CATALYTIC CRACKING AGENT CONTAINING PHOSPHORUS-MODIFIED MOLECULAR SIEVE, PREPARATION PROCESS THEREOF, PREPARATION SYSTEM AND USE THEREOF

Abstract

A catalytic cracking agent has an active component consisting of a phosphorus-modified molecular sieve and a non-phosphorus-modified molecular sieve or only consisting of a phosphorus-modified molecular sieve. According to an electron probe microanalysis (EPMA), the D value of phosphorus in the catalytic cracking agent is 65%, preferably 68%, provided that the active component consists of the phosphorus-modified molecular sieve and the non-phosphorus-modified molecular sieve, or the D value of phosphorus in the catalytic cracking agent is 82%, preferably 84%, provided that the active component only consists of the phosphorus-modified molecular sieve.

Claims

1. A catalytic cracking agent, having an active component consisting of a phosphorus-modified molecular sieve and a non-phosphorus-modified molecular sieve or only consisting of a phosphorus-modified molecular sieve, characterized in that with an electron probe microanalysis (EPMA), the D value of phosphorus in the catalytic cracking agent is 65%, preferably 68%, provided that the active component consists of the phosphorus-modified molecular sieve and the non-phosphorus-modified molecular sieve, or the D value of phosphorus in the catalytic cracking agent is 82%, preferably 84%, provided that the active component only consists of the phosphorus-modified molecular sieve.

2. The catalytic cracking agent according to any of the previous claims, wherein said phosphorus-modified molecular sieve is a phosphorus-modified MFI-structured molecular sieve, for example a phosphorus-modified ZSM-5 molecular sieve; said non-phosphorus-modified molecular sieve is a FAU-structured molecular sieve, for example, a Y-type molecular sieve.

3. The catalytic cracking agent according to any of claims 1-2, wherein said catalytic cracking agent is a catalytic cracking catalyst, having an active component consisting of a phosphorus-modified molecular sieve (for example a phosphorus-modified MFI-structured molecular sieve, such as a phosphorus-modified ZSM-5 molecular sieve) and a non-phosphorus-modified molecular sieve (for example a FAU-structured molecular sieve, such as a Y-type molecular sieve), with the electron probe microanalysis (EPMA), the D-value of the phosphorus of the catalyst is 65%, preferably 68%.

4. The catalytic cracking agent according to any of claims 1-2, wherein said catalytic cracking agent is a catalytic cracking auxiliary, having an active component consisting of a phosphorus-modified molecular sieve (for example a phosphorus-modified MFI-structured molecular sieve, such as a phosphorus-modified ZSM-5 molecular sieve), with the electron probe microanalysis (EPMA), the D-value of phosphorus of the auxiliary is 82%, preferably 84%.

5. The catalytic cracking agent according to any of claims 1-2, wherein on the dry basis, said catalytic cracking agent contains: 1-25 wt % of a non-phosphorus-modified molecular sieve; 5-50 wt % of a phosphorus-modified molecular sieve; 1-60 wt % of an inorganic binder; and optionally, 0-60 wt % of a second clay.

6. The catalytic cracking agent according to any of claims 1-2, wherein on the dry basis, said catalytic cracking agent contains: 5-75 wt % of a phosphorus-modified molecular sieve (free of non-phosphorus-modified molecular sieve); 1-40 wt % of an inorganic binder; and optionally, 0-65 wt % of a second clay.

7. The catalytic cracking agent according to any of the previous claims, wherein said non-phosphorus-modified molecular sieve is at least one of a PSRY molecular sieve, a rare earth-containing PSRY molecular sieve, an USY molecular sieve, a rare earth-containing USY molecular sieve, a REY molecular sieve, a REHY molecular sieve and an HY molecular sieve.

8. The catalytic cracking agent according to any of the previous claims, wherein the inorganic binder comprises at least one of pseudo-boehmite, alumina sol, silica-alumina sol, water glass and phosphorus-aluminum inorganic binder; preferably, the inorganic binder contains a phosphorus-aluminum inorganic binder, more preferably, the inorganic binder is a phosphorus-aluminum inorganic binder.

9. The catalytic cracking agent according to any of the previous claims, wherein the phosphorus-aluminum inorganic binder is a phosphorus aluminate binder and/or a first clay-containing phosphorus-aluminum inorganic binder.

10. The catalytic cracking agent according to any of the previous claims, wherein the first clay-containing phosphorus-aluminum inorganic binder is based on the dry basis, the first clay-containing phosphorus-aluminum inorganic binder contains 15-40 wt % of an aluminum component (as Al.sub.2O.sub.3), 45-80 wt % of a phosphorus component (as P.sub.2O.sub.5) and greater than 0 and not more than 40 wt % of a first clay, and the first clay-containing phosphorus-aluminum inorganic binder has a P/Al weight ratio of 1.0-6.0, a pH of 1-3.5, and a solid content of 15-60 wt %; the first clay comprises at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite.

11. The catalytic cracking agent according to any of the previous claims, wherein the second clay is selected from at least one of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, glagerite, halloysite, hydrotalcite, bentonite and diatomite.

12. The catalytic cracking agent according to any of the previous claims, wherein based on the total amount of said catalytic cracking catalyst, the inorganic binder comprises, on the dry basis, 3-39 wt % of a phosphorus-aluminum inorganic binder and 1-30 wt % of at least one inorganic binder selected from pseudo-boehmite, alumina sol, silica alumina sol and water glass.

13. A process for preparing the catalytic cracking agent according to any of the previous claims, which is characterized in that the process comprises: (1) mixing the following components as raw material and slurrying the raw material, and shaping into shaped bodies: a phosphorus-modified molecular sieve, optionally, a non-phosphorus-modified molecular sieve, an inorganic binder, and optionally, a second clay; (2) a hydrothermal calcining treatment is performed on the shaped bodies under an atmosphere condition in which an external pressure is applied and an aqueous solution is externally added; said phosphorus-modified molecular sieve is obtained through contacting a molecular sieve to be phosphorus-modified having a temperature of 0-150 C. with an aqueous solution of a phosphorus-containing compound having a temperature of 0-150 C. by impregnation; said hydrothermal calcining treatment is performed under a gauge pressure of 0.01-1.0 MPa at a temperature of 200-800 C. in an atmosphere of 100% water vapor or in an air atmosphere having a moisture content of at least 1%.

14. The process according to any of the previous claims, wherein said molecular sieve to be phosphorus-modified is a micropore ZSM-5 molecular sieve or a hierarchical ZSM-5 molecular sieve; preferably, the micropore ZSM-5 molecular sieve has a silica/alumina molar ratio of 15-1000, preferably 20-200; preferably, the hierarchical ZSM-5 molecular sieve has a proportion of the mesopore volume relative to the total pore volume of greater than 10%, an average pore size of 2-20 nm, and a silica/alumina molar ratio of 15-1000, preferably 20-200.

15. The process according to any of the previous claims, wherein the molar ratio of the phosphorus-containing compound (as phosphorus) to the molecular sieve to be phosphorus-modified (as aluminum) is 0.01-2; preferably, 0.1-1.5; more preferably, 0.2-1.5.

16. The process according to any of the previous claims, wherein the phosphorus-containing compound is selected from an organic phosphorus compound and/or an inorganic phosphorus compound; preferably, the organic phosphorus compound is selected from trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium hydroxide, triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, triphenylbenzylphosphonium bromide, hexamethylphosphoric triamide, dibenzyl diethylphosphoramidite, and 1, 3-bis((triethyl-phosphaneyl)methyl)benzene; preferably, the inorganic phosphorus compound is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and boron phosphate.

17. The process according to any of the previous claims, wherein in said molecular sieve to be phosphorus-modified, Na.sub.2O<0.1 wt %.

18. The process according to any of the previous claims, the process further comprises: the first clay-containing phosphorus-aluminum inorganic binder is prepared with the following steps: an alumina source, a first clay and water are slurried to disperse into a slurry having a solid content of 5-48 wt %; wherein said alumina source is aluminum hydroxide that can be peptized with an acid and/or alumina, relative to 15-40 parts by weight of the alumina source as Al.sub.2O.sub.3, the used amount of the first clay based on the dry weight is greater than 0 part by weight and not more than 40 parts by weight; a concentrated phosphoric acid is added to the slurry under stirring according to the weight ratio of P/Al=1-6, and the resulting mixed slurry is reacted at 50-99 C. for 15-90 minutes; wherein P in the P/Al is the weight of phosphorus as simple substance in the phosphoric acid, Al is the weight of aluminum as simple substance in the alumina source.

19. The process according to any of the previous claims, wherein said shaping is pelleting by spray-drying.

20. The process according to any of the previous claims, wherein the conditions of said hydrothermal calcining treatment comprise: gauge pressure: 0.1-0.8 MPa, preferably 0.3-0.6 MPa; atmosphere: an atmosphere of 100% water vapor or an air atmosphere having a moisture content of at least 30%, preferably, an atmosphere of 100% water vapor or an air atmosphere having a moisture content of at least 60%; temperature: 200-800 C., preferably 300-500 C.; the conditions of said contacting by impregnation comprise: the weight ratio of water/molecular sieve: 0.5-1; temperature: 50-150 C., preferably 70-130 C.; time: 0.5-40 hours.

21. A catalytic cracking agent according to any of claims 1-12, which is prepared with the process according to any of claims 13-20.

22. A process for catalytically cracking a hydrocarbon oil, which is characterized in that the process comprises: the hydrocarbon oil is reacted by contacting the catalytic cracking agent according to any of the previous claims under a catalytic cracking condition.

23. The process for catalytically cracking the hydrocarbon oil according to any of the previous claims, wherein the process comprises the hydrocarbon oil is reacted by contacting a mixture containing the catalytic cracking auxiliary according to any of the previous claims and the catalytic cracking catalyst according to any of the previous claims under a catalytic cracking condition; in the mixture, the content of the catalytic cracking auxiliary is 0.1-30 wt %.

24. The process for catalytically cracking the hydrocarbon oil according to any of the previous claims, wherein the catalytic cracking condition includes: the reaction temperature is 500-800 C.; the hydrocarbon oil is one or more selected from crude oil, naphtha, gasoline, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight-run gas oil, propane light/heavy deasphalted oil, coker gas oil and coal liquefication product.

25. A preparation system of a catalytic cracking agent, which is characterized in that the system is mainly composed of a phosphorus-modification device, a raw material mixing device, a shaping device, and a pressurized hydrothermal calcining device; preferably, the phosphorus-modification device comprises an equipment for introducing a solution of a phosphorus-containing compound; and/or the raw material mixing device receives raw materials, and the raw materials include: an impregnation-treated (e.g. impregnation-exchanged) phosphorus-modified molecular sieve obtained from the phosphorus-modification device, a phosphorus-aluminum inorganic binder from a treatment device of phosphorus-aluminum inorganic binder; optionally a non-phosphorus-modified molecular sieve, and optionally a clay; and/or said shaping device is a device of shaping by spray-drying; and/or said pressurized hydrothermal calcining device is provided with an aqueous solution inlet and a gas pressurization joint.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0163] FIG. 1 is the flowchart for preparing a conventional catalyst in the prior art.

[0164] FIG. 2 is the flowchart for preparing a conventional auxiliary in the prior art.

[0165] FIG. 3 is the flowchart for preparing a catalyst provided by the present invention.

[0166] FIG. 4 is the flowchart for preparing an auxiliary provided by the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0167] The present invention will be further described below in conjunction with specific examples, but the present invention is not limited thereby.

[0168] The instruments and reagents used in the examples of the present invention are all those commonly used by those skilled in the art unless otherwise specified.

[0169] A micro-reaction apparatus was used to evaluate the effect of the catalytic cracking catalyst or the catalytic cracking auxiliary of the present invention on the yield of lower carbon olefins in the catalytic cracking of petroleum hydrocarbons.

[0170] The prepared catalytic cracking catalyst sample/catalytic cracking auxiliary sample was subjected to the aging treatment at 800 C., 100% water vapor for 17 hours in a fixed-bed aging apparatus, and evaluated on a micro-reaction apparatus. The feedstock oil is VGO or naphtha. The evaluation condition included: the reaction temperature was 620 C., the regeneration temperature was 620 C., and the agent(catalyst/auxiliary)-oil ratio was 3.2. The micro-reactivity was measured by the ASTM D5154-2010 standard method.

[0171] EPMA (Model JXA-8230 Electron Probe Microanalyzer) was used to quantitatively analyze the D value of phosphorus in the sample section. Specifically, the D value is determined by randomly selecting 5 sections of a sample with a spacing greater than 50 nm between each other; selecting 20 squares with a side length of 10 nm on each section, and obtaining the phosphorus content (number of atoms/number of atoms) within each square through electron probe microanalysis (EPMA), taking the ratio of the lowest value of the 20 phosphorus contents to the average value of the 20 phosphorus contents as the d value of the section, and taking the average value of the d values of 5 sections as the D value of phosphorus of said sample.

[0172] The properties of some raw materials used in the Examples were as follows:

TABLE-US-00001 Pseudo-boehmite An industrial product produced by Shandong Aluminum Company, with a solid content of 60 wt %. Alumina sol An industrial product produced by Sinopec Catalyst Qilu Branch, and had the Al.sub.2O.sub.3 content of 21.5 wt %. Silica sol An industrial product produced by Sinopec Catalyst Qilu Branch, with a SiO2 content of 28.9 wt % and a Na.sub.2O content of 8.9%. Kaolin A kaolin special for catalytic cracking catalyst produced by Suzhou Kaolin Company, with a solid content of 78% by weight. Rectorite Produced by Hubei Zhongxiang Mingliu Rectorite Development Co., Ltd., with the quartz sand content of <3.5 wt %, the Al.sub.2O.sub.3 content of 39.0 wt %, the Na.sub.2O content of 0.03 wt %, and the solid content of 77 wt %. SB aluminum Produced by Condex Corporation, Germany, with an Al.sub.2O.sub.3 content of hydroxide powder 75 wt %. -alumina Produced by Condex Corporation, Germany, with an Al.sub.2O.sub.3 content of 95 wt %. Hydrochloric acid Chemically pure, with a concentration of 36-38 wt %, produced by Beijing Chemical Plant. PSRY molecular sieve An industrial product produced by Sinopec Catalyst Changling Branch, with the Na.sub.2O content of <1.5 wt %, the P.sub.2O.sub.5 content of 0.8- 1.2 wt %, the unit cell constant of <2.456 nm, and the crystallinity of 64%. HRY-1 commercial An industrial product produced by Sinopec Catalyst Changling molecular sieve Branch, with the La2O3 content of 11-13 wt %, the unit cell constant of <2.464 nm, and the crystallinity of 40%.

[0173] The phosphorus-aluminum inorganic binder, Binder 1, that was used in examples was prepared as follows: 1.91 kg of pseudo-boehmite (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 mixed and stirred for 30 minutes to form a slurry, and 5.37 kg of concentrated phosphoric acid (mass concentration 85%) was added to the slurry under stirring, wherein the addition rate of phosphoric acid was 0.04 kilogram phosphoric acid/min/kg alumina source. The mixture was warmed up to 70 C., and then reacted at this temperature for 45 minutes to produce the phosphorus-aluminum inorganic binder. The material proportions were shown in Table 1.

[0174] Phosphorus-aluminum inorganic binders Binder 2, Binder 3, and Binder 4 were also prepared according to the above-mentioned method, the difference lies in that the material proportions were different, and the material proportions were shown in Table 1.

TABLE-US-00002 TABLE 1 Inorganic binder No. Bind- Bind- Bind- Bind- er 1 er 2 er 3 er 4 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 -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 Weight, kg 11.11 14.29 25.00 12.5 Total Dry Basis, kg 5.00 5.00 5.00 5.00 Inorganic Binder Solid Content, kg/kg 0.45 0.35 0.20 0.40 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 2.20 2.37 1.78 2.46

TABLE-US-00003 TABLE 2 Item Feedstock oil Density (20 C.), g/cm.sup.3 0.9334 Refraction (70 C.) 1.5061 SARA, m % Saturates 55.6 Aromatics 30 Resins 14.4 Asphaltenes <0.1 freezing point, C. 34 Metal contents, ppm Ca 3.9 Fe 1.1 Mg <0.1 Na 0.9 Ni 3.1 Pb <0.1 V 0.5 Cm % 86.88 Hm % 11.94 Sm % 0.7 Carbon Residue m % 1.77

[0175] Example F1.X to Example F24.X (X=1 or 2, the same below) provided the catalytic cracking catalysts of the present invention, and Comparative Example F1 to Comparative Example F17 illustrated the catalytic cracking catalysts for comparison. Among them, the MFI-structured molecular sieves in Example F1.X to Example F10.X were micropore ZSM-5 molecular sieves, and the MFI-structured molecular sieves in Example F11.X to Example F20.X were hierarchical ZSM-5 molecular sieves. Comparative Example F8 was a comparative catalytic cracking catalyst containing the micropore ZSM-5 MFI-structured molecular sieve prepared by the prior art, and Comparative Example F16 was a comparative catalytic cracking catalyst containing the hierarchical ZSM-5 MFI-structured molecular sieve prepared by the prior art.

Example F1.1

[0176] 16.2 g of diammonium hydrogen phosphate (Tianjin Guangfu Science and Technology Development Co., Ltd., analysis pure, the same below) was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company and having a relative crystallinity of 91.1%, a silica/alumina molar ratio of 24.1, a Na.sub.2O content of 0.039 wt %, a specific surface area of 353 m.sup.2/g, and a total pore volume of 0.177 mL/g, the same below) was added to the solution and modified by impregnation, i.e., impregnated at 20 C. for 2 hours; the resulting mixture was mixed with a Y-type molecular sieve (PSRY molecular sieve), kaolin and pseudo-boehmite; decationized water and alumina sol were added and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30 wt %; hydrochloric acid was added to adjust the pH value of the slurry to 3.0; then the mixture continued to be stirred for 45 minutes; then the phosphorus-aluminum inorganic binder, Binder 1, was added, and the resulting mixture was stirred for 30 minutes; the resulting slurry was shaped by spray-drying to produce microspheres (having a diameter of 1-150 m); the microspheres were treated at 500 C. for 0.5 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.5 MPa in a 50% water vapor atmosphere to produce a catalytic cracking catalyst sample, which was denoted as CFZY1.1, the composition of which comprised 40% of phosphorus-modified ZSM-5 molecular sieve, 10% of PSRY molecular sieve, 23% of kaolin, 18% of Binder 1, 5% of pseudo-boehmite (as Al.sub.2O.sub.3), and 4% of alumina sol (as Al.sub.2O.sub.3).

[0177] A fixed bed micro-reaction apparatus was used to evaluate the reaction performances of a 100% equilibrium catalyst and an equilibrium catalyst to which the catalytic cracking catalyst CFZY1.1 prepared in Example F1.1 was incorporated, in order to illustrate the catalytic cracking reaction effect of the catalytic cracking catalyst provided in the present disclosure.

[0178] The catalyst CFZY1.1 was aged at 800 C. in a 100% water vapor atmosphere for 17 hours. The aged CFZY1.1 was mixed with an industrial FCC equilibrium catalyst (an FCC equilibrium catalyst with the industry brand of DVR-3 having a light oil micro-activity of 63). A mixture of the equilibrium catalyst and the catalyst was loaded into the fixed-bed micro-reaction reactor, and the feedstock oil shown in Table 2 was catalytically cracked. The evaluation condition included: the reaction temperature was 620 C., the regeneration temperature was 620 C., and the catalyst-oil ratio was 3.2. Table 3 provided the reaction results, including the blank test agent.

Example F1.2

[0179] This example was performed in the same manner as Example F1.1, except for the preparation of the phosphorus-modified molecular sieve, wherein diammonium hydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry; and the slurry was heated to 100 C. and maintained for 2 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY1.2.

[0180] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F1

[0181] This example was performed in the same manner as Example F1.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY1.

[0182] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F2.1

[0183] This example was performed in the same manner as Example F1.1, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at 50 C., the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 600 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.5 MPa in a 30% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY2.1.

[0184] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F2.2

[0185] This example was performed in the same manner as Example F2.1, except that diammonium hydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 70 C. and maintained for 2 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY2.2.

[0186] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F2

[0187] This example was performed in the same manner as Example F2.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY2.

[0188] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F3.1

[0189] This example was performed in the same manner as Example F1.1, except that 10.4 g of phosphoric acid was dissolved in 60 g of deionized water at the ordinary temperature, the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 4 hours; a pressurized hydrothermal calcining treatment was performed at 400 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.3 MPa in a 100% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY3.1.

[0190] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F3.2

[0191] This example was performed in the same manner as Example F3.1, except that an aqueous solution of a phosphorus-containing compound having a temperature of 80 C. and the HZSM-5 molecular sieve heated to 80 C. were contacted and mixed for 4 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY3.2.

[0192] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F3

[0193] This example was performed in the same manner as Example F3.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY3.

[0194] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F4.1

[0195] This example was performed in the same manner as Example F1.1, except that 8.1 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at the ordinary temperature, the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 300 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.4 MPa in a 100% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY4.1.

[0196] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F4.2

[0197] This example was performed in the same manner as Example F4.1, except that ammonium dihydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 90 C. and maintained for 2 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY4.2.

[0198] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F4

[0199] This example was performed in the same manner as Example F4.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY4.

[0200] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F5.1

[0201] This example was performed in the same manner as Example F1.1, except that 8.5 g of trimethyl phosphate was dissolved in 80 g of deionized water at 90 C., the mixture was stirred for 1 hour to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 8 hours; a pressurized hydrothermal calcining treatment was performed at 500 C. for 4 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.8 MPa under a 80% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY5.1.

[0202] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F5.2

[0203] This example was performed in the same manner as Example F5.1, except that trimethyl phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 120 C. and maintained for 8 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY5.2.

[0204] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F5

[0205] This example was performed in the same manner as Example F5.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY5.

[0206] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F6.1

[0207] This example was performed in the same manner as Example F1.1, except that 11.6 g of boron phosphate was dissolved in 100 g of deionized water at 100 C., the mixture was stirred for 3 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 400 C. for 4 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.3 MPa under a 100% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY6.1.

[0208] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F6.2

[0209] This example was performed in the same manner as Example F6.1, except that boron phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 150 C. and maintained for 2 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY6.2.

[0210] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F6

[0211] This example was performed in the same manner as Example F6.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY6.

[0212] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F7.1

[0213] This example was performed in the same manner as Example F1.1, except that 14.2 g of triphenylphosphine was dissolved in 80 g of deionized water at 100 C., the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 4 hours; a pressurized hydrothermal calcining treatment was performed at 600 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 1 MPa under a 30% water vapor atmosphere, to produce a catalytic cracking catalyst sample, which was denoted as CFZY7.1.

[0214] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F7.2

[0215] This example was performed in the same manner as Example F7.1, except that boron phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 150 C. and maintained for 2 hours, to produce a catalytic cracking catalyst sample, which was denoted as CFZY7.2.

[0216] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F7

[0217] This example was performed in the same manner as Example F7.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY7.

[0218] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F8

[0219] Comparative Example F8 illustrated the current industry-conventional method and the obtained phosphorus-containing modified ZSM-5 comparative sample.

[0220] This example was performed in the same manner as Example F1.2, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve was added to the solution and modified by impregnation, i.e., impregnated at 100 C. for 2 hours; the resulting mixture was dried in an oven at 110 C. and then calcined under the normal pressure (gauge pressure: 0 MPa) in the air atmosphere at a temperature of 550 C. in a muffle furnace to produce a phosphorus-modified ZSM-5 molecular sieve sample; said sample was mixed with kaolin and pseudo-boehmite; decationized water and alumina sol were added and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30 wt %; hydrochloric acid was added to adjust the pH value of the slurry to 3.0; then the mixture continued to be stirred for 45 minutes; then the phosphorus-aluminum inorganic binder, Binder 1, was added, and the resulting mixture was stirred for 30 minutes; the resulting slurry was shaped by spray-drying to produce microspheres (having a diameter of 1-150 m); the microspheres were calcined at 500 C. for 1 hour to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY8.

[0221] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F8.1

[0222] This example was performed in the same manner as Example F1.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking catalyst, which was denoted as CFZY8.1.

[0223] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F8.2

[0224] This example was performed in the same manner as Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking catalyst, which was denoted as CFZY8.2.

[0225] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F9.1

[0226] This example was performed in the same manner as Example F5.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking catalyst, which was denoted as CFZY9.1.

[0227] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F9.2

[0228] This example was performed in the same manner as Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking catalyst, which was denoted as CFZY9.2.

[0229] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F10.1

[0230] This example was performed in the same manner as Example F1.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking catalyst, which was denoted as CFZY10.1.

[0231] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F10.2

[0232] This example was performed in the same manner as Example F1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking catalyst, which was denoted as CFZY10.2.

[0233] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

[0234] Example F11.X to Example F20.X illustrated the preparation of the catalytic cracking catalysts with the phosphorus-modified hierarchical ZSM-5 molecular sieves according to the present invention.

Example F11.1 to Example F17.1

[0235] Example F11.1 to Example F17.1 corresponded to Example F1.1 to Example F7.1 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company, and having a relative crystallinity of 88.6%, a silica/alumina molar ratio of 20.8, a Na.sub.2O content of 0.017 wt %, a specific surface area of 373 m.sup.2/g, a total pore volume of 0.256 mL/g, a mesoporous volume of 0.119 ml/g, and an average pore size of 5.8 nm, the same below), to produce catalytic cracking catalyst samples, which were denoted as CFZY11.1 to CFZY17.1.

[0236] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F11.2 to Example F17.2

[0237] Example F11.2 to Example F17.2 corresponded to Example F1.2 to Example F7.2 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce catalytic cracking catalyst samples, which were denoted as CFZY11.2 to CFZY17.2.

[0238] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F9 to Comparative Example F15

[0239] Comparative Example F9 to Comparative Example F15 corresponded to Comparative Example F1 to Comparative Example F7 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce catalytic cracking catalyst samples, which were denoted as DCFZY9 to DCFZY15.

[0240] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F16

[0241] Comparative Example F16 illustrated the current industry-conventional method and the obtained phosphorus-containing modified hierarchical ZSM-5 comparative sample. This example was performed in the same manner as Comparative Example F8, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce a catalytic cracking catalyst comparative sample, which was denoted as DCFZY16.

[0242] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F18.1

[0243] This example was performed in the same manner as Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking catalyst, which was denoted as CFZY18.1.

[0244] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F18.2

[0245] This example was performed in the same manner as Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking catalyst, which was denoted as CFZY18.2.

[0246] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F19.1

[0247] This example was performed in the same manner as Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking catalyst, which was denoted as CFZY19.1.

[0248] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F19.2

[0249] This example was performed in the same manner as Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking catalyst, which was denoted as CFZY19.2.

[0250] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F20.1

[0251] This example was performed in the same manner as Example F11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking catalyst, which was denoted as CFZY20.1.

[0252] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F20.2

[0253] This example was performed in the same manner as Example F11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking catalyst, which was denoted as CFZY20.2.

[0254] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

[0255] In Example F21.1, Example F22.1 and Comparative Example F17, another Y-type molecular sieve, HRY-1 commercial molecular sieve, was used.

Example F21.1

[0256] This example was performed in the same manner as Example F1.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, to produce a catalyst sample, which was denoted as CFZY21.1.

[0257] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F22.1

[0258] This example was performed in the same manner as Example F11.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, to produce a catalyst sample, which was denoted as CFZY22.1.

[0259] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Comparative Example F17

[0260] This example was performed in the same manner as Example F1.1, except that the Y-type molecular sieve (PSRY) was replaced with HRY-1, to produce a catalyst sample, which was denoted as DCFZY17.

[0261] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

[0262] In Example F23.1 and Example F24.1, the addition amounts of pseudo-boehmite and alumina sol were increased to replace the phosphorus-aluminum inorganic binder.

Example F23.1

[0263] This example was performed in the same manner as Example F1.1, except that the addition amounts of pseudo-boehmite and alumina sol were increased to replace the phosphorus-aluminum inorganic binder, Binder 1, to produce a catalytic cracking auxiliary sample, which was denoted as CFZY23.1.

[0264] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table 3.

Example F24.1

[0265] This example was performed in the same manner as Example F11.1, except that the addition amounts of pseudo-boehmite and alumina sol were increased to replace the phosphorus-aluminum inorganic binder, Binder 1, to produce a catalytic cracking auxiliary sample, which was denoted as CFZY24.1.

[0266] The evaluation was performed in the same manner as Example F1.1, and the result was shown in Table

TABLE-US-00004 TABLE 3 D-value of Example/ Catalytic Material Balance, wt % Comparative Cracking Liquefied Ethylene Propylene Example Catalyst Catalyst Mixture Gas Yield Yield Blank / / 100% equilibrium 18.54 1.39 8.05 catalyst F1.1 69% 10% 90% equilibrium 39.28 4.17 19.51 CFZY1.1 catalyst F1.2 74% 10% 90% equilibrium 46.92 5.09 21.68 CFZY1.2 catalyst F2.1 73% 10% 90% equilibrium 47.58 4.87 20.40 CFZY2.1 catalyst F2.2 75% 10% 90% equilibrium 52.40 5.42 21.27 CFZY2.2 catalyst F3.1 70% 10% 90% equilibrium 44.24 4.63 18.39 CFZY3.1 catalyst F3.2 74% 10% 90% equilibrium 48.15 5.09 19.82 CFZY3.2 catalyst F4.1 72% 10% 90% equilibrium 46.45 4.69 19.09 CFZY4.1 catalyst F4.2 74% 10% 90% equilibrium 50.57 5.21 20.11 CFZY4.2 catalyst F5.1 67% 10% 90% equilibrium 40.52 4.17 16.56 CFZY5.1 catalyst F5.2 72% 10% 90% equilibrium 44.25 4.54 18.39 CFZY5.2 catalyst F6.1 73% 10% 90% equilibrium 45.74 4.41 18.72 CFZY6.1 catalyst F6.2 75% 10% 90% equilibrium 50.51 5.21 19.86 CFZY6.2 catalyst F7.1 66% 10% 90% equilibrium 33.34 3.34 13.60 CFZY7.1 catalyst F7.2 67% 10% 90% equilibrium 38.72 4.17 16.52 CFZY7.2 catalyst F8.1 66% 10% 90% equilibrium 37.05 4.00 19.13 CFZY8.1 catalyst F8.2 72% 10% 90% equilibrium 46.06 4.41 20.32 CFZY8.2 catalyst F9.1 67% 10% 90% equilibrium 36.54 3.94 19.08 CFZY9.1 catalyst F9.2 73% 10% 90% equilibrium 45.21 4.17 19.79 CFZY9.2 catalyst F10.1 68% 10% 90% equilibrium 36.65 3.83 18.70 CFZY10.1 catalyst F10.2 71% 10% 90% equilibrium 45.38 4.19 19.77 CFZY10.2 catalyst F11.1 68% 10% 90% equilibrium 40.86 4.25 20.29 CFZY11.1 catalyst F11.2 75% 10% 90% equilibrium 48.80 5.19 22.55 CFZY11.2 catalyst F12.1 75% 10% 90% equilibrium 49.48 4.97 21.22 CFZY12.1 catalyst F12.2 78% 10% 90% equilibrium 54.50 5.53 22.12 CFZY12.2 catalyst F13.1 71% 10% 90% equilibrium 46.01 4.72 19.13 CFZY13.1 catalyst F13.2 72% 10% 90% equilibrium 50.07 5.19 20.61 CFZY13.2 catalyst F14.1 73% 10% 90% equilibrium 48.31 4.78 19.85 CFZY14.1 catalyst F14.2 76% 10% 90% equilibrium 52.59 5.31 20.91 CFZY14.2 catalyst F15.1 70% 10% 90% equilibrium 42.14 4.25 17.22 CFZY15.1 catalyst F15.2 74% 10% 90% equilibrium 46.02 4.63 19.13 CFZY15.2 catalyst F16.1 70% 10% 90% equilibrium 47.57 4.50 19.47 CFZY16.1 catalyst F16.2 74% 10% 90% equilibrium 52.52 5.31 20.65 CFZY16.2 catalyst F17.1 66% 10% 90% equilibrium 34.67 3.41 14.14 CFZY17.1 catalyst F17.2 70% 10% 90% equilibrium 40.28 4.25 17.18 CFZY17.2 catalyst F18.1 66% 10% 90% equilibrium 38.54 4.08 19.90 CFZY18.1 catalyst F18.2 75% 10% 90% equilibrium 47.90 4.50 21.13 CFZY18.2 catalyst F19.1 66% 10% 90% equilibrium 38.00 4.02 19.84 CFZY19.1 catalyst F19.2 72% 10% 90% equilibrium 47.02 4.25 20.58 CFZY19.2 catalyst F20.1 66% 10% 90% equilibrium 38.12 3.91 19.45 CFZY20.1 catalyst F20.2 73% 10% 90% equilibrium 47.20 4.27 20.56 CFZY20.2 catalyst F21.1 65% 10% 90% equilibrium 37.32 4.00 18.34 CFZY21.1 catalyst F22.1 71% 10% 90% equilibrium 44.57 4.89 20.38 CFZY22.1 catalyst F23.1 66% 10% 90% equilibrium 35.35 3.75 17.56 CFZY23.1 catalyst F24.1 66% 10% 90% equilibrium 36.77 3.83 18.26 CFZY24.1 catalyst F1 59% 10% 90% equilibrium 31.74 3.10 13.99 DCFZY1 catalyst F2 60% 10% 90% equilibrium 33.63 3.26 15.11 DCFZY2 catalyst F3 58% 10% 90% equilibrium 31.88 3.22 14.33 DCFZY3 catalyst F4 61% 10% 90% equilibrium 34.05 3.40 15.57 DCFZY4 catalyst F5 54% 10% 90% equilibrium 27.75 3.56 12.04 DCFZY5 catalyst F6 60% 10% 90% equilibrium 34.20 3.40 16.17 DCFZY6 catalyst F7 48% 10% 90% equilibrium 22.75 3.50 11.06 DCFZY7 catalyst F8 52% 10% 90% equilibrium 30.23 3.04 13.32 DCFZY8 catalyst F9 60% 10% 90% equilibrium 33.01 3.16 14.55 DCFZY9 catalyst F10 58% 10% 90% equilibrium 34.98 3.33 15.71 DCFZY10 catalyst F11 61% 10% 90% equilibrium 33.15 3.28 14.90 DCFZY11 catalyst F12 58% 10% 90% equilibrium 35.42 3.47 16.19 DCFZY12 catalyst F13 52% 10% 90% equilibrium 28.86 3.63 12.52 DCFZY13 catalyst F14 58% 10% 90% equilibrium 35.56 3.47 16.82 DCFZY14 catalyst F15 50% 10% 90% equilibrium 23.67 3.57 11.50 DCFZY15 catalyst F16 51% 10% 90% equilibrium 31.44 3.10 13.85 DCFZY16 catalyst F17 50% 10% 90% equilibrium 30.15 2.98 13.15 DCFZY17 catalyst

[0267] Example E1.X to Example E22.X provided the catalytic cracking auxiliaries of the present invention, and Comparative Example E1 to Comparative Example E16 illustrated the comparative catalytic cracking auxiliaries. Microporous ZSM-5 molecular sieves were used in Example E1.X to Example E10.X and Example E21.1, and hierarchical ZSM-5 molecular sieves were used in Example E11.X to Example E20.X and Example E22.1. Comparative Example E8 was a comparative catalytic cracking auxiliary containing the micropore ZSM-5 molecular sieve prepared by the prior art, and Comparative Example E16 was a comparative catalytic cracking auxiliary containing the hierarchical ZSM-5 molecular sieve prepared by the prior art.

Example E1.1

[0268] 16.2 g of diammonium hydrogen phosphate (Tianjin Guangfu Science and Technology Development Co., Ltd., analysis pure, the same below) was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company and having a relative crystallinity of 91.1%, a silica/alumina molar ratio of 24.1, a Na.sub.2O content of 0.039 wt %, a specific surface area of 353 m.sup.2/g, and a total pore volume of 0.177 mL/g, the same below) was added to the solution and modified by impregnation, i.e., impregnated at 20 C. for 2 hours; the resulting mixture was mixed with kaolin and pseudo-boehmite; decationized water and alumina sol were added and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30 wt %; hydrochloric acid was added to adjust the pH value of the slurry to 3.0; then the mixture continued to be stirred for 45 minutes; then the phosphorus-aluminum inorganic binder, Binder 1, was added, and the resulting mixture was stirred for 30 minutes; the resulting slurry was shaped by spray-drying to produce microspheres (having a diameter of 1-150 m); the microspheres were treated at 500 C. for 0.5 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.5 MPa in a 50% water vapor atmosphere to produce a catalytic cracking auxiliary sample, which was denoted as CEZ1.1, the composition of which comprised 50% of the molecular sieve, 23% of kaolin, 18% of Binder 1, 5% of pseudo-boehmite (as Al.sub.2O.sub.3), and 4% of alumina sol (as Al.sub.2O.sub.3).

[0269] A fixed bed micro-reaction apparatus was used to evaluate the reaction performances of a 100% equilibrium catalyst and an equilibrium catalyst to which the catalytic cracking auxiliary CEZ1.1 prepared in Example E1.1 was incorporated, in order to illustrate the catalytic cracking reaction effect of the catalytic cracking auxiliary provided in the present disclosure.

[0270] The auxiliary CEZ1.1 was aged at 800 C. in a 100% water vapor atmosphere for 17 hours. The aged CEZ1.1 was mixed with an industrial FCC equilibrium catalyst (an FCC equilibrium catalyst with the industry brand of DVR-3 having a light oil micro-activity of 63). A mixture of the equilibrium catalyst and the auxiliary was loaded into the fixed-bed micro-reaction reactor, and the feedstock oil shown in Table 2 was catalytically cracked. The evaluation condition included the reaction temperature of 620 C., the regeneration temperature of 620 C., and the catalyst-oil ratio was 3.2. Table 4 provided the reaction results, including the blank test agent.

Example E1.2

[0271] This example was performed in the same manner as Example E1.1, except for the preparation of the phosphorus-modified molecular sieve, wherein diammonium hydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry; and the slurry was heated to 100 C. and maintained for 2 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ1.2.

[0272] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E1

[0273] This example was performed in the same manner as Example E1.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ1.

[0274] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E2.1

[0275] This example was performed in the same manner as Example E1.1, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at 50 C., the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 600 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.5 MPa under a 30% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ2.1.

[0276] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E2.2

[0277] This example was performed in the same manner as Example E2.1, except that diammonium hydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 70 C. and maintained for 2 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ2.2.

[0278] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E2

[0279] This example was performed in the same manner as Example E2.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ2.

[0280] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E3.1

[0281] This example was performed in the same manner as Example E1.1, except that 10.4 g of phosphoric acid was dissolved in 60 g of deionized water at the ordinary temperature, the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 4 hours; a pressurized hydrothermal calcining treatment was performed at 400 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. under a pressure of 0.3 MPa in a 100% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ3.1.

[0282] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E3.2

[0283] This example was performed in the same manner as Example E3.1, except that an aqueous solution of a phosphorus-containing compound having a temperature of 80 C. and the HZSM-5 molecular sieve heated to 80 C. were contacted and mixed for 4 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ3.2.

[0284] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E3

[0285] This example was performed in the same manner as Example E3.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ3.

[0286] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E4.1

[0287] This example was performed in the same manner as Example E1.1, except that 8.1 g of diammonium hydrogen phosphate was dissolved in 120 g of deionized water at the ordinary temperature, the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 300 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.4 MPa under a 100% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ4.1.

[0288] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E4.2

[0289] This example was performed in the same manner as Example E4.1, except that ammonium dihydrogen phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 90 C. and maintained for 2 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ4.2.

[0290] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E4

[0291] This example was performed in the same manner as Example E4.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ4.

[0292] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E5.1

[0293] This example was performed in the same manner as Example E1.1, except that 8.5 g of trimethyl phosphate was dissolved in 80 g of deionized water at 90 C., the mixture was stirred for 1 hour to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 8 hours; a pressurized hydrothermal calcining treatment was performed at 500 C. for 4 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.8 MPa under a 80% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ5.1.

[0294] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E5.2

[0295] This example was performed in the same manner as Example E5.1, except that trimethyl phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 120 C. and maintained for 8 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ5.2.

[0296] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E5

[0297] This example was performed in the same manner as Example E5.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ5.

[0298] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E6.1

[0299] This example was performed in the same manner as Example E1.1, except that 11.6 g of boron phosphate was dissolved in 100 g of deionized water at 100 C., the mixture was stirred for 3 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 2 hours; a pressurized hydrothermal calcining treatment was performed at 400 C. for 4 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 0.3 MPa under a 100% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ6.1.

[0300] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E6.2

[0301] This example was performed in the same manner as Example E6.1, except that boron phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 150 C. and maintained for 2 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ6.2.

[0302] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E6

[0303] This example was performed in the same manner as Example E6.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ6.

[0304] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E7.1

[0305] This example was performed in the same manner as Example E1.1, except that 14.2 g of triphenylphosphine was dissolved in 80 g of deionized water at 100 C., the mixture was stirred for 2 hours to obtain an aqueous solution containing phosphorus; 113 g of an HZSM-5 molecular sieve was added; the modification was performed with the impregnation method at 20 C. for 4 hours; a pressurized hydrothermal calcining treatment was performed at 600 C. for 2 hours in a condition where an external pressure was applied and water was externally added, i.e. at a pressure of 1 MPa under a 30% water vapor atmosphere, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ7.1.

[0306] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E7.2

[0307] This example was performed in the same manner as Example E7.1, except that boron phosphate, an HZSM-5 molecular sieve and water were mixed and stirred to form a slurry, and the slurry was heated to 150 C. and maintained for 2 hours, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ7.2.

[0308] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E7

[0309] This example was performed in the same manner as Example E7.1, except that the calcining condition included normal pressure (gauge pressure: 0 MPa) and the calcining was performed in the air atmosphere at a temperature of 550 C. in a muffle furnace, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ7.

[0310] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E8

[0311] Comparative Example E8 illustrated the current industry-conventional method and the obtained phosphorus-containing modified ZSM-5 comparative sample.

[0312] This example was performed in the same manner as Example E1.2, except that 16.2 g of diammonium hydrogen phosphate was dissolved in 60 g of deionized water, and the mixture was stirred for 0.5 hours to obtain an aqueous solution containing phosphorus; 113 g of HZSM-5 molecular sieve was added to the solution and modified by impregnation, i.e., impregnated at 100 C. for 2 hours; the resulting mixture was dried in an oven at 110 C. and then calcined under the normal pressure (gauge pressure: 0 MPa) in the air atmosphere at a temperature of 550 C. in a muffle furnace to produce a phosphorus-modified ZSM-5 molecular sieve sample; said sample was mixed with kaolin and pseudo-boehmite; decationized water and alumina sol were added and the resulting mixture was stirred for 120 minutes to obtain a slurry with a solid content of 30 wt %; hydrochloric acid was added to adjust the pH value of the slurry to 3.0; then the mixture continued to be stirred for 45 minutes; then the phosphorus-aluminum inorganic binder, Binder 1, was added, and the resulting mixture was stirred for 30 minutes; the resulting slurry was shaped by spray-drying to produce microspheres (having a diameter of 1-150 m); the microspheres were calcined at 500 C. for 1 hour to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ8.

[0313] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E8.1

[0314] This example was performed in the same manner as Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking auxiliary, which was denoted as CEZ8.1.

[0315] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E8.2

[0316] This example was performed in the same manner as Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking auxiliary, which was denoted as CEZ8.2.

[0317] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E9.1

[0318] This example was performed in the same manner as Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking auxiliary, which was denoted as CEZ9.1.

[0319] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E9.2

[0320] This example was performed in the same manner as Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking auxiliary, which was denoted as CEZ9.2.

[0321] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E10.1

[0322] This example was performed in the same manner as Example E1.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking auxiliary, which was denoted as CEZ10.1. The evaluation was performed in the same manner as Example E5.1, and the result was shown in Table 4.

Example E10.2

[0323] This example was performed in the same manner as Example E1.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking auxiliary, which was denoted as CEZ10.2.

[0324] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

[0325] Example E11.X to Example E20.X illustrated the preparation of the catalytic cracking auxiliary with the phosphorus-modified hierarchical ZSM-5 molecular sieves according to the present invention.

Example E11.1 to Example E17.1

[0326] Example E11.1 to Example E17.1 corresponded to Example E1.1 to Example E7.1 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve (provided by Changling Division of Sinopec Catalyst Company, and having a relative crystallinity of 88.6%, a silica/alumina molar ratio of 20.8, a Na.sub.2O content of 0.017 wt %, a specific surface area of 373 m.sup.2/g, a total pore volume of 0.256 mL/g, a mesoporous volume of 0.119 ml/g, and an average pore size of 5.8 nm, the same below), to produce catalytic cracking auxiliary samples, which were denoted as CEZ11.1 to CEZ17.1. The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E11.2 to Example E17.2

[0327] Example E11.2 to Example E17.2 corresponded to Example E1.2 to Example E7.2 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce catalytic cracking auxiliary samples, which were denoted as CEZ11.2 to CEZ17.2.

[0328] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E9 to Comparative Example E15

[0329] Comparative Example E9 to Comparative Example E15 corresponded to Comparative Example E1 to Comparative Example E7 in sequence respectively, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce catalytic cracking auxiliary samples, which were denoted as DCEZ9 to DCEZ15.

[0330] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Comparative Example E16

[0331] Comparative Example E16 illustrated the current industry-conventional method and the obtained phosphorus-containing modified hierarchical ZSM-5 comparative sample. This example was performed in the same manner as Comparative Example E8, except that the HZSM-5 molecular sieve was replaced with a hierarchical ZSM-5 molecular sieve, to produce a catalytic cracking auxiliary comparative sample, which was denoted as DCEZ16.

[0332] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E18.1

[0333] This example was performed in the same manner as Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking auxiliary, which was denoted as CEZ18.1.

[0334] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E18.2

[0335] This example was performed in the same manner as Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 2, to produce a catalytic cracking auxiliary, which was denoted as CEZ18.2.

[0336] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E19.1

[0337] This example was performed in the same manner as Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking auxiliary, which was denoted as CEZ19.1.

[0338] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E19.2

[0339] This example was performed in the same manner as Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 3, to produce a catalytic cracking auxiliary, which was denoted as CEZ19.2.

[0340] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E20.1

[0341] This example was performed in the same manner as Example E11.1, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking auxiliary, which was denoted as CEZ20.1.

[0342] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E20.2

[0343] This example was performed in the same manner as Example E11.2, except that the phosphorus-aluminum inorganic binder was replaced with Binder 4, to produce a catalytic cracking auxiliary, which was denoted as CEZ20.2.

[0344] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E21.1

[0345] This example was performed in the same manner as Example E1.1, except that the addition amounts of pseudo-boehmite and alumina sol were increased to replace the phosphorus-aluminum inorganic binder, Binder 1, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ21.1.

[0346] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

Example E21.2

[0347] This example was performed in the same manner as Example E11.1, except that the addition amounts of pseudo-boehmite and alumina sol were increased to replace the phosphorus-aluminum inorganic binder, Binder 1, to produce a catalytic cracking auxiliary sample, which was denoted as CEZ21.2.

[0348] The evaluation was performed in the same manner as Example E1.1, and the result was shown in Table 4.

TABLE-US-00005 TABLE 4 D value of Example/ Catalytic Material Balance, wt % Comparative Cracking Liquefied Ethylene Propylene Example Auxiliary Catalyst Mixture Gas Yield Yield Blank / / 100% 18.54 1.39 8.05 equilibrium catalyst E1.1 86% 10% 90% 37.41 4.09 18.76 CEZ1.1 equilibrium catalyst E1.2 92% 10% 90% 44.69 4.99 20.85 CEZ1.2 equilibrium catalyst E2.1 91% 10% 90% 45.31 4.77 19.62 CEZ2.1 equilibrium catalyst E2.2 94% 10% 90% 49.90 5.31 20.45 CEZ2.2 equilibrium catalyst E3.1 88% 10% 90% 42.13 4.54 17.68 CEZ3.1 equilibrium catalyst E3.2 93% 10% 90% 45.86 4.99 19.06 CEZ3.2 equilibrium catalyst E4.1 90% 10% 90% 44.24 4.60 18.36 CEZ4.1 equilibrium catalyst E4.2 93% 10% 90% 48.16 5.11 19.34 CEZ4.2 equilibrium catalyst E5.1 84% 10% 90% 38.59 4.09 15.92 CEZ5.1 equilibrium catalyst E5.2 90% 10% 90% 42.14 4.45 17.68 CEZ5.2 equilibrium catalyst E6.1 91% 10% 90% 43.56 4.32 18.00 CEZ6.1 equilibrium catalyst E6.2 94% 10% 90% 48.10 5.11 19.10 CEZ6.2 equilibrium catalyst E7.1 82% 10% 90% 31.75 3.27 13.08 CEZ7.1 equilibrium catalyst E7.2 84% 10% 90% 36.88 4.09 15.88 CEZ7.2 equilibrium catalyst E8.1 83% 10% 90% 35.29 3.92 18.39 CEZ8.1 equilibrium catalyst E8.2 90% 10% 90% 43.87 4.32 19.54 CEZ8.2 equilibrium catalyst E9.1 84% 10% 90% 34.80 3.86 18.35 CEZ9.1 equilibrium catalyst E9.2 91% 10% 90% 43.06 4.09 19.03 CEZ9.2 equilibrium catalyst E10.1 85% 10% 90% 34.90 3.75 17.98 CEZ10.1 equilibrium catalyst E10.2 89% 10% 90% 43.22 4.11 19.01 CEZ10.2 equilibrium catalyst E11.1 85% 10% 90% 38.91 4.17 19.51 CEZ11.1 equilibrium catalyst E11.2 94% 10% 90% 46.48 5.09 21.68 CEZ11.2 equilibrium catalyst E12.1 94% 10% 90% 47.12 4.87 20.40 CEZ12.1 equilibrium catalyst E12.2 97% 10% 90% 51.90 5.42 21.27 CEZ12.2 equilibrium catalyst E13.1 89% 10% 90% 43.82 4.63 18.39 CEZ13.1 equilibrium catalyst E13.2 90% 10% 90% 47.69 5.09 19.82 CEZ13.2 equilibrium catalyst E14.1 91% 10% 90% 46.01 4.69 19.09 CEZ14.1 equilibrium catalyst E14.2 95% 10% 90% 50.09 5.21 20.11 CEZ14.2 equilibrium catalyst E15.1 87% 10% 90% 40.13 4.17 16.56 CEZ15.1 equilibrium catalyst E15.2 92% 10% 90% 43.83 4.54 18.39 CEZ15.2 equilibrium catalyst E16.1 88% 10% 90% 45.30 4.41 18.72 CEZ16.1 equilibrium catalyst E16.2 93% 10% 90% 50.02 5.21 19.86 CEZ16.2 equilibrium catalyst E17.1 83% 10% 90% 33.02 3.34 13.60 CEZ17.1 equilibrium catalyst E17.2 88% 10% 90% 38.36 4.17 16.52 CEZ17.2 equilibrium catalyst E18.1 83% 10% 90% 36.70 4.00 19.13 CEZ18.1 equilibrium catalyst E18.2 94% 10% 90% 45.62 4.41 20.32 CEZ18.2 equilibrium catalyst E19.1 83% 10% 90% 36.19 3.94 19.08 CEZ19.1 equilibrium catalyst E19.2 90% 10% 90% 44.78 4.17 19.79 CEZ19.2 equilibrium catalyst E20.1 83% 10% 90% 36.30 3.83 18.70 CEZ20.1 equilibrium catalyst E20.2 91% 10% 90% 44.95 4.19 19.77 CEZ20.2 equilibrium catalyst E21.1 82% 10% 90% 33.67 3.68 16.88 CEZ21.1 equilibrium catalyst E21.2 83% 10% 90% 35.02 3.75 17.56 CEZ21.2 equilibrium catalyst E1 74% 10% 90% 30.23 3.04 13.45 DCEZ1 equilibrium catalyst E2 75% 10% 90% 32.03 3.20 14.53 DCEZ2 equilibrium catalyst E3 72% 10% 90% 30.36 3.16 13.78 DCEZ3 equilibrium catalyst E4 76% 10% 90% 32.43 3.33 14.97 DCEZ4 equilibrium catalyst E5 68% 10% 90% 26.43 3.49 11.58 DCEZ5 equilibrium catalyst E6 75% 10% 90% 32.57 3.33 15.55 DCEZ6 equilibrium catalyst E7 60% 10% 90% 21.67 3.43 10.63 DCEZ7 equilibrium catalyst E8 65% 10% 90% 28.79 2.98 12.81 DCEZ8 equilibrium catalyst E9 75% 10% 90% 31.44 3.10 13.99 DCEZ9 equilibrium catalyst E10 73% 10% 90% 33.31 3.26 15.11 DCEZ10 equilibrium catalyst E11 76% 10% 90% 31.57 3.22 14.33 DCEZ11 equilibrium catalyst E12 73% 10% 90% 33.73 3.40 15.57 DCEZ12 equilibrium catalyst E13 65% 10% 90% 27.49 3.56 12.04 DCEZ13 equilibrium catalyst E14 73% 10% 90% 33.87 3.40 16.17 DCEZ14 equilibrium catalyst E15 63% 10% 90% 22.54 3.50 11.06 DCEZ15 equilibrium catalyst E16 64% 10% 90% 29.94 3.04 13.32 DCEZ16 equilibrium catalyst

[0349] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications all belong to the protection scope of the present invention.

[0350] In addition, it should be noted that each specific technical feature described in the above-mentioned embodiments may be combined in any suitable manner under the circumstance that there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not described in the Detailed Description of the Invention.

[0351] In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed contents of the present invention.