CN112536003B - Catalytic conversion reactor and system suitable for preparing olefin and aromatic hydrocarbon - Google Patents

Catalytic conversion reactor and system suitable for preparing olefin and aromatic hydrocarbon Download PDF

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CN112536003B
CN112536003B CN201910891583.4A CN201910891583A CN112536003B CN 112536003 B CN112536003 B CN 112536003B CN 201910891583 A CN201910891583 A CN 201910891583A CN 112536003 B CN112536003 B CN 112536003B
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reactor
section
height
diameter
reaction zone
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CN112536003A (en
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龚剑洪
张执刚
魏晓丽
常学良
张久顺
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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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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
    • C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
    • C07C4/18—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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "fluidised-bed" technique
    • 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

Abstract

The invention relates to a catalytic conversion reactor and a system suitable for preparing olefin and aromatic hydrocarbon, wherein the reactor sequentially comprises an optional pre-lifting section, a fully dense phase reaction zone, a transition section and an outlet section from bottom to top, the fully dense phase reaction zone is in the form of a hollow cylinder which is approximately circular in cross section, is open at the bottom end and the top end and comprises one or more expanding sections and one or more equal-diameter sections, at least one catalyst inlet is arranged on the optional pre-lifting section and/or the bottom of the fully dense phase reaction zone, and the expanding section and the equal-diameter sections of the fully dense phase reaction zone are respectively and independently provided with one or more supplementary catalyst inlets. When the reactor and the system are used for catalytic conversion reaction, the contact efficiency of the raw materials and the catalyst is high, so that the yield of dry gas and coke can be effectively reduced, the catalytic reaction selectivity is improved, the yield of high-added-value products such as ethylene, propylene, light aromatic hydrocarbon and the like is improved, and particularly the selectivity of the high-added-value products to the light aromatic hydrocarbon is improved.

Description

Catalytic conversion reactor and system suitable for preparing olefin and aromatic hydrocarbon
Technical Field
The present application relates to the field of catalytic conversion technology, and more particularly to a catalytic conversion reactor and system suitable for the production of olefins and aromatics.
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%. By 2020, the equivalent consumption of propylene in China is expected to reach 3900 ten thousand tons, and a certain space exists in the gap of the productivity. Benzene, toluene and xylene (BTX) are important basic chemical raw materials, wherein the Paraxylene (PX) accounts for about 45 percent of the total consumption amount of the BTX. With the development of polyester and other industries in China, the demand of BTX is expected to continue to increase at a high speed. 90% of ethylene, 70% of propylene, 90% of butadiene and 30% of aromatic hydrocarbons are all from steam cracking by-products. Although the steam cracking technology is developed for decades and the technology is continuously improved, the method still has the advantages of high energy consumption, high production cost and CO 2 The discharge amount is large, the product structure is not easy to adjust, and other technical limitations are imposed, if the petrochemical industry adopts the traditional route of preparing ethylene and propylene by steam cracking, the petrochemical industry faces a plurality of large factors such as shortage of light raw oil, insufficient production capacity, high cost and the like, and in addition, along with the lightening of the steam cracking raw material, the reduction of the yield of propylene and light aromatic hydrocarbon is more an aggravated supply-demand contradiction. The catalytic cracking technology can be used as a beneficial supplement to the production process for producing the low-carbon olefin and the light aromatic hydrocarbon, and has obvious social and economic benefits for oil refining and chemical engineering integrated enterprises by adopting a catalytic technical route to produce chemical raw materials.
Chinese patent application publication CN1234426A discloses a method for simultaneously preparing low-carbon olefin and high-aromatic gasoline from heavy oil, which comprises subjecting heavy petroleum hydrocarbon and steam to catalytic cracking reaction in a composite reactor composed of a lift pipe and a dense-phase fluidized bed, so as to increase the yield of low-carbon olefin, especially propylene, and increase the aromatic content in gasoline to about 80 wt%.
Chinese patent application publication CN1393510A discloses a method for increasing the yield of ethylene and propylene by catalytic conversion of heavy petroleum hydrocarbon, which comprises contacting and reacting a hydrocarbon oil raw material with a catalyst containing pentasil zeolite in a riser or fluidized bed reactor.
Chinese patent application publication CN1721510A discloses a method for producing low-carbon olefins and aromatics by catalytic cracking in two reaction zones, which achieves the purpose of producing low-carbon olefins such as propylene, ethylene and the like from heavy raw oil to the maximum extent by adopting different weight hourly space velocities in the two reaction zones, wherein the yield of propylene exceeds 20 wt%, and simultaneously co-producing aromatics such as toluene, xylene and the like.
U.S. patent application publications US2002003103A and US2002189973A disclose FCC units employing dual risers for propylene stimulation, wherein gasoline (60-300 ° f/15-150 ℃) produced by the cracking reaction is fed to a second riser for further reaction, and the catalyst is a mixture of USY molecular sieve and ZSM-5 molecular sieve catalyst.
U.S. patent application publication No. US2002195373A discloses a process that uses a downflow reactor operating at high temperatures (1020-. The procatalyst (Y-type faujasite) has low hydrogen transfer activity and is formulated to maximize light olefin yield in conjunction with operating conditions. The high efficiency separator separates the product from the catalyst within 0.1 seconds, minimizing secondary reactions and coke formation. In addition, LCO is used to quench the separated gaseous product to 930 ° f/500 ℃ and prevent further cracking.
US patent US6153089A discloses a process for converting olefin rich hydrocarbons to hydrogen and C2-C4 olefins using a circulating fluidized bed apparatus/regenerator. It uses a catalyst containing dehydrogenation metal, shape-selective molecular sieve and macroporous acidic component, and its equipment/regenerator is used at 840-1380 ℉/450-750 deg.C and WHSV 0.1-60h -1 The operation was carried out under the conditions.
The processes disclosed in US6538169A and US patent application publication US2003121825A are also reaction-regeneration systems employing two reaction zones and a common regenerator. In the first reaction zone, the heavy feedstock is cracked to light olefins or intermediates that can be converted to light olefins using high temperature and high catalyst to oil ratios. The second reaction zone consists of a second riser where the operating conditions are more severe and more light components are produced from the gasoline product. The conversion of gasoline to light olefins is aided by the use of shape selective molecular sieves such as ZSM-5, suitable feedstocks include VGO, HVGO and hydrogenated gas oil.
As the situation of the heaviness and deterioration of crude oil increases, a combination technique of hydrogenation and catalytic cracking attracts attention from researchers. Chinese patent application publication CN101747935A discloses a method for producing low-carbon olefins and monocyclic aromatics from heavy hydrocarbons, which uses wax oil and residual oil as raw materials to produce qualified catalytic cracking raw materials by hydrogenation, and simultaneously returns the light cycle oil and heavy cycle oil, which are byproducts of catalytic cracking, to the catalytic cracking raw material hydrogenation unit, and hydrogenates the catalytic cracking raw materials together to produce low-carbon olefins and monocyclic aromatics. The method introduces the catalytic cracking light and heavy cycle oil into the hydrogenation unit for hydrogenation and then uses the hydrogenated catalytic cracking light and heavy cycle oil as a catalytic cracking raw material, so that the yield of high-value products of the catalytic cracking unit can be increased.
Chinese patent application publication CN1667089A discloses a chemical oil refining method for producing low-carbon olefins and aromatics, heavy raw oil is first hydrofined and then used as feed of a catalytic cracking device, and a catalytic cracking reaction system is composed of a riser and fluidized bed equipment. The method produces the low-carbon olefins such as propylene, ethylene and the like from the heavy raw materials to the maximum extent, wherein the yield of the propylene exceeds 30 percent by weight, and simultaneously produces the aromatics such as toluene, xylene and the like.
The structural contradiction of the oil refining chemical industry in China is increasingly serious, on one hand, the traditional petrochemical products have excessive capacity, and the contradiction between the supply and the demand of the finished oil is remarkable, on the other hand, the resource products and high-end petrochemical products have remarkable shortage, and the transformation of oil refining to the chemical industry is in great tendency. Catalytic cracking devices used as bridges for oil refining and chemical engineering face unprecedented pressure and challenge. At present, the proportion of blending atmospheric residue oil in a catalytic cracking device is getting larger and larger, and even the requirement of blending vacuum residue oil is provided, the vacuum residue oil is difficult to process by taking vacuum wax oil or paraffin-based atmospheric residue oil as a raw material in the existing catalytic cracking technology, and in order to efficiently utilize inferior heavy oil resources and meet the increasing requirements of chemical raw materials such as low-carbon olefins and light aromatics, it is necessary to develop a catalytic cracking device for converting the inferior heavy oil raw materials into high value-added products.
Disclosure of Invention
An object of the present invention is to provide a catalytic conversion reactor and system which can greatly improve the contact efficiency of a reaction raw material, such as a hydrocarbon oil, particularly inferior heavy oil, with a catalyst, thereby effectively reducing the yield of dry gas and coke, improving the catalytic reaction selectivity, and improving the yield of ethylene, propylene, and light aromatic hydrocarbons.
In order to achieve the above objects, in one aspect, the present invention provides a catalytic conversion reactor comprising, in order from bottom to top, an optional pre-lift section, a fully dense phase reaction zone, a transition section, and an outlet section, the fully dense phase reaction zone is in the form of a hollow cylinder with a generally circular cross section, open at the bottom and top, and comprising one or more expanded diameter sections and one or more equal diameter sections, the optional pre-lift section is in communication with the bottom end of the fully dense phase reaction zone, the top end of the fully dense phase reaction zone is in communication with the outlet zone via the transition section, at least one catalytic cracking catalyst inlet is arranged on the optional pre-lifting section and/or at the bottom of the full-dense phase reaction zone, and at least one feed inlet is arranged on the optional pre-lifting section and/or at the bottom of the fully dense phase reaction zone,
wherein the cross-sectional diameter of the bottom end of the fully dense phase reaction zone is greater than or equal to the diameter of the optional pre-lift section and the cross-sectional diameter of the top end is greater than the diameter of the optional pre-lift section and the diameter of the outlet zone, and the side wall of the fully dense phase reaction zone is provided with one or more supplemental catalyst inlets each independently located at a height of greater than 0% to 90% of the total height of the fully dense phase reaction zone, preferably at a height of 20% to 80%, more preferably at a height of 30% to 75%,
preferably, the ratio of the total height of the equal diameter section to the total height of the expanded diameter section of the fully dense phase reaction zone is 0.4: 1 to 2.5: 1, preferably 0.8: 1 to 1.5: 1.
in another aspect, the present invention provides a catalytic conversion reaction system comprising a catalytic conversion reactor, an oil agent separating device, an optional reaction product separating device, and a regenerator,
the catalytic conversion reactor is provided with a catalyst inlet at the bottom, a raw material feed 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 optional reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis naphtha outlet, a pyrolysis light oil outlet and a pyrolysis heavy oil outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet,
a catalyst inlet of the catalytic conversion reactor is in fluid communication with a catalyst outlet of the regenerator, a finish oil outlet of the catalytic conversion reactor is in fluid communication with a finish oil inlet of the finish oil separation device, a reaction product outlet of the finish oil separation device is in fluid communication with a reaction product inlet of the optional reaction product separation device, a catalyst outlet of the finish oil separation device is in fluid communication with a catalyst inlet of the regenerator,
wherein the catalytic conversion reactor comprises one or more reactors according to the invention.
In yet another aspect, the present invention provides a catalytic conversion method comprising the step of contact-reacting a reaction raw material with a catalyst in a catalytic conversion reactor according to the present invention or a catalytic conversion reaction system according to the present invention.
In the catalytic conversion reactor and the system, the arranged full-dense phase reaction zone can effectively improve the density of the catalyst in the reactor, thereby greatly improving the ratio of the instantaneous catalyst in the reactor to the reaction raw material, controlling relatively long reaction time, leading the catalyst to be capable of fully reacting with the raw material, not only improving the reaction conversion rate, but also improving the yield of low-carbon olefin and light aromatic hydrocarbon, simultaneously reducing the reaction temperature, effectively reducing the generation of dry gas and coke, and leading the product distribution and the product quality to be improved.
In particular, in certain embodiments, the fully dense phase reaction zone of the present invention comprises a lower expanded diameter section and an upper equal diameter section, and the reaction effluent from the expanded diameter section enters the equal diameter section with a larger diameter to continue the reaction, so that the residence time of oil and gas can be further prolonged, and more light aromatic hydrocarbons can be produced.
When the reactor and the system are used for catalytic cracking of inferior heavy oil, chemical raw materials with high added values can be produced from the cheap inferior heavy oil to the maximum extent by petrochemical enterprises, the refining and chemical integration process of oil refining enterprises in China is facilitated to be promoted, the problem of petrochemical raw material shortage is solved, and the economic benefit and the social benefit of the petrochemical industry are improved.
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 is a schematic view of a preferred embodiment of the present invention.
Description of the reference numerals
1 pre-lifting section 2 expanding section 3 transition section
4 outlet zone 5 regeneration inclined pipe 6 complement pipeline
7 equal diameter section 8 pre-lift media line 9 feed line
10 make-up line.
Detailed Description
The present application will now be described in further detail with reference to specific embodiments thereof, it being understood that the specific embodiments described herein are merely illustrative and explanatory of the present application and are not restrictive thereof in any way.
Any specific value disclosed herein (including endpoints of ranges of values) is not to be limited to the precise value of that value, but rather should be construed to also encompass values close to the precise value, for example, all possible values within 5% of the precise value. Also, for the disclosed ranges of values, any combination between the endpoints of the range, between the endpoints of the range and the specific points within the range, and between the specific points in the range can result in one or more new ranges of values, and such new ranges of values should also be considered to be specifically disclosed herein.
In this application, the term "fast fluidized bed" or "fast fluidized reaction zone/reactor" refers to a fluidized bed reaction zone/reactor in which the catalyst is in a fast fluidized state, wherein fast fluidization is a bubble-free gas-solid contact fluidization, the important feature being that the solid particles tend to move in clusters. The axial solids fraction epsilon of the catalyst in the reaction zone/reactor is typically in the range of 0.05 to 0.4 when the catalyst is in a fast fluidized state. However, in a conventional fast fluidized bed, the catalyst is typically distributed in a lean-down rich manner, e.g., the upper catalyst axial solids fraction ε may be in the range of 0.05 to 0.1, while the lower catalyst axial solids fraction ε may be in the range of 0.3 to 0.4.
According to the present application, in a fast fluidized reaction zone, when the axial solid fraction ε of the catalyst is maintained in the range of 0.1 to 0.2 from the bottom to the top (i.e., the axial solid fractions ε of the catalyst measured in the upper, middle and lower three portions of the reaction zone divided in the axial direction are each 0.1 or more and 0.2 or less), the catalyst in the whole fast fluidized reaction zone is distributed in a quasi-uniform fully concentrated phase, and the fast fluidized reaction zone is referred to as a "fully concentrated phase reaction zone".
In this application, the term "water to oil weight ratio" refers to the ratio of the total steam weight injected into the reactor to the weight of the feedstock.
In the present application, the terms "upstream" and "downstream" are used with reference to the direction of flow of the reactant materials. For example, when the reactant stream flows from bottom to top, "upstream" refers to a position located below, and "downstream" refers to a position located above.
Unless otherwise defined, 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 that commonly understood in the art, the definition herein controls.
In the present application, anything or things that are not mentioned are directly applicable to those known in the art without any change except what is explicitly stated. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.
All patent and non-patent documents referred to herein, including but not limited to textbooks and journal articles and the like, are incorporated by reference in their entirety.
As described above, in one aspect, the present invention provides a catalytic conversion reactor comprising, in order from bottom to top, an optional pre-lift section, a fully dense phase reaction zone, a transition section and an outlet section, the fully dense phase reaction zone being in the form of a hollow cylinder having a substantially circular cross-section with open bottom and top ends and comprising one or more expanded diameter sections and one or more equal diameter sections, the optional pre-lift section being in communication with the bottom end of the fully dense phase reaction zone, the top end of the fully dense phase reaction zone being in communication with the outlet section via the transition section, at least one catalytic cracking catalyst inlet being provided on the optional pre-lift section and/or on the bottom of the fully dense phase reaction zone, and at least one feedstock inlet being provided on the optional pre-lift section and/or on the bottom of the fully dense phase reaction zone,
wherein the bottom end of the fully dense phase reaction zone, preferably the bottom end of each expanded diameter section and each equal diameter section, has a cross-sectional diameter greater than or equal to the diameter of the optional pre-lift section, and the top end of the fully dense phase reaction zone, preferably the top end of each expanded diameter section and each equal diameter section, has a cross-sectional diameter greater than the diameter of the optional pre-lift section and the diameter of the outlet zone, and the side wall of the fully dense phase reaction zone is provided with one or more supplemental catalyst inlets, each independently located at a height greater than 0% to 90% of the total height of the fully dense phase reaction zone, preferably at a height from 20% to 80% of the total height of the fully dense phase reaction zone, more preferably at a height from 30% to 75%.
In a preferred embodiment, the cross-sectional diameter of the top end of the fully dense phase reaction zone is greater than or equal to the cross-sectional diameter of the bottom end thereof, more preferably greater than the cross-sectional diameter of the bottom end thereof.
According to the application, the axial solid fraction epsilon of the catalyst in the fully dense phase reaction zone always satisfies from bottom to top: epsilon is more than or equal to 0.1 and less than or equal to 0.2, and at the moment, the catalyst is distributed in a fully concentrated phase in the fully concentrated phase reaction zone, so that the actual catalyst-oil ratio above and below the fully concentrated phase reaction zone is kept consistent, the dry gas coke yield is reduced, and the target product yield is improved.
According to the present application, the pre-lift section is not essential, for example when the reactor of the present invention is used in series with other reactors, such as riser reactors, the fully dense phase reaction zone may be in direct communication with the outlet of the reactor located upstream without the need to employ the pre-lift section.
According to the present application, the phrase "substantially circular in cross-section" refers to a shape having a circular or nearly circular cross-section, such as an ellipse, an oval, a regular polygon, or the like, as long as the ratio of the diameter of the circumscribed circle to the diameter of the inscribed circle of the cross-section is in the range of 1:0.9 to 1: 1. When the cross section is approximately circular, the diameter of the cross section (or simply diameter) refers to the average value of the diameter of the circumscribed circle and the diameter of the inscribed circle of the cross section.
According to the present application, the fully dense phase reaction zone may comprise one or more expanded diameter sections and one or more equal diameter sections, preferably, the ratio of the total height of the equal diameter sections to the total height of the expanded diameter sections of the fully dense phase reaction zone is 0.4: 1 to 2.5: 1, preferably 0.8: 1 to 1.5: 1.
in a preferred embodiment, the fully dense phase reaction zone is in the form of a hollow cylinder comprised of one or more expanded diameter sections and one or more equal diameter sections, optionally with connecting sections for connecting adjacent expanded diameter sections and/or equal diameter sections.
According to the present application, when the fully dense phase reaction zone comprises two or more expanding sections, the expanding sections may have the same or different heights, and the present invention is not limited thereto. Similarly, when the fully dense phase reaction zone comprises two or more equal diameter sections, the equal diameter sections may have the same or different heights, and the invention is not limited in this regard.
In certain embodiments, the fully dense phase reaction zone comprises expanded diameter sections and equal diameter sections arranged alternately, wherein the lowermost portion of the fully dense phase reaction zone is an expanded diameter section on which one or more of the equal diameter sections and expanded diameter sections are arranged alternately. Preferably, the diameter of each equal diameter section is greater than or equal to the diameter of the largest cross section of the adjacent lower expanded diameter section.
In other embodiments, the fully dense phase reaction zone comprises one or more expanded diameter sections in the lower portion and one or more equal diameter sections in the upper portion, for example, one expanded diameter section in the lower portion and one equal diameter section in the upper portion. Preferably, the diameter of each equal diameter section is greater than or equal to the diameter of the largest cross section of all of the expanded diameter sections.
According to the present application, by "expanded diameter section" is meant a reactor section whose diameter increases continuously from bottom to top in a linear or non-linear manner. As an example of said "expanding section" there may be mentioned a reactor section of the inverted hollow frustoconical type.
By "constant diameter section" is meant, according to the present application, a reactor section whose diameter remains substantially constant from bottom to top, for example a reactor section of the hollow cylinder type.
In certain preferred embodiments, a catalyst distribution plate is arranged at the bottom of the fully dense phase reaction zone.
In a preferred embodiment, the diameter of the pre-lift section is from 0.2 to 5 meters, preferably from 0.4 to 4 meters, more preferably from 0.6 to 3 meters; the ratio of its height to the total height of the reactor was 0.01: 1 to 0.2: 1, preferably 0.03: 1 to 0.18: 1, more preferably 0.05: 1 to 0.15: 1.
in a preferred embodiment, the ratio of the diameter of the largest cross-section of the fully dense phase reaction zone to the total reactor height is 0.005: 1 to 1:1, preferably 0.01: 1 to 0.8: 1, more preferably 0.05: 1 to 0.5: 1; the ratio of the height of the fully dense phase reaction zone to the total height of the reactor was 0.1: 1 to 0.9: 1, preferably 0.15: 1 to 0.8: 1, more preferably 0.2: 1 to 0.75: 1.
in a preferred embodiment, the fully dense phase reaction zone is in the form of a column consisting of a section of inverted hollow truncated cone and a section of hollow cylinder from bottom to top, wherein the longitudinal section of the truncated cone is an isosceles trapezoid, and the diameter of the cross section at the bottom end is 0.2-10 m, preferably 0.5-8 m, more preferably 1-5 m; a ratio of the top end cross-sectional diameter to the bottom end cross-sectional diameter is greater than 1 to 50, preferably 1.2 to 10, more preferably 1.5 to 5; the diameter of the cylinder is approximately the same as the diameter of the top end cross section of the truncated cone, and the ratio of the height of the cylinder to the height of the truncated cone is 0.4: 1 to 2.5: 1, preferably 0.8: 1 to 1.5: 1; the ratio of the diameter of the maximum cross-section of the fully dense phase reaction zone to the total reactor height is 0.005: 1 to 1:1, preferably 0.01: 1 to 0.8: 1, more preferably 0.05: 1 to 0.5: 1; the ratio of the height of the fully dense phase reaction zone to the total height of the reactor was 0.1: 1 to 0.9: 1, preferably 0.15: 1 to 0.8: 1, more preferably 0.2: 1 to 0.75: 1.
in a preferred embodiment, the height of the fully dense phase reaction zone is from 2 to 50 meters, preferably from 5 to 40 meters, more preferably from 8 to 20 meters.
According to the present application, the catalyst distribution plate may be provided at the location where the catalyst enters the bottom of the fully dense phase reaction zone, for example at the outlet end of the pre-lift section.
The catalyst distribution plate may be any of various types of distribution plates commonly used in the industry, such as one or more of flat, arched, dished, annular, and umbrella-shaped, according to the application. The adoption of the catalyst distribution plate is helpful for enabling the catalyst to uniformly contact with the raw material in the axial direction of the full-dense phase reaction zone in concentration to carry out catalytic conversion reaction, thereby reducing the generation of agent-oil specific coke and thermal reaction coke caused by overhigh or overlow concentration of the catalyst.
In a preferred embodiment, the ratio of the height of the transition section to the total reactor height is 0.01: 1 to 0.1: 1, preferably 0.02: 1 to 0.05: 1. further preferably, the transition section is in the form of a hollow truncated cone, the longitudinal section of which is an isosceles trapezoid, the internal inclination angle alpha of the side of the isosceles trapezoid being 5-85 o Preferably 15 to 75 o 。
In a preferred embodiment, the outlet zone has a diameter of 0.2 to 5 meters, preferably 0.4 to 4 meters, more preferably 0.6 to 3 meters, and a ratio of its height to the total reactor height of 0.05: 1 to 0.2: 1, preferably 0.08: 1 to 0.18: 1, more preferably 0.1: 1 to 0.15: 1, the outlet end of the outlet area can be opened or can be directly connected with the inlet of the cyclone separator.
In certain embodiments, the reactor of the present application may further comprise one or more other forms of reaction zones, such as dilute phase transport beds, dense phase fluidized beds, fast fluidized beds, etc., upstream of the fully dense phase reaction zone (e.g., between the optional pre-lift section and the fully dense phase reaction zone), and/or downstream of the fully dense phase reaction zone (e.g., between the transition section and the outlet zone).
In other embodiments, the reactor of the present application does not include additional reaction zones upstream and downstream of the fully dense phase reaction zone.
According to the application, the reactor may be provided with one or more, e.g. one, two or more, feed inlets, which may each be provided independently at the outlet end of the pre-lift section, at a position on the pre-lift section at a distance from its outlet end which is less than or equal to 1/3 of the height of the pre-lift section, or at the bottom of the fully dense phase reaction zone.
Optionally, when a raw material feed port is provided at the bottom of the fully dense phase reaction zone, a gas distributor may be provided at the raw material feed port.
According to the present application, the supplemental catalyst inlets provided on the side walls of the fully dense phase reaction zone may be 1, 2 or more, each independently located at a height greater than 0% to 90% of the total height of the fully dense phase reaction zone, preferably at a height of 20% to 80% of the total height of the fully dense phase reaction zone, more preferably at a height of 30% to 75%, for example at a height of 2/3% of the fully dense phase reaction zone.
In certain preferred embodiments, one or more supplemental catalyst inlets are provided on at least one expanded diameter section and at least one equal diameter section of the fully dense phase reaction zone, preferably on each expanded diameter section (e.g., inverted hollow frustum section) and each equal diameter section (e.g., hollow cylinder section), independently of each other. Further preferably, the locations of the supplementary catalyst inlets are each independently located at a height of more than 0% to 90%, preferably 20% to 80%, more preferably 30% to 75% of the height of the respective expanded diameter section or the respective equal diameter section.
According to the present application, the carbon content of the make-up catalyst may be in the range of from 0 to 1% by weight, and may for example be selected from one or more of regenerated catalyst, spent catalyst and semi-regenerated catalyst. The temperature of the supplementary catalyst can be adjusted according to the reaction temperature, for example, cold and/or hot regenerated catalyst can be introduced, and cold and/or hot spent catalyst can also be introduced. The catalyst can be supplemented in the full-dense phase reaction zone to adjust the oil ratio of the catalyst in a larger range, more active centers are provided for the cracking reaction, meanwhile, the flexibility of adjusting the reaction temperature is enhanced, and the gradient of the temperature in equipment of the full-dense phase reaction zone and the activity of the catalyst can be effectively adjusted. In addition, the supplementary catalyst is introduced into the full-dense phase reaction zone, so that the density uniformity of the catalyst in the equipment 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.
In a second aspect, the present application provides a catalytic conversion reaction system comprising a catalytic conversion reactor, an oil separation device, an optional reaction product separation device, and a regenerator,
the catalytic conversion reactor is provided with a catalyst inlet at the bottom, a raw material feed 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 optional reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis naphtha outlet, a pyrolysis light oil outlet and a pyrolysis heavy oil outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet,
the catalyst inlet of the catalytic conversion reactor is in fluid communication with the catalyst outlet of the regenerator, the finish oil outlet of the catalytic conversion reactor is in fluid communication with the finish oil inlet of the finish oil separation device, the reaction product outlet of the finish oil separation device is in fluid communication with the reaction product inlet of the optional reaction product separation device, and the catalyst outlet of the finish oil separation device is in fluid communication with the catalyst inlet of the regenerator.
In a preferred embodiment, the catalytic conversion reactor comprises one or more reactors according to the present application.
In certain further preferred embodiments, the catalytic conversion reactor further comprises one or more other forms of reactor, such as dilute phase transport beds, dense phase fluidized beds, fast fluidized beds, etc., in series and/or in parallel with the reactor of the present application.
In yet other further preferred embodiments, the catalytic conversion reactor consists of the reactor of the present application.
According to the present application, the oil separation device and the reaction product separation device may be any devices known to those skilled in the art. For example, the oil separation device may include a cyclone, a settler, a stripper, and the like, and the reaction product separation device may be a fractionation column, and the like.
In certain embodiments, the oil separation device comprises a settler arranged coaxially or in high-low juxtaposition with the catalytic conversion reactor.
The catalytic conversion reactor and the system are suitable for catalytic conversion reaction of various raw materials, such as catalytic cracking reaction of petroleum hydrocarbon, in particular to the reaction for producing low-carbon olefin by catalytic cracking heavy oil.
In certain embodiments, the properties of heavy oils suitable for processing using the reactors and systems of the present invention can meet one, two, three, or four of the following criteria: the density at 20 ℃ is 850- 3 Preferably 890- 3 Carbon residue in an amount of 0 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.
For example, the heavy oil may be a heavy petroleum hydrocarbon and/or other mineral oil; the heavy petroleum hydrocarbon may be selected from one or more of Vacuum Residue (VR), low quality Atmospheric Residue (AR), low quality 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 selected from one or more of coal liquefied oil, oil sand oil, and shale oil. The carbon residue in the heavy oil can be measured by adopting an ASTMD-189 Conradson carbon residue experimental method.
In a third aspect, the present invention provides a catalytic conversion method comprising the step of contact-reacting a reaction raw material with a catalyst in a catalytic conversion reactor according to the present invention or in a catalytic conversion reaction system according to the present invention.
In a preferred embodiment, the reaction feedstock is a heavy feedstock oil, the properties of which meet at least one of the following criteria: the density at 20 ℃ is 850- 3 Preferably 890- 3 Carbon residue of 0 to 10 wt.%, preferably 2 to 8 wt.%, nickel and vanadium content of 2 to 30ppm, preferably 5 to 20ppm, and a characteristic factor K of less than 12.1, preferably less than 12.0.
In a preferred embodiment, the reaction conditions within the fully dense phase reaction zone include: the reaction temperature is 510-700 ℃, the reaction time is 1-20 seconds, and the weight ratio of the catalyst to the oil is 3:1 to 50: 1, the weight ratio of water to oil is 0.03: 1 to 0.8: 1, catalyst density of 120- 3 The gas linear velocity is 0.8-2.5 m/s, the reaction pressure is 130-450 kPa, and the mass flow rate of the catalyst is 15-150 kg/(m) 2 Second).
In a further preferred embodiment, the reaction conditions within the fully dense phase reaction zone include: the reaction temperature is 550-650 ℃, the reaction time is 3-15 seconds, and the weight ratio of the catalyst to the oil is 10: 1 to 30: 1, the weight ratio of water to oil is 0.05: 1 to 0.5: 1, catalyst density of 150- 3 The gas linear speed is 1-1.8 m/s, the reaction pressure is 130-450 kPa, and the mass flow rate of the catalyst is 20-130 kg/(m) 2 Seconds).
In a preferred embodiment, the catalyst comprises from 1 to 50 wt%, preferably from 5 to 45 wt%, more preferably from 10 to 40 wt% zeolite on a dry basis and based on the weight of the catalyst on a dry basis; 5-99 wt%, preferably 10-80 wt%, more preferably 20-70 wt% of an inorganic oxide, and 0-70 wt%, preferably 5-60 wt%, more preferably 10-50 wt% of a clay.
In a further preferred embodiment, the zeolite comprises an intermediate pore zeolite selected from the group consisting of ZSM series zeolites, ZRP zeolites, and any combination thereof, and optionally a large pore zeolite; the large pore zeolite is selected from the group consisting of 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.
In a still further preferred embodiment, the medium pore zeolite comprises from 0 to 50 wt%, preferably from 0 to 20 wt%, of the total weight of the zeolite on a dry basis.
In the present application, the medium and large pore zeolites follow the conventional definition in the art, i.e., the medium pore size of the medium pore zeolite is from 0.5 to 0.6 nm and the large pore size of the large pore zeolite is from 0.7 to 1.0 nm.
By way of example, the large-pore zeolite may be selected from one or more of rare earth Y (rey) type zeolites, rare earth hydrogen Y (rehy) type zeolites, ultrastable Y-type zeolites obtained by different processes, and high-silica Y-type zeolites. The medium pore zeolite may be selected from zeolites having the MFI structure, such as ZSM series zeolites and/or ZRP zeolites. Optionally, the mesoporous zeolite may be modified with a nonmetallic element such as phosphorus and/or a transition metal element such as iron, cobalt, nickel. For a more detailed description of ZRP zeolites, see us patent US5,232,675A. The ZSM-series zeolite is preferably one or a mixture of more selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure. A more detailed description of ZSM-5 is described in U.S. Pat. No. US3,702,886A.
According to the application, the inorganic oxide is preferably silicon dioxide (SiO) as a binder 2 ) And/or aluminum oxide (Al) 2 O 3 ). The clay acts as a matrix (i.e., carrier), preferably kaolin and/or halloysite.
In a preferred embodiment, the process comprises introducing one or more make-up catalysts into the fully dense phase reaction zone, the total amount of make-up catalyst may range from 0 to 50 wt%, preferably from 5 to 45 wt%, more preferably from 10 to 40 wt% of the reactor catalyst circulation.
Preferably, the one or more supplemental catalysts each independently have a carbon content of from 0 to 1.0 wt%, e.g., the one or more supplemental catalysts may each independently be selected from regenerated catalysts, spent catalysts, and semi-regenerated catalysts, e.g., regenerated, spent, and semi-regenerated catalytic cracking catalysts.
The present application will be further described with reference to preferred embodiments shown in the drawings, but the application is not limited thereto.
Fig. 1 shows a preferred embodiment of the catalytic conversion reactor of the present application, wherein the reactor comprises, from bottom to top, a pre-lift section 1, a fully dense phase reaction zone, comprising an expanded diameter section 2 and an equal diameter section 7, a transition section 3 and an outlet section 4. The diameter expanding section 2 is in the form of an inverted hollow truncated cone, the longitudinal section of the diameter expanding section is in the form of an isosceles trapezoid, the equal-diameter section 7 is in the form of a hollow cylinder, and the height ratio of the equal-diameter section 7 to the diameter expanding section 2 is 0.4: 1 to 2.5: 1, preferably 0.8: 1 to 1.5: 1. the transition section 3 is in the form of a hollow truncated cone, the longitudinal section of which is an isosceles trapezoidThe inner inclination angle alpha of the side edge of the isosceles trapezoid is 5-85 o Preferably 15 to 75 o . The lower part of the pre-lifting section 1 is provided with a catalyst inlet, and the upper part of the pre-lifting section 1 and/or the bottom of the full-dense phase reaction zone (namely the bottom of the diameter-expanding section 2) is provided with a raw material inlet. The cross-sectional diameter of the bottom end of the fully dense phase reaction zone is larger than the diameter of the pre-lifting section, and the cross-sectional diameter of the top end is larger than the diameter of the pre-lifting section and the diameter of the outlet zone. The side wall of the fully dense phase reaction zone is provided with one or more, e.g., one, two or more, make-up catalyst inlets, e.g., for make-up line 6 or make-up line 10, wherein the make-up catalyst inlet corresponding to make-up line 6 is disposed on the constant diameter section 7 and the make-up catalyst inlet corresponding to make-up line 10 is disposed on the expanded diameter section 2. The one or more supplemental catalyst inlets are each independently located at a height that is between greater than 0% and 90% of the total height of the fully dense phase reaction zone, preferably at a height of 20% to 80%, more preferably at a height of 30% to 75%. For example, the make-up catalyst inlet corresponding to make-up line 6 may be located at a height between greater than 0% and 90% of the height of the constant diameter section, preferably at a height of 20% to 80%, more preferably at a height of 30% to 75%; while the make-up catalyst inlet corresponding to make-up line 10 may be located at a height between more than 0% and 90% of the height of the expanded diameter section, preferably at a height of 20% to 80%, more preferably at a height of 30% to 75%.
The pre-lift medium enters the catalytic conversion reactor from the bottom of the pre-lift section 1 through a pre-lift medium line 8, and the pre-lift medium can be dry gas, water vapor or a mixture thereof. The hot regenerated catalyst, with or without cooling, from the regeneration chute 5 enters the lower part of the pre-lift section 1 and moves upwards under the action of the pre-lift medium. Reaction raw materials such as preheated heavy raw oil and atomized steam are injected into the upper part of the pre-lifting section 1 and/or the bottom of the full-dense phase reaction zone through a feed pipeline 9, are mixed and contacted with the existing material flow in the diameter expanding section 2, and carry out catalytic conversion reaction in the process of passing through the diameter expanding section 2 from bottom to top. The reaction effluent of the expanding section 2 enters the equal-diameter section 7 for further catalytic conversion reaction. One or more make-up catalysts are introduced in the fully dense phase reaction zone via make-up line 6 and/or make-up line 10 to contact the feed in the fully dense phase reaction zone for catalytic conversion reactions. The reaction effluent of the equal-diameter section 7 enters an outlet area 4 through a transition section 3, and then enters subsequent oil agent separation equipment and product separation equipment through the outlet area 4.
The definition and calculation of each parameter in the application are as follows:
(1) the axial solids fraction of the catalyst, ε = the pressure difference between two points in the reaction zone in the axial direction measured by a pressure difference meter divided by the distance between the two points in the axial direction divided by the catalyst particle density;
wherein the unit of the pressure difference is kilogram/meter 2 The distance between two axial points is expressed in meters and the density of the catalyst particles is expressed in kilograms per meter 3 。
Catalyst particle density = framework density/(catalyst pore volume x framework density + 1), where the unit of framework density is kg/m 3 The unit of pore volume of the catalyst is meter 3 The skeletal density and the pore volume of the catalyst were determined by the pycnometer method and the water titration method, respectively.
(2) Reaction time = volume of reaction zone/oil gas log mean volume flow;
wherein the volume of the reaction zone is measured in meters 3 The unit of the logarithmic mean volume flow of oil and gas is meter 3 A second;
oil gas log mean volume flow = (V) out -V in ）/ln（V out /V in ），V out And V in The volume flow of oil gas at the outlet and the inlet of the reaction zone respectively;
volume flow V of oil gas at outlet of reaction zone out =m/ρ 3 ；
Volume flow V of oil gas at inlet of reaction zone in =m/ρ 4 ；
Wherein m is the feeding amount of raw oil and atomized steam in unit time, and the unit is kilogram/second; ρ is a unit of a gradient 3 The density of oil gas at the outlet of the reaction zone is in kilograms/meter 3 ；ρ 4 The density of oil gas at the inlet of the reaction zone is measured in kg/m 3 。
(3) The catalyst density of the reaction zone (or upper, middle and lower parts thereof) is = the pressure difference between two points in the axial direction in the reaction zone (or upper, middle and lower parts thereof) measured by a pressure difference meter divided by the distance between the two points in the axial direction;
wherein the unit of the pressure difference is kilogram/meter 2 The reaction zone is axially divided into an upper part, a middle part and a lower part, and the unit of the distance between the two axial points is meter.
(4) Gas linear velocity = oil gas logarithmic mean volume flow ÷ reaction zone cross-sectional area;
when the reaction zone is of a non-cylindrical type, the gas linear velocity is the logarithmic average of the gas linear velocity at the bottom of the reaction zone and the gas linear velocity at the top of the reaction zone.
(5) Catalyst mass flow rate G s = reactor catalyst circulation volume ÷ reaction zone cross-sectional area;
when the reaction zone is of a non-cylindrical type, the catalyst mass flow rate G s Taking the bottom G of the reaction zone s G from the top of the reaction zone s A logarithmic average of;
wherein the unit of the catalyst circulating amount is kilogram/second;
reactor catalyst circulation = coke formation speed ÷ (spent catalyst carbon content-regenerated catalyst carbon content);
wherein the coke generation speed unit is kilogram/second, and the carbon content of the spent catalyst and the carbon content of the regenerated catalyst are both weight content;
coke formation rate = flue gas amount × (CO) 2 %+CO%）÷Vm×M；
Wherein Vm is the molar volume of gas and is 22.4 multiplied by 10 -3 Rice made of glutinous rice 3 M is the molar mass of carbon and takes the value of 12 multiplied by 10 -3 Kilogram/mole;
flue gas amount = (regeneration air amount × 79 vol%)/(1-CO 2 %-CO%-O 2 %）；
Wherein the regeneration air quantity is in meters 3 Second, the unit of smoke is meter 3 Second, CO 2 %、CO%、O 2 % of CO in the flue gas 2 CO and O 2 Volume percent of (c).
Examples
The following examples further illustrate the invention but are not intended to limit the invention thereto.
The raw oils used in the following examples and comparative examples were hydrogenated residual oil, properties of which are shown in Table 1, and the catalysts used in the examples and comparative examples were commercial catalytic cracking catalysts available from catalyst division of petrochemical Co., Ltd., China, under the trade name DMMC-2.
TABLE 1 Properties of the stock oils used
Density (20 deg.C)/g cm -3 0.9237
Refractive index/70 deg.C 1.4914
Basic nitrogen/microgram g -1 506
Carbon residue/weight% 3.11
Value of characteristic factor K 11.8
Distillation range/. degree.C
5% by volume 357
10% by volume 387
30% by volume 443
50% by volume 490
70% by volume 550
Metal content/microgram g -1
Fe 34.4
Ni 4.4
Ca 7.8
V 4.3
Na 2.0
Example 1
The experiments were carried out on a medium-sized apparatus using the feed oil and DMMC-2 catalyst shown in Table 1, the reactor being in the form of the reactor shown in FIG. 1, wherein the pre-lift section had a diameter of 0.2 m and a height of 1 m; lower section of full-dense phase reaction zone expanding section is straightThe diameter is 0.4 m, the diameter of the upper section is 0.5 m, and the height is 4 m; the diameter of the equal-diameter section of the fully-concentrated phase reaction zone is 0.5 meter, and the height of the equal-diameter section of the fully-concentrated phase reaction zone is 1.5 meters; the height of the transition section is 0.4 m, and the inclination angle alpha of the isosceles trapezoid side edge of the longitudinal section is 45 o (ii) a The exit zone was 0.3 meters in diameter and 1 meter in height.
The preheated raw oil enters the upper part of the pre-lifting section to contact with a catalytic cracking catalyst and enters a full-dense phase reaction zone from bottom to top to perform catalytic cracking reaction, the catalyst in the full-dense phase reaction zone is distributed in a full-dense phase, and the axial solid fraction epsilon is distributed in the range of 0.1-0.2 from bottom to top. And the reacted material flow enters a transition section and then enters subsequent oil agent separation equipment and product separation equipment through an outlet area. Wherein, a stream of hot regenerated catalyst (temperature 695 ℃, carbon content 0.05 wt%) is respectively supplemented to the diameter expanding section and the equal diameter section of the full dense phase reaction zone, the catalyst supplementing position of the diameter expanding section is positioned at the height of 60% of the height of the diameter expanding section, and the catalyst supplementing position of the equal diameter section is positioned at the height of 60% of the height of the equal diameter section, wherein the amount of the supplemented catalyst introduced into the diameter expanding section and the equal diameter section respectively accounts for 5 wt% and 10 wt% of the catalyst circulation amount of the reactor; the operating conditions and product distribution are listed in table 2.
As can be seen from table 2, the ethylene yield of this example reached 5.2 wt%, the propylene yield reached 19.4 wt%, the light aromatic hydrocarbons (BTX) yield reached 14.9 wt%, and the dry gas and coke yields were 10.6 wt% and 8.3 wt%, respectively.
Example 2
The experiments were carried out on a medium-sized apparatus using the base oil and DMMC-2 catalyst shown in Table 1, the reactor being in the form of the reactor shown in FIG. 1, with a pre-lift section of 0.6 m diameter and a height of 2 m; the diameter of the lower section of the diameter-expanding section of the fully-concentrated phase reaction zone is 0.8 meter, the diameter of the upper section of the diameter-expanding section of the fully-concentrated phase reaction zone is 1.6 meters, and the height of the diameter-expanding section of the fully-concentrated phase reaction zone is 3.5 meters; the diameter of the equal-diameter section of the full-dense phase reaction zone is 1.6 meters, and the height of the equal-diameter section of the full-dense phase reaction zone is 4.5 meters; the height of the transition section is 0.6 m, and the inclination angle alpha of the isosceles trapezoid side edge of the longitudinal section is 17 o (ii) a The exit zone was 0.6 meters in diameter and 2 meters in height.
The preheated raw oil enters the upper part of the pre-lifting section to contact with a catalytic cracking catalyst and enters a full-dense phase reaction zone from bottom to top to perform catalytic cracking reaction, the catalyst in the full-dense phase reaction zone is distributed in a full-dense phase, and the axial solid fraction epsilon is distributed in the range of 0.1-0.2 from bottom to top. And the reacted material flow enters a transition section and then enters subsequent oil agent separation equipment and product separation equipment through an outlet area. Wherein, a diameter expanding section of the full-dense phase reaction zone is supplemented with a strand of cooled regenerated catalyst (the temperature is 630 ℃, and the carbon content is 0.05 weight percent), and the supplementing position is positioned at the height of 60 percent of the height of the diameter expanding section; simultaneously, supplementing a spent catalyst (the carbon content is 0.8 wt%) to the equal-diameter section of the full-dense phase reaction zone, wherein the supplementing position is positioned at the height of 40% of the height of the equal-diameter section, and the supplemented amounts of the regenerated catalyst and the spent catalyst respectively account for 5 wt% and 10 wt% of the catalyst circulation amount of the reactor; the operating conditions and product distribution are listed in table 2.
As can be seen from table 2, the ethylene yield of this example reached 5.3 wt%, the propylene yield reached 19.2 wt%, the light aromatic hydrocarbons (BTX) yield reached 15.5 wt%, and the dry gas and coke yields were 10.5 wt% and 8.5 wt%, respectively.
Comparative example 1
The test was carried out on a medium-sized apparatus using the raw oil and DMMC-2 catalyst shown in Table 1, the reactor being a combined reactor in which a riser having a diameter of 0.2 m and a height of 5 m was connected in series with a dense-phase fluidized bed having a diameter of 0.4 m and a height of 1.5 m. The preheated raw oil enters the lower part of a riser reaction zone to contact with a catalytic cracking catalyst for catalytic cracking reaction, the reaction oil, the water vapor and the spent catalyst enter a dense-phase fluidized bed reaction zone from an outlet of the riser for continuous reaction, and the material flow after the reaction enters subsequent oil agent separation equipment and product separation equipment; the operating conditions and the product distribution are listed in table 2.
As can be seen from the results of table 2, the comparative example had an ethylene yield of only 3.7 wt%, a propylene yield of only 12.8 wt%, a light aromatic hydrocarbon (BTX) yield of only 5.5 wt%, and dry gas and coke yields of 12.9 wt% and 13.3 wt%, respectively.
Comparative example 2
The tests were carried out on a medium-sized apparatus using the raw oil and DMMC-2 catalyst shown in Table 1, and the reactor was a conventional fast fluidized bed reactor having a diameter of 1.2 m and a height of 10 m. The preheated raw oil enters the lower part of a fast fluidized bed reactor to contact with a catalytic cracking catalyst for catalytic cracking reaction, and the reacted material flow enters subsequent oil agent separation equipment and product separation equipment, wherein the axial solid fraction epsilon of the catalyst in the fast fluidized bed reactor is gradually increased from top to bottom by 0.1 → 0.2 → 0.3; the operating conditions and the product distribution are listed in table 2.
As can be seen from the results of table 2, the comparative example had an ethylene yield of only 4.3 wt%, a propylene yield of only 16.0 wt%, a light aromatic hydrocarbon (BTX) yield of only 9.6 wt%, and dry gas and coke yields of 11.4 wt% and 10.4 wt%, respectively.
TABLE 2 comparison of reaction results of examples 1-2 and comparative examples 1-2
Example 1 Example 2 Comparative example 1 Comparative example 2
Riser/fast bed/full dense phase reaction zone conditions
Outlet temperature of reaction zone,. deg.C 585 585 585 585
Reaction time in seconds 4 4 2 4
Water to oil weight ratio 0.25 0.25 0.25 0.25
Weight ratio of solvent to oil 22 23 10 20
Lower catalyst density, kg/m 3 220 223 60 190
Upper catalyst density, kg/m 3 217 219 110
Linear velocity of gas, m/s 2 2 12 2
Reaction pressure, kPa 210 210 210 210
Gs, kg/(meter) 2 Second) 74 75 300 74
Dense phase fluidized bed conditions
Outlet temperature of reaction zone, deg.C / / 565 /
Weight hourly space velocity, hours -1 / / 4 /
Catalyst density in kg/m 3 / / 480 /
Linear velocity of gas, m/s / / 0.6 /
Product distribution, weight%
Dry gas 10.6 10.5 12.9 11.4
Wherein ethylene 5.2 5.3 3.7 4.3
Liquefied gas 39.2 38.1 26.1 32.8
Wherein propylene is 19.4 19.2 12.8 16.0
Gasoline (gasoline) 30.5 31.8 22.9 25.5
Wherein BTX 14.9 15.5 5.5 9.6
Diesel oil 8.2 8.0 16.4 14.0
Heavy oil 3.2 3.1 8.4 5.9
Coke 8.3 8.5 13.3 10.4
Total up to 100 100 100 100
As can be seen from the results of the above examples and comparative examples, when the reactor of the present invention is used for catalytic cracking of heavy oil, the yields of ethylene, propylene and light aromatic hydrocarbons are significantly increased, while the yields of dry gas and coke are reduced.
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.

Claims (38)

1. A catalytic conversion reactor comprises an optional pre-lifting section, a fully dense phase reaction zone, a transition section and an outlet zone from bottom to top in sequence, wherein the fully dense phase reaction zone is in the form of a hollow cylinder with a cross section which is approximately circular, an opening at the bottom end and the top end and comprises one or more expanding sections and one or more equal-diameter sections, the optional pre-lifting section is communicated with the bottom end of the fully dense phase reaction zone, the top end of the fully dense phase reaction zone is communicated with the outlet zone through the transition section, at least one catalytic cracking catalyst inlet is arranged on the optional pre-lifting section and/or the bottom of the fully dense phase reaction zone, at least one raw material feeding hole is arranged on the optional pre-lifting section and/or the bottom of the fully dense phase reaction zone,
wherein the axial solids fraction epsilon of the catalyst in the fully dense phase reaction zone is maintained in the range of from 0.1 to 0.2 throughout from bottom to top, the cross-sectional diameter of the bottom end of the fully dense phase reaction zone is greater than or equal to the diameter of the optional pre-lift section and the cross-sectional diameter of the top end is greater than the diameter of the optional pre-lift section and the diameter of the outlet zone, and the side wall of the fully dense phase reaction zone is provided with one or more supplemental catalyst inlets each independently located at a height of from greater than 0% to 90% of the total height of the fully dense phase reaction zone.
2. The reactor of claim 1, wherein the one or more supplemental catalyst inlets are each independently located at 20% to 80% of the height of the fully dense phase reaction zone.
3. The reactor of claim 1, wherein the one or more supplemental catalyst inlets are each independently located at 30% to 75% of the height of the fully dense phase reaction zone.
4. The reactor of claim 1, wherein the ratio of the height of the equal diameter section and the expanded diameter section of the fully dense phase reaction zone is 0.4: 1 to 2.5: 1.
5. the reactor of claim 1, wherein the fully dense phase reaction zone has a ratio of the height of the equal diameter section to the height of the expanded diameter section of 0.8: 1 to 1.5: 1.
6. the reactor of any one of claims 1-5, wherein the one or more expanded diameter sections are each independently an inverted hollow frustoconical pattern and the one or more equal diameter sections are each independently a hollow cylindrical pattern.
7. The reactor of claim 6 wherein the bottom of the fully dense phase reaction zone is provided with a catalyst distribution plate.
8. The reactor according to any one of claims 1-5, wherein the pre-lift section has a diameter of 0.2-5 meters and a ratio of its height to the total reactor height of 0.01: 1 to 0.2: 1.
9. the reactor according to any one of claims 1-5, wherein the pre-lift section has a diameter of 0.4-4 meters and a height to total reactor height ratio of 0.03: 1 to 0.18: 1.
10. the reactor according to any one of claims 1-5, wherein the pre-lift section has a diameter of 0.6-3 meters and a ratio of height to total reactor height of 0.05: 1 to 0.15: 1.
11. the reactor of any one of claims 1-5, wherein the ratio of the diameter of the maximum cross-section of the fully dense phase reaction zone to the total reactor height is 0.005: 1 to 1:1, the ratio of the total height of the fully dense phase reaction zone to the total height of the reactor is 0.1: 1 to 0.9: 1.
12. the reactor of any one of claims 1-5, wherein the ratio of the diameter of the maximum cross-section of the fully dense phase reaction zone to the total reactor height is from 0.01: 1 to 0.8: 1, the ratio of the total height of the fully dense phase reaction zone to the total height of the reactor is 0.15: 1 to 0.8: 1.
13. the reactor of any one of claims 1-5, wherein the ratio of the diameter of the maximum cross-section of the fully dense phase reaction zone to the total reactor height is 0.05: 1 to 0.5: 1, the ratio of the total height of the fully dense phase reaction zone to the total height of the reactor is 0.2: 1 to 0.75: 1.
14. the reactor of any one of claims 1-5, wherein the fully dense phase reaction zone is in the form of a hollow cylinder comprising a lower expanded diameter section or sections and an upper equal diameter section or sections, wherein the diameter of the smallest cross section of the equal diameter section or sections is greater than or equal to the diameter of the largest cross section of the expanded diameter section or sections.
15. The reactor of claim 14, wherein the fully dense phase reaction zone is of a column type consisting of a section of inverted hollow truncated cone and a section of hollow cylinder from bottom to top, wherein the longitudinal section of the hollow truncated cone is an isosceles trapezoid, the diameter of the cross section at the bottom end is 0.2-10 m, and the ratio of the diameter of the cross section at the top end to the diameter of the cross section at the bottom end is greater than 1 to 50; the diameter of the hollow cylinder is substantially the same as the diameter of the top end cross section of the hollow truncated cone, and the ratio of the height of the hollow cylinder to the height of the hollow truncated cone is 0.4: 1 to 2.5: 1; the ratio of the diameter of the maximum cross section of the fully dense phase reaction zone to the total height of the reactor is 0.005: 1 to 1: 1; the ratio of the height of the fully dense phase reaction zone to the total height of the reactor was 0.1: 1 to 0.9: 1.
16. the reactor of claim 15, wherein the diameter of the bottom end cross-section of the hollow frustoconical body is 0.5-8 meters, and the ratio of the top end cross-section diameter to the bottom end cross-section diameter is 1.2 to 10; the diameter of the hollow cylinder is substantially the same as the diameter of the top end cross section of the hollow truncated cone, and the ratio of the height of the hollow cylinder to the height of the hollow truncated cone is 0.8: 1 to 1.5: 1; the ratio of the diameter of the maximum cross section of the fully dense phase reaction zone to the total reactor height is 0.01: 1 to 0.8: 1; the ratio of the height of the fully dense phase reaction zone to the total height of the reactor was 0.15: 1 to 0.8: 1.
17. the reactor of claim 15, wherein the diameter of the bottom end cross-section of the hollow frustoconical body is 1-5 meters, and the ratio of the top end cross-section diameter to the bottom end cross-section diameter is 1.5 to 5; the diameter of the hollow cylinder is substantially the same as the diameter of the top end cross section of the hollow truncated cone, and the ratio of the height of the hollow cylinder to the height of the hollow truncated cone is 0.8: 1 to 1.5: 1; the ratio of the diameter of the maximum cross section of the fully dense phase reaction zone to the total reactor height is 0.05: 1 to 0.5: 1; the ratio of the height of the fully dense phase reaction zone to the total height of the reactor was 0.2: 1 to 0.75: 1.
18. the reactor of any of claims 1-5, wherein the ratio of the height of the transition section to the total reactor height is 0.01: 1 to 0.1: 1.
19. the reactor of any of claims 1-5, wherein the ratio of the height of the transition section to the total reactor height is 0.02: 1 to 0.05: 1.
20. the reactor of claim 18 wherein said transition section is of the hollow frustoconical type with a longitudinal section in the form of an isosceles trapezoid having sides with an included angle a of from 5 to 85 o 。
21. The reactor of claim 19 wherein said transition section is of the hollow frusto-conical type with a longitudinal section of an isosceles trapezoid having sides with an included angle α of 15-75 o 。
22. The reactor of any one of claims 1-5 wherein the outlet zone has a diameter of 0.2 to 5 meters and a ratio of height to total reactor height of 0.05: 1 to 0.2: 1, the outlet end of the outlet area is open or is directly connected with the inlet of the cyclone separator.
23. The reactor of claim 22 wherein the outlet zone has a diameter of 0.4 to 4 meters and a height to total reactor height ratio of 0.08: 1 to 0.18: 1.
24. the reactor of claim 22 wherein the outlet zone has a diameter of 0.6 to 3 meters and a height to total reactor height ratio of 0.1: 1 to 0.15: 1.
25. the reactor according to any one of claims 1-5, wherein each of the at least one feedstock feeds is independently provided at a location 1/3 on the pre-lift section at a distance from its outlet end that is less than or equal to the height of the pre-lift section, at the outlet end of the pre-lift section, or at the bottom of the fully dense phase reaction zone.
26. The reactor of claim 25, wherein a feed inlet is provided at the bottom of the fully dense phase reaction zone and a gas distributor is provided at the feed inlet.
27. The reactor of any one of claims 1-5, wherein at least one expanded diameter section and at least one equal diameter section of the fully dense phase reaction zone are each independently provided with one or more supplemental catalyst inlets.
28. The reactor of claim 27, wherein each expanded diameter section and each equal diameter section of the fully dense phase reaction zone are each independently provided with one or more supplemental catalyst inlets.
29. The reactor of claim 28, wherein the locations of the supplemental catalyst inlets are each independently located at a height greater than 0% to 90% of the height of the respective expanded diameter section or the height of the respective equal diameter section.
30. The reactor of claim 28, wherein the locations of the supplemental catalyst inlets are each independently located at a height of 20% to 80% of the height of the respective expanded diameter section or the height of the respective equal diameter section.
31. The reactor of claim 28, wherein the locations of the supplemental catalyst inlets are each independently located at a height of 30% to 75% of the height of the respective expanded diameter section or the respective equal diameter section.
32. The reactor of any one of claims 1-5, wherein the reactor further comprises one or more additional reaction zones selected from dilute phase transport beds, dense phase fluidized beds, and fast fluidized beds upstream and/or downstream of the fully dense phase reaction zone.
33. The reactor of any one of claims 1-5, wherein the reactor does not include additional reaction zones upstream and downstream of the fully dense phase reaction zone.
34. A catalytic conversion reaction system comprises a catalytic conversion reactor, an oil agent separation device, an optional reaction product separation device and a regenerator,
the catalytic conversion reactor is provided with a catalyst inlet at the bottom, a raw material feed 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 optional reaction product separation equipment is provided with a reaction product inlet, a dry gas outlet, a liquefied gas outlet, a pyrolysis naphtha outlet, a pyrolysis light oil outlet and a pyrolysis heavy oil outlet, the regenerator is provided with a catalyst inlet and a catalyst outlet,
a catalyst inlet of the catalytic conversion reactor is in fluid communication with a catalyst outlet of the regenerator, a finish oil outlet of the catalytic conversion reactor is in fluid communication with a finish oil inlet of the finish oil separation device, a reaction product outlet of the finish oil separation device is in fluid communication with a reaction product inlet of the optional reaction product separation device, a catalyst outlet of the finish oil separation device is in fluid communication with a catalyst inlet of the regenerator,
wherein the catalytic conversion reactor comprises a reactor according to any one of claims 1-32.
35. The reaction system of claim 34, wherein the catalytic conversion reactor further comprises one or more reactors selected from the group consisting of dilute phase transport beds, dense phase fluidized beds, and fast fluidized beds in series or in parallel with the reactor of any of claims 1-33.
36. The reaction system of claim 34, wherein the catalytic conversion reactor is comprised of one or more reactors of any of claims 1-33.
37. The reaction system of any one of claims 34-36, wherein the oil separation device comprises a settler arranged coaxially or in high-low juxtaposition with the catalytic conversion reactor.
38. A catalytic conversion process comprising the step of contact reacting a reactant feedstock with a catalyst in a catalytic conversion reactor according to any one of claims 1-33 or in a catalytic conversion reaction system according to any one of claims 34-37.
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