阅读说明：本技术 一种石油烃原料催化转化制烯烃和芳烃的方法及其装置 (Method and device for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material ) 是由 石宝珍 李荻 郭江伟 于 2020-07-09 设计创作，主要内容包括：本发明涉及一种石油烃原料催化转化制烯烃和芳烃的方法,属于石油烃类催化转化技术领域。所述方法采用重质石油烃原料分别在第一反应再生系统和第二反应再生系统进行催化转化,原料先第一反应再生系统的第一催化剂环境下催化转化,生成的气相产品全部或部分进入第二反应再生系统,在第二催化剂环境下,依次进行次高温反应和高温反应,制备乙烯丙烯和芳烃。本发明设置了逐渐升温的三级温度梯度串联即第一反应器低温区、第二反应器次高温区和第二反应器高温区,同时为低温裂解和高温裂解分别配置适宜的专用催化剂,实现双反应系统和双催化剂循环,提高了高价值目的产品乙烯和丙烯的收率。(The invention relates to a method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw materials, belonging to the technical field of catalytic conversion of petroleum hydrocarbons. The method comprises the steps of carrying out catalytic conversion on a heavy petroleum hydrocarbon raw material in a first reaction regeneration system and a second reaction regeneration system respectively, carrying out catalytic conversion on the raw material in a first catalyst environment of the first reaction regeneration system, allowing all or part of generated gas-phase products to enter the second reaction regeneration system, and carrying out secondary high-temperature reaction and high-temperature reaction in sequence in a second catalyst environment to prepare ethylene propylene and aromatic hydrocarbon. The invention arranges three-stage temperature gradient series connection of gradual temperature rise, namely a first reactor low-temperature area, a second reactor secondary high-temperature area and a second reactor high-temperature area, and simultaneously respectively configures proper special catalysts for low-temperature cracking and high-temperature cracking, thereby realizing double-reaction system and double-catalyst circulation and improving the yield of high-value target products ethylene and propylene.)

1. A method for preparing olefin and aromatic hydrocarbon by petroleum hydrocarbon raw material catalytic conversion, heavy petroleum hydrocarbon raw material (R12) carries on the catalytic conversion in first reaction regeneration system and second reaction regeneration system separately, the first reaction regeneration system uses the first catalyst, the second reaction regeneration system uses the second catalyst; the method is characterized in that: the method comprises the following steps:

(1) the method comprises the steps of firstly, carrying out catalytic conversion on a raw material in a first reaction regeneration system, enabling the raw material to enter a first reactor (R10), and carrying out catalytic cracking reaction under the environment of a first catalyst from a first regenerator (G10), wherein the reaction temperature of a reactor outlet of the first reactor (R10) is 490-600 ℃, the reaction time is 0.5-5.0 s, and the absolute pressure of the reaction pressure is 0.23-0.50 MPa; after the stream formed by the reaction in the first reactor (R10) enters a first settler (D10) to separate out the first catalyst, a first reaction system product (R14) is formed; the first catalyst separated by the first settler (D10) enters a first regenerator (G10) for regeneration after being stripped in a first stripping section (S10) and is recycled;

(2) the first reaction system product (R14) or the light component (R14G) of the first reaction system product after the heavy component is separated enters a second reactor (R20) of an upper partition and a lower partition of a second reaction regeneration system to be continuously subjected to catalytic conversion, the light component enters the bottom of a second high-temperature reaction zone (R27) first, and is subjected to second high-temperature reaction under the environment of a second catalyst I introduced from a second regenerator (G20) through a second regeneration vertical pipe I (G24), the reaction temperature is 520-600 ℃, the reaction time is 0.1-5.0 s, and the absolute pressure of the reaction pressure is 0.22-0.40 MPa; the product and the catalyst in the secondary high-temperature reaction zone (R27) flow upwards and enter the high-temperature reaction zone (R28), and the high-temperature reaction with further increased temperature is carried out under the environment of a second catalyst II introduced from a second regenerator (G20) through a second regeneration vertical pipe II (G22), the reaction temperature is 550-750 ℃, the reaction time is 0.1-5.0 s, and the absolute pressure of the reaction pressure is 0.20-0.40 MPa; after the material flow formed by the reaction of the second reactor (R20) enters a second settler (D20) to separate the catalyst, a second reaction system product (R24) is obtained; the catalyst separated by the second precipitator (D20) enters a second regenerator (G20) for regeneration after being stripped in a second stripping section (S20) and is recycled.

2. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the first reaction system product (R14) is separated into heavy components through a separation tower or a fractionating tower to form a first reaction system product light component (R14G), and the first reaction system product light component (R14G) enters a second reaction regeneration system in a gas phase state.

3. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the heavy petroleum hydrocarbon raw material (R12) is one or a mixture of vacuum wax oil, atmospheric heavy oil, residual oil, coker wax oil, deasphalted oil, hydrogenated wax oil, hydrogenated residual oil, hydrogenated catalytic diesel oil, crude oil and condensate oil, and the boiling point is higher than 320 ℃.

4. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the petroleum hydrocarbon feedstock also includes an independent light hydrocarbon (R32);

or the light hydrocarbon (R32) directly enters a second reactor (R20) of a second reaction regeneration system to perform catalytic cracking reaction to prepare ethylene, or the light hydrocarbon (R32) enters a third reactor (R30) additionally arranged in the second reaction regeneration system, the third reactor (R30) and the second reactor (R20) share a second settler (D20) and a second regenerator (G20), and a material flow formed by the reaction of the light hydrocarbon (R32) in the third reactor (R30) enters the second settler (D20);

the light hydrocarbon is petroleum hydrocarbon with the boiling point lower than 360 ℃.

5. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 4, further comprising: the light hydrocarbon (R32) is naphtha and/or C4 components.

6. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 4, further comprising: when the light hydrocarbon (R32) is reacted in the second reactor (R20), the light hydrocarbon (R32) directly enters the high temperature reaction zone (R28).

7. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the active component of the first catalyst is selected from one or a mixture of HY, USY, REY, REHY, REUSY and H-ZSM-5; the active component of the second catalyst is selected from Y-type zeolite, L-type zeolite, ZSM-5 zeolite, beta zeolite, aluminum phosphate zeolite, mordenite, or one or a mixture of modified zeolites.

8. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the temperature of the second catalyst I introduced into the secondary high-temperature reaction zone (R27) through the second regeneration vertical pipe I (G24) is 660-820 ℃, and the temperature of the second catalyst II introduced into the high-temperature reaction zone (R28) through the second regeneration vertical pipe II (G22) is 700-850 ℃.

9. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the carbon content of the second catalyst I introduced into the secondary high-temperature reaction zone (R27) through the second regeneration vertical pipe I (G24) is lower than 0.15%, and the carbon content of the second catalyst II introduced into the high-temperature reaction zone (R28) through the second regeneration vertical pipe II (G22) is lower than 0.5%.

10. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: the second regenerator (G20) of the second reaction regeneration system is replenished with fuel (G28).

11. The process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 1, further comprising: when the light component (R14G) of the product of the first reaction system enters the second reaction regeneration system, the light component (R14G) of the product of the first reaction system exchanges heat with the product (R24) of the second reaction system, and the heated light component (R14G) of the product of the first reaction system enters the second reaction regeneration system for reaction.

12. A device for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material is provided with a first reaction regeneration system and a second reaction regeneration system, wherein the first reaction regeneration system is provided with a first reactor (R10), a first settler (D10), a first stripping section (S10) and a first regenerator (G10), and a heavy petroleum hydrocarbon raw material inlet (R12A) is arranged at the lower part of the first reactor (R10); the second reaction regeneration system is provided with a second reactor (R20), a second settler (D20), a second stripping section (S20) and a second regenerator (G20); -a flow line is provided between the first reaction gas product outlet (R14A) of the first settler (D10) and the bottom of the second reactor (R20), or a flow line is provided between the first reaction gas product outlet (R14A) and the bottom of the second reactor (R20), on which flow line a separation column or a fractionation column is simultaneously provided; the first reactor (R10) and the second reactor (R20) are selected from a riser, a fluidized bed, a circulating or fast fluidized bed single or hybrid reactor; the method is characterized in that:

the second reactor (R20) comprising a lower, secondary high temperature reaction zone (R27) and an upper high temperature reaction zone (R28); the second regenerant I inlet (R25A) at the lower part of the secondary high temperature reaction zone (R27) is communicated with the second regenerant I outlet (G24A) of the second regenerator (G20) through a second regeneration riser I (G24), and the second regenerant II inlet (R22A) at the lower part of the high temperature reaction zone (R28) is communicated with the second regenerant II outlet (G22A) of the second regenerator (G20) through a second regeneration riser II (G22).

13. The apparatus for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins and aromatics as recited in claim 12, wherein: the second reaction regeneration system is further provided with a third reactor (R30), the third reactor (R30) sharing a second settler (D20), a second stripping section (S20) and a second regenerator (G20) with the second reactor (R20); a light hydrocarbon feed inlet is arranged at the lower part of the third reactor (R30); a third reactor regenerant inlet (R35A) at the lower part of the third reactor (R30) is communicated with a second regenerant III outlet (G34A) of the second regenerator (G20) through a second regeneration riser III (G34).

Technical Field

The invention belongs to the technical field of petroleum hydrocarbon catalytic conversion, and particularly relates to a method for preparing olefin and aromatic hydrocarbon by catalytic conversion of a petroleum hydrocarbon raw material.

Background

The low-carbon olefin represented by ethylene and propylene is the most basic raw material in chemical industry, and the existing catalytic conversion technology is used for producing gasoline and diesel oil and simultaneously producing the low-carbon olefin as a byproduct, so that the requirement of the current market on organic chemical raw materials can not be met. Aromatic hydrocarbon is an important organic chemical raw material with the yield and the scale second only to ethylene and propylene, and derivatives thereof are widely used for producing chemical products such as chemical fibers, plastics, rubber and the like and fine chemicals, and with the continuous development of petrochemical industry and textile industry, the demand of aromatic hydrocarbon in the world is continuously increased. Natural gas or light petroleum fractions are mostly used as raw materials at home and abroad, low-carbon olefin is produced by adopting a steam cracking process in an ethylene combined device, and a large amount of other basic raw materials such as olefin, aromatic hydrocarbon and the like are produced as byproducts during the production of ethylene. Although the steam cracking technology is developed for decades and the technology is continuously improved, the steam cracking technology still has the advantages of high energy consumption, high production cost and CO₂The discharge amount is large, the product structure is not easy to adjust, and other technical limitations, and the traditional technology for producing ethylene and propylene by steam cracking is facing a severe test. The catalytic conversion method for preparing ethylene and the byproduct of low-carbon olefins such as propylene and butylene and chemical raw materials such as aromatic hydrocarbon are new ways to solve the problem of resource shortage and low-cost production of chemical products, and become important research subjects and hot problems at present.

In the aspect of preparing low-carbon olefins such as ethylene, propylene, butylene and the like by catalytic conversion, the following ideas are mainly provided:

1. the reaction raw material is divided into different fractions by a distillation tower, and the different fractions are respectively subjected to catalytic reaction in different reactors. For example, CN109575982A provides a method for preparing low-carbon olefins and aromatics by catalytic cracking of crude oil, which comprises desalting and dehydrating crude oil, heating in a heating furnace, and then feeding into a distillation tower to separate the crude oil into light and heavy components with a cutting point of 150-300 ℃; the light components coming out of the top of the tower and the heavy components coming out of the bottom of the tower contact and react with the high-temperature catalyst in the atmosphere of water vapor in the two reactors.

2. The materials in the reactor are fed and reacted layer by layer. For example, CN1898362 provides a method for producing light olefins and aromatics, in which a raw material is contacted with a catalytic cracking catalyst, the reaction is divided into at least two layers of feeding materials according to the nature of the raw material, and different liquid reaction products from a fractionating tower are returned to a reactor from different positions to be converted again except for target products. CN1215041A provides a method for preparing ethylene, propylene, aromatic hydrocarbon and the like by directly converting various feeding hydrocarbons, wherein a plurality of groups of feeding holes are arranged on a reactor, so that hydrocarbons with different properties enter a device from different feeding holes, and the cracking reaction is carried out under the same process conditions of all parts. CN104560154A provides a hydrocarbon catalytic conversion method for increasing the yield of light olefins and light aromatics, which comprises the following steps: contacting a heavy hydrocarbon raw material with a cracking catalyst in a first reactor to perform catalytic cracking reaction, and then separating to obtain a first carbon deposition catalyst and a first reaction product; injecting light hydrocarbon raw materials from the upstream of the second reactor, and injecting medium hydrocarbon raw materials from the middle part of the second reactor to perform catalytic cracking reaction; and introducing the reaction mixture generated in the second reactor into a third reactor for continuous reaction, and then separating to obtain a second carbon deposition catalyst and a second reaction product. Wherein the cracking catalyst is a cracking catalyst containing modified beta zeolite, and the modified beta zeolite is beta zeolite modified by phosphorus and transition metal M.

3. Outside the raw oil riser, additionally establishing a reactor to convert different fractions by catalysis again, namely adopting a multi-reactor form, carrying out conventional raw oil reaction in the first reactor, and feeding one or more fractions such as crude gasoline into the additionally established reactor for further conversion to obtain a target product after fractionation; for example, CN1388216 discloses a catalytic conversion method for preparing propylene, butylene and gasoline with low olefin content, comprising the following steps: (1) injecting preheated hydrocarbon oil (still liquid) into a riser, contacting and reacting with a catalyst containing pentasil zeolite and Y-type zeolite, and introducing an oil agent mixture into a fluidized bed through the riser; (2) injecting gasoline into the fluidized bed, contacting and reacting with the catalyst from the riser; (3) separating the oil mixture, stripping the reacted catalyst, regenerating in a regenerator, and returning the regenerated catalyst to the riser for reuse. The method can not only increase the yield of low-carbon olefin, but also produce high-quality gasoline with low olefin content. CN1258580C discloses a method and a system for upgrading gasoline by deeply reducing olefin and increasing octane number by catalytic conversion, wherein a catalytic upgrading reactor is added in a reaction-regeneration system of a heavy oil catalytic conversion device to perform catalytic upgrading reaction on gasoline fraction by catalytic conversion. The upgraded catalytically converted gasoline fraction may be a naphtha whole fraction, a naphtha light fraction or a naphtha heavy fraction obtained by establishing a secondary condensation system at the top of the fractionator.

4. The light raw material is used for producing low-carbon olefin. CN104557378A discloses a method for producing propylene by naphtha catalytic cracking. The method comprises the following steps: (1) under the pretreatment condition, contacting naphtha with a pretreatment agent to obtain treated oil with reduced alkaline nitrogen content; (2) and (2) under the condition of naphtha catalytic cracking reaction, contacting the treated oil and water obtained in the step (1) with a catalyst to obtain a catalytic cracking product.

5. In order to increase the yield of the light olefins, a 'cocatalyst' suitable for cracking the small-molecular hydrocarbons can be added, and the propylene can be increased by 1-1.5% by adding 5-8% of the heavy oil reaction catalyst.

The above technologies for reducing olefins by Fluidized Catalytic Conversion (FCC) and increasing the production of chemical feedstocks have some common drawbacks as follows:

1. different raw materials require different catalysts, heavy oil cracking requires high macromolecule cracking capability of the catalyst, and generally requires a larger aperture; c4 and C5 cracking need catalysts with low carbon olefin selectivity, and generally need smaller pore diameter; the prior art processes described above all use the same catalyst, i.e., only one catalyst. Although 5-8% of auxiliary agent can be added into the regenerator to further convert the small molecules in order to increase the yield of the low-carbon olefins, when the auxiliary agent is added into the FCC catalyst, the catalyst cracking activity is inevitably reduced due to the dilution effect on the catalyst. The heavy oil cracking conversion rate is reduced by 1 percentage point per 5% of the addition of the promoter, which is an important factor that seriously affects the economy of the FCC technology, and the improvement of the objective product is limited due to the low concentration of the promoter after mixing with the heavy oil cracking catalyst.

2. Because the second reaction system needs more reaction heat and generally has less coke formation, the heat generated by the regeneration of the coke formation can not provide the heat required by the reaction, and if the independent second reaction system is established by utilizing the prior art, the heat balance problem is restricted.

3. In all the recycling methods, the fraction is separated by a fractionating tower, cooled into liquid by heat exchange and then returned to the reactor, different fractions are firstly cooled into liquid by the heat exchange of the fractionating tower, and the liquid is returned to the original reactor or is further converted by another reactor directly after separation or after proper re-preheating (still liquid). Through the processes of cooling and heating, the investment of equipment and energy consumption is increased, and the economical efficiency of the process technology is greatly reduced.

4. The preparation of ethylene from petroleum hydrocarbon requires higher reaction temperature, generally higher than 600 ℃; the reaction process of catalytically preparing olefin from catalytically cracked material oil, especially heavy material oil, is a process of gradually cracking and gradually reducing molecular weight; smaller molecules are more difficult to activate, the required reaction temperature is higher, the temperature is high, and the thermal cracking reaction is naturally performed, so that the selectivity of a target product is influenced; how to allocate the reaction temperature and the molecular characteristics of petroleum hydrocarbon well, balance the catalytic cracking reaction and the thermal cracking reaction well, and have important significance for realizing the limit control of the reaction; the expected reaction process is that the specific gravity of catalytic reaction is increased as much as possible in the large molecule cracking stage of heavy oil and the like, thermal cracking is limited, the temperature is gradually increased in the small molecule cracking stage, and the proportion of thermal cracking reaction is increased; however, in the prior art, heat is provided in the inlet area of the reactor in the reaction process, the reaction is a gradual cooling process, particularly for the reaction for preparing ethylene, the reaction temperature is higher in the initial stage, namely the heavy oil cracking stage at the lower part of the reactor, and heavy components are directly subjected to thermal cracking reaction, so that the effect of catalytic cracking reaction is reduced.

CN101323798A (application No. 200810140866.7) discloses a catalytic conversion method, which is sequentially performed in a first reaction system and a second reaction system, wherein all or part of fractions generated after raw oil enters the first reaction system for catalytic reaction enter the second reaction system in a gaseous and/or liquid form for further catalytic reaction, and the first reaction system and the second reaction system respectively use corresponding catalysts according to the difference between the reaction raw material and the target product. The method overcomes the defects of poor selectivity, low auxiliary agent content, dilution effect on the catalyst and the like when a single catalyst is adopted by using two reaction systems and using a specific catalyst to carry out selective catalytic conversion on different fractions. However, the following problems still remain in this method:

no matter the raw oil of the first reaction system is cracked, or the gas-phase intermediate component of the second reaction system is further catalytically cracked, the heat in the reaction process is still provided in the inlet area of the reactor, the reaction is a gradual temperature rise process, the molecules are gradually reduced in the continuous reaction process of the intermediate component, and the heat condition for re-cracking the small molecules is insufficient in the rear section of the reactor, so that the production of high-value product ethylene is greatly reduced.

Disclosure of Invention

The invention aims to provide a method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw materials on the basis of the prior art, which adopts a double-reaction regeneration system and an upper and lower subarea reactor arranged in a second reaction regeneration system to carry out gradual temperature rise, three-stage temperature gradient double catalysis and gas phase relay catalytic conversion on heavy raw oil, can realize high-yield preparation of ethylene and propylene low-carbon olefin products, has low equipment investment and low energy consumption, and can be used for treating the heavy petroleum hydrocarbon raw materials or simultaneously treating the heavy petroleum hydrocarbon raw materials and light hydrocarbon raw materials to produce ethylene and propylene products and simultaneously produce aromatic hydrocarbon by-products. The invention also provides a device for preparing olefin and aromatic hydrocarbon by catalytic conversion of the petroleum hydrocarbon raw material.

The invention adopts the following technical scheme:

a method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material, the heavy petroleum hydrocarbon raw material is respectively subjected to catalytic conversion in a first reaction regeneration system and a second reaction regeneration system, the first reaction regeneration system uses a first catalyst, and the second reaction regeneration system uses a second catalyst; the method comprises the following steps:

(1) the method comprises the steps that raw materials are firstly subjected to catalytic conversion in a first reaction regeneration system, enter a first reactor, and undergo catalytic cracking reaction mainly comprising heavy petroleum hydrocarbon macromolecules under the environment of a first catalyst (or called a first regenerant or a first regenerated catalyst) from the first regenerator, wherein the reaction temperature of a reactor outlet of a first reactor R10 is 490-600 ℃, the reaction time is 0.5-5.0 s, and the absolute pressure of the reaction pressure is 0.23-0.50 MPa; when propylene is targeted and the ethylene yield is limited, the outlet temperature of the first reactor is preferably 490 ℃ to 545 ℃; after a material flow formed by the reaction of the first reactor enters a first settler and a first catalyst is separated out, a first reaction system product is formed; the first catalyst separated by the first settler enters a first regenerator for regeneration after being stripped in a first stripping section, and is recycled;

(2) the first reaction system product or the light component of the first reaction system product after the heavy component is separated enters a second reactor of an upper subarea and a lower subarea of a second reaction regeneration system to be continuously subjected to catalytic conversion, and firstly enters the bottom of a secondary high-temperature reaction zone, secondary high-temperature reaction is carried out in the environment of a second catalyst I (or called a second regenerant I or a second regenerated catalyst I) introduced from a second regenerator through a second regeneration vertical pipe I, the reaction temperature is 520-600 ℃, the reaction time is 0.1-5.0 s, the gas flow rate is 0.6-25 m/s, the absolute reaction pressure is 0.22-0.40 MPa, and the actual reaction temperature is controlled by the catalyst entering the secondary high-temperature reaction zone; enabling the product and the catalyst in the secondary high-temperature reaction zone to flow upwards and enter the high-temperature reaction zone, and carrying out high-temperature reaction with increased temperature under the environment of a second catalyst II (or called a second regenerant II or a second regenerated catalyst II) introduced from a second regenerator through a second regeneration vertical pipe II, wherein the reaction temperature is 550-750 ℃, the reaction time is 0.1-5.0 s, the gas flow rate is 0.6-30 m/s, the absolute pressure of the reaction pressure is 0.20-0.40 MPa, and the actual reaction temperature is controlled by the catalyst entering the high-temperature reaction zone; after the material flow formed by the reaction in the second reactor enters a second settler and the catalyst is separated out, a second reaction system product is obtained; and the catalyst separated by the second settler enters a second regenerator for regeneration after the second stripping section carries out steam stripping, and is recycled.

Drawings

FIG. 1 is a schematic process diagram according to one embodiment of the present invention;

FIG. 2 is a schematic process diagram according to a second embodiment of the present invention;

FIG. 3 is a schematic diagram of a third process according to an embodiment of the present invention;

FIG. 4 is a schematic diagram of a fourth process of the present invention;

FIG. 5 is a schematic diagram of a fifth process according to an embodiment of the present invention;

FIG. 6 is a schematic diagram of a sixth process of an embodiment of the present invention;

the numbering in the figures illustrates:

r10 first reactor; r11 catalyst pre-lift gas; R11A catalyst pre-lift gas inlet, R12 heavy petroleum hydrocarbon feedstock; an inlet of a R12A heavy petroleum hydrocarbon raw material, atomizing steam of a R13 raw material, a product of a R14 first reaction system, an outlet of a product of a R14A first reaction gas, a product liquid heavy component of the R14L first reaction system, R14L2 recycle oil, a hydrogenated heavy component of R14L3, a product light component of the R14G first reaction system, a R15 first regeneration slide valve, an inlet of a R15A first reactor regenerant, a R16A first standby riser, a R16 first standby slide valve and a R17 first reaction zone;

s10 first stripping section, S11 first stripping member;

a D10 first settler, a D11 first cyclone;

g10 first regenerator, G11 catalyst regeneration gas, G11A first regeneration gas inlet, G12A first regenerant inlet, G14A first regenerant outlet, G14 first regeneration standpipe; g15 first regenerator freeboard, G16 first regenerator cyclone, G17 first regenerator burnt flue gas, G17A first flue gas outlet.

The system comprises a R20 second reactor, a R21 times high-temperature reaction zone is supplemented with steam, a R22 second regeneration slide valve II, a R22A second regenerant II inlet, a R23 high-temperature reaction zone is supplemented with steam, a R24 second reaction system product, a R25 second regeneration slide valve I, a R25A second regenerant I inlet, a R26 second regenerant valve, a R26A second regenerant vertical pipe or a second spent catalyst vertical pipe, a R27 times high-temperature reaction zone and a R28 high-temperature reaction zone; r30 third reactor; r31 third reactor steam; r32 light hydrocarbons; r33 light hydrocarbon atomizing steam; r35 second regeneration slide valve iii, R35A third reactor regenerant inlet, R60 hydrogenation reactor; g20 second regenerator, G21 charring air, G21A charring gas inlet, G22 second regeneration vertical pipe II, G22A second regenerant II outlet, G24 second regeneration vertical pipe I, G24A second regenerant I outlet, G25 second regenerator dilute phase, G27 charred flue gas, G27A second flue gas outlet and G28 fuel; g34 second regeneration standpipe III, G34A second regenerant III outlet;

s20 second stripping section, S21 second stripping section components;

d20 second settler;

a T10 first reaction system product heavy component separation tower, a T20 fractionating tower and a T30 second fractionating tower; a1 Heat exchanger, B steam Generator, H₂Hydrogen gas;

f3 water, F4 steam, F21 liquefied gas and dry gas products, F22 gasoline component, F23 light cycle oil component (or LCO component), and F24 tower bottom heavy component; LS low-pressure steam;

TIC-1, TIC-2, TIC-3, and TIC-4, temperature display controls.

In particular, when propylene is targeted and ethylene is minimized, the preferred reaction temperature in the second high temperature reaction zone is 520 ℃ to 560 ℃ and the preferred reaction temperature in the high temperature reaction zone is 550 ℃ to 570 ℃.

In the method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material, further, the heavy component of the product of the first reaction system is separated by a separation tower or a fractionating tower to form the light component of the product of the first reaction system, and the light component of the product of the first reaction system enters the second reaction regeneration system in a gas phase state.

In the method for preparing olefins and aromatics by catalytic conversion of the petroleum hydrocarbon raw material, the heavy petroleum hydrocarbon raw material is one or a mixture of vacuum wax oil, atmospheric heavy oil, residual oil, coker wax oil, deasphalted oil, hydrogenated wax oil, hydrogenated residual oil, hydrogenated catalytic diesel oil, crude oil and condensate oil, and the boiling point of the heavy petroleum hydrocarbon raw material is higher than 320 ℃.

In the method for preparing olefins and aromatics by catalytic conversion of the petroleum hydrocarbon raw material, the petroleum hydrocarbon raw material further comprises independent light hydrocarbon;

or the light hydrocarbon directly enters a second reactor of the second reaction regeneration system to carry out catalytic cracking reaction to prepare ethylene, or the light hydrocarbon enters a third reactor additionally arranged in the second reaction regeneration system, the third reactor and the second reactor share a second settler and a second regenerator, and a material flow formed by the reaction of the light hydrocarbon in the third reactor enters the second settler;

the light hydrocarbon is petroleum hydrocarbon with the boiling point or the dry point lower than 360 ℃, and preferably, the light hydrocarbon is petroleum hydrocarbon with the boiling point lower than 320 ℃. In specific implementation, the preheating temperature of the heavy petroleum hydrocarbon raw material is 200-370 ℃, and the feeding temperature of the light raw material is 40-600 ℃.

In the above method for preparing olefins and aromatics by catalytic conversion of petroleum hydrocarbon feedstock, preferably, the light hydrocarbon is naphtha and/or C4, C5 components.

In the method for preparing olefins and aromatics by catalytic conversion of petroleum hydrocarbon raw materials, preferably, when the light hydrocarbon reacts in the second reactor, the light hydrocarbon directly enters the high-temperature reaction zone.

In the method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material, further, the active component of the first catalyst is selected from one or a mixture of HY, USY, REY, REHY, REUSY and H-ZSM-5, and belongs to a catalyst with high activity or strong catalytic capability for heavy raw oil catalytic cracking; the active component of the second catalyst is selected from one or a mixture of Y-type zeolite, L-zeolite, ZSM-5 zeolite, beta zeolite, aluminum phosphate zeolite and mordenite, or modified zeolite, and belongs to a catalyst with strong intermediate component or micromolecular cracking capability and high selectivity of low-carbon olefin.

The method for preparing the olefin and the aromatic hydrocarbon by catalytic conversion of the petroleum hydrocarbon raw material further comprises the steps of introducing the second catalyst I into the secondary high-temperature reaction zone through the second regeneration vertical pipe I at the temperature of 660-820 ℃, and introducing the second catalyst II into the high-temperature reaction zone through the second regeneration vertical pipe II at the temperature of 700-850 ℃.

The method for preparing olefin and aromatic hydrocarbon by catalytic conversion of petroleum hydrocarbon raw material further comprises the following steps that the carbon content of the second catalyst I introduced into the secondary high-temperature reaction zone through the second regeneration vertical pipe I is lower than 0.15%, and the carbon content of the second catalyst II introduced into the high-temperature reaction zone through the second regeneration vertical pipe II is lower than 0.5%.

In the method for preparing the olefin and the aromatic hydrocarbon by catalytic conversion of the petroleum hydrocarbon raw material, fuel is supplemented to a second regenerator of a second reaction regeneration system to supplement heat for the second reaction regeneration system.

Further, when the light components of the product of the first reaction system enter the second reaction regeneration system, the light components of the product of the first reaction system exchange heat with the product of the second reaction system, and the heated light components of the product of the first reaction system enter the second reaction regeneration system for reaction.

The invention also provides a device for realizing the method, and the device for preparing olefin and aromatic hydrocarbon by catalytic conversion of the petroleum hydrocarbon raw material adopts the following technical scheme:

arranging a first reaction regeneration system and a second reaction regeneration system, wherein the first reaction regeneration system is provided with a first reactor, a first settler, a first stripping section and a first regenerator, and the lower part of the first reactor is provided with a heavy petroleum hydrocarbon raw material inlet; the second reaction regeneration system is provided with a second reactor, a second settler, a second stripping section and a second regenerator; a material flow pipeline is arranged between the first reaction gas product outlet of the first settler and the bottom of the second reactor, or a material flow pipeline is arranged between the first reaction gas product outlet of the first settler and the bottom (or the lower part) of the second reactor, and a separation tower or a fractionating tower is simultaneously arranged on the material flow pipeline; the first reactor and the second reactor are selected from a riser, a fluidized bed, a circulating or fast fluidized bed single or composite reactor;

the second reactor is arranged in the form of an upper and lower partitioned reactor with upper and lower catalyst circulation paths and twice heat supply, and comprises a lower sub-high-temperature reaction zone and an upper high-temperature reaction zone; and a second regenerant I inlet at the lower part of the secondary high-temperature reaction zone is communicated with a second regenerant I outlet of the second regenerator through a second regeneration vertical pipe I, and a second regenerant II inlet at the lower part of the high-temperature reaction zone is communicated with a second regenerant II outlet of the second regenerator through a second regeneration vertical pipe II.

The device for preparing the olefin and the aromatic hydrocarbon by catalytic conversion of the petroleum hydrocarbon raw material is further provided with a light hydrocarbon feeding hole above the second regenerant II inlet of the high-temperature reaction zone, so that light hydrocarbon feeding is realized.

In the above apparatus for producing olefins and aromatics by catalytic conversion of petroleum hydrocarbon feedstock, the second reaction regeneration system is further provided with a third reactor R30, and the third reactor and the second reactor share a second settler, a second stripping section and a second regenerator; a light hydrocarbon feed inlet is formed in the lower part of the third reactor; and a third reactor regenerant inlet at the lower part of the third reactor is communicated with a second regenerant III outlet of the second regenerator through a second regeneration vertical pipe III.

The technical scheme of the invention is as follows:

1. in the first reaction regeneration system, a heavy petroleum hydrocarbon raw material or heavy raw oil is subjected to catalytic cracking reaction in a first reactor to preliminarily complete catalytic cracking conversion, decarburization and demetalization of heavy components and macromolecules of the heavy petroleum hydrocarbon to generate intermediate components mainly comprising liquefied gas, high-olefin gasoline and diesel oil components and form an intermediate raw material for preparing olefin;

in the invention, the reaction regeneration system is known and provided with a reactor, a settler, a steam stripping section and a regenerator, wherein the outlet of the reactor is communicated with a gas-solid separation device in the settler, the steam stripping section is arranged below the settler, the lower part of the steam stripping section is communicated with the regenerator through a stand pipe to be regenerated, and the regenerator is communicated with a regenerant inlet of the reactor through a regeneration stand pipe; in the specific implementation and arrangement: the reactor and the regenerator are preferably arranged in parallel, and the reactor and the settler can be coaxially arranged or arranged in parallel; the top of the settler is provided with a product outlet of the reaction system; one or more reactors can be arranged in one set of reaction regeneration system to meet the requirements of different raw materials, and the outlets of the reactors can be communicated with the same settler to carry out gas-solid separation operation on the reacted material flow; the lower part of the reactor is provided with a petroleum hydrocarbon feed inlet (a feed nozzle when liquid phase feeding is carried out), the feed inlet is arranged above or below a regenerant inlet of the reactor, and a lifting or fluidizing medium gas inlet is arranged at the bottom of the reactor. The conventional specific arrangement and connection positions of the reactor, the settler, the stripping section and the regenerator in the reaction regeneration system, and the inlet and outlet positions and specification requirements of various material flows can be grasped by engineering technicians, and are not described in detail below. As is known, the reaction process of the reactor using a reaction regeneration system in the form of a riser is as follows: the regenerated catalyst or called regenerating agent enters the lower part of the reactor through the regeneration vertical pipe, goes upward along the reactor, petroleum hydrocarbon enters the reactor through the feed inlet, contacts with the catalyst and flows upward together to realize reaction, the material flow after the reaction enters the settler to separate the catalyst, the product flows out through the product outlet, the catalyst enters the stripping section for stripping, and the spent catalyst or called spent agent enters the regenerator through the spent vertical pipe to realize regeneration and recycle.

2. In the implementation of the invention, the product of the first reaction system, although containing heavy components similar to oil slurry recycle oil, can directly enter the second reaction regeneration system in a gas phase state. The reaction for preparing the olefin requires high temperature of more than 600 ℃, and the core problem to be solved is that the reaction coke formation can not provide enough reaction heat; the first reaction regeneration system can conveniently provide heat by heating the raw materials, and the second reaction regeneration system can increase coke formation and realize heat supply because light components generate less coke, heat required by high-temperature cracking is more, and heat lacking in the second reaction regeneration system is more, and heavy components in the product of the first reaction system are properly introduced; part of heavy components enter the second reaction regeneration system, so that the heat is transferred from the first reaction regeneration system to the second reaction regeneration system skillfully, and other supplementary heat needed by the second reaction regeneration system is reduced; meanwhile, as all the gas phase enters the second reaction regeneration system without being cooled, more heat can be transferred to the second reaction regeneration system. In addition, from the view of reaction catalytic chemistry, the heavy component is well separated, but the separated heavy component can be liquefied only by taking heat and reducing the temperature, and meanwhile, the temperature of the light component is also reduced, so that the heat brought into a second reaction regeneration system is reduced, and as a result, the heat of the system is insufficient, and particularly, the second system needs to supplement more heat;

the heavy component can be separated from the product of the first reaction system, and the light component enters the second reaction regeneration system in a gas phase state, so that the reaction efficiency of the second reaction regeneration system is improved; all or part of the separated heavy components return to the first reaction regeneration system for continuous catalytic conversion, and the heavy components which do not return to the first reaction regeneration system are sent out of the device; heavy components separated from a product of the first reaction system are subjected to hydrogenation treatment, appropriate aromatic hydrocarbon ring opening and side chain saturation are carried out, the hydrogen content is increased, the properties of the heavy components are improved, and then the heavy components are returned to the first reaction regeneration system for reaction, so that the catalytic conversion efficiency of the first reaction regeneration system is improved;

the separated light components can exchange heat with a product stream of the second reaction regeneration system, and enter the second reaction regeneration system for continuous reaction after being heated;

heavy components are separated, and the heavy components can be separated through cooling of a heat exchange device; or the heavy components are separated by a fractionating tower (namely a fractionating system) or a separating tower, the fractionating tower or the separating tower is arranged in a material flow link between the product outlet of the first settler and the bottom of the second reactor, the fractionating tower or the separating tower is provided with a tower bottom reflux device or a device combining the tower bottom reflux and the middle heat exchange, and the fractionating tower or the separating tower separates the heavy components by the way of combining the tower bottom heat exchange or the tower bottom heat exchange and the middle heat exchange; separation of heavy components is a common process and is well known to engineering designers. It is known that a fractionating column and a separating column both work on the basis of the principle of fractionation to separate components, both according to different boiling points, the fractionating column has a side product in addition to separating the components into gas and liquid components, and the separating column only separates the gas and liquid components without a side product.

3. When the heavy component separated from the product of the first reaction system returns to the first reaction system for continuous reaction, the heavy component enters the first reactor again for reaction or enters an additional independent reactor for reaction, the cutting temperature of the heavy component is controlled according to the boiling point of 350-360 ℃, and part or all of the high-boiling component returns to the first reaction regeneration system; or the heavy component cutting temperature is controlled according to the boiling point of 480-500 ℃, and the components with the boiling point higher than 480-500 ℃ are separated and then sent out of the device or returned to the first reaction regeneration system after being subjected to hydrogenation treatment.

4. In the invention, heavy raw oil reacts in sequence under the condition of three-stage temperature gradient to prepare ethylene and propylene, firstly the heavy raw oil enters a first reaction zone, namely a low-temperature reaction zone in a first reaction regeneration system to carry out cracking reaction, and all or part of generated components enter a second high-temperature reaction zone and a high-temperature reaction zone of a second reaction regeneration system in sequence in a gaseous form to carry out cracking reaction; the method comprises the following specific steps:

in the second reaction regeneration system, at least one reactor, namely the second reactor, is provided with an upper stage and a lower stage of heat supply and catalyst circulation, the second reactor is divided into an upper reaction zone and a lower reaction zone by the catalyst and the heat supply position, namely a regenerant inlet II, at the upper part, the lower part is a secondary high-temperature reaction zone, and the upper part is a high-temperature reaction zone; heat is provided by the catalyst entering the upper part of the second reactor, and the catalyst further improves the reaction temperature and the catalyst-to-oil ratio to form high-temperature reaction; the selective reaction in the upper and lower reactors of two-stage heat supply and two-stage catalyst supply is realized, the reaction mode of gradually rising reaction temperature is adapted to the molecular structure of the reactant with gradually reduced molecular weight and the change of the requirement on the reaction condition, and the efficiency of preparing ethylene and propylene and the selectivity of products at different levels are improved;

in the second reactor, the material firstly enters a secondary high-temperature reaction zone to carry out catalytic cracking reaction mainly for converting the residual heavier components or larger molecules and intermediate components to C3-C8; and the product and the catalyst in the secondary high-temperature area flow upwards to enter a high-temperature reaction area, and then a new catalyst is supplemented, heat is provided, the temperature is increased, and then the catalytic cracking and thermal cracking combined reaction is continuously carried out to generate an olefin product.

5. In the invention, the temperature of the second catalyst I introduced through the second regeneration vertical pipe I and the temperature of the second catalyst II introduced through the second regeneration vertical pipe II can be the same or different; the second regenerator can adopt single-stage regeneration or multi-stage regeneration when being implemented, preferably adopt the two-stage regeneration form of upper and lower series connection used in the embodiment, the second spent catalyst from the second stripping section firstly enters a first-stage regeneration zone from the lower part of the second regenerator, contacts and reacts with the charring air, flows upwards and enters a second-stage regeneration zone to be regenerated continuously, and supplements fuel in the first-stage regeneration zone or the second-stage regeneration zone to realize regenerator heat supplement; the second regenerant II is from a second stage regeneration zone, and the second regenerant I is from either the second stage regeneration zone or the first stage regeneration zone.

6. In the first reaction regeneration system, the mass ratio of the steam used by the first reactor to the raw oil is 5-30%, in the second reaction regeneration system, the mass ratio of the supplemented steam to the second reactor to the raw oil is 5-30%, and the mass ratio of the steam to the raw oil in the reaction process of the second reaction regeneration system is 15-50%; the steam supplemented to the second reaction regeneration system is supplemented in the second high-temperature reaction zone or respectively supplemented in the second high-temperature reaction zone and the high-temperature reaction zone.

7. The treatment of the product of the second reaction system after flowing out of the second settler is a conventional engineering process, which relates to product quenching, heat exchange, fractionation and the like, if a steam generator can be arranged at the outlet of the second settler of the second reaction regeneration system, steam is generated by utilizing the heat of high-temperature product material flow, and the engineering design unit of the steam generator is mastered; or the low-temperature medium can be directly mixed with the product material flow to realize the quenching and cooling of the product; as is known to the engineer.

Has the advantages that:

the invention provides a method for preparing ethylene and propylene by gradual temperature rise, three-stage temperature gradient dual catalysis and gas phase relay conversion based on a catalytic cracking mechanism. As is well known to those skilled in the art, the heavy oil catalytic cracking process can be regarded as a parallel sequential reaction, heavy oil macromolecules (C18 or more) are firstly cracked to generate middle molecular (C5-C12) products such as gasoline, diesel oil and the like, and the lower cracking temperature can highlight the catalytic cracking reaction, generally 490-530 ℃; part of gasoline and diesel oil is cracked into C3-C8 at 530-600 deg.c; at higher temperature, 600-750 ℃, C3-C8 will further crack into C1, C2, C3 small molecule products. The invention follows the reaction rule and arranges three-stage temperature gradient series connection with gradual temperature rise: a low temperature zone, a sub-high temperature zone, a high temperature zone; simultaneously, proper special catalysts are respectively prepared for low-temperature cracking and high-temperature cracking, a double reaction system is arranged, and double catalysts circulate to strive for exerting the maximum effectiveness of the catalysts; the raw material gas phase relay also provides heat for the second reaction regeneration system to make up for the heat deficiency. The invention reduces the yield of low-value target products such as coke and dry gas on the premise of lower energy consumption; the yield of high-value target products such as ethylene and propylene is improved.

Specifically, the method comprises the following steps:

the second reaction regeneration system adopts a three-stage temperature gradient scheme of two-stage heat supply and formation of a low-temperature reaction of the first reaction regeneration system and a second high-temperature reaction and a high-temperature reaction of the second reaction regeneration system, so that the temperature gradually rises along with the reaction, the molecules gradually become smaller with the gradual cracking of petroleum hydrocarbon along with the reaction, the required cracking energy level is gradually increased, the required temperature gradually rises to adapt to the gradual cracking, the efficiency of preparing ethylene and propylene by cracking is improved, and the selectivity of a target product is also improved;

compared with the conventional catalytic cracking, the method of the invention realizes multiple catalytic conversion reactions of heavy raw oil by two reaction regeneration systems, and can use different catalysts according to specific feeding properties and product requirements due to the fact that the catalytic conversion reactions are carried out in different reaction regeneration systems, thereby increasing the selectivity and improving the efficiency, for example, raw oil can be decarbonized, demetallized and cracked with heavy oil in a first reaction system, and a catalyst suitable for small molecule reaction is used in a second reaction regeneration system to further carry out catalytic conversion to produce chemical raw materials such as ethylene, propylene, aromatic hydrocarbon and the like. In addition, all or part of fractions from the first reaction regeneration system directly enter the second reaction regeneration system in a gaseous state, so that more heat is provided for the second reaction regeneration system, the requirement on heat supply capacity is reduced, the problem of insufficient heat caused by insufficient coke generation of the second reaction regeneration system is solved, and the method that the fractions are cooled and separated firstly and then preheated and returned to the reactor is changed, so that the equipment investment is greatly saved, and the energy consumption is reduced;

according to the invention, two reaction regeneration systems are used, and a specific catalyst is used for carrying out selective catalytic conversion on different raw material components, so that the defects of poor selectivity, low auxiliary agent content, dilution effect on the catalyst and the like when a single catalyst is adopted are overcome, the yield of chemical raw materials such as ethylene, propylene and the like can be improved, and the product yield can be improved;

the heavy components of the product of the first reaction system are separated, so that the selection of the catalyst of the second reaction regeneration system and the adjustment of reaction conditions are facilitated, and the catalytic cracking reaction effect of the light components and the recovery of the target product are facilitated to be improved.