TW201200236A - Higher-selectivity catalytic pyrolysis catalyst and processing method and purpose thereof - Google Patents

Abstract

A catalytic pyrolysis catalyst, in which when the catalytic pyrolysis catalyst is added in an industrial catalytic pyrolysis device, its initial activity is not greater than 80, and a preference is not greater than 75, and a more preference is not greater than 70, and a self-balancing time is 0.1 to 50 hours, and an equilibrium activity is 35 to 60; and processing method and purpose are provided. The method can uniformly distribute the activity and selectivity of the catalyst in the catalytic pyrolysis device to obviously improve the selectivity of the catalytic pyrolysis catalyst so that dry gas and coke yields can be obviously reduced to sufficiently utilize water vapor, thereby further reducing energy consumption of the catalytic pyrolysis device.

Description

201200236 VI. Description of the Invention: [Technical Field] The present invention relates to a catalyst in the field of catalytic cracking and a treatment method thereof, and a use of 'more specifically' is a catalytic cracking catalyst having higher selectivity, a treatment method thereof and use thereof . [Prior Art] The γ-type zeolite which was first used in the early 1960s was a rare earth-exchanged REY zeolite. The REY zeolite has a lanthanum to aluminum ratio of less than 5, the rare earth content is not less than 17% by weight (based on the weight of the zeolite), the acid center density is high, the hydrogen transfer property is high, and the olefin and naphthenic content in the gasoline is low, resulting in gasoline octane. The value is lowered, and tetraethyl lead has to be used as an additive to increase the octane number. Despite this, gamma-type zeolites have been the main active component of catalysts for fluidized catalytic cracking (FCC) of heavy petroleum hydrocarbons. In 1975, the United States canceled the leaded gasoline, and a cracking catalyst in which REY zeolite was replaced by ultra-stable gamma (USY) zeolite as an active component appeared. Υ§γ is a kind of high-yield Y zeolite prepared by dealuminating the γ-type zeolite skeleton by hydrothermal treatment. The zeolite has a ratio of 5 1 1 〇, and contains no or less rare earth rare earth. Since the USY framework has an increased yttrium aluminum ratio and a lower acid center density, its hydrogen transfer performance is weakened. Thus, the olefin content of gasoline increases and the octane number increases. Such as 1;" 4,242,237 彼露 - a cracking catalyst for the production of high-octane gasoline, the active component of which includes a rare earth content < 1.15 mil % (based on RE2 〇 3, based on the weight of the zeolite) and another - A small-pore zeolite comprising a zeolite, a zeolite, a chabazite, a chabazite, and a rhomboid 3 201200236 zeolite. USP 4,259,212 discloses a cracking catalyst containing a zeolite of US, having a rare earth content of USY zeolite of 15 weight/ 〇 (based on RE2〇3 '% of zeolite weight' unit cell size <24 41 a. The USY zeolites used in the above two patents all contain a small amount of rare earth. In the early 1980s, ZSM-5 type Zeolite began to be It is used in a pee catalyst to increase the octane number of gasoline. It is disclosed in USP 4,3,9,280 that HZSM_5 zeolite, which comprises 0.01-1% by weight of the catalyst, can be directly added to the FCC unit. USP 3,758,083 discloses the ratio of the two. It is a catalyst of 3〇_3: 1 with ZSM-5 zeolite and large pore zeolite (such as χ type, γ type) as the active component, aiming to raise the smoldering value of the gasoline of the product, and make c3=+c4 = increased yield. The role of ZSM-5 in FCC is actually to selectively gasoline The linear hydrocarbons with low octane number are cracked into low-carbon olefins, and some low-carbon olefins are aromatized, so that the octane of gasoline is worthwhile. Therefore, the application of ZSM-5 will inevitably result in gasoline. The content of olefins and aromatics is increased. There are many patent documents of sorghum Y zeolite as a catalyst active component. For example, USP 4,880,787 discloses a zeolite containing a ruthenium-aluminum ratio of 51 Å and a zeolite catalyst having a Constraint Index of 1-12. The carrier contains aluminum and rare earth elements 'the rare earth content is 催化剂11〇% by weight of the catalyst. This catalyst is mainly used to increase the yield of FCC gasoline and distillate oil and reduce the coke and gas yield of the FCC process. , or the range of the yttrium-aluminum ratio, the prepared catalyst does not meet the requirements for the selectivity of the FCc product. Because of the REY zeolite catalyst, the USY zeolite catalyst 'When it is added to the industrial catalytic cracking unit, it reminds 201200236

The initial activity of the chemical agent is above 85, and the initial activity of the REY zeolite catalyst is above 90. Under the high-strength hydrothermal treatment, the activity of the two zeolite catalysts is continuously decreased, and the activity of the REY-type zeolite catalyst is in a linear decrease, while the activity of the USY-type zeolite catalyst decreases with the aging time, the initial activity decays rapidly, and then decreases slowly ( See Fluid Catalytic Cracking Handbook: Design, Operation, and Troubleshooting of FCC

Facilities, Reza Sadeghbeigi, 2nd edition, P92, Figure 3-5). The quality of crude oil is getting worse with the increase of crude oil production. The main reason is that the density of crude oil becomes larger, the viscosity becomes higher, the content of heavy metal, sulfur content, nitrogen content, colloid and asphaltene content and acid value become higher. At present, the price difference between inferior crude oil and high-quality crude oil is increasing with the shortage of petroleum resources, resulting in more and more attention to low-quality crude oil mining and processing methods, that is, from poor quality crude oil. The improvement of the yield of light oil has brought enormous challenges to the processing technology of traditional crude oil. In order to meet the demand for low-carbon olefin chemical raw materials and motor gasoline for the growth of profit, φ PCT/CN2〇〇9/000272 discloses a method for preparing light fuel oil and propylene from inferior raw material oil, and inferior raw material oil is sequentially introduced. The first reaction zone and the second reaction zone of the catalytic conversion reactor are respectively reacted with the catalytic conversion catalyst to generate a primary reaction and a secondary reaction respectively. After the reaction product and the catalyst to be produced are separated by gas-solid separation, the catalyst to be produced is sequentially stripped, charred and then returned. The reactor is recycled; the reaction product is separated to obtain propylene, gasoline, catalytic wax oil and other products, wherein the catalytic wax oil enters an aromatic hydrocarbon extraction device, and the extracted oil and the raffinate oil are separated; the raffinate oil is recycled to the catalyst The first reaction zone of the conversion reactor or / and other catalytic converters are further reacted to obtain the desired product propylene and steam 201200236 oil. In this method, after the catastrophic catalytic conversion of the inferior raw material oil, the obtained catalytic eucalyptus oil is extracted by aromatic smoke, and the oil is extracted. (4) Although the bicyclic aromatic hydrocarbon is contained in the oil, it is a good remnant oil rich in paraffin. And naphthenes, very suitable for catalytic conversion 2: the efficient use of petroleum resources. This method can greatly reduce the dry milk yield and coke yield. The catalyst used in the process is based on the selectivity of the catalyst for the desired product. The catalyst in the industrial catalytic cracking unit has a broken grinding machine and loses its operation during operation. In addition, in order to maintain the equilibrium catalyst activity required for the reaction, a part of the equilibrium catalyst is often discharged, and at the same time, it is forced to replenish fresh chemicals. At present, the activity of the fresh catalyst is above 85, and the dry gas and the ',, and reverse selections are extremely poor.' Thus there is a reasonable replacement rate of the equilibrium catalyst reserves of the fresh catalytic riding system. Therefore, the equilibrium catalyst is the result of the continuous addition of the fresh catalyst to the system to balance the continuous loss of the catalyst (including the artificial unloading agent). At present, the catalytic cracking unit is supplemented with fresh catalyst method. The method is adopted. The fresh catalyst from the catalyst storage tank is used to enter the manual or automatic feeding device. After weighing, the air is fluidized and discharged. It is delivered to the regenerator of the catalytic cracker. There are many patents on how to achieve automatic metering of catalysts and reduce equipment failure during automatic feeding. For example, CN121〇〇29A and CN2407 1 74A disclose automatic small-feeding systems for catalytic cracking catalysts. The hydrothermal deactivation of the catalyst is a slow process with an average life of 3〇1〇〇, the activity of the fresh catalyst, the metal content and other properties of the feedstock, the operating conditions of the plant, and the catalyst loss rate during the deactivation process. Both the discharge rate and the unloading rate are difficult to 'simultaneous' single-particle fresh catalyst 201200236 == The moment of full-mix flow regenerator loses its physical and: qualitative, these problems give an accurate prediction of the age of the catalyst in the industrial catalytic cracking unit The distribution and its activity distribution lead to the direct use of equilibrium catalysis in the cracker = catalyzed σ port to measure the activity or other properties of the equilibrium catalyst or based on a simplified mathematical model to calculate the activity or other properties of the equilibrium catalyst, the resulting Balancing pure agent activity or other properties is only an average of average activity or other properties. These values are key parameters in guiding the production operation of the unit and optimizing product distribution and product properties, but at the same time a serious problem is the neglect of the difference in product distribution and product properties of all individual particulate catalysts in industrial catalytic crackers. CN1382528A discloses a catalyst circulating pollution and aging method, the physicochemical properties of the fresh catalyst after treatment by the method are close to the industrial balance agent. This method is primarily designed for laboratory catalyst-to-industrial equilibrium catalysts but does not improve the difference in activity between industrially balanced catalysts. CN1602999A discloses a method for external pretreatment of a hydrogenation catalyst, which pre-vulcanizes the external gas phase of the hydrogenation catalyst in an oxidation state, and then passivates the sulfided catalyst through an oxygen-containing passivation gas, which can be remarkable Improve the activity and stability of the catalyst. This method is only suitable for treating hydrogenation catalysts and is not suitable for treating catalytic cracking catalysts. SUMMARY OF THE INVENTION An object of the present invention is to provide a catalytic cracking catalyst having higher selectivity, a treatment method thereof and use thereof on the basis of the prior art. 201200236 The inventors have found that all individual particulate catalysts have different cleavage activities and selectivities due to different residence times in industrial catalytic cracking units, and the findings of the present inventors indicate that most catalysts in industrial catalytic cracking units are older. The contribution to the activity is small. When the device is operated for 100 days, about half of the added catalyst remains in the system, but only 5% of the activity is provided, while the catalyst with a lifetime of only 25 days accounts for only 1 of the total system. /6, but the contribution to the activity of the entire system accounted for 2/3. The activity of the catalyst in the industrial catalytic cracking unit is approximately a function of the regeneration temperature and the partial pressure of water vapor. The water vapor causes the catalyst to deactivate in the process of “self-balancing, over-, ie, its deactivation effect is weakened with the aging time. At the same time, the results show that the catalyst converts the catalyst from a fresh catalyst (higher microreactivity) to a catalyst (lower microreactivity), and the selectivity of dry gas and coke is rapidly improved until equilibrium is reached. The selective best method is to add a catalyst with higher selectivity to the industrial catalytic cracking unit instead of directly adding the fresh catalyst with higher activity to the catalytic cracking unit of the 2 industry. In the first aspect, the present invention Providing a catalytic cracking catalyst having a higher selectivity, characterized in that when the catalyst is added to an industrial catalytic cracking unit, its initial activity is not more than 80% by weight, preferably not more than 75, more preferably not more than 70; The self-equilibration time of the catalyst is 〇丄 small = • 50 hours, preferably 0.2-30 hours, more preferably 〇 5_1 〇, The pH of the fresh catalyst is 35-60, preferably 40-55. The initial activity of the catalyst which can be passed through the catalyst described above or the catalyst property described later refers to the catalyst activity evaluated by the light oil microreactor. 201200236 Measurement method in measurement: Enterprise standard RIPP 92-90 - Micro-reaction activity test method for catalytic cracking of fresh catalyst "Petrochemical analysis method (Rip p test method)", Yang Cuiding et al., 1990, hereinafter referred to as RIPP. 92_9〇. The initial activity of the forging agent or the activity of the fresh catalyst described later is represented by the light oil micro-reaction activity (MA), which is calculated as MA = (the gasoline production below the 204 ° C in the product + gas production) + coke yield) / total feed amount * 100% = gasoline yield below the ° ° ° ° gas yield + gas yield + coke yield. Light oil micro-reverse device (refer to RIPP 92-90) evaluation conditions are: The catalyst was broken into particles with a particle diameter of 4 2 0 - 8 41 μm and the loading amount was 5 g. The reaction raw material was straight-run light diesel oil with a distillation range of 235-337 ° C. The reaction temperature was 460 ° C. 16 hours -1, the ratio of the agent to the oil is 3.2. The catalyst is self-balancing Time refers to the time required for the catalyst to age to reach equilibrium activity at 8 Å >> and 1% water vapor conditions (refer to RIPP 92-90). The catalyst may be subjected to the following second, 3. The method of Process 0 of the fourth aspect. The catalyst comprises zeolite, inorganic oxide and optionally clay, and each component accounts for the total weight of the catalyst: zeolite i% by weight _5% by weight, inorganic oxide 5 % by weight - 99% by weight, clay, % by weight, 7% by weight, wherein zeolite is used as the active component, selected from medium pore zeolites and/or large pore zeolites, and the medium pore zeolite comprises 0% by weight based on the total weight of the zeolite. /"% by weight, the large pore zeolite accounts for 0% by weight to 1% by weight of the total weight of the fossil. The medium hole Hongshi is selected from the series of gems and/or ZRP zeolites. The stone uses non-metallic elements such as phosphorus and/or transition metal vowels such as iron, Ming, and recorded, and is modified by Zhai Jingjin. For more details, please refer to us 5,232.675,. ·》·,

A more detailed description of ZSM-5 can be found in us 3,702,886. Large hole Buddha, a mixture of one or more of the zeolites consisting of rare earth Y (REY), rare earth hydrogen Y (REHY), different methods = stable Y, high yttrium Y

In a second aspect, the invention provides a method for improving the selectivity of a catalytic cracking catalyst, the method comprising the steps of: (1) charging a fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, in contact with water vapor Obtaining an aged catalyst after aging in a certain hydrothermal environment; (2) adding the aged catalyst to an industrial catalytic cracking device. The technical solution of the present invention is embodied as follows: The fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, water vapor is injected into the bottom of the fluidized bed, and the catalyst is fluidized under the action of water vapor. The steam aging the catalyst, the aging temperature is 400 ° C - 850 t:, preferably 500 ° C - 75 (TC, preferably 60 (rc_7 〇 (rc, the apparent line speed of the fluidized bed is 0.1 m / s - 0, 6 m / sec, preferably 〇 15 sec _ 〇 5 m / sec 'aging 1 hour - 720 hours, preferably 5 hours - 360 hours, after obtaining the aging catalyst described in the first aspect, the aged catalyst is industrially catalyzed Split 10 201200236 The requirements of the device are added to the industrial catalytic cracker, preferably to the regenerator of the industrial catalytic cracker. It should be noted that part of the device is solved here. #生- is regarded as industrial catalysis The catalyst comprises a zeolite, a kiln, and optionally a clay, and each component comprises 0.1% by weight to 50% by weight, and 1% by weight of the beneficial organic oxide, respectively, of the catalyst. Active component 'selected from mesoporous boiling The stone and/or large pore zeolite, the medium pore zeolite accounts for 〇% by weight of the total weight of the zeolite 〇〇 秘 去 ΛΑ 大 A large pore zeolite accounts for 0% by weight of the total weight of the zeolite.

The T-zeolite is selected from the group consisting of ZSM stone and domain ZRP zeolite. It can also modify non-metal elements such as the above-mentioned medium-porosity zeolite (4) or transition metal elements such as iron and australis. For the description of ZRP, please refer to US 5,232,675,zs.夕赫佛石 is selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM_35 zsM-38, ZSM-48 σ, and a mixture of four kinds of scorpions among his similar structures. For a more detailed description of ZSM-5, see _ &amp of this group of zeolites consisting of super-IY and Shangyu Y obtained by the same method of rare earth Y (REY), rare earth hydrogen γ (REHY), and 疋曰德v. As a binder, the inorganic oxide is selected from the group consisting of dioxins and/or alumina (Al2〇3). The soil is used as a substrate (ie, a carrier) selected from the soil and/or soil. Or the water vapor after the multi-water kaolin aging step can be used as a steam connection q π 杈瘵夂, anti-隹蒗 雾化 atomized steam, one or more of the lifting steam ^ '''*''', the knife enters the catalysis The stripper, settler, feed nozzle, and/or pre-lift section of the crushing unit 201200236 can also be used for other purposes such as loose steam In the first aspect, another treatment method for improving the selectivity of the catalytic cracking catalyst is provided, which comprises the following steps: (1) 'Loading fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, and aging with S steaming The medium contact is subjected to aging in a hydrothermal environment to obtain an aged catalyst; (2) the aging catalyst is added to the industrial catalytic cracking device. The technical solution of the present invention is specifically embodied as follows: The fluidized bed is preferably placed in a dense phase fluidized bed, in the low port P of the fluidized bed; the aging medium which is mainly introduced into the water vapor, the catalyst is fluidized under the action of the aging medium containing water vapor, and the aging medium containing water vapor Catalysis

The agent is aged, and the aging temperature is _t_85 (r(:, excellent _ 5 峨 heart I is preferably 60 (TC-700t 'the apparent line speed of the fluidized bed is 〇) m / s _ 〇 6 m / s ' Preferably, the weight ratio of water vapor to the aged medium is from 0.20 to 0.99 m. After an hour-360 hours, the aged catalyst described in the first aspect is obtained, and the aged catalyst is added to the industrial catalytic cracking unit, preferably to the regenerator of the industrial catalytic cracking unit, as required by the industrial catalytic cracking unit. Zeolite, inorganic oxide and optionally earth-boring, each component occupies the total weight of the catalyst: zeolite i% by weight, 5% by weight, inorganic oxide, 5 parts by weight, /--99% by weight, % by weight Q% by weight, wherein zeolite as the active component 'selected from medium pore zeolite and or large pore Buddha stone, medium pore zeolite accounts for 0% by weight to 100% by weight of the total weight of the fossil, and large pore zeolite accounts for the total weight of zeolite 12 201200236. 0% by weight to 100% by weight. The medium pore zeolite is selected from the group consisting of ZSM series zeolites and/or ZRP zeolites' The above-mentioned medium-porosity zeolite may be modified with a non-metal element such as phosphorus and/or a transition metal element such as iron, cobalt or nickel. For a more detailed description of ZRp, see US 5,232,675, and the ZSM series zeolite is selected from ZSm_5, ZSM-11, A mixture of one or more of ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similarly structured zeolites. For a more detailed description of ZSM-5, see US 3,702,886. A mixture of one or more of the group consisting of rare earth Y (REY), rare earth hydrogen Y (reHY), and super-stable gamma and sorghum γ obtained by different methods. The inorganic oxide is used as a binder and is selected from the group consisting of Ceria (Si02) and/or lanthanum trioxide (ai2o3). Clay as a substrate (ie carrier) is selected from kaolin and/or kaolin. The aging medium includes air, dry gas, regenerated flue gas, air. The gas after combustion of the dry gas or the gas and the combustion of the combustion oil, or other gas, such as nitrogen, has a weight ratio of 水2_〇9, preferably 0.40-0.60. The regenerated flue gas may be from Ben Dun, or may be from He installs. The aging medium of water vapor after the aging step enters the regenerator. In a fourth aspect, the present invention provides a further treatment method for improving the selectivity of the catalytic cracking catalyst, which comprises the following steps: (1) fresh catalyst Input to a fluidized bed, preferably a dense phase fluidized bed, while delivering a thermal regeneration catalyst of the regenerator to the fluidized bed for heat exchange in the fluidized bed; 13 201200236 (2), fresh after heat exchange The catalyst is contacted with an aging medium of steam or water vapor, and is subjected to a certain hydrothermal environment. After aging, an aged catalyst is obtained; (3) the aged catalyst is added to an industrial catalytic cracking apparatus. The technical solution of the present invention is embodied, for example, by: delivering fresh catalyst to a fluidized bed, preferably a dense phase fluidized bed, while also delivering a thermal regeneration catalyst of the regenerator to the fluidized bed, where the fluidization Heat exchange takes place in the bed. The aging medium of steam or water vapor is injected into the bottom of the fluidized bed, and the fresh catalyst is fluidized by the aging medium of steam or water vapor. Meanwhile, the aging medium of steam or water vapor ages the fresh catalyst and ages. The temperature is 4 〇{rc_85〇c>c, preferably 50 (TC -75 (TC, preferably 60 (rc _7〇〇t:, the apparent linear velocity of the fluidized bed is 0.1 m/sec - 0.6 m/sec) Preferably, it is 0.15 seconds _ 〇 5 -, preferably 5 hours (10) hours, in the case of aging of water vapor, the weight ratio of the water vapor to the aging medium is greater than 〇 4, preferably 0.5-L 5 , The aging catalyst of the first aspect is obtained, the aging catalyst is added to the industrial catalytic cracking unit as required by the industrial catalytic cracking unit, preferably to the regenerator of the industrial catalytic cracking unit. Further, the water vapor after the aging step enters the reaction system. (as stripping steam, anti-coke steam, atomizing steam, lifting steam, or several stripper, settler, feed nozzle, pre-lift section, or regeneration) Ageing The aging medium of the water vapor entering the regeneration system enters the regeneration system: the regenerated catalyst after the heat exchange is returned to the regenerator. The catalyst includes fossil, inorganic oxide and optionally dry soil, 14 201200236 each component respectively Catalyst her, the limit is K ~ reset., Fu; 5! wt% 〇 〇% by weight, inorganic oxide 5% by weight - " wt%, dry soil weight% - 70% by weight β: medium As the active component, the zeolite is selected from the group consisting of medium pore zeolite and/or large pore zeolite, and the mesoporous stone accounts for the total weight of the zeolite. The weight %_1% by weight, the large pore zeolite accounts for the weight of the total weight of the stone.中% by weight. The medium-porosity zeolite is selected from the ZSM series of phoenix and/or ZRP phoenix. It can also modify the non-metallic elements such as the above-mentioned medium-porosity zeolite (4) and/or transition metal elements such as iron H. For a description, see US 5,232,675, a series of zeolites selected from the group consisting of Μ..., ZSM-11 ^ ZSM-12 ^ ZSM-23 ^ ZSM-35 ^ ZSM-38 . Mixture of one or more of ZSM-48 and other similarly structured zeolites For a more detailed description of the fine-5, see US3, 7G2, 886m stone selected from rare earth j An EY), a mixture of rare earth hydrogen Y (REHY), ultra-stable Y obtained by different methods, and high-stone gamma γ. A mixture of one or more of the group of fluorites. The inorganic oxide is used as a binder and is selected from the group consisting of cerium oxide ( SiO2 as a substrate (ie carrier) selected from kaolin and/or halloysite 0. The aging medium includes air, dry gas, regenerated flue gas, air and dry gas. The gas or air after combustion is combusted with combustion oil, or other gases such as nitrogen. The regenerated flue gas may be from the device or from other devices. In a fifth aspect, the present invention provides the use of a catalyst according to the first aspect or a catalyst obtainable by the method of the second, third or fourth aspect in a catalytic cracking process, wherein the catalyst is added to an industrial catalytic cracking unit 15 The 201200236 (preferably regenerator) is used to carry out the catalytic cracking process. It will be apparent to those skilled in the art that various features of the first, second, third, or fourth aspects described above are applicable to the fifth aspect. In a sixth aspect, the present invention provides a process for the preparation of a catalyst according to the first aspect, wherein the fresh catalyst described above is subjected to an aging treatment according to the method of the second, third, or fourth aspect, and then the catalyst can be added to the industrial catalyst. A cracking unit, preferably a regenerator, is used to carry out the catalytic cracking process. For example, the aging treatment is selected from any one of the following methods 2 and 3: Method: loading fresh catalyst into a fluidized bed, contacting with water vapor, and aging after obtaining a certain hydrothermal environment to obtain an aged catalyst; Reference may also be made to the description of the second aspect above. Method 2: charging fresh catalyst into a fluidized bed, contacting with an aging medium containing water vapor, and aging after aging in a hydrothermal environment; (see also Description of the third aspect) Method 3: introducing a fresh catalyst into a fluidized bed while delivering a thermally regenerated catalyst of the regenerator to the fluidized bed, performing heat exchange in the fluidized bed; The fresh catalyst is contacted with an aging medium of steam or water vapor, and an aged catalyst is obtained after aging in a certain hydrothermal environment. (Also refer to the description of the fourth aspect above.) It will be apparent to those skilled in the art that the preferred or further features of the above methods 丨, 2, or 3 correspond to the features of the second, third, and surface, respectively. The present invention has the following technical effects as compared with the prior art: The activity and selectivity distribution of the catalyst in the catalytic cracking unit are more uniform 201200236. 2. Significantly improve the selectivity of the catalytic cracking catalyst, so that dry gas yield and coke yield are significantly reduced. 3. The catalytic cracking unit's own resources are fully produced, thereby reducing the cost of catalyst aging. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise indicated. Although methods and materials similar or equivalent to those described herein can be used (4) in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the patent specification (including definitions) shall prevail. In addition, the materials, methods, and examples are illustrative only and not limiting. The term "includes," as used herein, refers to other steps and ingredients that can be added without affecting the end result. This term includes the terms "consisting of, and consisting essentially of." The term "method," or "process " means the means, means, techniques, and procedures used to clarify the use of the specified tasks, including but not limited to, the chemical and chemical industries, or they are readily known by known means, hands & , methods, techniques, and programs developed by technology, programs, and programs. In the present disclosure, various aspects of the present invention of the present invention can be expressed in the format of the format 11. It should be understood that the description of the 'range format' is for convenience and brief use only and should not be considered as a limitation of the scope of the invention. Accordingly, a description of a range should be considered as specifically disclosing all possible sub-ranges and values in the currency. For example, 17 201200236, such as the range of 丨 to 6, should be considered to specifically disclose sub-ranges such as to -6, ... to 5, ..., 2 such as Bu 2, 3, 4, Η 卩 and The value of each line within the 5 line is applicable. . 6. Regardless of the width of the range, it is intended to include any numerical value (fraction or integer) in this document. The phrase "between, the second value shown in the first-T", and the household value is not the value "and" (four) household "Λ ~ the first - no value "to" the second value shown in this article It is used interchangeably and is intended to include (four) values and all the fractions and integers between the embodiments. 帛 所 所 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 , , , , , , , , , , , BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of the basic flow of a catalytic conversion process associated with the present invention. The pre-lifting medium is passed from the bottom of the riser reactor 2 via line 1 and the catalyst from line 16 (iv) is lifted up along the lift of the pre-lifting medium. Accelerated movement, part of the feedstock oil is injected into the bottom of the reaction zone of the riser 2 via line 3 together with the atomized steam from line 4, mixed with the existing stream of the riser reactor, and the feedstock is cracked on the hot catalyst. And accelerate upward movement. Part of the feedstock oil is injected into the middle and upper part of the reaction zone I of the riser 2 via the pipeline 5 together with the atomized steam from the pipeline 6, and is mixed with the existing stream of the riser reactor. The feedstock oil undergoes a cracking reaction on a lower catalyst containing a certain carbon' and accelerates upward into the reaction zone. The reaction is continued. The resulting reaction product oil and gas and the deactivated spent catalyst enter the settler via line 7. In the cyclone separator, the separation of the catalyst to be reacted and the reaction product is carried out, the reaction product oil and gas enters the gas collection chamber 9, and the catalyst = powder is returned to the settler by the material leg. The catalyst to be produced in the settler flows to the stripping section 10' and from The water vapor of the pipeline 11 is contacted. The reaction product vaporized from the catalyst to be produced passes through the cyclone and enters the gas collection t9. The steamed raw catalytic waste 12 enters the person (4) U, and the main wind enters through the pipeline 14 Regenerate H, burn off the coke on the catalyst to be produced, and regenerate the deactivated catalyst to be regenerated. The regenerated catalyst enters the riser via the inclined tube 16. The reaction of collecting milk to 9 The product oil and gas passes through the large oil and gas pipeline p, and enters the subsequent separation system. The dry gas separated by the 18' is taken out through the pipeline 19; the separated liquefied gas is led out through the pipeline 2, and the knife is separated from the knives. The oil is taken out through the pipeline, and the separated diesel bismuth eucalyptus oil is taken out through the line 23. The medium is extracted for a long time; the separated catalysis is adjusted. The distillation range of each fraction is according to the actual needs of the refinery. One of the alternative treatment methods... Cheng-Yin: Catalytic cracking catalyst selection is not intended. However, the location of fresh catalyst aging is not limited to the settler limitation back to the regenerator.彡, the aging catalyst can not be placed next to the settler, the fluidized bed 32, the new shoes recognized as a fresh catalyst aging device, that is, in the dense phase, the water f is ~, the catalytic cracking catalyst is charged into the dense phase fluidization The water vapor A in the bed 32 enters the bottom of the fresh machine _ machine 32 from the line 31 through the line 31, and the water vapor after the aging step of the concentrating agent is returned to the settling point from the injection port a through the 19 201200236 line 33. The device 8' is used as anti-coke steam and/or connected to the line 11' by injection ports b and c to the stripper for use as stripping steam. The aged catalyst is fed via line 34 to regenerator i3 of an industrial catalytic cracking unit as required by an industrial catalytic cracking unit. 3 is a schematic flow diagram of a process for improving the selective treatment of a catalytic cracking catalyst according to a third aspect of the present invention, but the position of the fresh catalyst aging device is not limited to the regenerator, and the aged catalyst is not limited to return. Inside the regenerator. A fresh catalyst aging device, i.e., a dense phase fluidized bed 32, may be designed next to the regenerator 13 to charge the fresh catalytic cracking catalyst into the dense phase fluidized bed 3 2, water vaporized & via line 31 and from line 3 9 The flue gas is mixed in the pipeline 34, and the mixed gas enters from the bottom of the dense phase fluidized bed 32, and the fresh catalyst in the dense phase fluidized bed 32 is aged, and the gas after the aging step (water steaming + again + smoke) The gas is returned from the injection port a to the regenerator 3 via the pipeline 3 3 , and the flue gas is separated by the cyclone separator 36 for the gas-solid separation. The separated flue gas leaves the regenerator via the pipeline 15 and is then divided into two paths - the road flue gas The line is introduced into the hood via line w, and the other line of flue gas is mixed with water vapor from line 31 via line 39. The aged catalyst is added to the regenerator 3 of the industrial catalytic cracking unit via I, line 37, according to the requirements of the industrial catalytic cracking unit, and the main air enters the regenerator 13 via line 14 to regenerate the catalyst. Fig. 4 is a schematic view showing a process flow for improving the method for selecting a taste of a catalytic cracking catalyst according to the fourth aspect of the present invention. However, the location of the fresh catalyst aging device is not limited to the regenerator, and the aged catalyst is not limited to return to the regenerator. The heat exchanger type and mode are not limited to those shown. 20 201200236 A fresh catalyst aging device, ie, a dense phase fluidized bed 32", can be designed next to the regenerator 13" to introduce the hot catalyst in the regenerator 13" to the heat exchanger in the dense phase fluidized bed 32" via line 42" 40", the fresh catalytic cracking catalyst is charged into the dense phase fluidized bed 32" to exchange heat with the hot catalyst in the heat exchanger 40", and the heat exchanger after heat exchange in the heat exchanger 40" , returning to the regenerator 13" in the 'water vapor from the pipeline 31 " from the dense phase fluidized bed 32 " bottom, the fresh catalyst in the dense phase fluidized bed 32" after aging, the aged water vapor through the tube Line 33" is returned from the inlet a" to the settler, used as anti-fogging steam and/or connected to the line u ", injected into the stripper by the injection port b" and c", used as stripping steam. The catalyst is added to the regenerator 13" of the industrial catalytic cracking unit via line 34" according to the requirements of the industrial catalytic cracking unit. The main air is regenerated by the line 14" entering the regenerator 13", and the flue gas is passed through the cyclone 36. The gas-solid separation is carried out, and the separated flue gas leaves the regenerator via line 15". The following examples will be further illustrated in the following examples, but the invention is not limited thereby. The nature of the feedstock oil Catalyst A used in the example 1 is an aging treated Gaoshixi/Furstone. The preparation of the high stone Xifo stone is as follows: gas phase treatment with NaY via SiSi4 and rare earth ion exchange, The prepared and prepared samples have an yttrium-aluminum ratio of 18, and the rare earth content of RE2〇3 is 2 weights. /, 妒# #β σ + 1ΛΛ0/ . .. is further set/〇, and then the sample is at 800. 〇C, 100 /. Under the steam, the old 969 grams of water for the treatment of 1 4300 grams of cationized water will see the evening water Shangling soil (Lieutenant General Lingling soil company products, solid content 73%) beating, then add 781克 / /; Ming Shi (Shandong Zibo aluminum stone factory products, 21 201200236 solid content 64%) and 144ml hydrochloric acid (concentration 30%, specific gravity 156) stirred evenly 'at 60t: standing aging 丨 hours' to maintain a pH of 2 -4, down to normal temperature, and then added 800 g of sorghum zeolite (dry basis) and 2 The zeolite slurry of 000 g of chemical water was uniformly spray-dried, and the free Na+ was washed away to obtain a catalyst sample a. The properties thereof are shown in Table 2. The fresh catalytic cracking catalysts used in Examples 2 and 3 and the comparative examples were obtained from PetroChina. Chemical Co., Ltd. Catalyst Branch Qilu Catalyst Factory, the commodity code is MLC_5〇〇, its properties are listed in Table 2.

Example 1

This example was tested according to the schemes of Figures 1 and 4, freshly catalyzed A (the activity of the fresh catalyst was 81 'at a temperature of 8 〇〇. and (10)% water and gas, the self-equilibration time was 1 〇h, and the equilibrium activity was 55) The initial activity of the catalyst after 6 generations of 100/water 4 gas, apparent line speed 〇25 m/s, and aging time 2q ^ aging was 62. The aging catalyst is replenished with the vacuum residue feedstock oil A as a raw material for catalytic cracking. The test is carried out on the medium-sized device of the s: the inferior raw material enters the lift-theft base and contacts with the catalyst A and catalyzes. In the cracking reaction, the reaction temperature in the zone I' is 600t, the hourly space velocity is called, and the weight ratio of the catalyst is 6, and the weight ratio of water vapor to raw material is. 〇5; in my response degree 5〇〇C, heavy hourly space velocity 3〇 h 1, water vapor and the original, the amount ratio is 0.05. The operating conditions and product distribution are listed in Table 1 Comparative Example 1 22 201200236 / For example, for example, according to the flow of Figure 1, fresh catalyst A (fresh catalyst activity is 8 b at temperature, c and 1 GG% steam strip) <The bovine self-equilibrium time is 10h 'the equilibrium activity is 55), and the raw material oil used in the regenerator is added to the regenerator's raw material without the aging. Operating conditions and product distribution are listed in Table 3. As can be seen from Table 3, the dry gas yield and coke yield of the Example 〇 were reduced by 个6 percentage points ".98 percentage points" compared to the control 丨. Example 2 忒 Examples according to Figures 1 and 2 The procedure was carried out to test the fresh catalyst MLC-500 (fresh catalyst activity is %, self-equilibration time is 6〇^, equilibrium activity is 45) by 65crc, 1〇〇% water vapor apparent line speed 〇 3〇Ws, old 匕After aging for 30 h, the initial activity of the obtained catalyst was 6 8. The aged catalyst was replenished to a regenerator, and the vacuum residue feedstock A was used as a raw material for catalytic cracking on a medium-sized plant of the riser reactor. Test and inspection, the inferior raw materials enter the bottom of the riser reactor, contact with the catalyst MLC-500 and undergo catalytic cracking reaction. In the reaction zone, the reaction temperature is 6 〇〇. 〇, heavy hourly space velocity is 100 h·1, catalyst The weight ratio to the raw material is 6, the weight ratio of water vapor to the raw material is 〇.〇5; in the reaction zone j [, the reaction temperature, the weight hourly space velocity is 30 Γ1, and the weight ratio of water vapor to the raw material is 〇〇5. Conditions and product distribution are listed in Table 4. 3 This example was tested according to the flow of Figures 1 and 3, fresh catalyst 23 201200236 MLC-500 (fresh catalyst activity 96, self-equilibration time 乜, equilibrium activity 45) via 600 ° C, water vapor and flue gas The weight ratio is j 1, the apparent line speed is 0.30 m/s, and the initial activity of the obtained catalyst is 65 after the aging time is 40 h. The aged catalyst is replenished to the regenerator, and the vacuum residue feedstock A is used as a catalyst. The cracked raw material is tested on the medium-sized device of the riser reactor, and the inferior raw material enters the bottom of the riser reactor, contacts with the catalyst MLC-500 and undergoes catalytic cracking reaction, and the reaction temperature in the reaction zone is 60 (TC, heavy space-time The speed is 1〇〇h., the weight ratio of catalyst to raw material is 6, the weight ratio of water vapor to raw material is 〇〇5; in reaction zone η, reaction temperature is 50 (TC, heavy hourly space velocity -, water vapor The weight ratio to the raw materials is 〇. The operating conditions and product distribution are listed in Table 4. Comparative Example 2 - Comparative Example 试验 Test according to the procedure of Figure i, fresh catalyst MLC-5 〇〇 (fresh catalyst activity 96, self-balancing The time is 60h, and the activity is 4 5, go to μ soil & 丄, 丄

No, the aging is directly added to the regenerator, and the same applies to Example 1_3. Operating conditions and product distribution are listed in Table 4 " Table 4 can be seen 'relative to Comparative Example 2, Example 2 dry;: rate spear', ., anaesthetic yield decreased by 115 percentage points and 夂 (10) percentage points = 4 It can also be seen that (4) in Comparative Example 2, the dry gas and the ruler yield of Example 3 are reduced by 1.25 percentage points and 3.29 percentage points. 24 201200236 Table 1

Raw material oil name Vacuum residue Raw material oil code A Density (2 (TC), kg / m 3 920.9 Kinematic viscosity, mm 2 / sec 80 ° C / 100 ° C 114.4 Carbon residue, wt% 8.2 Condensation point, °c 25 Acid value, mg KOH/g / total nitrogen, weight % 0.33 sulfur, weight % 0.21 carbon, weight % 86.91 hydrogen, weight % 12.55 metal content, ppm nickel 8.8 hungry 0.1 iron 1.8 copper < 0.1 nano 3.0 calcium distillation range, t Initial point 415 10% 545 30% / 50% / 70% / 90% / Final boiling point / 25 201200236 Table 2 Catalyst number A MLC-500 Chemical composition, weight % Alumina 25 50.2 Oxide nano-0.321 Rare earth apparent density, Kg/m3 790 700 pore volume, ml/g 0.38 specific surface area, meter 2/g 156 229 wear index, weight % _1 1.0 1.9 sieve composition, weight % 0-40 micron 12.0 17.3 40-80 micron 65.0 49.3 &gt ; 80 microns 23 33.4 fresh catalyst activity 81 96 self-equilibration time, hour 10 60 equilibrium activity 55 45

26 201200236 Table 3 Example 1 Comparative Example 1 Catalyst No. AA aging conditions • Aging temperature, °c 600 - Apparent line speed of fluidized bed, m/s 0.25 - Aging time, hour 20 - Weight of water vapor and aging medium 100% water vapor - initial activity of the catalyst when added to an industrial catalytic cracker 62 81 feedstock number AA reaction zone I operating conditions reaction temperature, °c 600 600 weight hourly space velocity (WHSV), IT1 100 100 water vapor / feedstock Weight ratio, m/m 0.05 0.05 agent/oil ratio, m/m 6 6 reaction zone Π operating conditions reaction temperature, °C 500 500 weight hourly space velocity (WHSV), h·1 30 30 water vapor/raw material weight ratio, m/m 0.05 0.05 product distribution, wt% dry gas 2.25 2.85 liquefied gas 16.04 17.34 gasoline 40.03 40.55 diesel 20.89 19.01 catalytic wax oil 13.56 11.04 coke 7.23 9.21 total 100.00 100.00 27 201200236 Table 4 Example 2 Example 3 Catalyst No. MLC-500 MLC-500 MLC-500 aging condition aging temperature, °c 650 600 - apparent line speed of fluidized bed, m/s 0.30 0.30 - aging time, hour 30 40 - Weight ratio of water vapor to aging medium 1:1 water vapor 1:1 (water vapor: flue gas) - Catalyst initial activity when added to an industrial catalytic cracker 68 65 96 Feedstock number AAA Reaction zone I Operating conditions reaction Temperature, °c 600 600 600 weight hourly space velocity (WHSV), h·1 100 100 100 water vapor/feedstock weight ratio, m/m 0.05 0.05 0.05 agent/oil ratio, m/m 6 6 6 reaction zone I [operation Conditional reaction temperature, °C 500 500 500 hourly space velocity (WHSV), h_1 30 30 30 steam/feedstock weight ratio, m/m 0.05 0.05 0.05 product distribution, weight % dry gas 2.45 2.35 3.60 liquefied gas 15.46 15.40 16.22 gasoline 38.31 38.05 37.62 Diesel 23.32 23.67 21.23 Catalytic oil 12.34 12.61 10.12 Coke 8.12 7.92 11.21 Total 100.00 100.00 100.00 28 201200236 Invention For the sake of clarity, the description in the separate embodiments is for various aspects and the special fJt can also be implemented early The formula of the invention described in the scheme is provided. The levy can also be provided separately or in any suitable sub-combination. The text mentioned in this manual is quoted as I 4 jin. There are publications, patents and patent applications, and 'i this 5 丨 is used to incorporate this description, # b 啧 啧 π 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃 胃Although the present invention has been described in connection with the specific implementation of the invention, it is apparent that many alternatives, modifications, and variations can be seen in the art. Accordingly, All such stipulations, modifications and variations within the spirit and scope of the appended claims are hereby incorporated by reference to the accompanying drawings. FIG. With particular reference to the drawings, it is emphasized that the preferred embodiments of the invention are broadly described, and that J Fei and Zhi, and '疋 are most useful in order to provide the principles of the principles of the present invention. In the aspect of the court, in addition to the basic understanding of the hair of the hair, do not try to be more detailed. Show the structural details of the invention, contact, 'persons figure out how can the specific implementation of the invention The present invention is directed to several forms of the invention. Figure 1 is a schematic flow diagram of a catalytic conversion process associated with the present invention. 29 201200236 Figure 2 is an illustration of improved catalytic cracking catalyst selection provided by the present invention. Schematic diagram of a process flow of the treatment method; Optional FIG. 3 is a schematic diagram of another process flow for improving the catalytic cracking catalyst method provided by the present invention; FIG. 4 is a preferred embodiment of the present invention. A schematic diagram of another process flow of the catalytic cracking catalyst method. [Main component symbol description] 1, 3~7, 11, 11", U, 14", 15, 15", " 7 ' 19-23 > 31 &gt ; 31", 33, 33", 34, 34", 37, 38, 39, 4 Bu 1 ' 4 2,,.. Camp Green · 2 · Tube reactor; 8 · Settler; 9.. Air chamber; 1 〇 stripping 俨.,, 12, 16·· inclined tube; 13, 13, regenerator; 18 • Separation; I, II · · reaction zone, relocation, b, c, a ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,

Claims (1)

201200236 VII. Patent application scope: Bu-catalyzed cracking catalyst, which is characterized in that it is pulled into the catalyzed catalyst in an industrial catalytic cracking unit and its initial activity does not exceed the self-equilibration time of the agent from 〇1 to 80. The equilibrium activity was 35, at -50 hours of catalysis. 2. For example, if the catalyst for applying the patent No. 1 of the Fan Weiwei is added to the industrial catalytic cracking unit, the initial activity of the catalyst is not more than 7 and the self-equilibration time of the catalyst is over 75; 30 hours 'balance activity is H 3, as the catalyst of the scope of claim i is added to the industrial catalytic cracking, the field μ catalyst catalyst self-equilibration time is two: Shen: Patent No. 1, the catalyst, wherein the catalyst includes Stone, inorganic oxide and optional dry soil, each component accounted for: total weight of the agent: Foshan 1 weight W inorganic oxide 5 wt%-% by weight, dry soil weight % _70 wt%, ^ Buddha ^ Medium pore zeolite and / or large pore zeolite. Item 5, a treatment method for improving the selectivity of the catalytic cracking catalyst is characterized in that the method comprises the following steps: 〃, (D, charging fresh catalyst into a fluidized bed, contacting with water vapor in a certain hydrothermal environment for aging The aging catalyst is obtained; (2) The aging catalyst is added to an industrial catalytic cracking unit. The method of claim 5, wherein the hydrothermal environment comprises an aging temperature of 400. (:-8501 ' The fluidized bed has an apparent line speed of 0.1 m/s to 0.6 m/s and an aging time of 1 hour to 72 hours. 7 The method of claim 6, wherein the hydrothermal environment comprises an aging temperature of 500. - 750. (:, the apparent line speed of the fluidized bed is 0.15 sec - 0.5 m / s ' aging time 5 hours - 360 hours. 8. The method of claim 5, wherein the water vapor after the aging step As a stripper, anti-cavity steam, atomized steam, one or several types of stripper, settler, raw material nozzle, or pre-lifting section respectively entering the catalytic cracking unit. Cracking reminder The method of selective treatment agent, characterized in that the beans method comprising the steps of:. " 八曾^), the fresh catalyst is loaded into a fluidized bed, with an aging agent containing water vapor; "After aging, the aging catalysis is obtained", the aging catalyst is added to the industrial catalytic cracking device, such as a patent application The method of the ninth item of the scope includes the method of water, i Μ A 纽法', wherein the weight ratio of the hydrothermal environment point π to the aging medium is 0 24.9. 32 201200236 U. The method of claim 10, wherein the water The thermal environment includes the weight ratio of water vapor to aging medium 〇4_〇6. 12. The method of claim 9, wherein the hydrothermal environment includes an aging temperature of 4 〇 (rc_85 (rc, apparent of the fluidized bed) Wire speed glutinous rice "·/^ -0.6 m / s, aging time 1 hour _72 〇 hours. 13. The method of claim 12, wherein the hydrothermal environment includes an aging temperature of 5 〇〇. -75 〇. The apparent line speed of the fluidized bed is 15 seconds _ 〇 $ m / s, and the aging time is 5 hours · 36 〇 hours. Μ, as in the method of claim 9, wherein the aging step After the aging medium containing water vapor enters the regenerator. A method for improving the selectivity of a catalytic cracking catalyst, characterized in that the method comprises the following steps: (1) feeding fresh catalyst to a fluidized bed/while delivering a thermally regenerated catalyst of the regenerator to the fluidization The bed is replaced in the fluidized bed to obtain an aging reminder after aging (2), and the fresh catalyst after heat exchange is contacted with water vapour or water vapour, in a certain hydrothermal environment agent; The aging catalyst is added to a method of a chemical catalytic cracking apparatus. The method of claim 15, wherein the hydrothermal soil comprises a weight ratio of water vapor to an aging medium greater than 〇_4. The method of claim 16, wherein the hydrothermal environment comprises a weight ratio of water vapor to an aging medium of 0.54.5. 18. The method of claim 15, wherein the hydrothermal environment comprises an aging temperature 400. 〇-850. (:, the apparent line speed of the fluidized bed. 1 m / s - 0.6 m / s, aging time 1 hour _ 72 〇 hours. 19, as claimed in the patent scope is is, The hydrothermal environment Including the aging temperature of 500. 〇-750. (:, the apparent line speed of the fluidized bed is 0.15 sec _ 〇 5 m / s, the aging time is 5 hours - 360 hours. 20, as in the method of claim 15th, It further comprises the steps of: (4) water vapor entering the reaction system or regeneration system, or an aging medium containing water vapor entering the regeneration system; and (5) returning the regenerated catalyst after heat exchange to the regenerator. The method of claim 9 or claim 15, wherein the aging medium is regenerated flue gas. The method of claim 2012, wherein the aged catalyst is added to a regenerator of an industrial catalytic cracking unit, in accordance with any of the preceding claims. 23. The method of any of claims 5, 9 & 15, wherein the fluidized bed is a dense phase fluidized bed. The method of any one of the preceding claims, wherein the fresh catalyst comprises zeolite, inorganic oxide and optionally dry soil, each component respectively accounting for the total weight of the catalyst: Buddha Stone ^ heavy in /. -50% by weight, 5 parts by weight of inorganic oxide. Stone, weight. ,. , clay 〇 weight 〇 /. -70% by weight, wherein, the dragon' wherein the Buddha stone is selected from the medium hole Buddha stone and / or the large hole boiling 7a. 25. A catalyst according to the above-mentioned application of the patent range of the first to fourth term of the patent or the term of the fifth aspect of the patent application of the above-mentioned patent scope - the catalyst obtained in the catalytic cracking process + _ . / 35