MFI STRUCTURE MOLECULAR SIEVE RICH IN MESOPORE, PREPARATION METHOD THEREFOR, AND CATALYST CONTAINING SAME AND APPLICATION THEREOF

Abstract

A molecular sieve of MFI structure has a ratio of n(SiO2)/n(Al2O3) of more than 15 and less than 70. It has a content of phosphorus of 1-15 wt %, calculated as P.sub.2O.sub.5 and based on the dry weight of the molecular sieve and a content of the supported metal in the molecular sieve 1-10 wt % based on the oxide of the supported metal and the dry weight of the molecular sieve. The supported metal is one or two selected from lanthanum and cerium. The volume of mesopores in the molecular sieve represents 40-70% by volume of the total pore volume of the molecular sieve by volume, measured by a nitrogen adsorption BET specific surface area method, and the volume of mesopores means the pore volume of the pores having a diameter of more than 2 nm and less than 100 nm.

Claims

1. A molecular sieve of MFI structure rich in mesopores, comprising a silicon component, an aluminum component, a phosphorus component and a supported metal component, wherein the molecular sieve has a ratio of n(SiO.sub.2)/n(Al.sub.2O.sub.3) of more than 15 and less than 70; the molecular sieve has a content of phosphorus, calculated as P.sub.2O.sub.5, of 1-15 wt % based on the dry weight of the molecular sieve; the molecular sieve has a supported metal content, calculated as the oxide of the supported metal, of 1-10 wt % based on the dry weight of the molecular sieve, wherein the supported metal is one or more selected from rare earth elements, preferably one or two selected from lanthanum and cerium; the volume of mesopores in the molecular sieve represents 40-70% by volume of the total pore volume of the molecular sieve, the volume of mesopores and the total pore volume of the molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the volume of mesopores means the pore volume of the pores having a diameter of more than 2 nm and less than 100 nm.

2. The molecular sieve of MFI structure rich in mesopores according to claim 1, wherein the molecular sieve has a RE distribution parameter, D, satisfying: 0.9≤D≤1.3, preferably 0.9≤D≤1.1, wherein D=RE (S)/RE (C), RE (S) represents the content of rare earth in any region of more than 100 nm.sup.2 in a distance H inward from the edge of a crystal face of the molecular sieve crystal grain measured by a TEM-EDS method, and RE (C) represents the content of rare earth in any region of more than 100 nm.sup.2 in a distance H outward from the geometric center of the crystal face of the molecular sieve crystal grain measured by a TEM-EDS method, wherein H is 10% of the distance from a certain point on the edge of the crystal face to the geometric center of the crystal face.

3. The molecular sieve of MFI structure rich in mesopores according to claim 1, wherein the molecular sieve of MFI structure has a ratio of n(SiO.sub.2)/n(Al.sub.2O.sub.3) of greater than 18 and less than 60; the molecular sieve has a content of phosphorus, calculated as P.sub.2O.sub.5, of 3-12 wt % based on the dry weight of the molecular sieve; the molecular sieve has a supported metal content, calculated as the oxide of the supported metal, of 3-8 wt % based on the dry weight of the molecular sieve; and the volume of mesopores in the molecular sieve represents 45-65% by volume of the total pore volume of the molecular sieve.

4. A process of producing the molecular sieve of MFI structure rich in mesopores of according to claim 1, comprising: a. filtering and washing a slurry of a molecular sieve of MFI structure obtained by crystallization to provide a water-washed molecular sieve; wherein, the water-washed molecular sieve has a sodium content, calculated as sodium oxide, of less than 5 wt % based on the total dry weight of the water-washed molecular sieve calculated as sodium oxide; b. desiliconizing the water-washed molecular sieve obtained in step a in an alkaline solution, and then filtering and washing to provide a base washed molecular sieve; c. carrying out an ammonium exchange treatment on the base washed molecular sieve obtained in step b to provide an ammonium exchanged molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium content, calculated as sodium oxide, of less than 0.2 wt %, based on the total dry weight of the ammonium exchanged molecular sieve; and d. carrying out a phosphorus modification treatment, a supporting treatment with the supported metal and a baking treatment on the ammonium exchanged molecular sieve obtained in step c to provide the molecular sieve of MFI structure rich in mesopores.

5. The process according to claim 4, wherein step d is carried out by one or more modes selected from the group consisting of: mode (1): simultaneously carrying out a phosphorus modification treatment and a supporting treatment with the supported metal on the ammonium exchanged molecular sieve obtained in step c, and then carrying out a baking treatment; mode (2): the baking treatment comprising a baking treatment in a steam atmosphere and a baking treatment in an air atmosphere, wherein the ammonium exchanged molecular sieve obtained in step c is sequentially subjected to the supporting treatment with the supported metal, a baking treatment in a steam atmosphere, the phosphorus modification treatment and a baking treatment in the air atmosphere; mode (3): sequentially carrying out a supporting treatment with the supported metal, a phosphorus modification treatment and a baking treatment on the ammonium exchanged molecular sieve obtained in step c; and mode (4): the baking treatment comprising a baking in a steam atmosphere and a baking in an air atmosphere, wherein the ammonium exchanged molecular sieve obtained in step c is sequentially subjected to a phosphorus modification treatment, a baking in the air atmosphere, a supporting treatment with the supported metal and a baking in the steam atmosphere in sequence.

6. The process according to claim 4, wherein the molecular sieve of MFI structure in the slurry of the molecular sieve of MFI structure obtained by crystallization is a ZSM-5 molecular sieve having a silica-to-alumina ratio of less than 80.

7. The process according to claim 4, wherein the slurry of the molecular sieve of MFI structure obtained by crystallization is prepared by a template method, and step b further comprises: drying and carrying out a second baking on the water-washed molecular sieve to remove the template agent, and then carrying out the desiliconization treatment.

8. The process according to claim 4, wherein in step b, the alkaline solution is an aqueous solution of sodium hydroxide and/or potassium hydroxide; and/or the conditions for the desiliconization treatment comprise: a weight ratio of the molecular sieve calculated on a dry basis to the base and water in the alkaline solution of 1:(0.1-2):(5-15), a temperature of 10-100° C., preferably from room temperature to 100° C., and/or a treatment duration of 0.2-4 hours.

9. The process according to claim 4, wherein in step c, the ammonium exchange treatment comprises treating the base washed molecular sieve with an aqueous solution of an ammonium salt, and the conditions for the ammonium exchange treatment comprise: a weight ratio of the molecular sieve on a dry basis to the ammonium salt and water of 1:(0.1-1):(5-10), a temperature of 10-100° C., preferably from room temperature to 100° C., and/or a treatment duration of 0.2-4 hours; and the ammonium salt is one or more selected from ammonium chloride, ammonium sulfate and ammonium nitrate.

10. The process according to claim 4, wherein in step d, the phosphorus modification treatment comprises: carrying out impregnation and/or ion exchange with at least one phosphorus-containing compound selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium phosphate; the supporting treatment with the supported metal comprises: supporting the supported metal with a compound containing the supported metal by impregnation and/or ion exchange in a single time or in batches; and the conditions for the baking treatment comprise: an atmosphere of air atmosphere and/or steam atmosphere, a baking temperature of 400-800° C., and/or a baking duration of 0.5-8 hours.

11. A catalytic cracking catalyst, characterized in comprising, based on the dry weight of the catalytic cracking catalyst: 5 to 78 wt % of the molecular sieve of MFI structure rich in mesopores of according to claim 1; 1-60 wt % of an inorganic binder comprising a phosphorus-aluminum inorganic binder and optionally an additional inorganic binder; and optionally 0 to 65 wt % of a second clay.

12. The catalytic cracking catalyst according to claim 11, wherein the catalytic cracking catalyst comprises 3 to 40 wt %, preferably 3 to 39 wt %, on a dry basis of the phosphorus-aluminum inorganic binder and 1 to 30 wt % on a dry basis of the additional inorganic binder, based on the dry weight of the catalytic cracking catalyst.

13. The catalytic cracking catalyst according to claim 11, wherein the phosphorus-aluminum inorganic binder is an aluminophosphate gel and/or a first clay-containing phosphorus-aluminum inorganic binder; the first clay-containing phosphorus-aluminum inorganic binder comprises, based on the dry weight of the first clay-containing phosphorus-aluminum inorganic binder: 10-40 wt %, preferably 15-40 wt %, of an aluminum component calculated as Al.sub.2O.sub.3, 40-80 wt %, preferably 45-80 wt %, of phosphorus component calculated as P.sub.2O.sub.5, and more than 0 and not more than 42 wt %, preferably not more than 40 wt %, of the first clay on a dry basis, wherein the first clay-containing phosphorus-aluminum inorganic binder has a weight ratio of P/Al of 1.0-6.0, a pH value of 1-3.5, and a solid content of 15-60 wt %; and the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite; and the additional inorganic binder comprises at least one of pseudo-boehmite, alumina sol, silica-alumina sol and water glass.

14. The catalytic cracking catalyst according to claim 11, comprising the second clay, which is at least one selected from the group consisting of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, halloysite, hydrotalcite, bentonite, and diatomaceous earth, preferably at least one selected from the group consisting of kaolin, metakaolin, diatomaceous earth, sepiolite, attapulgite, montmorillonite, and rectorite.

15. The catalytic cracking catalyst according to claim 11, wherein the catalytic cracking catalyst is a I-type catalytic cracking catalyst comprising: 8-78 wt % of the molecular sieve of MFI structure rich in mesopores; 1-40 wt % of the binder; and 0 to 65 wt %, preferably 10 to 55 wt %, of a second clay.

16. The catalytic cracking catalyst according to claim 11, wherein the catalytic cracking catalyst is a II-type catalytic cracking catalyst comprising, based on the dry weight of the catalytic cracking catalyst: 5-50 wt % of the molecular sieve of MFI structure rich in mesopores; 1 to 60 wt % of an inorganic binder; 1-25 wt % of a Y-type molecular sieve; and optionally 0 to 60 wt %, preferably 10 to 50 wt %, of the second clay.

17. The catalytic cracking catalyst according to claim 16, wherein the Y-type molecular sieve comprises at least one selected from the group consisting of a PSRY molecular sieve, a PSRY-S molecular sieve, a rare earth-containing PSRY molecular sieve, a rare earth-containing PSRY-S molecular sieve, a USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, a REHY molecular sieve, and an HY molecular sieve.

18. A process of producing the catalytic cracking catalyst according to claim 11, comprising: mixing the molecular sieve of MFI structure rich in mesopores according to claim 1 with an inorganic binder and optionally a second clay and formulating into a slurry; spray drying the slurry; and optionally carrying out a third baking treatment; wherein, relative to 5 to 78 parts by weight of the molecular sieve of MFI structure rich in mesopores on a dry basis, the amount of the inorganic binder on a dry basis is 1 to 60 parts by weight, and the amount of the second clay on a dry basis is 0 to 65 parts by weight; and wherein the binder comprises a phosphorus-aluminum inorganic binder and optionally an additional inorganic binder.

19. The process according to claim 18, wherein the process comprises the third firing, and further comprises: washing and optionally drying the product obtained by the third baking; wherein the third baking is carried out at a baking temperature of 300-650° C. for 0.5-12 h, preferably 0.5-8 h; and the drying is carried out at a temperature of 100-200° C. for 0.5-24 h.

20. The process according to claim 18, wherein the phosphorus-aluminum inorganic binder comprises a first clay-containing phosphorus-aluminum inorganic binder, and the process further comprises: preparing the first clay-containing phosphorus-aluminum inorganic binder by the steps of: formulating an alumina source, the first clay and water into a slurry with a solid content of 5-48 wt %; wherein the alumina source is aluminum hydroxide and/or alumina capable of being peptized by an acid, and the first clay is used in an amount of more than 0 part by weight and not more than 42 parts by weight, preferably not more than 40 parts by weight on a dry basis, relative to 15-40 parts by weight of the alumina source calculated as Al.sub.2O.sub.3; and adding concentrated phosphoric acid into the slurry at a weight ratio of P/Al=1-6 under stirring, and reacting the mixed slurry at 50-99° C. for 15-90 minutes; wherein in the P/A1, P represents the weight of phosphorus in the phosphoric acid calculated as a simple substance, and Al represents the weight of aluminum in the alumina source calculated as a simple substance.

21. The process according to claim 18, wherein Y-type molecular sieves are further added and mixed before formulating the slurry.

22. A method for catalytically cracking a hydrocarbon oil using the catalytic cracking catalyst according to claim 11, comprising: contacting and reacting a hydrocarbon oil with the catalytic cracking catalyst, under the condition of catalytic cracking reaction, wherein the catalytic cracking reaction is carried out at a temperature of 500-800° C.

23. The method according to claim 22, wherein the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, straight-run wax oil, propane light/heavy deoiling, coked wax oil, and coal liquefaction product.

24. The method according to claim 22, wherein the hydrocarbon oil is contacted and reacted with a catalytic mixture containing the catalytic cracking catalyst and an additional catalytic cracking catalyst.

25. The method according to claim 24, wherein the catalytic cracking catalyst is present in the catalytic mixture in an amount of 0.1 to 30 wt %.

Description

EXAMPLES

[0251] The present invention will be further illustrated by the following examples, whilst the present invention is not limited thereto. The instruments and reagents used in the examples of the present invention are those conventionally used by those skilled in the art unless otherwise specified.

[0252] The effects by the catalyst on the yield, selectivity and the like of low-carbon olefins in the catalytic cracking of petroleum hydrocarbons were evaluated by a fixed bed micro-reaction. The catalyst sample prepared was aged for 17 hours at 800° C. under 100% steam on a fixed bed aging device, and was evaluated on the micro-reaction device, wherein the raw material oil was VGO or naphtha under the conditions of a reaction temperature at 620° C., a regeneration temperature at 620° C. and a catalyst-oil ratio of 3.2.

[0253] The crystallinity involved in the process of the present invention was measured by a standard method of ASTM D5758-2001 (2011) e 1.

[0254] The ratio of n(SiO.sub.2)/n(Al.sub.2O.sub.3), namely the silicon-aluminum ratio, involved in the process of the present invention was obtained by calculating the contents of silicon oxide and aluminum oxide, where the contents of the silicon oxide and the aluminum oxide were measured by a GB/T30905-2014 standard method.

[0255] The content of phosphorus involved in the process of the present invention was determined by a GB/T30905-2014 standard method, and the content of the supported metal was determined by the GB/T30905-2014 standard method.

[0256] The specific surface area involved in the process of the invention was determined using the GB5816 standard method.

[0257] The pore volume involved in the process of the invention was determined using the GB5816 standard method.

[0258] The sodium content involved in the process of the invention was determined by a GB/T30905-2014 standard method.

[0259] The RIPP standard method (if related) involved in the invention can be seen in “Petrochemical Analysis Methods”, edited by YANG Cuiding et al, 1990.

[0260] The micro-activity (conversion, etc.) of the process of the invention was determined using the ASTM D5154-2010 standard method.

[0261] The D value was calculated as follows: selecting a crystal grain and a certain crystal face of the crystal grain under a Transmission Electron Microscopy to form a polygon, wherein the polygon has a geometric center, an edge and a 10% distance H from the geometric center to a certain point of the edge (different edge points and different H values); respectively selecting any one region in the inward H distance from the edge of the crystal face which was greater than 100 nm.sup.2 and any one region in the outward H distance from the geometric center of the crystal face which was greater than 100 nm.sup.2, measuring the content of rare earth (if two kinds of rare earth existing, measuring the total content of the rare earth), namely RE (S1) and RE (C1), calculating D1=RE (S1)/RE (C1), respectively selecting different crystal grains to measure for 5 times, and calculating the average value, provide the D value.

[0262] Some of the raw materials used in the examples had the following properties:

[0263] the pseudoboehmite was an industrial product produced by Shandong Aluminum Industry Company, having a solid content of 60 wt %; the alumina sol was an industrial product produced by Qilu Division of Sinopec catalyst Co., Ltd., having a content of Al.sub.2O.sub.3 of 21.5 wt %; the silica sol was an industrial product produced by Qilu Division of Sinopec Catalyst Co., Ltd., having a content of SiO.sub.2 of 28.9 wt %, and a content of Na.sub.2O of 8.9%; the kaolin was a kaolin special for a catalytic cracking catalyst produced by Suzhou Kaolin Company, having a solid content of 78 wt %; the rectorite was produced by Hubei Zhongxiang Mingliu Rectorite Company, having a content of quartz sand of less than 3.5 wt %, a content of Al.sub.2O.sub.3 of 39.0 wt %, a content of Na.sub.2O of 0.03 wt %, and a solid content of 77 wt %; the SB aluminum hydroxide powder was manufactured by Condex, Germany, having an Al.sub.2O.sub.3 content of 75 wt %; the γ-alumina was manufactured by Condex, Germany, having an Al.sub.2O.sub.3 content of 95 wt %, and the hydrochloric acid, chemical purity, having concentration 36-38 wt %, was produced by Beijing Chemworks.

[0264] The following examples were provided to prepare the molecular sieve of MFI structure rich in mesopores according to the present invention and comparative examples were provided to prepare molecular sieves for comparison.

Example 1

[0265] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 9.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) and 8.1 g La(NO.sub.3).sub.3.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-A was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Example 2

[0266] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) and 4.9 g Ce(NO.sub.3).sub.2.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-B was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Example 3

[0267] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 11.6 g H.sub.3PO.sub.4 (having a concentration of 85 wt %), 8.1 g La(NO.sub.3).sub.3.6H.sub.2O and 4.9 g Ce(NO.sub.3).sub.2.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 3 hours. The molecular sieve MS-C was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Example 4

[0268] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) and 3.3 g Ce(NO.sub.3).sub.2.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-D was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Example 5

[0269] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) and 14.7 g Ce(NO.sub.3).sub.2.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-E was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Example 6

[0270] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 8.1 g La(NO.sub.3).sub.3.6H.sub.2O was added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 9.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-A-1 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 7

[0271] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 4.9 g Ce(NO.sub.3).sub.2.6H.sub.2O was added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-B-1 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 8

[0272] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 8.1 g La(NO.sub.3).sub.3.6H.sub.2O and 4.9 g Ce(NO.sub.3).sub.2. 6H.sub.2O were added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 11.6 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-C-1 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 9

[0273] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 3.3 g Ce(NO.sub.3).sub.2.6H.sub.2O was added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-D-1 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 10

[0274] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 14.7 g Ce(NO.sub.3).sub.2.6H.sub.2O was added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 5.8 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-E-1 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 11

[0275] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 8.1 g La(NO.sub.3).sub.3.6H.sub.2O was added, uniformly mixed, immersed, and dried. The molecular sieve was added with water to obtain a molecular sieve slurry with a solid content of 40 wt %. 9.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-A-2 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Example 12

[0276] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 9.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve was added with water to provide a molecular sieve slurry with a solid content of 40 wt %. 8.1 g La(NO.sub.3).sub.3.6H.sub.2O was added, uniformly mixed, immersed, dried and treated in a steam atmosphere at 550° C. for 2 hours. The molecular sieve MS-A-3 was thus obtained, for which the physicochemical property data were listed in Table 1-2.

Comparative Example 1

[0277] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was exchanged and washed by NH.sub.4Cl until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 7.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) and 8.1 g La(NO.sub.3).sub.3.6H.sub.2O were added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 3 hours. The molecular sieve MS-DB1 was thus obtained, for which the physicochemical property data were listed in Table 1-1.

Comparative Example 2

[0278] A crystallized ZSM-5 molecular sieve (produced by Qilu Division of Sinopec Catalyst Co., Ltd., synthesized by an amine-free method, n(SiO.sub.2)/n(Al.sub.2O.sub.3)=27 was filtered off the mother liquor, washed with water until the content of Na.sub.2O (on dry basis) was lower than 5.0 wt %, and filtered to provide a filter cake. 100 g (dry basis) of the molecular sieve was added into 1000 g of 2.0 wt % NaOH solution, heated to 65° C., reacted for 30 min, rapidly cooled to room temperature, filtered, and washed until the filtrate was neutral. Then, 800 g of water was added into the filter cake for formulating slurry, 40 g of NH.sub.4Cl was added, heated to 75° C., for exchange treatment for 1 h until the content of Na.sub.2O (on dry basis) was lower than 0.2 wt %, filtered, and washed to provide a molecular sieve filter cake. 50 g (dry basis) of the molecular sieve filter cake was added with water to obtain a slurry, so as to provide a molecular sieve slurry with a solid content of 40 wt %. 9.7 g H.sub.3PO.sub.4 (having a concentration of 85 wt %) was added, uniformly mixed, immersed, dried and treated in an air atmosphere at 550° C. for 2 hours. The molecular sieve MS-DB2 was thus obtained, for which the physicochemical property data were listed in Table 1-1.

TABLE-US-00001 TABLE 1-1 Item MS-A MS-B MS-C MS-D MS-E MS-DB1 MS-DB2 Degree of crystallization/%) 51 53 50 53 50 51 65 n(SiO.sub.2)/n(Al.sub.2O.sub.3) 24 24 23 24 24 27 23 P.sub.2O.sub.5 content/% 10 6 12 6 6 8 10 Content of supported rare earth 5 3 8 2 9 5 0 oxide/%) S.sub.BET/(m.sup.2/g) 325 345 318 346 320 312 350 (V.sub.mesopore/V.sub.Total pore)/% 56 62 50 61 58 18 60 RE distribution parameter, D 1.27 1.25 1.29 1.21 1.34 2.78 —

TABLE-US-00002 TABLE 1-2 Item MS-A-1 MS-B-1 MS-C-1 MS-D-1 MS-E-1 MS-A-2 MS-A-3 Degree of crystallization/%) 51 53 50 53 50 51 51 n(SiO.sub.2)/n(Al.sub.2O.sub.3) 24 24 23 24 24 24 24 P.sub.2O.sub.5 content/% 10 6 12 6 6 10 10 Content of supported rare earth 5 3 8 2 9 5 5 oxide/%) S.sub.BET/(m.sup.2/g) 332 349 323 351 328 325 325 (V.sub.mesopore/V.sub.Total pore)/% 58 65 51 63 60 56 56 RE distribution parameter, D 1.01 0.95 1.05 0.92 1.08 1.31 1.28

[0279] The following examples were provided to prepare the phosphorus-aluminum inorganic binders used in the present invention.

Example 13

[0280] This example was provided to prepare a phosphorus-aluminum inorganic binder according to the present invention.

[0281] 1.91 kg of pseudoboehmite (containing Al.sub.2O.sub.3, 1.19 kg), 0.56 kg of kaolin (0.5 kg on a dry basis) and 3.27 kg of decationized water were formulated into a slurry for 30 minutes, 5.37 kg of concentrated phosphoric acid (85% by mass) was added to the slurry with stirring at a rate of 0.04 kg of phosphoric acid/min/kg of alumina source. The temperature was raised to 70° C. and the reaction was carried out at this temperature for 45 minutes, so as to provide the phosphorus-aluminum inorganic binder. The formulation of materials was shown in Table 2, and the binder Binder1 was obtained.

Examples 14 to 16

[0282] Phosphorus-aluminum inorganic binders were prepared according to the process of example 14, and the formulation of materials was as shown in Table 2, to provide binders Binder 2-4.

TABLE-US-00003 TABLE 2 Examples Exam- Exam- Exam- Exam- ple 13 ple 14 ple 15 ple 16 Binder No. Binder1 Binder2 Binder3 Binder4 Pseudo-boehmite, kg 1.91 1.60 Al.sub.2O.sub.3, kg 1.19 1.00 SB, kg 0.94 Al.sub.2O.sub.3, kg 0.70 γ-Al.sub.2O.sub.3, kg 0.58 Al.sub.2O.sub.3, kg 0.58 Rectorite, kg 1.28 1.93 Dry basis, kg 1.00 1.50 Kaolin, kg 0.56 Dry basis, kg 0.50 Phosphoric acid, kg 5.37 5.36 4.03 6.50 P.sub.2O.sub.5, kg 3.31 3.30 2.92 4.0 Decationized water, kg 3.27 6.71 20.18 4.40 Total amount, kg 11.11 14.29 25.00 12.5 Total dry basis, kg 5.00 5.00 5.00 5.00 Solid content of 0.45 0.35 0.20 0.40 binder, kg/kg P/Al 2.29 3.89 4.19 3.30 Al.sub.2O.sub.3, wt % 23.82 14.00 11.53 20.00 P.sub.2O.sub.5, wt % 66.18 66.00 58.47 80.00 First clay, wt % 10.00 20.00 30.00 0.00 pH value 2.20 2.37 1.78 2.46

[0283] The following examples were provided to prepare the catalytic cracking catalysts of the present invention, and the following comparative examples 3-1, 4-1 were provided to prepare comparative catalytic cracking catalysts.

Example 17-1

[0284] A molecular sieve MS-A, Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 13 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide C1, for which the formulation was shown in Table 3-1.

Comparative Examples 3-1 and 4-1

[0285] Catalytic cracking catalysts were prepared according to the process as described in example 17-1, except that molecular sieves MS-DB1 and MS-DB2 were used in place of MS-A, respectively, to provide DC1 and DC2, for which the formulations were shown in Table 3-1.

Example 18-1

[0286] A molecular sieve MS-B, Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 14 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide C2, for which the formulation was shown in Table 3-1.

Example 19-1

[0287] A molecular sieve MS-C, Y-type molecular sieve (HRY molecular sieve), kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 15 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide C3, for which the formulation was shown in Table 3-1.

Example 20-1

[0288] A molecular sieve MS-A, Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite were added with decationized water and silica sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 16 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide C4, for which the formulation was shown in Table 3-1.

Example 21-1

[0289] A molecular sieve MS-A, Y-type molecular sieve (PSRY molecular sieve) and kaolin were added with decationized water for formulating slurry for 120 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 13 was added, to provide a slurry with a solid content of 30 wt %. After stirring for 30 minutes, the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide C5, for which the formulation was shown in Table 3-1.

Example 22-1

[0290] A precursor of an inorganic oxidation binder (alumina sol) and kaolin were mixed according to the formulation of raw materials in the Table 3-1, formulated into a slurry with a solid content of 30 wt % using decationized water, and uniformly stirred. pH value of the slurry was adjusted to 2.8 using hydrochloric acid, stood and aged at 55° C. for 1 hour. A molecular sieve of MFI structure rich in mesopores and a Y-type molecular sieve (PSRY molecular sieve) were added to form a catalyst slurry (with a solid content of 35 wt %), continuously stirred, and spray dried to provide the microspherical catalyst. The microspherical catalyst was then baked at 500° C. for 1 hour, washed with ammonium sulfate (where ammonium sulfate:microspherical catalyst:water=0.5:1:10) at 60° C. to have a sodium oxide content of less than 0.25 wt %, rinsed with deionized water and filtered, and then dried at 110° C. to give catalyst C6, the formulation of which was shown in Table 3-1.

TABLE-US-00004 TABLE 3-1 Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. Item 17-1 3-1 4-1 18-1 19-1 20-1 21-1 22-1 Catalyst No. C1 DC1 DC2 C2 C3 C4 C5 C6 Molecular sieve, wt % Molecular sieve of MFI MS-A 40 30 40 40 structure, wt % MS-DB1 40 MS-DB2 40 MS-B 40 MS-C 35 Content of Y molecular PSRY 10 10 10 10 16 10 10 sieve, wt % HRY 10 Clay, wt % Kaolin clay 18 18 18 18 18 18 25 25 Phosphorus-aluminum inorganic binder, wt % Binder1 18 18 18 25 Binder2 18 Binder3 22 Binder4 20 Additional binder, wt % Pseudo-boehmite, calculated as Al.sub.2O.sub.3 5 5 5 5 10 6 Aluminum sol, calculated as Al.sub.2O.sub.3 9 9 9 9 5 25 Silica sol, calculated as SiO.sub.2 10

[0291] The following examples were provided to prepare catalytic cracking aids according to the present invention, and comparative examples 3-2, 4-2 were provided to prepare comparative catalytic cracking aids.

Example 17-2

[0292] A molecular sieve MS-A, kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 13 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide ZJ1, for which the formulation was shown in Table 3-2.

Comparative Examples 3-2 and 4-2

[0293] Catalytic cracking aids were prepared according to example 17-2, except that molecular sieves MS-DB1 and MS-DB2 were used in place of MS-A to provide DZJ1 and DZJ2, respectively, for which the formulations were shown in Table 3-2.

Example 18-2

[0294] A molecular sieve MS-B, kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 14 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide ZJ1, for which the formulation was shown in Table 3-2.

Example 19-2

[0295] A molecular sieve MS-C, kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 15 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide ZJ3, for which the formulation was shown in Table 3-2.

Example 20-2

[0296] A molecular sieve MS-A, kaolin and pseudo-boehmite were added with decationized water and alumina sol for formulating slurry for 120 minutes, to provide a slurry with a solid content of 30 wt %. Hydrochloric acid was added to adjust the pH value of the slurry to be 3.0, and then continued to formulate the slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 16 was added, stirred for 30 minutes, and the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. for 1 hour to provide ZJ4, for which the formulation was shown in Table 3-2.

Example 21-2

[0297] A molecular sieve MS-A and kaolin were added with decationized water for formulating slurry for 120 minutes, followed by additionally formulating slurry for 45 minutes. Then the phosphorus-aluminum inorganic binder prepared in example 13 was added, to provide a slurry with a solid content of 30 wt %. After stirring for 30 minutes, the slurry obtained was spray-dried to provide microspheres. The microspheres were baked at 500° C. with 1 hour to provide ZJ5, for which the formulation was shown in Table 3-2.

Example 22-2

[0298] A binder of alumina sol and kaolin were mixed according to the formulation of raw materials shown in the Table 3-2, formulated into a slurry with a solid content of 30 wt % using decationized water, and uniformly stirred. The pH value of the slurry was adjusted to 2.8 using hydrochloric acid, stood and aged for 1 hour at 55° C. A molecular sieve MS-A was added to form a catalyst slurry (with a solid content of 35 wt %), continuously stirred, and spray dried to provide the microspherical catalyst. The microspherical catalyst was then baked at 500° C. for 1 hour, washed with ammonium sulfate (where ammonium sulfate:microspherical catalyst:water=0.5:1:10) at 60° C. to a sodium oxide content of less than 0.25 wt %, rinsed with deionized water and filtered, and then dried at 110° C. to provide catalyst ZJ6, for which the formulation was shown in Tables 3-2.

TABLE-US-00005 TABLE 3-2 Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. Item 17-2 3-2 4-2 18-2 19-2 20-2 21-2 22-2 No. of aid ZJ1 DZJ1 DZJ2 ZJ2 ZJ3 ZJ4 ZJ5 ZJ6 Molecular sieve, wt % MS-A 51 39 51 51 MS-DB1 51 MS-DB2 51 MS-B 51 MS-C 44 Clay, wt % Kaolin clay 22 22 22 22 19 25 22 22 Phosphorus-aluminum inorganic binder, wt % Binder1 18 18 18 27 Binder2 18 Binder3 22 Binder4 20 Additional binder, wt % Pseudo-boehmite, calculated 5 5 5 5 10 6 as Al.sub.2O.sub.3 Aluminum sol, calculated as Al.sub.2O.sub.3 4 4 4 4 5 27 Silica sol, calculated as SiO.sub.2 10

[0299] In the following examples, a fixed bed micro-reaction evaluation device was used to evaluate the reaction performance of the catalysts C1-C6 prepared in the examples of the invention, so as to illustrate the catalytic cracking reaction effect of the catalytic cracking catalyst provided by the invention.

Examples 23-1 to 28-1

[0300] The catalysts C1-C6 were respectively subjected to aging treatment at 800° C. under the condition of 100% steam atmosphere for 17 hours. The aged catalyst was loaded into a fixed bed micro-reactor, and the raw oil shown in Table 4 was catalytically cracked under the evaluation conditions of a reaction temperature of 620° C., a regeneration temperature of 620° C. and a catalyst-to-oil ratio of 3.2. The reaction results of the respective catalysts were shown in Table 5-1.

TABLE-US-00006 TABLE 4 Item Raw oil Density (20° C.), g/cm3 0.9334 Refraction (70 degree) 1.5061 Four components, m % Saturated hydrocarbons 55.6 Aromatic hydrocarbons 30 Gum material 14.4 Asphaltenes <0.1 Freezing point, ° C 34 Metal content, ppm Ca 3.9 Fe 1.1 Mg (Mg) <0.1 Na (Na) 0.9 Ni 3.1 Pb <0.1 V 0.5 C m % 86.88 H m % 11.94 S m % 0.7 Carbon residue, m % 1.77

[0301] Comparative examples 5-1 and 6-1 were provided to evaluate catalysts DC1 and DC2 prepared in comparative examples of the present invention in a fixed bed micro-reaction evaluation device to illustrate the comparative catalysts.

[0302] Comparative examples 5-1 and 6-1 catalytically cracked the same feed oil by the same method as in example 23-1, except that the catalysts used were DC1 and DC2, respectively, which had been subjected to the same aging process as in example 23-1. The reaction results of the respective catalysts were shown in Table 5-1.

TABLE-US-00007 TABLE 5-1 Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. Item 23-1 5-1 6-1 24-1 25-1 26-1 27-1 28-1 Catalyst C1 DC1 DC2 C2 C3 C4 C5 C6 Balance of materials/%, wt % Dry gas 17.66 15.18 16.61 20.87 21.98 19.27 20.61 24.47 Liquefied gas 29.07 24.57 27.1 28.8 30.43 28.05 32.12 28.12 Gasoline 24.88 28.0 24.21 19.61 17.18 21.32 16.38 17.38 Diesel oil 8.42 12.38 11.14 10.42 6.42 10.03 8.61 8.55 Heavy oil 3.93 3.92 4.08 3.47 3.95 5.04 4.41 4.61 Coke 16.04 15.95 16.86 16.83 20.04 16.29 17.87 16.87 Ethylene yield 8.89 2.86 3.54 7.35 5.26 5.83 7.81 9.31 Propylene yield 13.44 8.68 9.85 11.96 10.41 11.03 13.91 11.01

[0303] In examples 29-1 to 34-1, the catalysts C1 to C6 were subjected to aging treatment at 800° C. in a 100% steam atmosphere for 17 hours. The aged catalyst was loaded into a fixed bed micro-reactor, and naphtha shown in Table 6 was catalytically cracked under the evaluation conditions of a reaction temperature of 620° C., a regeneration temperature of 620° C. and a catalyst-to-oil ratio of 3.2. The results of the respective catalyst reactions were shown in Table 7-1.

[0304] Comparative examples 7-1 and 8-1 were provided to evaluate catalysts DC1, DC2, and DC3 prepared in comparative examples of the present invention using a fixed bed micro-reaction evaluation device to illustrate the comparative catalysts.

[0305] Comparative examples 7-1 and 8-1 catalytically cracked the same feed oil by the same method as in example 29-1, except that the catalysts used were catalysts DC1, DC2 and DC3 which had been subjected to the same aging process as in example 29-1, respectively. The results of the respective catalyst reactions were shown in Table 7-1.

TABLE-US-00008 TABLE 6 Materials Naphtha fraction Density (20° C.)/(g .Math. m.sup.−3) 735.8 Vapor pressure/kPa 32 Composition in mass/% Paraffin hydrocarbon 51.01 n-alkanes 29.40 Cycloalkanes 38.24 Olefins 0.12 Aromatic hydrocarbons 10.52 Distillation range/° C. First distillation 45.5  5% 72.5 10% 86.7 30% 106.5 50% 120.0 70% 132.7 90% 148.5 95% 155.2 End point of distillation 166.5

TABLE-US-00009 TABLE 7-1 Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. 29-1 7-1 8-1 30-1 31-1 32-1 33-1 34-1 Catalyst C1 DC1 DC2 C2 C3 C4 C5 C6 Cracking gas product yield/wt % Ethylene yield 11.13 3.54 4.92 9.92 8.55 9.11 9.17 12.88 Propylene yield 14.37 9.25 10.93 12.51 11.61 12.15 14.34 11.34

[0306] As seen from the data in Tables 5-1 and 7-1, when different raw oils were catalytically cracked, the catalysts containing the ZSM-5 molecular sieve rich in mesopores and modified with rare earth and phosphorus according to the present invention showed excellent performance of producing ethylene and propylene in high yield, wherein the yields of ethylene and propylene were the highest when a catalytic cracking catalyst containing a proper amount of aluminophosphate and an additional inorganic binder was used, while the yield of ethylene was significantly lower when a catalyst containing the molecular sieve without rare earth or phosphorus modification, or a catalyst containing the ZSM-5 molecular sieve modified with rare earth and phosphorus without a pore expansion treatment, was used.

[0307] The blank test examples and inventive examples described below used a fixed bed micro-reaction evaluation device to evaluate the reaction performance of 100% of equilibrium agent and the aids ZJ1-ZJ6 prepared by incorporating the equilibrium agent into the invention examples, so as to demonstrate the catalytic cracking reaction effect of the catalytic cracking aid provided by the invention.

Blank Test Example, and Examples 23-2 to 28-2

[0308] The aids ZJ1-ZJ6 were respectively subjected to aging treatment at 800° C. under the condition of 100% steam atmosphere for 17 hours. The aged ZJ1-ZJ6 and an industrial FCC equilibrium catalyst (a FCC equilibrium catalyst under an industrial brand of DVR-3, having a Micro-activity of 63) were respectively mixed. The mixture of the equilibrium agent and the catalyst was loaded into a fixed bed micro-reactor, and the raw oil as shown in Table 4 was catalytically cracked under the evaluation conditions of a reaction temperature of 620° C., a regeneration temperature of 620° C., and a catalyst-to-oil ratio of 3.2. The weight composition of each catalyst mixture and the reaction results were given in Table 5-2.

[0309] Comparative examples 5-2 and 6-2 were provided to evaluate the performance of the aids DZJ1 and DZJ2 incorporated with the equilibrium agent prepared in the comparative examples of the present invention in a fixed bed micro-reaction evaluation device to illustrate the use of the comparative aids.

[0310] Comparative examples 5-2 and 6-2 catalytically cracked the same feed oil by the same method as in example 23-2, except that the catalysts used were mixtures of the aids DZJ1 and DZJ2, respectively, which had been subjected to the same aging process as in example 23-2, with commercial FCC equilibrium catalysts. The weight composition of each catalyst mixture and the reaction results were given in Table 5-2.

TABLE-US-00010 TABLE 5-2 Blank Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. Item test Ex. 23-2 5-2 6 - 2 24-2 25-2 26-2 27-2 28-2 Catalyst / 10% 10% 10% 10% 10% 10% 10% 10% mixture ZJ1 DZJ1 DZJ2 ZJ2 ZJ3 ZJ4 ZJ5 ZJ6 100% of 90% of 90% of 90% of 90% of 90% of 90% of 90% of 90% of equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium agent agent agent agent agent agent agent agent agent Balance of materials/%, wt % Dry gas 8.07 15.24 9.28 9.43 12.98 13.12 10.98 10.15 15.95 Liquefied 18.54 25.07 19.61 21.11 22.06 23.10 22.05 29.98 24.48 gas Gasoline 38.28 30.05 37.64 36.58 34.04 34.38 35.08 30.07 30.18 Diesel oil 14.93 9.52 13.36 11.31 10.42 9.25 11.04 8.91 9.13 Heavy oil 11.42 3.84 10.01 6.79 5.57 4.07 6.43 3.44 5.32 Coke 8.76 16.28 10.10 14.78 14.93 16.08 14.42 17.45 14.94 Ethylene 1.39 4.89 1.79 2.04 3.07 4.09 3.57 2.75 5.25 yield Propylene 8.05 14.44 10.75 12.07 12.53 13.58 13.09 15.11 12.99 yield

[0311] The aids ZJ1-ZJ6 were respectively subjected to aging treatment at 800° C. under 100% steam atmosphere for 17 hours in the blank test example, and examples 29-2 to 34-2. The aged ZJ1-ZJ6 were respectively mixed with an industrial FCC equilibrium catalyst (a FCC equilibrium catalyst under an industrial brand DVR-3, having a Micro-activity of 63). The mixture of equilibrium agent and catalyst was loaded into a fixed bed microreactor and naphtha as shown in Table 6 above was catalytically cracked under the evaluation conditions of a reaction temperature of 620° C., a regeneration temperature of 620° C. and a catalyst-to-oil ratio of 3.2. The weight composition of each catalyst mixture and the reaction results were given in Table 7-2.

[0312] Comparative examples 7-2 and 8-2 were provided to evaluate the performance of the aids DZJ1 and DZJ2 incorporated with the equilibrium agent prepared in the comparative examples of the present invention in a fixed bed micro-reaction evaluation device to illustrate the use of the comparative aids.

[0313] Comparative examples 7-2 and 8-2 catalytically cracked the same feed oil by the same method as in example 29-2, except that the catalysts used were mixtures of the aids DZJ1 and DZJ2, respectively, which had been subjected to the same aging process as in example 29-2, with commercial FCC equilibrium catalysts. The weight composition of each catalyst mixture and the reaction results were given in Table 7-2.

TABLE-US-00011 TABLE 7-2 Blank test Ex. C. Ex. C. Ex. Ex. Ex. Ex. Ex. Ex. Example 29-2 7-2 8-2 30-2 31-2 32-2 33-2 34-2 Catalyst / 10% 10% 10% 10% 10% 10% 10% 10% mixture ZJ1 DZJ1 DZJ2 ZJ2 ZJ3 ZJ4 ZJ5 ZJ6 100% of 90% of 90% of 90% of 90% of 90% of 90% of 90% of 90% of equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium equilibrium agent agent agent agent agent agent agent agent agent Cracking gas product yield/wt % Ethylene 2.01 6.31 2.83 3.33 4.21 5.55 4.81 4.06 7.08 yield Propylene 8.42 12.99 8.79 9.34 10.51 11.61 10.81 13.17 10.25 yield

[0314] As seen from the data in Tables 5-2 and 7-2 when different raw oils were catalytically cracked, the catalysts containing the ZSM-5 molecular sieve rich in mesopores and modified with rare earth and phosphorus according to the present invention showed excellent performance of producing ethylene and propylene in high yield, wherein the yields of ethylene and propylene were the highest when a catalytic cracking catalyst containing a proper amount of aluminophosphate and an additional inorganic binder was used, while the yield of ethylene was significantly lower when a catalyst containing the molecular sieve without rare earth or phosphorus modification, or a catalyst containing the ZSM-5 molecular sieve modified with rare earth and phosphorus without a pore expansion treatment.

[0315] The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be formulated to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are all within the protection scope of the present invention.

[0316] It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.

[0317] In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the content of the present invention as long as the idea of the present invention is not violated.