TW201217512A - wherein a raw oil is contacted and reacted with a catalyst mainly containing large-pore zeolite and having a relatively uniform activity in a catalytic conversion reactor - Google Patents

Abstract

The present invention relates to a catalytic conversion method for increasing the cetane value of diesel, wherein a raw oil is contacted and reacted with a catalyst mainly containing large-pore zeolite and having a relatively uniform activity in a catalytic conversion reactor, and the reaction temperature, the oil gas retention time and the weight ratio of the catalyst to the raw oil ensure that the reaction products containing diesel-containing catalytic wax oil of 12 to 60 wt% of the raw oil can be obtained; the reaction temperature is from about 420 to about 550 DEG C; the oil gas retention time is from about 0.1 to about 5 seconds; the weight ratio of the catalyst to the raw oil is about 1 to about 10; and the catalytic wax oil is further processed by being added into other devices or returned back to the original catalytic conversion reactor. By using the disclosed method, the high-cetane diesel can be maximally produced. The cracking catalyst having oversized particle distribution can further improve the selectivity of dry gas and coke and can reduce the breaking tendency of the catalyst and the consumption of the catalyst.

Description

201217512 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a catalytic conversion process, and more particularly to a catalytic conversion process for converting a maximum amount of heavy feedstock to high hexadecane ruthenium diesel. [Prior Art] The demand for high quality diesel oil is increasing worldwide, and the demand for fuel oil is decreasing. Although the increase in demand for gasoline and diesel varies from region to region, the global demand for diesel fuel will increase faster than the demand for gasoline. Therefore, more low-hexadecane ruthenium catalytic cracking (FCC) light diesel oil is being used as a blending component of diesel. In order to meet the demand for high-quality diesel, it is necessary to upgrade FCC light diesel oil or directly produce a large amount of high-quality FCC light diesel oil through FCC. In the prior art, the methods for upgrading light diesel oil mainly include hydrotreating and Decentralization. U S P 5 5 4 3 0 3 6 discloses a method for the upgrading of F C C light loop oil by hydrotreating. c N 1 2 8 9 8 3 2 A also discloses a method for upgrading catalytic cracking diesel by hydrotreating, which is to pass the raw materials through a single-stage series hydrotreating catalyst and hydrocracking under hydrogenation conditions. The catalyst is separated without intermediate. The method makes the hexadecane oxime of the diesel fraction of the product increase by more than 10 units compared with the raw material, and the sulfur and nitrogen contents thereof are remarkably lowered. USP 4 8 7 1 4 4 4 discloses a method for improving the FCC light-returning oil hexadecane hydrazine by conducting an FCC light loop oil in the presence of a solid acid catalyst and a linear olefin of 3 to 9 carbon atoms. The base reaction. u SP 5 1 7 1 9 1 6 discloses a 5--201217512 FCC light-return oil modification method, which is to use FCC light-return oil on solid acid catalyst and α-C 14 olefin or coking gas (gas oil) is subjected to an alkylation reaction. Another way to directly improve the quality of catalytic light diesel oil is by changing the catalytic cracking process parameters or catalyst. CN 1 900226A discloses a catalytic cracking cocatalyst for producing diesel fuel and a preparation method thereof, and adding a certain amount of the cocatalyst can improve the diesel oil yield of the FCC catalytic device without changing the original catalyst used in the refinery device, Improve product distribution, but this method does not mention improvements in diesel properties. C N 1 6 8 3 4 7 4 A is also a catalytic cracking cocatalyst for producing diesel fuel and a preparation method thereof. CN1473908A relates to a process for producing diesel oil from heavy oil and residual oil by catalytic cracking of Ca2+-EDTA. CN101171063A relates to a fluid catalytic cracking (F C C ) process for improving the quality of distillate suitable as a blending oil for diesel fuel. The FCC process combines the staged FCC conversion process with interstage molecular separation of polycyclic aromatic hydrocarbon species. The less stringent and higher reaction zones in the riser of the F C C reactor together with the selective molecular separation increase the yield of diesel quality distillate. This method focuses on the separation of the saturated hydrocarbon-rich heptahexane-rich diesel fraction by membrane separation. Another way to improve the quality of catalytic light diesel oil is to utilize a two-way combination of hydrotreating and catalytic cracking. For example, CN 1 8 9 6 1 9 2 A will transfer the wax oil together with the catalytic cracking heavy loop oil 'catalytic cracking diesel into the hydrotreating unit, and the hydrogenated tail oil enters the catalytic cracking unit'. This method can reduce the aromatic content of diesel and Sulfur content and increase its hexadecane oxime. CN1382776A is a combination of hydrotreating of residual oil and catalytic cracking of heavy oil. The above patented method does not require any catalytic cracking -6 - 201217512 process, but only by hydrogenation to upgrade diesel. CN 1 0 1 3 62 9 5 9A discloses a catalytic conversion method for preparing propylene and high octane oxime gasoline, and the refractory raw material is first contacted with a thermal regeneration catalyst at a temperature of 600 to 750 ° C and a weight hourly space velocity of 100 〜 800 hours", pressure 〇.1〇~l.OMPa, catalyst to raw material weight ratio 30~150, water vapor to raw material weight ratio of 0.05~1.0, cracking reaction, reaction stream and cracking The raw material oil is mixed at a temperature of 4 5 0 to 6 2 0 ° C, a weight hourly space velocity of 0.1 to 100 hours ^, a pressure of 0. 10~1 .OMPa 'the weight ratio of the catalyst to the raw material is 1.0 to 3 0, water The cracking reaction is carried out under the condition that the weight ratio of steam to raw material is 0.0 5~1. 0; after the catalyst to be produced and the reaction oil and gas are separated, the catalyst to be produced enters the stripper, is regenerated by steam stripping, charring, and returns to the reactor. The oil and gas are separated to obtain a target product of propylene and high octane oxime gasoline and a re-cracked raw material, and the re-cracking raw material comprises a fraction having a distillation range of 180 to 260 ° C and a heavy aromatic residual oil. In this method, the yield and selectivity of propylene are greatly increased, the yield of gasoline and octane oxime are remarkably improved, and the dry gas yield is reduced by more than 80% by weight. SUMMARY OF THE INVENTION The object of the present invention is to provide a method for converting the maximum amount of heavy oil into high hexadecane ruthenium diesel based on the prior art, which is to increase the hexadecane oxime of diesel and increase the yield of diesel oil. That is, the diesel cetane barrel is improved. The "hexadecane barrel" here refers to the product of the yield of diesel heptane and diesel. It mainly by selectively cracking hydrocarbons such as mid-stream hydrocarbons and side chains of catalytic raw materials, while minimizing the conversion of aromatics in raw materials into the oil fraction of 201217512, and avoiding the reaction of other components in the product through aromatization. The aromatic hydrocarbons are formed and remain in the diesel fraction, and the cracked raw materials are converted into high hexadecane ruthenium diesel, and the yields of dry gas and coke are greatly reduced, thereby realizing the effective utilization of petroleum resources. In one aspect of the invention, there is provided a method for catalytically reforming a diesel cetanezepoxide barrel, wherein the feedstock oil is reacted in a catalytic conversion reactor with a catalyst having a relatively uniform activity of a predominantly large pore zeolite, wherein the reaction The temperature, the residence time of the oil and gas, and the weight ratio of the catalyst to the feedstock oil are sufficient for the reaction to obtain a reaction product comprising diesel fuel, about 12 to about 60% by weight of the catalytic wax oil of the feedstock oil, wherein the reaction temperature is about 420 to about 55 (TC, The hydrocarbon gas residence time is from about 0.1 to about 5 seconds, and the weight ratio of the catalyst to the feedstock oil is from about 1 to about 10. In a more preferred embodiment, the reaction temperature is from about 43 to about 500 ° C, preferably from about 430 to about 480 ° C 8 In a more preferred embodiment, the hydrocarbon residence time is from about 0.5 to about 4 seconds 'preferably from about 8 to about 3 seconds. In a more preferred embodiment, the catalyst to feedstock weight ratio is from about 2 to about 8, preferably from about 3 to about 6. In a more preferred embodiment, the reaction pressure is from about 0.1 MPa to about 1.0 MPa, preferably from about 0.15 MPa to about 0.6 MPa. In a more preferred embodiment, the feedstock oil Selected from or package Including petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from one or both of a reduced pressure gas oil, a normally compressed gas oil, a coking gas oil, a deasphalted oil, a vacuum residue, and an atmospheric residue. A mixture of the above (including two, similar expressions below - 8 - 201217512), the other mineral oil is one or a mixture of two or more of coal liquefied oil, oil sand oil, shale oil. In a more preferred embodiment The catalyst mainly containing large pore zeolite comprises zeolite, inorganic oxide and clay. The components respectively comprise, on a dry basis, the total weight of the catalyst: about 5 to about 50% by weight of the zeolite, preferably about 10% by weight. About 30% by weight; inorganic oxide: about 0.5% by weight to about 50% by weight: clay 〇 weight ~ about 70% by weight, wherein zeolite as an active fraction, selected from large pore zeolite. a mixture of one or more of the group consisting of rare earth Y, rare earth hydrogen Y, ultra-stable Y, and high yttrium Y obtained by different methods. The inorganic oxide is used as a matrix selected from the group consisting of cerium oxide (Si 〇 2 ) and / or aluminum oxide (A1203) In the inorganic oxide, the cerium oxide in the inorganic oxide accounts for about 50% by weight to about 90% by weight, and the aluminum oxide accounts for about 10% by weight to about 5% by weight. The clay is used as a binder, and is selected from the group consisting of kaolin, One or more of polyhydrate kaolin, montmorillonite, diatomaceous earth, halloysite, saponite 'rectile soil' sepiolite 'attapulgite, hydrotalcite, bentonite. The catalyst with relatively uniform activity ( By catalytic cracking catalyst and prolific diesel catalyst, it is meant that the initial activity does not exceed about 80, preferably does not exceed about 75, more preferably does not exceed about 7 Torr; the catalyst has a self-equilibration time of from about 1 hour to about 50 hours. Preferably, it is from about 0.2 to about 30 hours, more preferably from about 0.5 to about 10 hours; and the equilibrium activity is from about 3 5 to about 60, preferably from about 40 to about 5 5 . The initial activity of the catalyst or the freshly catalyzed activity described hereinafter refers to the catalyst activity evaluated by the light oil microreactor. It can be measured by the measurement method in the existing -9-201217512 technology: Enterprise Standard RIPP 92-90 - Micro-reaction activity test method for catalytic cracking fresh catalyst "Petrochemical Analysis Method (RIP P Test Method)" - Yang Cuiding et al. 1990, hereinafter referred to as RIPP 92-90. The initial activity of the catalyst is represented by the light oil micro-reaction activity (ΜΑ), which is calculated as ΜΑ = (gasoline production below the 204 ° C + gas production + coke production) / total amount of feed x l 〇〇 % = Gasoline yield + gas yield + coke yield below 204 ° C in the product. The light oil micro-reverse device (refer to RIPP 92-9 0) is evaluated by crushing the catalyst into particles having a particle diameter of about 42 0 to 8 4 1 μm, a loading of 5 g, and a reaction material having a distillation range of 2 3 5 . ~3 3 7 t straight-run light diesel oil, reaction temperature 460 °C, weight airspeed of 16 hours -1, ratio of agent to oil 3.2. The catalyst self-equilibration time refers to the time required for the catalyst to age to reach equilibrium activity at 800 ° C and 1% water vapor conditions (refer to RIPP 92-90). 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, A catalyst having a relatively uniform activity after aging in a certain hydrothermal environment; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The treatment method 1 is embodied, for example, as follows: The fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and water vapor is injected into the bottom of the stream at the flow of the liquid - 10, 2012, 175, 'the catalyst is flowed under the action of water vapor. At the same time, the steam aging of the catalyst 'aging temperature is about 400 ° C ~ about 85 (TC, preferably about 500 ° C ~ about 7 50 ° C, preferably about 600 ° C ~ about 700 ° C, fluidized bed The apparent line speed is from about 0.1 m/sec to about 0.6 m/s, preferably from about 1 hr to about 0.5 m/sec, and aged from about 1 hour to about 720 hours, preferably from about 5 hours to about 3 hours. Thereafter, the catalyst having relatively uniform activity is obtained, and the catalyst having relatively uniform activity is added to the industrial unit as required by the industrial apparatus, preferably to the regenerator of the industrial unit. Catalyst treatment method 2: (1), fresh catalyst is loaded Into a fluidized bed, preferably a dense phase fluidized bed, in contact with an aging medium containing water vapor, and aging after a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) adding the catalyst having relatively uniform activity Go to the corresponding reaction unit. The technical solution of the catalyst treatment method 2 is, for example, such that the catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and an aging medium containing water vapor is injected into the bottom of the fluidized bed, and the catalyst acts on an aging medium containing water vapor. The fluidization is carried out while the aging medium containing water vapor ages the catalyst at an aging temperature of from about 400 ° C to about 850 t, preferably from about 500 ° C to about 75 ° C, preferably from about 600 ° C to about 700 ° C. The apparent linear velocity of the fluidized bed is about 0.1 m/s to about 0 -6 m/s, preferably about 0 · 15 seconds to about 〇. 5 m/sec, and the weight ratio of water vapor to aged medium is about 〇. 2 0~约〇. 9, preferably about 〇· 4 0~ about 〇 _ 6 0, aging about 1 hour ~ about 7 2 0 hours, preferably about 5 hours ~ about 3 6 〇 small -11 - 201217512 A catalyst having a relatively uniform activity is obtained, and a catalyst having a relatively uniform activity is added to an industrial device as required by an industrial plant, preferably to a regenerator of an industrial device. The aging medium includes air, dry gas, regenerated flue gas, Combustion of air or dry gas and air and combustion oil a gas, or other gas such as nitrogen. The weight ratio of the water vapor to the aging medium is from about 0.2 to about 0.9, preferably from about 0.40 to about 0.60. Catalyst Treatment Method 3: (1), introducing fresh catalyst into the fluidized bed, Preferably, a dense phase fluidized bed is simultaneously delivered to the fluidized bed of the regenerator thermal regeneration catalyst, and heat exchange is performed in the fluidized bed; (2) fresh catalyst after heat exchange with water vapor or water vapor The aging medium is contacted, and after aging in a certain hydrothermal environment, a catalyst having relatively uniform activity is obtained; (3) the catalyst having relatively uniform activity is added to the corresponding reaction device. 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 simultaneously delivering a thermally regenerated catalyst of the regenerator to the fluidized bed, in the stream Heat exchange takes place in the chemical 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, and the aging medium of water vapor or water vapor ages the fresh catalyst. The temperature is about 400 ° C to about 850 ° C. Preferably, about 500 ° C to about 75 ° C, preferably about 60 ° C to about 7 〇〇 ° C 'the apparent line speed of the fluidized bed. 1. 1 m / sec ~ about 〇. 6 m / sec 'preferably about 〇 · 1 5 seconds ~ about -12- 201217512 0 · 5 m / s, aging about 1 hour ~ about 7 2 0 hours, preferably about 5 hours ~ about 3 60 hours, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aging medium is greater than about 0 to about 4, preferably from about 0.5 to about 1.5, obtained in the activity relative to The catalyst of the uniform sentence, the catalyst with relatively uniform activity is added to the industrial device as required by the industrial device, preferably to the regenerator of the industrial device. In addition, the water vapor after the aging step enters the reaction system (as one of the stripping steam, the anti-coke steam, the atomized steam, the elevated steam, or the stripper, the settler, the raw material nozzle, respectively, which enters the catalytic cracking unit, 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 after combustion of air and dry gas, or gas after combustion of 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, the selectivity of the catalyst is remarkably improved, and the dry gas yield and the coke yield are remarkably lowered. The particle size distribution of the catalyst may be a particle size distribution of a conventional catalytic cracking 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 grouping of the coarse particle size distribution catalyst is such that the volume ratio of the particles smaller than 4 μm to the total particles is less than about 1%, preferably less than about 5%: the particles larger than 80 μm account for the volume of all the particles. The ratio is less than about 15%, preferably less than about 1%, and the balance is 40 to 80 microns. In a more preferred embodiment, the reactor is selected from the group consisting of a riser, a 13-201217512 line-rate fluidized bed, an equal diameter fluidized bed 'upstream conveyor line, and a down conveyor line. Combinations of the above, or a combination of two or more of the same reactors, the combination comprising series or/and parallels, 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 reactor at one location or the feedstock oil is introduced into the reactor at one or more locations of the same or different heights. In a more preferred embodiment, the process further comprises separating the reaction product from the catalyst. The catalyst is stripped, charred, and returned to the reactor. The separated product comprises high hexadecane diesel and catalytic wax oil. In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 340 ° C and a hydrogen content of not less than 10.8% by weight. In a more preferred embodiment, the catalytic eucalyptus oil is a fraction having an initial boiling point of not less than 3 50 ° C, and the catalytic wax oil has a hydrogen content of not less than 11.5%. In still another aspect of the present invention, there is provided a process for improving catalytic conversion of a diesel cetanequinone drum, characterized in that the process comprises relatively uniform activity of the feedstock oil in the catalytic conversion reactor with the predominantly large pore-containing zeolite. The catalyst is contacted to carry out the reaction, wherein the reaction temperature, the residence time of the oil and gas, and the weight ratio of the catalyst to the feedstock oil are sufficient for the reaction to obtain a reaction product comprising diesel fuel, about 12 to about 60% by weight of the catalytic oil of the feedstock oil, wherein the reaction temperature From about 420 to about 5 50 ° C, the hydrocarbon residence time is from about 0.1 to about 5 seconds, the catalyst to feedstock weight ratio is from about 1 to about 1 Torr; and the catalytic wax oil is brought into full or part of the conventional The catalytic cracking or reduction riser reaction-14-201217512 further produces a product comprising diesel and gasoline, or/and the catalytic wax oil is returned to the original catalytic conversion reactor or fed to another catalytic conversion reactor. In a more preferred embodiment, the reaction temperature is from about 430 to about 500 ° C', preferably from about 430 to about 480 °C. In a more preferred embodiment, the hydrocarbon residence time is from about 0.5 to about 4 seconds' preferably from about 〇8 to about 3 seconds. In a more preferred embodiment, the catalyst to feedstock weight ratio is from about 2 to about 8, preferably from about 3 to about 6. In a more preferred embodiment, the reaction pressure is from about 0.1 OMPa to about 1.0 MPa, preferably from about 0.15 MPa to about 0-6 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 reduced pressure gas oils, normally compressed gas oils, coker gas oils, deasphalted oils, One or a mixture of two or more of vacuum residue and atmospheric residue, and other mineral oils are one or a mixture of two or more of coal liquefied oil, oil sand oil, and shale oil. In a more preferred embodiment, the catalyst comprising predominantly large pore zeolite comprises zeolite, inorganic oxide, clay. On a dry basis, each component comprises from about 5 wt% to about 50 wt%, preferably from about 1 wt% to about 30 wt%, of the zeolite, and from about 5 wt% to about 5 wt%. ; clay 〇 weight ~ about 7 〇 wt%. Among them, zeolite is used as an active fraction and is selected from a large pore zeolite. The large pore zeolite refers to one or a mixture of two or more of the zeolites composed of rare earth Y, rare earth hydrogen γ, and ultra-stable Y and sorghum γ obtained by different methods. The inorganic oxide is used as a substrate selected from the group consisting of cerium oxide (SiO 2 ) and/or tri- 15 - 201217512 aluminum oxide (Al 2 〇 3 ). In the inorganic oxide, cerium oxide accounts for from about 50% by weight to about 90% by weight based on the dry basis, and aluminum oxide accounts for from about 10% by weight to about 5% by weight. As an adhesive, clay is selected from one or more of kaolin, kaolin, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Kind. The relatively homogeneous catalyst (including catalytic cracking catalyst and prolific diesel catalyst) means that its initial activity does not exceed about 80, preferably does not exceed about 75, more preferably does not exceed about 70; the self-equilibration time of the catalyst is about 0. From 1 hour to about 50 hours, preferably from about 0.2 to about 30 hours, more preferably from about 0.5 to about 10 hours: an equilibrium activity of from about 35 to about 60, preferably from about 40 to about 55. The initial activity of the catalyst 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: enterprise standard RIPP 92-90 - micro-reaction activity test method of catalytic cracking fresh catalyst "Petrochemical analysis method (R IP P test method)", Yang Cuiding et al., 1990, below Referred to as RIPP pa-go. The initial activity of the catalyst is represented by the light oil micro-reaction activity ( Μ A ), which is calculated as Μ A = (gasoline production below the 204 ° C + gas production + coke production) / total amount of feed * 1 〇 〇% = gasoline yield + gas yield + coke yield below 200 °C in the product. The light oil micro-reverse device (refer to RIPP 92-90) is evaluated as: the catalyst is broken into particles having a particle diameter of about 420 to 841 μm, the loading is 5 g, and the reaction raw material is a distillation range of 23 5 to 3 3 7 t. The straight-run light diesel oil has a reaction temperature of 460 ° C and a weight space velocity of 16 hours_ι, a ratio of agent to oil of 3.2. -16 - 201217512 The catalyst self-equilibration time refers to the time required for the catalyst to age to reach equilibrium activity at 800 ° C and 1 〇 〇 % water vapor conditions (refer to RI Ρ Ρ 9 2 - 9 Ο). 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, A catalyst having a relatively uniform activity after aging in a certain hydrothermal environment; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The treatment method 1 is embodied, for example, as follows: The fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, water vapor is injected into the bottom of the fluidized bed, and the catalyst is fluidized by the action of water vapor, while water The catalyst is aged by steam, and the aging temperature is from about 400 ° C to about 850 ° C, preferably from about 50,000 ° C to about 750 ° C, preferably from about 60 ° C to about 7 ° C. The fluidized bed has an apparent line speed of from about 0.1 m/sec to about 0.6 m/sec, preferably from about 0.15 seconds to about 0.5 m/sec, and aged from about 1 hour to about 720 hours, preferably from about 5 hours to about 3 hours after 60 hours. 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. Catalyst treatment method 2: (1), the fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and contacted with an aging medium containing water vapor, and the activity is relatively obtained after aging in a certain hydrothermal environment -17-201217512 a homogeneous catalyst; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The technical solution of the catalyst treatment method 2 is, for example, such that the catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and an aging medium containing water vapor is injected into the bottom of the fluidized bed, and the catalyst acts on an aging medium containing water vapor. The fluidization is carried out while the aging medium containing water vapor ages the catalyst at an aging temperature of about 40 (TC~about 850 ° C, preferably about 500 ° C to about 750 ° C, preferably about 600 ° C to about 70 ( TC, the apparent linear velocity of the fluidized bed is from about 0.1 m/s to about 0.6 m/s, preferably from about 0.15 seconds to about 0.5 m/s, and the weight ratio of water vapor to the aged medium is from about 0-20 to about 0.9. Preferably, from about 0.40 to about 0. 60, after aging for about 1 hour to about 720 hours, preferably from about 5 hours to about 366 hours, the catalyst having relatively uniform activity is obtained, and the catalyst having relatively relatively uniform activity is industrially The requirements of the device are added to the industrial device, preferably to the regenerator of the industrial device. 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 water vapor to aging medium is from about 0.2 to about 0.9, preferably from about 0.40 to about 0.60. Catalyst treatment method 3: (1), the fresh catalyst is input to a fluidized bed, preferably a dense phase fluidized bed, while regenerating The hot regenerated catalyst is delivered to the fluidized bed for heat exchange in the fluidized bed; (2) the fresh catalyst after heat exchange is in contact with water vapor or aging medium containing water vapor-18-201217512 - obtaining a catalyst having relatively uniform activity after aging in a hydrothermal environment; (3) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The technical solution of the present invention is embodied as follows: The fresh catalyst is delivered to the fluidized bed 'preferably in a dense fluidized bed' while the hot regenerated catalyst of the regenerator is also delivered to the fluidized bed' for heat exchange within the fluidized bed. At the bottom of the fluidized bed An aging medium that injects steam or water vapor. 'Fresh catalysts are fluidized by the aging medium of steam or water vapor'. At the same time, the aging medium of steam or water vapor is new. The fresh catalyst is aged, and the aging temperature is about 4 ° C to about 850 ° C. Preferably, about 500 ° C to about 75 ° C, preferably about 60 ° C to about 7 ° C. The apparent line speed of the fluidized bed is from about 0.1 m/s to about 0.6 m/s, preferably from about 0.15 seconds to about 〇. 5 m/sec, aged from about 1 hour to about 720 hours, preferably about 5小时~约约约约约约约约约约约约约约5。 5 The catalyst having a relatively uniform activity, 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. In addition, the water vapor after the aging step enters the reaction system (as one of the stripping steam, the anti-coke steam, the atomized steam, the elevated steam, or the stripper, the settler, the raw material nozzle, respectively, which enters the catalytic cracking unit, 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, regeneration -19-201217512 flue gas, air or dry gas burning gas or air and combustion oil burning gas, 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, the selectivity of the catalyst is remarkably improved, and the dry gas yield and the coke yield are remarkably lowered. The particle size distribution of the catalyst may be a particle size distribution of a conventional catalytic cracking 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 grouping of the coarse particle size distribution catalyst is such that the volume ratio of particles smaller than 40 μm to all particles is less than about 1%, preferably less than about 5%; and the particles larger than 80 μm account for a lower proportion of all particles. About about 5%, preferably less than about 10%, the balance being 40 to 80 microns. For a more detailed description of the reduced-diameter riser reactor fed with the catalytic wax oil, see CN 1 2 3 7477A » In a more preferred embodiment, the catalytic wax oil is fed to another conversion reactor for cracking The reaction, the generated oil and gas undergo hydrogen transfer reaction and isomerization reaction under a certain reaction environment, and the reaction product including the low olefin gasoline is separated into two reaction zones, and the reaction conditions of each reaction zone are as follows: The first reaction zone is mainly subjected to a cracking reaction at a reaction temperature of about 480 t to about 600 ° C, preferably about 48 5 to about 580 ° C, and a reaction time of about 0.1 to about 3 seconds, preferably about 〇 5 to about 2 seconds. The weight ratio of the harsh conversion catalyst to the catalytic wax oil is from about 0.5 to about 25:1, preferably from about 1 to about 15:1; the weight ratio of the pre-lifting medium to the catalytic wax oil is from about 〇·〇1 to about 2:1. Preferably, the reaction is from about 0.05 to about 1:1; the reaction is from -20 to 201217512 and the pressure is from about 130 to about 45 kPa, preferably from about 2,500 to about 400 kPa. The second reaction zone mainly performs a hydrogen transfer reaction and an isomerization reaction 'reaction temperature of about 45 0 Ό to about 550 ° C, preferably about 460 to about 530 ° C; maintaining a dense phase operation in the second reaction zone' The dense phase density of the catalyst bed is from about 100 to about 750 kg/m3, preferably from about 120 to about 500 kg/m3; the weight hourly space velocity of the second reaction zone is from about 1 to about 50 hours _1, preferably From about 1 to about 40 hours·1; the reaction pressure is from about 1 30 to about 4,500 kPa, preferably from about 2,500 to about 4,000 kPa. In a more preferred embodiment, the method further comprises separating the other conversion reaction product and the conversion catalyst, and the conversion catalyst is subjected to stripping, charring regeneration, and returned to the other conversion reactor, and the separated product includes low Olefin gasoline, etc. In a more preferred embodiment, the 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 down conveyor line, Or a combination of two or more reactors of the same type, including series or/and parallel, 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 reactor at one location, or the feedstock oil is introduced into the reactor at one or more locations of the same or different heights. In a more preferred embodiment, the process further comprises separating the reaction product from the catalyst. The catalyst is stripped, charred, and returned to the reactor. The product after separation comprises high hexadecane diesel and catalytic wax oil. In a more preferred embodiment, the catalytic wax oil is not less than the initial boiling point - 21 - 201217512 to 3 3 (the fraction of TC, the hydrogen content is not less than 1 〇 8% by weight. In a more preferred embodiment The catalytic eucalyptus oil is a fraction at 350 ° C, and the catalytic wax oil has a hydrogen content of not less than 1: In another aspect of the present invention, a catalytic conversion method for extracting a hydrazine barrel is provided, Characterized in that the process oil is reacted in a catalytic conversion reactor with a living catalyst mainly containing a large pore zeolite, wherein the reaction temperature, the weight ratio of the hydrocarbon catalyst to the feedstock oil is sufficient to allow the reaction to obtain from about 12 to about 60% by weight of the diesel fuel. Catalyzing the reaction product of the wax oil at a temperature of about 420 to about 550 ° C, the hydrocarbon residence time is about 〇 _ the catalyst to feedstock oil weight ratio of about 1 to about 1 〇; its special catalytic wax oil enters all or part of The hydrocracking unit is further alkane diesel. In a preferred embodiment, the treated hydrogenation is re-entered into a conventional catalytic cracking or reduction riser reactor to include diesel and gasoline products. In a preferred embodiment The tail oil can be returned to the catalytic conversion reactor. In a more preferred embodiment, the reaction temperature is about 43 0<at preferably about 430 to about 480 C. In a more preferred embodiment, the hydrocarbon residence time is about 'preferably about 0.8~ About 3 seconds. In a more preferred embodiment, the catalyst is from about 8 to about 8, preferably from about 3 to about 6. In a more preferred embodiment, the reaction pressure is about 0. The initial boiling point is not less than 1.5%. 6 includes relatively uniform residence time of the raw material, oil, and the reaction in the raw material for 1 to about 5 seconds, which is characterized in that the production of the high-six cracking tail oil can be produced in one step, hydrocracking, about 500 ° C, I 0.5 to about 4 seconds & weight ratio of about 2 • 1 OMPa to about -22-201217512 l.OMPa, preferably about 0-15 MPa to about 0.6 MPa. In a more preferred embodiment, the stock oil is selected from or included Petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from one or more of a reduced pressure gas oil, a normally compressed gas oil, a coking gas oil, a deasphalted oil, a vacuum oil, and a normal oil. Mixture, other mineral oils are coal liquefied oil, oil sand oil One or a mixture of two or more of shale oils. In a more preferred embodiment, the catalyst mainly comprising large pore zeolite comprises zeolite, inorganic oxide, clay, and each component accounts for the catalyst on a dry basis. Total weight: about 5 to about 50% by weight of the zeolite, preferably about 1 to about 30% by weight; from about 0.5 to about 50% by weight of the inorganic oxide: from 0 to about 70% by weight of the clay. The active fraction is selected from the group consisting of large pore zeolites, and the large pore zeolite refers to one or more of the group of zeolites composed of rare earth Y, rare earth hydrogen Y, super stable Y obtained by different methods, and high yttrium Y. mixture. The inorganic oxide is used as a substrate selected from the group consisting of cerium oxide (Si〇2) and/or aluminum oxide (Al2〇3). In the inorganic oxide, cerium oxide accounts for from about 50% by weight to about 90% by weight based on the dry basis, and aluminum oxide accounts for from about 10% by weight to about 5% by weight. As an adhesive, clay is selected from one or more of kaolin, kaolin, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Kind. The relatively homogeneous catalyst (including catalytic cracking catalyst and prolific diesel catalyst) means that its initial activity does not exceed about 80, preferably does not exceed about 75, more preferably does not exceed about 70; the self-equilibration time of the catalyst From about -23 to 201217512, from 0.1 hour to about 50 hours, preferably from about 0.2 to about 30 hours, more preferably from about 0.5 to about 10 hours; and an equilibrium activity of from about 35 to about 60, preferably from about 40 to about 55. The initial activity of the catalyst 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: enterprise standard RIPP 92-90 - micro-reaction activity test method for catalytic cracking fresh catalyst "Petrochemical Analysis Method (RIPP Test Method)", Yang Cuiding et al., 1 990, hereinafter referred to as RIPP 92-90. The initial activity of the catalyst is represented by the light oil micro-reaction activity (MA), which is calculated as MA = (gasoline production below the 204 ° C + gas production + coke production) / total amount of feed * 1% = gasoline yield below the ° ° ° C + gas yield + coke yield. The light oil micro-reverse device (refer to RIPP 92-90) is evaluated by crushing the catalyst into particles having a particle diameter of about 420-841 μm and having a capacity of 5 g. The reaction raw material is a straight line of 235-337 ° C. The light diesel oil is distilled at a reaction temperature of 460 ° C, a weight space velocity of 16 hours -1, and a ratio of the agent to the oil of 3 · 2. The catalyst self-equilibration time refers to the time required for the catalyst to age at 800 ° C and 1 〇〇 % water vapor conditions (refer to RIPP 92-90) to achieve equilibrium activity. The catalyst having a relative activity can be obtained, for example, by the following three treatment methods: Catalyst treatment method 1: (1) charging a 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 relatively uniform activity is obtained: -24 - 201217512 (2), the catalyst having relatively uniform activity is added to the corresponding reaction device. The treatment method 1 is embodied, for example, as follows: The fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, water vapor is injected into the bottom of the fluidized bed, and the catalyst is fluidized by the action of water vapor, while water The catalyst is aged by steam, and the aging temperature is about 400 ° C to about 8 5 0 ΐ: preferably from about 50,000 ° C to about 750 ° C, preferably from about 60 ° C to about 70 ° C. The apparent linear velocity of the fluidized bed is from about 0.1 m/sec to about 0.6 m/sec, preferably from about 〇·15 sec to about 0 m 5 m/sec, and aged from about 1 hour to about 720 hours, preferably about 5 After an hour to about 3 60 hours, the catalyst having a relatively uniform activity is obtained, and the catalyst having a relatively uniform activity is added to an industrial plant, preferably to a regenerator of an industrial plant, as required by an industrial plant. Catalyst treatment method 2: (1), the fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and contacted with an aging medium containing water vapor, and aging is performed under a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The technical solution of the catalyst treatment method 2 is, for example, embodied in this way.

The catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and an aging medium containing water vapor is injected into the bottom of the fluidized bed, and the catalyst is fluidized under the action of an aging medium containing water vapor, and at the same time, the aging medium of the water vapor is The catalyst is aged, and the aging temperature is from about 4,000 ° C to about 850 ° C, preferably from about 50,000 ° C -25 to from 2012, 175 00 00 to about 75 ° C, preferably from about 600 ° C to about 7 ° C. The fluidized bed has an apparent line speed of from about 0.1 m/sec to about 0.6 m/sec, preferably from about 0.15 seconds to about 0.5 m/sec, and a weight ratio of water vapor to aged medium of from about 0.20 to about 0.9, preferably from about 0.40 to about 0.60, aging for about 1 hour to about 720 hours, preferably about 5 hours to about 366 hours, to obtain the catalyst having relatively uniform activity, and the catalyst having relatively uniform activity is added to the industry according to the requirements of industrial equipment. The apparatus is preferably added to the regenerator of the industrial unit. 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 water vapor to aging medium is about 0 .2 to about 0 · 9, preferably about 0 · 40 0 to about 0 · 60. Catalyst treatment method 3: (1), input fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while regenerating the regenerator The hot regenerated catalyst is delivered to the fluidized bed for heat exchange in the fluidized bed; (2) the fresh catalyst after heat exchange is in contact with the aging medium of steam or water vapor, in a certain hydrothermal environment After aging, a catalyst having relatively uniform activity is obtained; (3) a catalyst having a relatively uniform activity is added to the corresponding reaction device. The technical solution of the present invention is specifically embodied as follows: conveying fresh catalyst to fluidization The bed, preferably in a dense phase fluidized bed, simultaneously delivers the thermal regenerated catalyst of the regenerator to the fluidized bed for heat exchange within the fluidized bed. Injecting water vapor or water vapor at the bottom of the fluidized bed The aging medium, the fresh catalyst in the water vapor or water vapor aging -26- 201217512 medium to achieve fluidization 'simultaneous' water vapor or water vapor aging medium to age the fresh catalyst, aging The temperature is about 40 ° C to about 8 50 ° C, preferably about 50,000 ° C ~ about 7 5 0 ° C 'preferably about 60 ° C ~ about 70 ° C, the table of the fluidized bed The line speed is about 1 m / s to about 〇 · 6 m / sec, preferably about 〇 · 1 5 seconds ~ about 〇 · 5 m / sec, aging about 1 hour ~ about 7 2 0 hours, preferably about 5 hours ~ about 3 60 hours, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aging medium is greater than about 〇 ~ about 4, preferably from about 0 · 5 to about 1.5, obtained in the Catalysts having relatively uniform activity, relatively active catalysts are added to industrial plants as required by industrial plants, preferably to regenerators of industrial plants. In addition, the water vapor after the aging step enters the reaction system (as one of the stripping steam, the anti-coke steam, the atomized steam, the elevated steam, or the stripper, the settler, the raw material nozzle, respectively, which enters the catalytic cracking unit, 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 after combustion of air and dry gas, or gas after combustion of combustion oil, or other gases such as nitrogen. By the above treatment method, the activity and selectivity distribution of the catalyst in the industrial reactor are more uniform, and the selectivity of the catalyst is remarkably improved', whereby the dry gas yield and the coke yield are remarkably lowered. The particle size distribution of the catalyst may be a particle size distribution of a conventional catalytic cracking 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 catalyst is grouped into: less than 40 micrometers -27 - 201217512 particles accounted for less than about 1% by volume of all particles, preferably less than about 5%: particles larger than 80 microns account for all particles The volume ratio is less than about 1 5%, preferably less than about 10%, and the balance is 40 to 80 micron particles. A more detailed description of the reduced diameter riser reactor to which the catalytic wax oil is fed is provided in CN 1 237 477 A. In a more preferred embodiment, the 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 down conveyor line, Or a combination of two or more reactors of the same type, including series or/and parallel, 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 reactor at one location' or the feedstock oil is introduced into the reactor at one or more locations of the same or different heights. In a more preferred embodiment, the method further comprises separating the reaction product from the catalyst, and the catalyst is stripped and charred and returned to the reactor. The separated product comprises high hexadecane diesel and catalytic eucalyptus oil. In a more preferred embodiment, the catalytic eucalyptus oil is not less than 3 3 (the fraction of TC, the hydrogen content is not less than 1 〇. 8 wt%. In a more preferred embodiment, the catalytic wax The oil is a fraction having an initial boiling point of not less than 305 ° C. The hydrogen content of the catalytic wax oil is not less than π. 5 %. The reaction system of the hydrocracking unit usually includes a refining reactor and a cracking reactor. The bed reactor may also be a reductive reactor and a cracking reaction generally equipped with a refining catalyst and a hydrocracking catalyst as described in other types of reactors -28-201217512. The hydrotreating catalyst is supported on amorphous alumina. Or a group VIB or/and a Group VIII non-noble metal catalyst on a ruthenium support; the hydrocracking catalyst is a Group VIB or/and Group VIII non-noble metal catalyst supported on a molecular sieve. The Group VIB non-precious metal is molybdenum Or / and tungsten; the Group VIII non-noble metal is one or more of nickel, cobalt, iron. The hydrocracking catalyst supported molecules are selected from Y type molecular sieves, /3 type molecular sieves, ZSM-5 type molecular sieves, SAPO Series of molecular sieves One or more of the hydrocracking process conditions are: hydrogen partial pressure of about 4.0 to about 20.0 MPa - reaction temperature of about 280 to about 450 ° C, volumetric space velocity of about 0.1 to about 20 hours", hydrogen to oil ratio 300 to about 2000 v/v. The hydrogen to oil ratio in the present invention refers to the volume ratio of hydrogen to catalytic wax oil. In another aspect of the present invention, there is provided a catalytic conversion method for improving diesel cetanequinone barrel, Characterized in that the method comprises reacting a feedstock oil in a catalytic conversion reactor with a catalyst having a relatively uniform activity of a predominantly large pore zeolite, wherein the reaction temperature, the residence time of the hydrocarbon, and the weight ratio of the catalyst to the feedstock are sufficient to allow the reaction to be included Diesel oil, which comprises from about 12 to about 60% by weight of the reaction product of the catalytic wax oil, wherein the reaction temperature is about 4 2 0 to about 550 ° C, and the hydrocarbon residence time is about 0.1 to about 5 seconds. The weight ratio of the catalyst to the feedstock oil is from about 1 to about 1 Torr; and the catalytic wax oil is wholly or partially introduced into the hydrotreating unit for further treatment to obtain a high quality hydrogenated catalytic wax oil. In a preferred embodiment The treated hydrocatalytic wax oil can be further processed into a conventional catalytic cracking or reduction riser reactor to further produce a product including diesel and gasoline. -29-201217512. In a preferred embodiment, the hydrogenated catalytic wax oil can be Returning to the catalytic conversion reactor. In a more preferred embodiment, the reaction temperature is from about 430 to about 500 ° C, preferably from about 430 to about 480 C. In a more preferred embodiment, the hydrocarbon residence time is from about 0.5 to about 4 seconds, preferably. 8〜约3秒。 In a more preferred embodiment, the catalyst to feedstock weight ratio of from about 2 to about 8, preferably from about 3 to about 6. In a more preferred embodiment, the reaction pressure is about O.10MPa ~ about 1.0 MPa, preferably about 0.15 MPa to about 0.6 MPa. In a more preferred embodiment, the hydrocracking tail oil of the catalytic wax oil is fed to a conventional catalytic cracking or/and variable diameter riser reactor, or/and the present catalytic converter, or/and the hydrocracking unit for further processing. 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 reduced pressure gas oils, normally compressed gas oils, coker gas oils, and celite oils. One or a mixture of two or more of vacuum oil and atmospheric residue, and other mineral oils are one or a mixture of two or more of coal liquefied oil, oil sand oil, and shale oil. In a more preferred embodiment, the catalyst comprising predominantly large pore zeolite comprises zeolite, inorganic oxide, clay. On a dry basis, the components comprise, respectively, the total weight of the catalyst: from about 5 to about 50% by weight of the zeolite, preferably from about 1 to about 30% by weight; from about 0.5 to about 50% by weight of the inorganic oxide: The clay has a weight of from 0 to about 70% by weight. Among them, zeolite is used as an active fraction and is selected from the group consisting of macroporous -30-201217512 zeolite. The large pore zeolite refers to one or a mixture of two or more of the group of zeolites consisting of rare earth γ, rare earth hydrogen γ, and different methods. The inorganic oxide is used as a substrate selected from the group consisting of cerium oxide (Si 〇 2 ) and/or aluminum oxide (A12 Ο 3 ). In the inorganic oxide, cerium oxide accounts for from about 50% by weight to about 90% by weight based on the dry basis, and aluminum oxide accounts for from about 1% by weight to about 5% by weight. As an adhesive, clay is selected from one or more of kaolin, kaolin, montmorillonite, diatomaceous earth, halloysite, stiletto, sepiolite, attapulgite, hydrotalcite, and bentonite. Kind. The relatively homogeneous catalyst (including catalytic cracking catalyst and prolific diesel catalyst) means that its initial activity does not exceed about 80, preferably does not exceed about 75, more preferably does not exceed about 70; the catalyst has a self-equilibration time of about 0.1. From about 0 to about 50 hours, preferably from about 0. 2 to about 30 hours, more preferably from about 0.5 to about 10 hours; and an equilibrium activity of from about 35 to about 60, preferably from about 40 to about 55. The initial activity of the catalyst 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 micro-reaction activity test method of the catalytic cracking fresh catalyst "Petrochemical Analysis Method (RIPP Test Method)", Yang Cuiding et al., 199 〇, hereinafter referred to as RIPP 92-90. The initial activity of the catalyst is represented by light oil micro-reaction activity (MA)', which is calculated as MA = (gasoline production below the 204 °C + gas production + coke production) / total feed * 1 0 0 % = gasoline yield below the 2 0 4 °C + gas yield + coke yield. The light oil micro-reverse device (refer to RIP P 92- -31 - 201217512 90) is evaluated by crushing the catalyst into particles having a particle diameter of about 420 to 841 μm, and the loading amount is 5 g. The reaction raw material is a distillation range of 235~ Straight-run light diesel oil at 337 °C, reaction temperature 460 °C 'weight airspeed is 16 hours η, ratio of agent to oil 3.2. The catalyst self-equilibration time refers to the time required for the catalyst to age to reach equilibrium activity at 800 ° C and 100% water vapor conditions (refer to RIPP 92-90). 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, A catalyst having a relatively uniform activity after aging in a certain hydrothermal environment; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The treatment method 1 is embodied, for example, as follows: The fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, water vapor is injected into the bottom of the fluidized bed, and the catalyst is fluidized by the action of water vapor, while water The catalyst is aged by steam, and the aging temperature is from about 400 ° C to about 850 ° C, preferably from about 50,000 ° C to about 75 ° C, preferably from about 60 ° C to about 70 ° C. The fluidized bed has an apparent line speed of from about 0.1 m/sec to about 0.6 m/sec, preferably from about 0.15 seconds to about 0.5 m/sec, and aged from about 1 hour to about 720 hours, preferably from about 5 hours to about 360 hours. The catalyst having relatively uniform activity is obtained, and the catalyst having relatively uniform activity is added to the industrial device - 32 - 201217512 as required by the industrial device, preferably to the regenerator of the industrial device. Catalyst treatment method 2: (1), the fresh catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and contacted with an aging medium containing water vapor, and aging is performed under a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) adding the catalyst having a relatively uniform activity to the corresponding reaction device. The technical solution of the catalyst treatment method 2 is, for example, such that the catalyst is charged into a fluidized bed, preferably a dense phase fluidized bed, and an aging medium containing water vapor is injected into the bottom of the fluidized bed, and the catalyst acts on an aging medium containing water vapor. The fluidization is carried out, and at the same time, the aging medium containing water vapor ages the catalyst and the aging temperature is about 4 Torr. (: ~ about 8 5 0 X:, preferably about 50,000 ° C ~ about 75 ° ° C 'preferably about 600 ° C ~ about 70 (TC, the apparent line speed of the fluidized bed is about 0 · 1 m / Seconds ~ about 0 · 6 m / s, preferably about 0 i 5 seconds ~ about 米 5 m / s, the weight ratio of water vapor to aging medium is about 〇 2 〇 ~ about 〇 · 9, preferably about 〇. 4 〇 ~ About 0.60' aging for about 1 hour to about 72 hours, preferably about 5 hours to about 36 hours, to obtain a catalyst having relatively uniform activity, and a catalyst having relatively uniform activity is added to an industrial device according to the requirements of an industrial device. Preferably, it is added to a regenerator of an industrial unit. The aging medium includes air, dry gas, regenerated flue gas, a gas after combustion of air and dry gas, or a gas after combustion of the combustion oil, or other gas such as nitrogen. The weight ratio of the vapor to the aging medium is from about 〇2 to about 0.9, preferably from about 0.40 to about 0.60. Catalyst Treatment Method 3: -33- 201217512 (1), the fresh catalyst is fed to the fluidized bed, preferably the dense phase fluidized bed. At the same time, the thermal regeneration catalyst of the regenerator is delivered to the fluidized bed, and heat is exchanged in the fluidized bed. (2), the fresh catalyst after heat exchange is contacted with the aging medium of steam or water vapor, and the catalyst is relatively uniform after being aged in a certain hydrothermal environment; (3) the activity is relatively uniform The catalyst is added to the corresponding reaction device. The technical solution of the invention is embodied, for example, by: feeding the fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while conveying the thermal regeneration catalyst of the regenerator to the reactor The fluidized bed is subjected to heat exchange in the fluidized 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 water vapor or water vapor aging the fresh catalyst at an aging temperature of about 4 ° C to about 8 50 ° C, preferably about 500 ° C to about 750 t: preferably about 600 ° C to about 700 °. C, the fluidized bed has an apparent line speed of from about 0.1 m/sec to about 0.6 m/sec, preferably from about 0.15 seconds to about 0.5 m/sec, and aged from about 1 hour to about 720 hours, preferably from about 5 hours to about 3 60 hours, In the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aging medium is greater than about 〇~about 4', preferably from about 0.5 to about 1.5, to obtain a catalyst having relatively uniform activity and relatively uniform activity. According to the requirements of the industrial device, it is added to the industrial device, preferably to the regenerator of the industrial device. In addition, the water vapor after the aging step enters the reaction system (as stripping steam, anti-coke steam, atomizing steam, lifting steam -34 - One or more of the 201217512 stripping, feedstock nozzles, pre-lift sections, or regeneration systems, respectively, entering the catalytic cracking unit, and the aged medium of the aged water vapor enters the regeneration system and is returned to the regenerator after heat exchange. The aging medium includes air, flue gas, air and dry gas or air and combustion gas, or other gases such as nitrogen. By the above treatment method, the catalytic and selective distribution in the industrial reaction apparatus is more uniform, and the selectivity of the catalyst is obtained so that the dry gas yield and the coke yield are remarkably lowered. The particle size distribution of the catalyst may be a conventional catalytic crack particle size distribution or a coarse particle size distribution. More preferably, the catalyst is characterized in that the sieve grouping of the catalyst having the coarse particle size distribution and the coarse particle size distribution is: the volume ratio of the particles to all the particles is less than about 10%, preferably: greater than 8 The 0 micron particles account for less than about 1% by volume of all particles, and the rest are 40 to 80 micron particles. The catalytic converter is fed with a reduced diameter riser reactor. See CN 1 2 3 747 7A. In a more preferred embodiment, the reactor is selected from the group consisting of a line-rate fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, or a combination of one or more, or one or more In combination, the combination comprises a tandem or/and the riser is a conventional equal diameter riser or various forms of tube. After the step, the regenerated catalyst containing the regenerated catalyst and the regenerated oil are significantly improved in the activity of the chemical agent. Less than 40 microns is selected to be less than about 5% i at about 15%, and the crucible is i-thin, the riser, the isoline, and the down reactor are connected in parallel, wherein the reduction of the diameter is -35-201217512. In an embodiment, the feedstock oil is introduced into the reactor at one location' or the feedstock oil is introduced into the reactor at one or more locations of the same or different heights. In a more preferred embodiment, the method further comprises separating the reaction product from the catalyst, and the catalyst is subjected to stripping, charring regeneration, and returned to the reactor, the separated product comprising high hexadecane diesel and catalytic eucalyptus oil. In a more preferred embodiment, the catalytic eucalyptus oil is a fraction having an initial boiling point of not less than 3 30 ° 〇: and a hydrogen content of not less than 10.8% by weight. In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 3 50 ° C, and the catalytic wax oil has a hydrogen content of not less than 1 1.5%. The reaction system of the hydrotreating unit is usually a fixed bed reactor, and other types of reactors can also be used. The catalytic wax oil hydrogenation catalyst composition is composed of a metal of Group VI and VI B of the periodic table, and alumina and zeolite as carriers. Specifically, the hydrogenation catalyst contains a support and molybdenum and/or tungsten and nickel and/or cobalt supported on the support. The content of molybdenum and/or tungsten in the hydrogenation catalyst is from about 10 to about 35 wt%, preferably from about 18 to about 32 wt%, based on the total amount of the catalyst, nickel and/or cobalt. The content is from about 1 to about 15% by weight, preferably from about 3 to about 12% by weight. The support is comprised of alumina and zeolite, and the weight ratio of alumina to zeolite is from about 90:10 to about 50:50, preferably from about 90:10 to about 60:40. The alumina is a composite of alumina and macroporous alumina in a weight ratio of from about 75:25 to about 50:50, wherein the small pore alumina has a diameter of less than 80 A. The pore volume accounts for about 95% or more of the total pore volume of alumina, and the pore volume of the macroporous alumina of 60 to 600 A pores accounts for -36-201217512 total pore volume of about 70% or more of alumina. The zeolite is selected from one or more of faujasite, mordenite, erionite, L-type zeolite, omega zeolite, ZS Μ-4 zeolite, β zeolite, preferably Υ type zeolite 'particularly preferred zeolite is total acid amount From about 0. 0 2 to less than about 〇. 5 mmol/g, preferably about 〇. 〇5 to about 〇·2 mmol/g of the cerium type zeolite. The process conditions of the hydrotreating are: hydrogen partial pressure of about 3. 〇~about 2 0.0 Μ P a, the reaction temperature is about 280 ° to about 4 5 0 ° C, and the volumetric space velocity is about 〇. 1~about 2 0 Hour_1 'hydrogen oil ratio is about 300 to about 2000 v/v. The hydrogen to oil ratio in the present invention refers to the volume ratio of hydrogen to catalytic wax oil. The preparation method of the catalytic wax oil hydrogenation catalyst comprises: mixing a precursor of alumina with zeolite, calcining, impregnating with an aqueous solution containing nickel and/or cobalt and molybdenum and/or tungsten, and then drying and calcining, the alumina The precursor of the pores having a pore diameter of less than 80 angstroms and having a pore volume of about 95% or more of the total volume of the pores and the pore diameter of the pores having a pore diameter of 60 to 600 angstroms is about 70% of the total pore volume. The above mixture of precursors of macroporous alumina, small pore alumina precursor, macroporous alumina precursor and zeolite are used in an amount such that the weight ratio of small pore alumina to macroporous alumina in the catalyst is about 7 5 : 2 5 ~ about 50:50, the ratio of the total weight of alumina to the weight of the zeolite is about 90:1 0~about 5 0 : 5 0, preferably about 9 0 : 1 0 to about 6 0 : 4 0. The precursor of the small pore alumina is hydrated alumina having a boehmite content of greater than about 60% by weight, and the precursor of the macroporous alumina is hydrated alumina having a boehmite content of greater than about 50% by weight. The technical solution combines catalytic cracking, hydrotreating and hydrocracking processes to maximize the production of high-grade diesel fuel from heavy raw materials with low hydrogen content. Compared with the prior art, the present invention has the following technical effects: 1. By optimally controlling the process parameters and catalyst properties, the alkane, alkyl aromatic hydrocarbon side chain and the like in the raw material are selectively cracked into the product diesel fraction. In order to ensure that the composition of the diesel fraction is mainly alkane, it is finally possible to produce high hexadecane diesel by catalytic conversion; 2. Selective reaction of different hydrocarbons under respective suitable reaction conditions, selectivity of dry gas and coke Improved, the coarse particle size distribution catalyst can further improve the selectivity of dry gas and coke; 3. After the heavy oil is catalytically converted by the method provided by the invention, the obtained catalytic wax oil is mainly an aromatic hydrocarbon component, and its properties vary with the nature of the raw material. The change is small, so the raw materials of the hydrotreating or/and hydrocracking unit are stable, and the operation cycle is correspondingly improved. 4. Because the particles are more uniform, the local temperature distribution is more uniform during the regeneration process, and the catalyst crushing tendency is also Correspondingly reduced; 5, reduced catalyst consumption, catalytic catalyst entrained in wax oil The content is reduced. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains, unless otherwise indicated, although similar or equivalent to those described herein may be used in the practice or testing of the present invention. Methods and materials, but suitable methods and I materials are still described below. In the case of conflict, the patent specification (including definitions) is used. Further, the materials, methods, and examples are illustrative only and not limiting. -38- 201217512 The term "comprising" as used herein means that other steps and ingredients that do not affect the results can be added. The term includes the term "consisting of "consisting essentially of." The term "method" or "process" means the use of specified tasks, means, techniques, and procedures, including but not limited to, chemical and chemical practitioners. Those methods, means, techniques, and procedures that are known or developed by known means, means, techniques, and methods. In the present disclosure, various aspects of the invention may be in a range format. It should be understood that the description of the range format For the sake of convenience and ease of use, it should not be considered as limiting the scope of the invention. Accordingly, the description of the enclosure should be considered to specifically disclose all possible sub-ranges and the number of ranges within the range. For example, The description of such a range to 6 is regarded as specifically disclosing sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, and number-by-numbers within the range, for example 1 3, 4, 5 and 6. This applies regardless of the width of the range. As far as the range of numbers is indicated herein, it is intended to include any recited number (score or integer) of the range indicated. "First show "and" and "between" and "from" All scores and integers between. The invention is described herein by way of example only with reference to the drawings. The detailed description is to be considered in all respect The description and presentation of the terminology of the square domain program indicates that the scope should be the number of the first special case in the case of 3 to 6 2. In the present invention, in addition to the basic understanding of the invention, it is not intended to describe the details of the invention in detail. Forms. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic flow diagram of an embodiment of the invention. Figure 2 is a schematic illustration of one embodiment of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The method provided by the present invention will be further described below with reference to the drawings, but does not limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic flow diagram of an embodiment of the invention. The schematic flow is as follows: As shown in Fig. 1, the feedstock oil enters the catalytic cracking reactor 1' to obtain components such as catalytic diesel oil and catalytic wax oil, wherein the catalytic diesel oil is taken out through the pipeline 5': all or part of the catalytic oil is discharged through the pipeline 6 'And line 8' is taken. Or / and, wherein all or part of the catalytic wax oil is fed to the conventional catalytic cracking or reduction riser reactor 2' via line 6' and line 7' for the production of other products such as diesel and gasoline. Or / and, wherein all or part of the catalytic wax oil is fed to the hydrotreating unit 2' via line 6', line 9' and line 1 ', and the hydrotreated catalytic wax oil is fed to the conventional catalytic cracking via line 1 1 ' or The variable diameter riser reactor 3' is used to produce other products such as diesel and gasoline. Or / and, wherein all or part of the catalytic wax oil is sent to the hydrocracking unit 4' via the line 6', the line 9' and the line 1 2', and the catalytic wax oil hydrocracking tail oil can be taken to the conventional catalytic cracking and change Diameter riser reactor, this device and other anti-40- 201217512 reactors are used to produce other products such as diesel and gasoline. [Embodiment] The method provided by the present invention will be further described below in conjunction with the drawings, but does not limit the present invention. The process flow is as follows: As shown in Fig. 2, the regenerated catalyst is controlled by the regenerative inclined pipe 2, controlled by the slide valve 1 into the pre-lifting section 2 at the bottom of the riser reactor 4, and the pre-lifting medium also enters the pre-lifting section via the pipeline 1. 2. Under the action of the pre-lifting medium, the regenerated catalyst enters the reaction zone I in the lower part of the riser reactor 4 through the pre-lifting section 2, and the catalytic feedstock oil also enters the reaction zone I in the lower part of the riser reactor via the pipeline 3, and is in contact with the catalyst. The reaction proceeds to the reaction zone II. The reacted oil mixture enters the cyclone 7 from the outlet of the riser, is subjected to gas-solid separation by the cyclone 7, and the separated oil and gas enters the settler plenum 6. The carbon-containing spent catalyst separated from the reacted oil and gas is descended into the stripping section 5, and the stripping section 5 is stripped by superheated steam, and the stripped charcoal catalyst is controlled by the slip tube 8' to be controlled by the slide valve 9 The regenerator 10 is regenerated, the main wind enters the regenerator 10 via the pipeline 20, the coke on the catalyst to be produced is burned off, the deactivated catalyst is regenerated, and the flue gas enters the hood through the pipeline 21, and the regenerated catalyst is passed through. The regenerative inclined pipe 1 is controlled by the slide valve 1 to return to the pre-lift section 2 for use. The reaction product oil in the plenum 6 passes through the large oil and gas pipeline 13 and enters the subsequent separation system 14 . The separated dry gas, liquefied gas, gasoline, diesel oil and catalytic wax oil are respectively passed through the pipeline 1 5 , 1 6 ' 1 7, 8 and 1 9 lead. All or part of the catalytic wax oil from line 19 may be optionally taken directly from -41 - 201217512: or / and directly introduced into a conventional catalytic cracking or reduction riser reactor; or / and introduced into a hydrotreating unit to obtain a hydrotreating catalytic wax The oil, hydrotreating catalytic wax oil is fed to the riser reactor; or / and introduced into the hydrocracking reactor. The catalytic wax oil is further processed to obtain the intended product. The method will be further illustrated by the following examples, but does not limit the method. The raw materials used in the examples were reduced pressure gas oil (VGO-D) and atmospheric residue (A R ), and their properties are shown in Table 1.

The catalyst zeolite used in the examples of the present invention is an aging treated cerium zeolite. The sorghum zeolite is prepared as follows: a sample prepared by gas phase treatment of NaY by SiCl4 and rare earth ion exchange, the ratio of lanthanum to aluminum is 18.8, and the rare earth content by RE203 is 2% by weight, and then the sample is at 800. °C, aging treatment under 100% steam. Using 439 grams of deionized water, 969 grams of water kaolin (China Kaolin Company product, solid content 73%) was beaten, and then 718 grams of pseudo-boehmite (Shandong Zibo Aluminum Stone Factory product, solid content 64%) was added. Stir well with 144ml hydrochloric acid (concentration 30%, specific gravity 1.56), stand still at 60 ° C for 1 hour, keep the pH at 2~4, reduce to normal temperature, and then add 800 g of sorghum zeolite (dry basis) prepared in advance. And 2000 grams of chemical water zeolite slurry, stirred evenly, spray dried, washed away free Na + to obtain a catalyst (the fresh catalyst activity of 79, at a temperature of 80 (TC and 100% water vapor conditions, self-equilibration time of 1 〇 hours, the equilibrium activity is 5 5 ). The catalyst is aged at 800 ° C and 100% steam, and the catalyst code after aging is A. The partial aging agent is subjected to decantation to remove fine particles and more than 1000 μη The particles obtained a catalyst having a coarse particle size distribution, which is coded as B-42-201217512. The catalyst properties are listed in Table 2. The commercial brands of the hydrofinishing catalyst and the hydrocracking catalyst used in the examples were RN-2 and RT - 1, both by Chinese stone Catalyst Branch Changling Catalyst Plant produces. EXAMPLE 1 This example illustrates the use of the method provided by the present invention for selective cracking reaction to produce high quality light diesel oil and catalytic wax oil. The flow chart of the medium catalytic cracking unit is shown in Figure 2. The feedstock oil VG Ο - D is injected into the riser reactor via line 3, and is contacted and reacted with the catalyst B raised by the steam in the lower portion of the riser reactor. The weight ratio of the catalyst B to the feedstock in the riser reactor is 4 : 1, the residence time of the feedstock in the riser reactor is 1.6 seconds, the reaction temperature is 460 ° C. The pressure of the plenum is 〇 · 15 MPa, and the oil and gas are separated from the riser by cyclone separation. After separation, the reactor enters the rear fractionation system, while the charcoal-containing catalyst enters the stripping section, the stripped catalyst is regenerated by the regenerator, and the regenerated catalyst is returned to the riser reactor loop for use. Test conditions, tests The results are shown in Table 3. The properties of the diesel oil are shown in Table 4. The comparative examples were tested using the same riser reactor as in the above examples, and the raw material oil used was the same as in the above embodiment. The test procedure and method were identical to those of Example 1, except that the catalyst used was changed from Catalyst B of the example to Catalyst A. The operating conditions and product distribution are listed in Table 3. The test results are shown in Table 3 -43 - 201217512, Diesel Properties Table 4, Catalytic Wax Oil Properties are listed in Table 5. As can be seen from Table 3, the dry gas and coke yields of the examples were significantly lower than the comparative examples; as can be seen from Table 4, the diesel properties and comparative examples of the examples Slightly better, respectively 53 and 52. Table 1 Raw material oil type VGO-D AR Density (20 ° C), g / cm3 0.8653 0.9029 Residual carbon, wt% 0.15 4.0 Total nitrogen, wt% 0.04 0.26 Sulfur, wt% 0.09 0.13 Carbon, wt% 86.12 86.86 Hydrogen, wt% 13.47 12.86 Heavy metal content, PPm Nickel 0.12 5.3 Vanadium <0.1 1.1 Distillation range, °C Initial boiling point 284 308 10% 342 395 30% 390 440 50% 420 479 70% 449 550 90% 497 / -44- 201217512 Table 2 Catalyst No. AB Particle Size Type Conventional Particle Size Coarse Particle Size Chemical Composition, Weight % Alumina 25 25 Apparent Density of Sodium Oxide, kg/m3 790 778 Pore Volume, cc/g Specific Surface Area , 2/g 156 141 Abrasion index, 1.0% by weight, 1.0% by weight, 0% to 40 μm, 12 8 40 to 80 μm, 65 78 > 80 μm 23 14 Table 3 Example 1 Comparative Example 1 Catalyst number BA Reaction temperature , °c 460 460 Reaction time, second 1.6 1.6 oil ratio 4 4 water injection (accounting amount), % 10 10 product distribution, weight % dry gas 0.48 0.57 liquefied gas 7.01 7.03 gasoline 20.76 20.91 diesel 29.76 29.46 catalytic wax oil 39.83 39.67 Coke 1.78 1.98 Loss 0.38 0.38 -45- 201217512 Table 4 Example 1 Comparative Example 1 Diesel property density, g/cm3 0.8457 0.8463 Refraction 1.4771 1.4775 Freezing point, °c 12 12 Distillation range, t Initial boiling point 210 211 5% 242 244 10% 245 246 30% 282 282 50% 308 308 70% 332 331 90% 352 350 final boiling point / / composition, % paraffin 47.1 45.9 cycloalkane 27.9 28 aromatics 25.0 26.1 hexadecane 53 52 diesel hexadecane値桶* 1577.28 1531.92 * Diesel hexadecane 値 barrel = diesel hexadecane 値 X diesel yield -46- 201217512 Table 5 Example 1 Comparative Example 1 Catalytic wax oil property density, g/cm3 0.8 517 0.8522 Refractive 1.4561 1.4565 Freezing point, °C 42 42 Distillation range, °C Initial boiling point 300 301 5% 374 / 10% 384 387 30% 400 / 50% 416 417 70% 437 90% 466 464 Final boiling point / / element Composition, % C 86.07 86.08 Η 13.76 13.75 Example 2 This example illustrates the use of the process provided by the present invention for the selective cracking reaction to produce high quality light diesel oil and low olefin gasoline. The flow chart of the medium-sized catalytic cracking unit is shown in Fig. 2. The feedstock oil VGO-D is injected into the riser reactor via line 3, and is contacted and reacted with the catalyst B raised by the steam in the lower part of the riser reactor, in the riser reactor. The weight ratio of the internal catalyst B to the feedstock oil was 4: 1, the residence time of the feedstock oil in the riser reactor was 1.6 seconds, and the reaction temperature was 460 °C. The gas collection chamber pressure is 0.15 MPa. The oil and gas are separated from the riser and separated by the cyclone separator and then separated into the rear fractionation system to obtain the target product diesel oil and catalytic wax oil. The catalyst to be produced with charcoal -47-201217512 enters the stripping section, and the stripped catalyst is regenerated by the regenerator, and the regenerated catalyst is returned to the riser reactor for use in the loop. The obtained catalytic wax oil is directly sent into the variable diameter riser reactor for catalytic conversion, and the same catalyst B is used, and the weight ratio of the catalyst B to the catalytic wax oil in the variable diameter riser reactor is 6:1, the catalytic wax The residence time of the oil in the riser reactor is 5.5 seconds, the temperature of the first reaction zone (referred to as a reverse) is 51 (TC, the temperature of the first reaction zone (referred to as the second reverse) is 490 ° C, and the oil and gas from the variable diameter riser After being separated, it is separated by a cyclone separator and then separated into a fractionation system at the rear to obtain the target product diesel oil, gasoline, etc. The test conditions and test results are shown in Table 6. The properties of the diesel oil are comparable to those of the fuel of Example 1, and the properties of the gasoline are listed in Table 7. As can be seen from Table 6, the dry gas yield of the examples was only 0.96%, the coke yield was only 2.78%, the heavy oil yield was only 2.24%, and the total liquid yield (liquefied gas yield + gasoline yield + light diesel oil). Yield + light loop oil yield) up to 93.63%; as can be seen from Table 4 and Table 7, while producing high quality diesel, a gasoline product with low olefin content was produced. -48- 201217512 Table 6 Example 2 Catalytic cracking unit reaction temperature, °c 460 reaction time, second 1.6 oil ratio 4 water injection (accounting for feed), % 10 more productive low carbon olefin gasoline catalytic cracking unit a reverse temperature, t 510 two reverse temperature, °c 490 reaction time, second 5.5 Agent oil ratio 6 water injection (accounting amount), % 5 product distribution, weight % dry gas 0.96 liquefied gas 18.03 gasoline 39.79 light diesel 29.76 light loop oil 6.05 heavy oil 2.24 coke 2.78 loss 0.39 -49- 201217512 Table 7 Example 2 Gasoline-based gasoline density, g/cm3 0.7358 refraction 1.4174 induction period, minutes >500 distillation range, °C initial boiling point 43 5% 61 10% 67 30% 86 50% 108 70% 134 90% 166 Final boiling point 194 Composition, % saturated hydrocarbon 49.0 olefin 34.9 aromatic hydrocarbon 16.1 RON 89.0 Example 3 This example illustrates the use of the process provided by the present invention to produce high quality diesel by selective cracking reaction in combination with a catalytic cracking and hydrocracking process. Medium catalytic cracking unit The flow chart is shown in Figure 2. The feedstock oil (vgO-D) is injected into the riser reactor via line 3 and reacted with the catalyst B lifted by the steam in the riser. The lower contact, reaction 'in the riser reactor, the weight ratio of catalyst B to feedstock oil is 4:1'. The residence time of the feedstock in the riser reactor is 1.6 seconds, and the reaction temperature is 460 ° C. The gas collection chamber The pressure is 50-201217512 0.1 5 MPa. After the oil and gas exits the riser, it is separated by a cyclone and then enters the rear fractionation system to separate the target product diesel and catalytic wax oil. The spent catalyst with charcoal enters the stripping section, and the stripped catalyst is regenerated by the regenerator, and the regenerated catalyst is returned to the riser reactor for use in the loop. The catalytic wax oil enters the subsequent hydrocracking unit, and the reaction conditions for the hydrocracking are: the refining reaction temperature is 3 70 ° C, the cracking reaction temperature is 3 80 ° C, the hydrogen partial pressure is 1 2.0 MP a, and the volumetric space velocity is 1 · 2 hours · 1. The test conditions and test results are shown in Table 8. The catalytic diesel oil properties are comparable to those of the light diesel oil of Example 1. The properties of the hydrocracked diesel oil are listed in Table 9. The properties of the hydrocracking tail oil are listed in Table 1. 从° It can be seen from Table 8. The catalytic diesel oil yield of the embodiment is as high as 29.76% by weight, the hydrocracked diesel oil yield is up to 8.63% by weight, the dry gas yield is only 〇·48% by weight, and the coke yield is only 1.78% by weight. % : As can be seen from Table 4 and Table 9, the catalytic diesel hexadecane produced in this example is as high as 5 3 'force 13 stomach gasified diesel hexadecane 値 up to 68.2, diesel hexadecane 値 barrel up to 2 847 · 846 (ie 29.76x53 + 18.63x68.2) by-product hydrocracking tail oil BMCI値 reaches 15.6, which is a good raw material for reactors such as catalytic cracking. -51 - 201217512 Table 8 Example 3 Catalytic cracking unit reaction temperature, t 460 reaction time, second 1.6 oil ratio 4 water injection (accounting amount), % 10 hydrocracking unit purification reaction temperature, °C 370 cracking reaction Temperature, t 380 Hydrogen partial pressure, MPa 12.0 Volumetric airspeed, hour u 1.2 Product distribution, % by weight Dry gas 0.48 Liquefied gas 7.01 Gasoline 20.76 Naphtha 15.93 Catalytic diesel 29.76 Hydrocracked diesel 18.62 Hydrocracked tail oil 6.77 Coke 1.78 Loss 0.38 Total 101.49 -52- 201217512 Table 9 Example 3 Product Properties Hydrocracking Diesel Hydrocracking Tail Oil Density, g/cm3 0.8153 0.8430 Refraction 1.4525 1.4481 Solidification Point, °C -28 20 Distillation Range, °C Initial Distillation Point 233 295 5% 244 378 10% 252 385 30% 269 397 50% 282 409 70% 304 422 90% 327 449 Final boiling point 344 512 Composition, % paraffin / 53.3 naphthene / 45.0 aromatics / 1.7 hexadecane 68.2 BMCI 15.6 Example 4 This example illustrates the selective cracking by a combination of catalytic cracking and hydrotreating processes using the method provided by the present invention. It should produce high-quality diesel fuel situation.

The flow chart of the medium-sized catalytic cracking unit is shown in Figure 2. The atmospheric residue (AR)

) is injected into the riser reactor via line 3, and is contacted and reacted with the catalyst A lifted by the water vapor in the lower portion of the riser reactor. The weight ratio of the catalyst B to the feedstock in the riser reactor is 3: 1, the feedstock oil The residence time in the riser reactor was 1.6 seconds and the reaction temperature was 45 °C. The gas collection chamber pressure is 0.2 MPa. After the oil and gas is discharged from the riser, it is separated by a cyclone and then enters the rear part of the -53-201217512 fractionation system to obtain the target product diesel and catalytic wax oil. The charcoal-containing catalyst enters the stripping section, and the stripped catalyst is regenerated by the regenerator, and the regenerated catalyst is returned to the riser reactor for use. The catalytic wax oil enters the subsequent hydrotreating unit, and the hydrogenation reaction conditions are: hydrogen partial pressure of 14 MPa, reaction temperature of 385 ° C, and volumetric space velocity of 0.235 hours °. The hydrotreating of the unit catalyzes the return of the wax oil to the catalytic cracking unit. The test conditions and test results are shown in Table 1. The diesel properties are listed in Table 11. As can be seen from Table 10, the diesel fuel yield of this example was as high as 46.51% by weight: as can be seen from Table 4, the diesel hexadecane oxime of this example was as high as 5 2.5 and the diesel hexadecane oxime was as high as 2441.78. Example 5 The same riser reactor as in the above Example 4 was used for the test. The raw material oil used was the same as that of the above examples, and the test procedures and methods were identical to those of the examples except that the catalyst used was the crude particle size catalyst of Example 4. B is changed to conventional particle size catalyst A. The test conditions and test results are shown in Table 1. The diesel properties are listed in Table 11. As can be seen from Table 10, the diesel yield of this example was as high as 45.8 8% by weight: as can be seen from Table 11, the diesel hexadecane oxime of this example was as high as 51.4, and the diesel hexadecane bismuth was as high as 23 5 8.23. It can also be seen from Table 10 that the dry gas and coke yield of Example 5 is significantly higher than that of Example 4, indicating that the coarse particle size cracking catalyst B can reduce the dry gas and coke yield more than the conventional particle size cracking catalyst A. . -54- 201217512 Table 1 〇 Example 4 Example 5 Catalyst No. BA Reaction temperature, °c 450 450 Reaction time, seconds 1.6 1.6 Agent oil ratio 3 3 Water to oil ratio 0.05 0.05 Product distribution*, weight % Dry gas 1.52 1.72 Liquefaction Gas 13.95 13.98 Gasoline 33.50 33.75 Diesel 46.51 45.88 Heavy oil 0.00 0.00 Coke 4.12 4.27 Loss 0.40 0.40 Based on the total weight of atmospheric residue and hydrogen Table 1 1 Example 4 Example 5 Diesel density, g/cm3 0.8461 0.8468 Refraction 1.4782 1.4785 Freezing point, t 12 12 Distillation range, t Initial boiling point 200 201 5% 240 243 10% 245 247 30% 275 275 50% 300 301 70% 335 336 90% 348 350 Hexadecane 52.5 51.4 Diesel hexadecane Barrels * 2441.78 2358.23 * Diesel cetane barrels = diesel cetane x diesel yield - 55 - 201217512 It will be appreciated that certain aspects and features of the invention are described in separate embodiments for clarity. It can also be provided in combination in a single embodiment. In contrast, the various aspects and features of the invention described in the individual embodiments may be provided separately or in any suitable sub-combination. All of the publications, patents, and patent applications mentioned in this specification are hereby incorporated by reference in their entirety in the entireties in the the the the the the Although the present invention has been described in connection with the specific embodiments and embodiments thereof, it is apparent that many alternatives, modifications and variations can be seen by those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications and BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart of an embodiment of the present invention. Figure 2 is a schematic illustration of one embodiment of the invention. [Explanation of main component symbols] 1' : Catalytic cracking reactor 2': Conventional catalytic cracking or reduction riser reactor / hydrotreating unit 3 ': Conventional catalytic cracking or variable diameter riser reactor 4 ': Hydrocracking Apparatus 5 ', 6 ', 7 ', 8 ', 9 ', 1 0 ', 1 1 ', 1 2 ': Line 1: Line - 56 - 201217512 2 : Pre-lift section 3: Line 4: riser reactor 5: stripping section 6: plenum 7: cyclone 8: waiting tube 9: slid valve 10: regenerator 1 1 : slid valve 1 2 : regenerative tube 1 3 : line 1 4 : separation System 15, 16, 17, 18, 19, 20, 21: Lines I, 11: Reaction zone

S -57-

Claims (1)

201217512 VII. Patent application scope: 1 · A catalytic conversion method for improving diesel cetane barrel, characterized in that the method comprises the catalyst for making the feedstock oil in the catalytic conversion reactor relatively uniform with the activity mainly containing large pore zeolite. The reaction is carried out by contacting, wherein the reaction temperature, the residence time of the oil and gas, and the weight ratio of the catalyst to the feedstock oil are sufficient to obtain a reaction product comprising diesel oil, which comprises from about 12 to about 60% by weight of the catalytic wax oil of the feedstock oil, wherein the reaction temperature is about 420. ~ about 550 ° C, the gas and gas residence time is about 1. 1~ about 5 seconds, the catalyst to feedstock oil weight ratio of about 1 ~ about 10 〇 2. - a catalyst for improving diesel hexadecane barrel A conversion process characterized in that the process comprises reacting a feedstock oil in a catalytic conversion reactor with a catalyst having a relatively uniform activity of a predominantly large pore zeolite, wherein the reaction temperature, the residence time of the oil and gas, and the weight ratio of the catalyst to the feedstock oil are sufficient The reaction is carried out to obtain a reaction product comprising diesel fuel in an amount of from about 12 to about 60% by weight of the catalytic oil of the feedstock oil, wherein the reaction temperature is about 420. At about 550 ° C, the hydrocarbon residence time is about 1 to about 5 seconds, the weight ratio of the catalyst to the feedstock oil is from about j to about 10; and the catalytic wax oil is wholly or partially introduced into a conventional catalytic cracking or reduction. The riser reactor further produces a product comprising diesel and gasoline, or/and the catalytic wax oil is returned to the original catalytic conversion reactor or fed to another catalytic conversion reactor. A method for catalytically reforming a diesel cetane-tantalum barrel, characterized in that the method comprises reacting a feedstock oil in a catalytic conversion reactor with a catalyst having a relatively uniform activity mainly containing a large pore zeolite, wherein the reaction The temperature, the residence time of the oil and gas, and the weight ratio of the catalyst to the feedstock oil are sufficient for the anti-58-201217512 to contain about 12 to about the reaction product containing the diesel oil, wherein the reaction temperature is about 420" the residence time is about 0.1 to about 5 In seconds, the catalyst is homogeneous! ~ about 1 〇; characterized in that the catalytic wax oil refining device further produces high hexadecane ruthenium diesel. 4. A method for improving the diesel cetane-tantalum barrel, wherein the method comprises the catalyst coupling temperature of the feedstock oil in the catalytically-transferred large-pore zeolite, the residence time of the oil and gas, the catalyst and the original should contain the diesel oil, and the raw material oil About 12 to about a reaction product, wherein the reaction temperature is about 420 - a residence time of about 〇 1 to about 5 seconds, the catalysis is ! ~ ~ about 10; and the catalytic wax oil is further processed in whole or in part to produce Including diesel and gasoline. 5. The method of claim 3, then enters the conventional catalytic cracking or reduction riser anti-diesel and gasoline products. 6. The method of claim 4, in whole or in part, enters conventional catalytic cracking or variable diameter production of products including diesel and gasoline, or / and 〇 7. As described in the scope of claims 1 to 4, the raw material oil selection From or including petroleum hydrocarbons and/or hydrocarbons thereof selected from the group consisting of reduced pressure gas oils, normally compressed gas oils, and coke I 60% by weight of catalytic wax oil - about 550 ° C, the ratio of the oil and gas 1 to the feedstock oil is about 1 Part or part of the hydrocracking conversion process, characterized in that the reactor reacts with the main contact, wherein the counter oil weight ratio is sufficient to make the reverse 60% by weight of the catalytic wax oil, about 550 ° C, the oil and gas The weight ratio of hydrazine to feedstock oil is about 1 minute into the hydrotreating unit product. , wherein the hydrocracking tail oil reactor further comprises a method in which the hydrogenation catalytic wax oil riser reactor is further returned to the catalytic conversion reactor, wherein the mineral oil thereof, the petroleum gasification oil, the deasphalted oil -59- 201217512, one or a mixture of two or more of vacuum residue and atmospheric residue. Other mineral oils are one or a mixture of two or more of coal liquefied oil, oil sand oil, and shale oil. 8. The method of any one of claims 1 to 4, wherein the catalyst comprises zeolite, inorganic oxide, clay, and the components are respectively based on the total weight of the catalyst on a dry basis: about 5 wt% of the zeolite ~ About 35% by weight, preferably about 10% by weight to about 30% by weight; about 0.5% by weight to about 50% by weight of the inorganic oxide; about 7% by weight of the clay; wherein the zeolite is used as an active fraction, selected from the group consisting of large pore zeolites, The large pore zeolite refers to one or a mixture of two or more of the zeolites consisting of rare earth Y, rare earth hydrogen Y, and ultra-stable Y and high yttrium γ obtained by different methods. 9. The method of any one of claims 1 to 4, wherein the particle size distribution of the catalyst is a particle size distribution of a conventional catalytic cracking catalyst, or a coarse particle size distribution. The method of claim 9, wherein the sieve grouping of the coarse particle size distribution catalyst becomes less than about 40 microns, and the volume ratio of the particles to all particles is less than about 10%, preferably less than about 5%. The particles having a volume greater than about 80 microns account for less than about 5%, preferably less than about 10%, by volume of all of the particles: the remainder are from about 40 to about 80 microns. The method of any one of claims 1 to 4, wherein the catalytic conversion reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, and an upstream conveyor line. One or more combinations of down-conveying lines, or a combination of two or more of the same reactor, the combination comprising series or / and parallel, wherein the riser is conventional straight-60-201217512 A riser of a diameter or a riser of various types of diameters. The method of any one of claims 1 to 4, wherein the feedstock oil is introduced into the catalytic conversion reactor at one location, or the feedstock oil is at one or more locations of the same or different heights. Introduced into the catalytic conversion reactor. The method of any one of claims 1-4, wherein the catalytic conversion reaction temperature is from about 4 3 0 to about 50,000 ° C, preferably from about 4 3 0 to about 48 ° C: oil and gas The residence time is from about 0.5 to about 4 seconds, preferably from about 0.8 to about 3 seconds; the weight ratio of catalyst to feedstock oil is from about 2 to about 8, preferably from about 3 to about 6, and the reaction is at a pressure of from about 0.10 MPa to about 1.0 MPa, preferably. About 〇15MPa ~ about 〇.6MPa. The method according to any one of claims 1 to 4, wherein the catalytic wax oil is a fraction having an initial boiling point of not less than about 305 ° C and a hydrogen content of not less than about 11.5% by weight. It is preferably not less than about 12.0% by weight. The method of any one of claims 1 to 4 wherein the catalytically-converting catalyst having a relative activity means that its initial activity does not exceed about 80, preferably does not exceed about 75, more preferably. Not more than about 7 Torr; the self-equilibration time of the catalyst is from about 1 hour to about 50 hours, preferably from about 0. 2 to about 30 hours, more preferably from about 0.5 to about 1 hour; 5 to about 6 0 ' is preferably about 4 0 to about 5 5 . The method of any one of claims 1 to 4, wherein the catalytic conversion catalyst in the catalytic conversion reactor is obtained by the following treatment method: (1) charging a fresh catalyst a fluidized bed, preferably a dense-phase fluidized bed, in contact with water vapor, and obtained a relatively homogeneous catalyst after aging in a certain hydrothermal environment; (2) a catalyst having relatively uniform activity Adding to the corresponding reaction device; and wherein the certain hydrothermal environment comprises: an aging temperature of about 400 ° C to about 850 ° C, preferably about 50,000 ° C to about 750 ° C, preferably about From 60 ° C to about 70 ° C, the apparent line speed of the fluidized bed is from about 0.1 m/s to about 0.6 m/s, preferably from about 0.15 seconds to about 0.5 m/s, and aging is about 1 hour to about 7 2 0 0, preferably about 5 hours to about 360 hours. The method of any one of claims 1 to 4, wherein the catalytic conversion catalyst in the catalytic conversion reactor is obtained by the following treatment method: (1) loading a fresh catalyst a fluidized bed, preferably a dense-phase fluidized bed, in contact with an aging medium containing water vapor, and aging after a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) adding the catalyst having relatively uniform activity to Corresponding reaction device; wherein the certain hydrothermal environment comprises: an aging temperature of about 400 ° C ~ about 85 (TC, preferably about 500 ° C ~ about 750 ° C, preferably about 600 ° C ~ about 700 ° C, The apparent linear velocity of the fluidized bed is from about 0.1 m/sec to about 0.6 m/sec, preferably from about 0.15 seconds to about 0.5 m/sec, and the weight ratio of water vapor to aged medium is from about 0.20 to about 0.9, preferably about 0. The method of any one of claims 1 to 4, wherein the method is as described in any one of claims 1 to 4, wherein the aging is about 1 hour to about 720 hours, preferably about 5 hours to about 3 hours. The catalytic conversion catalyst in the catalytic conversion reactor is treated as follows - 62 - 201217512 And obtaining: (1) introducing fresh catalyst into the fluidized bed, preferably a dense phase fluidized bed, while conveying the thermal regeneration catalyst of the regenerator to the fluidized bed, and performing heat exchange in the fluidized bed; (2) The fresh catalyst after heat exchange is contacted with an aging medium of steam or water vapor, and after aging in a certain hydrothermal environment, a catalyst having relatively uniform activity is obtained: and (3), the activity is relatively uniform. The catalyst is added to the corresponding reaction device; wherein the certain hydrothermal environment comprises: an aging temperature of about 400 ° C to about 850 ° C, preferably about 500 ° C to about 750 ° C, preferably about 600 ° C ~ about 700 ° C, the apparent line speed of the fluidized bed is about 1. 1 m / s ~ about 0.6 m / s, preferably about 〇. 1 5 seconds ~ about 0 · 5 m / s, aging about 1 hour ~ about 7 hr, preferably from about 5 hours to about 366 hours, the weight ratio of the water vapor to the aging medium (if any) is from greater than about 〇 to about 4, preferably from about 0.5 to about 1.5. 1 9. The method of claim 4, wherein the hydrogenation process condition is: hydrogen partial pressure of about 3.0 to about 2 0 · 0 Μ P a 'reaction temperature is about 30,000 to about 4 5 0 V, volumetric space velocity is about 1. 1~about 3 hours^, hydrogen to oil ratio is about 30,000 to about 2000v/v ° 2 0 . The method of claim 4, wherein the hydrogenation catalyst comprises a support and molybdenum and/or tungsten and nickel and/or cobalt supported on the support, the support consisting of alumina and zeolite, and the weight ratio of alumina to zeolite Approximately 90: 10 to about 5 0: 5 0, the alumina is a composite of alumina made from small pore alumina and macroporous alumina in a weight ratio of about 7 5 : 2 5 to about 5 0 : 50 , -63- 201217512 medium-porosity alumina is alumina having a pore volume of less than about 80 A in diameter and about 95% or more of the total pore volume, and macroporous alumina is a pore volume of pores having a diameter of about 60 to about 600 A. Alumina having a volume of about 70% or more. 21. The method of claim 20, wherein the content of molybdenum and/or tungsten is from about 10 to about 35% by weight based on the total amount of the catalyst, and the content of lanthanum and/or uran is about 1 〜1. About 15% by weight. 22. The method of claim 20, wherein the weight ratio of alumina to zeolite is from about 90:10 to about 60:40. 23. The method of claim 20, wherein the zeolite is a gamma type zeolite. 2. The method of claim 2, wherein the catalytic wax oil is subjected to a cracking reaction in another conversion reactor, and the generated oil and gas undergoes a hydrogen transfer reaction and an isomerization reaction under a certain reaction environment, and is separated. A reaction product comprising low olefin gasoline is obtained. The method of claim 24, wherein the reaction condition of the cracking reaction is: a reaction temperature of about 480 ° C to about 600 ° C, preferably about 4 8 5 to about 5 8 0 °C, the reaction time is about 0.1 to about 3 seconds, preferably about 〇 5 to about 2 seconds, the weight ratio of the conversion catalyst to the catalytic wax oil is from about 0.5 to about 2 5 : 1, preferably from about 1 to about 15:1; The weight ratio of the lifting medium to the catalytic wax oil is from about 〇1 to about 2:1, preferably about 〇.〇5 to about 1:1. The method of claim 24, wherein the hydrogen transfer reaction and the isomerization reaction are carried out under the following conditions: a reaction temperature of about 405 ° C to about 550 ° C, preferably from about 460 to about 53 0 ° C; heavy hourly space velocity of about 1 to about 50 hours -1 'preferably about 1 to about 40 hours ^. -64-