CN110724562B - Catalytic cracking method and system for producing propylene and high-octane gasoline - Google Patents

Catalytic cracking method and system for producing propylene and high-octane gasoline Download PDF

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CN110724562B
CN110724562B CN201810779916.XA CN201810779916A CN110724562B CN 110724562 B CN110724562 B CN 110724562B CN 201810779916 A CN201810779916 A CN 201810779916A CN 110724562 B CN110724562 B CN 110724562B
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catalyst
fluidized bed
oil
fast fluidized
catalytic cracking
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CN110724562A (en
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张执刚
龚剑洪
魏晓丽
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/026—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only catalytic cracking steps
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a catalytic cracking method and a system for producing propylene and high-octane gasoline, wherein the method comprises the following steps: introducing preheated high-quality heavy oil into the first fast fluidized bed from the lower part of the first fast fluidized bed to contact with the first catalytic cracking catalyst and perform a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be generated; introducing preheated inferior heavy oil into the second rapid fluidized bed from the bottom of the second rapid fluidized bed to contact with a second catalytic cracking catalyst and perform a second catalytic cracking reaction from bottom to top to obtain a second reaction product and a second spent catalyst; and separating the obtained first reaction product and the second reaction product to obtain dry gas, liquefied gas, pyrolysis gasoline, pyrolysis diesel oil and pyrolysis heavy oil. The method and the system have low yield of coke and dry gas for catalytic cracking and high yield of propylene and high-octane gasoline.

Description

Catalytic cracking method and system for producing propylene and high-octane gasoline
Technical Field
The invention relates to a catalytic cracking method and a catalytic cracking system for producing propylene and high-octane gasoline.
Background
Propylene is an important organic chemical raw material, the equivalent consumption of propylene in 2016 years is 3380 ten thousand tons, and the equivalent self-supporting rate is 75.2%. The equivalent consumption of propylene in China can reach 3900 ten thousand tons by 2020, and a certain space exists in the gap of the capacity. At present, 61% of propylene in the world comes from a byproduct of ethylene production by steam cracking, 34% of propylene comes from a byproduct of gasoline and diesel oil production by a catalytic cracking unit in an oil refinery, wherein the steam cracking uses light oil such as naphtha as a raw material to produce ethylene and propylene by thermal cracking, the amount of propylene produced by the steam cracking unit tends to decrease with the lightening of the raw material of the steam cracking, and the technical advantage of propylene production from the heavy oil will face a great challenge with the aggravation of the lightening and deterioration of crude oil in the catalytic cracking unit serving as a second major source of propylene production.
Driven by the requirements of environmental protection laws and regulations and increasingly strict requirements of the automobile industry on the quality of fuel, the global automobile gasoline has very fast quality improvement in recent years, and the pace of upgrading the quality of oil products is obviously accelerated. At present, the quantity of catalytic cracking gasoline in China is about 70 percent of the total quantity of a gasoline pool, and the quality of the catalytic cracking gasoline plays a significant role in the overall level of the gasoline pool. The octane number RON of the catalytic cracking gasoline is 90-92 at most, the average octane number RON is 89-90, and the difference between the gasoline quality of the catalytic cracking gasoline and the gasoline quality of other developed countries is large, so that the octane number of the gasoline is improved, and the upgrading and updating of the gasoline are facilitated. In addition, in the process of cleaning gasoline, measures such as controlling the olefin content of the gasoline and desulfurizing all result in different octane number losses, and the contradiction of octane number shortage is more prominent. In conclusion, the development of catalytic cracking technology for producing propylene and producing high-quality fuel oil such as high-octane gasoline to meet the production requirements of chemical raw materials and high-quality fuel oil with continuously improved quality requirements is undoubtedly of great practical significance.
Chinese patent CN 200810246522.4 discloses a catalytic conversion method for preparing propylene and high-octane gasoline, raw oil with different cracking performances enters different reactors of a first riser reactor to contact with a catalytic conversion catalyst for cracking reaction, and a crackable component in a product is sent into a second riser reactor for reaction.
Chinese patent CN101724430A proposes that inferior raw oil is sequentially injected into a first reaction zone and a second reaction zone of a catalytic conversion reactor to contact and react with a catalytic conversion catalyst to obtain propylene, gasoline, catalytic wax oil and other products, wherein the catalytic wax oil enters an aromatic hydrocarbon extraction device and is separated to obtain extract oil and raffinate oil; the raffinate oil is recycled to the first reaction zone of the reactor or/and other catalytic conversion devices for further reaction to obtain the target products of propylene and gasoline.
Chinese patent CN98101765.7 discloses a method for simultaneously preparing low-carbon olefin and high-aromatic gasoline from heavy oil, which is to make heavy petroleum hydrocarbon and steam undergo catalytic conversion reaction in a composite reactor composed of a lift pipe and a dense-phase fluidized bed to achieve the purpose of improving the yield of low-carbon olefin, especially propylene, and simultaneously increase the aromatic content in gasoline to about 80 wt%.
Chinese patent CN01119807.9 discloses a method for increasing the yield of ethylene and propylene by catalytic conversion of heavy petroleum hydrocarbon, which is to make hydrocarbon oil raw material contact and react with a catalyst containing pentasil zeolite in a riser or fluidized bed reactor.
From the prior art, the development of the technology for producing propylene and fuel oil by catalytic conversion of hydrocarbons mainly focuses on the catalytic cracking of heavy oil and the development of combined process technology. The catalytic cracking reactor still adopts the technology of a lifting pipe or a lifting pipe connected with a dense-phase bed reactor in series. Because the distillation range of heavy oil is wider, hydrocarbon molecules are larger, the product structure is complicated, the yield of inferior heavy oil propylene is low, and in order to improve the yield of propylene, the yield of dry gas and coke is greatly increased under the condition of increasing the yield of propylene by adopting higher reaction temperature. In order to efficiently utilize inferior heavy oil resources and meet the increasing demands for propylene and high-quality fuel oil, it is necessary to develop a catalytic conversion method for converting inferior heavy oil feedstock into high value-added products.
Disclosure of Invention
The invention aims to provide a catalytic cracking method and a catalytic cracking system for producing propylene and high-octane gasoline.
In order to achieve the above object, the present invention provides a catalytic cracking process for producing propylene and high octane gasoline, the process comprising:
introducing preheated high-quality heavy oil into the first fast fluidized bed from the lower part of the first fast fluidized bed to contact with the first catalytic cracking catalyst and perform a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be generated; the high-quality heavy oil is one or more selected from vacuum wax oil, coking wax oil, hydrogenated coking wax oil, deasphalted oil, hydrogenated deasphalted oil, paraffin-based atmospheric residue oil, hydrogenated paraffin oil, atmospheric residue oil and hydrocracking tail oil; wherein the catalyst in the first fast fluidized bed is distributed in a full dense phase, and the distribution of the axial solid fraction epsilon in the first fast fluidized bed meets the following conditions: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
introducing preheated inferior heavy oil into the second rapid fluidized bed from the lower part of the second rapid fluidized bed to contact with the second catalytic cracking catalyst and perform a second catalytic cracking reaction from bottom to top to obtain a second reaction product and a second spent catalyst; the properties of the inferior heavy oil meet one, two, three or four of the following indexes: the density at 20 ℃ is 900-32-10 wt% of carbon residue, 2-30ppm of total content of nickel and vanadium, and a characteristic factor K value less than 12.1; wherein the catalyst in the second fast fluidized bed is distributed in a fully dense phase, and the axial solid fraction epsilon distribution in the second fast fluidized bed meets the following requirements: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
separating the obtained first reaction product and the second reaction product to obtain dry gas, liquefied gas, pyrolysis gasoline, pyrolysis diesel oil and pyrolysis heavy oil;
and feeding the first spent catalyst and the second spent catalyst into a regenerator for coke burning regeneration, and returning the obtained regenerated catalyst serving as the first catalytic cracking catalyst and the second catalytic cracking catalyst to the bottoms of the first fast fluidized bed and the second fast fluidized bed.
Optionally, the properties of the inferior heavy oil meet one, two, three or four of the following criteria: the density at 20 ℃ is 910-3The carbon residue is 3-8 wt%The total content of nickel and vanadium is 5-20ppm, and the characteristic factor K value is less than 12.0.
Optionally, the inferior heavy oil is heavy petroleum hydrocarbon and/or other mineral oil; the heavy petroleum hydrocarbon is one or more selected from vacuum residue, poor atmospheric residue, poor hydrogenated residue, coker gas oil, deasphalted oil, vacuum wax oil, high acid value crude oil and high metal crude oil, and the other mineral oil is one or more selected from coal liquefied oil, oil sand oil and shale oil.
Optionally, the first catalytic cracking catalyst comprises, on a dry basis and by weight on a dry basis of the first catalytic cracking catalyst, from 1 to 50 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay;
on a dry basis and based on the weight of the second catalytic cracking catalyst on a dry basis, the second catalytic cracking catalyst comprising from 1 to 50 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay;
the zeolites include medium pore zeolites which are ZSM series zeolites and/or ZRP zeolites and optionally large pore zeolites which are one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silica Y.
Optionally, the medium pore zeolite of the first catalytic cracking catalyst comprises from 0 to 50 wt% of the total weight of zeolite on a dry basis;
the medium pore zeolite of the second catalytic cracking catalyst comprises from 0 to 50 wt% of the total weight of zeolite on a dry basis.
Optionally, the medium pore zeolite of the first catalytic cracking catalyst comprises 0 to 20 wt% of the total weight of zeolite on a dry basis;
the medium pore zeolite of the second catalytic cracking catalyst comprises from 0 to 20 wt% of the total weight of zeolite on a dry basis.
Optionally, the conditions of the first catalytic cracking reaction include: the reaction temperature is 450-550 ℃, the reaction time is 1-15 seconds, and the weight ratio of the catalyst to the oil is (5-50): 1, the weight ratio of water to oil is (0.03-0.5): 1, catalyst density of 120-3The linear speed of the gas is 0.8-2.5 m/s,the reaction pressure is 130-450 kPa, and the mass flow rate G of the catalystsIs 15-150 kg/(meter)2Seconds);
the conditions of the second catalytic cracking reaction include: the reaction temperature is 480-620 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is (3-50): 1, the weight ratio of water to oil is (0.03-0.8): 1, catalyst density of 120-3Gas linear speed of 0.8-2.5 m/s, reaction pressure of 130-450 kPa, and catalyst mass flow rate GsIs 15-150 kg/(meter)2Seconds).
Optionally, the conditions of the second catalytic cracking reaction include: the reaction temperature is 500-600 ℃, the reaction time is 3-15 seconds, and the weight ratio of the catalyst to the oil is (10-30): 1, the weight ratio of water to oil is (0.05-0.5): 1, catalyst density of 150-3Gas linear velocity of 1-1.8 m/s, catalyst mass flow rate GsIs 20-130 kg/(meter)2Seconds).
Optionally, the method further includes: filling the first fast fluidized bed and/or the second fast fluidized bed with catalyst; wherein the carbon content of the supplemented catalyst is 0-1.0 wt.%.
Optionally, the replenished catalyst of the first fast fluidized bed accounts for 0-50 wt% of the catalyst circulation amount of the first fast fluidized bed; the second fast fluidized bed is replenished with 0-50 wt% of the second fast fluidized bed catalyst circulation volume.
Optionally, the supplemented catalyst of the first fast fluidized bed accounts for 5-30 wt% of the catalyst circulation amount of the first fast fluidized bed; the second fast fluidized bed is replenished with 5-30 wt% of the second fast fluidized bed catalyst circulation volume.
Optionally, the distance between the catalyst replenishing position of the first fast fluidized bed and the bottom of the first fast fluidized bed accounts for 0-2/3 of the total height of the first fast fluidized bed;
the distance between the catalyst replenishing position of the second fast fluidized bed and the bottom of the second fast fluidized bed accounts for 0-2/3 of the total height of the second fast fluidized bed.
Optionally, the regenerated catalyst obtained by the regeneration of the regenerator through coking is cooled to 600-680 ℃ by a cooler and then returns to the bottom of the first fast fluidized bed and/or the second fast fluidized bed.
The invention also provides a catalytic cracking system, which comprises a first fast fluidized bed, a second fast fluidized bed, oil agent separation equipment, reaction product separation equipment and a regenerator;
the first fast fluidized bed is provided with a catalyst inlet at the bottom, a high-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the second fast fluidized bed is provided with a catalyst inlet at the bottom, a low-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and a reaction product outlet, the reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis gasoline outlet, a pyrolysis diesel oil outlet and a pyrolysis heavy oil outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
catalyst inlets of the first fast fluidized bed and the second fast fluidized bed are in fluid communication with a catalyst outlet of the regenerator, oil outlets of the first fast fluidized bed and the second fast fluidized bed are in fluid communication with an oil inlet of an oil separating device, a reaction product outlet of the oil separating device is in fluid communication with a reaction product inlet of the reaction product separating device, and a catalyst outlet of the oil separating device is in fluid communication with a catalyst inlet of the regenerator.
The high-quality heavy oil and the low-quality heavy oil are subjected to catalytic cracking reaction in different reactors respectively, and different reactors can adopt different reaction conditions according to the properties of the raw materials, so that the raw material conversion rate and the target product yield are improved.
According to the invention, the first fast fluidized bed and the second fast fluidized bed both adopt fast fluidized beds, so that the density of a reaction catalyst can be effectively improved, the ratio of the instantaneous catalyst to raw oil in a reactor is greatly improved, the relatively long reaction time is controlled, the catalyst can be reacted with heavy oil fully, the reaction conversion rate is improved, the yield of propylene and high-octane gasoline is improved, meanwhile, the generation of dry gas and coke is effectively reduced, and the product distribution and the product quality are improved.
The invention can enable petrochemical enterprises to produce high-added-value chemical raw materials from cheap heavy oil to the maximum extent, is beneficial to promoting the refining and chemical integration process of oil refining enterprises in China, not only solves the problem of petrochemical raw material shortage, but also improves the economic benefit and social benefit of petrochemical industry.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 includes a schematic flow diagram of one embodiment of the method of the present invention and also includes a schematic structural diagram of one embodiment of the system of the present invention.
Fig. 2 includes a schematic flow diagram of another embodiment of the method of the present invention and a schematic structural diagram of another embodiment of the system of the present invention.
Description of the reference numerals
I first fast fluidized bed II second fast fluidized bed
1 pipeline 2 pre-lifting section 3 outlet section
4 settler 5 stripping section 6 cyclone
7 gas collection chamber, 8 pipeline, 9 to-be-grown inclined tube
10 regenerator 11 regeneration inclined tube 12 pipeline
13 air distributor 14 line 15 regeneration chute
16 line 17 outlet section 18 cooler
19 mending thread
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In the invention:
(1) the axial solid fraction is the pressure difference between two points in the axial direction of the reactor measured by a pressure difference meter, the distance between two points in the axial direction divided by the density of the catalyst particles; the unit of the pressure difference is kilogram/meter2The distance between two axial points is measured in meters, and the density of catalyst particles is kg/m3And the two axial points are any two axial points of the reactor.
(2) The reaction time is equal to the volume of the reactor/the logarithmic mean volume flow of oil gas; volume unit of the reactor is meter3The unit of logarithmic mean volume flow of oil and gas is meter3A/second;
logarithmic mean volume flow rate of oil and gas (V)out-Vin)/ln(Vout/Vin)，VoutAnd VinThe volume flow of oil gas at the outlet and the inlet of the reactor respectively;
the volume flow of oil gas at the outlet of the reactor is m/rho3The volume flow of oil gas at the inlet of the reactor is m/rho4(ii) a m is the feeding amount of raw oil and atomized steam in unit time, and the unit is kilogram/second; rho3The density of oil gas at the outlet of the reactor is measured in kg/m3；ρ4The density of the oil gas at the inlet of the reactor is measured in kg/m3。
(3) The density of the catalyst in the reactor is the reaction time multiplied by the catalyst circulation volume divided by the volume of the reactor; the reaction time is in seconds, the catalyst circulation is in kilograms per second, and the reactor volume is in meters3。
(4) And the linear gas velocity is the logarithmic mean volume flow of oil gas/sectional area of the reactor.
(5) Catalyst mass flow rate GsCatalyst circulation rate ÷ reactor cross-sectional area; the unit of the circulating amount of the catalyst is kilogram/second;
the catalyst circulation amount is divided by the coke generation speed (the carbon content of the spent catalyst-the carbon content of the regenerated catalyst), the unit of the coke generation speed is kilogram/second, and the carbon content of the spent catalyst and the carbon content of the regenerated catalyst are both weight contents;
coke formation rate ═ flue gas mass × (CO)2% + CO%) +/-Vm × M; vm is the molar volume of gas and takes the value of 22.4 multiplied by 10-3Rice and its production process3M is the molar mass of carbon and takes the value of 12 multiplied by 10-3Kilogram/mole;
flue gas amount (regeneration air amount × 79 vol%)/(1-CO)2％-CO％-O2%) of the amount of regenerated air in meters3Second, the unit of smoke is meter3Second, CO2％、CO％、O2% of CO in the flue gas2、CO、O2Volume percent of (c).
The invention provides a catalytic cracking method for producing propylene and high-octane gasoline, which comprises the following steps:
introducing preheated high-quality heavy oil into the first fast fluidized bed from the lower part of the first fast fluidized bed to contact with the first catalytic cracking catalyst and perform a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be generated; the high-quality heavy oil can be one or more selected from vacuum wax oil, coker wax oil, hydrogenated coker wax oil, deasphalted oil, hydrogenated deasphalted oil, paraffin-based atmospheric residue oil, hydrogenated paraffin oil, atmospheric residue oil and hydrocracking tail oil; wherein the catalyst in the first fast fluidized bed is distributed in a full dense phase, and the distribution of the axial solid fraction epsilon in the first fast fluidized bed meets the following conditions: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
introducing preheated inferior heavy oil into the second rapid fluidized bed from the lower part of the second rapid fluidized bed to contact with the second catalytic cracking catalyst and perform a second catalytic cracking reaction from bottom to top to obtain a second reaction product and a second spent catalyst; the properties of the inferior heavy oil meet one, two, three or four of the following indexes: the density at 20 ℃ is 900-32-10 wt% of carbon residue, 2-30ppm of total content of nickel and vanadium, and a characteristic factor K value less than 12.1; wherein the catalyst in the first fast fluidized bed is distributed in a full dense phase, and the distribution of the axial solid fraction epsilon in the first fast fluidized bed meets the following conditions: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
separating the obtained first reaction product and the second reaction product to obtain dry gas, liquefied gas, pyrolysis gasoline, pyrolysis diesel oil and pyrolysis heavy oil;
and feeding the first spent catalyst and the second spent catalyst into a regenerator for coke burning regeneration, and returning the obtained regenerated catalyst serving as the first catalytic cracking catalyst and the second catalytic cracking catalyst to the bottoms of the first fast fluidized bed and the second fast fluidized bed.
In the invention, the fast fluidized bed refers to a reactor in which a catalyst is in fast fluidization, the fast fluidization is bubble-free gas-solid contact fluidization, and the important characteristic is that solid particles tend to move in an agglomeration manner. The axial solid fraction epsilon distribution of all heights in the fast fluidized bed meets the following requirements: epsilon is more than or equal to 0.1 and less than or equal to 0.2, the catalyst in the rapid fluidized bed is distributed in a full-dense phase, the catalyst is prevented from being distributed in a dilute-down-dense mode, the actual agent-oil ratio above and below the rapid fluidized bed is kept consistent, the dry gas coke yield is reduced, and the target product yield is improved.
According to the invention, the catalyst is regulated to be in full-dense phase distribution by regulating the linear velocity of gas in the fast fluidized bed and arranging a gas distributor at the feeding position of the fast fluidized bed, wherein the gas distributor can be one or more of gas distributors which are common in industry, such as flat plates, arches, discs, rings and umbrella-shaped gas distributors, so that the raw oil atomized by atomized steam is contacted with the catalyst in a uniform concentration in the axial direction of the reactor to carry out catalytic cracking reaction, and the generation of catalyst-oil ratio coke and thermal reaction coke caused by overhigh or overlow concentration of the catalyst is reduced.
According to the invention, the inferior heavy oil and/or the superior heavy oil can be introduced into the fast fluidized bed at one feeding position, or can be introduced into the fast fluidized bed from two or more feeding positions in the same or different proportions.
According to the invention, the high-quality heavy oil is heavy oil which is more suitable for catalytic cracking processing, and the low-quality heavy oil is heavy oil which is more unsuitable for catalytic cracking processing than conventional heavy oil, for example, the properties of the low-quality heavy oil can meet one, two, three or four of the following indexes: density at 20 ℃ of 900-0 kg/m3Preferably 910-3Carbon residue of 2 to 10 wt.%, preferably 3 to 8 wt.%, a total nickel and vanadium content of 2 to 30ppm, preferably 5 to 20ppm, and a characteristic factor K value of less than 12.1, preferably less than 12.0. In particular, the low-grade heavy oil can be heavy petroleum hydrocarbons and/or other mineral oils; the heavy petroleum hydrocarbon may be one or more selected from Vacuum Residue (VR), low-grade Atmospheric Residue (AR), low-grade hydrogenated residue, coker gas oil, deasphalted oil, vacuum wax oil, high acid number crude oil, and high metal crude oil, and the other mineral oil may be one or more selected from coal liquefied oil, oil sand oil, and shale oil. The carbon residue in the inferior heavy oil is measured by adopting an ASTMD-189 Conradson carbon residue experimental method.
Catalytic cracking catalysts are well known to those skilled in the art in accordance with the present invention, and for the process of the present invention, the first catalytic cracking catalyst may comprise, on a dry basis and based on the weight of the first catalytic cracking catalyst on a dry basis, from 1 to 50 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay; the second catalytic cracking catalyst may include, on a dry basis and by weight of the second catalytic cracking catalyst on a dry basis, from 1 to 50 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay; the content and type of zeolite, inorganic oxide and clay in the first catalytic cracking catalyst and the second catalytic cracking catalyst may be the same or different, preferably the same. The zeolite may comprise, as active components, a medium pore zeolite and optionally a large pore zeolite, and the medium pore zeolite in the first catalytic cracking catalyst may comprise from 0 to 50 wt%, preferably from 0 to 20 wt%, of the total weight of zeolite on a dry basis; the medium pore zeolite in the second catalytic cracking catalyst may be present in an amount of from 0 to 50 wt%, preferably from 0 to 20 wt%, based on the total weight of zeolite on a dry basis. The medium and large pore zeolites are defined as conventional in the art, i.e., the medium pore zeolite has an average pore size of 0.5 to 0.6nm and the large pore zeolite has an average pore size of 0.7 to 1.0 nm. The large-pore zeolite can be selected from one or more of Rare Earth Y (REY), Rare Earth Hydrogen Y (REHY), ultrastable Y obtained by different methods and high-silicon Y. The medium pore zeolite may be selected from the group consisting of zeolite having an MFI structureThe medium pore size zeolite can also be modified with nonmetallic elements such as phosphorus and/or transition metals such as iron, cobalt, nickel, etc., as described in more detail in U.S. Pat. No. 5,232,675, and the ZSM series zeolite is preferably one or more mixtures of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure, and the ZSM-5 is described in more detail in U.S. Pat. No. 3,702,886. The inorganic oxide is preferably silicon dioxide (SiO) as a binder2) And/or aluminum oxide (Al)2O3). The clay acts as a matrix (i.e., carrier) and is preferably selected from kaolin and/or halloysite.
Catalytic cracking is well known to those skilled in the art according to the present invention, and for the catalytic cracking of the fast fluidized bed of the present application, the conditions of the first catalytic cracking reaction may include: the reaction temperature is 450-550 ℃, the reaction time is 1-15 seconds, and the weight ratio of the catalyst to the oil is (5-50): 1, the weight ratio of water to oil is (0.03-0.5): 1, catalyst density of 120-3Gas linear velocity of 0.8-2.5 m/s, preferably 1-1.8 m/s, reaction pressure of 130-450 kPa, catalyst mass flow rate GsIs 15-150 kg/(meter)2Second), preferably 20 to 130 kg/(m)2Seconds); the conditions of the second catalytic cracking reaction may include: the reaction temperature is 480-620 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is (3-50): 1, the weight ratio of water to oil is (0.03-0.8): 1, catalyst density of 120-3Gas linear speed of 0.9-2.5 m/s, reaction pressure of 130-450 kPa, and catalyst mass flow rate GsIs 15-150 kg/(meter)2Seconds); the conditions of the second catalytic cracking reaction preferably include: the reaction temperature is 500-600 ℃, the reaction time is 3-15 seconds, and the weight ratio of the catalyst to the oil is (10-30): 1, the weight ratio of water to oil is (0.05-0.5): 1, catalyst density of 150-3Gas linear velocity of 1-1.8 m/s, catalyst mass flow rate GsIs 20-130 kg/(meter)2Seconds).
The separation of the first reaction product and the second reaction product from the spent catalyst according to the present invention is well known to those skilled in the art, and may be performed, for example, in a settler using a cyclone separator, and the further separation of the first reaction product and the second reaction product to obtain dry gas, liquefied gas, pyrolysis gasoline, pyrolysis diesel oil and pyrolysis heavy oil is also well known to those skilled in the art, and the dry gas and liquefied gas may be further separated to obtain the desired products such as ethylene, propylene, etc. by separation means conventional in the art. The first reaction product and the second reaction product may be separated in the same separation apparatus, or may be separated in different separation apparatuses, and the present invention is not particularly limited.
According to the present invention, the first spent catalyst and the second spent catalyst are regenerated by burning, which is well known to those skilled in the art, and can be carried out in a regenerator, an oxygen-containing gas such as air can be introduced into the regenerator to contact with the first spent catalyst and the second spent catalyst, and flue gas obtained by burning regeneration can be separated from the catalyst in the regenerator and then sent to a subsequent energy recovery system. The coking regeneration of the first spent catalyst and the second spent catalyst can be carried out in the same regenerator or in different regenerators.
According to the invention, the method may further comprise: filling the first fast fluidized bed and/or the second fast fluidized bed with catalyst; wherein the carbon content of the supplemented catalyst is 0 to 1.0 wt%, and may be, for example, one or more selected from the group consisting of a regenerated catalyst, a spent catalyst and a semi-regenerated catalyst. The first fast fluidized bed is replenished with 0 to 50 wt%, preferably 5 to 30 wt% of the first fast fluidized bed catalyst circulation amount; the second fast fluidized bed is replenished with 0 to 50 wt%, preferably 5 to 30 wt% of the second fast fluidized bed catalyst circulation. The distance between the catalyst replenishing position of the first fast fluidized bed and the bottom of the first fast fluidized bed can be 0-2/3 of the total height of the first fast fluidized bed; the distance between the catalyst replenishment position of the second fast fluidized bed and the bottom of the second fast fluidized bed may be 0 to 2/3 of the total height of the second fast fluidized bed. Since the catalytic cracking reaction is a volume expansion reaction, in order to maintain the density at the inlet of the reactor and the density at the outlet of the reactor to be substantially equal or increased, the supplementary spent catalyst in the fast fluidized bed can adjust or maintain the density of the reactor within a wide range to ensure the time required for the cracking reaction. The temperature of the replenished catalyst can be adjusted according to the reaction temperature requirements, for example cold and/or hot regenerated catalyst can be introduced. In addition, the catalytic cracking catalyst is supplemented in the fast fluidized bed reactor, so that the density uniformity of the catalyst in the reactor can be maintained as much as possible, the density distribution of the catalyst is effectively adjusted, the cracking reaction is ensured to be fully and effectively carried out, and the selectivity of a target product is improved.
According to the invention, the regenerated catalyst obtained by the coke-burning regeneration of the regenerator can be cooled to 600-680 ℃ by a cooler and then returned to the bottom of the first fast fluidized bed and/or the second fast fluidized bed. The hot regenerated catalyst returns to the reactor after being cooled, which is beneficial to reducing the contact temperature of the oil agent, improving the contact state of the raw oil and the catalyst and improving the selectivity of dry gas and coke formation.
The invention also provides a catalytic cracking system, which comprises a first fast fluidized bed, a second fast fluidized bed, oil agent separation equipment, reaction product separation equipment and a regenerator;
the first fast fluidized bed is provided with a catalyst inlet at the bottom, a high-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the second fast fluidized bed is provided with a catalyst inlet at the bottom, a low-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and a reaction product outlet, the reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis gasoline outlet, a pyrolysis diesel oil outlet and a pyrolysis heavy oil outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
catalyst inlets of the first fast fluidized bed and the second fast fluidized bed are in fluid communication with a catalyst outlet of the regenerator, oil outlets of the first fast fluidized bed and the second fast fluidized bed are in fluid communication with an oil inlet of an oil separating device, a reaction product outlet of the oil separating device is in fluid communication with a reaction product inlet of the reaction product separating device, and a catalyst outlet of the oil separating device is in fluid communication with a catalyst inlet of the regenerator.
According to the present invention, the oil separating device and the reaction product separating device are well known to those skilled in the art, for example, the oil separating device may include a cyclone, a settler, a stripper, and the like, and the reaction product separating device may be a fractionating tower, and the like.
The invention will be further illustrated by means of specific embodiments in the following description with reference to the drawings, but the invention is not limited thereto.
As shown in FIG. 1, a pre-lifting medium enters the bottom of a first fast fluidized bed I from the bottom of a pre-lifting section 2 through a pipeline 1, a regenerated catalyst from a regeneration inclined tube 11 enters the bottom of the first fast fluidized bed I, and moves upwards in an accelerated manner along the first fast fluidized bed I under the lifting action of the pre-lifting medium, high-quality heavy oil is injected into the lower part of the first fast fluidized bed I through a pipeline 14, is mixed and contacted with a material flow existing in the first fast fluidized bed and generates a first catalytic cracking reaction, a first reaction product and a first to-be-generated catalyst move upwards in an accelerated manner, and the catalyst is supplemented into the first fast fluidized bed I through a supplementing line 19; the regenerated catalyst from the regenerated inclined pipe 15 enters the bottom of the second fast fluidized bed II and moves upwards in an accelerated manner along the second fast fluidized bed II under the lifting action of a pre-lifting medium, the inferior heavy oil is injected into the lower part of the second fast fluidized bed II through a pipeline 16, the inferior heavy oil is subjected to a second catalytic cracking reaction on the hot catalyst, and a second reaction product and a second spent catalyst move upwards in an accelerated manner; the generated first reaction product, the inactivated first spent catalyst, the second reaction product and the inactivated second spent catalyst respectively enter the cyclone separator 6 in the settler 4 through the outlet section 3 and the outlet section 17 to realize the separation of the spent catalyst and the reaction product, the reaction product enters the gas collection chamber 7, and the fine catalyst powder returns to the settler 4 through the dipleg. Spent catalyst in the settler 4 flows to the stripping section 5. The reaction product stripped from the spent catalyst enters the gas collection chamber 7 after passing through the cyclone separator. The stripped spent catalyst enters a regenerator 10 through a spent inclined tube 9, air is distributed by an air distributor 13 and then enters the regenerator 10, coke on the spent catalyst in a dense bed layer at the bottom of the regenerator 10 is burned off, the inactivated spent catalyst is regenerated, and flue gas enters a subsequent energy recovery system through a pipeline 12. The reaction products in the plenum 7 enter the subsequent separation system through a large oil gas line 8. Wherein the pre-lifting medium may be dry gas, water vapor or a mixture thereof.
Fig. 2 differs from fig. 1 in that: the hot regenerated catalyst from the regenerator 10 is cooled by a cooler 18 provided on line 11 and then enters the bottom of the first fast fluidized bed i.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The high-quality heavy oil used in example 1 and comparative example 1 was hydrogenated wax oil, and the low-quality heavy oil was hydrogenated residual oil, and the properties thereof are shown in table 1. The catalyst used was a commercial catalyst sold under the trade designation CGP.
Comparative example 1
The raw oil is mixed oil of hydrogenated residual oil and hydrogenated wax oil, and the ratio of the hydrogenated wax oil to the hydrogenated residual oil is 1: 1, adopting CGP catalyst, and carrying out test on a medium-sized device, wherein the reactor is an advanced reducing riser with double reaction zones for producing propylene and high-quality fuel oil at present. The preheated raw oil enters a first reaction zone to contact with a regenerated catalyst and carry out a first catalytic cracking reaction, the reaction oil, the steam and the carbon-deposited catalyst enter a second reaction zone to continue a second catalytic cracking reaction, the material flow after the reaction enters a closed cyclone separator, the reaction oil gas and the spent catalyst are quickly separated, and the reaction oil gas is cut in a separation system according to the distillation range; the spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst directly enters a regenerator without heat exchange and is in contact with air for regeneration; the regenerated catalyst returns to the bottom of the riser reactor for recycling; the operating conditions and the product distribution are listed in table 2.
As can be seen from the results in table 2, the propylene yield was about 6.2 wt%, the gasoline yield was about 36.9 wt%, the research octane number was about 92, and the dry gas and coke yields were 2.9 wt% and 9.3 wt%, respectively.
Example 1
According to the process shown in FIG. 1, the high-quality heavy oil is hydrogenated wax oil, the low-quality heavy oil is hydrogenated residual oil, and the feeding amounts of the two raw materials in different reactors are the same. The method comprises the following steps of (1) carrying out a test on a medium-sized device by adopting a CGP catalyst, dividing a reactor into a first fast fluidized bed and a second fast fluidized bed, enabling preheated high-quality heavy oil to enter the lower part of the first fast fluidized bed to contact with a regenerated catalyst and carry out a first catalytic cracking reaction, controlling the catalyst in the first fast fluidized bed to be in full-dense phase distribution by adjusting the linear velocity of gas and arranging an umbrella-shaped gas distributor at a feeding position, enabling the axial solid fraction epsilon distribution in the first fast fluidized bed to be in a range of 0.1-0.2 from bottom to top, and enabling a first reaction product and a first catalyst to be regenerated to enter a subsequent separation system; the preheated inferior heavy oil enters the lower part of the second fast fluidized bed to contact with the regenerated catalyst and carry out a second catalytic cracking reaction, the catalyst in the second fast fluidized bed is controlled to be distributed in a full dense phase by adjusting the linear velocity of gas and arranging an umbrella-shaped gas distributor at a feeding position, the axial solid fraction epsilon in the second fast fluidized bed is in the range of 0.1-0.2 from bottom to top, and a second reaction product and a second catalyst to be generated enter a subsequent separation system. Cutting the second reaction product in a separation system according to the distillation range; the spent catalyst enters a stripping section under the action of gravity, reaction products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst directly enters a regenerator without heat exchange and is in contact with air for regeneration; the regenerated catalyst is cooled and then returns to the reactor for recycling; the operating conditions and the product distribution are listed in table 2.
As can be seen from table 2, the propylene yield was 9.6 wt%, the gasoline yield was about 45.1 wt%, the research octane number was as high as 101, and the dry gas and coke yields were 2.6 wt% and 8.6 wt%, respectively.
The heavy oil of high quality used in comparative example 2 and example 2 was hydrogenated wax oil, and the heavy oil of low quality was hydrogenated residual oil, and the properties thereof are shown in table 1. The catalyst used was a commercial catalyst sold under the trade designation DMMC-2.
Comparative example 2
The experiment was carried out according to the flow of fig. 2, the ratio of hydrogenated wax oil to hydrogenated residue oil was 1: 1, tests were carried out on a medium-sized apparatus using DMMC-2 catalyst, the reactor type being a combined reactor with riser and dense-phase fluidized bed in series. The preheated high-quality heavy oil and the low-quality heavy oil enter the lower part of a lifting pipe to contact with a hot regenerated catalyst and carry out catalytic cracking reaction, reaction oil, water vapor and a spent catalyst enter a dense-phase fluidized bed from the outlet of a reactor to carry out continuous reaction, the material flow after the reaction enters a closed cyclone separator, the reaction oil gas and the spent catalyst are quickly separated, and the reaction oil gas is cut in a separation system according to the distillation range; the spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst directly enters a regenerator without heat exchange and is in contact with air for regeneration; the regenerated catalyst returns to the riser to be recycled; the operating conditions and the product distribution are listed in Table 3.
As can be seen from the results in table 3, the propylene yield was about 12.8 wt%, the gasoline yield was 22.9 wt%, and the research octane number was about 92, while the dry gas and coke yields were 12.9 wt% and 13.3 wt%, respectively.
Example 2
The test is carried out according to the flow of a figure 2, high-quality heavy oil is hydrogenation wax oil, poor-quality heavy oil hydrogenation residual oil, DMMC-2 catalyst is adopted, the feeding amount of the two raw materials in different reactors is the same, the test is carried out on a medium-sized device, the reactors are divided into a first fast fluidized bed and a second fast fluidized bed, the cooled regenerated catalyst and the preheated high-quality heavy oil enter the lower part of the first fast fluidized bed to carry out a first catalytic cracking reaction, the catalyst in the first fast fluidized bed is controlled to be in full dense phase distribution by adjusting the linear velocity of gas and arranging an umbrella-shaped gas distributor at the feeding position, the axial solid fraction epsilon distribution in the first fast fluidized bed is in the range of 0.1-0.2 from bottom to top, and the first reaction product and the first catalyst to be regenerated enter a subsequent separation; the preheated inferior heavy oil enters the lower part of the second fast fluidized bed to contact with the cooled regenerated catalyst and carry out a second catalytic cracking reaction, the catalyst in the second fast fluidized bed is controlled to be in full dense phase distribution by adjusting the linear velocity of gas and arranging an umbrella-shaped gas distributor at the feeding position, the axial solid fraction epsilon in the second fast fluidized bed is in the range of 0.1-0.2 from bottom to top, and a second reaction product and a second catalyst to be generated enter a subsequent separation system. Cutting the reaction product in a separation system according to the distillation range; the spent catalyst enters a stripping section under the action of gravity, reaction products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst directly enters a regenerator without heat exchange and is in contact with air for regeneration; the regenerated catalyst is returned for recycling; the operating conditions and the product distribution are listed in Table 3.
As can be seen from table 3, the propylene yield was about 19.7 wt%, the gasoline yield was 30.2 wt%, and the research octane number was about 95, while the dry gas and coke yields were 10.4 wt% and 10.1 wt%, respectively.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that no gas distributor is provided, the axial solids fraction ε distribution in the two fast fluidized beds is increased from top to bottom by 0.1 → 0.2 → 0.3, respectively, the operating conditions are the same as in example 1, and the product distribution is shown in Table 2.
It can be seen from the results of the examples that the process of the present invention has high propylene yield, high gasoline yield and research octane number, and, at the same time, has low dry gas and coke yields.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the content of the present invention as long as it does not depart from the gist of the present invention.
TABLE 1
Raw materials Hydrogenated wax oil Hydrogenated residual oil
Density (20 deg.C)/g.cm-3 0.8993 0.9342
Refractive index/70 deg.C 1.4794 1.5075
Basic nitrogen/microgram g-1 293 767
Carbon residue/weight% 0.3 5.58
Value of characteristic factor K 12.6 11.8
Distillation range/. degree.C
5% by volume 381 365
10% by volume 394 403
30% by volume 433 479
50% by volume 463 545
70% by volume 495 617
Metal content/microgram g-1
Fe / 26.3
Ni / 9
Ca / 5.5
V / 8
Na / 1.2
TABLE 2
Comparative example 1 Example 1 Comparative example 3
First reaction zone or first fast fluidized bed conditions
Reaction temperature of 535 525 /
Reaction time in seconds 2 3 /
Water to oil weight ratio 0.10 0.10 /
Weight ratio of solvent to oil 10 10 /
Catalyst density in kg/m3 60 200 /
Linear velocity of gas, m/s 12 2 /
Reaction pressure (absolute pressure), kPa 340 310 /
Gs, kg/(meter)2Second) 300 75 /
Second reaction zone or second fast fluidized bed conditions /
Reaction temperature of 525 545 /
Reaction time in seconds 3 4 /
Water to oil weight ratio 0.20 0.20 /
Weight ratio of solvent to oil 10 10 /
Catalyst density in kg/m3 80 210 /
Linear velocity of gas, m/s 8 2 /
Reaction pressure (absolute pressure), kPa 340 310 /
Gs, kg/(meter)2Second) 260 80 /
Product distribution, weight%
Dry gas 2.9 2.6 2.7
Liquefied gas 14.1 20.7 17.6
Wherein propylene is 6.2 9.6 7.4
Gasoline (gasoline) 36.9 45.1 43.0
Diesel oil 29.4 17.9 21.3
Heavy oil 7.4 5.1 6.4
Coke 9.3 8.6 9.0
Research octane number of gasoline 92 101 97
Total up to 100.0 100.0 100.0
TABLE 3
Comparative example 2 Example 2
Temperature of regenerated catalyst, DEG C 705 695
Temperature of regenerated catalyst after cooling, DEG C / 680
Riser or first fast fluidized bed reaction conditions
Reactor temperature,. deg.C 585 565
Reaction time in seconds 2 3
Water to oil weight ratio 0.25 0.25
Weight ratio of solvent to oil 20 22
Catalyst density in kg/m3 60 200
Linear velocity of gas, m/s 12 2
Reaction pressure, kPa 340 310
Gs, kg/(meter)2Second) 300 75
Dense bed or second fast fluidized bed reaction conditions
Bed/outlet temperature,. deg.C 565 575
Weight hourly space velocity, hours -1 4 /
Reaction time in seconds / 3
Water to oil weight ratio 0.25 0.25
Weight ratio of solvent to oil 20 22
Catalyst density in kg/m3 480 210
Linear velocity of gas, m/s 0.6 2.1
Reaction pressure, kPa 340 310
Gs, kg/(meter)2Second) / 76
Product distribution, weight%
Dry gas 12.9 10.4
Liquefied gas 32.1 39.2
Wherein propylene is 12.8 19.7
Gasoline (gasoline) 22.9 30.2
Diesel oil 13.4 7.0
Heavy oil 5.4 3.1
Coke 13.3 10.1
Research octane number of gasoline 92 95
Total up to 100.0 100.0

Claims (15)

1. A catalytic cracking process for producing propylene and high octane gasoline, the process comprising:
introducing preheated high-quality heavy oil into the first fast fluidized bed from the lower part of the first fast fluidized bed to contact with the first catalytic cracking catalyst and perform a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be generated; the high-quality heavy oil is one or more selected from vacuum wax oil, coking wax oil, hydrogenated coking wax oil, deasphalted oil, hydrogenated paraffin oil, atmospheric residue oil and hydrocracking tail oil; wherein the catalyst in the first fast fluidized bed is distributed in a full dense phase, and the distribution of the axial solid fraction epsilon in the first fast fluidized bed meets the following conditions: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
introducing preheated poor-quality heavy oil into the second rapid fluidized bed from the lower part of the second rapid fluidized bed to contact with the second catalytic cracking catalyst and carrying out a second catalytic cracking reaction from bottom to top to obtain a second reaction productAnd a second spent catalyst; the properties of the inferior heavy oil meet one, two, three or four of the following indexes: the density at 20 ℃ is 900-32-10 wt% of carbon residue, 2-30ppm of total content of nickel and vanadium, and a characteristic factor K value less than 12.1; wherein the catalyst in the second fast fluidized bed is distributed in a fully dense phase, and the axial solid fraction epsilon distribution in the second fast fluidized bed meets the following requirements: epsilon is more than or equal to 0.1 and less than or equal to 0.2;
separating the obtained first reaction product and the second reaction product to obtain dry gas, liquefied gas, pyrolysis gasoline, pyrolysis diesel oil and pyrolysis heavy oil;
and feeding the first spent catalyst and the second spent catalyst into a regenerator for coke burning regeneration, and returning the obtained regenerated catalyst serving as the first catalytic cracking catalyst and the second catalytic cracking catalyst to the bottoms of the first fast fluidized bed and the second fast fluidized bed.
2. The method of claim 1, wherein the high quality heavy oil is a paraffin-based atmospheric residue.
3. The method of claim 1 wherein the properties of the low quality heavy oil meet one, two, three or four of the following criteria: the density at 20 ℃ is 910-3The carbon residue is 3-8 wt%, the total content of nickel and vanadium is 5-20ppm, and the characteristic factor K value is less than 12.0.
4. The method of claim 1 wherein the low quality heavy oil is heavy petroleum hydrocarbons and/or other mineral oils; the heavy petroleum hydrocarbon is one or more selected from vacuum residue, poor atmospheric residue, poor hydrogenated residue, coker gas oil, deasphalted oil, vacuum wax oil, high acid value crude oil and high metal crude oil, and the other mineral oil is one or more selected from coal liquefied oil, oil sand oil and shale oil.
5. The process of claim 1 wherein the first catalytic cracking catalyst comprises, on a dry basis and based on the weight of the first catalytic cracking catalyst on a dry basis, from 1 to 50 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay;
on a dry basis and based on the weight of the second catalytic cracking catalyst on a dry basis, the second catalytic cracking catalyst comprising from 1 to 50 wt% of a zeolite, from 5 to 99 wt% of an inorganic oxide, and from 0 to 70 wt% of a clay;
the zeolites include medium pore zeolites which are ZSM series zeolites and/or ZRP zeolites and optionally large pore zeolites which are one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silica Y.
6. The process of claim 5, wherein the medium pore zeolite of the first catalytic cracking catalyst comprises from 0 to 50 wt% of the total weight of zeolite on a dry basis;
the medium pore zeolite of the second catalytic cracking catalyst comprises from 0 to 50 wt% of the total weight of zeolite on a dry basis.
7. The process of claim 5, wherein the medium pore zeolite of the first catalytic cracking catalyst comprises from 0 to 20 wt% of the total weight of zeolite on a dry basis;
the medium pore zeolite of the second catalytic cracking catalyst comprises from 0 to 20 wt% of the total weight of zeolite on a dry basis.
8. The method of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 450-550 ℃, the reaction time is 1-15 seconds, and the weight ratio of the catalyst to the oil is (5-50): 1, the weight ratio of water to oil is (0.03-0.5): 1, catalyst density of 120-3Gas linear speed of 0.8-2.5 m/s, reaction pressure of 130-450 kPa, and catalyst mass flow rate GsIs 15-150 kg/(meter)2Seconds);
the conditions of the second catalytic cracking reaction include: the reaction temperature is 480-620 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is (3-50): 1, the weight ratio of water to oil is (0.03-0.8): 1, catalyst Density120-290 kg/m3Gas linear speed of 0.8-2.5 m/s, reaction pressure of 130-450 kPa, and catalyst mass flow rate GsIs 15-150 kg/(meter)2Seconds).
9. The method of claim 1, wherein the conditions of the second catalytic cracking reaction comprise: the reaction temperature is 500-600 ℃, the reaction time is 3-15 seconds, and the weight ratio of the catalyst to the oil is (10-30): 1, the weight ratio of water to oil is (0.05-0.5): 1, catalyst density of 150-3Gas linear velocity of 1-1.8 m/s, catalyst mass flow rate GsIs 20-130 kg/(meter)2Seconds).
10. The method of claim 1, further comprising: filling the first fast fluidized bed and/or the second fast fluidized bed with catalyst; wherein the carbon content of the supplemented catalyst is 0-1.0 wt.%.
11. The process of claim 10, wherein the first fast fluidized bed is replenished with catalyst in the range of 0 to 50 weight percent of the first fast fluidized bed catalyst circulation; the second fast fluidized bed is replenished with 0-50 wt% of the second fast fluidized bed catalyst circulation volume.
12. The process of claim 10, wherein the first fast fluidized bed is replenished with catalyst in the range of 5 to 30 weight percent of the first fast fluidized bed catalyst circulation; the second fast fluidized bed is replenished with 5-30 wt% of the second fast fluidized bed catalyst circulation volume.
13. The process as claimed in claim 10, wherein the first fast fluidized bed has a catalyst replenishment position at a distance from the bottom of the first fast fluidized bed of from 0 to 2/3 of the total height of the first fast fluidized bed;
the distance between the catalyst replenishing position of the second fast fluidized bed and the bottom of the second fast fluidized bed accounts for 0-2/3 of the total height of the second fast fluidized bed.
14. The method as claimed in claim 1, wherein the regenerated catalyst obtained by regenerating the regenerator by burning is cooled to 680 ℃ by a cooler and then returned to the bottom of the first fast fluidized bed and/or the second fast fluidized bed.
15. A catalytic cracking system comprises a first fast fluidized bed, a second fast fluidized bed, an oil agent separation device, a reaction product separation device and a regenerator;
the first fast fluidized bed is provided with a catalyst inlet at the bottom, a high-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the second fast fluidized bed is provided with a catalyst inlet at the bottom, a low-quality heavy oil inlet at the lower part and an oil agent outlet at the top, the oil agent separation equipment is provided with an oil agent inlet, a catalyst outlet and a reaction product outlet, the reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis gasoline outlet, a pyrolysis diesel oil outlet and a pyrolysis heavy oil outlet, and the regenerator is provided with a catalyst inlet and a catalyst outlet;
catalyst inlets of the first fast fluidized bed and the second fast fluidized bed are both communicated with a catalyst outlet of the regenerator in a fluid mode, oil outlets of the first fast fluidized bed and the second fast fluidized bed are both communicated with an oil inlet of the oil separating device in a fluid mode, a reaction product outlet of the oil separating device is communicated with a reaction product inlet of the reaction product separating device in a fluid mode, and a catalyst outlet of the oil separating device is communicated with a catalyst inlet of the regenerator in a fluid mode;
wherein the catalyst in the first fast fluidized bed and the second fast fluidized bed is distributed in a fully dense phase, and the axial solid fraction epsilon distribution in the first fast fluidized bed and the second fast fluidized bed satisfies the following conditions: epsilon is more than or equal to 0.1 and less than or equal to 0.2; the distance between the catalyst replenishing position of the first fast fluidized bed and the bottom of the first fast fluidized bed accounts for 0-2/3 of the total height of the first fast fluidized bed; and/or the distance between the catalyst replenishing position of the second fast fluidized bed and the bottom of the second fast fluidized bed is 0-2/3 of the total height of the second fast fluidized bed; the catalyst is adjusted to be in full dense phase distribution by adjusting the linear velocity of gas in the fast fluidized bed and arranging a gas distributor at the feeding position of the fast fluidized bed.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760342A (en) * 2005-10-12 2006-04-19 洛阳石化设备研究所 Catalytic cracking method and equipment for producing more propylene
CN101942340A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司 Method for preparing light fuel oil and propylene from inferior raw material oil

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1760342A (en) * 2005-10-12 2006-04-19 洛阳石化设备研究所 Catalytic cracking method and equipment for producing more propylene
CN101942340A (en) * 2009-07-09 2011-01-12 中国石油化工股份有限公司 Method for preparing light fuel oil and propylene from inferior raw material oil

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