CN111807918B

CN111807918B - Method and device for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material

Info

Publication number: CN111807918B
Application number: CN202010658106.6A
Authority: CN
Inventors: 石宝珍; 李荻; 郭江伟
Original assignee: Qingdao Jingrun Petrochemical Design & Research Institute Co ltd
Current assignee: Qingdao Jingrun Petrochemical Design & Research Institute Co ltd
Priority date: 2020-07-09
Filing date: 2020-07-09
Publication date: 2022-12-02
Anticipated expiration: 2040-07-09
Also published as: CN111807918A

Abstract

The invention relates to a method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw materials, belonging to the technical field of catalytic conversion of petroleum hydrocarbons. The method adopts heavy petroleum hydrocarbon and hydrocracking tail oil as raw materials to produce olefin, the heavy petroleum hydrocarbon is firstly subjected to catalytic conversion in the first catalyst environment of a first reaction regeneration system, part or all of generated gas-phase products enter a second reaction regeneration system, and the gas-phase products and the hydrocracking tail oil are subjected to secondary high-temperature reaction and high-temperature reaction in the second catalyst environment to prepare the olefin. The invention arranges three-stage temperature gradient series connection of gradual temperature rise, namely a low-temperature area of a first reactor, a secondary high-temperature area of a second reactor and a high-temperature area of the second reactor, 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.

Description

Method and device for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material

Technical Field

The invention belongs to the technical field of petroleum hydrocarbon catalytic conversion, and particularly relates to a method for preparing olefin 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 second only to ethylene and propylene in yield and scale, derivatives of the aromatic hydrocarbon are widely used for producing chemical products and fine chemicals such as chemical fibers, plastics, rubber and the like, and the demand of the aromatic hydrocarbon in the world is continuously increased along with the continuous development of petrochemical industry and textile industry. 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 energy consumption is high, and the production cost is highHigh, CO ₂ The discharge amount is large, the product structure is not easy to adjust, and the like, and the traditional technology for producing ethylene and propylene by steam cracking faces severe tests. The catalytic conversion method is used for preparing olefins, and meanwhile, the by-products of chemical raw materials such as low-carbon olefins such as propylene and butylene, and aromatic hydrocarbons are new directions for solving the problems 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 light olefins and aromatics by catalytic cracking of crude oil, wherein the crude oil is desalted and dehydrated, then enters a heating furnace for heating, then enters a distillation tower for separating the crude oil into light and heavy components, and the cutting point is between 150 ℃ and 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 properties of the raw material, and different liquid reaction products from a fractionating tower return to a reactor from different positions for conversion again except for target products. CN1215041A provides a method for preparing ethylene, propylene, aromatic hydrocarbon and the like by directly converting various feed hydrocarbons into olefins, and a reactor is provided with a plurality of groups of feed inlets, so that hydrocarbons with different properties enter a device from different feed inlets, and are subjected to cracking reaction under the same process conditions of all parts. CN104560154A provides a hydrocarbon catalytic conversion method for producing light olefins and light aromatics in high yield, 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 to continue reacting, 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, which is to add a catalytic upgrading reactor in a reaction-regeneration system of a heavy oil catalytic conversion device to carry out 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 low-carbon olefin, an auxiliary catalyst suitable for cracking small-molecular hydrocarbons can be added, and 1-1.5% of propylene can be added, wherein the amount of the auxiliary catalyst is generally 5-8% of that of a heavy oil reaction catalyst.

The above technologies for reducing olefins by Fluidized Catalytic Conversion (FCC) and increasing the production of chemical raw materials 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; the cracking of C4 and C5 requires a catalyst with low carbon olefin selectivity, and generally requires a 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 cracking activity of the catalyst 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 650 ℃; 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 temperature reduction process, particularly for the reaction for preparing olefin, the reaction temperature is higher in the initial stage, namely the heavy oil cracking stage at the lower part of the reactor, because of the high reaction temperature, the heavy components are directly subjected to thermal cracking reaction, and the effect of catalytic cracking reaction is reduced.

CN200810140866.7 discloses a catalytic conversion method, which is carried out in a first reaction system and a second reaction system in sequence, all or part of fractions generated after raw oil enters the first reaction system for catalytic reaction enter the second reaction system in a gas state and/or a liquid state for further catalytic reaction, and the first reaction system and the second reaction system respectively use corresponding catalysts according to the difference of reaction raw materials and target products. 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.

In addition, with the increasing of the heavy degree of crude oil and the increasing of the demand for clean fuels, china has built a plurality of large hydrocracking units, and the hydrocracking processing capacity is higher. As the raw materials are hydrofined before the cracking reaction, non-hydrocarbon impurities such as sulfur, nitrogen and the like are removed, and reactions such as aromatic saturation, ring opening, dealkylation, isomerization and the like are simultaneously carried out, after the crude oil is subjected to hydrocracking treatment, the content of tail oil, namely hydrocracking tail oil saturated hydrocarbon (mainly C20-C30 normal paraffin) is up to over 96.8 percent, the content of aromatic hydrocarbon is less than 1 percent, and the content of impurities such as sulfur, nitrogen, metal and the like is low, thus the tail oil is high-quality oil. The hydrocracking tail oil is reasonably utilized, and the method is a new choice for oil refining enterprises. Compared with heavy petroleum hydrocarbon, the hydrocracking tail oil is easy to produce ethylene by catalytic cracking at high temperature due to long chain and high hydrocarbon content, and accounts for 10-30% of the raw material for producing ethylene.

Disclosure of Invention

The invention aims to provide a method for preparing olefin by catalytic conversion of a petroleum hydrocarbon raw material on the basis of the prior art, which takes a heavy petroleum hydrocarbon raw material and hydrocracking tail oil as raw materials, adopts a double-reaction regeneration system and arranges an upper and a lower subarea reactors in a second reaction regeneration system, and carries out gradual temperature rise, three-stage temperature gradient double catalysis and gas phase relay catalytic conversion on the heavy petroleum hydrocarbon raw material and the hydrocracking tail oil, thereby realizing high-yield preparation of the olefin, and having low equipment investment and low energy consumption. The invention also provides a device for preparing olefin by catalytic conversion of the petroleum hydrocarbon raw material.

The invention adopts the following technical scheme:

a method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, taking heavy petroleum hydrocarbon and hydrocracking tail oil as raw materials, carrying out catalytic conversion in a first reaction regeneration system and a second reaction regeneration system to prepare olefin, wherein 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 heavy petroleum hydrocarbon is firstly subjected to catalytic conversion in a first reaction regeneration system, enters a first reactor, and is subjected to catalytic cracking reaction in the environment of a first catalyst from the first regenerator, wherein the reaction temperature of the reactor outlet of the first reactor 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 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; the first reactor outlet reaction temperature is optimized to 490 c to 550 c when propylene is the objective and ethylene is minimized.

(2) The first reaction system product or the light component of the first reaction system product after heavy component separation and the hydrocracking tail oil R32 enter a second reaction regeneration system for catalytic conversion;

the first reaction system product or the light component of the first reaction system product and the hydrocracking tail oil enter a second reactor of an upper zone and a lower zone of a second reaction regeneration system to carry out catalytic conversion in any mode:

the first catalytic conversion mode: the first reaction system product or the light component of the first reaction system product firstly enters the bottom of a secondary high-temperature reaction zone of a second reactor, the secondary high-temperature reaction mainly comprising the catalytic cracking of the heavy component or the larger molecule and the intermediate component is carried out under 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 reaction pressure is 0.20-0.40 MPa, the actual reaction temperature is controlled by the catalyst entering the secondary high-temperature reaction zone, the product and the catalyst in the secondary high-temperature reaction zone flow upwards to enter the high-temperature reaction zone of the second reactor and are mixed with the hydrocracking tail oil directly entering the high-temperature reaction zone, the catalytic cracking and thermal cracking combined high-temperature reaction with the increased temperature is carried out under the environment of a second catalyst II (or called a second regenerant II or a second catalyst II) introduced from the second regenerator through the second regeneration vertical pipe II, the high-temperature reaction zone is carried out, the high-temperature reaction of the catalytic cracking and the thermal cracking combined high-temperature reaction is carried out, the conversion of the intermediate component to ethylene and propylene, the ethylene and propylene is formed, the ethylene and propylene conversion temperature is controlled by the reaction time of 0.0.5-0.5 MPa, the actual reaction zone, the reaction time is controlled by the reaction zone, and the reaction time of 0.0.0.0-0.20-0.40 MPa;

and a second catalytic conversion mode: the first reaction system product or the light component of the first reaction system product directly reacts in a high-temperature reaction zone, the hydrocracking tail oil firstly enters a secondary high-temperature reaction zone for secondary high-temperature reaction, then flows upwards with a catalyst to enter the high-temperature reaction zone, and is mixed with the first reaction system product or the light component of the first reaction system product directly entering the high-temperature reaction zone for high-temperature reaction; and (3) a catalytic conversion mode III: directly feeding the first reaction system product or the light components of the first reaction system product and the hydrocracking tail oil into a secondary high-temperature reaction zone for secondary high-temperature reaction, and then feeding the product and the catalyst to the high-temperature reaction zone for continuous reaction;

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 mainly comprising ethylene, propylene and aromatic hydrocarbon is obtained; the catalyst separated by the second settler enters a second regenerator for regeneration after being stripped in a second stripping section, and is recycled;

or the first reaction system product or the light component of the first reaction system product enters a second reactor of an upper and lower subarea of a second reaction regeneration system, and reacts in a secondary high-temperature reaction zone and a high-temperature reaction zone in sequence, and meanwhile, the hydrocracking tail oil reacts in a third reactor independent of the second reaction regeneration system; the first reaction system product or light component firstly enters the bottom of a secondary high-temperature reaction zone, a secondary high-temperature reaction is carried out in the environment of a second catalyst I introduced from a second regenerator through a second regeneration vertical pipe I, the product and the catalyst in the secondary high-temperature reaction zone flow upwards and enter the high-temperature reaction zone, the high-temperature reaction with the temperature rise is carried out in the environment of a second catalyst II introduced from the second regenerator through a second regeneration vertical pipe II, the hydrocracking tail oil enters the lower part of a third reactor, and the high-temperature reaction mainly comprising the catalytic cracking of larger molecules is carried out in the environment of a second catalyst III (or called second regenerant III or second regenerated catalyst III) introduced from the second regenerator through a second regeneration vertical pipe III, wherein the reaction temperature of the third reactor is 550-720 ℃, the reaction time is 0.5-5.0 s, and the absolute pressure of the reaction pressure is 0.2-0.4 MPa; after the material flow formed by the reaction of the second reactor and the third reactor enters a second settler and the catalyst is separated out, a second reaction system product mainly comprising ethylene, propylene and aromatic hydrocarbon 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.

When propylene is taken as a target and ethylene is reduced as much as possible, the reaction temperature of the secondary high-temperature reaction zone is 520-560 ℃, and the reaction temperature of the high-temperature reaction zone is 550-570 ℃;

the gas flow velocity in the secondary high-temperature reaction zone is 0.6-25 m/s, and the gas flow velocity in the high-temperature reaction zone is 0.6-30 m/s.

In the method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, 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 olefin by catalytic conversion of petroleum hydrocarbon raw material, the heavy petroleum hydrocarbon raw material is one or a mixture of vacuum wax 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 ℃.

In the method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, 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.

The method for preparing olefin by catalytic conversion of 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 ℃.

In the method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, 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 producing olefins by catalytic conversion of petroleum hydrocarbon feedstock, the second regenerator of the second reaction regeneration system is further supplemented with fuel.

In the method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, further, when the light component of the product of the first reaction system enters the second reaction regeneration system, the light component of the product of the first reaction system exchanges heat with the product of the second reaction system, and the heated light component of the product of the first reaction system enters the second reaction regeneration system for reaction.

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

the first technical scheme is as follows: a device for preparing olefin 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, 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 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 second reactor, or a material flow pipeline is arranged between the first reaction gas product outlet and the second reactor, and a separation tower or a fractionating tower is arranged on the material flow pipeline at the same time; the first reactor and the second reactor are selected from a riser, a single reactor of a fluidized bed or a 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; 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;

a hydrocracking tail oil inlet is formed in the bottom of the secondary high-temperature reaction zone, and the material flow pipeline is arranged between a first reaction gas product outlet and the bottom of the high-temperature reaction zone; or a hydrocracking tail oil inlet is arranged at the bottom of the high-temperature reaction zone, and the material flow pipeline is arranged between the first reaction gas product outlet and the bottom of the secondary high-temperature reaction zone;

the second technical scheme is as follows: a device for preparing olefin hydrocarbon through catalytic conversion of petroleum hydrocarbon raw materials 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, 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 inlet; the second reaction regeneration system is provided with a second reactor, a second settler, a second stripping section, a second regenerator and a third reactor; 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 and the bottom of the second reactor, and a separation tower or a fractionating tower is arranged on the material flow pipeline at the same time; the first reactor and the second reactor are selected from a riser, a single reactor of a fluidized bed or a 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; 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 third reactor and the second reactor share a second settler, a second stripping section and a second regenerator, and a second regenerant III 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; and a hydrocracking tail oil inlet is formed in the bottom of the third reactor.

The technical scheme of the invention is as follows:

1. in the first reaction regeneration system, heavy petroleum hydrocarbon or heavy raw oil is firstly subjected to catalytic cracking reaction in a first reactor, catalytic cracking conversion, decarburization and demetalization of heavy components and macromolecules of the heavy petroleum hydrocarbon are preliminarily completed, and an intermediate component mainly comprising high-olefin gasoline and diesel oil components is generated to 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 port (a feed nozzle when liquid phase feeding is carried out), the feed port 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. When the method is implemented specifically, heavy components are preferentially separated from the product of the first reaction system, 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;

heavy components are separated, and the heavy components can be separated through cooling of a heat exchange device; or separating heavy components through a fractionation system, wherein the fractionation system is arranged on a material flow pipeline between a product outlet of the first settler and the bottom of the second reactor, the fractionation system is provided with a tower bottom reflux device or a device combining tower bottom reflux and middle heat exchange, and the fractionation system separates the heavy components through the mode combining tower bottom heat exchange or tower bottom heat exchange and middle section heat exchange; separation of heavy components is a common process and is well known to engineering designers.

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 ℃, and part or all of the components with the boiling points higher than 350 ℃ return to the first reaction regeneration system; or the heavy component cutting temperature is controlled according to the boiling point of 480 ℃, and the components with the boiling point higher than 480 ℃ are sent out of the device after being separated or returned to the first reaction regeneration system after being subjected to hydrogenation treatment.

4. In the invention, petroleum hydrocarbon raw materials react to prepare olefin under the condition of three-stage temperature gradient, firstly, heavy petroleum hydrocarbon enters a first reaction zone, namely a low-temperature reaction zone in a first reaction regeneration system to carry out cracking reaction, all or part of generated components enter a second reaction regeneration system in a gaseous state, and enter the second reaction regeneration system together with hydrocracking tail oil 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 an upper catalyst and heat supply position, namely a second regenerant II inlet, 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 reaction temperature and the catalyst-to-oil ratio are further increased by the catalyst 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 reactants with gradually reduced molecular weight and the change of the requirement on reaction conditions, and the efficiency of olefin production 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; the product of the secondary high-temperature area and the catalyst 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 combined reaction of catalytic cracking and thermal cracking is continuously carried out to generate an ethylene propylene product;

in the mode of feeding the material into the second reactor, or the hydrocracking tail oil directly reacts in the high-temperature reaction zone, or the gaseous material of the first reaction system directly reacts in the high-temperature reaction zone, or the hydrocracking tail oil and the gaseous material of the first reaction system simultaneously and sequentially react in the secondary high-temperature reaction zone and the high-temperature reaction zone, and within the preferable implementation parameter range of the invention, a person skilled in the art can select proper implementation conditions, so that the distribution of the catalytic conversion products for improving the yield of the olefin is obtained.

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 precipitator is a conventional engineering process, which relates to product quenching, heat exchange, fractionation and the like, if a steam generator can be arranged, steam is generated by utilizing the heat of high-temperature product material flow, and the engineering design unit of the steam generator is mastered; the product can be quenched and cooled by directly mixing a low-temperature medium with the product material flow; as is known to the engineer.

Has the advantages that:

the invention provides a method for preparing olefin 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 (not less than C18) are firstly cracked to generate medium molecule (C5-C12) products such as gasoline, diesel oil and the like, and the catalytic cracking reaction can be highlighted by a lower cracking temperature, which is usually 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 be further cracked into C1, C2, C3 small molecular 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 the high-value target product olefin is improved.

Specifically, the method comprises the following steps:

the second system adopts a three-level temperature gradient scheme of two-level heat supply and formation of a low-temperature reaction of the first system and a second high-temperature and high-temperature reaction of the second system, so that the temperature is gradually increased along with the reaction, the petroleum hydrocarbon is gradually cracked, molecules are gradually reduced along with the reaction, the required cracking energy level is gradually increased, and the required temperature is gradually increased; the efficiency of cracking to olefin is improved, and the selectivity of the target product is also improved;

compared with the conventional catalytic cracking, the method of the invention can use different catalysts according to the specific feeding property and the product requirement due to the fact that the catalytic conversion reaction of the heavy petroleum hydrocarbon raw material and the hydrocracking tail oil is realized through two reaction regeneration systems, thereby increasing the selectivity and improving the efficiency, for example, the heavy petroleum hydrocarbon can be subjected to decarburization, demetalization and heavy oil cracking in the first reaction system, and the catalyst suitable for small molecule reaction is used in the second reaction regeneration system for further catalytic conversion to produce chemical raw materials such as ethylene, propylene and the like. In addition, as all or part of fractions from the first reaction regeneration system directly enter the second reaction regeneration system in a gaseous state, 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 need to be cooled and separated firstly and then preheated again and then 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 more convenient, and the catalytic cracking reaction effect of the light components and the recovery of the target product are favorably improved.

Drawings

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

FIG. 2 is a schematic process diagram of 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;

the numbering in the figures illustrates:

r10 first reactor; r11 catalyst pre-lift gas; an R11A catalyst pre-lift gas inlet, R12 heavy petroleum hydrocarbon; an R12A heavy petroleum hydrocarbon inlet, R13 raw material atomized steam, an R14 first reaction system product, an R14A first reaction gas product outlet, an R14L first reaction system product liquid heavy component, an R14G first reaction system product light component, an R15 first regeneration slide valve, an R15A first reactor regenerant inlet, an R16A first stand pipe to be regenerated, an R16 first slide valve to be regenerated and an R17 first reaction zone;

s10, a first stripping section, S11, a first stripping component;

a first settler, a first cyclone separator D11;

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 a dilute phase zone of a first regenerator, G16 a cyclone separator of the first regenerator, G17A flue gas generated after the first reactor is burnt, and G17A a first flue gas outlet;

r20 of a second reactor, R21 times of high-temperature reaction zone is supplemented with steam, R22 of a second regeneration slide valve II, R22A of a second regenerant II inlet, R23 of high-temperature reaction zone is supplemented with steam, R24 of a second reaction system product, R25 of a second regeneration slide valve I, R25A of a second regenerant I inlet, R26 of a second regenerant valve, R26A of a second spent riser or a second spent catalyst riser, R27 times of high-temperature reaction zone and R28 of high-temperature reaction zone; r30 third reactor; r31 third reactor steam; r32 hydrocracking tail oil; r33 hydrocracking tail oil atomized steam; r35 second regenerative spool valve iii; an inlet for a second regenerant III R35A;

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; G34A second regeneration standpipe III, and a G34A second regenerant III outlet;

s20, a second stripping section, and S21, a second stripping section component;

d20 a second settler;

t10, a first reaction system product heavy component separation tower, a T20 fractionating tower, an A1 heat exchanger and a B steam generator;

f3 water, F4 steam, F21 liquefied gas and dry gas products, an F22 gasoline component, an F23 light cycle oil component (or LCO component), and a heavy component at the bottom of an F24 tower;

TIC temperature display control.

The specific implementation mode is as follows:

the technical solutions of the present invention are described below with specific embodiments and examples, but the scope of the present invention is not limited thereto.

The first implementation mode comprises the following steps:

in the method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material of the embodiment, the catalytic conversion device shown in fig. 1 is adopted, the first reaction regeneration system and the second reaction regeneration system are arranged, and the heavy petroleum hydrocarbon and the hydrocracking tail oil are used as raw materials, and in specific implementation, the heavy petroleum hydrocarbon raw material can be one or a mixture of vacuum wax oil, residual oil, coking wax oil, deasphalted oil, hydrogenation wax oil, hydrogenation residual oil, hydrogenation catalytic diesel oil, crude oil and condensate oil, and the boiling point is higher than 320 ℃; in the invention, hydrocracking tail oil is a technical term which is fixedly known in the field, the property of the hydrocracking tail oil is related to raw oil adopted in hydrocracking, and in the specific implementation, the BMCI value of the hydrocracking tail oil capable of performing catalytic conversion is less than or equal to 20;

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, wherein the first reactor R10 and the first regenerator G10 are arranged in parallel; the outlet of the first reactor R10 is communicated with a first cyclone separator D11 of a gas-solid separation device in a first settler D10, a first stripping section S10 is arranged below the first settler D10, and a first stripping component S11 is arranged in the first stripping section S10; the lower part of the first stripping section S10 is communicated with a first regenerator G10 through a first to-be-regenerated stand pipe R16A from a first to-be-regenerated agent inlet G12A, and a first to-be-regenerated slide valve R16 is arranged on the first to-be-regenerated stand pipe R16A; in specific implementation, the first regenerator G10 adopts a regeneration form of a fast fluidized bed and a dense-phase fluidized bed of a coking tank, the first regenerator G10 is communicated with a first reactor regenerant inlet R15A of the first reactor R10 through a first regeneration riser G14 from a first regenerant outlet G14A, the first regeneration riser G14 is provided with a first regeneration slide valve R15, a first regenerator cyclone separator G16 is arranged in a first regenerator dilute-phase zone G15 of the first regenerator G10, the coked flue gas G17 of the first regenerator is discharged from a first flue gas outlet G17A at the top of the first regenerator G10, and the catalyst regeneration gas G11 is introduced from a first regeneration gas inlet G11A at the bottom of the first regenerator G10; a heavy petroleum hydrocarbon inlet R12A is arranged at the lower part of the first reactor R10 to introduce the heavy petroleum hydrocarbon R12 and the raw material atomization steam R13, and a catalyst pre-lifting gas inlet R11A is arranged at the lower part of the first reactor R10 to introduce the catalyst pre-lifting gas R11; the top of the first settler D10 is provided with a first reaction gas product outlet R14A;

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, the second reactor R20 and the second regenerator G20 are arranged in parallel, the outlet of the second reactor R20 is communicated with a gas-solid separation device (not shown in the figure) in the second settler D20, the second stripping section S20 is arranged below the second settler D20, and a second stripping component S21 is arranged in the second stripping section S20; the lower part of the second stripping section S20 is communicated with a second regenerator G20 through a second spent riser R26A and a second spent agent valve R26; in specific implementation, a gas-solid separation device (not shown in the figure) is arranged in the dilute phase zone G25 of the second regenerator G20, the burned flue gas G27 is discharged from a second flue gas outlet G27A at the upper part of the second regenerator G20, the burning air G21 is introduced from a burning gas inlet G21A at the bottom part of the second regenerator G20, and the second spent reagent from the second stripping section S20 firstly enters the second regenerator G20 from a second spent reagent valve R26 at the lower part of the second regenerator for regeneration; in specific implementation, the second regenerator G20 adopts a two-stage regeneration mode of up-down series connection, the second spent catalyst firstly enters a first-stage regeneration zone from a second spent catalyst valve R26, contacts and reacts with the scorching air G21, flows upwards to enter the second-stage regeneration zone for continuous regeneration, and is supplemented with fuel G28 in the second-stage regeneration zone to realize heat supplement of the regenerator. In the embodiment, the second regenerant I is from a first section regeneration zone and is a lower catalyst, the second regenerant II is from a second section regeneration zone and is an upper catalyst, the second reactor R20 is divided into an upper reaction zone and a lower reaction zone by an upper catalyst and a heat supply position, namely a second regenerant inlet IIR 22A, and the second reactor R20 is arranged in the form of an upper and lower subarea reactor with upper and lower catalyst circulation and twice heat supply and comprises a lower sub-high temperature reaction zone R27 and an upper high temperature reaction zone R28; wherein a second regenerant I inlet R25A at the lower part of the secondary high temperature reaction zone R27 is communicated with a second regenerant I outlet G24A of the second regenerator G20 through a second regeneration vertical pipe IG 24, a second regeneration slide valve IR25 is arranged on the second regeneration vertical pipe IG 24, a second regenerant II inlet R22A at the lower part of the high temperature reaction zone R28 is communicated with a second regenerant II outlet G22A of the second regenerator G20 through a second regeneration vertical pipe IG 22, and a second regeneration slide valve IIR 22 is arranged on the second regeneration vertical pipe IG 22; introducing supplementary steam R21 of the secondary high-temperature reaction zone above or below an inlet R25A of a second regenerant I at the lower part of the secondary high-temperature reaction zone R27, and introducing supplementary steam R23 of the high-temperature reaction zone above or below an inlet R22A of a second regenerant II at the lower part of the high-temperature reaction zone R28;

a material flow pipeline is arranged between the first reaction gas product outlet R14A and the bottom of the high-temperature reaction zone R28, a first reaction system product R14 can directly enter the high-temperature reaction zone R28 in a gas phase state through the material flow pipeline, a hydrocracking tail oil inlet is arranged at the bottom of the second reactor R20, namely the bottom of the second high-temperature reaction zone R27, the hydrocracking tail oil R32 sequentially enters the second high-temperature reaction zone R27 and the high-temperature reaction zone R28 to participate in the reaction in the second reactor R20, and the hydrocracking tail oil R32 is atomized by hydrocracking tail oil atomization steam R33; in specific implementation, the first reactor R10 and the second reactor R20 may adopt a riser, a single reactor of a fluidized bed or a composite reactor, in this embodiment, the first reactor R10 and the second reactor R20 adopt a riser form;

in the method for preparing olefins by catalytic conversion of petroleum hydrocarbon raw material according to the embodiment, the heavy petroleum hydrocarbon R12 is firstly catalytically converted in the first reaction regeneration system, and the reaction product is catalytically converted in a gaseous form together with the hydrocracking tail oil in the second reaction regeneration system, wherein the first reaction regeneration system is mainly used for decarbonization, demetalization and catalytic conversion of the heavy petroleum hydrocarbon raw material, and the second reaction regeneration system is used for cracking to prepare olefins; the first reaction regeneration system uses a first catalyst, and the second reaction regeneration system uses a second catalyst; in the specific implementation, 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 the catalytic cracking of heavy raw oil; the active component of the second catalyst is selected from one or a mixture of Y-type zeolite, L-type zeolite, ZSM-5 zeolite, beta zeolite, aluminum phosphate zeolite and mordenite, or modified zeolite, and belongs to a catalyst with strong intermediate component or micromolecule cracking capability and high selectivity of low-carbon olefin. The specific process flow is as follows:

(1) The preheated heavy petroleum hydrocarbon R12 is firstly subjected to catalytic conversion in a first reaction regeneration system, enters a reaction zone R17 of a first reactor R10, and is subjected to catalytic cracking reaction mainly for heavy petroleum hydrocarbon macromolecules under the action of a first catalyst from the first regenerator G10, the reaction temperature of the 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 material flow formed by the reaction in the first reactor R10 enters a first cyclone separator D11 in a first settler D10 to separate out a first catalyst, a first reaction system product R14 formed by heavier components or larger molecules and intermediate components 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 for recycling;

(2) The first reaction system product R14 directly enters the high temperature reaction zone R28 of the second reactor R20 in gaseous form through a flow line;

the atomized hydrocracking tail oil R32 firstly enters the bottom of a secondary high-temperature reaction zone R27, and is subjected to secondary high-temperature reaction mainly comprising catalytic cracking of heavier components or larger molecules and intermediate components under the environment of a second catalyst I introduced from a second regenerator G20 through a second regeneration vertical pipe IG 24, wherein the reaction temperature is 520-600 ℃, the reaction time is 0.1-5.0 s, the absolute reaction pressure is 0.20-0.40 MPa, the actual reaction temperature is controlled by the catalyst entering the secondary high-temperature reaction zone R27, and in the specific implementation, the temperature of the second catalyst I is 660-820 ℃, and the carbon content is lower than 0.15%; the product and the catalyst in the secondary high-temperature reaction zone R27 flow upwards to enter a high-temperature reaction zone R28, and the high-temperature reaction of the combination of catalytic cracking and thermal cracking with increased temperature is carried out in the environment of a second catalyst II introduced from a second regenerator G20 through a second regeneration vertical pipe II G22, so that the conversion of the intermediate component into ethylene and propylene is realized, the ethylene and the propylene are formed, the reaction temperature is 550-750 ℃, the reaction time is 0.1-5.0 s, the absolute reaction pressure is 0.20-0.40 MPa, the actual reaction temperature is controlled by the catalyst entering the high-temperature reaction zone R28, and in the specific implementation, the temperature of the second catalyst II is 700-850 ℃, and the carbon content is lower than 0.5%; after the material flow formed by the reaction in the second reactor R20 enters a second precipitator D20 to separate out the catalyst, a second reaction system product R24 mainly containing olefin is obtained, namely a target product is sent out of the device and enters a subsequent process for treatment; 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.

Example 1:

the device and the process are shown in figure 1, and the implementation parameters are as follows:

the reaction materials are normal pressure heavy oil and hydrocracking tail oil, and the hydrocracking tail oil is fed separately. Atmospheric heavy oil with density of 0.91, hydrogen content of 12.8 wt%, residual carbon of 3.8%, saturated hydrocarbon content of 61%, ni less than 4.0ppm, V less than 0.1ppm; the density of the hydrocracking tail oil is 0.82, and the BMCI value is 10.6; the hydrocracking tail oil accounts for 10% of the raw oil;

the preheating temperature of the heavy oil at normal pressure is 220 ℃; the hydrocracking tail oil temperature is 300 ℃;

first reactor reaction conditions: the reaction temperature (i.e. the reactor outlet reaction temperature) TIC-1 was 530 ℃ and the reaction time was 1.0s (sec); the temperature of the regenerant (namely the first catalyst) entering the regenerant inlet of the first reactor is 680 ℃, atomized steam is 4% of the normal pressure heavy oil, and catalyst pre-lifting steam is 2% of the normal pressure heavy oil; reaction pressure (first settler D10 pressure) 170KPa (gauge pressure) (i.e. 0.27 MPa);

reaction conditions of the second reactor: the reaction pressure (second settler pressure) was 120kpa (gauge pressure) (i.e., 0.22 MPa);

reaction conditions of the secondary high-temperature reaction zone R27: the temperature of a catalyst (second regenerant I) entering from an inlet of the second regenerant I is 730 ℃, the reaction temperature TIC-2 is 620 ℃, the reaction time is 0.4s, the proportion of supplemented steam is 4 percent (accounting for the mass ratio of the raw oil), and the proportion of steam in a reaction zone is 10 percent of the weight of the raw oil;

reaction conditions of the high-temperature reaction zone R28: the temperature of a catalyst (a second regenerant II) entering from an inlet of the second regenerant II is 730 ℃, the reaction temperature TIC-3 is 670 ℃, the reaction time is 1.5 seconds, the supplemented steam is 14 percent of the oil mass of the raw material, the atomized steam of the hydrocracking tail oil is 3 percent of the hydrocracking tail oil, and the proportion of the total steam to the raw material oil in the reaction zone is 31 percent;

the implementation process is as follows:

the normal pressure heavy oil steam is atomized and then enters a first reactor, heavy oil catalytic cracking conversion is carried out under the heat provided by a regenerant and entering from a regenerant inlet of the first reactor and a catalytic environment, the cracking conversion from macromolecules to intermediate molecules is realized, intermediate component raw materials with the molecular weight of 80-200 are obtained as far as possible, and raw materials are provided for further conversion into olefin; after the reaction of the first reactor is finished, the product enters a settler to separate out the catalyst, the product of the first reaction system flows out of the first settler, then directly enters a high-temperature reaction zone of the second reactor, and the cracking reaction of the residual heavy oil and the middle distillate of larger molecules is continuously carried out;

after steam atomization of hydrocracking tail oil, the hydrocracking tail oil enters a second reactor at the bottom of a secondary high-temperature reaction zone and reacts in the secondary high-temperature reaction zone at the lower part of the second reactor; the second regenerant I from the second regenerator enters a secondary high-temperature reaction zone to realize the catalytic conversion of the hydrocracking tail oil; supplementing steam accounting for 4% of the raw oil in the secondary high-temperature reaction zone;

the gas material flow and the catalyst generated in the secondary reaction zone continuously flow upwards and enter the high-temperature reaction zone; the high-temperature catalyst from the regenerator, namely a second regenerant II, enters a second reactor, is conveyed upwards by gas from a secondary high-temperature reaction zone of the reactor to enter a high-temperature reaction zone, further provides heat for the high-temperature reaction zone, improves the reaction temperature in the high-temperature reaction zone, reduces the activation energy level of C5 to C12 components under the action of the catalyst, realizes the catalytic conversion and thermal cracking mixed reaction of alkane, alkene and cycloalkane, and generates alkene;

carrying out gas-solid separation on the reaction product material flow in the high-temperature reaction zone in a second precipitator, and enabling the product gas (a second reaction system product) from which the catalyst is separated to flow out of the second precipitator and enter a subsequent treatment system;

the high-temperature reaction zone further supplements steam, so that the steam amount in the high-temperature reaction zone reaches 31% of the atmospheric heavy oil amount;

the catalyst separated from the first settler enters a first regenerator for catalyst regeneration after being stripped; the catalyst separated in the second precipitator enters a second regenerator for catalyst regeneration after being stripped;

the second regenerator is provided with supplementary fuel oil G28 which is 1.5 percent of the normal pressure heavy oil and supplements heat for reaction, thereby realizing the required regeneration temperature.

The regeneration of the catalyst, the gas-solid separation and the subsequent oil gas treatment are common technologies and are not described in detail.

Catalyst used in the first reaction regeneration system (first catalyst): the rare earth modified Y-type molecular sieve is used as a main active component, and the main parameters are as follows: balancer activity 65%, abrasion index 2.0%, D, v (0.5) =68 μm.

Catalyst used in the second reaction regeneration system (second catalyst): ZSM-5 is taken as a main active component, and the main parameters are as follows:

balancer activity 47%, abrasion index 1.0%, D, v (0.5) =60 μm.

Example 1 the product distribution is shown in table 1:

table 1 example 1 product distribution

The second embodiment:

the method for producing olefins by catalytic conversion of a petroleum hydrocarbon feedstock according to the present embodiment employs a catalytic conversion apparatus shown in fig. 2, and includes a first reaction regeneration system and a second reaction regeneration system;

the second regenerator G20 adopts a two-stage regeneration mode which is connected in series up and down, when the concrete operation is implemented, the temperature and the carbon content of the first stage regeneration are controlled according to the amount of the catalyst introduced into the first stage regeneration zone and the amount of the coke-burning air G21, and the temperature and the carbon content of the second stage regeneration are controlled according to the amount of the catalyst introduced into the second stage regeneration zone; a second reaction system product R24 led out from an outlet at the top of the second settler D20 enters a fractionating tower T20 after heat exchange and temperature reduction by a heat exchanger A1, and the second reaction system product R24 is separated into a liquefied gas and dry gas product F21, a gasoline component F22, a light cycle oil component F23 and a tower bottom heavy component F24;

a material flow pipeline is arranged between the first reaction gas product outlet R14A and the bottom of the second reactor R20, and a first reaction system product heavy component separation tower T10 is arranged on the material flow pipeline; the first reaction system product R14 is firstly separated into heavy components, namely a first reaction system product liquid heavy component R14L, through a first reaction system product heavy component separation tower T10 to form a first reaction system product light component R14G, the first reaction system product light component R14G firstly enters a heat exchanger A1 to exchange heat with a second reaction system product R24, and the heated first reaction system product light component R14G enters a second reaction regeneration system in a gas phase state; in the embodiment, the light component R14G of the first reaction system product sequentially enters the secondary high temperature reaction zone R27 and the high temperature reaction zone R28 to participate in the reaction in the second reactor R20, and the hydrocracking tail oil R32 directly enters the high temperature reaction zone R28 for catalytic conversion; the other part of the device structure of this embodiment is the same as that of the first embodiment;

the specific implementation process of the embodiment is as follows:

(1) The preheated heavy petroleum hydrocarbon R12 is firstly subjected to catalytic conversion in a first reaction regeneration system to form a first reaction system product R14; the first catalyst is separated, stripped and regenerated for recycling;

(2) The first reaction system product R14 is separated into a first reaction system product liquid heavy component R14L with the temperature of more than 500 ℃ through a first reaction system product heavy component separation tower T10 to form a first reaction system product light component R14G; the light component R14G of the product of the first reaction system enters a heat exchanger A1, is heated by a product R24 of the second reaction system, then enters a second reactor R20 in a gas phase state through a material flow pipeline to continue catalytic conversion, firstly enters a secondary high-temperature reaction zone R27 to carry out catalytic cracking reaction of residual heavy oil and middle distillate of larger molecules, namely secondary high-temperature reaction, and steam accounting for 8 percent of the heavy petroleum hydrocarbon raw material is supplemented in the secondary high-temperature reaction zone; the product and the catalyst in the secondary high-temperature reaction zone R27 flow upwards to enter a high-temperature reaction zone R28, and together with the atomized hydrocracking tail oil R32, the product and the catalyst in the secondary high-temperature reaction zone R28 are subjected to high-temperature reaction of catalytic conversion and thermal cracking mixing of alkane, alkene and cycloalkane with increased temperature to generate alkene, the temperature of the catalyst (second regenerant I) entering from the inlet of the second regenerant I is 730 ℃, and the temperature of the catalyst (second regenerant II) entering from the inlet of the second regenerant II is 700 ℃; after a catalyst is separated from a material flow formed by the reaction of the second reactor R20, a product R24 of a second reaction system, namely a target product, is obtained, and the target product flows through the heat exchanger A1 to be cooled and enters the fractionating tower T20 to be separated into a liquefied gas product, a dry gas product F21, a gasoline component F22, a light cycle oil component F23 and a tower bottom heavy component F24; the separated catalyst is stripped and then enters a second regenerator G20 for regeneration and recycling.

Heat exchangers are well known to those skilled in the art and will not be described in detail.

The third embodiment is as follows:

the method for producing olefins by catalytic conversion of a petroleum hydrocarbon feedstock according to the present embodiment employs a catalytic converter shown in fig. 3, and includes a first reaction regeneration system and a second reaction regeneration system;

the second reaction regeneration system is provided with a second reactor R20, a second settler D20, a second stripping section S20, a second regenerator G20 and a third reactor R30; a material flow pipeline is arranged between the first reaction gas product outlet R14A of the first precipitator D10 and the bottom of the second reactor R20;

the second reactor R20 is arranged in the form of an upper and lower partitioned reactor with upper and lower catalyst circulation and twice heat supply, and comprises a lower sub-high temperature reaction zone R27 and an upper high temperature reaction zone R28; introducing supplementary steam R21 of the secondary high-temperature reaction zone above a second regenerant I inlet R25A at the lower part of the secondary high-temperature reaction zone R27, and introducing supplementary steam R23 of the high-temperature reaction zone above a second regenerant II inlet R22A at the lower part of the high-temperature reaction zone R28;

a second reaction system product R24 led out from an outlet at the top of the second settler D20 enters a steam generator B, water F3 is heated into steam F4, and then enters a fractionating tower T20, and the second reaction system product R24 is separated into a liquefied gas and dry gas product F21, a gasoline component F22, a light cycle oil component F23 and a tower bottom heavy component F24;

the third reactor R30 and the second reactor R20 share a second settler D20, a second stripping section S20 and a second regenerator G20, and a second regenerant III 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 vertical pipe III G34; a hydrocracking tail oil inlet (not shown in the figure) is arranged at the bottom of the third reactor R30, the hydrocracking tail oil R32 is atomized by hydrocracking tail oil atomization steam R33 and then enters the third reactor R30 from the hydrocracking tail oil inlet, and third reactor steam R31 is introduced from the bottom of the third reactor R30;

the other part of the device structure of this embodiment is the same as that of the first embodiment;

one specific example parameter of this embodiment is as follows:

the reaction temperature of the second reactor is 660 ℃, the steam supplementing quantity of the secondary high-temperature reaction zone is determined according to the fact that the total quantity of steam in the second reactor is 35 percent of the oil quantity of the raw material, the reaction time is 1.5 seconds, and the temperature of a catalyst (namely a second regenerant I) from the second regenerator is 730 ℃; after being atomized by steam, the hydrocracking tail oil enters a third reactor, and is subjected to catalytic cracking and thermal cracking mixed reaction in an independent riser; the reaction temperature was 670 ℃ and the reaction time was 1.4 seconds. The catalyst (i.e. the second regenerant III) from the second regenerator enters a third reactor; the third reactor is supplemented with steam which is provided by 30 percent of hydrocracking tail oil, and a second regenerant III is 730 ℃;

the product of the second reaction system is firstly put into a steam generator to be cooled to 560 ℃, the water inlet temperature is 220 ℃, the steam pressure is 11MPa, and the temperature is the saturation temperature. The steam generator is a common device and is well known to the skilled person.

Claims

1. A method for preparing olefin by catalytic conversion of petroleum hydrocarbon raw material, which takes heavy petroleum hydrocarbon (R12) and hydrocracking tail oil (R32) as raw materials, and carries out catalytic conversion in a first reaction regeneration system and a second reaction regeneration system to prepare olefin, wherein the first reaction regeneration system uses a first catalyst, and the second reaction regeneration system uses a second catalyst; the method is characterized in that: the method comprises the following steps:

(1) The heavy petroleum hydrocarbon (R12) is firstly subjected to catalytic conversion in a first reaction regeneration system, enters a first reactor (R10) and is subjected to catalytic cracking reaction in the environment of a first catalyst from the first regenerator (G10), the reaction temperature of the 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 material flow 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) is stripped in a first stripping section (S10) and then enters a first regenerator (G10) for regeneration and recycling;

(2) The first reaction system product (R14) or the light component (R14G) of the first reaction system product after the heavy component is separated and the hydrocracking tail oil (R32) enter a second reaction regeneration system for catalytic conversion;

the first reaction system product (R14) or the light component (R14G) of the first reaction system product and the hydrocracking tail oil (R32) enter a second reactor (R20) of an upper and a lower subareas of a second reaction regeneration system to carry out the following catalytic conversion:

or the first reaction system product (R14) or the first reaction system product light component (R14G) firstly enters the bottom of a secondary high-temperature reaction zone (R27) of a second reactor (R20), secondary high-temperature reaction is carried out under the environment of a second catalyst I introduced from the 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, the absolute pressure of the reaction pressure is 0.20 MPa-0.40 MPa, the actual reaction temperature is controlled by the catalyst entering the secondary high-temperature reaction zone (R27), the product and the catalyst in the secondary high-temperature reaction zone (R27) flow upwards to enter a high-temperature reaction zone (R28) of the second reactor (R20) to be mixed with hydrocracking tail oil (R32) directly entering the high-temperature reaction zone (R28), the temperature-raised high-temperature reaction is carried out under the environment of the second catalyst II introduced from the second regenerator (G20) through a second regeneration vertical pipe II (G22), the reaction temperature is 550-550 ℃, the reaction temperature is 0.5-0.5 MPa, the actual reaction temperature is controlled by the absolute pressure of the reaction zone (R27-0.0.0.1-0.0.0.0.0.0.0.0.0.40 MPa; or the first reaction system product (R14) or the first reaction system product light component (R14G) directly reacts in the high-temperature reaction zone (R28), the hydrocracking tail oil (R32) firstly enters the second high-temperature reaction zone (R27) to carry out the second high-temperature reaction, then flows upwards with the catalyst to enter the high-temperature reaction zone (R28), and is mixed with the first reaction system product (R14) or the first reaction system product light component (R14G) directly entering the high-temperature reaction zone (R28) to carry out the high-temperature reaction; or the first reaction system product (R14) or the light component (R14G) of the first reaction system product and the hydrocracking tail oil (R32) directly enter a secondary high-temperature reaction zone (R27) to carry out secondary high-temperature reaction, and then flow upwards with the catalyst to enter a high-temperature reaction zone (R28) to continue the reaction; after the material flow formed by the reaction in 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) is stripped in a second stripping section (S20) and then enters a second regenerator (G20) for regeneration and recycling;

or the first reaction system product (R14) or the first reaction system product light component (R14G) enters a second reactor (R20) of an upper zone and a lower zone of a second reaction regeneration system, and sequentially reacts in a secondary high-temperature reaction zone (R27) and a high-temperature reaction zone (R28), and meanwhile, hydrocracking tail oil (R32) reacts in a third reactor (R30) which is independent of the second reaction regeneration system; a first reaction system product (R14) or a first reaction system product light component (R14G) firstly enters the bottom of a secondary high-temperature reaction zone (R27), a secondary high-temperature reaction is carried out in the environment of a second catalyst I introduced from a second regenerator (G20) through a second regeneration vertical pipe I (G24), a product and a catalyst in the secondary high-temperature reaction zone (R27) flow upwards and enter a high-temperature reaction zone (R28), a high-temperature reaction with increased temperature is carried out in the environment of a second catalyst II introduced from the second regenerator (G20) through a second regeneration vertical pipe II (G22), hydrocracking tail oil (R32) enters the lower part of a third reactor (R30), a high-temperature reaction is carried out in the environment of a second catalyst III introduced from the second regenerator (G20) through a second regeneration vertical pipe III (G34), and the third reactor (R30) has the reaction temperature of 550-720 ℃, the reaction time of 0.5-5.0 s and the absolute pressure of 0.2-0.4 MPa; after the material flow formed by the reaction of the second reactor (R20) and the third reactor (R30) enters a second settler (D20) to separate the catalyst, a second reaction system product (R24) is obtained; and 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. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: and 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. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as claimed in claim 1, wherein: the heavy petroleum hydrocarbon (R12) is one or a mixture of vacuum wax oil, residual oil, coking 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. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: 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.

5. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: 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 ℃.

6. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: 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%.

7. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: the second regenerator (G20) of the second reaction regeneration system is replenished with fuel (G28).

8. A process for the catalytic conversion of a petroleum hydrocarbon feedstock to olefins as defined in claim 1, wherein: 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.

9. A device for preparing olefin 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 the lower part of the first reactor (R10) is provided with a heavy petroleum hydrocarbon inlet (R12A); 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 arranged between the first reaction gas product outlet (R14A) of the first settler (D10) and the second reactor (R20), or a flow line is arranged between the first reaction gas product outlet (R14A) and the second reactor (R20), on which flow line a separation column or a fractionation column is arranged at the same time; the first reactor (R10) and the second reactor (R20) are selected from the group consisting of a riser, a single reactor of a fluidized bed or a composite 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); a second regenerant I inlet (R25A) at the lower part of the secondary high-temperature reaction zone (R27) is communicated with a second regenerant I outlet (G24A) of the second regenerator (G20) through a second regeneration vertical pipe I (G24), and a second regenerant II inlet (R22A) at the lower part of the high-temperature reaction zone (R28) is communicated with a second regenerant II outlet (G22A) of the second regenerator (G20) through a second regeneration vertical pipe II (G22);

a hydrocracking tail oil inlet is arranged at the bottom of the secondary high-temperature reaction zone (R27), and the material flow pipeline is arranged between the first reaction gas product outlet (R14A) and the bottom of the high-temperature reaction zone (R28); or a hydrocracking tail oil inlet is arranged at the bottom of the high-temperature reaction zone (R28), and the material flow pipeline is arranged between the first reaction gas product outlet (R14A) and the bottom of the secondary high-temperature reaction zone (R27).

10. A device for preparing olefin 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 the lower part of the first reactor (R10) is provided with a heavy petroleum hydrocarbon inlet (R12A); the second reaction regeneration system is provided with a second reactor (R20), a second settler (D20), a second stripping section (S20), a second regenerator (G20) and a third reactor (R30); a stream line is arranged between the first reaction gas product outlet (R14A) of the first settler (D10) and the bottom of the second reactor (R20), or a stream line is arranged between the first reaction gas product outlet (R14A) and the bottom of the second reactor (R20), while a separation column or a fractionation column is arranged on the stream line; the first reactor (R10), the second reactor (R20) and the third reactor (R30) are selected from a riser, a single or a composite reactor of a fluidized bed; the method is characterized in that:

said second reactor (R20) comprising a lower, secondary high temperature reaction zone (R27) and an upper, high temperature reaction zone (R28); a second regenerant I inlet (R25A) at the lower part of the secondary high-temperature reaction zone (R27) is communicated with a second regenerant I outlet (G24A) of the second regenerator (G20) through a second regeneration vertical pipe I (G24), and a second regenerant II inlet (R22A) at the lower part of the high-temperature reaction zone (R28) is communicated with a second regenerant II outlet (G22A) of the second regenerator (G20) through a second regeneration vertical pipe II (G22); the third reactor (R30) and the second reactor (R20) share a second settler (D20), a second stripping section (S20) and a second regenerator (G20), and a second regenerant III 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); a hydrocracking tail oil inlet is arranged at the lower part of the third reactor (R30).