

3. The catalytic cracking catalyst adjunct of claim 1, wherein, 6.A method for preparing the catalytic cracking catalyst additive according to any one of claims 1-5, the method comprising: S1, mixing and slurrying second aluminum-based binder and silicon-based binder, and aging at 50-90℃ for 30-60min to obtain silicon-aluminum inorganic binder; S2, mixing and slurrying the silicon-aluminum inorganic binder, MFI molecular sieve, optional clay, first aluminum-based binder and water, and controlling the pH value of the obtained first slurry to be 2-5 to obtain a second mixture; S3, mixing and slurrying the second mixture with phosphorus-aluminum binder, and spray drying and calcining the obtained second slurry to obtain the catalytic cracking catalyst additive.

4. The catalytic cracking catalyst adjunct of claim 1, wherein, The phospho-aluminum binder contains 3-12 wt% of AI2O3, 15-32 wt% of P2O5, and 0.5-5 wt% of a stabilizer, the P / Al weight ratio of the phospho-aluminum binder is 1.7-5.8, the pH value is 0.5-2.5, and QP0 2 / QP0 0 1.5-5.

5. The catalytic cracking catalyst adjunct of claim 1, wherein, 7.The method according to claim 6, wherein the phosphorus-aluminum binder is prepared by a method comprising the following steps: (1) mixing aluminum source, water and stabilizer under stirring at a temperature of 50-95℃ to obtain an alumina precursor solution with a solid content of 5-40 wt%; (2) mixing the alumina precursor solution with phosphorus source to obtain a phosphorus-aluminum binder. ​ ​ ​ ​ ​ ​ 7. The method of claim 6, wherein, ​ ​ (2) mixing the alumina precursor solution with phosphate under the condition of 25-70℃ and stirring to obtain the phosphorus-aluminum binder.

8. The method of claim 7, wherein, In step (1), the weight ratio of the aluminum source, water and stabilizer is 100:(50-800):(5-40), and the aluminum source is calculated as alumina; In step (2), the weight ratio of the alumina precursor solution and the phosphate is 100:(50-200), and the phosphate is calculated as phosphorus oxide.

9. The method of claim 8, wherein, In step (1), the weight ratio of the aluminum source, water and stabilizer is 100:(100-750):(6-35), and the aluminum source is calculated as alumina; In step (2), the weight ratio of the alumina precursor solution and the phosphate is 100:(60-150), and the phosphate is calculated as phosphorus oxide.

10. The method of claim 7, wherein, The aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride; The phosphate is diammonium hydrogen phosphate and / or ammonium dihydrogen phosphate; The stabilizer is selected from acetic acid or citric acid.

11. A process for the catalytic cracking of hydrocarbon oils, which process comprises: Contacting a hydrocarbon oil with a catalyst containing the catalytic aid of any one of claims 1-5.

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