CN117186935A - Catalytic cracking reaction method and system for improving product selectivity - Google Patents
Catalytic cracking reaction method and system for improving product selectivity Download PDFInfo
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The application relates to a catalytic cracking reaction method and a catalytic cracking reaction system for improving product selectivity, wherein the method comprises the steps of conveying light oil and regenerated catalyst to a cracking reactor for catalytic cracking reaction; and (3) conveying the raw coke material and the regenerated catalyst to a coke generator for coke generation reaction, mixing and conveying the reactant flow and C4 fraction or C5-C6 light gasoline to a settling section for continuous cracking reaction, and conveying the obtained reaction product to a separation system, wherein the obtained spent catalyst is conveyed to the regenerator for coke burning regeneration and recycling. The catalytic cracking method of the application can improve the selectivity of ethylene and propylene, reduce methane generation, and simultaneously solve the problem of reaction heat balance without damaging the physical and chemical properties of the catalyst.
Description
Technical Field
The application relates to the technical field of fluidized catalytic cracking, in particular to a catalytic cracking reaction method and system for improving product selectivity.
Background
At present, the oil refining capability is excessive, the terminal consumption of the finished oil is slowed down, and the excessive structure of the finished oil becomes a urgent need for solving the problem of oil refining enterprises. In the aspect of chemical raw material market, ethylene and propylene are taken as basic chemical raw materials, and market demands are still vigorous. The consumption of ethylene and propylene rises year by year, taking China as an example, the estimated 2023 year end, the production capacity of ethylene and propylene in China can reach about 4400 ten thousand tons/year and 5200 ten thousand tons/year respectively, and the annual average composite acceleration rate is 11.5% and 8.7% respectively. Therefore, the domestic oil refining pattern and the resource flow direction can be structurally recombined, the terminal consumption of the finished oil is accelerated and slowed down, and the consumption of the chemical light oil is greatly increased. Therefore, the transformation of oil refining to chemical industry has become the necessary direction of the development of refineries, and catalytic cracking is a key technology in the transformation process of oil refining to chemical industry as a tie between oil refining and chemical industry.
The catalytic cracking process generally uses heavy petroleum hydrocarbon as raw material, such as paraffin-based vacuum fraction or atmospheric residuum, and has the characteristic of higher yield of low-carbon olefin such as propylene. With the heavy and inferior quality of global crude oil, high-quality heavy petroleum hydrocarbon resources are less and less, and the raw material application range of the catalytic cracking technology needs to be widened. Along with the structural adjustment transformation of the products, the refinery improves the quality of the oil products and simultaneously produces a large amount of light petroleum hydrocarbon resources as byproducts. For a typical ten million ton class fuel oil refinery, the light petroleum hydrocarbon yield per year of the whole plant can reach millions of tons, accounting for about 10% of the crude oil processing amount. For a refining integrated enterprise or a chemical oil refinery, as the conversion depth of crude oil resources is further improved, the yield and proportion of light petroleum hydrocarbon of the whole plant are greatly increased, and how to efficiently utilize the light hydrocarbon resources becomes the focus of attention and research of the refining industry.
In the catalytic cracking technology using low-carbon olefin as a main target product, the conversion rate of the cracking reaction is high, the reaction temperature is high, the reaction heat is large, more heat is required in the reaction aspect than that of a conventional fluidized catalytic regenerator or other catalytic conversion methods, the coke generated by self-cracking can not meet the self-heat balance requirement of a reaction-regeneration system, and if the raw materials are light, the problem of serious shortage of heat sources is aggravated. When coke formation is insufficient in the reaction process, the required heat is usually provided for the reaction by adopting a mode of slurry oil recycling or fuel oil supplementing outside the regenerator. Because the slurry oil contains more polycyclic aromatic hydrocarbon, the slurry oil is easy to adsorb in the active center of the catalyst, the accessibility of the active center of raw material molecules is influenced, and the catalytic reaction selectivity is influenced. To solve this problem, the prior art solutions start from a regenerator system, such as an oxygen-deficient area arranged in the regenerator, and introduce fuel oil into the oxygen-deficient area to mix with the catalyst, and enter the regenerator to burn and regenerate; or disposing a heater within the regenerator and employing a fuel nozzle configured to inject a mixture of fuel and an oxygen-containing gas for combustion of supplemental heat; or injecting methane, and supplementing heat for the reaction by means of the combustion heat release of methane. The heat supplementing mode in the technology relieves the adverse effect on the catalyst, but does not fundamentally solve the influence of high-temperature hot spots generated by local combustion of the external fuel oil on the skeleton structure and the reaction performance of the catalyst, thereby seriously affecting the reaction selectivity. Therefore, developing a light oil catalytic cracking technology is a technical problem that the heat balance is insufficient while the selectivity of the low-carbon olefin is improved.
Disclosure of Invention
The application aims to provide a catalytic cracking reaction method and a catalytic cracking reaction system for improving the selectivity of products, improving the selectivity of ethylene and propylene, reducing the selectivity of methane, providing a coke source for a regeneration process and solving the problem of heat balance in the reaction process from the aspect of reaction.
In one aspect, the present application provides a light oil catalytic cracking method, comprising:
1) Introducing preheated light oil from the lower part of a cracking reactor, contacting with a regenerated catalyst from a regenerator and performing a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be regenerated,
2) Introducing raw coke into a coke formation reaction zone of a coke formation device, contacting with a regenerated catalyst from the regenerator and performing coke formation reaction to obtain a coke formation device oiling agent; mixing a C4 hydrocarbon fraction and/or a C5-C6 light gasoline fraction into the coke making oil at one or more positions of an outlet area of the coke making device, introducing the mixture into a dense phase settling section of a settling device for a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst,
3) Delivering a settler catalyst from a settler to a regenerator for scorching and regeneration, and recycling the obtained regenerated catalyst, wherein the settler catalyst comprises a first spent catalyst and a second spent catalyst;
4) The first reaction product and the second reaction product are introduced into a separation system for separation.
In one embodiment, the light oil comprises gaseous hydrocarbons and light distillate; preferably, the light oil has properties satisfying one, two, three or four of the following indices: the density at 20 ℃ is less than 860 kg/cubic meter, the carbon residue is 0-0.5 wt%, the total aromatic hydrocarbon content is 0-30 wt%, and the final distillation point of the distillation range is less than 360 ℃.
In one embodiment, the conditions of the first catalytic cracking reaction include: the reaction temperature is 510-750 ℃, the reaction time is 0.5-10 seconds, and the weight ratio of the catalyst to the oil is 10:1 to 50:1, the weight ratio of the pre-lifting gas to the raw oil is 0.05:1 to 2.0:1, the catalyst density is 20-100 kg/cubic meter, the linear speed is 4-18 m/s, and the reaction pressure is 130-450 kilopascals.
In one embodiment, the conditions of the coking reaction include: the reaction temperature is 460-650 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is 3:1 to 30:1, the weight ratio of the pre-lifting gas to the raw coke is 0.01:1 to 0.05:1, the linear velocity is 0.2-0.8 m/s, and the catalyst particle density is 300-700 kg/cubic meter.
In one embodiment, the conditions of the second catalytic cracking reaction include: reaction temperature of 4 90-730 ℃ and 0.5-20 hours of weight hourly space velocity -1 。
In one embodiment, the raw coke feedstock is selected from the group consisting of a plant self-produced cracked heavy oil and a secondary processing distillate, or a mixture thereof; preferably, the secondary processing distillate oil can be selected from one or more of catalytic cracking diesel oil, catalytic cracking slurry oil, coker gasoline, coker diesel oil and coker wax oil; more preferably, the coke-producing feedstock is a plant self-produced pyrolysis heavy oil.
In another aspect, the present application provides a catalytic cracking reaction-regeneration system comprising:
a catalytic cracking reactor, wherein the catalyst is a catalyst,
a coke-producing device,
an oil agent separating device is provided with a plurality of oil agent separating devices,
a settler, and
the regeneration device comprises a regenerator, a first heat exchanger, a second heat exchanger, a third heat exchanger and a,
wherein, catalytic cracking reactor includes from the bottom up in proper order:
an optional pre-lift zone;
the reaction zone comprises at least one reducing reaction section, the reducing reaction section is in a hollow cylinder shape with a cross section of a general circular shape and an opening at the bottom end and the top end, and the inner diameter of the reducing reaction section is continuously or discontinuously reduced from bottom to top; and
an outlet zone;
wherein the optional pre-lifting zone is communicated with the bottom end of the reaction zone, the top end of the reaction zone is communicated with the outlet zone, and at least one raw material feeding port is arranged on the optional pre-lifting zone and/or the bottom of the reaction zone;
The cross-sectional inner diameter of the bottom end of the reaction zone is greater than or equal to the cross-sectional inner diameter of the optional pre-lift zone, and the cross-sectional inner diameter of the top end is equal to or less than the cross-sectional inner diameter of the optional pre-lift zone and the cross-sectional inner diameter of the outlet zone; the regenerated catalyst inlet is arranged at the bottom of the reaction zone and/or the optional pre-lifting zone;
the catalytic cracking reactor is coaxially arranged with the settler, the oil separating device is accommodated in the settler, and the outlet area of the catalytic cracking reactor is communicated with the oil separating device, so that the oil of the catalytic cracking reactor enters the oil separating device to be separated into a first reaction product and a first spent catalyst;
the lower part of the settler is provided with a dense-phase sedimentation section, and the dense-phase sedimentation section of the settler is provided with a catalyst outlet; the catalyst outlet of the settler is in communication with the regenerator such that the settler catalyst within the settler is conveyed to the regenerator;
the coke generator sequentially comprises the following components from bottom to top:
a pre-lifting area is provided for the pre-lifting area,
a coking reaction zone which is a bubbling fluidized bed or a turbulent fluidized bed, and
An outlet region for the fluid to flow from the fluid outlet,
the top end of the pre-lifting area is communicated with the coking reaction area, and the top end of the coking reaction area is communicated with the outlet area;
the coke generator is provided with at least one fuel oil feed inlet;
the coke generator is arranged outside the settler, and an outlet area of the coke generator is communicated with a dense-phase sedimentation section of the settler, so that materials of the coke generator enter the dense-phase sedimentation section of the settler;
the regenerator is provided with a first regenerated catalyst outlet and a second regenerated catalyst outlet, the first regenerated catalyst outlet being in communication with the regenerated catalyst inlet of the catalytic cracking reactor such that at least a portion of the regenerated catalyst is recycled back to the catalytic cracking reactor;
the bottom end of the pre-lift zone of the coke breeder and/or the bottom end of the coke breeder reaction zone is configured to communicate with a second regenerated catalyst outlet of a regenerator such that at least a portion of the regenerated catalyst of the regenerator is conveyed to the coke breeder.
In one embodiment, the ratio of the inner diameter to the height of the pre-lift zone of the catalytic cracking reactor is from 0.02 to 0.4:1, a step of; the ratio of the height to the total height of the catalytic cracking reactor is 0.01:1 to 0.2:1, a step of;
And/or the ratio of the inner diameter of the cross section of the bottom of the reaction zone of the catalytic cracking reactor to the total height of the catalytic cracking reactor is 0.01:1 to 0.5:1, a step of; the ratio of the total height of the reaction zone to the total height of the catalytic cracking reactor was 0.15:1 to 0.8:1, a step of;
and/or the ratio of the inner diameter of the cross section of the outlet zone of the reactor to the height is 0.01-0.3:1, the ratio of the height of the outlet zone to the total reactor height being 0.05:1 to 0.5:1.
in one embodiment, the reaction zone of the catalytic cracking reactor comprises 1-3 reduced diameter reaction sections,
preferably, the diameter-reducing reaction section of the catalytic cracking reactor is in a hollow truncated cone shape, and the longitudinal section of the diameter-reducing reaction section is in an isosceles trapezoid shape; the ratio of the inner diameter of the top cross section to the height of the reducing reaction section is respectively and independently 0.005-0.3:1, the ratio of the inner diameter of the cross section of the bottom end to the height of the reducing reaction section is respectively and independently 0.015-0.25:1, the ratio of the inner diameter of the cross section of the bottom end to the inner diameter of the cross section of the top end is respectively more than 1.2 and less than or equal to 10; the ratio of the height of the diameter-reduced reaction section to the total height of the catalytic cracking reactor is 0.15 independently: 1 to 0.8:1.
in one embodiment, the pre-lifting area of the catalytic cracking reactor is connected with the reaction area by a first connecting section, the longitudinal section of the first connecting section is an isosceles trapezoid, and the camber angle alpha of the side edge of the isosceles trapezoid is 5-85 degrees.
In one embodiment, the coke generator is provided with the pre-lifting gas inlet, the catalyst inlet and two fuel oil inlets in sequence from bottom to top;
wherein one of the fuel oil inlets is disposed upstream of the coking reaction zone of the coker and one of the fuel oil inlets is disposed downstream of the coking reaction zone of the coker.
In one embodiment, the green coke reaction zone is hollow cylindrical with an aspect ratio of 20:1 to 2:1.
in one embodiment, the pre-lift zone of the coke oven is hollow cylindrical with an aspect ratio of 10:1-2:1, a step of;
the outlet area of the coke generator is hollow cylindrical, and the length-diameter ratio of the outlet area is 30:1-5:1, a step of;
preferably, the ratio of the inner diameters of the pre-lifting zone of the coke generator, the coke generation reaction zone of the coke generator and the outlet zone of the coke generator is 1:2:1 to 1:10:2.
in the application, the diameter-reducing structure of the diameter-reducing reaction section, particularly the conical reaction section, arranged in the cracking reactor in the system is beneficial to accelerating the reaction oil gas to leave the reaction zone, shortening the reaction time, reducing the back mixing of the catalyst, reducing the secondary conversion reaction of the low-carbon olefin generated by the primary reaction and improving the selectivity of the low-carbon olefin.
In the application, C4 hydrocarbon or C5-C6 light gasoline fraction is conveyed to a dense-phase settling section through an outlet pipeline of a coke generator for carrying out a second cracking reaction, thereby avoiding the competition reaction of olefin components in a cracking reactor, providing a proper reaction environment for the polymerization and re-cracking reaction of C4 hydrocarbon or C5-C6 light gasoline fraction and improving the selectivity of ethylene and propylene.
In the application, the fuel oil can be mixed with the catalyst under the low-temperature and oxygen-free fluidization condition by arranging the coke generator, and the coke generation reaction occurs in the coke generator reaction zone with the characteristics of a bubbling bed or a turbulent fluidized bed, so that the coke selectivity is high, the coke is uniformly distributed on the catalyst, and the uniform combustion in a regeneration system is facilitated.
In the application, the coke-carrying catalyst generated by the coke generator can be mixed with the coke-carrying catalyst generated by the cracking reactor to enter a regeneration system, and the coke on the catalyst can be fully burnt and released under the action of high-temperature oxygen-enriched gas, so that the heat required by the reaction is supplied, the property of the catalyst is not damaged, the coke source is supplemented from the reaction system end, and the heat balance problem of the catalytic cracking device is solved.
When the method and the system are used for catalytic cracking reaction, the contact efficiency of the raw materials and the catalyst is high, the catalytic reaction selectivity is good, the yield of high-value-added products such as ethylene and propylene is high, and the yield of byproducts such as methane is low. The transformation, development and extension of the booster refinery from oil refining to chemical raw material production not only solve the problem of petrochemical raw material shortage, but also improve the economic benefit of the refinery.
Drawings
The accompanying drawings are included to provide a further understanding of the application, and are incorporated in and constitute a part of this specification, illustrate the application and together with the description serve to explain, without limitation, the application. In the drawings:
FIG. 1 is a schematic diagram of a catalytic cracking reactor in the system of the present application;
FIG. 2 is a schematic diagram of a coke oven in the system of the present application;
fig. 3 is a schematic diagram of a catalytic cracking system according to an embodiment of the present application.
Detailed Description
The application is further described in detail below by means of the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
Any particular value disclosed herein (including the endpoints of the numerical ranges) is not limited to the precise value of the value, and is to be understood to also encompass values near the precise value, such as all possible values within the range of + -5% of the precise value. Also, for a range of values disclosed, any combination of one or more new ranges of values between the endpoints of the range, between the endpoints and the specific points within the range, and between the specific points is contemplated as being specifically disclosed herein.
In the present application, both the terms "upstream" and "downstream" are based on the flow direction of the reaction mass. For example, when the reactant stream flows from bottom to top, "upstream" means a location below, and "downstream" means a location above.
Unless otherwise indicated, terms used herein have the same meaning as commonly understood by one of ordinary skill in the art, and if a term is defined herein and its definition is different from the ordinary understanding in the art, then the definition herein controls.
The application provides a light oil catalytic cracking method, which comprises the following steps:
1) Introducing preheated light oil from the lower part of a cracking reactor, contacting with a regenerated catalyst from a regenerator and performing a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be regenerated,
2) Introducing raw coke into a coke formation reaction zone of a coke formation device, contacting with a regenerated catalyst from the regenerator and performing coke formation reaction to obtain a coke formation device oiling agent; mixing a C4 hydrocarbon fraction and/or a C5-C6 light gasoline fraction into the coke making oil at one or more positions of an outlet area of the coke making device, introducing the mixture into a dense phase settling section of a settling device for a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst,
3) Delivering a settler catalyst from a settler to a regenerator for scorching and regeneration, and recycling the obtained regenerated catalyst, wherein the settler catalyst comprises a first spent catalyst and a second spent catalyst;
4) The first reaction product and the second reaction product are introduced into a separation system for separation.
The application also provides a catalytic cracking reaction-regeneration system, comprising:
a catalytic cracking reactor, wherein the catalyst is a catalyst,
a coke-producing device,
an oil agent separating device is provided with a plurality of oil agent separating devices,
a settler, and
the regeneration device comprises a regenerator, a first heat exchanger, a second heat exchanger, a third heat exchanger and a,
wherein, catalytic cracking reactor includes from the bottom up in proper order:
an optional pre-lift zone;
the reaction zone comprises at least one reducing reaction section, the reducing reaction section is in a hollow cylinder shape with a cross section of a general circular shape and an opening at the bottom end and the top end, and the inner diameter of the reducing reaction section is continuously or discontinuously reduced from bottom to top; and
an outlet zone;
wherein the optional pre-lifting zone is communicated with the bottom end of the reaction zone, the top end of the reaction zone is communicated with the outlet zone, and at least one raw material feeding port is arranged on the optional pre-lifting zone and/or the bottom of the reaction zone;
the cross-sectional inner diameter of the bottom end of the reaction zone is greater than or equal to the cross-sectional inner diameter of the optional pre-lift zone, and the cross-sectional inner diameter of the top end is equal to or less than the cross-sectional inner diameter of the optional pre-lift zone and the cross-sectional inner diameter of the outlet zone; the regenerated catalyst inlet is arranged at the bottom of the reaction zone and/or the optional pre-lifting zone;
The catalytic cracking reactor is coaxially arranged with the settler, the oil separating device is accommodated in the settler, and the outlet area of the catalytic cracking reactor is communicated with the oil separating device, so that the oil of the catalytic cracking reactor enters the oil separating device to be separated into a first reaction product and a first spent catalyst;
the lower part of the settler is provided with a dense-phase sedimentation section, and the dense-phase sedimentation section of the settler is provided with a catalyst outlet; the catalyst outlet of the settler is in communication with the regenerator such that the settler catalyst within the settler is conveyed to the regenerator;
the coke generator sequentially comprises the following components from bottom to top:
a pre-lifting area is provided for the pre-lifting area,
a coking reaction zone which is a bubbling fluidized bed or a turbulent fluidized bed, and
an outlet region for the fluid to flow from the fluid outlet,
the top end of the pre-lifting area is communicated with the coking reaction area, and the top end of the coking reaction area is communicated with the outlet area;
the coke generator is provided with at least one fuel oil feed inlet;
the coke generator is arranged outside the settler, and an outlet area of the coke generator is communicated with a dense-phase sedimentation section of the settler, so that materials of the coke generator enter the dense-phase sedimentation section of the settler;
The regenerator is provided with a first regenerated catalyst outlet and a second regenerated catalyst outlet, the first regenerated catalyst outlet being in communication with the regenerated catalyst inlet of the catalytic cracking reactor such that at least a portion of the regenerated catalyst is recycled back to the catalytic cracking reactor;
the bottom end of the pre-lift zone of the coke breeder and/or the bottom end of the coke breeder reaction zone is configured to communicate with a second regenerated catalyst outlet of a regenerator such that at least a portion of the regenerated catalyst of the regenerator is conveyed to the coke breeder.
The method of the present application may be performed in the system of the present application. The catalytic cracking process of the present application is further described below in conjunction with the catalytic cracking reaction-regeneration system. The following description of the catalytic cracking process according to the application applies equally to the catalytic cracking reaction-regeneration system according to the application and vice versa.
Fig. 3 shows a catalytic cracking reaction-regeneration system of the present application, comprising:
the catalytic cracking reactor 100 is configured to operate,
the coke oven 300 is configured to receive a plurality of coke oven parameters,
the oil agent separating apparatus 201,
settler 200, and
regenerator 500.
As shown in fig. 1, the catalytic cracking reactor 100 may be provided with a pre-lift gas inlet 101, one or more pyrolysis feedstock oil inlets (e.g., a lower pyrolysis feedstock feed inlet 102, etc.), a bottom catalyst inlet 103, and a top oil outlet 104. The oil outlet 104 of the cracking reactor is in fluid communication with the oil separation device 201 such that the first reaction oil gas and the first spent catalyst from the catalytic cracking reactor 100 are separated in the oil separation device 201.
In one embodiment, the catalytic cracking reactor 100 comprises, in order from bottom to top:
an optional pre-lift zone I is provided,
the reaction zone II comprises at least one reducing reaction section, wherein the reducing reaction section is a hollow cylinder with a cross section of a general circular shape and an opening at the bottom end and the top end, and the inner diameter of the hollow cylinder is continuously or discontinuously reduced from bottom to top; and
an outlet region III,
wherein the optional pre-lifting zone I is communicated with the bottom end of the reaction zone II, the top end of the reaction zone II is communicated with the outlet zone III, and at least one raw material feeding port 102 is arranged on the optional pre-lifting zone and/or the bottom of the reaction zone;
the cross-sectional inner diameter of the bottom end of the reaction zone II is greater than or equal to the cross-sectional inner diameter of the optional pre-lifting zone I, and the cross-sectional inner diameter of the top end is equal to or less than the cross-sectional inner diameter of the optional pre-lifting zone and the cross-sectional inner diameter of the outlet zone.
As shown in fig. 1, the catalytic cracking reactor may include the pre-lift region I provided at the lowermost portion of the catalytic cracking reactor for pre-lifting the catalyst or the like entering the reactor. As shown in fig. 1, the lower part of the pre-lift zone I is provided with a catalyst inlet 103 for inputting catalyst. The pre-lift zone I may be a hollow cylindrical structure having an inner diameter to height ratio of 0.02-0.4:1, a step of; the ratio of the height to the total height of the reactor was 0.01:1 to 0.2:1, preferably 0.05:1 to 0.15:1. in one embodiment, the pre-lift zone I may have an inner diameter of 0.2 to 5 meters, preferably 0.4 to 3 meters. In embodiments where a pre-lift zone I is present, pre-lift medium may be input to the pre-lift zone I through the pre-lift gas inlet 101. In embodiments where a pre-lift zone I is present, the bottom of the pre-lift zone I may also be provided with at least one catalyst inlet 103 for allowing catalyst to enter the reactor through the pre-lift zone I.
According to the application, the pre-lift zone I is not necessary, for example when the reaction zone II of the reactor according to the application is used in series with other reactors, such as riser reactors, the reaction zone II may be in direct communication with the outlet of the other reactor located upstream, without the need to employ the pre-lift zone I. In one embodiment, the catalytic cracking reactor may not include the pre-lift zone I. At this time, the bottom of the reaction zone II may be provided with at least one raw material feed port 102 to facilitate the entry of raw materials and the like into the catalytic cracking reactor. In embodiments where there is no pre-lift zone I, the bottom of the reaction zone II may be provided with at least one catalyst inlet (not shown) for allowing catalyst to enter the reactor. Of course, the reaction zone II may be provided without a catalyst inlet, wherein the catalyst may originate from catalyst carried in other reactor streams. Both of these embodiments are within the scope of the present application.
As shown in fig. 1, the catalytic cracking reactor may include a reaction zone II. The pre-lifting area I is communicated with the bottom end 110 of the reaction area II, the top end 120 of the reaction area II is communicated with the outlet area III, and at least one catalyst inlet 103 and at least one raw material feeding port 102 are arranged on the pre-lifting area and/or at the bottom of the reaction area. The cross-sectional inner diameter of the bottom end 110 of the reaction zone II is greater than or equal to the cross-sectional inner diameter of the pre-lift zone I, and the cross-sectional inner diameter of the top end 120 is equal to or less than the cross-sectional inner diameter of the pre-lift zone I and the cross-sectional inner diameter of the outlet zone III.
In the catalytic cracking reactor provided by the application, the reaction zone II is a fluidized bed, preferably, the fluidized bed is one or a combination of a plurality of conveying fluidized bed, turbulent fluidized bed and rapid bed.
In one embodiment, the pre-lift zone I is connected to the reaction zone II via a first transition section I-1. The longitudinal section of the first transition section I-1 may be an isosceles trapezoid, and the camber angle α of the sides of the isosceles trapezoid may be 5-85 °, preferably 15-75 °.
As shown in fig. 1, the raw material feed port may be provided in the upper portion of the pre-lift zone I, in the first transition section I-1, or in the lower portion of the reaction zone II. In particular, in embodiments where there is no pre-lift zone I, the lower portion of the reaction zone II may be provided with a feedstock feed port 102 for feeding feedstock.
In one embodiment, the ratio of the bottom cross-sectional inner diameter of the reaction zone II to the total reactor height is 0.01:1 to 0.5:1, preferably 0.05:1 to 0.2:1, a step of; the ratio of the total height of the reaction zone II to the total height of the reactor was 0.15:1 to 0.8:1, for example 0.2:1 to 0.75:1.
as shown in FIG. 1, the reaction zone II comprises at least one reduced diameter reaction section which is a hollow cylinder having a substantially circular cross section and open at the bottom and top ends, and the inner diameter of which continuously or discontinuously decreases from bottom to top.
According to the application, by "reduced diameter" is meant that the inner diameter decreases in a discontinuous manner, for example in a stepwise or jump-like manner or in a continuous manner. As an example of the "reduced diameter section having a discontinuous inner diameter decreasing from bottom to top", there may be mentioned a column body composed of two or more hollow cylinders having a decreasing inner diameter.
As an example, the reaction zone II may be a cylindrical pattern comprising one or more hollow frustoconical sections, or a cylindrical pattern comprising two or more hollow cylindrical sections. According to the present application, when the reaction zone includes two or more reduced diameter reaction sections, each reduced diameter reaction section may have the same or different heights, to which the present application is not strictly limited.
In a preferred embodiment, the reaction zone II comprises a column pattern consisting of one or more hollow frustoconical sections and optionally connecting sections for connecting adjacent hollow frustoconical sections, or a column pattern consisting of two or more hollow cylindrical sections and optionally connecting sections for connecting adjacent hollow cylindrical sections.
In one embodiment, as shown in fig. 1, the reaction zone II comprises a 1-stage reduced diameter reaction stage in the form of a hollow truncated cone with a longitudinal section in the form of an isosceles trapezoid; its top cross-section inner diameter D 120 Height h of the reduced diameter reaction section II The ratio of each is independently 0.005-0.3:1, cross section of bottom endInside diameter D of (2) 110 Height h of the reduced diameter reaction section II The ratio of each is independently 0.015 to 0.25:1, bottom end cross section inner diameter D 110 With the top cross-section inside diameter D 120 Each independently greater than 1.2 and less than or equal to 10, more preferably 1.5 to 5; the diameter-reducing reaction section h II The ratio of the height of (2) to the total reactor height h was 0.15:1 to 0.8:1, preferably 0.2:1 to 0.75:1. in one embodiment, the inner diameter D of the bottom end cross section 110 The ratio to the total reactor height h was 0.01:1 to 0.5:1, preferably 0.05:1 to 0.2; the ratio of the height h1 of the diameter-reduced reaction section to the total height h of the reactor is 0.15:1 to 0.8:1, preferably 0.2:1 to 0.75:1, and the total height h of the reaction zone II II The ratio to the total reactor height h was 0.15:1 to 0.8:1, preferably 0.2:1 to 0.75:1. in one embodiment, the diameter D of the top cross section of the reduced diameter reaction section 100 110 0.2 to 5 meters, preferably 0.4 to 3 meters. In one embodiment, the total height h of the reaction zone II II May be about 2-50 meters, preferably about 5-40 meters, more preferably about 8-20 meters.
In the catalytic cracking reactor, the bottom space of the arranged reduced diameter reaction section, particularly the conical reaction section, is large, and can effectively improve the catalyst density in the reactor, thereby greatly improving the ratio of the catalyst to the reaction raw materials in the reactor, strengthening the primary cracking reaction of the raw materials, improving the reaction conversion rate and improving the yield of the low-carbon olefin; in addition, the diameter-reducing structure of the arranged diameter-reducing reaction section, particularly the conical reaction section, is beneficial to accelerating the reaction oil gas to leave the reaction zone, shortens the reaction time, reduces the back mixing of the catalyst, is beneficial to reducing the secondary conversion reaction of the low-carbon olefin generated by the primary reaction, and improves the selectivity of the low-carbon olefin.
In the catalytic cracking reactor provided by the application, one or more, such as one, two or more raw material feed openings can be arranged in the reactor, wherein the raw material feed openings can be independently arranged at the outlet end of the pre-lifting zone I or arranged at the bottom of the reaction zone II. Further preferably, the positions of the plurality of feedstock inlets are each independently located at the same height or at different heights of the reaction zone II. Thus, raw materials with different properties can be fed into different raw material feed ports respectively.
As shown in fig. 1, the catalytic cracking reactor may include an outlet zone III. In one embodiment, the outlet region III may be in the form of a hollow cylinder having a cross-sectional inner diameter and a height h III The ratio is 0.01-0.3:1 height h of the outlet zone III The ratio to the total reactor height h was 0.05:1 to 0.5:1, more preferably 0.1:1 to 0.35:1. in one embodiment, the inner diameter of the outlet zone III is from 0.2 to 5 meters, preferably from 0.4 to 3 meters.
As mentioned before, the inside diameter of the cross section at the top end of the reaction zone II is equal to or smaller than the inside diameter of the cross section of the outlet zone III. In one embodiment, the cross-sectional inner diameter of the top end of the reaction zone II is equal to the cross-sectional inner diameter of the outlet zone III.
In one embodiment, the cross-sectional inner diameter of the top end of the reaction zone II is smaller than the cross-sectional inner diameter of the outlet zone III. In this case, the reaction zone II and the outlet zone III may be connected by a third transition (not shown). The longitudinal section of the third transition section may be an isosceles trapezoid, and the camber angle of the sides of the isosceles trapezoid may be 5-85 °, preferably 15-75 °.
In the present application, the catalytic cracking reactor 100 is disposed coaxially with the settler 200, and the oil separating apparatus 201 is accommodated inside the settler 200, and an outlet area of the catalytic cracking reactor communicates with the oil separating apparatus, so that the oil of the catalytic cracking reactor enters the oil separating apparatus to be separated into a first reaction product and a first spent catalyst. In one embodiment, the outlet end 104 of the outlet zone III may be directly connected to an inlet of an oil separation device 201, such as a cyclone. In the present application, the oil separating apparatus 201 may employ an apparatus well known to those skilled in the art, such as a cyclone.
In one embodiment, the light oil comprises gaseous hydrocarbons and light distillate. The light oil meets one, two, three or four of the following indexes: the density at 20 ℃ is less than 860 kg/cubic meter, the carbon residue is 0-0.5 wt%, the total aromatic hydrocarbon content is 0-30 wt%, and the final distillation point of the distillation range is less than 360 ℃.
In one embodiment, the gaseous hydrocarbon may be selected from one or more of saturated liquefied gas, unsaturated liquefied gas, and carbon four fractions; the light distillate oil comprises petroleum hydrocarbon with a distillation range of 25-360 ℃, oxygen-containing compounds and distillate oil of biomass or waste plastic generated oil; the petroleum hydrocarbon can be selected from one or more of straight-run naphtha, straight-run kerosene and straight-run diesel oil which are processed at one time; and mixing oil of one or more of secondary processed topped oil, raffinate oil, hydrocracking light naphtha, pentane oil, coker gasoline, fischer-Tropsch synthetic oil, catalytic cracking light gasoline, hydrogenated gasoline and hydrogenated diesel oil.
In one embodiment, the catalyst comprises 1 to 50 wt% on a dry basis and based on the weight of the catalyst on a dry basis; from 5 to 99% by weight of an inorganic oxide, and from 0 to 70% by weight of clay. The zeolite comprises a medium pore zeolite and optionally a large pore zeolite, the medium pore zeolite being selected from the group consisting of ZSM-series zeolites, ZRP zeolites, and any combination thereof; the large pore zeolite is selected from rare earth Y-type zeolite, rare earth hydrogen Y-type zeolite, ultrastable Y-type zeolite, and high silicon Y-type zeolite, and any combination thereof. The medium pore zeolite comprises 10 to 100 wt%, preferably 50 to 90 wt%, of the total weight of the zeolite on a dry basis.
In the present application, the medium pore zeolite and the large pore zeolite are as defined conventionally in the art, i.e., the average pore size of the medium pore zeolite is about 0.5 to 0.6nm and the average pore size of the large pore zeolite is about 0.7 to 1.0nm.
As an example, the large pore zeolite may be selected from one or more of Rare Earth Y (REY) type zeolite, rare Earth Hydrogen Y (REHY) type zeolite, ultrastable Y type zeolite and high silicon Y type zeolite obtained by different methods. The mesoporous zeolite may be selected from zeolites having MFI structure, such as ZSM-series zeolites and/or ZRP zeolites. Optionally, the above mesoporous zeolite may be modified with a non-metal element such as phosphorus and/or a transition metal element such as iron, cobalt, nickel and the like. For a more detailed description of ZRP zeolites see U.S. patent US5,232,675A. The ZSM series of zeolites is preferably selected from one or more of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure. For a more detailed description of ZSM-5, see U.S. patent US3,702,886A.
According to the application, the inorganic oxide is used as a binder, preferably silica (SiO 2 ) And/or aluminum oxide (Al) 2 O 3 ). The clay is preferably kaolin and/or halloysite as a matrix (i.e., carrier).
In one embodiment, the conditions of the catalytic cracking reaction include: the reaction temperature is 550-750 ℃, the reaction time is 0.5-10 seconds, and the weight ratio of the catalyst to the oil is 10:1 to 50:1, the weight ratio of the pre-lifting gas to the raw oil is 0.05:1 to 2.0:1, the catalyst density is 20-100 kg/cubic meter, the linear speed is 4-18 m/s, and the reaction pressure is 130-450 kilopascals.
In one embodiment, the feedstock is introduced into the cracking reactor at one location or at more than one same or different locations.
In one embodiment, the process further comprises introducing a C4 hydrocarbon fraction and/or a C5-C6 light gasoline fraction into the dense phase settling section for a second catalytic cracking reaction.
In the present application, the C4 hydrocarbon fraction refers to low molecular hydrocarbons in the form of gas at normal temperature and normal pressure, which mainly contains the C4 fraction, and include alkanes, alkenes and alkynes having 4 carbon atoms in the molecule, and may include gaseous hydrocarbon products (such as liquefied gas) rich in the C4 hydrocarbon fraction produced by the method of the present application, and may include gaseous hydrocarbons rich in the C4 fraction produced by other devices, wherein the C4 hydrocarbon fraction produced by the method of the present application is preferred. The C4 hydrocarbon fraction is preferably an olefin-rich C4 hydrocarbon fraction, and the content of C4 olefins may be greater than 50 wt%, preferably greater than 60 wt%, more preferably above 70 wt%.
In the present application, the C5-C6 light gasoline fraction may include pyrolysis gasoline produced by the method of the present application, and may also include gasoline fractions produced by other apparatuses, for example, may be at least one C5-C6 fraction selected from the group consisting of catalytic pyrolysis gasoline, straight run gasoline, coker gasoline, thermal pyrolysis gasoline, and hydrogenated gasoline. The C5-C6 light gasoline is preferably an olefin-rich fraction, wherein the olefin content is more than 50wt%, preferably more than 60 wt%.
In one embodiment, a C4 hydrocarbon or C5-C6 light gasoline fraction is introduced at one or more locations in the exit zone of the coke breeder. As described below.
In one embodiment, the conditions of the second catalytic cracking reaction include: the reaction temperature is 490-730 ℃ and the weight hourly space velocity is 0.5-20 hours -1 。
In one embodiment, the amount of raw coke material introduced into the raw coke vessel is from 10 to 50wt% of the feed amount of raw coke material to the cracking reactor; the amount of C4 hydrocarbon or C5-C6 light gasoline fraction introduced into the coke generator is 3-30wt% of the raw material feed amount of the cracking reactor.
As shown in FIG. 2, the catalytic pyrolysis coke generator 300 of the present application is suitable for adjusting the heat balance. The coke oven 300 comprises, in order from bottom to top: a pre-lift zone I ', a raw coke reaction zone II ', and an exit zone III '.
The coke breeder 300 is provided with a pre-lift gas inlet 301, a catalyst inlet 303, and fuel oil inlets 302, 305 in order from bottom to top, and is used for inputting a C4 hydrocarbon fraction and/or a C5-C6 light gasoline fraction. The pre-lift gas inlet 301 is typically disposed at the pre-lift region I 'and typically at the bottom of the pre-lift region I'. The catalyst inlet 303 may be disposed in the pre-lift zone I 'and/or the raw coke reaction zone II', but is typically disposed in the pre-lift zone I ', below the pre-lift zone I', but above the pre-lift gas inlet 301, to enable the pre-lift gas to lift the incoming catalyst. Therefore, the regenerated catalyst can be pre-accelerated and pre-fluidized, the distribution condition of the catalyst is improved, and the catalyst is beneficial to uniform contact and rapid mixing with fuel oil.
The bottom of the regenerator 500 (as shown in fig. 3) communicates with the coker 300 through a catalyst inlet 303 so that catalyst can enter the coker to be coked, resulting in a coked catalyst. The top of the coke generator 300 is communicated with the oil separating device 201, so that the catalyst with coke is separated from the reaction oil and gas.
In one embodiment, the pre-lift zone I ', the green coke reaction zone II ', and the exit zone III ' are connected in sequence, i.e., the top of the pre-lift zone I ' is in communication with the green coke reaction zone II ', and the top of the green coke reaction zone II ' is in communication with the exit zone III '.
In the present application, the pre-lift gas inlet 301, the regenerated catalyst inlet 303, and the one or more fuel oil inlets 302, each independently provided on the coke oven 300, are located at different heights of the coke oven 300. Preferably, the coke generator is provided with a pre-lifting gas inlet 301 and a regenerated catalyst inlet 303 in sequence from bottom to top.
In the present application, the reaction zone of the coke oven 300 is a bubbling bed or a turbulent fluidized bed. In one embodiment, the reaction zone is hollow cylindrical with an aspect ratio of 20:1 to 2:1.
in one embodiment, the raw coke is introduced into the coker from more than one identical or different location at the coker inlet. In one embodiment, the raw coke is introduced into the coker outlet from one or more of the same or different locations.
In the present application, the coke breeder may be provided with one or more, for example one, two or more fuel oil inlets 302, 305. As shown in fig. 3, one fuel oil inlet 302 is located upstream of the raw coke reaction zone and one fuel oil inlet 305 is located downstream of the raw coke reaction zone. Pre-lift gas enters the coke breeder from the bottom of the coke breeder 300 through a pre-lift gas inlet 301, high-temperature regenerated catalyst from the regenerator and/or settler catalyst from the dense-phase settling section enters the lower part of the coke breeder 300, is mixed with the pre-lift gas and moves upwards, raw coke crude oil is injected into the coke breeder through a fuel oil inlet 302, and enters the coke breeder together with the regenerated catalyst for coking reaction. C4 hydrocarbon or C5-C6 light gasoline fraction is introduced into the coke breeder through fuel oil inlet 305 to be mixed with the material from the coke breeder reaction zone of the coke breeder and introduced into the dense phase settling section of the settler together for the second catalytic cracking reaction as described above.
In the present application, the fuel oil injected through the fuel oil inlet 302 may include straight distillate or secondary process distillate. Preferably, the secondary processing distillate oil can be selected from a mixed oil of one or more of catalytic pyrolysis diesel oil, catalytic pyrolysis slurry oil, coker gasoline, coker diesel oil and coker wax oil.
In one embodiment, the pre-lift region I' is hollow cylindrical with an aspect ratio of 10:1-2:1. in one embodiment, the outlet zone III' is hollow cylindrical with an aspect ratio of 30:1-5:1. in one embodiment, the ratio of the inner diameters of the pre-lift zone I ', the raw coke reaction zone II ', the exit zone III ' is 1:2:1-:1:10:1.
in one embodiment, the conditions of the coking reaction include: the reaction temperature is 460-560 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is (3-30): 1, the weight ratio of the pre-lifting gas to the raw coke is (0.01-0.5): 1, the linear velocity is 0.2 m/s to 1.2 m/s, and the catalyst particle density is 300 kg/cubic meter to 700 kg/cubic meter.
In one embodiment, the raw coke feedstock is a plant self-produced cracked heavy oil and a secondary processing distillate, or a mixture thereof. Preferably, the secondary processed distillate oil can be selected from one or more of catalytic cracking diesel oil, catalytic cracking slurry oil, coker gasoline, coker diesel oil and coker wax oil. More preferably, the coke-producing feedstock is a plant self-produced pyrolysis heavy oil.
In one embodiment, the coke breeder has a reaction zone linear velocity of from 0.2 meters/second to 1.2 meters/second and a catalyst particle density of from 300 kilograms per cubic meter to 700 kilograms per cubic meter.
In one embodiment, the pre-lift gas is selected from steam, nitrogen, dry gas, rich gas or carbon four fraction or mixtures thereof, the mass ratio of the pre-lift gas to the fuel oil is 0.01:1 to 0.05:1.
in one embodiment, the fuel oil comprises a straight run distillate or a secondary process distillate. Preferably, the secondary processing distillate oil can be selected from a mixed oil of one or more of catalytic pyrolysis diesel, coker gasoline, coker diesel and coker wax oil.
In one embodiment, the fuel oil atomizing medium may be selected from steam, nitrogen, or a mixture thereof, the mass ratio of the atomizing medium to the combustion oil being 0.01:1 to 0.5:1.
in one embodiment, the exit temperature of the coke oven is 460-560 ℃.
In one embodiment, the coke breeder 300 is disposed outside the settler 200 and is disposed in parallel with the catalytic cracking reactor 100. The outlet zone III' of the coke breeder is in communication with a dense phase settling section 205 located in the lower portion of the settler such that the coke breeder material enters the dense phase settling section 205. In the dense phase settling section 205, the C4 hydrocarbon or C5-C6 light gasoline fraction injected through the fuel oil inlet 305 and the material from the coke breeder (including oil gas and oil gas) are contacted with a first spent catalyst separated by the oil separation apparatus 201, and a second catalytic cracking reaction is performed, to obtain a second reaction product and a second spent catalyst. In one embodiment, the outlet end 304 of the coke oven 300 communicates with the dense phase settling section 205 of the settler. In one embodiment, the oil separating apparatus 201 is accommodated inside the settler 200 for allowing the catalyst separated by the oil separating apparatus 201 to settle in the settler 200. Meanwhile, a stripping gas inlet 207 is provided at the lower part of the dense phase settling section 205 for inputting a stripping gas such as steam or the like for stripping the catalyst (including the first spent catalyst and the second spent catalyst, collectively referred to as a settler catalyst) in the dense phase settling section 205. The regenerator 500 is in communication with the dense phase settling section 205 such that stripped settler catalyst is transferred to the regenerator 500.
In one embodiment, the dense phase settling section 205 of the settler is provided with a catalyst outlet 206; the catalyst outlet 206 of the settler is in communication with the regenerator 500 such that the settler catalyst within the settler is transported to the regenerator.
As shown in fig. 3, the regenerator 500 is used for regenerating a spent catalyst, an oxygen-containing gas inlet 501, a spent catalyst inlet 505, two regenerated catalyst outlets 506 and outlets 508 are arranged at the lower part, a cyclone 503 is arranged inside, and a flue gas outlet 504 is arranged at the top.
As shown in fig. 3, the first regenerated catalyst outlet 506 communicates with the regenerated catalyst inlet 103 of the catalytic cracking reactor such that at least a portion of the regenerated catalyst is recycled back to the catalytic cracking reactor 100. In one embodiment, the bottom end of the pre-lift zone I 'of the coke breeder and/or the bottom end of the coke breeder reaction zone II' is configured to communicate with the second regenerated catalyst outlet 508 of the regenerator; in one embodiment, the catalyst inlet 303 of the coker is connected to a second regenerated catalyst outlet 508 of the regenerator such that at least a portion of the regenerated catalyst of the regenerator is recycled back to the coker 300 such that catalyst can enter the coker to be coked, resulting in a coked catalyst.
In one embodiment, the conditions of the regenerator are: the regeneration temperature is 550-750deg.C, preferably 600-730 deg.C, more preferably 650-700 deg.C; the gas superficial linear velocity is 0.5 to 3 m/s, preferably 0.8 to 2.5 m/s, more preferably 1 to 2 m/s, and the average residence time of the spent catalyst is 0.6 to 3 minutes, preferably 0.8 to 2.5 minutes, more preferably 1 to 2 minutes.
In one embodiment, the regenerated catalyst recycled to the catalytic cracking reactor 100 comprises 50-90% of the total amount of regenerated catalyst, based on the total weight of regenerated catalyst; the regenerated catalyst recycled to the coke generator 300 accounts for 10-50% of the total amount of regenerated catalyst, based on the total weight of regenerated catalyst.
The reaction oil gas (i.e., reaction product) separated by the oil agent separating device 201 is collected in the gas collection chamber 202 and then transferred to a subsequent reaction product separating device (not shown) through a line 203 for separation. The reaction product separation device may be provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis gasoline outlet, and a pyrolysis heavy oil outlet for separation into dry gas, liquefied gas, pyrolysis gasoline, pyrolysis heavy oil, and the like according to the distillation range of the reaction product. And then the dry gas and the liquefied gas are further separated by a gas separation device to obtain methane, ethylene, propylene, mixed C4 components and the like, the pyrolysis gasoline is further separated to obtain pyrolysis light gasoline and heavy gasoline, and the method for separating ethylene, propylene and the like from the reaction product is similar to the conventional technical method in the field, and the invention is not limited thereto and is not described in detail herein.
In the catalytic cracking system provided by the application, the settler, the oil separation device, the regenerator, other devices, the reaction product separation system and the like can be devices which are well known to those skilled in the art, and the connection mode between the devices can be performed in a manner known in the art. For example, the oil separation device may comprise a cyclone separator, an outlet flash separator.
The catalytic cracking method and the system can be used for efficiently producing the chemical raw materials such as ethylene, propylene and the like from the light petroleum hydrocarbon, so that the problem of heat balance can be fundamentally solved, the damage to a catalyst and a regeneration system caused by the traditional fuel injection mode is reduced, the cost of the catalyst is saved, the conversion, development and extension of a booster refinery from oil refining to chemical raw material production are realized, the problem of shortage of the petrochemical raw materials is solved, and the economic benefit of the refinery is improved.
The application will be further described with reference to the preferred embodiments shown in the drawings to which, however, the application is not limited.
FIG. 3 shows a preferred embodiment of the catalytic cracking reaction system of the present application.
The pre-lifting gas enters a pre-lifting zone I of the cracking reactor from the bottom of the cracking reactor 100 through a pre-lifting gas inlet 101, a high-temperature regenerated catalyst of the self-regenerator enters the pre-lifting zone I at the lower part of the cracking reactor 100 through a catalyst inlet 103, and is mixed with the pre-lifting gas to move upwards, and contacts with raw oil from a raw oil inlet 102 to generate a first catalytic cracking reaction in a reaction zone II; the catalyst with carbon and the generated oil gas flow upwards and enter an outlet area III to enter the oil agent separation equipment 201 through an outlet 104;
The pre-lifting gas enters the coke generator from the bottom of the coke generator 300 through a pre-lifting gas inlet 301, the high-temperature regenerated catalyst from the regenerator enters the lower part of the coke generator 300 through a catalyst inlet 303, and is mixed with the pre-lifting gas to move upwards, and enters the coke generator together with the raw coke crude oil from a fuel oil inlet 302 to generate a coking reaction; the coked catalyst and reaction product oil and gas flow upward, mix with the C4 hydrocarbon fraction or C5-C6 light gasoline fraction introduced through fuel oil inlet 305, and enter dense phase settling section 205 through outlet zone 304.
The reaction oil gas separated by the oil agent separating device 201 enters the gas collection chamber 202 and is introduced into a product separating system through an oil gas pipeline 203; the separated spent catalyst enters a dense-phase sedimentation section 205 of a settler, contacts with C4 hydrocarbon fraction or C5-C6 light gasoline fraction introduced through a fuel oil inlet 305 and undergoes a second cracking reaction, and the reacted spent catalyst enters a regenerator 500; the oxygen-containing gas from the oxygen-containing gas inlet 501 enters the regenerator after passing through the gas distributor 502, contacts with the catalyst with coke to generate complete combustion reaction, thoroughly emits heat, and part of regenerated catalyst returns to the catalytic cracking reactor for recycling, and part of regenerated catalyst returns to the coke generator for recycling, and the regenerated flue gas is sent to a subsequent energy recovery system through the flue gas outlet 504 after the entrained catalyst is recovered through the cyclone 503.
Examples
The following examples further illustrate the application, but are not intended to limit it. The industrial catalyst of the catalyst used in the test has the trade mark of NCC, and the raw oil for the cracking reaction is straight run Yanshan naphtha which is taken from a Yanshan petrochemical atmospheric and vacuum device. Raw coke raw material is catalytic diesel oil, which is taken from an Anqing petrochemical catalytic cracking device, and the properties of the two raw materials are shown in table 1.
Example 1
The test was performed in the system of fig. 3, wherein,
the catalytic cracking reactor used had the following structure:
the total height of the reactor is 10 meters, wherein the pre-lifting area is 2 meters, and the inner diameter is 0.2 meter; the height of the reaction zone is 5 m, the inner diameter of the cross section of the top end is 0.2 m, and the inner diameter of the cross section of the bottom end is 0.3 m; the outlet zone has a height of 3 meters and an inner diameter of 0.2 meters.
The coke oven 300 used comprises:
a pre-lifting zone I, the length of which is 1 meter and the inner diameter of which is 0.2 meter;
the raw coke reaction zone II is a turbulent bed reactor, the length of the reactor is 3 meters, and the inner diameter of the reactor is 0.4 meter;
the outlet zone III has a length of 2 meters and an inner diameter of 0.2 meters.
The coke generator is provided with a pre-lifting gas inlet 301, a regenerated catalyst inlet 303 and a fuel oil inlet 302 in sequence from bottom to top, and is positioned at the lower part of the coke generator 300.
The distance of the fuel oil inlet 302 from the bottom of the coke breeder is 10% of Jiao Qigao degrees each independently.
And (3) carrying out a cracking reaction test of straight-run naphtha on a catalytic cracking reactor, introducing preheated raw oil from the lower part of the cracking reactor, contacting with a regenerated catalyst from a regenerator and carrying out catalytic cracking reaction from bottom to top to obtain an oil mixture of a reaction product and a spent catalyst, enabling the oil mixture to enter a cyclone separator from an outlet of the reactor, quickly separating the reaction product and the spent catalyst, and cooling and collecting the reaction product.
The nitrogen gas of the pre-lifting medium enters the lower part of the coke making device to be mixed with the regenerated catalyst and then flows upwards, the mixture of the Anqing slurry oil (raw coke making material) and the atomizing medium (steam) enters the coke making device through a fuel oil inlet to be contacted with the hot regenerated catalyst and carry out coke making reaction, and a reaction product and an oil mixture with the carbon catalyst are obtained; and injecting a C5-C6 light gasoline fraction at the outlet zone of the coke generator, and feeding the light gasoline fraction together with the oil mixture into a dense phase settling section below the settler.
The spent catalyst and the catalyst with carbon enter a dense-phase sedimentation section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be in contact with air for regeneration; the regenerated catalyst is returned to the catalytic cracking reactor and the coke generator for recycling. Wherein, the regenerated catalyst recycled to the catalytic cracking reactor accounts for 85 percent of the total regenerated catalyst by weight, and the regenerated catalyst recycled to the coke generator accounts for 15 percent of the total regenerated catalyst by weight. The operating conditions and product distribution are listed in Table 2.
As can be seen from the results in Table 2, the ethylene yield was 24.95 wt%, the propylene yield was 25.13 wt%, the total selectivity to ethylene and propylene was 57.88%, the methane yield was 10.10%, the methane selectivity was 11.67%, and the coke yield was 5.97%.
Comparative example 1
The procedure of fig. 3 was followed and tested with reference to example 1, except that comparative example 1 did not turn on the coke breeder, i.e., regeneration of the catalyst was performed as follows:
the spent catalyst enters a stripping section of a settler under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, the stripped spent catalyst directly enters a regenerator to be regenerated by contacting with air, and simultaneously fuel oil is sprayed into a bed layer of the regenerator to burn and release heat so as to supplement the heat of the regenerator; the regenerated catalyst is returned to the reactor for recycling. The operating conditions and product distribution are listed in Table 2.
As can be seen from the results in Table 2, the ethylene yield was 23.81 wt%, the propylene yield was 24.36 wt%, the total selectivity to ethylene and propylene was 56.57%, the methane yield was 10.54%, the methane selectivity was 12.38%, and the coke yield was 3.7%.
From the results of the above examples, it can be seen that the catalytic cracking reaction system of the present application can not only reduce methane yield and improve ethylene and propylene selectivity, but also can produce coke with high selectivity, and provides a heat source for the regenerator from the aspect of the reaction system, has no influence on the regeneration system, and helps to maintain the physical and chemical properties of the catalyst.
In the description of the present application, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are directions or positional relationships based on the operation state of the present application are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the description of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly, unless otherwise specifically defined and limited. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
TABLE 1 cracking reaction feedstock and raw coke feedstock Properties
| Straight run naphtha | Anqing oil slurry | |
| Density at 20 ℃ kilogram/meter 3 | 752.5 | 1068.6 |
| Refractive index at 70 DEG C | 1.6361 | |
| Viscosity at 100 ℃ of millimeter 2 Per second | 11.5 | |
| Carbon residue,% (by weight) | 0 | 4.79 |
| Carbon content,% (by weight) | 87.47 | 91.22 |
| Hydrogen content,% (by weight) | 14.53 | 8.06 |
| Sulfur content,% (by weight) | 0.014 | 0.331 |
| Nitrogen content, mg/kg | 1.2 | 2100 |
| Basic nitrogen, mg/kg | / | 86 |
| Distillation range, DEG C | ||
| 5% (volume) | / | 364.5 |
| 10% (volume) | 90.9 | 373.2 |
| 30% (volume) | 121.7 | 400.6 |
| 50% (volume) | 145.8 | 425.6 |
| 70% (volume) | 167.3 | 464.8 |
| 95% (volume) | 197.5 | / |
Table 2 operating conditions and results for examples and comparative examples
| Examples | Comparative example | |
| Cracking reactor conditions | ||
| The outlet temperature of the cracking reactor, DEG C | 670 | 670 |
| Weight ratio of catalyst to raw material feed | 30：1 | 30：1 |
| Reaction time, seconds | 2.1 | 2 |
| Weight ratio of steam to raw material feed | 0.3 | 0.3 |
| Coke generator conditions | ||
| Outlet temperature of coke generator, DEG C | 650 | |
| Catalyst and raw coke raw material feed weight ratio | 30 | |
| Reaction time, seconds | 5 | |
| Steam to raw coke raw material feed weight ratio | 0.3 | |
| Raw coke raw material accounts for the proportion of the raw material feed amount of the cracking reactor, percent | 35 | |
| C5-C6 light gasoline fraction feed accounts for the feed amount proportion of the raw materials of the cracking reactor, percent | 5 | |
| Regenerator conditions | ||
| Temperature in regenerator, DEG C | 720 | 720 |
| The feed amount of the slurry oil in the regenerator accounts for the feed amount proportion of the cracking reactor, percent | 30 | |
| Product yield, wt% | ||
| Dry gas | 40.53 | 40.13 |
| Wherein methane is | 10.10 | 10.54 |
| Wherein ethylene is | 24.95 | 23.81 |
| Liquefied gas | 38.39 | 39.00 |
| Wherein propylene is | 25.13 | 24.36 |
| Pyrolysis gasoline | 13.48 | 14.85 |
| Cracking heavy oil | 1.63 | 2.30 |
| Coke | 5.97 | 3.7 |
| Totalizing | 100.00 | 100.00 |
| Methane selectivity,% | 11.67 | 12.38 |
| Total selectivity of ethylene and propylene% | 57.88 | 56.57 |
Claims (13)
1. A light oil catalytic cracking method, comprising:
1) Introducing preheated light oil from the lower part of a cracking reactor, contacting with a regenerated catalyst from a regenerator and performing a first catalytic cracking reaction from bottom to top to obtain a first reaction product and a first catalyst to be regenerated,
2) Introducing raw coke into a coke formation reaction zone of a coke formation device, contacting with a regenerated catalyst from the regenerator and performing coke formation reaction to obtain a coke formation device oiling agent; mixing a C4 hydrocarbon fraction and/or a C5-C6 light gasoline fraction into the coke making oil at one or more positions of an outlet area of the coke making device, introducing the mixture into a dense phase settling section of a settling device for a second catalytic cracking reaction to obtain a second reaction product and a second spent catalyst,
3) Delivering a settler catalyst from a settler to a regenerator for scorching and regeneration, and recycling the obtained regenerated catalyst, wherein the settler catalyst comprises a first spent catalyst and a second spent catalyst;
4) The first reaction product and the second reaction product are introduced into a separation system for separation.
2. The method of claim 1, wherein the light oil comprises gaseous hydrocarbons and light distillate; preferably, the light oil has properties satisfying one, two, three or four of the following indices: the density at 20 ℃ is less than 860 kg/cubic meter, the carbon residue is 0-0.5 wt%, the total aromatic hydrocarbon content is 0-30 wt%, and the final distillation point of the distillation range is less than 360 ℃.
3. The method of claim 1, wherein the conditions of the first catalytic cracking reaction comprise: the reaction temperature is 510-750 ℃, the reaction time is 0.5-10 seconds, and the weight ratio of the catalyst to the oil is 10:1 to 50:1, the weight ratio of the pre-lifting gas to the raw oil is 0.05:1 to 2.0:1, the catalyst density is 20-100 kg/cubic meter, the linear speed is 4-18 m/s, and the reaction pressure is 130-450 kilopascals.
4. The method of claim 1, wherein the conditions of the coking reaction comprise: the reaction temperature is 460-650 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is 3:1 to 30:1, the weight ratio of the pre-lifting gas to the raw coke is 0.01:1 to 0.05:1, the linear velocity is 0.2-0.8 m/s, and the catalyst particle density is 300-700 kg/cubic meter.
5. The method of claim 1, wherein the conditions of the second catalytic cracking reaction comprise: the reaction temperature is 490-730 ℃ and the weight hourly space velocity is 0.5-20 hours -1 。
6. The method of claim 1, wherein the raw coke feedstock is selected from the group consisting of plant self-produced cracked heavy oil and secondary process distillate, or mixtures thereof; preferably, the secondary processing distillate oil can be selected from one or more of catalytic cracking diesel oil, catalytic cracking slurry oil, coker gasoline, coker diesel oil and coker wax oil; more preferably, the coke-producing feedstock is a plant self-produced pyrolysis heavy oil.
7. A catalytic cracking reaction-regeneration system, comprising:
a catalytic cracking reactor, wherein the catalyst is a catalyst,
a coke-producing device,
an oil agent separating device is provided with a plurality of oil agent separating devices,
a settler, and
the regeneration device comprises a regenerator, a first heat exchanger, a second heat exchanger, a third heat exchanger and a,
wherein, catalytic cracking reactor includes from the bottom up in proper order:
an optional pre-lift zone;
the reaction zone comprises at least one reducing reaction section, the reducing reaction section is in a hollow cylinder shape with a cross section of a general circular shape and an opening at the bottom end and the top end, and the inner diameter of the reducing reaction section is continuously or discontinuously reduced from bottom to top; and
an outlet zone;
wherein the optional pre-lifting zone is communicated with the bottom end of the reaction zone, the top end of the reaction zone is communicated with the outlet zone, and at least one raw material feeding port is arranged on the optional pre-lifting zone and/or the bottom of the reaction zone;
the cross-sectional inner diameter of the bottom end of the reaction zone is greater than or equal to the cross-sectional inner diameter of the optional pre-lift zone, and the cross-sectional inner diameter of the top end is equal to or less than the cross-sectional inner diameter of the optional pre-lift zone and the cross-sectional inner diameter of the outlet zone; the regenerated catalyst inlet is arranged at the bottom of the reaction zone and/or the optional pre-lifting zone;
the catalytic cracking reactor is coaxially arranged with the settler, the oil separating device is accommodated in the settler, and the outlet area of the catalytic cracking reactor is communicated with the oil separating device, so that the oil of the catalytic cracking reactor enters the oil separating device to be separated into a first reaction product and a first spent catalyst;
The lower part of the settler is provided with a dense-phase sedimentation section, and the dense-phase sedimentation section of the settler is provided with a catalyst outlet; the catalyst outlet of the settler is in communication with the regenerator such that the settler catalyst within the settler is conveyed to the regenerator;
the coke generator sequentially comprises the following components from bottom to top:
a pre-lifting area is provided for the pre-lifting area,
a coking reaction zone which is a bubbling fluidized bed or a turbulent fluidized bed, and
an outlet region for the fluid to flow from the fluid outlet,
the top end of the pre-lifting area is communicated with the coking reaction area, and the top end of the coking reaction area is communicated with the outlet area;
the coke generator is provided with at least one fuel oil feed inlet;
the coke generator is arranged outside the settler, and an outlet area of the coke generator is communicated with a dense-phase sedimentation section of the settler, so that materials of the coke generator enter the dense-phase sedimentation section of the settler;
the regenerator is provided with a first regenerated catalyst outlet and a second regenerated catalyst outlet, the first regenerated catalyst outlet being in communication with the regenerated catalyst inlet of the catalytic cracking reactor such that at least a portion of the regenerated catalyst is recycled back to the catalytic cracking reactor;
The bottom end of the pre-lift zone of the coke breeder and/or the bottom end of the coke breeder reaction zone is configured to communicate with a second regenerated catalyst outlet of a regenerator such that at least a portion of the regenerated catalyst of the regenerator is conveyed to the coke breeder.
8. The catalytic cracking reaction-regeneration system according to claim 7, wherein,
the ratio of the inner diameter to the height of the pre-lifting zone of the catalytic cracking reactor is 0.02-0.4:1, a step of; the ratio of the height to the total height of the catalytic cracking reactor is 0.01:1 to 0.2:1, a step of;
and/or the ratio of the inner diameter of the cross section of the bottom of the reaction zone of the catalytic cracking reactor to the total height of the catalytic cracking reactor is 0.01:1 to 0.5:1, a step of; the ratio of the total height of the reaction zone to the total height of the catalytic cracking reactor was 0.15:1 to 0.8:1, a step of;
and/or the ratio of the inner diameter of the cross section of the outlet zone of the reactor to the height is 0.01-0.3:1, the ratio of the height of the outlet zone to the total reactor height being 0.05:1 to 0.5:1.
9. the catalytic cracking reaction-regeneration system according to claim 7, wherein the reaction zone of the catalytic cracking reactor comprises 1-3 reduced diameter reaction sections,
preferably, the diameter-reducing reaction section of the catalytic cracking reactor is in a hollow truncated cone shape, and the longitudinal section of the diameter-reducing reaction section is in an isosceles trapezoid shape; the ratio of the inner diameter of the top cross section to the height of the reducing reaction section is respectively and independently 0.005-0.3:1, the ratio of the inner diameter of the cross section of the bottom end to the height of the reducing reaction section is respectively and independently 0.015-0.25:1, the ratio of the inner diameter of the cross section of the bottom end to the inner diameter of the cross section of the top end is respectively more than 1.2 and less than or equal to 10; the ratio of the height of the diameter-reduced reaction section to the total height of the catalytic cracking reactor is 0.15 independently: 1 to 0.8:1.
10. The catalytic cracking reaction-regeneration system according to claim 9, wherein the pre-lift zone of the catalytic cracking reactor is connected to the reaction zone by a first connection section, the longitudinal section of the first connection section is isosceles trapezoid, and the camber angle α of the side of the isosceles trapezoid is 5-85 °.
11. The system of claim 7, wherein the coke oven is provided with the pre-lift gas inlet, catalyst inlet and two fuel oil inlets in order from bottom to top;
wherein one of the fuel oil inlets is disposed upstream of the coking reaction zone of the coker and one of the fuel oil inlets is disposed downstream of the coking reaction zone of the coker.
12. The system of claim 7, wherein the green coke reaction zone is hollow cylindrical with an aspect ratio of 20:1 to 2:1.
13. the system of claim 12, wherein the system further comprises a controller configured to control the controller,
the pre-lifting area of the coke generator is hollow cylindrical, and the length-diameter ratio of the pre-lifting area is 10:1-2:1, a step of;
the outlet area of the coke generator is hollow cylindrical, and the length-diameter ratio of the outlet area is 30:1-5:1, a step of;
preferably, the ratio of the inner diameters of the pre-lifting zone of the coke generator, the coke generation reaction zone of the coke generator and the outlet zone of the coke generator is 1:2:1 to 1:10:2.
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