TW201213529A - Catalytic conversion method for producing more diesel and propylene - Google Patents

Abstract

A catalytic conversion method for producing more diesel and propylene includes: performing contact reaction between raw oil and catalyst having relatively uniform activity in a reactor, wherein the reaction temperature, weight hourly space velocity and the weight ratio of the catalyst to the raw oil are sufficient to obtain a reaction product containing 12 to 60 wt% of catalyst paraffine oil based on the weight of the raw oil; and delivering the catalyst paraffine oil to a catalytic paraffine oil-treating device for further treatment. By adopting catalyst cracking, hydrogenation treatment, solvent extraction and hydrogenation cracking to perform organic combination with productive diesel technique, selectively cracking and catalyzing the isomerization of hydrocarbon, such as alkane hydrocarbon, side chain of alkyl group, etc., in the raw material, maximally reducing the entry of aromatic hydrocarbons in the raw material into the distillation fraction of diesel and preventing other components in the product from performing aromatization to produce aromatic hydrocarbons which may be retained in the distillation fraction of diesel, this method can not only convert the raw material into diesel with a high cetane number, but also greatly reduce the productivity of dry gas and coke, the tendency of crushing the catalyst and the consumption of the catalyst.

Description

201213529 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a process for catalytic conversion of hydrocarbon oil in the absence of hydrogen, and more particularly to conversion of heavy feedstock to high cetane diesel and A catalytic conversion process for propylene. [Prior Art] At present, the global demand for high-quality gasoline is increasing, and the production of high-quality gasoline is rapidly developing, while the production of high-firing diesel technology is relatively slow. Although the demand for R&D and diesel varies from region to region, the global demand for diesel fuel will gradually increase faster than the demand for gasoline. The conventional catalytic cracking process produces diesel fuel with a relatively low 16th yard value, which is often used as a blending component for diesel. In order to meet the demand for high quality diesel, it is necessary to modify the catalytic light diesel. In the prior art, the methods for catalyzing the upgrading of light diesel oil mainly include hydrogenation treatment and alkylation. CN1289832A likewise discloses a method for upgrading catalytic cracking diesel by nitriding treatment, in which the raw materials are sequentially passed through a single-stage series of hydrorefining catalyst and hydrocracking under hydrogenation conditions without intermediate separation. The method increases the cetane number of the diesel fraction of the product by more than 10 units compared with the raw material, and the sulfur and nitrogen contents thereof are remarkably lowered. CN1900226A discloses a catalytic cracking cocatalyst for producing diesel oil and a preparation method thereof, and adding a certain amount of the cocatalyst can improve the diesel yield of the catalytic device and improve the product without changing the original catalyst used in the refining device. Distribution, but the method did not mention 201213529 to improve the properties of diesel. Propylene H low-carbon flue-cured tobacco is an important organic chemical raw material, and (iv) is a demanding fast ball: #product synthetic monomer. With the demand for derivatives such as polypropylene, β and Zeng's daughters are also increasing. The demand for the world propylene market has increased from 9 η && μ, Mao from 15.2 million tons 20 years ago to 51.2 million towns with an average annual growth rate of 6.3%. It is expected that the demand for propylene in the next year will reach the climax, with an average annual growth rate of about 5%. The methods for producing propylene are mainly steam cracking and catalytic cracking () in which steaming/purling is carried out by using light oil such as naphtha as raw material to produce ethylene and propylene by thermal cracking, but the yield of propylene is only 15 weight. /. Left and right, while the coffee is made of heavy oil such as vacuum gas oil (VG〇). At present, 61% of the world's propylene is from the by-product of steam cracking to produce ethylene, 34〇/〇 from the refinery FCC production steam, some, from one, the by-product of the sept π diesel, a small amount (about 5%) from the propane Hydrogen and ethylene-butene metathesis are obtained. If petrochemicals follow the traditional steam cracking process to produce ethylene and propylene routes, they will face several constraints of light feedstock shortage, insufficient production capacity and high cost. FCC has received increasing attention due to its wide adaptability to raw materials and flexible operation. In the United States, almost all of the demand for coffee in the market is derived from FCC devices. The improved catalytic cracking technology for increasing propylene production has developed rapidly. US 4,422,925 discloses a method for contacting and converting a plurality of tobaccos having different cracking properties with a thermal regeneration catalyst, the hydrocarbons comprising at least one gas-fired hydrocarbon feedstock and one liquid hydrocarbon feedstock. The method is different according to Hydrocarbon molecules have different cracking properties, and the reaction is distinguished by 4 201213529 "Closing reaction in multiple reaction zones.] The polymorphic low-molecular-dilution CNU79270A discloses a catalytic conversion method of Duo Ershier diesel and liquefied gas. The method is carried out in a four-stage riser or fluidized bed reactor, and the steam, κ, and the cracking raw materials and the reaction terminator are injected into different positions, and the square and the soil Atm method are simultaneously The yield of two liquefied gases and diesel. However, the 4 methods have relatively high dry gas and coke yields. For a long time, those skilled in the art believe that the higher the conversion rate of heavy oil catalytic cracking, the better. The inventors have creatively thought and repeated experiments found that the conversion rate of heavy oil catalytic cracking is not as high as possible, when the conversion rate is high to the extent The target product is increased little, and the yield of dry gas and μ is greatly increased. Conventional catalytic cracking catalysts have a fine fraction of less than 40 μm and a fine particle of about 2 Q % by volume. It has been found that these fine particle catalysts have higher cracking ability, but the selectivity of time gas and coke is poor. Optimizing the screening composition of the catalyst can change the selectivity of C dry gas and coke. In order to efficiently use inferior heavy oil resources and meet the demand for fuel oil, it is necessary to develop a catalytic conversion method for converting heavy oil raw materials into a large amount of > Yuejie diesel and propylene. SUMMARY OF THE INVENTION It is an object of the present invention to provide a process for converting a quality oil to high cetane number diesel and propylene on the basis of the prior art. It selectively cleaves and isomerizes the catalytic feedstock (4), the base of the base = the smoke, while minimizing the loss of aromatic smoke in the feedstock into the diesel residue 5 201213529 injury and avoiding aromatization of other components in the product When the reaction forms aromatic hydrocarbons and remains in the diesel fuel, the cracking feedstock is converted into high cetane number diesel spear propylene, and the yield of dry gas and coke is greatly reduced, thereby realizing the effective utilization of petroleum resources. <1 In one aspect of the present invention, there is provided a catalytic conversion process in which a feedstock oil is contacted with a catalytic cracking catalyst in a catalytic cracking reactor, preferably a catalyst having a relatively uniform activity, at a reaction temperature of 're-time-space velocity The weight ratio of the catalyst to the feedstock oil is sufficient to obtain a reaction product of the catalytic wax oil comprising 12% by weight of the feedstock oil, and 2% by weight of the feedstock oil, wherein the weight hourly space velocity is 25-100h. The reaction temperature is 3%, the weight ratio of the catalytic cracking catalyst to the feedstock oil is 1-3 Torr, and the catalytic wax oil is further processed into at least one of the hydrogenation treatment device, the solvent extraction device, and the hydrocracking device. In a more preferred embodiment, the hydrogenation-catalyzed eucalyptus oil or/and the solvent-derived catalyzed eucalyptus oil or/and the gasification cracking catalyzed hydrazine hydrocracking tail oil obtained as a prolific diesel fuel The apparatus, the reactor, the hydrocracking unit, the steam cracking unit, and the like: a raw material of one or more of the equipment, preferably used as a raw material for a prolific diesel unit. In a more preferred embodiment, the prolific diesel unit is a diesel-producing catalytic cracking unit. In a more preferred embodiment, the multi-diesel catalytic cracking unit is such that the catalyst used is relatively homogeneous: a prolific diesel catalyst. In a more preferred embodiment, the reaction temperature is preferably 6 201213529 460-580 ° C, more preferably 480-540. In a more preferred embodiment, the weight hourly space velocity is M10 Oh!, preferably, 40-601Γ1. In a more preferred embodiment, the catalyst to feedstock weight ratio is preferably from 2 to 25, more preferably from 2 to 15, more preferably from 0.3 to 14. The weight ratio of water vapor to cracked feedstock oil is 0 054. In a more preferred embodiment, the reaction pressure is from 0.10 MPa to 1.0 MPa.

In a more preferred embodiment, the feedstock oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, arm gas oil, coker gas oil, de-leaching, and reduction Oil, often (d) oil, or a mixture of two or more, the other mineral oil is one or a mixture of two or more of coal (iv) oil, oil sand oil, shale oil. In a more preferred embodiment, the catalytic cracking catalyst comprises a zeolite, an inorganic oxide and optionally a dry soil, each component constituting a catalyst. 〜重量/弗石石1-50重❶/〇, inorganic oxide 5_99% by weight, % by weight of clay' wherein zeolite is mesoporphyrin and optionally large-pore zeolite, and mesoporous stone accounts for 51-100% by weight of 1 λ η -=£_ 1 of total euphorbia 70%%-100% by weight (Golden hole Buddha stone accounts for Λ1 λ of the total weight of the Buddha stone. 0-49% by weight, preferably 〇 weight%_3〇重0/〇Mesoporous zeolite is selected from ZSM series boiling π Spears j zeolite and / or ZRp zeolite, large pore boiling λ selected, self-twisting series of Fossil. The activity of the catalyst relative to the 0 9 hook (including catalytic cracking used in the catalytic cracking he / μ 丨 ^ solution catalyst And the diesel catalyst used in the prolific diesel unit means that the initial activity of the catalyst is not more than 80, preferably not more than 201213529, more preferably not more than 70; the self-equilibration time of the catalyst is 〇丨 hours·5〇 hours. Preferably, it is 0.2-30 hours, more preferably 〇5_1〇 hours; the equilibrium activity is 35-60, preferably 40-55. The initial activity or the fresh catalyst activity described hereinafter refers to the catalyst activity evaluated by the light oil microreactor. It can be measured by the measurement method in the prior art: the enterprise standard Ripp 92-90 - the microreaction activity of the catalytic cracking fresh catalyst Test method "Petrochemical analysis method (RIPP test method)", Yang Cuiding et al., 99 〇, hereinafter referred to as RIPP 92-90. The initial activity of the catalyst is represented by light oil micro-reaction activity (ΜΑ), its calculation The formula is ΜΑ = (gasoline production below 2〇4π + gas production + coke production) / total feed *1〇〇% = gasoline yield below 200 ° C in the product + gas yield + coke The yield of the light oil micro-reverse device (refer to RIPP 92-90) is as follows: the catalyst is broken into particles having a particle diameter of 420-841 μm, the loading is 5 g, and the reaction raw material is a distillation range of 235-337 C. The straight-run light diesel oil has a reaction temperature of 46 〇〇c, a weight space velocity of 16 hr-1, and a ratio of agent to oil of 3.2. The self-equilibration time of the catalyst refers to the catalyst at 8 Torr and 100% water vapor ( Refer to RIPP 92_90) when aging is required to achieve equilibrium activity The catalyst having relatively uniform activity can be obtained, for example, by the following three treatment methods: Catalyst treatment method 1: (1), charging fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, in contact with water vapor. After aging in a certain hydrothermal environment, a catalyst having a relatively uniform activity of 201213529 is obtained; (7) a catalyst having a relatively uniform activity is added to the reaction device. The treatment method 1 is embodied as follows: Fresh Catalyst (4) The human fluidized bed is preferably in a dense-phase fluidized bed. Water vapor is injected into the bottom of the fluidized bed. The catalyst is activated by water vapor: Fluidization 'At the same time, the steam aging the catalyst, and the aging temperature is 40〇. . 〇850. (:, preferably 5〇〇t_75 (rc, preferably 6〇〇dt fluidized bed, the apparent line speed is “m/s^m/s”, preferably (10) seconds-0.5 m/s, aging! hours After _72 hrs, preferably 5 hours to 36 hrs, a catalyst having a relatively uniform activity is obtained, and a catalyst having a relatively uniform activity is added to an industrial plant as required by an industrial plant, preferably to a regenerator of an industrial plant. Method 2: (1) The fresh catalyst is loaded into a fluidized bed, preferably a dense phase fluidized bed, and contacted with an aging medium containing water vapor to obtain a catalyst having relatively uniform activity after aging in a hydrothermal environment; (7) The catalyst having a relatively uniform activity is added to the corresponding reaction device. The technical solution of the catalyst treatment method 2 is, for example, specifically implemented. ▲ The catalyst is charged into a fluidized bed, preferably a dense fluidized bed, in a fluidized bed. The bottom sump is mainly aging medium containing water vapor, and the catalyst is fluidized under the action of aging medium containing water vapor. Meanwhile, the aging medium containing water vapor 201213529 aging the catalyst at 500 ° C - 750 ° C, preferably 0 · 1 m / s - 0.6 m / s, the weight ratio of the aging medium is aging temperature is 400 ° C -85 (TC, preferably 600 C-700 C 'The apparent line speed of the fluidized bed is preferably 0.15 Sec -0.5 m / sec, water vapor and 0.20-0.9' is preferably 〇4〇_〇6〇, aging i hour - 720 hours, preferably 5 hours _36 〇 hours to obtain the activity 0 relative catalyst The catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, and preferably added to the regenerator of the industrial device. The aging medium includes air, dry gas, regenerated flue gas, air and dry gas after combustion. Gas or air and combustion gas, or other gases such as nitrogen. The weight ratio of the water vapor to the aging medium is 0.2-0.9, preferably 0.40-0.60. Catalyst treatment method 3: (1), will be fresh The catalyst is fed to the fluidized bed, preferably the dense phase fluidized bed, while the hot regenerated catalyst of the regenerator is sent to the fluidized bed for heat exchange in the fluidized bed; ❿ (2), fresh after heat exchange The catalyst is in contact with the aging medium of steam or water vapor 'in a certain amount of water A catalyst having relatively uniform activity is obtained after aging in the environment; (3) adding the catalyst having relatively uniform activity to the corresponding reaction device. The technical solution of the present invention is embodied as follows: conveying fresh catalyst to The fluidized bed is preferably in a dense phase fluidized bed, and the hot regenerated catalyst of the regenerator is also sent to the fluidized bed, and heat exchange is performed in the fluidized bed. Water vapor or water is injected into the bottom of the fluidized bed. 10 201213529 Aging medium for water vapor, fresh catalyst is fluidized under the action of aging medium of steam or water vapor. At the same time, the aging medium of steam or water vapor aging the fresh catalyst, the aging temperature is 400〇C-85 ( TC, preferably 5 〇 (rc_75 (rc, preferably 6 〇 (^_7〇〇). 〇, Λιι. The apparent line speed of the chemical bed is 〇1 m / s _ 〇 6 m / s, preferably 〇Η sec -0.5 m / sec 'aging i hours _ 72 〇 hours, preferably $ hours _ 36 〇 In the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aging medium is greater than 〇4, preferably 〇51 5, to obtain a catalyst having relatively uniform activity, and the activity is relatively uniform. The catalyst is added to the industrial unit as required by the industrial unit, preferably to the regenerator of the industrial unit. In addition, the water vapor after the aging step enters the reaction system (as one of the stripping steam, the anti-coke steam, the atomizing steam, the elevated steam, or the stripper, the settler, the raw material nozzle respectively entering the catalytic cracking device) The pre-lifting section or the regeneration system, and the aging medium of the water vapor after the aging step enters the regeneration system, and the regenerated catalyst after the heat exchange is returned to the regenerator. The aging medium includes air, dry gas, regenerated flue gas, gas or air after combustion of air and dry gas, gas burned with combustion oil, or other gases such as nitrogen. By the above treatment method, the activity and selectivity distribution of the catalyst in the industrial reaction apparatus are more uniform, and the selectivity of the catalyst is remarkably improved, so that the dry gas yield and the coke yield are remarkably lowered. The particle size distribution of the catalyst (including the catalytic cracking catalyst and the prolific diesel catalyst) may be a particle size distribution of a conventional catalyst or a coarse particle size distribution. In a more preferred embodiment, the catalyst 11 201213529 is characterized by a catalyst having a coarse particle size distribution. The sieve of the coarse particle size distribution catalytic cracking catalyst is grouped into a catalytic cracking catalyst particle of less than 40 micrometers, and the volume ratio of all catalytic cracking catalyst particles is less than 1%, preferably less than 5%; more than 8 μm The catalytic cracking catalyst particles account for less than 15% by volume of all of the catalytic cracking catalyst particles, preferably less than 1%, and the rest are catalytic cracking catalyst particles of 4 〇 8 8 μm. The particle size distribution of the prolific diesel catalyst in the prolific diesel device is preferably a coarse particle size distribution, and the sieve grouping becomes a prolific product of less than 4 〇 micron _ diesel catalyst particles occupies a volume ratio of all prolific diesel catalyst particles. Less than 10%, preferably less than 5%, more than 80 microns of prolific diesel catalyst particles account for less than 15% by volume of all prolific diesel catalyst particles, preferably less than 1%, and the rest are 4〇8 〇Micron prolific diesel catalyst particles. In a more preferred embodiment, the catalytic cracking reactor is selected from the group consisting of a lifter, a linear velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. The combination, or two or more combinations of the same type of reactor, includes a series or a parallel connection, wherein the riser is a conventional equal diameter riser or a riser of various forms. In a more preferred embodiment, the feedstock oil is introduced into the catalytic cracking reactor at one location, or the feedstock oil is introduced into the catalytic cracking reactor at more than one location of the same or different heights. In a more preferred embodiment, the method further comprises separating the catalytic crack 12 201213529 - decomposing reaction product and the catalytic cracking catalyst, and separating the separated catalytic cracking catalyst by steam stripping, charring regeneration, and returning to the catalytic cracking reactor. The separated products include propylene, diesel and catalytic wax oils. In a more preferred embodiment, the catalytic wax oil has a hydrogen content of not less than 1 〇 5% by weight in an initial boiling point of not less than 260 °C. In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 330 ° C and a hydrogen content of not less than 1 8% by weight. The reaction system of the φ hydrotreating unit is usually a fixed bed reactor, and the hydrotreating catalyst is a group VIB or/and VI „ family of non-precious metal catalysts supported on an amorphous alumina or/and a ruthenium aluminum support, wherein the vib group is non- The precious metal is turned or/and tungsten, and the non-precious metal of the vm group is one or more of recording, drilling and iron. The process conditions of the hydrogenation treatment are: hydrogen partial pressure 4. ()-20.0 MPa' reaction temperature 28 〇 _45 〇〇c, volumetric space velocity, hydrogen to oil ratio 300-2000v/v. • The aromatics extraction unit of the method is applicable to an existing aromatic hydrocarbon extraction unit. The aromatic hydrocarbon extraction solvent is selected from the group consisting of furfural, dimethyl hydrazine, and dimethylformamidine. One or more of an amine, monoethanolamine, ethylene glycol, and 12-propylene glycol, the solvent can be recovered, the extraction temperature is 4〇12〇c>c, and the volume ratio of the solvent to the catalytic soil oil is 〇5:1. - 5.0:1. The reaction system of the deuteration cracking unit usually comprises a refining reactor and a cracking reactor, both of which are fixed bed reactors, and the refining reactor is usually filled with a hydrotreating catalyst which is supported on an amorphous hydroquinone. Lu Lu or / and stone a Group VIB or/and a νπι group of non-noble metals on an aluminum support 13 201213529; a hydrocracking catalyst is a Group VIB or/and Group VIII non-noble metal catalyst supported on a gamma-type Fossil molecular sieve. The molybdenum or/and tungsten, the νΠΙ non-precious metal is one or more of nickel, cobalt and iron. The hydrocracking process conditions are: hydrogen partial pressure 4.0-20.0 MPa, reaction temperature 280-450. O.ldOh·1, hydrogen to oil ratio 300-2000v/v. In a more preferred embodiment, the catalytic cracking unit for producing diesel fuel has a reaction temperature of 400-650. <:, preferably 430-500 ° C, more Preferably, 430-480. (:; oil and gas residence time is 〇〇5_5 seconds, preferably 〇14 seconds, and the reaction pressure is 〇.l〇MPa-l.〇MPa. In a more preferred embodiment, the plurality The diesel-producing catalyst comprises 'fuss stone, inorganic oxide, dry soil. The total weight of each component in the dry basis is: 5 weight·6〇 weight% of the zeolite, preferably 1〇 weight·3〇% by weight; inorganic oxidation 0.5 to 50 weight% of the weight of the clay. The weight of the clay is _70% by weight. It is selected from the group consisting of large pore zeolites, which are one or a mixture of two or more of the zeolites consisting of rare earth lanthanum, rare earth argon gamma, super stable γ, and high yttrium γ obtained by different methods. As a substrate, it is selected from the group consisting of cerium oxide (Si〇2) and/or aluminum oxide (ΑΙΑ3). In terms of dry basis, cerium oxide in inorganic oxide accounts for 50-90% by weight, and aluminum oxide accounts for 10% _5〇% by weight. Clay as a binder selected from kaolin, kaolin, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, erectite, One or more of hydrotalcite and bentonite. 201213529 In a more preferred embodiment, the prolific diesel reactor is selected from the group consisting of a lifter, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. Combinations of the above, or a combination of two or more of the same reactor, including series or / and parallel 'where the riser is a conventional equal diameter riser or a riser of various forms. In a more preferred embodiment, the catalytic wax oil raffinate oil obtained by the hydrogenation of the hydrogenated ruthenium oil or/and solvent extraction or/and the catalytic wax oil hydrocracking tail oil obtained by hydrocracking are introduced at one position. The hydrogenated catalytic wax oil is introduced into the prolific diesel reactor in a prolific diesel reactor or at more than one location of the same or different heights. In a more preferred embodiment, the method for producing diesel fuel further comprises separating the reaction product in the multi-product miscellaneous oil reactor and the prolific diesel catalyst, and the separated prolific diesel catalyst is subjected to stripping and charring regeneration. Returning to the prolific diesel reactor, the separated product includes high cetane diesel Φ and propylene. In another aspect of the invention, there is provided a catalytic conversion process for producing diesel and propylene, characterized in that the feedstock oil is reacted in a catalytic cracking reactor with a catalytic cracking catalyst, preferably a catalytically cracking catalyst having a relatively uniform activity, and Including (1) the feedstock oil comprising a re-cracking feedstock oil and a cracking feedstock oil' into which the feedstock oil is also introduced into the catalytic cracking reactor, or at a position exceeding - the same or different heights Introduced into the catalytic cracking reactor; 201213529 (2) re-cracking fresh feedstock oil in the catalytic cracking reactor is not later than cracking the feedstock oil for reaction; (3) reaction temperature in the catalytic cracking reaction, heavy space-time The weight ratio of the rapid catalytic cracking catalyst to the feedstock oil is sufficient to cause the reaction to obtain a reaction product comprising 12-60% by weight of the catalytic wax oil of the cracked feedstock oil; wherein the weight hourly space velocity of the cracked feedstock oil is 5-1 〇〇h- 1; (5) Catalytic eucalyptus oil is introduced into the hydrotreating treatment and/or solvent extraction device and/or hydrocracking device for further treatment; 0 (6) Hydrogenation catalysis obtained by catalytic wax oil hydrogenation treatment Oil and / or solvent extraction apparatus resulting catalytic midges raffinate oil or oil / hydrocracking and hydrocracking the resultant yield of diesel oil as a feedstock oil the end device. The catalytic cracking apparatus in a more preferred embodiment is a catalytic oil catalyst used in a more preferred catalytic cracking apparatus. In the embodiment where the prolific diesel unit is a prolific diesel fuel, the diesel-producing agent is a relatively homogeneous active multi-cast pyrolysis feedstock oil selected from the group consisting of 4-8 hydrocarbons. In a more preferred embodiment, The slurry further includes a slurry, diesel, gasoline, a carbon number or a mixture of two or more. In a more preferred embodiment, one or both of petroleum hydrocarbon and/or other mineral oil, atmospheric gas oil, coker gas atmospheric residue are described in terms of coal liquefied oil, oil sand oil, shale oil 0 The cracking feedstock oil is selected from or encapsulated in which the petroleum hydrocarbon is selected from the group consisting of vacuum gas oil, deasphalted oil, vacuum residue, and other mineral oils. One of the other mineral oils is tantalum or two or more corpses. In a more preferred embodiment, the catalytic cracking catalyst comprises zeolite, an inorganic oxide and optionally a sulfonium-containing alumina, each component constituting the total weight of the catalyst: zeolite 1-50 (%), 妩〆 妩〆 ( (4) ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ ❶ 5 1 · l oo of the total weight of the zeolite 0 weight / ❶ 'preferably 70 weight % _ 〇〇 weight 0 / 〇. The large pore zeolite accounts for 4% by weight of the total weight of the zeolite. The mesoporous zeolite is selected from the group consisting of Svr series zeolites and/or ZRP zeolites, and the Schiffon macroporous zeolite is selected from the Y series zeolites. The activity of the relative agent of the catalyst C includes the catalytic cracking catalyst used in the catalytic cracking reactor, and the diesel catalyst used in the production of the diesel fuel I means that the initial activity does not exceed 80. Preferably, the catalyst does not exceed 75, more preferably does not exceed 70'. The self-equilibration time of the catalyst is 1 hour, hour, preferably 0.2 to 30 hours, more preferably 1 to 0.5 to 10 hours; and the equilibrium activity is 35-60, preferably It is 40-55. The initial H❹ of the catalyst described below is the activity of the fresh catalyst as described in the light oil microreactor. It can be measured by the measurement method in the prior art. · Enterprise Standard Grinding 92-90 __The micro-reaction activity test method for catalytic cracking of fresh catalysts, "Petroleum Chemical Analysis Method (RIPP Test Method)", Yang Cuiding, early post, 199 〇, hereinafter referred to as deleted 92. The initial activity of the catalyst (four) line micro-reaction activity (referred to as 'the calculation formula is MA = (the product below the occupation of gasoline production - gas production + coke production) / total amount of feed * ! 〇〇% = low in the product Yu Gang. (: gasoline yield + gas yield + coke yield. The light oil micro-reverse device (refer to RIPP92_9 ()) is evaluated by crushing the catalyst into particles with a particle diameter of 42 〇 _ 841 μm. The amount is 5 grams of reaction raw material 17 201213529 is straight-run light diesel oil with a distillation range of 235-337 ° C, the reaction temperature is 46 〇t:, the weight space velocity is 16 hours · 1 'agent oil ratio 3 2 . Equilibrium time refers to the time required for the catalyst to age to achieve equilibrium activity under the conditions of c and loo% water vapor (refer to RIPP 92_9G). The relatively homogeneous catalyst can be obtained, for example, by the following three treatment methods: Catalyst treatment method 1: (1), the fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, in contact with water vapor, and aging after a aging in a hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) The activity relative to the homogeneous catalyst is added to the phase In the reaction device, the treatment method 1 is embodied as follows: a fresh catalyst is charged, and the children are charged into the machine bed, preferably in a dense fluidized bed, and water is injected into the bottom of the fluidized bed. Steam, tipping + + + ..., the catalyst is fluidized under the action of water vapor, and the water vapor is delayed by the catalyst. The aging temperature is 400 ° C - 850 ° C, preferably 500 t _ 5 5 ° C, preferably 600t-70 (TC, ~ apparent bed line speed of leap seconds Μ m / s, aging ... " seconds 'preferably 〇.15 接..., aging 1 hour heart hour is preferably 5 hours - 鸠 hours, In order to achieve the activity relative to the catalyst of the 9-hook, the catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, preferably to the regenerator of the industrial device. Catalyst treatment method 2: 18 201213529 (", will The fresh catalyst is charged into the fluidized bed, preferably in a dense fluidized bed, and contacted with the aging medium containing water vapor to obtain a relatively uniform activity catalyst after aging in a predetermined hydrothermal environment; (2) The hook catalyst is added to the corresponding counter The technical solution of the catalyst treatment method 2 is embodied, for example, in such a manner that the catalyst is packed in a fluidized bed, preferably in a dense fluidized bed, and an aging medium containing water vapor is injected into the bottom of the fluidized bed. The fluidization is carried out under the action of the aging medium. At the same time, the aging medium containing water vapor ages the catalyst, and the aging temperature is 4〇〇r_85 (rc, preferably 5〇 (TC-75 (TC, preferably 6m: -7 (Hrc) The apparent line speed of the fluidized bed is 〇.: 1 m / sec - 0.6 m / s, preferably 015 sec _ 〇 5 m / s, the weight ratio of water vapor to aging medium is 0.20.0.9, preferably For Q4(4)6(), aging; hour-720 hours, preferably 5 hours-36 hours, to obtain the above-mentioned activity_relatively uniform catalyst, the catalyst with relatively uniform activity is added to the industrial device according to the requirements of the industrial device, preferably added to Regenerator for industrial plants. The aging medium includes air, dry gas, regenerated flue gas, gas after combustion of air and dry gas or gas after combustion of combustion oil, or other gases such as nitrogen. The weight ratio of the water vapor to the aged medium is 〇, 2-〇.9, preferably 0.40-0.60. Catalyst treatment method 3: (1), input fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while conveying the thermal regeneration catalyst of the regenerator to the fluidized bed, 19 201213529 in the fluidized bed (2), the fresh catalyst after heat exchange is contacted with the aging medium of steam or water vapor to obtain a catalyst with relatively uniform activity after aging in a hydrothermal environment; (3), the activity is A relatively uniform catalyst is added to the corresponding reaction unit. 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. At the same time, the aging medium of steam or water vapor ages the fresh catalyst and ages. The temperature is from 400 ° C to 850 ° C, preferably 5 〇 (TC_75 〇 t, preferably 6 〇〇 t: _7 〇 (rc, the apparent line speed of the fluidized bed is 1. 1 m / s _ 〇 6 m) / sec, preferably 〇i 5 seconds - 0.5 m / sec, aged 1 hour - 72 hrs, preferably 5 hours _ 36 hrs, in the case of aging medium containing water vapor, the water vapor and aging medium The weight ratio is greater than 〇_4, preferably 〇5_15, to give a catalyst having a relatively uniform activity, and the catalyst having a relatively uniform activity is added to an industrial unit, preferably to a regenerator of an industrial unit, as required by an industrial plant. In addition, the water vapor after the aging step enters the reaction system (as a stripper, settler, raw material nozzle, one or more of the stripping steam, anti-coke steam, atomizing steam, and elevated steam, respectively, entering the catalytic cracking unit, Pre-upgrade ) Or reproducing system, and the step of aging the aqueous medium after aging 201 213 529 steam entering the regeneration system is returned to the agent of the regenerator. The aging medium,

A burnt gas, or other gas such as nitrogen.

The particle size distribution of the catalyst (including the catalytic cracking catalyst and the prolific diesel catalyst) may be a particle size distribution of a conventional catalyst or a coarse particle size distribution. In a more preferred embodiment, the catalyst is characterized by a catalyst having a coarse particle size distribution. The sieve of the coarse particle size distribution catalytic cracking catalyst is grouped into: the catalytic cracking catalyst particles of less than 40 micrometers account for less than 10% by volume of all catalytic cracking catalyst particles, preferably less than 5%; more than 8 〇 • micron The catalytic cracking catalyst particles account for less than 15% by volume of all of the catalytic cracking catalyst particles, preferably less than 丨〇%, and the rest are catalytic cracking catalyst particles of 4 〇 8 μm. The particle size distribution of the prolific diesel catalyst in the prolific oil smashing device is preferably a coarse particle size distribution, and the sieve grouping becomes a volume ratio of the prolific diesel catalyst particles of less than 4 〇 micrometer to all the prolific diesel catalyst particles. Less than 10% 'preferably less than 5%, more than 80 microns of prolific diesel catalyst particles accounted for less than 15% by volume of all prolific diesel catalyst particles, preferably less than 10%, the rest are 4〇_80 Micron's prolific diesel 21 201213529 catalyst particles. In a more preferred embodiment, the catalytic cracking reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream transfer line, and a downstream conveyor line. Combination of the above, or two or two 徊丨v Α of the same reactor, and s, the combination includes series or / and parallel, wherein the 善 鸿 θ θ 徒 疋 疋 traditional equal equal diameter Pipe or various types of risers. In a more preferred embodiment, the reaction conditions for re-cracking the feedstock oil are: reaction temperature _-750. . The weight hourly space velocity is 100-800 h-丨, the reaction pressure is 0.10-l, 0 MPa, the weight ratio of the catalyst to the re-cracking feedstock oil is 30-150 ′, and the weight ratio of the water vapor to the re-cracking feedstock oil is 0.05-1.0. In a more preferred embodiment, the reaction conditions for the cracking of the feedstock oil are: a reaction temperature of 450-600 〇C, a weight hourly space velocity of 5 〇〇ΙΓΐ, a reaction pressure of 0_10-1.0 MPa, a weight ratio of the catalyst to the cracked feedstock oil of 1 〇- 3〇, the weight ratio of water vapor to cracked feedstock oil is 〇〇5_丨〇. Φ In a more preferred embodiment, the reaction temperature for cracking the feedstock oil is 460-580 ° C. The weight hourly space velocity is 1 〇 〇 9 〇hi, preferably 2 〇 6 〇hi, more preferably 30 501 Γ 1 'catalyst. The weight ratio to the feedstock oil is ι_14, preferably 3-14. In a more preferred embodiment, the method further comprises separating the catalytic cracking reaction product and the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to stripping and charring regeneration and then returned to the catalytic cracking reactor, and the separated product includes Propylene, high cetane diesel and catalytic wax oil. In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of 22 201213529 and less than 260 ° C, and a hydrogen content of not less than 1 〇 5 weight. In a more preferred embodiment, the promoter oil is not less than 330 at the initial splash point. The fraction of (: the hydrogen content is not less than 1 〇 8 wt%. The reaction system of the hydrotreating unit is usually a fixed bed reactor, and the hydrotreating catalyst is a group VIB supported on an amorphous alumina or/and yttrium aluminum support. Or a group VIII non-precious metal catalyst, wherein the να group non-noble metal is molybdenum or/and tungsten, and the group VIII non-noble metal is one or more of nickel cobalt and iron. The hydrogenation treatment process condition is: hydrogen demonization 4.0-20.0MPa, reaction temperature 28〇_45〇〇c, volumetric space velocity 〇Μ., hydrogen oil ratio 300·2〇〇〇ν/ν.

The oxime method aromatics extraction unit is applicable to an existing aromatic hydrocarbon extraction apparatus, and the solvent for extracting the aromatic hydrocarbon is selected from the group consisting of furfural, disulfoxide, dimethylformamide, monoethanolamine, ethylene glycol, 1>2 propanediol or More, the solvent can be recovered, the extraction temperature is 4〇_12〇〇c, and the volume ratio of the solvent to the catalytic wax oil is 〇.mu. The reaction system of the hydrocracking unit usually comprises a refining reactor and a cleavage reactor, both of which are HJ fixed bed reactors, and the refining reactor is usually filled with a hydrogen fluoride treatment catalyst which is supported on amorphous alumina or/and The Group VIB or/and Group VIII non-noble metal catalysts on the ruthenium aluminum support' gasification cracking catalyst are Group VIB or/and VIn family non-precious metal catalysts supported on Y zeolite molecular sieves. Wherein the non-precious metal of group VIB is molybdenum or/and tungsten, and the non-precious metal of group vm is one or more of nickel, cobalt and iron. 23 201213529 The hydrogenation cracking process conditions are: hydrogen partial pressure 4_0-20.0MPa' reaction temperature 280-450.体积 Volume airspeed 0.1-201Γ1, hydrogen to oil ratio 300-2000v/v. In a more preferred embodiment, the catalytic cracking unit for the production of diesel fuel has a reaction temperature of from 400 to 650. (:, preferably 430-500 ° C, more preferably 430-480 ° C. The gas-gas residence time is 〇.05_5 seconds, preferably 〇丨_4 seconds. The reaction pressure is 0·l〇MPa-l.〇 In a more preferred embodiment, the prolific diesel catalyst comprises phoenix, inorganic oxide, clay. On a dry basis, each component comprises the total weight of the catalyst: 5 to 60% by weight of the zeolite, preferably 1 Torr. _3〇% by weight; inorganic oxide 0.5%-50% by weight; clay 〇 weight _7〇% by weight. Among them, zeolite as active fraction, selected from large pore zeolite. The large pore zeolite refers to rare earth Y, Rare earth hydrogen Y, ultra-stable Y, high 矽 γ obtained by different methods, the mixture of zeolites or mixtures of two or more. The inorganic oxide as a matrix is selected from the group consisting of nitric oxide (or) and/or trioxide (Abo). With dry basis 50, cerium oxide in inorganic oxide accounted for 5 〇% by weight, ruthenium oxyhydroxide 10 weight · 50% by weight. Clay as binder is selected from kaolin, kaolin, Montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, erbium violation I. <. coffee, _ .. ', ❶ β is better In an embodiment, the prolific diesel reactor is selected from the group consisting of a riser, a linear velocity fluidized bed, a fluidized bed of equal diameter, an upstream transfer line, a descending transfer line, or two or more Combination, or a combination of two or more of the same reactor, including a series of 24 201213529 or / and parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms of reduced diameter. In a preferred embodiment, the catalytic wax oil raffinate oil obtained by extracting the hydrogenated catalytic wax oil or/and solvent at a position or/and the hydrocracking tail oil obtained by hydrocracking is introduced into a prolific diesel oil. The hydrogenation catalytic wax oil is introduced into the productive diesel reactor in the reactor or at more than one location of the same or different heights. In a more preferred embodiment, the method of producing a more productive diesel further comprises reacting a prolific diesel fuel. The reaction product in the reactor is separated from the prolific diesel catalyst, and the separated prolific diesel catalyst is returned to the prolific diesel reactor after being stripped and charred, and the separated product includes high hexadecane. The value of diesel and propylene. In order to increase the ratio of the agent to oil in the downstream zone of the reaction and increase the catalytic activity of the catalyst, it can be supplemented by hot or cold regenerated catalyst, semi-regenerated catalyst, and the catalyst (four) 'fresh catalyst. Cooled regenerated catalyst and The cooled semi-regenerated catalyst is obtained by two-stage regeneration and one-stage regeneration of the catalyst to be produced, and the carbon content of the regenerated catalyst is 〇1% by weight or less, preferably less than 3% by weight, and the carbon content of the semi-regenerated catalyst is % by weight. Preferably, the carbon content is 15% by weight to 0.7% by weight; the carbon content of the catalyst to be produced is 〇, 9% by weight or more, preferably the carbon content is 〇9% by weight and 12% by weight. The method for separating propylene from the reaction product is The method is well known to those skilled in the art. The technical solution combines catalytic cracking, catalytic hydrogenation, and the like with the organic combination of 'heavy raw materials with low nitrogen content to maximize the production of high 25 201213529 cetane diesel low carbon Olefins, especially propylene. Compared with the prior art, the invention has the following technical effects: 1. The yield of propylene and the selectivity of propylene in the liquefied gas are greatly increased while the diesel oil is produced, and the cetane number of the diesel is obviously improved; With a significant increase in the rate and diesel, the dry gas yield and coke are significantly reduced. "3, light oil yield. Significantly increased, the oil beam yield is significantly reduced, so the utilization efficiency of petroleum resources is improved. Hydrogenation or / and 彡 @ #取或\ and hydrocracking unit operating cycles are significantly improved. 5, the catalyst due to the particles more uniform, so in the regeneration process, the 'knife knife cloth is also more uniform, the catalyst crushing tendency is correspondingly reduced; less, the catalyst consumption is reduced 'catalyst ant oil to reduce the catalyst content unless otherwise It is to be understood that all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. The methods and materials similar or equivalent to those described herein can be used in the practice of the present invention or in that, and the appropriate methods and materials are described below. . In the context of conflicts, 'Sym ^ ^ is constitutional from this patent specification (including definitions). The methods and examples are merely exemplary and not limiting as to the terms "including," and "the other + ^ 1 疋 可以 can be added to the steps and ingredients that do not affect the final result. These include the term "consisting of," , "Basic 26 201213529 is composed of." The term "method," or "process" refers to the manner, means, techniques, and procedures used to accomplish a specified task 'including but not limited to' known to those skilled in the chemical and chemical arts, or they are readily known by known means, means, techniques. And the means, means, techniques, and programs developed by the program. In the present disclosure, various aspects of the invention may be expressed in a range format. It should be understood that the description of the range format is used for convenience and brief purposes only and should not be used. Rather, the scope of the invention is to be construed as being limited by the scope of the invention. Sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6' 3 to 6, and numerical values within the range, such as 1, 2, 3, 4, are disclosed. 5 and 6. This applies regardless of the width of the range. In this paper, the numerical range 'is intended to include the numerical value (v-number or integer) in the range shown. The phrase "at" One value shown" The second numerical values "between" and "from" the numerical values "to, the second"; numerical values are used interchangeably herein and are intended to include the first and second illustrated values and [Embodiment] The method provided by the present invention will be further described below with reference to the accompanying drawings, but the invention is not limited thereto. The process flow is as follows: 27 201213529 Pre-lifting medium is lifted by pipeline 1 The bottom of the reactor 2 enters, and the regenerated catalyst from the pipeline 16 is accelerated upward along the riser under the lifting action of the pre-lifting medium, and the cracked feedstock is injected into the riser 2 reaction zone along with the atomized steam from the pipeline 4 via the pipeline 3 The bottom of I is mixed with the existing stream of the riser reactor. The re-cracking feedstock undergoes a cracking reaction on the hot catalyst and accelerates upward. The cracked feedstock oil is injected into the riser via line 5 together with the atomized steam from line 6. 2 The upper middle part of the reaction zone I is mixed with the existing stream of the riser reactor, and the cracking raw material is cracked on the lower catalyst containing a certain carbon. And the upward acceleration motion enters the reaction zone and continues to react. The generated oil and gas and the inactivated catalyst are introduced into the cyclone separator in the settler 8 through the pipeline 7, thereby realizing the separation of the catalyst to be produced and the oil and gas, and the oil and gas enters the gas collection chamber 9 The catalyst fine powder is returned from the feed leg to the settler. The catalyst to be produced in the settler flows to the stripper 10' and the steam from the line 11. The oil extracted from the catalyst to be produced passes through the cyclone and enters the plenum. 9. The catalyst after the stripping is regenerated by the inclined tube 12||13, the main wind enters the regenerator through the pipeline 14 to burn off the coke on the catalyst to be activated, and the deactivated catalyst is regenerated. The regenerative catalyst enters the riser via the pipeline 15. The oil in the plenum 9 passes through the large oil and gas pipeline 17 and enters the subsequent separation system 18, and the separated propylene is led out through the pipeline 19, and is separated. The obtained propane is taken out through the pipeline 28; and the carbon tetrahydrocarbon is extracted through the pipeline 2〇, and also returns to raise the f 2 ; the catalytic cracking dry gas passes through the pipeline 2! Bow A; the catalytic solution of the gasoline is discharged through the pipeline W, and the German process is smaller than 65~n〇〇c gasoline Gu 28 201213529 Via line 22, you are returned to the reactor as a re-cracking feedstock; diesel distillate line 29 is taken up, a ^ / from the fraction can also be heavy diesel fraction and catalytic wax oil - into the hydrogenation unit or The hydrogenation treatment gas product or/and the heavy aromatic hydrocarbon or/and the hydrocracking gas exiting the hydrogenation treatment unit to the hydrogenation treatment unit through the line 23 unit 24 and the aromatic hydrocarbon extraction unit or/and the hydrocracking 77 are introduced. ^ # , · S line 25 $ 丨 'Hydrogen catalyzed eucalyptus oil or / and catalytic eucalyptus oil or / and catalytic soil oil hydrocracking tail oil through the tube, line 26 into the prolific diesel device 27 . The oil and gas generated by the prolific diesel unit can be separated from the oil and gas pipeline 28 by the system 18 or/and into other branch systems, where the fractions are adjusted according to the actual needs of the refinery. The method will be further illustrated by the following examples, but does not limit the method accordingly. The stock oil used in the examples was VG〇, and its properties are shown in Table i. The preparation method of the catalytic cracking catalyst (cAT_Mp) used in the examples is as follows: Catalyst CAT-MP preparation method 1), 2〇g NH4Cl is dissolved in 1000 g of water, and l〇〇g (dry basis) crystallization is added to the solution. Product ZRP] Fo Shi (produced by Qilu Petrochemical Company Catalyst Plant, SiO2/Al2O3 = 30, rare earth content RE2〇3= 2 〇% by weight), exchanged at 9 °C for 5 hours, the transition is based on the cake; add 4 〇 gH3p〇4 (concentration 85%) & 4_5gFe(N〇3)3 dissolved in 90g of water, mixed with filter cake and dipped and dried; then calcined at 55 °C for 2 hours to obtain MFI structure containing phosphorus and iron The elemental analytical chemical composition of mesoporous zeolite is 0.1Na2O-5.1Al2〇3-2.4P2〇5.i.5Fe2〇3.3.8RE2〇3-88.1Si 29 201213529

2), using 25 0kg of deionized water to beat 75 4kg of multi-water kaolin (Suzhou Ceramics Industrial Products, solid content 716% by weight), and then add 54.8kg of pseudo-thin Mingshi (Shandong Aluminum Factory Industrial Products, solid content 63% by weight) 'Adjust the pH to 2-4 with hydrochloric acid, stir evenly, let stand for aging for 1 hour at 60_7〇〇c, keep the pH at 2-4, lower the temperature to below 60oC, and add 41.5Kg aluminum sol (Qilu Petrochemical Company) Catalyst factory products,

The content of Ah〇3 was 21.7 wt%) and the mixture was stirred for 4 minutes to obtain a mixed slurry. 3), the phosphorus- and iron-containing mfi structure prepared in step 1) is a hole-boiling vermiculite (dry basis is 22.5 kg) and DASY zeolite (Qilu Petrochemical Company catalyst 廒 industrial product' unit cell size is 2 445_2 448 nm, dry The base is 2.0kg), added to the mixed solution obtained in step 2), stirred evenly, spray-dried, and washed with ammonium dihydrogen phosphate solution (phosphorus content is 丨% by weight). Washing strips 'wash off free Na+' is dry. Catalytic cracking catalyst sample. CAT-MP, the composition of the catalyst is 18% by weight of phosphorus- and iron-containing MFI structure mesoporous zeolite, 2% by weight DASY zeolite, 28% by weight pseudoboehmite, 7% by weight aluminum sol and Amount of kaolin. 4) The prepared catalyst is aged in a dense bed by 7 〇〇〇C and ι〇〇〇/〇 steam, and the apparent line speed of the fluidized bed is 〇·28 m/s, and the aging time is 7 7 Hours, the catalyzed properties of the aging are listed in Table 2, which is code-named CAT-MP·1' and then the partial aging agent is decanted to remove fine particles and particles larger than 1 ΟΟμπι to obtain a catalyst with a coarse particle size distribution. CAT-MP-2, the properties of which are listed in Table 2. The prolific diesel catalyst (C AT-MD ) used in the examples is prepared as follows: 201213729 The method is briefly described as follows: Catalyst CAT-MD preparation method i), 2 liters of water glass solution having a concentration of 155 g/L of cerium oxide and 1 The acidified sulfuric acid solution having a free acid of 148 g/L and an Al203 content of 20 g/L was simultaneously subjected to a rapid mixer reaction to obtain a cerium sol. 2) Into the above-prepared cerium sol, 465 g of kaolin (Suzhou Bering Co., Ltd., solid content: 80 wt.%) was beaten for 1 hour to obtain a kaolin-ruthenium sol. 3), a mixture of Al2〇3 124g pseudo-boehmite (Shandong Aluminum Plant, ai2〇3 containing 33% by weight of yttrium) and 45〇g deionized water mixed for 3 minutes, 'after adding 25 ml concentration 3 1% by weight of hydrochloric acid (acid / ai2 〇 3 molar ratio of 0.2) peptization, continue to beat for 2 hours, then add 656 § molecular sieve content of 32 weight ° / 〇 ground DAS γ 〇〇 molecular sieve slurry (Qilu catalyst plant Production, unit cell size is 2 445nm), beating for 3 minutes, get a mixture of pseudo-boehmite and molecular sieve! liquid. 4) mixing the kaolin_矽 sol slurry prepared above with the mixed hydrolytic solution of the pseudoboehmite and the molecular sieve prepared above for 1 , to obtain a catalyst polymerization liquid, and drying the obtained poly liquid into a diameter of 20- 120 micro. The content of cerium oxide was 29.9% by weight and the content of kaolin was 359 重量 :'. , the alumina content is 13.9% by weight, the molecular sieve content is 2〇3 weight = the particle 'money temperature is determined by the water-free filament to the sodium-free ion, and the 15th generation is dried to obtain the prepared catalyst CM. The prepared catalyst was aged in a dense phase bed by 7 〇〇 and ι〇〇% 201213529 by steaming π, and the apparent line speed of the fluidized bed was 〇27 m/sec aging time 20 hours, aging catalyst properties Listed in Table 2, its code is CAT-MD.1, and then part of the aging agent is decomposed to remove fine particles and particles # greater than 1 〇〇 ', to obtain the catalyst of the coarse particle size distribution code CAT- The properties of MD-2' are listed in Table 2. The preparation method of the hydrogenation catalyst used in the examples is briefly described as follows: ammonium metatungstate ((NH4) 2W4〇ir18H20, chemically pure) and

Acetic acid (Ni ( n〇3 ) 2'i8h2 〇, chemically pure), prepared into 2 〇〇 mL of six liquids with water, and the liquid is poured into the oxidized carrier 5 gram, and immersed at room temperature. In the case of stain 3, the ultrasonic treatment was used for the dipping solution for 3 minutes in the dipping process, and it was dried in a microwave oven for about 15 minutes. The composition of the catalyst is: 3 〇 % wt% w 〇 3, 3 丄 weight % Ni 〇 and the balance aluminum oxide. The catalytic cracking catalysts CAT-MP-1 and CAT-MP-2 fresh catalysts had a steep (initial activity) of 73 at a temperature of 8 Torr. 〇 and 1〇〇% water The self-equilibration time is 9h under normal gas conditions, and the equilibrium activity is. Like the prolific diesel catalyst CAT-MD-1 and CAT-MD-2 fresh catalyst 'tongue (initial activity) is 8〇, self-balancing at a temperature of 8〇〇t>c and 1〇〇% water vapor The time is l〇h and the equilibrium activity is 52. The commercial cracking catalyst used in the comparative example was traded under the trade name MLC-500 > A tb ra Saki T-Petrochemical Catalyst Branch Qilu Catalyst Plant produced an initial/tongue of 91 and a self-equilibration time of 6 (jh, equilibrium activity was 43. Catalyst properties are listed in Table 2. Hydrotreating catalysts and hydrocracking catalysts 32 used in the examples 2012 1352929 * The product codes are RN-2 and RT-1, respectively, both of which are produced by China Gonger τ Petrochemical Catalyst Branch Changling Catalyst. Factory production. Example 1 This example was tested according to the flow of the drawing. The cracking feedstock oil was directly used as the raw material for catalytic cracking, and the catalyst CALMpq was used to test on the medium-sized device of the elevated reactor, and the cracking raw material entered the reaction zone. In the upper part, the cracking raw material is subjected to a cracking reaction at a reaction temperature of 530. 0, a weight hourly space velocity of 35 lrl, a catalytic cracking catalyst to a raw material weight ratio of 4, a water vapor to a raw material weight ratio of 0.15, and a reaction zone η, oil and gas in the reaction The temperature of 490 〇 C, the weight ratio of water vapor to the raw material is 〇15 under the conditions of the lamp cracking reaction, the oil and gas and the catalyst with carbon in the settler The off-production is cut in the separation system according to the distillation range to obtain propylene, butene, gasoline, diesel and catalytic sulphur reserves. The catalytic ant oil is sent to the hydrotreating unit for treatment at a hydrogen partial pressure of 6.0 MPa and a reaction temperature of 3.5. 〇〇c, volume empty, speed # 1.5 h, hydrogenation at the reaction conditions @, the catalyzed catalytic leaching oil is transported to the prolific diesel catalytic cracking unit, and the catalyst is contacted for catalytic conversion. The operating conditions and product distribution are listed in the table. 3. From Table 3, it can be seen that the 'propylene yield is as high as 1431% by weight, and the diesel multi-rate is 18.89% by weight. The cetane number is 41. Comparative Example 1 The medium-sized test in Comparative Example 1 is on a conventional catalytic cracking apparatus. The raw material oil was tested and the 丨 phase 33 201213529 was used. The catalyst used was a traditional particle size distribution of MLC_5 〇〇-based agent, the reaction temperature was 512 ° C, and the ratio of solvent to oil was 6. The operating conditions and product distribution are listed in Table 3. As can be seen from Table 3, the propylene yield can reach 6 53, the diesel yield is 12.58, and the diesel cetane number is 36. Compared with the examples " Example 1 I total liquid The calyx (liquefied gas yield + gasoline yield + diesel yield) was significantly reduced, and the ratio of liquefied gas yield / dry gas yield was significantly less than that of Example 1. Example 2 Example 2 was also carried out according to the flow of the drawing The test, the test feedstock oil and the test procedure and method are exactly the same as those in the example, except that the catalytic cracking catalyst used is changed from the conventional particle size distribution of CAT-Mpq to the coarse particle size distribution of CAT-MP-2 '·multi-product diesel. Catalysts from the traditional particle size distribution of CAT-MD-1 to the coarse particle size distribution of CAT MD_h operating conditions and product distribution are listed in Table 3 » As can be seen from Table 3, the acrylic yield is as high as 14 58 %, diesel production The rate is 19.77% by weight and the cetane number is 41. Example 3 This example was tested according to the flow of the drawing. The cracking feedstock oil was directly used as a raw material for catalytic cracking, and the catalyst was tested on a medium-sized device of a riser reactor using a catalyst CAT_Mp-b, and the cracked raw material was entered into the reaction zone. In the upper part, butene is used as the re-cracking raw material to enter the bottom of the reaction zone. In the reverse 34 201213529, the raw material of the 're-cracking at the bottom of the zone is at a reaction temperature of 6丨0〇 (:, heavy hourly space velocity of 1751Γ1, the weight ratio of catalytic cracking catalyst to raw material 7〇, the weight ratio of water vapor to raw material is 0,20, and the cracking reaction is carried out; in the upper part of reaction zone j, the catalytic raw material is at a reaction temperature of 53 〇. (:, heavy hourly space velocity 4〇lrl, catalytic cracking catalyst and raw material The weight ratio is 4, the weight ratio of water vapor to the raw material is 0.15, and the cracking reaction is carried out in the reaction zone π, the oil and gas is reacted at a reaction temperature of 480 ° C, and the weight ratio of water vapor to the raw material is 〇丨5, The oil and gas and charcoal-containing catalysts are separated in a settler, and the product® is cut in the separation system according to the distillation range to obtain propylene, butyl, gasoline, diesel and catalytic wax oil. Catalytic wax oil is sent to a hydrocracking unit for treatment. The reaction system of the hydrocracking unit comprises two reactors of a refining reactor and a cracking reactor. The hydrogen partial pressure is 17.9/17.4 MPa, the reaction temperature is 374/37 PC, and the volume is empty. Hydrogenation treatment under the reaction conditions of 〇.95/1.21ri 'Hydrogenation of hydrocracked tail oil to a prolific diesel catalytic cracker' is contacted with catalyst CAT-MD-1 for catalytic conversion. Operation _ conditions and product distribution are listed in Table 4. As can be seen from Table 4, the propylene yield was as high as 131% by weight, the diesel yield was 11.36% by weight, the diesel cetane number was as high as 52, and the jet fuel was 1333% by weight. Compared with Comparative Example 1, the implementation was as follows. Example 3 propylene yield increased significantly, an increase of 6.57 percentage points; diesel cetane number also increased significantly, increased by 16 units; total liquid yield (liquefied gas yield + gasoline yield + diesel yield 4 jet fuel The yield is significantly increased by 3 · 9 4 percentage points; the ratio of liquefied gas yield / dry gas yield is also relatively low. 35 201213529 Example 4 Example 4 was also tested according to the flow of the drawing, the test Raw oil and test The steps and methods are exactly the same as those in Example 3 except that the catalytic cracking catalyst used is changed from the conventional particle size distribution of CAT-MP-1 to the coarse particle size distribution of CAT-MP-2; the prolific diesel catalyst is distributed from the conventional particle. The CAT_MD_2e operating conditions and product distribution of CAT-MD-1 changed to coarse particle size distribution are listed in Table 4. As can be seen from Table 4, the propylene yield was as high as 13 16% by weight, and the diesel yield was 12.03% by weight, hexadecane. The value is 54 and the jet fuel is 138.5%. 36 201213529 - Table 1

Material properties Density (20 ° C), kg / m 3 858.6 Kinematic viscosity (100 ° C), mm 4.9 carbon residue, weight % 0.03 total nitrogen, weight % 0.05 sulfur, weight %. 0.06 carbon, weight % 86.3 hydrogen, weight % 13.64 heavy metal content, ppm nickel < 0.1 s < 0.1 distillation range. C Initial boiling point 290 10% 372 30% 415 50% 440 70% 470 90% 502 Final boiling point - 37 201213529 Table 2 Catalyst name CAT-MP-1 CAT-MP-2 CAT-MD-1 CAT-MD-2 MLC-500 particle type traditional particle size coarse particle size traditional particle size coarse particle size traditional particle size chemical property, weight % Al2〇3 50.4 50.1 13.9 14.2 48.5 FC2O3 0.6 0.6 Na20 0.07 0.06 0.09 0.06 0.35 physical properties specific surface, m2/g 104 97 106 97 / pore volume, mL / g 0.22 0.20 0.16 0.14 / particle size distribution, volume % 0-40μπι 25.8 6.8 20.2 7.6 18.5 40-80μπι 57.5 78.6 50.1 77.7 50.3 >80μιη 16.7 14.6 29.7 14.7 31.2 Φ 38 201213529 Table 3 Example 1 Comparative Example 1 Example 2 Catalytic cracking unit catalyst CAT-MP-1 CAT-MP-2 Operating conditions riser reaction zone II reaction temperature, °c 490 490 water vapor / feedstock weight ratio 0.15 0.15 riser reaction Zone I reaction temperature, °c -530 530 oil ratio, m/m 4 4 weight hourly space velocity, h_1 35 35 water vapor / feedstock weight ratio 0.15 0.15 catalytic cracking reaction product catalytic wax oil accounted for cracking Weight ratio of feedstock oil,% 37.13 38.38 Hydrogenation unit hydrogen partial pressure, MPa 16 16 Reaction temperature, °C 350 350 Volumetric space velocity, K1 1.5 1.5 Hydrogen to oil ratio, ν/ν 1500 1500 39 201213529 Prolific diesel catalytic cracking unit Prolific diesel traditional FCC prolific diesel catalyst CAT-MD-1 MLC-500 CAT-MD-2 reaction temperature, °c 480 512 480 oil ratio, m/m 3 6 3 product distribution, m% dry gas 4.34 2.78 3.98 Liquefied gas 38.46 19.81 38.08 Propylene 14.31 6.53 14.58 Gasoline 32.72 54.65 33.10 Diesel 18.89 12.58 19.77 Heavy oil 0.37 5.12 0.08 Coke 5.30 4.56 5.09 Loss 0.50 0.50 0.50 Total 100.58 100.00 100.60 Diesel 16 burning value 41 36 41 Total liquid yield 90.07 87.04 90.95 Liquefaction Gas yield / dry gas yield 8.86 7.13 9.57 40 201213529 Table 4 Example 3 Comparative Example 1 Example 4 Catalytic cracking unit catalyst CAT-MP-1 CAT-MP-2 Operating conditions riser reaction zone II reaction temperature, °c 480 480 water vapor / feedstock weight ratio 0.15 0.15 riser reaction zone I reaction temperature, °c 610/530 610/530 oil Ratio, m/m 70/4 70/4 weight hourly space velocity, IT1 175/40 175/40 water vapor/feedstock weight ratio 0.2/0.15 0.2/0.15 catalytic cracking reaction product catalytic wax oil accounted for 39.83 of cracking feedstock oil 40.19 by weight, % hydrocracking unit hydrogen partial pressure, MPa 17.9/17.4 17.9/17.4 reaction temperature, °C 374/371 374/371 volumetric space velocity, h-1 0.95/1.2 0.95/1.2 hydrogen to oil ratio, v/v 1500 1500 41 201213529 Prolific diesel catalytic cracking unit

It will be appreciated that certain aspects and features of this month described in the 'Invention' application are also provided for clarity. The phase diagrams have been jointly proposed in the prior implementation schemes, and conversely, the formulas of the present invention described in the various embodiments of the individual embodiments are provided for the sake of brevity. Knife open...without any suitable sub-combination, all the references mentioned in this manual are referenced by this reference λ ' 寻 利 and patent application are all incorporated herein by reference. 1U publication, patent or patent 42 201213529 And one by one is hereby incorporated by reference. Although the present invention has been described in connection with the specific embodiments and embodiments thereof, it is to be understood that Accordingly, all such alternatives, modifications, and (4) are intended to be encompassed within the spirit and scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be described by way of example only with reference to the accompanying drawings. DETAILED DESCRIPTION OF THE INVENTION Referring now in detail to the drawings, it is to be understood that the embodiments of the present invention are merely exemplary and are merely illustrative of the preferred embodiments of the invention. It is said to be the most s "...presented in a useful and easy to understand description. In this respect, it is not intended to show the present invention in more detail than the priests who have a basic understanding of the invention. The structure is thin green, and the description form of the drawing is attached. How can the 'months of how to implement the invention? FIG. 1 is a schematic diagram of an embodiment of the invention. 】 1 ~ 7, u, 14, 15, l7, i9 ~ 23, 25 ~ 29f [2.. riser; 8.. settlement.. official green', child descending, 9.. gas collection; 1〇 . steam 12,16.· inclined tube; ns ▲ Zhifeng and ' 13.. regenerator; 18. separation system; 24 · chlorination cracking unit; Ι, Π ·. reaction zone 43

Claims (1)

201213529 VII. Patent application scope: i.- A method for catalytic conversion of multi-product diesel and propylene, characterized in that the feedstock oil is reacted with the catalytic cracking catalyst in a catalytic cracking reactor for reaction temperature, weight hourly space velocity, catalyst and The feedstock oil weight ratio is sufficient The reaction is carried out to obtain a reaction product comprising a catalytic wax oil of from 12 to 60% by weight, wherein the weight hourly space velocity is 25.1 GQh.l, the reaction temperature is 450 to 600 cC, and the catalytic cracking catalyst and the feedstock oil are obtained. The weight ratio is 1-:30, and the catalytic wax oil is further processed into at least one of a hydrogenation treatment device, a solvent extraction device, and a hydrocracking device. 2. The method of claim 1, wherein the oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coking gas oil, One or a mixture of two or more of deasphalted oil, vacuum residue, and atmospheric residue. The other mineral oil is one or a mixture of two or more of coal liquefied oil, oil sand oil, and shale oil. 3. The method of claim 1, wherein the catalytic cracking catalyst in the catalytic cracking reactor comprises a sillimanite, an inorganic oxide, and optionally a clay, each component of the total weight of the catalyst: zeolite 丄% by weight, inorganic oxide 5_99% by weight, clay 〇7〇 weight 0/〇, wherein the zeolite is mesoporous and optional large-pore zeolite 'Mesofosite accounts for 51-100% by weight of the total weight of the zeolite, large The pore zeolite accounts for 〇 49% by weight of the total weight of the zeolite, the medium pore zeolite is selected from the ZSM series zeolite and/or the ZRP zeolite, and the large pore zeolite is selected from the group 1 201213529 γ series zeolite. 4. The method of claim 2, wherein the catalytic cracking reactor is selected from the group consisting of a riser, a linear velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. One or more sets of σ or a combination of two or more reactors of the same type, the combination comprising series or / and parallel, wherein the riser is a conventional equal diameter riser or various forms of diameter increase tube. The method of claim 1, wherein the feedstock oil is introduced into the catalytic cracking reactor at one location, or the feedstock oil is introduced into the catalytic cracking reactor at more than one location of the same or different heights. . 6. The method of claim 1, wherein the reaction temperature is 460-580 ° C, preferably 480-540 ° C, and the weight hourly space velocity is 3〇_8〇hi, preferably 40-60 h·1, catalytic cracking. The weight ratio of the catalyst to the feedstock oil is 2-15, preferably 3-14, and the weight ratio of the steam to the cracked feedstock oil is 〇〇51. 7. The method of claim 1, wherein the reaction is at a pressure of 0.10 MPa - Performed at 1.0 MPa. 8. The method of claim 1, wherein the method further comprises separating the reaction product from the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to stripping, charring regeneration, and returned to the reactor, and the separated 2 201213529 Products include propylene, high-firing diesel and catalytic oil. 9. The method of claim 1, wherein the catalytic wax oil has a primary point of not less than 260. C, preferably not less than 3 30. The hydrogen content of C is not less than 10.5% by weight, preferably not less than 10.8% by weight. 10. If you apply for a patent scope! And a method of catalyzing at least one of a hydrogenation catalytic wax oil obtained by hydrogenating a wax oil, a catalytic wax oil raffinate obtained by a solvent extraction device, and/or a hydrocracking tail oil obtained by hydrocracking as a prolific diesel device raw material. 11. The method of claim 10, wherein the prolific diesel unit has a reaction temperature of 400-65 0. (:, the oil and gas residence time is 〇05_5 seconds, and the reaction pressure is 〇.1〇MPa - 1.0 MPa. Lu 12. The method of the first application of the patent scope, wherein the prolific diesel fuel used in the production of diesel fuel is used. Including zeolite, inorganic oxide, #土, by, based on the basis of the total weight of the catalyst: zeolite 5 weight · 6 〇 weight%; inorganic oxide 0.5 weight, weight %; clay 〇 weight _7 〇 medium zeolite As an active fraction, it is selected from the group consisting of A, which is derived from a large-pore zeolite, and the large-pore zeolite is obtained from a rare earth lanthanum, a rare earth hydrogen γ, a different method, and an ultra-stable ruthenium. The method of claim 1, wherein the catalytic cracking catalyst in the catalysis 3 201213529 cleavage reactor and/or the prolific diesel device The particle size distribution of the prolific diesel catalyst is a coarse particle size distribution, and the sieve grouping is: the volume ratio of the prolific diesel catalyst particles smaller than 40 μm to the total mass of all the produced diesel catalyst particles is less than 丨〇%, preferably lower than 5 % 'greater than 8 0 micro The prolific diesel catalyst particles account for less than 15%, preferably less than 1% by volume of all of the prolific diesel catalyst particles, and the remainder are 40-80 microns of prolific diesel catalyst particles; and/or less than 4 microns. The catalytic cracking catalyst particles account for less than 10% by volume of all of the catalytic cracking catalyst particles, preferably less than 5%, and the catalytic cracking catalyst particles larger than 8 μm are less than 15% by volume of all the catalytic cracking catalyst particles. Preferably, the catalytic cracking catalyst particles are in the catalytic cracking reactor of less than 10%, the remainder being 4 〇 8 〇 micrometers. 14. The method of claim 1 or 1 wherein the catalytic cracking catalyst in the catalytic cracking reactor And/or the prolific diesel catalyst in the prolific diesel device is a relatively uniform catalytic cracking catalyst, wherein the relatively homogeneous catalyst means that its initial activity φ does not exceed 80, preferably does not exceed 75, more preferably Not more than 7〇; the self-equilibration time of the catalyst is 小时. 1 hour _ 5 〇 hours, preferably 〇 2-3 〇 hours, more preferably 0.5-10 hours; the equilibrium activity is 35_6 〇, preferably 4 The method of claim 1 or 1 wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant are as follows: According to the treatment method: 4 201213529 (1), the fresh catalyst is charged into the fluidized bed, preferably in a dense fluidized bed, in contact with water vapor, and aging after a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; 2) adding the relatively uniform activity catalyst to the corresponding reaction device; and wherein the certain hydrothermal environment comprises: an aging temperature of 4 Torr. 〇 _85 〇. 〇, preferably 500 ° C - 750 ° C, preferably 600 ^ 0 (^ 'the apparent line speed of the fluidized bed 0.1 m / sec - 0.6 m / s, preferably 0.15 _ _ 米 5 m / s, aging J The method of claim 1 or claim 1, wherein the catalytic cracking catalyst and/or the prolific diesel in the catalytic cracking reactor are used. The prolific diesel catalyst in the apparatus is obtained by the following treatment method: (1) charging fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, in contact with an aging medium containing steamed π, under a certain hydrothermal environment After aging _, a catalyst having relatively uniform activity is obtained; (2) adding a catalyst having a relatively uniform activity to the corresponding reaction device; wherein the certain hydrothermal environment includes: an aging temperature of 4 〇 (rc_85 (rc, Preferably 5 ° ° C-75 (TC ' best 60 (TC-70 (rc, fluidized bed apparent line speed 0.1 m / sec - 0.6 m / s, preferably 0.15 sec · 05 m / s, water The weight ratio of steam to aging medium is 0.20-0.9, preferably 〇4〇_〇6〇, aging i hour-720 hours, preferably 5 hours-360 hours. 201213529 17 The method of claim 1 or 10, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: (2) introducing fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while conveying a thermal regeneration catalyst of the regenerator to the fluidized bed, and performing heat exchange in the fluidized bed; The hot fresh catalyst is contacted with an aging medium of steam or water vapor, and a relatively homogeneous catalyst is obtained after aging in a certain hydrothermal environment; and (3) a catalyst having a relatively uniform activity is added to the corresponding In the reaction device; wherein the certain hydrothermal environment includes: aging temperature 4 〇〇 t &gt; c_85 〇 t &gt; c, preferably 5 〇 -7 thief, preferably 6 〇 (rc_7 〇 (rc, fluidized bed Apparent line speed of 0.1 m / sec - 0.6 m / sec, preferably 〇 15 sec _ 〇 5 m / s, aging t hours - 720 hours, preferably 5 hours _ 36 M, when the water vapor and aging medium (if If any, the weight ratio is greater than 〇 4, preferably 0.5-1.5 18. The method of claim 1G, wherein the prolific diesel reactor is selected from the group consisting of a riser, a line-rate fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line— Or a combination of two or more, or a combination of two or more of the same reactor, including a series or / and a parallel 'the middle riser is a conventional equal diameter riser or various forms of reducer 201213529 The method of claim </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> The wax oil hydrocracking tail oil is introduced into the productive diesel reactor or the hydrogenated catalytic samarium oil is introduced into the prolific diesel reactor at more than one location of the same or different heights. 20. The method of claim 10, wherein the method of performing in the prolific diesel device further comprises separating the reaction product from the township by a catalyst, and the prolific diesel catalyst is returned after being stripped and charred. The production of diesel reactors, (four) after the production of # including high sixteen yards of diesel and propylene. 21. A method for catalytic conversion of prolific diesel and propylene, characterized in that the raw material 'reacts from contact with the catalytic cracking catalyst in the catalytic cracking reactor to carry out reverse φ' also includes (1) feedstock oil including re-cracking feedstock oil and cracking a feedstock oil, the feedstock oil is introduced into the catalytic cracking reactor at one location, or the feedstock oil is introduced into the catalytic cracking reactor at a location that exceeds the same or different heights; The oil is reacted in the catalytic cracking reactor not later than the cracking of the feedstock oil; (3) the reaction temperature, the weight hourly space velocity, the weight ratio of the catalytic cracking catalyst to the feedstock oil in the catalytic cracking reaction is sufficient to cause the reaction to be contained Crack 201213529 The reaction product of 12-60 heavy hydrazine/hydrazine catalyzed wax oil of the feedstock oil; the weight hourly space velocity of the crude cracked feedstock oil is 5 _i〇〇hi; and/or hydrogen (4) catalyzes the wax oil to enter the hydrogenation treatment Or / and solvent extraction deuteration cracking device for further processing; (5) Catalytic eucalyptus oil hydrotreating to obtain hydrogenated catalytic oil or / and solvent extraction device obtained catalytic liquefied oil raffinate oil / / The hydrocracking tail oil obtained by chlorination cracking is used as a raw material of a prolific diesel unit. The method for re-cracking the original carbon atoms is 4-8. 22 The method of claim 21 is selected from the group consisting of or including oil. a mixture of one or more of pulp, diesel, gasoline, and smoke. 23. The method of claim 21, wherein the oil is selected from or includes petroleum hydrocarbons and/or other oils ^ ^ ^ m ττ ^ It is selected from the group consisting of vacuum gas oil, atmospheric gas oil, hydrazine, coil 4 ^ ', gas oil, deasphalted oil, and reduction of two or more mixtures, and one or more of the other oils. 24. The method according to claim 21, wherein the catalytic cracking catalyst comprises zeolite, inorganic oxidation: b cracking accounts for the total weight of the catalyst: zeolite b5.,: selected, each component is λ λ weight / 〇 , inorganic oxide 5-99 weight / 〇 〇 〇 〇 〇 〇 , , , , , , , ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The amount of 51_1〇〇% by weight, large pore zeolite 201213529 0-49% by weight of the total weight of the stone 'Mesoporous zeolite is selected from the group consisting of ZSM series zeolite and/or ZRP. "Fostone' large pore Foshan is selected from the γ series zeolite. 2 5. The method of claim 2, Wherein the particle size distribution of the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel catalyst in the prolific diesel device is a coarse particle size distribution, and the sieves are grouped into: more than 40 micrometers of prolific The proportion of diesel catalyst particles to all of the prolific diesel catalyst particles is less than i 〇 %, preferably less than 5%, and the proportion of the more probable diesel catalyst particles larger than 80 microns accounts for less than 1 5% of all prolific diesel catalyst particles. Preferably less than 1%%, the balance being 40-80 microns of prolific diesel catalyst particles; and/or less than 4 microns micron catalytic cracking catalyst particles account for less than 10% by volume of all catalytic cracking catalyst particles, preferably less than 5%, more than 8 〇 micron catalytic cracking catalyst particles account for less than 15% by volume of all catalytic cracking catalyst particles, preferably less than 1%, and the rest are 40-80 micron catalytic cracking φ catalyst particles. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel catalyst in the prolific diesel plant is a relatively uniform catalytic cracking catalyst The catalyst having a relatively uniform activity means that its initial activity does not exceed 80', preferably does not exceed 75, more preferably does not exceed 70; the self-equilibration time of the catalyst is from 1 hour to 50 hours, preferably from 0.2 to 30 hours, more Preferably it is from 0.5 to 10 hours; the equilibrium activity is from 35 to 6 Torr, preferably from 40 to 55. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel device is obtained by the following treatment method. (1), the fresh catalyst is charged into the fluidized bed, preferably the dense phase fluidized bed is contacted with water vapor, and the catalyst is relatively oxidized after aging in a S-shaped water-heating environment; (2) The catalyst having a relatively uniform activity is added to the corresponding reaction device, wherein the certain hydrothermal environment comprises: an aging temperature of 4 〇 (rc_85〇ec, preferably 500. 〇75 〇. (:, preferably 6 〇 (TC) Rhyme c, the apparent line speed of the fluidized bed is 0.1 m / s - 0.6 m / s, preferably 〇 15 sec _ 〇 5 m / s, aging i hours - 720 hours 'preferably 5 hours _ 36 〇 hours. 28 The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel device are obtained by the following treatment methods: (1) Loading fresh catalyst into a fluidized bed, preferably a dense fluidized bed Contacting with an aging medium containing water vapor to obtain a catalyst having relatively uniform activity after aging in a certain hydrothermal environment; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device; A certain hydrothermal environment includes: aging temperature 4 〇 (rc_85 〇 t, preferably 500. 〇 750. (:, best __7 〇〇χ:, apparent line of fluidized bed 201213529 speed 0.1 m / s - 〇 · 6 m / s, preferably 〇 15 seconds _ 〇. 5 m / sec, the weight ratio of water vapor to aging medium 〇. 2 〇 · 〇 9, preferably 〇 4 〇 _0.60, aging 1 hour - 720 hours, Preferably, the method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel catalyst in the prolific diesel plant is preferred. Obtained by the following treatment method: (1) introducing fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, and simultaneously delivering a thermal regeneration catalyst of the regenerator to the fluidized bed in the fluidization Heat exchange in the bed; (2), fresh catalyst after steam exchange with water vapor or Contacting the aging medium of the vapor to obtain a catalyst having relatively uniform activity after aging in a certain hydrothermal environment; and (3) adding the catalyst having a relatively uniform activity to the corresponding reaction device; The hydrothermal environment includes: aging temperature 400 ° C -850 ° C, preferably 500 ° C -750 ° C, preferably 60 (TC_700t:, the apparent line of the fluidized bed It is 0-4, preferably 0.5-1.5. 30. The method of claim 21, wherein the reactor is selected from the group consisting of a riser tube and an isobaric release, wherein the fluidized bed of the catalytic cracking line fan, a fluidized bed of equal diameter, 11 201213529, an upward conveying line, and a descending line One of the conveyor lines, „ promoting two or more group ports, or two or more J ancestors of the same reactor, the combination comprising series or / and parallel, wherein the riser is a conventional equal diameter The riser or the riser of various forms of variable diameter. • As in the method of claim 21 (4), the reaction conditions for re-cracking the feedstock are: reaction temperature explosion 75G〇c, heavy hourly space velocity, h.1, reaction pressure 0.1 (M.OMPa, weight ratio of catalyst to re-cracking feedstock 30.150'. The weight ratio of steam to re-cracking feedstock oil is 0.05-1.0 〇32. The method of claim 2, wherein the cracking feedstock oil The reaction conditions are: reaction temperature 450-600 ° C, preferably 460-580 ° C, weight hourly space velocity 5-100 h·1, preferably lo-goh·1, reaction pressure 〇.i〇-i.〇MPa, catalyst and The weight ratio of the cracked feedstock oil is L0-30, preferably 1_14, The weight ratio of water vapor to cracking feedstock oil is 〇. 〇5 -1. 〇. 3 3. The method of claim 21, wherein the method further comprises separating the catalytic cracking reaction product from the catalytic cracking catalyst, The separated catalytic cracking catalyst is returned to the reactor after being stripped and charred, and the separated products include propylene, high-firing diesel and catalytic wax oil. 3. The method of claim 21, Wherein the catalytic eucalyptus oil 12 201213529 is a fraction having an initial boiling point of not less than 260 ° C, preferably not less than 33 〇〇 c, and the hydrogen content is not less than 1 〇 5 % by weight, preferably not less than 1 〇 8 % by weight. 35. The method of claim 21, wherein the reaction temperature of the prolific diesel device is 400-650. (:, the oil and gas residence time is 〇〇5·5^, and the reaction pressure is 0.10 MPa - 1.0 MPa. 36 The method of claim 21, wherein the prolific diesel catalyst in the prolific diesel device comprises zeolite, inorganic oxide, clay, and the components are respectively based on the total weight of the catalyst: 5 weight of the zeolite. 6〇% by weight; inorganic oxide 0.5 to 50 weight %; clay 〇 _ 〇 〇 。 。 。 。 。 。 。 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石 沸石One or a mixture of two or more of the 24 groups of zeolites. The method of claim 2, wherein the prolific diesel reactor in the prolific diesel unit is selected from the group consisting of a riser, etc. a line-rate fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, a type of a downstream conveyor line, or a combination of two or more 'or two or more combinations of the same reactor, The combination includes series or / and parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms. The method of claim 21, wherein the hydrogenated catalytic wax oil or/and the oxidative cracking obtained hydrocracking tail 13 201213529 oil is introduced into a prolific diesel reactor in a multi-product diesel crucible. Internally, or at the same or different locations, the hydrogenation of the hydrogenated catalytic wax oil to obtain the μ _ &gt; 虱 虱 cleavage cracking tail oil into the productive diesel reactor in the multi-product diesel plant . 39. The method of claim 21, wherein the method of performing in the prolific diesel unit further comprises separating the reaction product in the multi-product diesel reactor and the prolific diesel catalyst, and separating the produced diesel The catalysis is returned to the prolific diesel reactor after being stripped and charred, and the separated ruthenium product includes high cetane diesel and C; ❿ 14