CN116601268A - Method and device for producing light olefins and BTX by catalytic cracking of hydrocarbon-containing feedstock oil - Google Patents

Abstract

A method and a device for producing light olefins and BTX by catalytic pyrolysis of hydrocarbon-containing raw oil, wherein the method comprises the following steps: cutting hydrocarbon-containing raw oil into light distillate and heavy distillate; introducing light distillate and a first stream of catalyst into a downlink reactor for catalytic pyrolysis to obtain a first catalytic pyrolysis material; carrying out gas-solid separation on the material after the first catalytic cracking to obtain first reaction oil gas and a first spent catalyst; or, sending the material after the first catalytic cracking into a fluidized bed reactor for catalytic cracking, and then carrying out gas-solid separation to obtain second reaction oil gas and a second spent catalyst; introducing the continuous catalyst, the heavy distillate oil and the second catalyst into an uplink reactor for catalytic pyrolysis and then gas-solid separation to obtain third oil gas and a third spent catalyst; separating light olefins and light aromatics from the reaction oil and gas, separating light olefin fraction, and returning the light olefin fraction to the fluidized bed reactor or the ascending reactor. The method can obviously improve the yield of the low-carbon olefin and the light aromatic hydrocarbon and the economical efficiency of the device.

Description

Method and device for producing light olefins and BTX by catalytic cracking of hydrocarbon-containing raw material oil technical field

This application relates to petroleum refining and petrochemical processing, in particular, to a method and device for producing light olefins and BTX by catalytic cracking of whole-fraction hydrocarbon-containing raw material oil.

Background technique

As the growth rate of refined oil consumption continues to slow down and the demand for basic organic raw materials represented by low-carbon olefins and aromatics grows rapidly, chemical refineries will become the future development trend. At present, the configurations of chemical refineries mainly include the following three types. One is that crude oil is pretreated by solvent deasphalting or hydrofining, and then directly enters the steam cracking unit to produce chemical materials, but this method is generally limited to light crude oil; The second is to maximize the production of heavy naphtha after hydrocracking of various fractions of crude oil, and then to maximize the production of aromatics through the reforming unit; Production of light olefins. The above three methods have all been industrialized, and the yield of chemicals is between 35% and 55%. It can be seen that the configuration of the existing chemical refinery mainly relies on the combination of steam cracking, reforming, hydrofining, hydrocracking, catalytic cracking and other core devices. Among them, the catalytic cracking process has its unique advantages in the production of chemical materials and the adaptability of raw materials, and can simultaneously produce propylene, ethylene and BTX.

Chinese patent CN1978411B discloses a combined process method for producing small molecular olefins. In this method, the catalytic cracking catalyst and the cracking raw material are mixed and contacted in a reactor, and the spent catalyst and reaction oil gas are separated, and the spent catalyst is sent into The regenerator performs coke regeneration, and the regenerated hot catalyst is divided into two parts, one part of the regenerated hot catalyst is returned to the above reactor; the other part of the regenerated hot catalyst is first mixed with heavy petroleum hydrocarbons in another reactor Contact, pre-coking, C4-C8-rich olefin raw material is mixed with the coked catalyst, catalytic cracking reaction occurs, and the unused catalyst is separated to react oil and gas. The unused catalyst and the unused catalyst described in the previous step are sent to regeneration The burner is used for coke regeneration; oil and gas are separated and reacted to obtain small molecule olefins such as propylene. The method can convert olefin-rich light raw materials into small molecular olefin products such as propylene with high selectivity, while maintaining the heat balance of the device itself.

Chinese patent CN102899078A discloses a catalytic cracking method for producing propylene. The method is based on a combined reactor composed of double risers and a fluidized bed. First, heavy feed oil and the first stream of catalyst are introduced into the first riser reactor for reaction. , the oil agent enters the separation system after separation. The cracked heavy oil is introduced into the second riser reactor and the catalyst introduced into the second riser reactor is contacted and reacted, and the light hydrocarbon is introduced into the second riser reactor to be contacted with the mixture formed by the cracked heavy oil and the second stream of cracking catalyst. , the light hydrocarbons include C4 hydrocarbons or gasoline fractions obtained from the product separation system. Then the oil gas and catalyst reacted in the second riser reactor are introduced into the fluidized bed reactor for reaction. Through the optimization of the process scheme and the allocation of suitable catalysts, different feedstocks can be selectively converted, with higher yields of propylene and butene.

Chinese patent CN101045667B discloses a combined catalytic conversion method for producing more light olefins. In this method, the heavy oil feedstock is contacted with a regenerated catalyst and an optional carbon deposition catalyst in a downcomer reactor, and the separated light olefins are removed. At least a part of the remaining products are introduced into the riser reactor to contact with the regenerated catalyst. After the riser reaction, the catalyst is introduced into the catalyst pre-lifting section of the downcomer reactor, mixed with the regenerated catalyst entering the downcomer reactor, and then contacted with the heavy oil feedstock. The method adopts a combined reactor form in which the heavy oil raw material is reacted in a down-flow reactor and the intermediate product olefins are reacted in a riser reactor, so as to increase the yield of light olefins.

Chinese patent CN109370644A discloses a method for producing light olefins and aromatics by catalytic cracking of crude oil. This method divides crude oil into light and heavy components, and the cut point is between 150°C and 300°C. The light fraction and the heavy fraction are separated in the same reactor. The reaction is carried out in the reaction zone. The catalyst uses aluminosilicate composed of silica and aluminum oxide as the main component, including alkali metal oxides, alkaline earth metal oxides, titanium, iron oxides, vanadium and nickel oxides . The method is based on a dense-phase transport bed reactor for catalytic cracking of heavy oil to generate light olefins, and is a solution for the catalytic cracking of crude oil to generate light olefins.

The above methods have been studied from the aspects of the development of new reactor structure, the development of new catalytic materials, and the control of reaction depth to improve the selectivity of propylene, and proposed a method of catalytic cracking to produce light olefins and aromatics, but there is still no way to maximize the production of crude oil. Material preparation method and reactor structure.

Contents of the invention

The purpose of the present disclosure is to propose a catalytic cracking method suitable for processing hydrocarbon-containing feedstock oil in view of the characteristics of different hydrocarbon compositions and different cutting temperatures of various hydrocarbon-containing feedstock oils, so as to maximize the use of hydrocarbon-containing feedstock oils to produce low-cost Apparatus and methods for carboolefins and BTX.

In order to achieve the above purpose, the present disclosure provides a method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil, the method comprising the following steps:

S1, cutting the hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil, the weight ratio of the light distillate oil relative to the heavy distillate oil (light distillate oil/heavy distillate oil) is X;

S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking;

Optional S2', introducing the first catalytically cracked material into a fluidized bed reactor for second catalytic cracking to obtain the second catalytically cracked material;

S3. Perform gas-solid separation on the material after the first catalytic cracking to obtain the first reaction oil gas and the first to-be-studied catalyst, or perform gas-solid separation on the second catalytic cracking material to obtain the second reaction oil gas and a second spent catalyst;

S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst; the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R ;

S5. From any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the mixture of the first reaction oil gas and the third reaction oil gas or the second reaction oil gas and the third reaction oil gas Light olefins and light aromatics are separated from the mixture, and light olefin fractions are separated, and the light olefin fractions are returned to the second ascending reactor in step S4 or the fluidized bed reactor in step S2′ middle,

The R and X satisfy the following relational formula:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor.

Optionally, in the method of the present disclosure, the outlet temperature T3 of the second upward reactor is 530-650°C, preferably 560-640°C, more preferably 580-630°C, even more preferably 600-630°C °C; and/or, the temperature T0 of the second strand of catalyst entering step S4 is 690-750°C, preferably 700-740°C, more preferably 705-730°C, even more preferably 710-725°C.

Optionally, in the method of the present disclosure, in step S1, the hydrocarbon-containing feed oil is cut into light distillate oil and heavy distillate oil at any temperature between the cut point 100-400° C. The weight ratio of the heavy distillate (light distillate/heavy distillate) is X.

Optionally, in the method of the present disclosure, in the first down-flow reactor, the conditions of the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 610-720°C, and the gas The solid residence time is 0.1-3.0 seconds, and the agent-oil ratio is 15-80; and/or, in the fluidized bed reactor, the conditions of the second catalytic cracking include: the reaction in the fluidized bed reactor The temperature is 600-690°C, the mass space velocity is 2-20h ^-1 ; and/or, in the second uplink reactor, the conditions for the third catalytic cracking include: the gas-solid residence time is 0.5-8 seconds , The agent-oil ratio is 8-40.

Optionally, in the method of the present disclosure, in the first down-flow reactor, the conditions of the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 650-690°C, and the gas The solid residence time is 0.5-1.5 seconds, and the agent-oil ratio is 25-65; and/or, in the fluidized bed reactor, the conditions of the second catalytic cracking include: the reaction in the fluidized bed reactor The temperature is 640-670°C, the mass space velocity is 4-12h ^-1 ; and/or, in the second uplink reactor, the conditions for the third catalytic cracking include: the gas-solid residence time is 1.5-5 seconds , The agent-oil ratio is 10-30.

Optionally, in the method of the present disclosure, in step S4, the continuous catalyst is first mixed with the second stream of catalyst, and then the subsequent catalytic cracking reaction is performed, and/or, when there is step S2′, in step S3 In the gas-solid separation, the separated catalyst is stripped to obtain the second spent catalyst; and/or, in step S4, the light olefin fraction from the step S5 is prior to the heavy distillate oil and the The mixture of the second catalyst and the continuous catalyst is contacted for catalytic cracking; preferably, the light olefins are contacted with the mixture of the second catalyst and the continuous catalyst for 0.3-1.0 seconds prior to the heavy distillate for catalytic cracking, more preferably Catalytic cracking by contacting the light olefin fraction with the mixture of the second stream catalyst and the continuous catalyst prior to the heavy distillate oil for 0.4-0.8 seconds; and/or, the method has a step S0 before step S1, wherein , subjecting the hydrocarbon-containing feedstock oil to desalting and dehydration treatment, and introducing the obtained dehydrated and desalted hydrocarbon-containing feedstock oil into step S1 for cutting.

Optionally, in the method of the present disclosure, the method further includes: in the gas-solid separation in step S4, stripping the separated catalyst to obtain a third spent catalyst; and/or, removing the third spent catalyst The raw catalyst and the optional first spent catalyst or the second spent catalyst not entering the second ascending reactor, at 690-750°C, preferably 700-740°C, more preferably 705-730°C, still more preferably 710 Coke regeneration is carried out at a temperature of -725°C to obtain a regenerated catalyst; and/or, any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the first reaction oil gas and The mixture of the third reaction oil gas or the mixture of the second reaction oil gas and the third reaction oil gas is separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins, light aromatics, and separate the light olefin fraction; and/or, when there is no step S2′, in step S5, separate the light olefin fraction from any one of the first reaction oil gas, the third reaction oil gas or a mixture of both , and return the light olefin fraction to the second uplink reactor of step S4; when there is step S2', in step S5, any one of the second reaction oil gas, the third reaction oil gas or a mixture of both The light olefin fraction is separated from the olefin fraction, and the light olefin fraction is returned to the fluidized bed reactor in step S2'.

Optionally, in the method of the present disclosure, the hydrocarbon-containing raw material oil is one or two or more of crude oil, coal liquefied oil, synthetic oil, oil sand oil, shale oil, tight oil, and animal and vegetable oils Mixtures, or their respective partial fractions, their respective heavy fractions, hydro-upgraded oils.

Optionally, in the method of the present disclosure, the first catalyst and the second catalyst each independently include an active component and a carrier, and the active component is selected from ultra-stable Y with or without rare earth At least one of type zeolite, ZSM-5 series zeolite, high silica zeolite with five-membered ring structure and beta zeolite, the carrier is selected from alumina, silica, amorphous silica alumina, zirconia, titania, At least one of boron oxide and alkaline earth metal oxides.

Optionally, in the method of the present disclosure, the first strand of catalyst and the second strand of catalyst each independently include a regenerated catalyst, preferably the first strand of catalyst and the second strand of catalyst are regenerated catalysts, and/ Or, use all of the first spent catalyst or all of the second spent catalyst as a continuous catalyst.

The present disclosure also provides a device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing raw material oil, the device includes the following units:

a hydrocarbonaceous feedstock cutting unit, wherein the hydrocarbonaceous feedstock is cut into light distillates and heavy distillates such that the weight ratio of the light distillate relative to the heavy distillate (light distillate/heavy distillate) is X,

The first descending reaction unit, introducing the light distillate oil and the first stream of catalyst from above the reaction unit, performing the first catalytic cracking, and obtaining the first catalytic cracked material below the reaction unit;

An optional fluidized bed reaction unit, wherein the material after the first catalytic cracking is introduced to perform the second catalytic cracking to obtain the second catalytic cracking material;

The first gas-solid separation unit, wherein the material after the first catalytic cracking is introduced for gas-solid separation to obtain the first reaction oil gas and the first catalyst to be produced, or the material after the second catalytic cracking is introduced for gas-solid separation Separating to obtain the second reaction oil gas and the second spent catalyst;

In the second ascending reaction unit, the continuous catalyst, the second stream of catalyst and the heavy distillate oil are introduced from below the reaction unit to carry out the third catalytic cracking, and the third catalytic cracking material is obtained above the reaction unit. The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst, and the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R,

The second gas-solid separation unit, wherein the material after the third catalytic cracking is introduced for gas-solid separation to obtain the third reaction oil gas and the third spent catalyst;

a separation unit wherein any one of said first reaction vapor, said second reaction vapor and said third reaction vapor or a mixture of first reaction vapor and third reaction vapor or second reaction vapor and third reaction vapor is introduced A mixture of oil and gas, separating light olefins and light aromatics, and separating light olefin fractions, and returning the light olefin fractions to the second upward reaction unit or the fluidized bed reaction unit;

Wherein, the R and X satisfy the following relationship:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit, and T3 is the outlet temperature (in °C) of the second upward reaction unit.

Optionally, in the device of the present disclosure, a regeneration unit is also included, wherein the third spent catalyst and optionally the first spent catalyst or the second spent catalyst that does not enter the second up-flow reactor are introduced, Burning regeneration is carried out at a temperature of 690-750°C, preferably 700-740°C, more preferably 705-730°C, and still more preferably 710-725°C, to obtain a regenerated catalyst.

Optionally, in the device of the present disclosure, when the device includes a fluidized bed reaction unit, the first gas-solid separation unit further includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped to obtain the second Secondary catalyst.

The second gas-solid separation unit further includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped to obtain a third spent catalyst.

Optionally, in the device of the present disclosure, the device further includes a dehydration and desalination unit, wherein the hydrocarbon-containing feed oil is subjected to desalting and dehydration treatment, and the obtained dehydrated and desalted hydrocarbon-containing feed oil is introduced into the hydrocarbon-containing feed oil cutting unit for cutting.

Optionally, in the device of the present disclosure, in the second upward reaction unit, the positions where the continuous catalyst and the second stream of catalyst are introduced are upstream of the feed inlet of the light olefin fraction.

Optionally, in the device of the present disclosure, in the second upward reaction unit, the feed port of the light olefin fraction from the separation unit is upstream of the feed port of the heavy distillate oil.

technical effect

In the present disclosure, through the above-mentioned specific method, according to the hydrocarbon composition characteristics and cracking reaction characteristics of different fractions of the hydrocarbon-containing feedstock oil, the hydrocarbon-containing feedstock oil is cut into two parts, light distillate oil and heavy distillate oil, and the light distillate oil is divided into two parts: Cracking at high temperature and short residence time in a down-flow reactor can produce light olefins and BTX with high selectivity, and at the same time can significantly reduce methane generation. At the same time, for heavy distillate oil, by using an uplink reactor, the production of light olefins and BTX can be maximized.

In addition, in the present disclosure, by arranging a fluidized bed reactor at the lower part of the first down-flow reactor, the light olefins in the catalytic cracking material can be further converted, and the production of light olefins can be maximized.

In the present disclosure, in the first down-flow reactor, the residence time of the light distillate is short, the coke formation of the reaction is low, and the yield of light olefins and BTX is high; in addition, in the fluidized bed reactor, the light olefin fraction is further transform. Thus, the first spent catalyst that goes out of the first down-flow reactor or the second spent catalyst that goes out of the fluidized bed reactor still has higher activity, and the catalyst is loaded with carbon deposits, and the catalyst When used in the catalytic cracking of heavy distillate oil in the second ascending reactor, the yield of light olefins can be increased, and the generation of dry gas and coke can be suppressed.

More importantly, in the present disclosure, by making the weight ratio (X) of the cut light distillate oil and heavy distillate oil and the weight ratio (R) of the second catalyst and the continuous catalyst satisfy a specific relationship, the Depending on the type of raw oil, the cutting ratio can be flexibly adjusted. Correspondingly, the weight ratio of the second stream catalyst to the continuous catalyst can be adjusted so that in the second ascending reactor, the catalyst activity is more closely related to the composition of the heavy distillate oil. Matching can significantly reduce the yield of by-products such as dry gas and coke while maximizing the production of light olefins and BTX.

In addition, through the above-mentioned technical solution, the method for producing light olefins and BTX by catalytic cracking of hydrocarbon-containing feedstock oil provided by the present disclosure can significantly improve the yield and device economics of light olefins and light aromatics.

Other features and advantages of the present disclosure will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present disclosure, and constitute a part of the description, together with the following specific embodiments, are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the attached picture:

Figure 1 is a schematic diagram of one embodiment of the device of the present disclosure.

Figure 2 is a schematic illustration of another embodiment of the device of the present disclosure.

Explanation of reference signs

1. Downward reactor 32. Second catalyst (regenerated catalyst) output

Delivery tube

11. Light Distillate Feed Nozzle 33. Heavy Distillate Feed Nozzle

12. The first stream of catalyst (regenerated catalyst) output 4. Settler

Delivery tube

13. Mushroom head distributor 41. Oil and gas outlet of the third reactor

2. Fluidized bed reactor 5. Stripper

51. First stripper

21. Light olefin fraction feed nozzle 52. Second stripper

22. First reaction oil and gas outlet/second reaction 53. Third spent catalyst delivery pipe

Oil and gas export

3. Upstream reactor 6. Regenerator

31. Continuous catalyst delivery pipe 7. Gas-solid separator

Detailed ways

Specific embodiments of the present disclosure will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present disclosure, and are not intended to limit the present disclosure.

Any specific numerical value disclosed herein (including the endpoints of the numerical range) is not limited to the exact value of the numerical value, but should be understood to also cover the value close to the exact value, such as within ± 5% of the exact value. all possible values. And, for the disclosed numerical range, one or more new Numerical ranges, these new numerical ranges are also considered to be specifically disclosed herein.

Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and its definition is different from the common understanding in the art, the definition herein shall prevail.

In this application, except for the contents explicitly stated, any matters or matters not mentioned are directly applicable to those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed therefrom are regarded as a part of the original disclosure or original record of the present disclosure, and should not be It is regarded as a new content that has not been disclosed or expected in this paper, unless those skilled in the art think that the combination is obviously unreasonable.

The disclosure provides a method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing raw material oil, the method comprising the following steps:

S1, cutting the hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil, the weight ratio of the light distillate oil relative to the heavy distillate oil (light distillate oil/heavy distillate oil) is X;

S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking;

Optional S2', introducing the first catalytically cracked material into a fluidized bed reactor for second catalytic cracking to obtain the second catalytically cracked material;

S3. Perform gas-solid separation on the material after the first catalytic cracking to obtain the first reaction oil gas and the first to-be-studied catalyst, or perform gas-solid separation on the second catalytic cracking material to obtain the second reaction oil gas and a second spent catalyst;

S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst; the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R ;

S5. From any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the mixture of the first reaction oil gas and the third reaction oil gas or the second reaction oil gas and the third reaction oil gas Light olefins and light aromatics are separated from the mixture, and light olefin fractions are separated, and the light olefin fractions are returned to the second ascending reactor in step S4 or the fluidized bed reactor in step S2′ middle,

The R and X satisfy the following relational formula:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor.

In the present disclosure, sometimes any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or a mixture of two or more of them is simply referred to as reaction oil gas.

In the present disclosure, light olefins refer to ethylene, propylene, butene and isomers thereof. Light aromatics refer to BTX, ie benzene, toluene and xylenes. In the present disclosure, light olefins can be separated from dry gas, C3 fraction and C4 fraction; light aromatics can be separated from light gasoline and heavy gasoline.

In this disclosure, the C3 fraction refers to the hydrocarbons with 3 carbons in the reaction oil and gas, including propane and propylene; the C4 fraction refers to the hydrocarbons with 4 carbons in the reaction oil and gas, including butane, butene and its iso structure; light gasoline refers to all fractions or partial fractions in the reaction oil and gas whose distillation range is within the range of 30-90°C, where "partial fraction" refers to fractions with a distillation range of a part of the temperature range between 30-90°C (such as fractions with a distillation range of 30-60°C or 40-60°C or 60-90°C, etc.); heavy gasoline refers to the fractions in the reaction oil gas whose distillation range is within the range of 30-200°C except for light gasoline .

In the present disclosure, light distillate oil and heavy distillate oil refer to the light distillate oil after cutting the hydrocarbon-containing raw material oil at a certain cutting temperature, and the cut out light distillate oil, and the remaining part is called heavy distillate oil. Those skilled in the art can cut hydrocarbon-containing feed oil according to methods known in the art (including but not limited to fractionation, distillation, etc.) as required, as long as the weight ratio of the light distillate to the heavy distillate ( (light distillate oil/heavy distillate oil) is X, and it is sufficient that X satisfies the following relational expression of the present disclosure. In one embodiment of the present disclosure, X is selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0 between any two value ranges. In one embodiment of the present disclosure, X is 0.1-2.0, preferably 0.12-1.0, more preferably 0.15-0.6.

In one embodiment of the present disclosure, in step S1, the hydrocarbon-containing feed oil is cut into light distillate oil and heavy distillate oil at any temperature between the cutting point 100-400° C., so that the light distillate oil is relatively The weight ratio of the heavy distillate (light distillate/heavy distillate) is X. In one embodiment of the present disclosure, the cutting point is, for example, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C °C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C.

In the present disclosure, the hydrocarbon-containing feedstock oil may be various feedstock oils known in the art (in the present invention, hydrocarbon-containing feedstock oil is sometimes referred to simply as feedstock oil), for example, it may be crude oil, coal liquefied oil, synthetic oil , oil sand oil, shale oil, tight oil and animal and vegetable oils or a mixture of two or more, or their respective partial fractions, and their respective heavy fractions of hydrogenated modified oil. In one embodiment of the present disclosure, the hydrocarbon-containing feed oil is preferably crude oil, a partial fraction of crude oil, or a hydro-upgraded oil of heavy oil derived from crude oil. Those skilled in the art know that "partial fractions" can be obtained by subjecting raw oil to conventional treatments in the art, including but not limited to atmospheric distillation, vacuum distillation, and the like. Those skilled in the art can determine the manner of this routine processing as needed. In one embodiment of the present disclosure, crude oil can be used as the hydrocarbon-containing raw material oil of the present disclosure, and the crude oil can also be subjected to atmospheric distillation or vacuum distillation as required, and the remaining fraction (partial fraction of crude oil) after extracting a partial fraction can be used as The hydrocarbon-containing feedstock oil of the present disclosure, or a product obtained by hydrotreating heavy oil derived from crude oil (hydro-upgraded oil of heavy oil) is the hydrocarbon-containing feedstock oil of the present disclosure. It is known in the art that hydroupgrading includes but not limited to hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrosaturation and other treatments.

In one embodiment of the present disclosure, the method has a step S0 before step S1, wherein the hydrocarbon-containing feed oil is subjected to desalting and dehydration treatment, and the obtained dehydrated and desalted hydrocarbon-containing feed oil is introduced into step S1 for cutting.

According to the present disclosure, in step S2, in the first down-flow reactor, the conditions of the first catalytic cracking include: the outlet temperature of the first down-down reactor is 610-720°C, preferably 650°C -690°C. The conditions for the first catalytic cracking also include: the gas-solid residence time is 0.1-3.0 seconds, preferably 0.5-1.5 seconds. In the first down-flow reactor, the catalyst-oil ratio of the catalyst to the light distillate oil can be a commonly used catalyst-oil ratio in catalytic cracking (in terms of catalyst/light distillate weight ratio), for example, it can be 15-80 , preferably 25-65.

In the present disclosure, there is no limitation on the way in which the light distillate oil and the first stream of catalyst are introduced into the first down-flow reactor, as long as the light distillate oil and the first stream of catalyst are introduced at the upper end of the first down-flow reactor. Can. Preferably, the light distillate oil and the first stream of catalyst are respectively introduced from different feed ports of the first down-flow reactor.

In the present disclosure, there is no limitation on the first catalyst, and it may be a catalyst known in the art that can be used for catalytic cracking of crude oil. For example, the first stream of catalysts may include an active component and a carrier, and the active component is selected from ultrastable Y-type zeolites containing or not containing rare earths, ZSM-5 series zeolites, high-silicon zeolite with a five-membered ring structure At least one of zeolite and zeolite beta. The carrier is at least one selected from alumina, silica, amorphous silica-alumina, zirconia, titania, boria and alkaline earth metal oxides.

In one embodiment of the present disclosure, the structure of the first down-flow reactor is not particularly limited, as long as it can realize feeding from the upper part and discharging from the lower part, for example, it can be equal diameter or variable diameter Downstream reactor.

In the present disclosure, since no additional heat source is used in the first down-flow reactor, the outlet temperature of the first down-flow reactor reflects the reaction temperature in the reactor. In the present disclosure, the catalysis of light distillate oil in the first down-flow reactor can be adjusted by adjusting the temperature of the first stream of catalyst, the gas-solid residence time in the reactor, the outlet temperature of the first down-flow reactor, etc. Cleavage degree.

In one embodiment of the present disclosure, the first stream of catalyst is fresh catalyst. In one embodiment of the present disclosure, the first stream of catalyst comprises regenerated catalyst from a regenerator. Preferably, said first stream of catalyst is regenerated catalyst from a regenerator.

In the present disclosure, there is no particular limitation on the temperature of the first stream of catalyst entering the down-flow reactor, as long as it can undergo catalytic cracking when in contact with light distillate oil and meets the above-mentioned first catalytic cracking conditions of the present disclosure. When the regenerated catalyst is used as the first stream of catalyst, the first stream of catalyst is directly fed from the regenerator through the first stream of catalyst (regenerated catalyst) delivery pipe, because the delivery pipe between the regenerator and the first down-flow reactor Short, therefore, the temperature of the first stream of catalyst can be regarded as the temperature of the regenerator or the temperature of the regenerated catalyst leaving the regenerator (the temperature of the outlet of the regenerator). In one embodiment of the present disclosure, the temperature of the first stream of catalyst entering the down-flow reactor is the temperature of the regenerator or the temperature of the regenerated catalyst leaving the regenerator (the temperature at the outlet of the regenerator), usually 690-750°C, Preferably it is 700-740°C, more preferably 705-730°C, still more preferably 710-725°C. In addition, at this time, the catalyst from the regenerator may be fed into the first down-flow reactor after being further heated or cooled according to needs. In the process of the present disclosure, at start-up, fresh catalyst can be heated to the desired temperature before being introduced into the first down-flow reactor; thereafter, the regenerated catalyst from the regenerator can be used directly. In one embodiment of the present disclosure, it is preferred that the first stream of catalyst is directly fed from the regenerator without further heating or cooling thereof.

In the present disclosure, when the light fraction oil is introduced into the first down-flow reactor, the light fraction oil may also be preheated first if necessary. The temperature of the preheated light distillate is, for example, 30-100°C. In addition, the light distillate oil can also be steam atomized first, and then the light distillate oil is introduced into the first down-flow reactor with water vapor as a carrier.

In the present disclosure, the material after the first catalytic cracking includes the first reaction oil gas obtained by catalytic cracking of light distillate oil and the first spent catalyst after the first stream of catalyst is coked (after carbonization). The first spent catalyst still has relatively high activity, and the catalyst is loaded with carbon deposits, and when it is introduced into the subsequent second uplink reactor as a continuous catalyst, it helps the catalytic cracking of the heavy distillate oil, Improve the yield of low-carbon olefins and suppress the formation of dry gas and coke.

In the present disclosure, in step S3, the material after the first catalytic cracking is subjected to gas-solid separation to obtain the first reaction oil gas and the first spent catalyst. The method of gas-solid separation is not particularly limited, and methods known in the art can be used, such as using a settler or a cyclone separator to separate the catalyst from the first reaction oil and gas.

In one embodiment of the present disclosure, the first reaction oil and gas are separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins and light aromatics are separated and separated Light olefin fractions. Wherein, the C4 fraction and/or light gasoline is the light olefin fraction. In one embodiment of the present disclosure, the first reacted oil gas is introduced into a fractionation device or a gas fractionation device for fractionation, so as to realize the above separation. In one embodiment of the present disclosure, the light olefin fraction is introduced into the second uplink reactor in the following step S4.

In one embodiment of the present disclosure, at least a portion of the first spent catalyst is introduced as a continuous catalyst into the second upwelling reactor described below. In one embodiment of the present disclosure, the first spent catalyst that does not enter the second uplink reactor described below is introduced into the regeneration step, where regeneration of the catalyst is performed. Preferably, all of the first spent catalyst is introduced as a continuous catalyst into the second upwelling reactor described below, where the amount of the first spent catalyst as continuous catalyst substantially corresponds to the amount of the first stream of catalyst.

In one embodiment of the present disclosure, gas-solid separation is performed on the material after the first catalytic cracking, and the separated catalyst is further stripped to remove hydrocarbon products adsorbed therein to obtain the first spent catalyst.

In one embodiment of the present disclosure, step S2' may also be included after step S2 and before step S3, wherein the material after the first catalytic cracking is introduced into a fluidized bed reactor for second catalytic cracking to obtain The material after the second catalytic cracking, thus, the light olefin fraction can be further converted, and the production of light olefin can be maximized.

In this disclosure, a "fluidized bed reactor" is also referred to as a "fluidized reactor", and its catalyst density is between 150-450 kg/m ³ .

According to the present disclosure, in step S2′, in the fluidized bed reactor, the conditions for the second catalytic cracking include: the reaction temperature in the fluidized bed reactor is 600-690° C., preferably 640-670° C. ℃. The conditions for the second catalytic cracking also include: the mass space velocity is 2-20h ^-1 , preferably 4-12h ^-1 .

According to an embodiment of the present disclosure, instead of introducing a new catalyst into the fluidized bed, the material after the first catalytic cracking can be directly introduced for catalytic cracking. According to one embodiment of the present disclosure, no additional heat source is applied to the fluidized bed, but the heat of the first catalytically cracked material can be used directly. The introduced first catalytic cracking material includes the first reaction oil gas obtained by catalytic cracking of light distillate oil and the first spent catalyst that is coked (carbonized) by the first catalyst. The first spent catalyst still has relatively high activity, and can continue to deepen the degree of catalytic cracking in the fluidized bed reactor to further convert light olefin fractions into light olefins.

According to one embodiment of the present disclosure, light olefin fractions are separated from the reaction oil and gas of the present disclosure, and the light olefin fractions are returned to the fluidized bed reactor for further conversion into light olefins. More specifically, the reaction oil and gas are separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins and light aromatics are separated, and light olefin fractions are separated. Wherein, the C4 fraction and/or light gasoline is the light olefin fraction. In one embodiment of the present disclosure, the reaction oil gas is introduced into a fractionation device or a gas separation device to achieve the above separation.

In the present disclosure, the material after the second catalytic cracking includes the second reaction oil gas and the second spent catalyst. The second spent catalyst still has relatively high activity, and the catalyst is loaded with carbon deposits. When it is introduced into the subsequent second uplink reactor as a continuous catalyst, it helps the catalytic cracking of heavy distillate oil, Improve the yield of low-carbon olefins and suppress the formation of dry gas and coke.

In the present disclosure, in step S3, the material after the second catalytic cracking is subjected to gas-solid separation to obtain the second reaction oil gas and the second spent catalyst. The method of gas-solid separation is not particularly limited, and methods known in the art can be used, such as using a settler or a cyclone separator to separate the catalyst from the second reaction oil and gas.

In one embodiment of the present disclosure, the second reaction oil gas is separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins and light aromatics are separated, and separated Light olefin fractions. Wherein, C4 fraction and/or light gasoline are light olefin fractions. In one embodiment of the present disclosure, the second reaction oil gas is introduced into a fractionation device or a gas separation device to achieve the above separation.

In one embodiment of the present disclosure, the gas-solid separation is performed on the material after the second catalytic cracking, and the separated catalyst is further stripped to remove the hydrocarbon products adsorbed therein to obtain the second spent catalyst. In the present disclosure, at least a portion of the second spent catalyst is introduced as a continuous catalyst into the second upwelling reactor described below.

In one embodiment of the present disclosure, the second spent catalyst that does not enter the second uplink reactor described below is introduced into the regeneration step, where catalyst regeneration is performed. Preferably, all of the second spent catalyst is introduced as a continuous catalyst into the second upwelling reactor described below, in which case the amount of the second spent catalyst as continuous catalyst substantially corresponds to the amount of the first stream of catalyst.

In the present disclosure, in step S4, the continuous catalyst, the heavy distillate oil and the second stream of catalyst are introduced into the second uplink reactor, the third catalytic cracking is performed, and then the gas-solid separation is performed to obtain the third reaction oil gas and the third Spent catalyst; said continuous catalyst being at least a portion of said first spent catalyst or at least a portion of said second spent catalyst.

In one embodiment of the present disclosure, in the second ascending reactor, the conditions for the third catalytic cracking include: the outlet temperature T3 of the second ascending reactor is 530-650°C, preferably 560-640°C °C, more preferably 580-630 °C, still more preferably 600-630 °C. The third catalytic cracking condition also includes: the gas-solid residence time is 0.5-8 seconds, preferably 1.5-5 seconds. In the second ascending reactor, the catalyst-to-oil ratio of the catalyst to the heavy distillate can be a commonly used catalyst-to-oil ratio in catalytic cracking (in terms of catalyst/heavy distillate weight ratio), for example, it can be 8-40, Preferably 10-30.

In one embodiment of the present disclosure, in step S4, the continuous catalyst is mixed with the second stream of catalyst first, and then the subsequent catalytic cracking reaction is performed. More specifically, in one embodiment of the present disclosure, the continuous catalyst and the second stream of catalyst are independently fed to the bottom of the second upward reactor, mixed, and the mixed catalyst (hereinafter , sometimes referred to as catalyst mixture or mixed catalyst) for the catalytic cracking reaction in the second uplink reactor. In one embodiment of the present disclosure, after mixing the continuous catalyst with the second stream of catalyst in the bottom region of the second upwelling reactor, the mixed catalyst is lifted in the second upwelling reactor using a prelift medium , for the downstream catalytic cracking reaction. In one embodiment of the present disclosure, the pre-lift medium may be dry gas, water vapor, or a mixture thereof.

In one embodiment of the present disclosure, in step S4, the second catalyst is not limited, and it can be a catalyst known in the art that can be used for catalytic cracking of crude oil. For example, the second catalyst includes an active component and a carrier, and the active component is selected from ultra-stable Y-type zeolite containing or not containing rare earth, ZSM-5 series zeolite, high-silica zeolite with five-membered ring structure and at least one of zeolite beta. The carrier is at least one selected from alumina, silica, amorphous silica-alumina, zirconia, titania, boria and alkaline earth metal oxides.

In one embodiment of the present disclosure, the structure of the second upward reactor is not particularly limited, as long as it can be fed from the bottom and discharged from the top, for example, it can be of equal diameter or variable diameter Riser reactors, riser reactors with equal or reduced diameters and fluidized bed composite reactors.

In one embodiment of the present disclosure, the second stream of catalyst is fresh catalyst. In one embodiment of the present disclosure, the second stream of catalyst comprises regenerated catalyst from a regenerator. In one embodiment of the present disclosure, the second stream of catalyst is regenerated catalyst from a regenerator. When fresh catalyst is used as the second strand of catalyst, the catalyst needs to be preheated so that the temperature of the fresh catalyst when it enters step S4 satisfies the relational expression of the present disclosure. Preferably, said second stream of catalyst is regenerated catalyst from a regenerator.

In the present disclosure, the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R, and the R and X satisfy the following relationship:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor.

The inventors of the present disclosure surprisingly found that by making the cut ratio of the light distillate oil and the heavy distillate oil of the hydrocarbon-containing feed oil in step S1 (the weight ratio of the light distillate oil/heavy distillate oil) The weight ratio of the continuous catalyst (the second strand of catalyst/continuous catalyst) satisfies the above relational formula, which can make the hydrocarbon-containing feedstock oil component, cutting ratio, catalyst activity (especially the catalyst activity in the second ascending reactor) more A good match can significantly reduce the yield of dry gas and coke while maximizing the production of light olefins and BTX. Without wishing to be bound by any theory, the inventors of the present disclosure speculate that the catalyst as continuous catalyst is from either the first spent catalyst or the second spent catalyst due to the generation of Coke is low, so that the first spent catalyst and the second spent catalyst have higher catalytic activity, and load a certain amount of carbon deposits. This catalyst is mixed with the second catalyst (fresh catalyst or from the regenerator) in a certain proportion The regenerated catalyst) is mixed, and the mixing ratio is matched with the cutting ratio of hydrocarbon-containing feedstock oil, so as to satisfy the above-mentioned relational formula of the present disclosure. Excessive coking of heavy distillate oil will not cause insufficient catalytic cracking of heavy distillate oil due to low catalyst activity. In the present disclosure, the ratio of cutting the hydrocarbon-containing feedstock oil into light distillate oil and heavy distillate oil and the mixing ratio of the continuous catalyst and the second strand of catalyst satisfy a specific relationship, and the second stream can be adjusted according to the composition of the hydrocarbon-containing feedstock oil, the cutting ratio, etc. The activity of the mixed catalyst in the two up-flow reactors maximizes the yield of light olefins and BTX from heavy distillates.

In one embodiment of the present disclosure, (4.84×T0-3340)/(780+5×T0-6×T3) is greater than 0. In the present disclosure, T0 is greater than T3.

In the present disclosure, T0 is the temperature when the second strand of catalyst enters step S4. Specifically, the temperature at which the second stream of catalyst (fresh or regenerated) enters the second up-flow reactor, ie, the temperature at which it enters the bottom of the second up-flow reactor before mixing with the continuous catalyst. When the regenerated catalyst is used as the second stream of catalyst, because the transfer pipe between the regenerator and the second uplink reactor is short, the temperature of the regenerator or the temperature of the catalyst when the regenerated catalyst exits the regenerator (the temperature at the outlet of the regenerator) It can be regarded as the temperature when the second strand of catalyst enters step S4.

In one embodiment of the present disclosure, the outlet temperature T3 of the second ascending reactor is 530-650°C, preferably 560-640°C, more preferably 580-630°C, even more preferably 600-630°C; And/or, the temperature T0 of the second strand of catalyst entering step S4 is 690-750°C, preferably 700-740°C, more preferably 705-730°C, even more preferably 710-725°C.

In one embodiment of the present disclosure, the third reaction oil gas is separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins and light aromatics are separated, and separated Light olefin fractions. Among them, the C4 fraction and/or light gasoline is the light olefin fraction. In one embodiment of the present disclosure, the third reaction oil gas is introduced into a fractionation device or a gas separation device to achieve the above separation.

In the present disclosure, when step S2' does not exist, in step S5, light olefins and light aromatics are separated from either the first reaction oil gas, the third reaction oil gas or a mixture of both, and the separated The light olefin fraction is returned to the second uplink reactor.

In the present disclosure, when there is step S2′, in step S5, light olefins and light aromatics are separated from any one of the second reaction oil gas, the third reaction oil gas, or a mixture of both, and the separated light The olefin fraction is returned to the fluidized bed reactor.

In one embodiment of the present disclosure, in step S4, the light olefin fraction from the following step S5 is contacted with the catalyst mixture prior to the heavy distillate oil to undergo a catalytic cracking reaction, and then the heavy distillate oil is contacted with the catalyst mixture , a catalytic cracking reaction occurs. Preferably, the light olefin fraction is contacted with the catalyst mixture 0.3-1.0 seconds prior to the heavy distillate. More preferably, the light olefin fraction is contacted with the catalyst mixture 0.4-0.8 seconds prior to the heavy distillate.

In one embodiment of the present disclosure, gas-solid separation is performed on the product of the third catalytic cracking to obtain the third reaction oil gas and the third spent catalyst. The method of gas-solid separation is not particularly limited, and methods known in the art can be used, such as using a settler or a cyclone separator to separate the catalyst from the third reaction oil and gas.

In one embodiment of the present disclosure, the gas-solid separation is performed on the material after the third catalytic cracking, and the separated catalyst is further stripped to remove the hydrocarbon products adsorbed therein to obtain the third spent catalyst. In one embodiment of the present disclosure, the third spent catalyst enters the regenerator to regenerate the catalyst.

In one embodiment of the present disclosure, the temperature of the regenerator is a temperature commonly used in the art, which may be 690-750°C, preferably 700-740°C, more preferably 705-730°C, and even more preferably 710-725°C ℃. In one embodiment of the present disclosure, the temperature of the regenerator or the temperature of the catalyst when the regenerated catalyst leaves the regenerator (the temperature at the outlet of the regenerator) can be regarded as the temperature when the second strand of catalyst enters step S4. Therefore, in one embodiment of the present disclosure, the temperature T0 when the second stream of catalyst enters step S4 can be 690-750°C, preferably 700-740°C, more preferably 705-730°C, even more preferably 710- 725°C.

In one embodiment of the present disclosure, the regenerated catalyst is used as the first strand catalyst and the second strand catalyst.

In the present disclosure, in step S5, from any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the mixture of the first reaction oil gas and the third reaction oil gas or the second reaction oil gas Light olefins and light aromatics are separated from the mixture of oil and gas and the third reaction oil and gas, and the light olefin fraction is separated, and the light olefin fraction is returned to the second ascending reactor in step S4 or to the step S2′ In the fluidized bed reactor. More specifically, the reaction oil and gas are separated to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins and light aromatics are separated, and light olefin fractions are separated. Wherein, the C4 fraction and/or light gasoline is the light olefin fraction. Preferably, the reaction oil gas is introduced into a fractionation device or a gas separation device to realize the above separation. In step S5, the first reaction oil and gas and the third reaction oil and gas can be separated separately, or both can be combined and then separated; or, the second reaction oil and gas, the third reaction oil and gas can be separated. The oil and gas are separated separately, or the two can be combined and then separated uniformly.

In one embodiment of the present disclosure, the method for separating the light olefin fraction from the reaction oil gas is not limited, and the separation can be carried out in a manner known in the art, including but not limited to the following method, after the reaction oil gas enters the fractionation and absorption stabilization unit , to separate the liquefied gas and stable gasoline, the liquefied gas enters the subsequent gas separation device to separate the C3 fraction and the C4 fraction, and the stable gasoline enters the light and heavy gasoline splitting tower to separate the light gasoline and heavy gasoline. The C4 fraction and/or light gasoline is the light olefin fraction. From it, light olefins and light aromatics can be separated.

In more detail, in one embodiment of the present disclosure, a method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil is provided, the method includes the following steps:

S1, cutting the hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil, the weight ratio of the light distillate oil relative to the heavy distillate oil (light distillate oil/heavy distillate oil) is X;

S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking;

S3, performing gas-solid separation on the material after the first catalytic cracking, to obtain the first reaction oil gas and the first spent catalyst;

S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is at least a part of the first spent catalyst; the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R;

S5. Separating light olefins and light aromatics from either or both of the first reaction oil and gas and the third reaction oil and gas, and separating the light olefin fraction, and returning the light olefin fraction In the second ascending reactor in step S4,

The R and X satisfy the following relational formula:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor.

In more detail, in one embodiment of the present disclosure, a method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil is provided, the method comprising the following steps:

S1, cutting the hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil, the weight ratio of the light distillate oil relative to the heavy distillate oil (light distillate oil/heavy distillate oil) is X;

S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking;

S2', introducing the material after the first catalytic cracking into a fluidized bed reactor for second catalytic cracking to obtain the second catalytic cracking material;

S3, performing gas-solid separation on the material after the second catalytic cracking to obtain a second reaction oil gas and a second spent catalyst;

S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is at least a part of the second spent catalyst; the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R;

S5. Separating light olefins and light aromatics from any one or both of the second reaction oil and gas and the third reaction oil and gas, and separating the light olefin fraction, and returning the light olefin fraction In the fluidized bed reactor of step S2',

The R and X satisfy the following relational formula:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor.

In one embodiment of the present disclosure, the light olefin fraction is the C4 fraction in the reaction oil gas and/or the light gasoline.

The present disclosure also provides the following technical solutions:

A1, a method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feed oil, the method comprising the steps of:

S1. Cutting the desalted and dehydrated hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil; the cutting point of the cutting is any temperature between 100-400°C;

S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking;

Optional S2', sending the material after the first catalytic cracking into a fluidized bed reactor for second catalytic cracking to obtain the second catalytic cracking material;

S3. Perform gas-solid separation on the material after the first catalytic cracking to obtain the first reaction oil gas and the first to-be-studied catalyst, or perform gas-solid separation on the second catalytic cracking material to obtain the second reaction oil gas and a second spent catalyst;

S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is the first spent catalyst or the second spent catalyst; the weight ratio of the second catalyst to the continuous catalyst is 0.2-5:1;

S5. Separating light olefin fractions from the first reaction oil and gas and the second reaction oil and gas, and returning the light olefin fractions to the fluidized bed reactor or the second ascending reactor.

A2. The method according to A1, wherein, in step S1, the cutting point of the cutting is any temperature between 200-380°C.

A3. The method according to A1, wherein, in step S4, the weight ratio of the second strand catalyst to the continuous catalyst is 0.5-3:1.

A4. The method of claim A1, wherein,

In the first down-flow reactor, the conditions for the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 610-720°C, and the gas-solid residence time is 0.1-3.0 seconds;

In the fluidized bed reactor, the conditions for the second catalytic cracking include: the reaction temperature in the fluidized bed reactor is 600-670°C, and the mass space velocity is 2-20h ^-1 ;

In the second ascending reactor, the conditions for the third catalytic cracking include: the outlet temperature of the second ascending reactor is 530-650° C., and the gas-solid residence time is 0.5-8 seconds.

A5. The method according to A4, wherein,

In the first down-flow reactor, the conditions for the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 650-690°C, and the gas-solid residence time is 0.5-1.5 seconds;

In the fluidized bed reactor, the conditions for the second catalytic cracking include: the reaction temperature in the fluidized bed reactor is 620-640°C, and the mass space velocity is 4-12h ^-1 ;

In the second ascending reactor, the conditions for the third catalytic cracking include: the outlet temperature of the second ascending reactor is 560-640°C, and the gas-solid residence time is 1.5-5 seconds.

A6. The method according to A1, wherein,

Catalytic cracking of the light olefin fraction with the second catalyst for 0.3-1.0 seconds prior to the heavy distillate oil; Two catalysts are used for catalytic cracking.

A7. The method according to A1, wherein the method also includes:

Burning and regenerating the third spent catalyst to obtain a regenerated catalyst;

Separating the first oil and gas from the second oil and gas to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry;

The light olefin fraction is the C4 fraction in the first oil gas and the second oil gas and/or the fraction in the range of 30-90°C in the first oil gas and the second oil gas.

A8. The method according to A1, wherein the hydrocarbon-containing raw material oil is one or more of conventional mineral oil, coal liquefied oil, synthetic oil, oil sand oil, shale oil, tight oil, and animal and vegetable oils mixture.

A9. The method according to A1, wherein the first catalyst and the second catalyst each independently include an active component and a carrier, and the active component is selected from superstable catalysts containing or not containing rare earth At least one of Y-type zeolite, ZSP series zeolite, high silica zeolite with five-membered ring structure and beta zeolite.

A10. The method according to A1, wherein the first strand of catalyst and the second strand of catalyst each independently comprise the regenerated catalyst.

The present disclosure also provides a device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing raw material oil, the device includes the following units:

a hydrocarbonaceous feedstock cutting unit, wherein the hydrocarbonaceous feedstock is cut into light distillates and heavy distillates such that the weight ratio of the light distillate relative to the heavy distillate (light distillate/heavy distillate) is X,

The first descending reaction unit, introducing the light distillate oil and the first stream of catalyst from above the reaction unit, performing the first catalytic cracking, and obtaining the first catalytic cracked material below the reaction unit;

An optional fluidized bed reaction unit, wherein the material after the first catalytic cracking is introduced to perform the second catalytic cracking to obtain the second catalytic cracking material;

The first gas-solid separation unit, wherein the material after the first catalytic cracking is introduced for gas-solid separation to obtain the first reaction oil gas and the first catalyst to be produced, or the material after the second catalytic cracking is introduced for gas-solid separation Separating to obtain the second reaction oil gas and the second spent catalyst;

In the second ascending reaction unit, the continuous catalyst, the second stream of catalyst and the heavy distillate oil are introduced from below the reaction unit to carry out the third catalytic cracking, and the third catalytic cracking material is obtained above the reaction unit. The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst, and the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R,

The second gas-solid separation unit, wherein the material after the third catalytic cracking is introduced for gas-solid separation to obtain the third reaction oil gas and the third spent catalyst;

a separation unit wherein any one of said first reaction vapor, said second reaction vapor and said third reaction vapor or a mixture of first reaction vapor and third reaction vapor or second reaction vapor and third reaction vapor is introduced A mixture of oil and gas, separating light olefins and light aromatics, and separating light olefin fractions, and returning the light olefin fractions to the second upward reaction unit or the fluidized bed reaction unit;

Wherein, the R and X satisfy the following relationship:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit, and T3 is the outlet temperature (in °C) of the second upward reaction unit.

In the present disclosure, T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit. Specifically, it refers to the temperature of the second stream of catalyst entering the bottom of the second ascending reaction unit before mixing with the continuous catalyst.

In one embodiment of the present disclosure, the device further includes a regeneration unit, wherein the third spent catalyst and optionally the first spent catalyst or the second spent catalyst that has not entered the second upwelling reactor are introduced , to perform coke regeneration to obtain a regenerated catalyst. Preferably, only said third spent catalyst is introduced into the regeneration unit. In one embodiment of the present disclosure, the temperature of the regeneration unit is a temperature commonly used in the art, which may be 690-750°C, preferably 700-740°C, more preferably 705-730°C, and even more preferably 710-725°C .

In one embodiment of the present disclosure, the outlet temperature T3 of the second ascending reaction unit is 530-650°C, preferably 560-640°C, more preferably 580-630°C, even more preferably 600-630°C.

In one embodiment of the present disclosure, the temperature T0 when the second stream of catalyst enters the second upward reaction unit is 690-750°C, preferably 700-740°C, more preferably 705-730°C, even more preferably 710°C -725°C.

In one embodiment of the present disclosure, the device further includes a dehydration and desalination unit, wherein the hydrocarbon-containing feed oil is subjected to desalting and dehydration treatment, and the obtained dehydrated and desalted hydrocarbon-containing feed oil is introduced into the hydrocarbon-containing feed oil cutting unit for cutting.

In one embodiment of the present disclosure, the structure of the first down-flow reaction unit is not particularly limited, as long as it can realize feeding from the upper part and realize discharging from the lower part, for example, it can be equal diameter or variable diameter Downstream reactor.

In one embodiment of the present disclosure, when there is no fluidized bed reaction unit, in the separation unit, light olefins and light olefins and light aromatics, and return the separated light olefin fraction to the second ascending reaction unit.

In the present disclosure, when there is a fluidized bed reaction unit, in the separation unit, light olefins and light aromatics are separated from any one of the second reaction oil gas, the third reaction oil gas, or a mixture of the two, and the separated The light olefin fraction is returned to the fluidized bed reactor.

In one embodiment of the present disclosure, the first gas-solid separation unit and the second gas-solid separation unit include devices known in the art that can realize gas-solid separation, such as a settler or a cyclone separator.

In one embodiment of the present disclosure, the device further includes at least one stripping unit, which can be arranged in the gas-solid separation unit, wherein the catalyst obtained by gas-solid separation is stripped to remove the hydrocarbon products adsorbed therein .

More specifically, in one embodiment of the present disclosure, when the device includes a fluidized bed reaction unit, the first gas-solid separation unit also includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped , to remove the hydrocarbon products adsorbed therein to obtain the second spent catalyst. In one embodiment of the present disclosure, the second gas-solid separation unit further includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped to remove hydrocarbon products adsorbed therein to obtain a third spent catalyst.

In one embodiment of the present disclosure, the continuous catalyst and the second stream of catalyst are introduced into the bottom of the second upward reaction unit, and after mixing, the mixed catalyst is used for the subsequent catalytic cracking reaction.

In one embodiment of the present disclosure, in the second upward reaction unit, the position of introducing the continuous catalyst and the second stream of catalyst is upstream of the light olefin fraction feed port.

In one embodiment of the present disclosure, in the second ascending reaction unit, the light olefin fraction feed port is upstream of the heavy distillate oil feed port.

In one embodiment of the present disclosure, the structure of the second upward reactor is not particularly limited, as long as it can be fed from the bottom and discharged from the top, for example, it can be of equal diameter or variable diameter Riser reactors, riser reactors with equal or reduced diameters and fluidized bed composite reactors.

In more detail, the present disclosure provides a device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil, which includes the following units:

a hydrocarbonaceous feedstock cutting unit, wherein the hydrocarbonaceous feedstock is cut into light distillates and heavy distillates such that the weight ratio of the light distillate relative to the heavy distillate (light distillate/heavy distillate) is X,

The first descending reaction unit, introducing the light distillate oil and the first stream of catalyst from above the reaction unit, performing the first catalytic cracking, and obtaining the first catalytic cracked material below the reaction unit;

The first gas-solid separation unit, wherein the material after the first catalytic cracking is introduced for gas-solid separation to obtain the first reaction oil gas and the first spent catalyst;

In the second ascending reaction unit, the continuous catalyst, the second stream of catalyst and the heavy distillate oil are introduced from below the reaction unit to carry out the third catalytic cracking, and the third catalytic cracking material is obtained above the reaction unit. The continuous catalyst is at least a part of the first spent catalyst, and the weight ratio of the second catalyst to the continuous catalyst (the second catalyst/continuous catalyst) is R,

The second gas-solid separation unit, wherein the material after the third catalytic cracking is introduced for gas-solid separation to obtain the third reaction oil gas and the third spent catalyst;

A separation unit, wherein a mixture of either or both of the first reaction oil gas and the third reaction oil gas is introduced, light olefins and light aromatics are separated, and a light olefin fraction is separated, and the light olefin fraction is returned to to the second ascending reaction unit;

Wherein, the R and X satisfy the following relationship:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit, and T3 is the outlet temperature (in °C) of the second upward reaction unit.

In more detail, the present disclosure provides a device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil, which includes the following units:

a hydrocarbonaceous feedstock cutting unit, wherein the hydrocarbonaceous feedstock is cut into light distillates and heavy distillates such that the weight ratio of the light distillate relative to the heavy distillate (light distillate/heavy distillate) is X,

The first descending reaction unit, introducing the light distillate oil and the first stream of catalyst from above the reaction unit, performing the first catalytic cracking, and obtaining the first catalytic cracked material below the reaction unit;

A fluidized bed reaction unit, wherein the material after the first catalytic cracking is introduced to perform the second catalytic cracking to obtain the second catalytic cracking material;

The first gas-solid separation unit, wherein the material after the second catalytic cracking is introduced for gas-solid separation to obtain the second reaction oil gas and the second spent catalyst;

In the second ascending reaction unit, the continuous catalyst, the second stream of catalyst and the heavy distillate oil are introduced from below the reaction unit to carry out the third catalytic cracking, and the third catalytic cracking material is obtained above the reaction unit. The continuous catalyst is at least a part of the second standby catalyst, and the weight ratio of the second catalyst to the continuous catalyst (the second catalyst/continuous catalyst) is R,

The second gas-solid separation unit, wherein the material after the third catalytic cracking is introduced for gas-solid separation to obtain the third reaction oil gas and the third spent catalyst;

A separation unit, wherein either one or a mixture of the second reaction oil gas and the third reaction oil gas is introduced, light olefins and light aromatics are separated, and light olefin fractions are separated, and the light olefin fractions are returned to to the fluidized bed reaction unit;

Wherein, the R and X satisfy the following relationship:

(4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3)

T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit, and T3 is the outlet temperature (in °C) of the second upward reaction unit.

The disclosed device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil is used to implement the method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing feedstock oil of the present disclosure.

Hereinafter, with reference to FIG. 1 and FIG. 2 , two embodiments of the present disclosure will be described in detail respectively, but the present disclosure is not limited thereto.

A specific embodiment of the present disclosure is shown in Figure 1, the hot first catalyst (regenerated catalyst) is transported to the first down-flow reactor 1 through the first catalyst delivery pipe (regenerated catalyst delivery pipe) 12. The light distillate oil is sprayed into the first down-flow reactor 1 through the feed nozzle 11, contacts with the first stream of catalyst and undergoes catalytic cracking reaction, and the reacted first catalytic cracked material is subjected to catalytic cracking in the gas-solid separator 7. Separated from the oil and gas, the first reaction oil and gas obtained is introduced into the separation device (not shown in the figure) through the oil and gas outlet 22 of the down-flow reactor, and the first spent catalyst is introduced into the second up-flow reactor 3 through the continuous catalyst delivery pipe 31 as a continuous catalyst At the bottom, the second catalyst (regenerated catalyst) is introduced into the bottom of the second ascending reactor 3 through the second catalyst delivery pipe (regenerated catalyst delivery pipe) 32, after the first spent catalyst (continuous catalyst) and the second catalyst are mixed The catalyst is lifted upwards through the pre-lift medium. The light olefin fraction is sprayed into the second ascending reactor 3 through the light olefin fraction feed nozzle 21, contacts with the catalyst and reacts. The heavy distillate oil is sprayed into the second ascending reactor 3 through the heavy distillate oil feed nozzle 33 to contact and react with the oil agent mixture from the bottom, and after the reaction, the third catalytic cracked material is obtained, and it enters the settler 4, where it is settled Carry out the separation of the 3rd standby catalyst and the 3rd reaction oil gas in device 4, the 3rd reaction oil gas enters separation device (not shown in the figure) through the 3rd reactor oil gas outlet 41, the 3rd standby catalyst enters stripper 5 , the adsorbed hydrocarbon products are stripped, and the third spent catalyst is sent to the regenerator 6 through the delivery pipe 53 for regeneration, and the regenerated catalyst is returned to the first down-flow reactor and the second up-down reactor for reuse. The reaction oil gas (the first reaction oil gas, the third reaction oil gas) is separated by a separation device (preferably a fractionation device, a gas separation device) to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil, oil slurry, from which Separated to obtain light olefins and light aromatics. In addition, the light olefin fraction is separated from the reaction oil and gas, and the light olefin fraction is introduced into the second upward reactor 3 through the light olefin fraction feed nozzle 21 .

Another specific embodiment of the present disclosure is shown in Figure 2, the hot first catalyst (regenerated catalyst) is transported to the first down-flow reactor 1 through the first catalyst delivery pipe (regenerated catalyst delivery pipe) 12 . The light distillate oil is sprayed into the first down-flow reactor 1 through the feed nozzle 11, contacts with the first stream of catalyst and undergoes catalytic cracking reaction, and the reacted first catalytic cracking material passes through the first down-flow reactor The outlet mushroom head distributor 13 is introduced into the fluidized bed reactor 2, and the cracking reaction continues to occur in the fluidized bed reactor. After the reaction, the second catalytic cracking material is obtained, and the second reaction oil gas is obtained after the material is subjected to cyclone separation. and a second spent catalyst. The second reaction oil gas is introduced into the separation device (not shown in the figure) from the second reaction oil gas outlet 22, and the second spent catalyst enters the first stripper 51 to strip the adsorbed hydrocarbon products, and passes through the continuous catalyst as a continuous catalyst. Catalyst delivery pipe 31 is introduced into the bottom of the second ascending reactor 3, and the second strand of catalyst (regenerated catalyst) is introduced into the bottom of the second ascending reactor 3 through the second strand of catalyst conveying pipe (regenerated catalyst conveying pipe) 32, and the second standby The mixed catalyst (continuous catalyst) and second stream of catalyst is lifted upwards through the pre-lift medium. The heavy distillate oil is sprayed into the second ascending reactor 3 through the heavy distillate oil feed nozzle 33 to contact and react with the catalyst. After the reaction, the material after the third catalytic cracking is obtained, and it enters the settler 4, and the second step is carried out in the settler 4. The separation of the third standby catalyst and the third reaction oil gas, the third reaction oil gas is introduced into the separation device (not shown in the figure) through the oil gas outlet 41 of the third reactor, the third standby catalyst enters the second stripper 52, and is stripped For the adsorbed hydrocarbon products, the third spent catalyst delivery pipe 53 sends the third spent catalyst to the regenerator 6 for regeneration, and the regenerated catalyst returns to the first downlink reactor and the second uplink reactor for reuse . The reaction oil gas (the second reaction oil gas, the third reaction oil gas) is separated by a separation device (preferably a fractionation device, a gas separation device) to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil, oil slurry, from which Separated to obtain light olefins and light aromatics. In addition, the light olefin fraction is separated from the reaction oil and gas, and the light olefin fraction is returned to the fluidized bed reactor 2 through the light olefin fraction feed nozzle 21 .

Example

The present disclosure is further described in detail through examples below. The raw materials used in the examples can all be obtained commercially. The catalytic cracking catalyst used in the examples and comparative examples of the present disclosure is industrially produced by China Petroleum & Chemical Corporation Catalyst Qilu Branch, and the brand name is DMMC-2. The catalyst contains ZSM-5 zeolite and ultra-stable Y-type zeolite with an average pore size of less than 0.7 nanometers. The catalyst is hydrothermally aged at 800°C for 17 hours with saturated steam before use. The main physical and chemical properties of the catalyst are shown in Table 1. The hydrocarbon-containing feedstock oil used in Examples and Comparative Examples is crude oil from Jiangsu Oilfield, and its properties are listed in Table 2.

Table 1

catalyst catalyst physical properties Specific surface/m ² ·g ^-1 125 Pore volume/cm ^-3 ·g ^-1 0.197 Apparent density g·cm ^-3 0.86 chemical components Al ₂ O ₃ /% 56.8 SiO ₂ /% 42.9 Microreactivity/% 68

Table 2

project Crude A Density(20℃)/(g·cm ^-3 ) 0.849 Freezing point/℃ 35 Kinematic viscosity(80℃)/(mm ² /s) 6.8 Carbon residue/% 3.5 Colloid content/% 8.4 Asphaltene content/% 0.2 Fraction mass fraction less than 250°C/% 16.3 Fraction mass fraction less than 320°C/% 28.6 Fraction mass fraction less than 350°C/% 34.6

Example 1

The light and heavy distillate oil cut point of crude oil A processed in this embodiment is 320° C., and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.4.

Adopt the medium-sized device of the continuous reaction of transformation-regenerating operation to carry out test, and its flow process is as shown in accompanying drawing 1. The high-temperature regenerated catalyst at 720°C is introduced from the regenerator to the top of downtube reactor 1 through the regenerated inclined tube, and the light distillate oil preheated to 45°C is atomized by water vapor, and then enters downflow tube reactor 1 through the feed nozzle. The first catalyst is contacted for catalytic cracking reaction, the catalyst-oil ratio is 40, the outlet temperature of the reactor is 665°C, and the gas-solid residence time is 0.8s. The material after the first catalytic cracking is separated by a cyclone to separate the first reaction oil gas and the second reaction. A spent catalyst, the first reacted oil gas enters the separation system, and all the first spent catalyst is introduced into the bottom of the riser reactor 3 . At the same time, the regenerated catalyst (the second stream of catalyst) at a temperature of 720° C. is introduced into the bottom of the riser reactor 3 by the regenerator through the regenerated catalyst delivery pipe 32 . The weight ratio (the second catalyst/the first spent catalyst) of the second strand of catalyst and the first spent catalyst is 0.25, after the first spent catalyst and the second strand of catalyst mix at the bottom of the riser reactor 3, mix The catalyst flows upward under the action of the pre-lift steam, and at the same time, the light olefin fraction enters the lower part of the riser reactor 3 through the light olefin fraction feed nozzle under the atomized water vapor medium, and reacts with the mixed catalyst. At 800 mm above the distillate feed nozzle, after the heavy distillate is atomized by water vapor, it is sprayed into the riser through the heavy distillate feed nozzle to react with catalytic cracking reaction, the ratio of agent to oil is 20, and the outlet temperature T3 of the reactor is 610°C, the gas-solid residence time in the reactor is 1.5s, the material after catalytic cracking is introduced into the settler for oil separation, separated into the third reaction oil gas and the third standby catalyst, and the third reaction oil gas is introduced into the separation system. The first reaction oil gas and the third reaction oil gas are separated into cracked gas, light gasoline, heavy gasoline, diesel oil and oil slurry in the separation system. Partial fraction of light gasoline (distillation range 30-60°C) is returned to riser reactor 3 as light olefin fraction through the light olefin fraction feed nozzle. The third spent catalyst enters the stripper, after the hydrocarbon products adsorbed on the third spent catalyst are stripped off, it enters the regenerator through the inclined tube of the spent catalyst, and is burnt and regenerated at 720°C in contact with air. The regenerated catalyst is returned to the reactor for recycling through the regeneration inclined tube. Medium-sized units use electric heating to maintain the temperature of the reaction-regeneration system. After the device is running stably (the composition of the product remains basically unchanged), the composition of the cracked gas and gasoline obtained from the reaction oil gas is analyzed to obtain low-carbon olefins (hereinafter referred to as triene) and light aromatics (hereinafter referred to as triene) in the product. BTX) yield.

The main operating conditions and results are listed in Table 3.

Example 2

Using the same device and reaction steps as in Example 1, the difference is that the cut point of the light and heavy components of the processed crude oil A is 250 ° C, and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.195. In addition, the first The weight ratio of the two strands of catalyst to the first spent catalyst (the second strand of catalyst/the first spent catalyst) is 0.03, and the temperature of the regenerator is 700°C (that is, the temperature T0 of the second strand of catalyst entering step S4 is 700°C °C), the outlet temperature T3 of the riser reactor was 570 °C.

The rest of the main operating conditions and results are listed in Table 3.

Example 3

Using the same device and reaction steps as in Example 1, the difference is that the cut point of the light and heavy components of the processed crude oil A is 350 ° C, and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.529. In addition, the first The weight ratio of the two strands of catalyst to the first spent catalyst (the second strand of catalyst/the first spent catalyst) is 0.6, and the temperature of the regenerator is 740°C (that is, the temperature T0 of the second strand of catalyst entering step S4 is 740°C °C), the outlet temperature T3 of the riser reactor was 630 °C.

The rest of the main operating conditions and results are listed in Table 3.

Example 4

The same apparatus and reaction steps as in Example 1 were used.

The light and heavy distillate oil cut point of crude oil A processed in this embodiment is 250° C., and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.195.

Except for the conditions listed in Table 3, the same conditions as in Example 1 were used.

The results are listed in Table 3.

Example 5

The same apparatus and reaction steps as in Example 1 were used.

The light and heavy distillate oil cut point of crude oil A processed in this embodiment is 350°C, and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.529,

Except for the conditions listed in Table 3, the same conditions as in Example 1 were used.

The results are listed in Table 3.

Example 6

The processed crude oil A light and heavy distillate cut point is 320° C., and the cut ratio (weight ratio of light distillate oil/heavy distillate oil) is 0.4.

The medium-sized device of the continuous reaction-regeneration operation of the transformation is adopted to carry out the test, and its flow process is as shown in accompanying drawing 2. The high-temperature regenerated catalyst at 720°C is introduced from the regenerator to the top of downtube reactor 1 through the regenerating inclined tube, and the light distillate oil preheated to 45°C is atomized by water vapor and then enters downflow tube reactor 1 through the feed nozzle. Contact with the first stream of catalyst for catalytic cracking reaction, the ratio of catalyst to oil is 40, the outlet temperature of the reactor is 670°C, the gas-solid residence time is 0.6s, and the material after the first catalytic cracking enters the fluidized bed reaction through the outlet distributor Reactor 2 further carries out the catalytic cracking reaction, the reaction temperature is 655°C, and the mass space velocity is 4h ^-1 ; in addition, the light olefin fraction enters the bottom of fluidized bed reactor 2 through the feed nozzle 21 after being atomized by steam, and is mixed with heat The catalyst contacted and reacted, the material after the second catalytic cracking was subjected to cyclone separation to obtain the second reaction oil gas and the second spent catalyst, the second reacted oil gas was introduced into the subsequent separation system, and the separated second spent catalyst was completely introduced after stripping Riser reactor 3 bottom. At the same time, the regenerated catalyst (the second stream of catalyst) at a temperature of 720° C. is introduced into the bottom of the second ascending tube reactor 3 through the regenerated catalyst delivery pipe 32 by the regenerator. The weight ratio (the second catalyzer/the second spent catalyzer) of the second catalyzer and the second spent catalyst is 0.25, and after the second spent catalyzer and the second catalyzer are mixed at the bottom of the reactor 3, the mixed catalyst is Under the action of pre-lifting steam, it flows upwards. After the heavy distillate oil is atomized by water vapor, it is sprayed into the riser reactor 3 through the heavy distillate oil nozzle, and it contacts with the catalyst for catalytic cracking reaction. The ratio of catalyst to oil is 20, and the outlet temperature of the reactor is T3 is 610°C, and the gas-solid residence time in the reactor is 1.5s. The material after catalytic cracking is introduced into the settler for oil separation, separated into the third reaction oil gas and the third standby catalyst, and the reaction oil gas is introduced into the separation system. The second reaction oil gas and the third reaction oil gas are separated into cracked gas, light gasoline, heavy gasoline, diesel oil and oil slurry in the separation system. Partial fraction of light gasoline (distillation range range 30-60° C.) is returned to fluidized bed reactor 2 as light olefin fraction. The third spent catalyst enters the stripper, strips out the hydrocarbon products adsorbed by the third spent catalyst, enters the regenerator through the inclined tube of the spent catalyst, contacts with air, and burns at 720°C for regeneration. The regenerated catalyst is returned to the reactor for recycling through the regeneration inclined tube. The medium-sized device adopts electric heating to maintain the temperature of the reaction and regeneration system. After the device is running stably (product composition remains basically unchanged), the composition of cracked gas and gasoline obtained from the reaction oil gas is analyzed to obtain the yields of triene and BTX in the product.

The main operating conditions and results are listed in Table 3.

Example 7

Using the same device and reaction steps as in Example 6, the difference is that the cut point of the light and heavy components of the processed crude oil A is 250 ° C, and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.195. In addition, the first The weight ratio of the second catalyst and the second spent catalyst (the second catalyst/the second spent catalyst) is 0.03, and the temperature of the regenerator is 700°C (that is, the temperature T0 when the second catalyst enters step S4 is 700 °C), the outlet temperature T3 of the riser reactor was 570 °C.

The rest of the main operating conditions and results are listed in Table 3.

Example 8

Using the same device and reaction steps as in Example 6, the difference is that the cut point of the light and heavy components of the processed crude oil A is 350 ° C, and the cut ratio is (weight ratio of light distillate oil/heavy distillate oil) 0.529. In addition, the first The weight ratio (second catalyst/second spent catalyst) of the second catalyst and the second spent catalyst is 0.6, and the temperature of the regenerator is 740°C (that is, the temperature T0 of the second catalyst entering step S4 is 740 °C), the outlet temperature T3 of the riser reactor was 630 °C.

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 1

The same device, reaction steps, and reaction conditions as in Example 1 were used, except that the light olefin fraction obtained from the separation of reaction oil and gas was not returned to the riser reactor 3 .

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 2

Adopting the same device and reaction steps as in Example 1, the difference is that the weight ratio of the second catalyzer to the first spent catalyst (the second catalyzer/the first spent catalyzer) is 0.1, and the temperature of the regenerator is 740 °C (that is, the temperature T0 of the second strand of catalyst entering step S4 is 740 °C), and the outlet temperature T3 of the riser reactor is 610 °C.

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 3

Adopting the same device and reaction steps as in Example 1, the difference is that the weight ratio of the second catalyzer to the first spent catalyst (the second catalyzer/the first spent catalyzer) is 0.5, and the temperature of the regenerator is 700 °C (that is, the temperature T0 of the second strand of catalyst entering step S4 is 700 °C), and the outlet temperature T3 of the riser reactor is 610 °C.

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 4

Adopt the same device and reaction steps, reaction conditions with embodiment 1, difference is not to introduce the second stock catalyst in riser reactor 3 bottoms, and only use the first spent catalyst.

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 5

The same device, reaction steps, and reaction conditions as in Example 1 were used, except that the first spent catalyst was not introduced into the lower part of the riser reactor 3, and only the second strand of catalyst was used.

The rest of the main operating conditions and results are listed in Table 3.

Comparative example 6

Adopt the same device and reaction steps, reaction conditions as in Example 1, the difference is that the light distillate oil enters the riser reactor, that is, the first downcomer reactor 1 becomes a riser reactor (the downcomer in table 3 In this comparative example 6, each parameter of the tubular reactor represents each parameter of the ascending tubular reactor).

The rest of the main operating conditions and results are listed in Table 3.

As can be seen from the data in Table 3, the method for producing light olefins and BTX by catalytic cracking of hydrocarbon-containing feedstock oil provided by the present disclosure can significantly increase the yield of light olefins and light aromatics. Meanwhile, by-products such as dry gas and coke The yield of product was suppressed.

The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure. These simple modifications All belong to the protection scope of the present disclosure.

In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in this disclosure.

In addition, various implementations of the present disclosure can be combined arbitrarily, as long as they do not violate the idea of the present disclosure, they should also be regarded as the content disclosed in the present disclosure.

Claims (17)

A method for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing raw material oil, the method comprising the steps of: S1, cutting the hydrocarbon-containing feed oil into light distillate oil and heavy distillate oil, the weight ratio of the light distillate oil relative to the heavy distillate oil (light distillate oil/heavy distillate oil) is X; S2. Introducing the light distillate oil and the first catalyst into the first down-flow reactor to perform the first catalytic cracking to obtain the material after the first catalytic cracking; Optional S2', introducing the first catalytically cracked material into a fluidized bed reactor for second catalytic cracking to obtain the second catalytically cracked material; S3. Perform gas-solid separation on the material after the first catalytic cracking to obtain the first reaction oil gas and the first to-be-studied catalyst, or perform gas-solid separation on the second catalytic cracking material to obtain the second reaction oil gas and a second spent catalyst; S4. Introduce the continuous catalyst, the heavy distillate oil and the second catalyst into the second uplink reactor, perform the third catalytic cracking, and then perform gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst; the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R ; S5. From any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the mixture of the first reaction oil gas and the third reaction oil gas or the second reaction oil gas and the third reaction oil gas Light olefins and light aromatics are separated from the mixture, and light olefin fractions are separated, and the light olefin fractions are returned to the second ascending reactor in step S4 or the fluidized bed reactor in step S2′ middle, The R and X satisfy the following relational formula: (4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3) T0 is the temperature (in °C) when the second stream of catalyst enters step S4, and T3 is the outlet temperature (in °C) of the second upward reactor. The method according to claim 1, wherein the outlet temperature T3 of the second ascending reactor is 530-650°C, preferably 560-640°C, more preferably 580-630°C, even more preferably 600-600°C 630°C; and/or The temperature T0 of the second strand of catalyst entering step S4 is 690-750°C, preferably 700-740°C, more preferably 705-730°C, even more preferably 710-725°C. The method according to claim 1 or 2, wherein, in step S1, the hydrocarbon-containing feed oil is cut into light distillate oil and heavy distillate oil at any temperature between the cut point 100-400°C, so that the light distillate oil The weight ratio (light distillate/heavy distillate) relative to the heavy distillate is X. The method according to any one of claims 1-3, wherein, In the first down-flow reactor, the conditions for the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 610-720°C, the gas-solid residence time is 0.1-3.0 seconds, and the an oil ratio of 15-80; and/or In the fluidized bed reactor, the conditions for the second catalytic cracking include: the reaction temperature in the fluidized bed reactor is 600-690°C, and the mass space velocity is 2-20h ^-1 ; and/or In the second ascending reactor, the conditions of the third catalytic cracking include: the gas-solid residence time is 0.5-8 seconds, and the solvent-oil ratio is 8-40. The method according to any one of claims 1-4, wherein, In the first down-flow reactor, the conditions for the first catalytic cracking include: the outlet temperature of the first down-flow reactor is 650-690°C, the gas-solid residence time is 0.5-1.5 seconds, and the an oil ratio of 25-65; and/or In the fluidized bed reactor, the conditions for the second catalytic cracking include: the reaction temperature in the fluidized bed reactor is 640-670°C, and the mass space velocity is 4-12h ^-1 ; and/or In the second ascending reactor, the conditions of the third catalytic cracking include: the gas-solid residence time is 1.5-5 seconds, and the solvent-oil ratio is 10-30. The method according to any one of claims 1-5, wherein, When there is step S2', in the gas-solid separation of step S3, the separated catalyst is stripped to obtain the second spent catalyst; and/or In step S4, the continuous catalyst is first mixed with the second strand of catalyst, and then the subsequent catalytic cracking reaction is carried out; and/or In step S4, said light olefin fraction from step S5 is contacted with said mixture of second catalyst and continuous catalyst prior to said heavy distillate; preferably said light olefin fraction is prior to said heavy distillate 0.3-1.0 seconds contact with the mixture of the second catalyst and the continuous catalyst, more preferably the light olefin fraction is contacted with the mixture of the second catalyst and the continuous catalyst 0.4-0.8 seconds before the heavy distillate ;and / or The method has a step S0 before step S1, wherein the hydrocarbon-containing feed oil is subjected to desalting and dehydration treatment, and the obtained dehydrated and desalted hydrocarbon-containing feed oil is introduced into step S1 for cutting. The method according to any one of claims 1-6, wherein the method further comprises: In the gas-solid separation in step S4, the separated catalyst is stripped to obtain the third spent catalyst; and/or The third spent catalyst and optionally the first spent catalyst or the second spent catalyst not entering the second up-flow reactor are heated at 690-750° C., preferably 700-740° C., more preferably 705-730° C. °C, more preferably at a temperature of 710-725 °C, char regeneration is carried out to obtain a regenerated catalyst; and/or any one of the first reaction oil gas, the second reaction oil gas and the third reaction oil gas or the mixture of the first reaction oil gas and the third reaction oil gas or the mixture of the second reaction oil gas and the third reaction oil gas Separation to obtain dry gas, C3 fraction, C4 fraction, light gasoline, heavy gasoline, diesel oil and oil slurry, from which light olefins, light aromatics are separated, and light olefin fractions are separated; and/or When there is no step S2', in step S5, the light olefin fraction is separated from any one of the first reaction oil gas, the third reaction oil gas, or a mixture of both, and the light olefin fraction is returned to the first step of step S4 In the second ascending reactor; when step S2' exists, in step S5, the light olefin fraction is separated from any one of the second reaction oil gas, the third reaction oil gas, or a mixture of both, and the light olefin fraction is The fraction is returned to the fluidized bed reactor of step S2'. The method according to any one of claims 1-7, wherein the hydrocarbon-containing raw material oil is one of crude oil, coal liquefied oil, synthetic oil, oil sand oil, shale oil, tight oil, and animal and vegetable oil One or a mixture of two or more, or their respective partial fractions, or their respective heavy fractions are hydro-upgraded oils. The method according to any one of claims 1-8, wherein the first strand of catalyst and the second strand of catalyst each independently comprise an active component and a carrier, the active component being selected from the group consisting of or At least one of rare earth-free ultra-stable Y-type zeolite, ZSM-5 series zeolite, high-silica zeolite and beta zeolite with a five-membered ring structure, the carrier is selected from alumina, silicon oxide, and amorphous silica-alumina , at least one of zirconia, titanium oxide, boron oxide and alkaline earth metal oxides. The method according to any one of claims 1-9, wherein said first strand of catalyst and said second strand of catalyst each independently comprise a regenerated catalyst, preferably said first strand of catalyst and said second strand the catalyst is a regenerated catalyst, and/or All of the first spent catalyst or all of the second spent catalyst is used as a continuous catalyst. A device for producing light olefins and light aromatics by catalytic cracking of hydrocarbon-containing raw material oil, the device includes the following units: a hydrocarbonaceous feedstock cutting unit, wherein the hydrocarbonaceous feedstock is cut into light distillates and heavy distillates such that the weight ratio of the light distillate relative to the heavy distillate (light distillate/heavy distillate) is X, The first descending reaction unit, introducing the light distillate oil and the first stream of catalyst from above the reaction unit, performing the first catalytic cracking, and obtaining the first catalytic cracked material below the reaction unit; An optional fluidized bed reaction unit, wherein the material after the first catalytic cracking is introduced to perform the second catalytic cracking to obtain the second catalytic cracking material; The first gas-solid separation unit, wherein the material after the first catalytic cracking is introduced for gas-solid separation to obtain the first reaction oil gas and the first catalyst to be produced, or the material after the second catalytic cracking is introduced for gas-solid separation Separating to obtain the second reaction oil gas and the second spent catalyst; In the second ascending reaction unit, the continuous catalyst, the second stream of catalyst and the heavy distillate oil are introduced from below the reaction unit to carry out the third catalytic cracking, and the third catalytic cracking material is obtained above the reaction unit. The continuous catalyst is at least a part of the first spent catalyst or at least a part of the second spent catalyst, and the weight ratio of the second catalyst to the continuous catalyst (second catalyst/continuous catalyst) is R, The second gas-solid separation unit, wherein the material after the third catalytic cracking is introduced for gas-solid separation to obtain the third reaction oil gas and the third spent catalyst; a separation unit wherein any one of said first reaction vapor, said second reaction vapor and said third reaction vapor or a mixture of first reaction vapor and third reaction vapor or second reaction vapor and third reaction vapor is introduced A mixture of oil and gas, separating light olefins and light aromatics, and separating light olefin fractions, and returning the light olefin fractions to the second upward reaction unit or the fluidized bed reaction unit; Wherein, the R and X satisfy the following relationship: (4.84×T0-3340)/(780+5×T0-6×T3)<R/X<(0.968×T0-630)/(668+0.2×T0-1.2×T3) T0 is the temperature (in °C) when the second stream of catalyst enters the second upward reaction unit, and T3 is the outlet temperature (in °C) of the second upward reaction unit. The device according to claim 11 , further comprising a regeneration unit, wherein the third spent catalyst and optionally the first spent catalyst or the second spent catalyst not entering the second upwelling reactor are introduced , at a temperature of 690-750°C, preferably 700-740°C, more preferably 705-730°C, and even more preferably 710-725°C, to obtain a regenerated catalyst. The device according to claim 11 or 12, wherein, when the device includes a fluidized bed reaction unit, the first gas-solid separation unit further includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped , to obtain the second spent catalyst. The device according to any one of claims 11-13, wherein the second gas-solid separation unit further includes a stripping unit, wherein the catalyst obtained by gas-solid separation is stripped to obtain a third spent catalyst. The device according to any one of claims 11-14, wherein the device further comprises a dehydration and desalination unit, wherein the hydrocarbon-containing feed oil is subjected to desalination and dehydration treatment, and the obtained dehydrated and desalted hydrocarbon-containing feed oil is introduced into The hydrocarbon-containing raw oil cutting unit performs cutting. The device according to any one of claims 11-15, wherein, in the second upward reaction unit, the position where the continuous catalyst and the second stream of catalyst are introduced is upstream of the feed inlet of the light olefin fraction. The device according to any one of claims 11-15, wherein, in the second upward reaction unit, the feed port of the light olefin fraction from the separation unit is upstream of the feed port of the heavy distillate oil.