TWI486434B - A Catalytic Conversion Method for Producing Diesel Oil and Propylene - Google Patents

Description

Catalytic conversion method for producing diesel and propylene

The present invention pertains to a catalytic conversion process for hydrocarbon oils in the absence of hydrogen, and more particularly to a catalytic conversion process for converting heavy feedstocks to high cetane diesel and propylene.

At present, the global demand for high-quality gasoline is increasing, and the production of high-quality gasoline is rapidly developing, while the development of high-carbon cetane diesel technology is relatively slow. Although the demand for gasoline and diesel varies from region to region, overall the global demand for diesel oil will gradually increase faster than the demand for gasoline. The diesel cyanide produced by the conventional catalytic cracking process is relatively low and is therefore often used as a blending component for diesel. In order to meet the demand for high quality diesel, it is necessary to upgrade the catalytic light diesel.

In the prior art, the method for catalyzing the upgrading of light diesel oil mainly includes hydrogenation treatment and alkylation. CN1289832A likewise discloses a process for upgrading catalytically cracked diesel by hydrotreating by sequentially passing the feedstock through a single stage series of hydrorefining catalyst and hydrocracking catalyst under hydrogenation conditions without intermediate separation. The method increases the cetane number of the diesel fraction of the product by more than 10 units compared with the raw material, and the sulfur and nitrogen contents thereof are remarkably lowered.

CN1900226A discloses a catalytic cracking cocatalyst for producing diesel fuel and a preparation method thereof, and adding a certain amount of the cocatalyst can improve the diesel yield of the FCC catalytic device and improve the product without changing the original catalyst used in the refinery device. Distribution, but this method does not mention improvements in diesel properties.

Low-carbon olefins such as propylene are important organic chemical raw materials, and propylene is a synthetic monomer for products such as polypropylene and acrylonitrile. With the rapid growth in demand for derivatives such as polypropylene, the demand for propylene is increasing year by year. The demand for the world propylene market has increased from 15.2 million tons 20 years ago to 51.2 million tons in 2000, with an average annual growth rate of 6.3%. It is estimated that the demand for propylene will reach 86 million tons by 2010, with an average annual growth rate of about 5.6%.

The main methods for producing propylene are steam cracking and catalytic cracking (FCC), in which steam cracking uses light oil such as naphtha as raw material to produce ethylene and propylene by thermal cracking, but the yield of propylene is only about 15% by weight, while FCC. Heavy oil such as vacuum gas oil (VGO) is used as a raw material. At present, 61% of the world's propylene is from by-products of steam cracking to produce ethylene, 34% from the refinery FCC to produce by-products of gasoline and diesel, and a small amount (about 5%) is obtained by dehydrogenation of propane and metathesis of ethylene-butene.

If petrochemicals take the traditional steam cracking process to produce ethylene and propylene, they will face several major constraints such as shortage of light feedstock, insufficient production capacity and high cost.

FCC has received increasing attention due to its wide adaptability to raw materials and flexible operation. In the United States, almost 50% of the market demand for propylene comes from FCC units. The improved catalytic cracking technology for increasing propylene production has developed rapidly.

No. 4,422,925 discloses a method of contacting and converting a plurality of hydrocarbons having different cracking properties with a thermally regenerated catalyst, the hydrocarbon comprising at least one gaseous alkane feedstock and one liquid hydrocarbon feedstock, the process being based on different hydrocarbons The molecules have different cracking properties, and the reaction is divided into a plurality of reaction zones for cracking reaction to produce low molecular olefins.

CN1279270A discloses a catalytic conversion method for prolific diesel oil and liquefied gas, which is carried out in a four-stage riser or fluidized bed reactor, in which gasoline raw materials, conventional cracking raw materials and reaction terminators are injected into different positions, The method can simultaneously increase the yield of liquefied gas and diesel. However, this method has a relatively high dry gas and coke yield.

It has long been recognized by those of ordinary skill in the art that the higher the conversion of heavy oil catalytic cracking, the better. However, the inventors have creatively thought and repeated experiments and found that the conversion rate of heavy oil catalytic cracking is not as high as possible. When the conversion rate is high to a certain extent, the target product increases little, and the yield of dry gas and coke is greatly increased. The fine particle size of less than 40 μm in the sieve composition of the conventional catalytic cracking catalyst is about 20% by volume. It has been found that these fine particle catalysts have high cracking ability, but have poor selectivity to dry gas and coke. Optimizing the sieve composition of the catalyst can improve the selectivity of dry gas and coke.

In order to efficiently utilize inferior heavy oil resources and meet the growing demand for light fuel oil, it is necessary to develop a catalytic conversion method for converting heavy oil feedstock into a large amount of clean diesel oil and propylene.

It is an object of the present invention to provide a process for converting heavy oil to high cetane diesel and propylene based on the prior art. It mainly by selectively cracking and isomerizing hydrocarbons such as alkanes and alkyl side chains in the catalytic feedstock, while minimizing the entry of aromatics in the feedstock into the diesel fraction and avoiding aromatization of other components in the product. The reaction forms aromatic hydrocarbons and remains in the diesel fraction. The cracking feedstock is converted into high cetane diesel and propylene, 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 catalytic conversion process wherein a feedstock oil is contacted with a catalytic cracking catalyst, preferably a relatively homogeneous catalytic cracking catalyst, in a catalytic cracking reactor, reaction temperature, weight hourly space velocity, catalyst The weight ratio to the feedstock oil is sufficient for the reaction to obtain a reaction product comprising a catalytic wax oil comprising from 12 to 60% by weight, preferably from 20 to 50% by weight, based on the feedstock oil, wherein the weight hourly space velocity is from 25 to 100 h ^-1 , the reaction The temperature is 450-600 ° C, the catalytic cracking catalyst and the feedstock oil weight ratio is 1-30, and the catalytic wax oil is further processed into at least one of a hydrotreating device, a solvent extraction device, and a hydrocracking device.

In a more preferred embodiment, the hydrogenated catalytic wax oil obtained by the hydrotreatment or the solvent or the solvent obtained by the solvent extraction or the catalytic wax oil hydrocracking tail oil obtained by hydrocracking is used as a prolific diesel device. The raw materials of one or more of the present reactor, hydrocracking unit, steam cracking unit, and other reactors are preferably used as raw materials for the production of diesel fuel units. In a more preferred embodiment, the prolific diesel unit is a catalytic cracking unit for producing diesel. In a more preferred embodiment, the catalyst used in the catalytic cracking unit for the production of diesel is a relatively productive, relatively productive diesel catalyst.

In a more preferred embodiment, the reaction temperature is preferably 460 to 580 ° C, more preferably 480 to 540 ° C.

In a more preferred embodiment, the weight hourly space velocity is from 30 to 80 h ^-1 , preferably from 40 to 60 h ^-1 .

In a more preferred embodiment, the weight ratio of catalyst to feedstock oil is preferably from 2 to 25, more preferably from 2 to 15, more preferably from 3 to 14.

The weight ratio of water vapor to cracked feedstock oil is from 0.05 to 1.0.

In a more preferred embodiment, the reaction pressure is from 0.10 MPa to 1.0 MPa.

In a more preferred embodiment, the feedstock oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, decompression One or a mixture of two or more of residual 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 catalytic cracking catalyst comprises a zeolite, an inorganic oxide, and optionally a clay, each component comprising a total weight of the catalyst: 1-50% by weight of the zeolite, 5-19% by weight of the inorganic oxide, The clay is 0-70% by weight, wherein the zeolite is a medium pore zeolite and optionally a large pore zeolite, and the medium pore zeolite comprises from 51 to 100% by weight, preferably from 70% to 100% by weight, based on the total weight of the zeolite. The macroporous zeolite comprises from 0 to 49% by weight, preferably from 0% to 30% by weight, based on the total weight of the zeolite. The medium pore zeolite is selected from the group consisting of ZSM series zeolites and/or ZRP zeolites, and the large pore zeolite is selected from the Y series zeolites.

The relatively homogeneous catalyst (including the catalytic cracking catalyst used in the catalytic cracking reactor and the prolific diesel catalyst used in the prolific diesel plant) means that its initial activity does not exceed 80, preferably does not exceed 75, more preferably does not exceed 70; The catalyst has a self-equilibration time of from 0.1 hour to 50 hours, preferably from 0.2 to 30 hours, more preferably from 0.5 to 10 hours; and an equilibrium activity of from 35 to 60, preferably from 40 to 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--the micro-reaction activity test method for catalytic cracking of fresh catalyst "Petrochemical Analysis Method (RIPP Test Method)", Yang Cuiding et al., 1990, 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 in the product + gas production + coke production) / total amount of feed * 100% = in the product Gasoline yield below + °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 420-841 μm and having a loading of 5 g. The reaction raw material is a straight run having a distillation range of 235-337 ° C. Light diesel oil, reaction temperature 460 ° C, weight space velocity 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 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, and aging after 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 treatment method 1 is embodied, for example, by charging fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, injecting steam at the bottom of the fluidized bed, and the catalyst is fluidized by the action of water vapor, while water vapor The catalyst is aged, the aging temperature is from 400 ° C to 850 ° C, preferably from 500 ° C to 750 ° C, preferably from 600 ° C to 700 ° C, and the apparent line speed of the fluidized bed is from 0.1 m / sec to 0.6 m / sec, most Preferably, it is 0.15 second to 0.5 m/sec, and after aging for 1 hour to 720 hours, preferably 5 hours to 360 hours, the catalyst having relatively uniform activity is obtained, and the catalyst having relatively uniform activity is added to the industrial device according to the requirements of the industrial device. It is preferably added to the regenerator of the industrial plant.

Catalyst treatment method 2:

(1) charging fresh catalyst 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 a relatively uniform activity to the corresponding reaction device.

The technical solution of the catalyst treatment method 2 is embodied, for example, by charging the catalyst into a fluidized bed, preferably a dense phase fluidized bed, injecting an aging medium containing water vapor at the bottom of the fluidized bed, and acting as an aging medium for the water vapor. The fluidization is carried out at the same time, and the aging medium containing water vapor aging the catalyst, and the aging temperature is 400 ° C - 850 ° C, preferably 500 ° C - 750 ° C, preferably 600 ° C - 700 ° C, the apparent line speed of the fluidized bed It is from 0.1 m/sec to 0.6 m/sec, preferably from 0.15 sec to 0.5 m/sec, and the weight ratio of water vapor to aging medium is from 0.20 to 0.9, preferably from 0.40 to 0.60, and aging is from 1 hour to 720 hours, preferably 5 After hours to 360 hours, the catalyst having a relatively uniform activity is obtained, and the catalyst having a relatively uniform activity is added to the industrial unit as required by the industrial apparatus, preferably 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 gas such as nitrogen. The weight ratio of the water vapor to the aged medium is from 0.2 to 0.9, preferably from 0.40 to 0.60.

Catalyst treatment method 3:

(1) introducing fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while conveying a thermal regeneration catalyst of the regenerator to the fluidized bed, and performing heat exchange in the fluidized bed;

(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) Adding the catalyst having a relatively uniform activity to the corresponding reaction device.

The technical solution of the present invention is embodied, for example, in that a fresh catalyst is delivered to a fluidized bed, preferably a dense phase fluidized bed, while a thermally regenerated catalyst of the regenerator is also delivered to the fluidized bed, where the fluidization Heat exchange takes place in the bed. The aging medium of steam or water vapor is injected into the bottom of the fluidized bed, and the fresh catalyst is fluidized by the aging medium of steam or water vapor. At the same time, the aging medium of steam or water vapor ages the fresh catalyst and ages. The temperature is from 400 ° C to 850 ° C, preferably from 500 ° C to 550 ° C, preferably from 600 ° C to 700 ° C, and the apparent line speed of the fluidized bed is from 0.1 m / sec to 0.6 m / sec, preferably from 0.15 sec - 0.5 Meters/second, aged from 1 hour to 720 hours, preferably from 5 hours to 360 hours, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aged medium is greater than 0-4, preferably 0.5-1.5 A catalyst having a relatively uniform activity is obtained, and a catalyst having a relatively uniform activity is added to an industrial unit, preferably to a regenerator of an industrial unit, as required by an industrial plant. In addition, the water vapor after the aging step enters the reaction system (as 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 device, The pre-lifting section) or the regeneration system, and the aging medium of the water vapor after the aging step enters the regeneration system, and the regenerated catalyst after the heat exchange is returned to the regenerator. The aging medium includes air, dry gas, regenerated flue gas, gas after combustion of air and dry gas or gas after combustion of combustion oil, or other gas such as nitrogen.

Through 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 (including the catalytic cracking catalyst and the prolific diesel catalyst) may be a particle size distribution of a conventional catalyst or a coarse particle size distribution. In a more preferred embodiment, the catalyst is characterized by a catalyst having a coarse particle size distribution.

The sieve of the coarse particle size distribution catalytic cracking catalyst is grouped into: catalytic cracking catalyst particles of less than 40 micrometers account for less than 10% by volume of all catalytic cracking catalyst particles, preferably less than 5%; catalytic cracking of more than 80 micrometers The catalyst particles constitute less than 15% by volume of all of the catalytic cracking catalyst particles, preferably less than 10%, and the remainder are 40-80 micron catalytic cracking catalyst particles.

The particle size distribution of the prolific diesel catalyst in the prolific diesel device is preferably a coarse particle size distribution, and the sieve grouping is: a volume ratio of the prolific diesel catalyst particles of less than 40 micrometers to all the prolific diesel catalyst particles is less than 10 %, preferably less than 5%, more than 80 microns of prolific diesel catalyst particles account for less than 15%, preferably less than 10% by volume of all prolific diesel catalyst particles, the rest are prolific 40-80 microns Diesel catalyst particles.

In a more preferred embodiment, the catalytic cracking reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. A combination, or a combination of two or more of the same reactor, 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 catalytic cracking reactor at one location, or the feedstock oil is introduced into the catalytic cracking reactor at more than one location of the same or different heights.

In a more preferred embodiment, the method further comprises separating the catalytic cracking reaction product and the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to stripping and charring regeneration and then returned to the catalytic cracking reactor, and the separated product includes Propylene, diesel and catalytic wax oils.

In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 260 ° C and a hydrogen content of not less than 10.5% by weight.

In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 330 ° C and a hydrogen content of not less than 10.8% by weight.

The reaction system of the hydrotreating unit is usually a fixed bed reactor, and the hydrotreating catalyst is a Group VIB or/and Group VIII non-precious metal catalyst supported on an amorphous alumina or/and a ruthenium aluminum support, wherein the Group VIB non-precious metal is Molybdenum or/and tungsten, the Group VIII non-noble metal is one or more of nickel, cobalt, and iron.

The process conditions of the hydrogenation treatment are: hydrogen partial pressure of 4.0-20.0 MPa, reaction temperature of 280-450 ° C, volumetric space velocity of 0.1-20 h ^-1 , and hydrogen oil ratio of 300-2000 v/v.

The method aromatics extraction unit is suitable for use in existing aromatics extraction units. The solvent for extracting the aromatic hydrocarbon is selected from one or more of furfural, dimethyl hydrazine, dimethylformamide, monoethanolamine, ethylene glycol, and 1,2-propanediol, and the solvent can be recovered, and the extraction temperature is The ratio of solvent to catalytic wax oil is from 0.5:1 to 5.0:1 at 40-120 °C.

The reaction system of the hydrocracking unit generally comprises a refining reactor and a cleavage reactor, both of which are fixed bed reactors, and the refining reactor is usually charged with a hydrotreating catalyst which is supported on an amorphous alumina or/and yttrium aluminum support. a Group VIB or/and Group VIII non-noble metal catalyst; the hydrocracking catalyst is a Group VIB or/and Group VIII non-noble metal catalyst supported on a Y zeolite molecular sieve. Wherein the non-precious metal of group VIB is molybdenum or/and tungsten, and the non-precious metal of group VIII is one or more of nickel, cobalt and iron.

The hydrocracking process conditions are: hydrogen partial pressure of 4.0-20.0 MPa, reaction temperature of 280-450 ° C, volumetric space velocity of 0.1-20 h ^-1 , and hydrogen oil ratio of 300-2000 v/v.

In a more preferred embodiment, the catalytic cracking unit for producing diesel fuel has a reaction temperature of 400 to 650 ° C, preferably 430 to 500 ° C, more preferably 430 to 480 ° C; and a hydrocarbon residence time of 0.05 to 5 seconds, preferably, 0.1-4 seconds; reaction pressure is 0.10 MPa-1.0 MPa.

In a more preferred embodiment, the prolific diesel catalyst comprises a zeolite, an inorganic oxide, a clay. On a dry basis, each component comprises the total weight of the catalyst: 5 to 60% by weight of the zeolite, preferably 10 to 30% by weight; 0.5 to 50% by weight of the inorganic oxide; and 0 to 70% by weight of the clay. Among them, zeolite is used as an active fraction and is selected from large pore zeolite. 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, super stable Y obtained by different methods, and high yttrium Y.

The inorganic oxide is used as a matrix selected from the group consisting of cerium oxide (SiO ₂ ) and/or aluminum oxide (Al ₂ O ₃ ). On the dry basis, the inorganic oxide contains cerium oxide in an amount of 50 to 90% by weight, and aluminum oxide accounts for 10 to 50% by weight.

a clay as a binder selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, erbium, hydrotalcite, bentonite or Several.

In a more preferred embodiment, the prolific diesel reactor is selected from one or both of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a down conveyor line. Combinations of the above, or a combination of two or more of the same reactors, 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 catalytic wax oil raffinate oil obtained by the hydrogenation catalytic wax oil or/and solvent extraction or/and the catalytic wax oil hydrocracking tail oil obtained by hydrocracking are introduced into a prolific product at one position. The hydrogenated catalytic wax oil is introduced into the productive diesel reactor within the diesel reactor or at locations above one or the same height.

In a more preferred embodiment, the method for producing diesel fuel further comprises separating the reaction product in the diesel fuel reactor and the diesel fuel catalyst, and separating the separated diesel fuel catalyst by steam stripping, charring regeneration and returning The diesel fuel reactor is produced, and the separated product includes high cetane diesel and propylene.

In another aspect of the invention, there is provided a catalytic conversion process for producing diesel and propylene, characterized in that the feedstock oil is reacted in a catalytic cracking reactor with a catalytic cracking catalyst, preferably a catalytically cracking catalyst having a relatively uniform activity, and include

(1) a feedstock oil comprising a re-cracking feedstock oil and a cracked feedstock oil, introducing the feedstock oil into the catalytic cracking reactor at a location, or introducing the feedstock oil to the location at more than one of the same or different heights Catalytic cracking reactor;

(2) re-cracking the feedstock oil in the catalytic cracking reactor to react not later than cracking the feedstock oil;

(3) The reaction temperature, the weight hourly space velocity, the weight ratio of the catalytic cracking catalyst to the feedstock oil in the catalytic cracking reaction are sufficient to obtain a reaction product comprising 12-60% by weight of the catalytic wax oil of the cracked feedstock oil; wherein the cracking raw material is obtained The weight hourly space velocity of the oil is 5-100 h ^-1 ;

(5) catalyzing the wax oil into a hydrotreatment or/and a solvent extraction device and/or a hydrocracking device for further processing;

(6) Catalytic wax oil hydrotreating to obtain a hydrogenated catalytic wax oil or/and a solvent extraction apparatus to obtain a catalytic wax oil raffinate oil or/and a hydrocracking tail oil obtained by hydrocracking as a raw material for a productive diesel unit.

In a more preferred embodiment, the prolific diesel unit is a catalytic cracking unit for producing diesel. In a more preferred embodiment, the catalyst used in the catalytic cracking unit for the production of diesel is a relatively productive, relatively productive diesel catalyst.

In a more preferred embodiment, the re-cracking feedstock oil is selected from or comprises one or a mixture of two or more of a slurry, diesel, gasoline, a hydrocarbon having 4 to 8 carbon atoms.

In a more preferred embodiment, the cracking feedstock oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, minus One or a mixture of two or more of the residual oil and the atmospheric residue, and the other mineral oil is one or a mixture of two or more of coal liquefied oil, oil sand oil, and shale oil.

In a more preferred embodiment, the catalytic cracking catalyst comprises a zeolite, an inorganic oxide, and optionally a clay, each component comprising a total weight of the catalyst: 1-50% by weight of the zeolite, 5-19% by weight of the inorganic oxide, The clay is 0-70% by weight, wherein the zeolite is a medium pore zeolite and optionally a large pore zeolite, and the medium pore zeolite comprises from 51 to 100% by weight, preferably from 70% to 100% by weight, based on the total weight of the zeolite. The macroporous zeolite comprises from 0 to 49% by weight based on the total weight of the zeolite, the medium pore zeolite is selected from the ZSM series zeolite and/or the ZRP zeolite, and the large pore zeolite is selected from the Y series zeolite.

The relatively homogeneous catalyst (including the catalytic cracking catalyst used in the catalytic cracking reactor and the prolific diesel catalyst used in the prolific diesel plant) means that its initial activity does not exceed 80, preferably does not exceed 75, more preferably does not exceed 70; The catalyst has a self-equilibration time of from 0.1 hour to 50 hours, preferably from 0.2 to 30 hours, more preferably from 0.5 to 10 hours; and an equilibrium activity of from 35 to 60, preferably from 40 to 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--the micro-reaction activity test method for catalytic cracking of fresh catalyst "Petrochemical Analysis Method (RIPP Test Method)", Yang Cuiding et al., 1990, 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 in the product + gas production + coke production) / total amount of feed * 100% = in the product Gasoline yield below + °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 420-841 μm and having a loading of 5 g. The reaction raw material is a straight run having a distillation range of 235-337 ° C. Light diesel oil, reaction temperature 460 ° C, weight space velocity 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 100% water vapor conditions (refer to RIPP 92-90).

The relatively uniform activity of the catalyst 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, and aging after 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 treatment method 1 is embodied, for example, by charging fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, injecting steam at the bottom of the fluidized bed, and the catalyst is fluidized by the action of water vapor, while water vapor The catalyst is aged, the aging temperature is from 400 ° C to 850 ° C, preferably from 500 ° C to 750 ° C, preferably from 600 ° C to 700 ° C, and the apparent line speed of the fluidized bed is from 0.1 m / sec to 0.6 m / sec, most Preferably, it is 0.15 second to 0.5 m/sec, and after aging for 1 hour to 720 hours, preferably 5 hours to 360 hours, the catalyst having relatively uniform activity is obtained, and the catalyst having relatively uniform activity is added to the industrial device according to the requirements of the industrial device. It is preferably added to the regenerator of the industrial plant.

Catalyst treatment method 2:

(1) charging fresh catalyst 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 a relatively uniform activity to the corresponding reaction device.

The technical solution of the catalyst treatment method 2 is embodied, for example, by charging the catalyst into a fluidized bed, preferably a dense phase fluidized bed, injecting an aging medium containing water vapor at the bottom of the fluidized bed, and acting as an aging medium for the water vapor. The fluidization is carried out at the same time, and the aging medium containing water vapor aging the catalyst, and the aging temperature is 400 ° C - 850 ° C, preferably 500 ° C - 750 ° C, preferably 600 ° C - 700 ° C, the apparent line speed of the fluidized bed It is from 0.1 m/sec to 0.6 m/sec, preferably from 0.15 sec to 0.5 m/sec, and the weight ratio of water vapor to aging medium is from 0.20 to 0.9, preferably from 0.40 to 0.60, and aging is from 1 hour to 720 hours, preferably 5 After hours to 360 hours, the catalyst having a relatively uniform activity is obtained, and the catalyst having a relatively uniform activity is added to the industrial unit as required by the industrial apparatus, preferably 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 gas such as nitrogen. The weight ratio of the water vapor to the aged medium is from 0.2 to 0.9, preferably from 0.40 to 0.60.

Catalyst treatment method 3:

(1) introducing fresh catalyst into a fluidized bed, preferably a dense phase fluidized bed, while conveying a thermal regeneration catalyst of the regenerator to the fluidized bed, and performing heat exchange in the fluidized bed;

(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) Adding the catalyst having a relatively uniform activity to the corresponding reaction device.

The technical solution of the present invention is embodied, for example, in that a fresh catalyst is delivered to a fluidized bed, preferably a dense phase fluidized bed, while a thermally regenerated catalyst of the regenerator is also delivered to the fluidized bed, where the fluidization Heat exchange takes place in the bed. The aging medium of steam or water vapor is injected into the bottom of the fluidized bed, and the fresh catalyst is fluidized by the aging medium of steam or water vapor. At the same time, the aging medium of steam or water vapor ages the fresh catalyst and ages. The temperature is from 400 ° C to 850 ° C, preferably from 500 ° C to 750 ° C, preferably from 600 ° C to 700 ° C, and the apparent line speed of the fluidized bed is from 0.1 m / sec to 0.6 m / sec, preferably from 0.15 sec - 0.5 Meters/second, aged from 1 hour to 720 hours, preferably from 5 hours to 360 hours, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aged medium is greater than 0-4, preferably 0.5-1.5 A catalyst having a relatively uniform activity is obtained, and a catalyst having a relatively uniform activity is added to an industrial unit, preferably to a regenerator of an industrial unit, as required by an industrial plant. In addition, the water vapor after the aging step enters the reaction system (as 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 device, The pre-lifting section) or the regeneration system, and the aging medium of the water vapor after the aging step enters the regeneration system, and the regenerated catalyst after the heat exchange is returned to the regenerator. The aging medium includes air, dry gas, regenerated flue gas, gas after combustion of air and dry gas or gas after combustion of combustion oil, or other gas such as nitrogen.

Surprisingly, it has been found that by the above treatment method, the activity and selectivity distribution of the catalyst in the industrial reactor 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 (including the catalytic cracking catalyst and the prolific diesel catalyst) may be a particle size distribution of a conventional catalyst or a coarse particle size distribution. In a more preferred embodiment, the catalyst is characterized by a catalyst having a coarse particle size distribution.

The sieve of the coarse particle size distribution catalytic cracking catalyst is grouped into: catalytic cracking catalyst particles of less than 40 micrometers account for less than 10% by volume of all catalytic cracking catalyst particles, preferably less than 5%; catalytic cracking of more than 80 micrometers The catalyst particles constitute less than 15% by volume of all of the catalytic cracking catalyst particles, preferably less than 10%, and the remainder are 40-80 micron catalytic cracking catalyst particles.

The particle size distribution of the prolific diesel catalyst in the prolific diesel device is preferably a coarse particle size distribution, and the sieve grouping is: a volume ratio of the prolific diesel catalyst particles of less than 40 micrometers to all the prolific diesel catalyst particles is less than 10 %, preferably less than 5%, more than 80 microns of prolific diesel catalyst particles account for less than 15%, preferably less than 10% by volume of all prolific diesel catalyst particles, the rest are prolific 40-80 microns Diesel catalyst particles.

In a more preferred embodiment, the catalytic cracking reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. A combination, or a combination of two or more of the same reactor, 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 reaction conditions for re-cracking the feedstock oil are: reaction temperature 600-750 ° C, weight hourly space velocity 100-800 h ^-1 , reaction pressure 0.10-1.0 MPa, weight ratio of catalyst to re-cracking feedstock oil 30-150, the weight ratio of water vapor to re-cracking feedstock oil is 0.05-1.0.

In a more preferred embodiment, the reaction conditions for cracking the feedstock oil are: reaction temperature 450-600 ° C, weight hourly space velocity 5-100 h ^-1 , reaction pressure 0.10-1.0 MPa, weight ratio of catalyst to cracked feedstock oil 1.0- 30. The weight ratio of water vapor to cracked feedstock oil is 0.05-1.0.

In a more preferred embodiment, the cracking feedstock oil has a reaction temperature of 460 to 580 ° C, a weight hourly space velocity of 10 to 90 h ^-1 , preferably 20 to 60 h ^-1 , more preferably 30 to 50 h ^-1 , of catalyst and raw materials. The oil weight ratio is from 1 to 14, preferably from 3 to 14.

In a more preferred embodiment, the method further comprises separating the catalytic cracking reaction product and the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to stripping and charring regeneration and then returned to the catalytic cracking reactor, and the separated product includes Propylene, high cetane diesel and catalytic wax oil.

In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 260 ° C and a hydrogen content of not less than 10.5% by weight.

In a more preferred embodiment, the catalytic wax oil is a fraction having an initial boiling point of not less than 330 ° C and a hydrogen content of not less than 10.8% by weight.

The reaction system of the hydrotreating unit is usually a fixed bed reactor, and the hydrotreating catalyst is a Group VIB or/and Group VIII non-precious metal catalyst supported on an amorphous alumina or/and a ruthenium aluminum support, wherein the Group VIB non-precious metal is Molybdenum or/and tungsten, the Group VIII non-noble metal is one or more of nickel, cobalt, and iron.

The process conditions of the hydrogenation treatment are: hydrogen partial pressure of 4.0-20.0 MPa, reaction temperature of 280-450 ° C, volumetric space velocity of 0.1-20 h ^-1 , and hydrogen oil ratio of 300-2000 v/v.

The method aromatics extraction unit is suitable for use in existing aromatics extraction units. The solvent for extracting the aromatic hydrocarbon is selected from one or more of furfural, dimethyl hydrazine, dimethylformamide, monoethanolamine, ethylene glycol, and 1,2-propanediol, and the solvent can be recovered, and the extraction temperature is The ratio of solvent to catalytic wax oil is from 0.5:1 to 5.0:1 at 40-120 °C.

The reaction system of the hydrocracking unit generally comprises a refining reactor and a cleavage reactor, both of which are fixed bed reactors, and the refining reactor is usually charged with a hydrotreating catalyst which is supported on an amorphous alumina or/and yttrium aluminum support. a Group VIB or/and Group VIII non-noble metal catalyst; the hydrocracking catalyst is a Group VIB or/and Group VIII non-noble metal catalyst supported on a Y zeolite molecular sieve. Wherein the non-precious metal of group VIB is molybdenum or/and tungsten, and the non-precious metal of group VIII is one or more of nickel, cobalt and iron.

The hydrocracking process conditions are: hydrogen partial pressure of 4.0-20.0 MPa, reaction temperature of 280-450 ° C, volumetric space velocity of 0.1-20 h ^-1 , and hydrogen oil ratio of 300-2000 v/v.

In a more preferred embodiment, the catalytic cracking unit for producing diesel fuel has a reaction temperature of from 400 to 650 ° C, preferably from 430 to 500 ° C, more preferably from 430 to 480 ° C. The oil and gas residence time is from 0.05 to 5 seconds, preferably from 0.1 to 4 seconds. The reaction pressure is from 0.10 MPa to 1.0 MPa.

In a more preferred embodiment, the prolific diesel fuel comprises zeolite, inorganic oxide, clay. On a dry basis, each component comprises the total weight of the catalyst: 5 to 60% by weight of the zeolite, preferably 10 to 30% by weight; 0.5 to 50% by weight of the inorganic oxide; and 0 to 70% by weight of the clay. Among them, zeolite is used as an active fraction and is selected from large pore zeolite. 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, super stable Y obtained by different methods, and high yttrium Y. The inorganic oxide is used as a matrix selected from the group consisting of cerium oxide (SiO ₂ ) and/or aluminum oxide (Al ₂ O ₃ ). On the dry basis, the inorganic oxide contains cerium oxide in an amount of 50 to 90% by weight, and aluminum oxide accounts for 10 to 50% by weight. a clay as a binder selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, erbium, hydrotalcite, bentonite or Several.

In a more preferred embodiment, the prolific diesel reactor is selected from one or both of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a down conveyor line. Combinations of the above, or a combination of two or more of the same reactors, 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 catalytic wax oil raffinate oil obtained by the hydrogenation catalytic wax oil or/and solvent extraction or/and the catalytic wax oil hydrocracking tail oil obtained by hydrocracking are introduced into a prolific product at one position. The hydrogenated catalytic wax oil is introduced into the productive diesel reactor within the diesel reactor or at locations above one or the same height.

In a more preferred embodiment, the method for producing diesel fuel further comprises separating the reaction product in the diesel fuel reactor and the diesel fuel catalyst, and separating the separated diesel fuel catalyst by steam stripping, charring regeneration and returning The diesel fuel reactor is produced, and the separated product includes high cetane diesel and propylene.

In order to increase the ratio of the agent to the oil in the downstream zone of the reaction and increase the catalytic activity of the catalyst, it may be supplemented with a hot or cold regenerated catalyst, a semi-regenerated catalyst, a catalyst to be produced, and a fresh catalyst. The cooled regenerated catalyst and the cooled semi-regenerated catalyst are obtained by two steps of regeneration and one stage of regeneration of the catalyst to be produced, and the carbon content of the regenerated catalyst is 0.1% by weight or less, preferably 0.05% by weight or less, and the semi-regenerated catalyst carbon content. It is 0.1% by weight to 0.9% by weight, preferably having a carbon content of 0.15% by weight to 0.7% by weight; the carbon content of the catalyst to be produced is 0.9% by weight or more, and preferably the carbon content is 0.9% by weight to 1.2% by weight.

The method of separating propylene from the reaction product is the same as that well known to those skilled in the art.

The technical scheme combines catalytic cracking, catalytic wax oil hydrogenation and other processes to maximize the production of high cetane diesel low-carbon olefins, especially propylene, from heavy raw materials with low hydrogen content. Compared with the prior art, the invention has the following technical effects:

1. The yield of propylene and the selectivity of propylene in liquefied gas are greatly increased while the diesel oil is produced, and the cetane number of diesel is obviously improved;

2. In the case of a large increase in propylene yield and diesel fuel, dry gas yield and coke are significantly reduced.

3. The light oil yield is obviously increased, the oil slurry yield is obviously reduced, and the utilization efficiency of petroleum resources is improved.

4. Hydrogenation or / and aromatics extraction or / and hydrocracking unit operating cycles are significantly improved.

5. The catalyst is more uniform due to the particles, so that the local temperature distribution is more uniform during the regeneration process, and the catalyst crushing tendency is correspondingly reduced;

6. The catalyst consumption is reduced, and the catalyst content in the catalytic wax oil 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 this invention belongs, unless otherwise indicated. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not limiting.

The term "comprising" as used herein means that other steps and ingredients that do not affect the end result can be added. This term includes the terms "consisting of" and "consisting essentially of."

The term "method" or "process" refers to the manner, means, techniques, and procedures used to accomplish a specified task, including but not limited to those known to those skilled in the chemical and chemical arts, or they are readily known by known means, means, techniques, and The methods, means, techniques, and programs developed by the program.

In the present disclosure, various aspects of the invention may be represented in a range format. It is to be understood that the description of the range format is used for convenience and brief purpose only and should not be construed as limiting the scope of the invention. Accordingly, a range of descriptions should be considered as specifically disclosing all possible sub-ranges and values that are within the range. For example, a description of a range such as 1 to 6 should be considered as specifically disclosing sub-ranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, and Values within this range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.

Any range of numerical values (fractions or integers) within the ranges indicated is intended to be included herein. The phrase "between" the first numerical value "and" and the second numerical value "between" and the first numerical value "to" the second numerical value are used interchangeably herein and are intended to include The first and second values shown and all the scores and integers between them.

The method provided by the present invention will be further described below with reference to the accompanying drawings, but does not limit the invention.

The process flow is as follows: the pre-lifting medium enters from the bottom of the riser reactor 2 via the pipeline 1 , and the regenerated catalyst from the pipeline 16 accelerates upward along the riser under the lifting action of the pre-lifting medium, and then cracks the raw material oil through the pipeline 3 and comes from The atomized steam of line 4 is injected into the bottom of reaction zone I of riser 2, mixed with the existing stream of the riser reactor, and the cracked feedstock undergoes a cracking reaction on the hot catalyst and accelerates upward. The cracked feedstock oil is injected into the upper middle portion of the reaction zone I of the riser 2 via line 5 together with the atomized steam from line 6, mixed with the existing stream of the riser reactor, and the cracked feedstock is produced on a lower catalyst containing a certain carbon. The cracking reaction is accelerated upward and enters the reaction zone II to continue the reaction. The generated oil and gas and the deactivated catalyst are introduced into the cyclone separator in the settler 8 through the pipeline 7, thereby realizing the separation of the catalyst to be produced and the oil and gas. Chamber 9, the catalyst fines are returned to the settler by the legs. The catalyst to be produced in the settler flows to the stripping section 10 in contact with the steam from line 11. The oil gas stripped from the catalyst to be produced enters the gas collection chamber 9 through the cyclone separator. The stripped catalyst after the stripping enters the regenerator 13 through the inclined tube 12, and the main wind enters the regenerator through the pipeline 14, burns off the coke on the catalyst to be produced, regenerates the deactivated catalyst, and the flue gas enters the smoke through the pipeline 15. machine. The regenerated catalyst enters the riser via the inclined tube 16.

The oil and gas in the plenum 9 passes through the large oil and gas pipeline 17 and enters the subsequent separation system 18, and the separated propylene is taken out through the pipeline 19, and the separated propane is taken out through the pipeline 28; and the carbon tetrahydrocarbon is taken out through the pipeline 20, and can also be returned. The riser 2; the catalytic cracking dry gas is taken out through the line 21; the catalytic cracked gasoline is taken out through the line 27, and the gasoline fraction having a distillation range of less than 65-110 ° C is taken out through the line 22 as a re-cracking raw material and returned to the reactor; the diesel fraction is passed through the pipeline 29 Alternatively, the heavy diesel fraction may be withdrawn to the hydrogenation unit or/and the aromatics extraction unit together with the catalytic wax oil; the catalytic wax oil feedstock is withdrawn via line 23 to the hydrotreating unit or/and the aromatics extraction unit or/and the hydrocracking unit 24 The separated hydrotreated gas product or/and heavy aromatics or/and hydrocracking gas are withdrawn via line 25, hydrogenated catalytic wax oil or/and catalytic wax oil raffinate oil and/or catalytic wax oil hydrocracking tail oil via line 26 The productive diesel unit 27 is fed. The oil and gas generated by the prolific diesel unit can be passed through the oil and gas line 28 into the fractionation system 18 or/and into other fractionation systems for separation. The distillation range of each fraction is adjusted according to the actual needs of the refinery.

The following examples will further illustrate the method, but do not limit the method accordingly.

The stock oil used in the examples was VGO, and its properties are shown in Table 1.

The preparation method of the catalytic cracking catalyst (CAT-MP) used in the examples is briefly described as follows:

Catalyst CAT-MP preparation method

1), 20g of NH ₄ Cl is dissolved in 1000g of water, and 100g (dry basis) crystallized product ZRP-1 zeolite is added to the solution (produced by Qilu Petrochemical Company catalyst plant, SiO ₂ /Al ₂ O ₃ =30, rare earth content RE ₂ O ₃ = 2.0% by weight), after exchanged at 90 ° C for 0.5 h, the filter cake was filtered; 4.0 g of H ₃ PO ₄ (concentration 85%) and 4.5 g of Fe(NO ₃ ) _{3 were} dissolved in 90 g of water and mixed with the filter cake. Immersion drying; followed by calcination at 550 ° C for 2 hours to obtain a MFI structure mesoporous zeolite containing phosphorus and iron, the elemental analytical chemical composition is

0.1Na ₂ O‧5.1Al ₂ O ₃ ‧2.4P ₂ O ₅ ‧1.5Fe ₂ O ₃ ‧3.8RE ₂ O ₃ ‧88.1SiO ₂ .

2), using 7500kg of polyhydrate kaolin (Suzhou Ceramics Industrial Products, solid content 71.6% by weight) with 250kg of deionized water, and then adding 54.8kg of pseudo-boehmite (Shandong Aluminum Factory industrial products, solid content 63% by weight) ), adjust the pH to 2-4 with hydrochloric acid, stir evenly, stand still at 60-70 ° C for 1 hour, keep the pH at 2-4, reduce the temperature to below 60 ° C, add 41.5Kg aluminum sol (Qilu) The petrochemical company's catalyst plant product, with an Al ₂ O ₃ content of 21.7 wt%), was stirred for 40 minutes to obtain a mixed slurry.

3), the phosphorus- and iron-containing MFI structure of the pore-prepared zeolite (dry basis is 22.5 kg) and DASY zeolite (Qilu Petrochemical Company catalyst factory industrial product, unit cell size is 2.445-2.448nm, dry basis) 2.0kg) is added to the mixed slurry obtained in the step 2), stirred uniformly, spray-dried, washed with ammonium dihydrogen phosphate solution (phosphorus content of 1% by weight), washed away with free Na ⁺ , and dried to obtain a catalytic cracking catalyst. Sample CAT-MP, the composition of the catalyst was 18% by weight of MFI structure mesoporous zeolite containing phosphorus and iron, 2% by weight of DASY zeolite, 28% by weight of pseudoboehmite, 7% by weight of aluminum sol and balance of kaolin.

4) The prepared catalyst was aged in a dense phase bed at 700 ° C and 100% steam, the apparent line speed of the fluidized bed was 0.28 m / s, and the aging time was 17 hours. The aged catalyst properties are listed in Table 2. The code name is CAT-MP-1, and then part of the aging agent is subjected to decantation to remove fine particles and particles larger than 100 μm to obtain a catalyst having a coarse particle size distribution, which is coded as CAT-MP-2, and its properties are listed in the table. 2.

The preparation method of the prolific diesel catalyst (CAT-MD) used in the examples is briefly described as follows:

Catalyst CAT-MD preparation method

1), 2 liters of a water glass solution having a concentration of 155 g/L of cerium oxide and 1 liter of an acidified aluminum sulfate solution having a free acid of 148 g/L and an Al ₂ O ₃ content of 20 g/L, both of which simultaneously enter the fast The mixer reacts to obtain a cerium sol.

2) Into the cerium sol prepared above, 465 g of kaolin (Suzhou Kaolin Company, solid content: 80% by weight) was added, and the kaolin-ruthenium sol was obtained by beating for 1 hour.

3), a pseudo-boehmite containing Al ₂ O ₃ 124g (Shandong Aluminum Factory, the content of Al ₂ O ₃ is 33% by weight) and 450g of deionized water mixed for 30 minutes, then adding 25 ml of the concentration of 31% by weight Hydrochloric acid (acid / Al ₂ O ₃ molar ratio of 0.2) peptization, continue to beat for 2 hours, and then add 656g molecular sieve content of 32% by weight of polished DASY0.0 molecular sieve slurry (Qilu catalyst plant production, unit cell size is 2.445 Nm), beaten for 30 minutes to obtain a mixed slurry of pseudoboehmite and molecular sieve.

4) mixing the kaolin-cerium sol slurry prepared above with the mixed slurry of pseudo-boehmite and molecular sieve prepared above for 10 minutes to obtain a catalyst slurry, and spray-drying the obtained slurry into a diameter of 20-120 μm and cerium oxide. The pellets had a content of 29.9% by weight, a kaolin content of 35.9% by weight, an alumina content of 13.9% by weight, and a molecular sieve content of 20.3% by weight, and a drying temperature of 180 °C. The sample was washed with deionized water until no sodium ions were detected, and dried at 150 ° C to obtain a prepared catalyst CAT-MD.

5) The prepared catalyst was aged in a dense phase bed at 700 ° C and 100% steam, the apparent line speed of the fluidized bed was 0.27 m / s, and the aging time was 20 hours. The aged catalyst properties are listed in Table 2. The code is CAT-MD-1, and then part of the aging agent is subjected to decantation to remove fine particles and particles larger than 100 μm to obtain a catalyst having a coarse particle size distribution, which is coded as CAT-MD-2, and its properties are listed in the table. 2.

The preparation method of the hydrotreating catalyst used in the examples is as follows: ammonium metatungstate ((NH ₄ ) ₂ W ₄ O ₁₃ ‧18H ₂ O, chemically pure) and nickel nitrate (Ni(NO ₃ ) ₂ ‧18H are weighed ₂ O, chemically pure), formulated into 200 mL of water with water. The solution was added to 50 g of an alumina carrier, immersed at room temperature for 3 hours, and the immersion liquid was ultrasonically treated for 30 minutes during the impregnation, cooled, filtered, and dried in a microwave oven for about 15 minutes. The composition of the catalyst was: 30.0% by weight of WO ₃ , 3.1% by weight of NiO and the balance of alumina.

The catalytic cracking catalysts CAT-MP-1 and CAT-MP-2 had a fresh catalyst activity (initial activity) of 73, a self-equilibration time of 9 h at a temperature of 800 ° C and 100% water vapor, and an equilibrium activity of 49.

The prolific diesel catalysts CAT-MD-1 and CAT-MD-2 had a fresh catalyst activity (initial activity) of 80, a self-equilibration time of 10 h at a temperature of 800 ° C and 100% water vapor, and an equilibrium activity of 52.

The catalytic cracking catalyst used in the comparative example was traded as MLC-500, and was produced by Qilu Catalyst Plant of Sinopec Catalyst Branch. Its initial activity was 91, the self-equilibration time was 60 h, and the equilibrium activity was 43. The catalyst properties are listed in Table 2.

The commercial versions of the hydrorefining catalyst and the hydrocracking catalyst used in the examples were RN-2 and RT-1, respectively, both of which were produced by Changling Catalyst Plant of Sinopec Catalyst Branch.

Example 1

This example was tested according to the flow of the drawing. The cracking feedstock oil was directly used as the raw material for catalytic cracking, and the catalyst CAT-MP-1 was used to test on the medium-sized device of the riser reactor, and the cracking raw material entered the upper part of the reaction zone I. The cracking feedstock is subjected to a cracking reaction at a reaction temperature of 530 ° C, a weight hourly space velocity of 35 h ^-1 , a catalytic cracking catalyst to a raw material weight ratio of 4, and a weight ratio of water vapor to a raw material of 0.15. In the reaction zone II, the oil and gas is at a reaction temperature of 490. The cracking reaction is carried out under the condition of a weight ratio of water vapor to the raw material of 0.15, and the oil and gas and the carbon-bearing catalyst are separated in a settler, and the product is cut in a separation system according to a distillation range to obtain propylene, butene, gasoline, diesel and catalytic Wax oil fraction. The catalytic wax oil is sent to a hydrogenation treatment device for hydrogenation treatment under a reaction condition of a hydrogen partial pressure of 16.0 MPa, a reaction temperature of 350 ° C, and a volume space velocity of 1.5 h ^-1 , and the hydrogenated catalytic wax oil is transported to a prolific diesel catalytic cracking device. Catalytic conversion was carried out by contacting the catalyst CAT-MD-1. Operating conditions and product distribution are listed in Table 3.

As can be seen from Table 3, the propylene yield was as high as 14.31% by weight, the diesel yield was as high as 18.89% by weight, and the cetane number was 41.

Comparative Example 1

The medium-sized test in Comparative Example 1 was carried out on a conventional catalytic cracking apparatus using a multi-product propylene scheme. The raw material oil tested was the same as in Example 1, and the catalyst used was a conventional particle size distribution MLC-500 catalyst at a reaction temperature of At 512 ° C, the ratio of agent to oil is 6. Operating conditions and product distribution are listed in Table 3.

As can be seen from Table 3, the propylene yield can reach 6.53, the diesel yield is 12.58, and the diesel cetane number is 36. The total liquid yield (liquefied gas yield + gasoline yield + diesel yield) of Comparative Example 1 was significantly lower than that of Example 1, and the ratio of the liquefied gas yield / dry gas yield was significantly smaller than that of Example 1.

Example 2

Example 2 was also tested according to the flow of the drawing. The raw material oil and the test procedure and method of the test were identical to those of Example 1, except that the catalytic cracking catalyst used was changed from the conventional particle size distribution of CAT-MP-1 to the coarse particle size. The distributed CAT-MP-2; the prolific diesel catalyst was changed from the traditional particle size distribution of CAT-MD-1 to the coarse particle size distribution of CAT-MD-2. Operating conditions and product distribution are listed in Table 3.

As can be seen from Table 3, the propylene yield was as high as 14.58% by weight, the diesel yield was 19.77% by weight, and the cetane number was 41.

Example 3

This example was tested according to the flow of the drawing. The cracking feedstock oil was directly used as the raw material for catalytic cracking, and the catalyst CAT-MP-1 was used to test on the medium-sized device of the riser reactor, and the cracking raw material entered the upper part of the reaction zone I. Butene is used as the re-cracking raw material to enter the bottom of the reaction zone I. At the bottom of the reaction zone I, the re-cracked raw material is at a reaction temperature of 610 ° C, a weight hourly space velocity of 175 h ^-1 , a catalytic cracking catalyst to a raw material weight ratio of 70, water vapor and raw materials. The cracking reaction is carried out at a weight ratio of 0.20; in the upper part of the reaction zone I, the catalytic raw material is at a reaction temperature of 530 ° C, a weight hourly space velocity of 40 h ^-1 , a weight ratio of the catalytic cracking catalyst to the raw material 4, and a weight ratio of water vapor to the raw material is The cracking reaction is carried out under the condition of 0.15. In the reaction zone II, the oil and gas is subjected to a cracking reaction at a reaction temperature of 480 ° C and a weight ratio of water vapor to the raw material of 0.15, and the oil and gas and the carbon-bearing catalyst are separated in a settler, and the product is separated in the separation system. The distillation range is cut to obtain propylene, butene, gasoline, diesel, and catalytic wax oil fractions. The catalytic wax oil is sent to a hydrocracking unit for treatment. The reaction system of the hydrocracking unit comprises two reactors of a refining reactor and a cracking reactor, and has a hydrogen partial pressure of 17.9/17.4 MPa, a reaction temperature of 374/371 ° C, and a volumetric space velocity of 0.95. Hydrogenation treatment was carried out under the reaction conditions of /1.2h ^-1 , and the hydrogenated cracked tail oil was sent to a multi-product diesel catalytic cracking unit for catalytic conversion with the catalyst CAT-MD-1. Operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, the propylene yield was as high as 13.10% by weight, the diesel yield was 11.36% by weight, the diesel cetane number was as high as 52, and the jet fuel was 13.33% by weight.

Compared with Comparative Example 1, the yield of propylene in Example 3 was significantly increased by 6.57 percentage points; the cetane number of diesel was also significantly increased by 16 units; the total liquid yield (liquefied gas yield + gasoline yield) + Diesel yield + jet fuel yield) increased significantly by 3.94 percentage points; the ratio of liquefied gas yield to dry gas yield was also relatively low.

Example 4

Example 4 was also tested according to the flow of the drawing. The raw material oil and the test procedure and method of the test were identical to those of Example 3 except that the catalytic cracking catalyst used was changed from the conventional particle size distribution of CAT-MP-1 to the coarse particle size. The distributed CAT-MP-2; the prolific diesel catalyst was changed from the traditional particle size distribution of CAT-MD-1 to the coarse particle size distribution of CAT-MD-2. Operating conditions and product distribution are listed in Table 4.

As can be seen from Table 4, the propylene yield was as high as 13.16% by weight, the diesel yield was 12.03% by weight, the cetane number was 54, and the jet fuel was 13.85% by weight.

It is to be understood that certain aspects and features of the invention described in the various embodiments may be Conversely, various aspects and features of the inventions disclosed in a single embodiment may be provided separately or in any suitable sub-combination.

All publications, patents, and patent applications mentioned in this specification are hereby incorporated by reference in their entirety in their entirety in the 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

1~7,11,14,15,17,19~23,25~29. . . Pipeline

2. . . Riser

8. . . Settler

9. . . Gas collection room

10. . . Stripping section

12, 16. . . Inclined tube

13. . . Regenerator

18. . . Separation system

twenty four. . . Hydrocracking unit

I, II. . . Reaction zone

The invention is described herein by way of example only with reference to the accompanying drawings. DETAILED DESCRIPTION OF THE INVENTION The detailed description is to be considered as illustrative of the preferred embodiments of the invention Described as described. In this regard, the structural details of the present invention are not intended to

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of one embodiment of the invention.

1~7,11,14,15,17,19~23,25~29. . . Pipeline

2. . . Riser

8. . . Settler

9. . . Gas collection room

10. . . Stripping section

12, 16. . . Inclined tube

13. . . Regenerator

18. . . Separation system

twenty four. . . Hydrocracking unit

I, II. . . Reaction zone

Claims (39)

A catalytic conversion method for producing diesel and propylene, characterized in that the feedstock oil is reacted with the catalytic cracking catalyst in a catalytic cracking reactor, and the reaction temperature, the weight hourly space velocity, and the weight ratio of the catalyst to the feedstock oil are sufficient for the reaction to be contained in the raw material. The reaction product of 12-60% by weight of the catalytic wax oil, wherein the weight hourly space velocity is 25-100 h ^-1 , the reaction temperature is 450-600 ° C, and the weight ratio of the catalytic cracking catalyst to the feedstock oil is 1- 30. The catalytic wax oil is further processed into at least one of a hydrogenation treatment device, a solvent extraction device, and a hydrocracking device, wherein the catalytic cracking catalyst in the catalytic cracking reactor has a coarse particle size distribution, wherein 40 micron catalytic cracking catalyst particles account for less than 10% by volume of all catalytic cracking catalyst particles, and catalytic cracking catalyst particles larger than 80 micrometers account for less than 15% by volume of all catalytic cracking catalyst particles, and the rest are 40-80 micrometers. Catalytic cracking catalyst particles. The method of claim 1, wherein the feedstock oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coker gas oil, and deasphalted oil. 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. The method of claim 1, wherein the catalytic cracking is reversed The catalytic cracking catalyst in the reactor comprises zeolite, inorganic oxide and optionally clay, and the components respectively constitute the total weight of the catalyst: 1-50% by weight of zeolite, 5-99% by weight of inorganic oxide, and 0-70 of clay. % by weight, wherein the zeolite is a medium pore zeolite and optionally a large pore zeolite, the medium pore zeolite comprises from 51 to 100% by weight based on the total weight of the zeolite, the large pore zeolite comprises from 0 to 49% by weight based on the total weight of the zeolite, and the medium pore zeolite is selected from the group consisting of ZSM series zeolite and / or ZRP zeolite, large pore zeolite is selected from Y series zeolite. The method of claim 1, wherein the catalytic cracking reactor is selected from the group consisting of a riser, a linear velocity fluidized bed, a fluidized bed of equal diameter, an ascending transport line, and a descending transport line. Two or more combinations, or a combination of two or more of the same reactor, including series or/and parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms. The method of claim 1, wherein the feedstock oil is introduced into the catalytic cracking reactor at one location, or the feedstock oil is introduced into the catalytic cracking reactor at a location that exceeds one or the same height. For example, the method of claim 1 wherein the reaction temperature is 460-580 ° C, the weight hourly space velocity is 30-80 h ^-1 , the weight ratio of the catalytic cracking catalyst to the feedstock oil is 2-15, and the weight of the steam and the cracked feedstock oil. The ratio is 0.05-1.0. The method of claim 1, wherein the reaction is carried out at a pressure of from 0.10 MPa to 1.0 MPa. The method of claim 1, wherein the method further comprises separating the reaction product and the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to steam stripping, charring regeneration, and returned to the reactor, and the separated product includes propylene. High cetane diesel and catalytic wax oil. The method of claim 1, wherein the catalytic wax oil has an initial boiling point of not less than 260 ° C and a hydrogen content of not less than 10.5% by weight. The method of claim 1, wherein at least one of the hydrogenated catalytic wax oil obtained by hydrogenating the wax oil, the catalytic wax oil raffinate obtained by the solvent extraction device, and/or the hydrocracking tail oil obtained by hydrocracking is used as Raw materials for prolific diesel engines. For example, the method of claim 10, wherein the reaction temperature of the prolific diesel device is 400-650 ° C, the residence time of the oil and gas is 0.05-5 seconds, and the reaction pressure is 0.10 MPa-1.0 MPa. The method of claim 10, wherein the prolific diesel catalyst used in the prolific diesel device comprises zeolite, inorganic oxide, clay, and each component accounts for the total weight of the catalyst on a dry basis: zeolite 5 weight - 60 Weight %; inorganic oxide 0.5 to 50% by weight; clay 0 to 70% by weight, The medium zeolite is used as an active fraction and is selected from the group consisting of large pore zeolites, and the large pore zeolite refers to one or two of the zeolites composed of rare earth Y, rare earth hydrogen Y, super stable Y obtained by different methods, and high yttrium Y. More than one mixture. The method of claim 1 or 10, wherein the particle size distribution of the catalytic cracking catalyst in the catalytic cracking reactor and/or the diesel fuel catalyst in the prolific diesel device is a coarse particle size distribution The sieve grouping is: less than 40 micrometers of prolific diesel catalyst particles account for less than 10% by volume of all prolific diesel catalyst particles, and more than 80 micrometers of prolific diesel catalyst particles account for a small proportion of all prolific diesel catalyst particles. At 15%, the rest are 40-80 microns of prolific diesel catalyst particles. The method of claim 1 or 10, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel catalyst in the prolific diesel fuel plant is a relatively uniform catalytic cracking catalyst, The catalyst having a relatively uniform activity means that its initial activity does not exceed 80; the self-equilibration time of the catalyst is from 0.1 hour to 50 hours; and the equilibrium activity is from 35 to 60. The method of claim 1 or 10, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: 1) loading fresh catalyst into the fluidized bed and contacting with water vapor, in one a catalyst having a relatively uniform activity after aging in a hydrothermal environment; (2) adding a catalyst having a relatively uniform activity to a corresponding reaction device; and wherein the certain hydrothermal environment includes: an aging temperature of 400 °C-850 ° C, the apparent line speed of the fluidized bed is 0.1 m / s - 0.6 m / s, aging 1 hour - 720 hours. The method of claim 1 or 10, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: 1) charging fresh catalyst into a fluidized bed, contacting 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 Into the corresponding reaction device; wherein the certain hydrothermal environment comprises: an aging temperature of 400 ° C - 850 ° C, an apparent line speed of the fluidized bed of 0.1 m / sec - 0.6 m / sec, the weight of water vapor and aging medium Aging from 0.20-0.9, aging for 1 hour - 720 hours. The method of claim 1 or 10, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: 1), input fresh catalyst into the fluidized bed while reheating the regenerator The raw catalyst is transported to the fluidized bed to perform heat exchange in the fluidized bed; (2) the fresh catalyst after heat exchange is contacted with the aging medium of steam or water vapor, and is carried out under a certain hydrothermal environment. a catalyst having relatively uniform activity after aging; and (3) adding a catalyst having a relatively uniform activity to the corresponding reaction device; wherein the certain hydrothermal environment comprises: an aging temperature of 400 ° C to 850 ° C, fluidization The apparent line speed of the bed is from 0.1 m/sec to 0.6 m/sec, aged from 1 hour to 720 hours, and the weight ratio of the water vapor to the aging medium (if any) is greater than 0-4. The method of claim 10, wherein the prolific diesel reactor is selected from the group consisting of a riser, a linear fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a downstream conveyor line. Combinations of the above, or a combination of two or more of the same reactor, including series or / and parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms. The method of claim 10, wherein the catalytic wax oil raffinate oil obtained by extracting the hydrogenated catalytic wax oil or/and a solvent at a position or/and the catalytic wax oil hydrocracking tail oil obtained by hydrocracking The hydrogenated catalytic wax oil is introduced into the productive diesel reactor or into more than one of the same or different heights. The method of claim 10, wherein the method performed in the prolific diesel device further comprises separating the reaction product from the prolific diesel catalyst, and the prolific diesel catalyst is returned to the prolific after being stripped and charred. In the diesel reactor, the separated product includes high cetane diesel and propylene. A catalytic conversion method for producing diesel and propylene, characterized in that the feedstock oil is reacted with the catalytic cracking catalyst in a catalytic cracking reactor, and further comprises (1) the feedstock oil comprises re-cracking the feedstock oil and cracking the feedstock oil in one position Introducing the feedstock oil into the catalytic cracking reactor, or introducing the feedstock oil into the catalytic cracking reactor at more than one location of the same or different height; (2) re-cracking the feedstock oil in the catalytic cracking The reaction is carried out in the reactor not later than the cracking of the feedstock oil; (3) the reaction temperature, the weight hourly space velocity, the weight ratio of the catalytic cracking catalyst to the feedstock oil in the catalytic cracking reaction is sufficient to allow the reaction to comprise 12-60 of the cracked feedstock oil. a heavy % catalyzed reaction product of the wax oil; wherein the weight hourly space velocity of the cracked feedstock oil is from 5 to 100 h ^-1 ; (4) the catalytic wax oil enters a hydrotreatment or/and a solvent extraction device and/or a hydrocracking device for further processing; (5) Catalytic wax oil hydrotreating to obtain a hydrogenated catalytic wax oil or/and a solvent extraction apparatus to obtain a catalytic wax oil raffinate oil or/and a hydrocracking tail oil obtained by hydrocracking as a prolific The raw material of the oil device is characterized in that: the catalytic cracking catalyst in the catalytic cracking reactor has a coarse particle size distribution, wherein a catalytic cracking catalyst particle of less than 40 micrometers accounts for less than 10% by volume of all catalytic cracking catalyst particles. %, catalytic cracking catalyst particles larger than 80 microns account for less than 15% by volume of all catalytic cracking catalyst particles, and the rest are 40-80 micron catalytic cracking catalyst particles. The method of claim 21, wherein the re-cracking feedstock oil is selected from or comprises one or a mixture of two or more of a slurry, diesel, gasoline, a hydrocarbon having 4 to 8 carbon atoms. The method of claim 21, wherein the cracking feedstock oil is selected from or comprises petroleum hydrocarbons and/or other mineral oils, wherein the petroleum hydrocarbons are selected from the group consisting of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalting. One or a mixture of two or more of oil, 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. The method of claim 21, wherein the catalytic cracking catalyst comprises a zeolite, an inorganic oxide, and optionally a clay, each component comprising a total weight of the catalyst: 1-50% by weight of the zeolite, and 5-99 of the inorganic oxide. Weight %, clay 0-70% by weight, wherein the zeolite is a medium pore zeolite and optionally a large pore zeolite, the medium pore zeolite accounts for 51-100% by weight of the total weight of the zeolite, and the large pore zeolite accounts for 0-49 weight of the total weight of the zeolite. %, medium pore zeolite is selected from ZSM series zeolite And/or ZRP zeolite, the large pore zeolite is selected from the Y series zeolite. The method of claim 21, wherein the particle size distribution of the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel catalyst in the prolific diesel device is a coarse particle size distribution, The sieve grouping is: the volume ratio of the prolific diesel catalyst particles smaller than 40 microns to the proportion of all the prolific diesel catalyst particles is less than 10%, and the volume ratio of the prolific diesel catalyst particles larger than 80 microns to the proportion of all the prolific diesel catalyst particles is less than 15 %, the rest are 40-80 micron prolific diesel catalyst particles. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel catalyst in the prolific diesel device is a relatively uniform catalytic cracking catalyst, A catalyst having a relatively uniform activity means that its initial activity does not exceed 80; the self-equilibration time of the catalyst is from 0.1 hour to 50 hours; and the equilibrium activity is from 35 to 60. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: (1) The fresh catalyst is charged into the fluidized bed, contacted with water vapor, and aging is performed under a certain hydrothermal environment to obtain a catalyst having relatively uniform activity; (2) adding the relatively uniform activity catalyst to a corresponding reaction device, wherein the certain hydrothermal environment comprises: an aging temperature of 400 ° C to 850 ° C, and an apparent line speed of the fluidized bed of 0.1 m / sec. -0.6 m / s, aged 1 hour - 720 hours. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: (1) The fresh catalyst is charged into the fluidized bed and contacted with the aging medium containing water vapor, and after aging in a certain hydrothermal environment, a catalyst having relatively uniform activity is obtained; (2) the catalyst having relatively uniform activity is added to the corresponding catalyst. The reaction device comprises: the certain hydrothermal environment comprises: an aging temperature of 400 ° C to 850 ° C, an apparent line speed of the fluidized bed of 0.1 m / sec - 0.6 m / sec, a weight ratio of water vapor to the aging medium of 0.20 - 0.9, aging 1 hour - 720 hours. The method of claim 21, wherein the catalytic cracking catalyst in the catalytic cracking reactor and/or the prolific diesel fuel in the prolific diesel plant is obtained by the following treatment method: (1) And feeding fresh catalyst to the 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 the aging medium of steam or water vapor, and the catalyst is relatively uniform after being aged in a certain hydrothermal environment; 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 400 ° C to 850 ° C, an apparent line speed of the fluidized bed of 0.1 m / sec - 0.6 m / sec, and aging for 1 hour - 720 Hour, in the case of an aging medium containing water vapor, the weight ratio of the water vapor to the aged medium is greater than 0-4. The method of claim 21, wherein the catalytic cracking reactor is selected from the group consisting of a riser, a constant velocity fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, or a down conveyor line. Two or more combinations, or a combination of two or more of the same reactor, including series or/and parallel, wherein the riser is a conventional equal diameter riser or a riser of various forms. For example, the method of claim 21, wherein the reaction conditions for re-cracking the feedstock oil are: a reaction temperature of 600-750 ° C, a weight hourly space velocity of 100-800 h ^-1 , a reaction pressure of 0.10-1.0 MPa, a catalyst and a re-cracking feedstock oil. The weight ratio of water vapor to re-cracking stock oil is from 0.05 to 1.0 by weight. The method of claim 21, wherein the reaction conditions for cracking the feedstock oil are: reaction temperature 450-600 ° C, weight hourly space velocity 5-100 h ^-1 , reaction pressure 0.10-1.0 MPa, weight ratio of catalyst to cracked feedstock oil 1.0-30, the weight ratio of water vapor to cracked feedstock oil is 0.05-1.0. The method of claim 21, wherein the method further comprises separating the catalytic cracking reaction product and the catalytic cracking catalyst, and the separated catalytic cracking catalyst is subjected to steam stripping, charring regeneration, and returned to the reactor, and the separated product is obtained. These include propylene, high cetane diesel and catalytic wax oils. The method of claim 21, wherein the catalytic wax oil is a fraction having an initial boiling point of not less than 260 ° C and a hydrogen content of not less than 10.5% by weight. For example, the method of claim 21, wherein the reaction temperature of the prolific diesel device is 400-650 ° C, the residence time of the oil and gas is 0.05-5 seconds, and the reaction pressure is 0.10 MPa-1.0 MPa. The method of claim 21, wherein the prolific diesel catalyst in the prolific diesel device comprises zeolite, inorganic oxide, clay, and the components are respectively based on the total weight of the catalyst: 5 to 60 weight of the zeolite. %; inorganic oxide 0.5 weight - 50% by weight; clay 0 weight - 70% by weight. The zeolite is used as an active component and is selected from the group consisting of large pore zeolites, and the large pore zeolite refers to one or two of the zeolites composed of rare earth Y, rare earth hydrogen Y, super stable Y obtained by different methods, and high yttrium Y. More than one mixture. The method of claim 21, wherein the prolific diesel reactor in the prolific diesel device is selected from the group consisting of a riser, a line-rate fluidized bed, a fluidized bed of equal diameter, an upstream conveyor line, and a descending line. One or a combination of two or more, or a combination of two or more of the same reactor, the combination comprising series or / and parallel, wherein the riser is a conventional equal diameter riser or various a riser of the form of a variable diameter. The method of claim 21, wherein the hydrocracking tail oil obtained by the hydrogenation catalytic wax oil or/and hydrocracking is introduced into a prolific diesel reactor in a multi-product diesel unit at a position, or The hydrocracking tail oil obtained by the hydrogenation catalytic wax oil or/and hydrocracking is introduced into a prolific diesel reactor in a multi-product diesel unit at a location of the same or different heights. The method of claim 21, wherein the method of performing in the prolific diesel device further comprises separating the reaction product in the diesel fuel reactor and the prolific diesel catalyst, and separating the produced diesel catalyst by steam After the regeneration and charring regeneration, it returns to the prolific diesel reactor, and the separated products include high cetane diesel and propylene.