CN116196850A - Device and method for preparing propylene by catalytic conversion of petroleum hydrocarbon - Google Patents
Device and method for preparing propylene by catalytic conversion of petroleum hydrocarbon Download PDFInfo
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- CN116196850A CN116196850A CN202111454788.XA CN202111454788A CN116196850A CN 116196850 A CN116196850 A CN 116196850A CN 202111454788 A CN202111454788 A CN 202111454788A CN 116196850 A CN116196850 A CN 116196850A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
- B01J8/28—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations the one above the other
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1809—Controlling processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J8/1836—Heating and cooling the reactor
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- B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
- B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- B01J8/1872—Details of the fluidised bed reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00327—Controlling the temperature by direct heat exchange
- B01J2208/00336—Controlling the temperature by direct heat exchange adding a temperature modifying medium to the reactants
- B01J2208/00353—Non-cryogenic fluids
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a device for preparing propylene by catalytic conversion of petroleum hydrocarbon, which comprises: the reactor comprises a sedimentation section, a stripping section, a fast fluidized bed reaction zone and a riser reaction zone which are communicated with each other from top to bottom; the top of the sedimentation section is provided with a hydrocarbon product outlet, the diameter of the rapid fluidized bed reaction zone is smaller than that of the stripping section and larger than that of the riser reaction zone, part or all of the rapid fluidized bed reaction zone is arranged in the stripping section, the top outlet of the rapid fluidized bed reaction zone is communicated with the sedimentation section, an annular space is formed between the shell of the stripping section and the rapid fluidized bed reaction zone, and the annular space is communicated with the middle part of the rapid fluidized bed reaction zone through an annular gap channel. The invention also relates to a method for preparing propylene by catalytic conversion of petroleum hydrocarbon. The device realizes the graded conversion from macromolecules to propylene in the reaction process in a graded control mode, and the two reaction areas are independently controlled.
Description
Technical Field
The invention belongs to the technical field of catalytic conversion of petroleum hydrocarbon, and particularly relates to a device and a method for preparing propylene by catalytic conversion of petroleum hydrocarbon.
Background
Propylene is one of the most important petrochemical feedstocks. 70% of the propylene is produced by tube furnace cracking of petroleum hydrocarbons and the other 30% of the propylene is provided by the catalytic cracking process. By referring to the operation and design experience of a conventional heavy oil catalytic cracking reaction-regeneration system, researchers at home and abroad develop a series of process technologies for producing olefin by heavy oil catalytic cracking.
TMP technology was developed by the university of China Petroleum (China east) on the basis of two-stage riser catalytic cracking technology. The technology takes heavy oil as a raw material, utilizes the process characteristics of sectional reaction, catalyst relay and large catalyst-oil ratio of a two-section riser catalytic cracking process, optimally combines the feeding modes of the reactant materials with different properties, and controls the proper reaction conditions of the different materials so as to achieve the aim of improving the propylene yield;
DCC technology using heavy oil as raw material and propylene as target product was developed by the national institute of petrochemical industry and petrochemistry in 90 th century. The technology adopts a riser and a turbulent fluid bed layer series reactor to catalyze heavy oil to prepare propylene under the condition of 4 (1/H) -6 (1/H) gas-solid fluidization at the weight hourly space velocity. Dan Keyuan an enhanced catalytic cracking technology (DCC-PLUS) using a novel combined reactor system was developed based on DCC technology, which is the same as DCC technology in that a riser reactor PLUS fluidized bed reactor is used, except that DCC-PLUS technology is additionally provided with a light gasoline and C4 recycle riser, and the stream after the light gasoline and C4 reactions is introduced into the fluidized bed reactor. The raw oil reaction is divided into a riser and a fluidized bed reaction whether DCC or DCC-PLUS; however, DCC and DCC-PLUS control the reaction temperature in the fluidized bed region through the amount of the regenerated material entering the reaction region of the material oil riser, i.e. the whole reaction process is controlled according to the condition of the fluidized bed catalytic cracking reaction region, so that the catalytic cracking condition in the reaction region of the riser, i.e. the heavy oil reaction region, is necessarily deviated from the ideal catalytic cracking reaction condition of the material oil, especially the thermal reaction is increased; in addition, the airspeed of the fluidized bed reaction zone with fixed raw material amount can only be controlled by the change of the catalyst level in the fluidized bed; because the catalyst carries and the gas-solid separation requirement, all are dilute phase space between fluidized bed layer reaction zone and the gas-solid separator, and still carry a large amount of catalyst when oil gas leaves the fluidized bed layer, and the dwell time that oil gas left the fluidized bed layer to the gas-solid separator is more than 20 seconds, carry and oil gas dwell time of catalyst above catalyst material level all must cause further side reaction to end when adopting fluidized bed layer reaction, propylene further thermal cracking, influence product distribution and propylene selectivity, the reaction is difficult to terminate in time, must lead to catalytic cracking reaction to be restricted, thermal reaction increases, reduce propylene's selectivity by a wide margin, lead to dry gas and coke yield to be higher.
The emphasis of the prior art is on propylene production, which is roughly divided into two types, namely a riser and fluidized bed series reaction and a double riser parallel reaction. It is considered that propylene in the heavy oil catalytic cracking reaction process is indirectly generated by secondary cracking of a gasoline fraction generated by primary cracking of heavy hydrocarbons, and C5-C8 olefins in the gasoline fraction are main precursors of propylene. The prior art has many common characteristics, including higher reaction temperature, catalyst-to-oil ratio and steam injection than conventional FCC processes, to increase the depth of cracking reaction and selectivity to propylene.
Petroleum hydrocarbons, particularly heavy oil, catalytic cracking reactions appear to be well known, and appear to be "nearly" in surface, but are all the reactions of regenerants and feedstock oils through tubular reactors. The petroleum hydrocarbon reaction raw materials have complex chemical composition, the reaction process has complex change of chemical components of the reaction process, different product requirements, different actual chemical reactions, and the improvement of reaction results by improving the conditions of catalyst activity, airspeed and the like in a reactor, and the improvement of process conditions of heat distribution, temperature distribution, time distribution and the like in the reaction process, is an advanced approach of petroleum hydrocarbon catalytic cracking technology. The catalytic conversion of petroleum hydrocarbon to prepare olefin is a strong endothermic and coking reaction, and the catalyst, reactants and products are obviously and complicated in the reaction process; the control of the actual catalyst conditions, temperature conditions and space velocity conditions in the reaction process in the reactor is extremely important to control the chemical reaction process, and different conditions in the reactor actually form different chemical reactions to obtain different products, especially the technology which needs pertinence when taking olefin as the product. The goal of catalytic cracking of petroleum hydrocarbon reaction feeds to produce olefins is to increase the olefins to the maximum possible and to reduce the products of carbon numbers of C2 and below.
Disclosure of Invention
Based on the foregoing, it is an object of the present invention to provide an apparatus and a method for producing propylene by catalytic conversion of petroleum hydrocarbon. The device realizes the graded conversion from macromolecules to propylene in the reaction process in a graded control mode, and the two reaction areas are independently controlled.
To this end, the invention provides an apparatus for the catalytic conversion of petroleum hydrocarbons to propylene, comprising: a reactor and a regenerator, wherein the reactor and the regenerator are arranged in a reactor,
the reactor comprises a sedimentation section, a stripping section, a rapid fluidized bed reaction zone and a riser reaction zone which are communicated with each other from top to bottom; the top of the settling section is provided with a hydrocarbon product outlet, the diameter of the rapid fluidized bed reaction zone is smaller than that of the stripping section and larger than that of the riser reaction zone, part or all of the rapid fluidized bed reaction zone is arranged in the stripping section, the top outlet of the rapid fluidized bed reaction zone is communicated with the settling section, an annular space is formed between the shell of the stripping section and the rapid fluidized bed reaction zone, the annular space is communicated with the middle part of the rapid fluidized bed reaction zone through an annular gap channel, a stripping member is arranged in the annular space, and the stripping section is provided with a spent catalyst outlet and a stripping steam inlet; the bottom of the riser reaction zone is provided with a catalyst lifting gas inlet, the lower part of the riser reaction zone is provided with a lower regenerant inlet, a reaction supplementary steam inlet and a reaction raw oil inlet from bottom to top, and the upper part or the upper part of the riser reaction zone is provided with an upper regenerant inlet;
the regeneration device comprises a regenerator, wherein the interior of the regenerator is divided into a dilute phase zone and a regeneration zone from top to bottom, a flue gas outlet is arranged at the top of the dilute phase zone, a spent catalyst inlet, an upper regenerant outlet and a lower regenerant outlet are arranged in the regeneration zone, the regeneration zone is respectively communicated with the spent catalyst outlet, the upper regenerant inlet and the lower regenerant inlet, and a regeneration gas inlet is arranged at the bottom of the regeneration zone.
The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to the present invention, wherein preferably, the regeneration zone comprises an upper regeneration zone and a lower regeneration zone, the agent inlet to be regenerated is provided in the upper regeneration zone, and the lower regeneration agent outlet and the regeneration gas inlet are provided in the lower regeneration zone.
The device for preparing propylene by catalytic conversion of petroleum hydrocarbon according to the invention is characterized in that the bottom of the upper regeneration zone is preferably provided with a second regeneration gas inlet.
The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to the present invention is preferably characterized in that at least one, preferably 2, 4 or 6, of the reaction raw oil inlets are provided.
The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to the present invention is preferably such that the spent catalyst outlet and the spent agent inlet are connected by a spent riser, the upper regenerator outlet and the upper regenerator inlet are connected by an upper regenerator riser, and the lower regenerator outlet and the lower regenerator inlet are connected by a lower regenerator riser.
The invention relates to a device for preparing propylene by catalytic conversion of petroleum hydrocarbon, wherein a sedimentation cyclone separator is preferably arranged in a sedimentation section; a regeneration cyclone separator is arranged in the dilute phase zone; slide valves are arranged on the stand pipe to be regenerated, the upper regeneration stand pipe and the lower regeneration stand pipe.
Therefore, the invention also provides a method for preparing propylene by catalytic conversion of petroleum hydrocarbon, which is based on the device for preparing propylene by catalytic conversion of petroleum hydrocarbon and comprises the following steps:
(1) The catalyst lifting gas enters from the bottom of the reactor, the regenerant is carried upwards by the catalyst lifting gas after entering from the lower part of the reactor, the reaction raw oil enters into the riser reaction zone and contacts with the regenerant to generate low-temperature catalytic cracking reaction to generate an intermediate product, the reaction temperature of the riser reaction zone is 515-550 ℃, the reaction time is 1.2-2.5 s, the catalyst-oil ratio is 5-15, and the reaction pressure is 0.20-0.26 MPa;
(2) The intermediate product and the catalyst flow upwards to enter the rapid fluidized bed reaction zone, the regenerant enters the rapid fluidized bed reaction zone through the upper regenerant inlet to perform high-temperature catalytic cracking reaction with the intermediate product, the reaction temperature of the rapid fluidized bed reaction zone is 550-580 ℃, the reaction time is 0.5-2.0 s, the reaction pressure is 0.20-0.26 MPa, and the catalyst-oil ratio is 5-20;
(3) And the reactant flow discharged from the rapid fluidized bed reaction zone enters the sedimentation section for gas-solid separation, hydrocarbon products obtained by separation are discharged from the sedimentation section, solid products, namely spent catalyst, are settled into the stripping section, enter the annular space after stripping, and then enter the regenerator for recycling after regeneration.
Specifically, the riser reaction zone in the device is mainly used for the catalytic conversion of macromolecular heavy oil; the rapid fluidized bed reaction zone mainly carries out the reaction of cracking to prepare olefin and aromatic hydrocarbon.
Specifically, the reaction process of the method for preparing propylene by catalytic conversion of petroleum hydrocarbon provided by the invention is as follows: the heavy component macromolecules (heavy oil macromolecules) of the raw oil are subjected to catalytic cracking conversion under the gas-solid conveying fluidization reaction condition, namely a riser reactor, a catalyst with micro-reaction activity of 50-70 and a lower temperature condition to form intermediate molecules mainly containing C4-C12, and then are subjected to catalytic cracking conversion under the conditions of improving the catalyst density, reducing the gas-solid fast fluidized bed morphology of the catalyst airspeed, moderate carbon-containing catalyst environment and high severity to produce olefin; the petroleum hydrocarbon catalytic conversion method is carried out in a two-stage reactor which is connected in series up and down, wherein the lower part is in a gas-solid conveying bed fluidization form, namely a riser fluidization form, the upper part is in a gas-solid rapid fluidization form, the reactor is provided with two stages of heat supply which are independently controlled up and down and two paths of catalyst circulation from a regenerator, namely a riser reaction zone and a rapid fluidized bed reaction zone, the lower part of the reactor is provided with a riser reaction zone, or a high-boiling petroleum hydrocarbon raw material low-temperature catalytic cracking reaction zone or a low-temperature reaction zone or a catalytic cracking reaction zone, and in the riser reaction zone, heavy component macromolecules are subjected to catalytic cracking reaction converted into C5-C12 intermediate components at a regenerated catalyst environment and a lower reaction temperature, so as to provide intermediate raw materials for olefin production; the upper part of the reactor is a rapid fluidized bed reaction zone, or a high-temperature cracking olefin preparation reaction zone, or a high-temperature reaction zone or a catalytic cracking reaction zone, the catalyst (namely an upper regenerant) entering from an inlet point above the reactor provides heat to further improve the reaction temperature of the rapid fluidized bed reaction zone to form the high-temperature reaction zone, and the intermediate components mainly containing C5-C12 are subjected to catalytic cracking reaction under the harsher conditions of higher temperature, higher catalyst-to-oil ratio (the upper reaction zone has a catalyst-to-oil ratio of 5-20, the lower reaction zone has a catalyst-to-oil ratio of 5-15) and lower weight hourly space velocity to convert petroleum hydrocarbon reaction raw materials into olefin; the method realizes the selective reaction of the high boiling point petroleum hydrocarbon reaction raw material in the two-stage heat supply, two-stage catalyst supply and two-stage control of the upper and lower two-zone reactors, and adopts the gradually rising reaction mode of the reaction temperature to adapt to the gradually decreasing molecular weight of the reactant and the change of the requirements on the reaction conditions, thereby improving the efficiency of olefin production and the selectivity of the target product.
The invention relates to a method for preparing propylene by catalytic conversion of petroleum hydrocarbon, wherein, a riser reaction zone adopts a gas-solid pneumatic conveying fluidization form, and the average flow velocity of gas in the riser reaction zone is 5.0 m/s-20 m/s; the diameter of the rapid fluidized bed reaction zone is larger than that of the riser reaction zone, rapid gas-solid fluidized bed conditions are adopted, the average gas flow rate of the rapid fluidized bed reaction zone is 1.8-5.0 m/s, and the weight hourly space velocity of the catalyst is 10 (1/H) -35 (1/H); preferably, the steam in the riser reaction zone accounts for 5-30% of the mass of the reaction raw materials, and the steam in the rapid fluidized bed reaction zone accounts for 15-50% of the mass of the reaction raw materials.
The method for preparing propylene by catalytic conversion of petroleum hydrocarbon according to the present invention is preferably that the reaction raw oil is one selected from vacuum wax oil, atmospheric residuum, coker wax oil, deasphalted oil and hydrotreated residuum.
The upper regeneration zone is a dense-phase fluidized bed regeneration zone, and when the method is implemented, the carbon content and the temperature of the catalysts in the two regeneration zones are regulated by regulating the distribution of the catalyst amount and the regenerated oxygen amount or the air amount in the two regeneration zones of the regenerator, so that the heat supply to the high-temperature reaction zone and the supply of the catalysts with different carbon contents to the two reaction zones are realized; when catalysts with different carbon contents are provided for the reactor, the catalyst with high carbon content is provided for the pyrolysis reaction zone at the upper part.
When the catalyst entering different reaction areas of the reactor needs to control the carbon content respectively or the catalyst with different carbon content needs to be used for reaction in different reaction areas, or the catalyst temperature needs to be obviously different in different reaction areas, the catalyst amount of the two regeneration areas or the amount of the entering burnt oxygen or air is regulated and controlled, so that the catalyst temperature and the carbon content of the two regeneration areas are different, and the catalyst with different carbon content and temperature is provided for the reactor from different regeneration areas according to the requirement.
The method for preparing propylene by catalytic conversion of petroleum hydrocarbon of the invention is characterized in that the temperature of the lower regenerant is preferably 680-720 ℃, and the carbon content is preferably lower than 0.10%; the temperature of the upper regenerant is 680-720 ℃, and the carbon content is lower than 0.3%.
The stripped catalyst to be regenerated enters an upper regeneration zone, the catalyst in the upper regeneration zone is a semi-regeneration agent with moderate carbon content, and the catalyst in the lower regeneration zone is a regenerated catalyst; catalyst is provided to the reactor fast fluidized bed reaction zone from the upper regeneration zone and catalyst is provided to the riser reaction zone from the lower regeneration zone.
The method for preparing propylene by catalytic conversion of petroleum hydrocarbon provided by the invention specifically comprises the following steps:
(1) The reaction raw oil is atomized by steam and then is subjected to catalytic cracking reaction in a riser reaction zone at the lower part of the reactor under the environment of a lower regenerant introduced from a regenerator through a lower regeneration vertical pipe; the riser reaction zone, namely the low-temperature reaction zone, is carried out according to the condition favorable for catalytic conversion of high-boiling-point heavy components, the catalyst is regenerated, the reaction temperature is 515-550 ℃, and the reaction time is 1.2-2.5 s; the actual reaction temperature and the catalyst-to-oil ratio in the riser reaction zone are independently controlled by the lower regeneration dosage entering the low-temperature reaction zone;
(2) After the reaction raw materials complete the low-temperature catalytic cracking reaction in the riser reaction zone, the generated product and the catalyst flow upwards to enter the fast fluidized bed reaction zone, the upper catalyst introduced from the regenerator through the upper regeneration vertical pipe enters the fast fluidized bed reaction zone, heat is provided for the fast fluidized bed reaction zone, the temperature and the catalyst-oil ratio are improved, and the catalytic cracking reaction is continued to generate olefin products; the reaction temperature of the rapid fluidized bed reaction zone is 550-580 ℃ and the reaction time is 1.5-3.0 s; the absolute pressure of the reaction pressure is 0.20-0.26 MPa, and the actual reaction temperature and the catalyst-oil ratio in the rapid fluidized bed reaction zone are controlled by the amount of the catalyst entering the rapid fluidized bed reaction zone;
(3) All or part of the upper reaction zone of the reactor is arranged in the stripping section, an annular gap is arranged between the periphery of the upper reaction zone and the stripping section, and the catalyst in the stripping section returns to the upper reaction zone from the annular gap;
(4) The level of the spent agent in the stripping section is controlled by a spent agent slide valve, the spent agent amount returned to the upper reaction zone is controlled by the level of the spent agent, the space velocity of the catalyst in the upper reaction zone is further controlled, and the distribution of reaction products is controlled;
(5) And (3) enabling the reacted material flow to enter a settling section for gas-solid separation to obtain a reaction product, and enabling the separated catalyst to enter a regenerator for regeneration after steam stripping in a steam stripping section for recycling.
The invention has the following beneficial effects:
the reaction raw oil is reacted in a low-temperature riser reaction zone and a high-temperature rapid fluidized bed reaction zone in sequence, so that low-temperature catalytic cracking reaction and high-temperature olefin preparation catalytic cracking reaction are realized, and the catalyst of the regenerator respectively enters the riser reaction zone and the rapid fluidized bed reaction zone, so that gradual temperature rise in the reaction process is realized in a staged heat supply mode; the petroleum hydrocarbon reaction material is first catalytically cracked in low temperature reaction area to produce high boiling point heavy component, and the heavy component and macromolecule are first catalytically cracked, converted and decarbonized to produce intermediate components with high olefin gasoline and diesel oil as main components, and these intermediate products and catalyst enter the high temperature reaction area upwards to the upper part of the reactor, and the catalyst from the regenerator is then supplied to the area via the other path of the catalyst, i.e. the upper regenerator to raise the temperature and catalyst-oil ratio of the reactant and realize the heavy component macromolecule catalytically cracked, intermediate component and micromolecular cracked and converted.
The invention provides a method for preparing olefin by catalytic conversion with gradually heating, two-stage temperature gradient and independent control of weight hourly space velocity based on the catalytic cracking principle. As known by the person skilled in the art, the heavy oil catalytic cracking process can be regarded as parallel sequential reaction, heavy oil macromolecules (more than or equal to C18) are firstly cracked to generate intermediate molecular (C5-C12) products such as gasoline, diesel oil and the like, the lower cracking temperature can highlight the catalytic cracking reaction, and the proper temperature of the catalytic cracking reaction is 490-530 ℃ in general; part of gasoline and diesel oil is continuously cracked into C3-C4 at 540-580 ℃. The invention follows the reaction rule, and sets up two stages of temperature gradients which gradually rise in series: a low temperature region and a high temperature region; the invention realizes the adjustment and control of the catalyst-oil ratio and the catalyst space velocity in the reaction process without affecting the heat balance by returning the spent catalyst to the reactor. The invention reduces the yield of low-value target products such as coke and dry gas on the premise of lower energy consumption; the yield of high-value target products such as olefin is improved.
In summary, the method of the invention makes the reaction conditions adapt to the reaction chemical conditions that the petroleum hydrocarbon molecules gradually become smaller and the required reaction severity gradually increases in the cracking process of petroleum hydrocarbon reaction raw materials by controlling the agent-oil ratio, airspeed and temperature of the reaction process in a grading manner, in particular to realize that the agent-oil ratio and the temperature gradually increase, the weight hourly airspeed decreases and the reaction severity gradually increases along with the progress of the reaction; the invention also well optimizes the common conversion effect of the raw materials with different properties of heavy components and light hydrocarbons, avoids the excessive cracking of small molecular light hydrocarbons, ensures the recombination and cracking conditions and ensures the light hydrocarbon cracking conditions; the method improves the efficiency and the selectivity of the target product.
Drawings
FIG. 1 is a schematic process flow diagram of a method for producing olefins by catalytic conversion of petroleum hydrocarbons according to the present invention;
the numbering in the figures illustrates:
r10, a reactor; r11, catalyst lifting gas; R11A, a catalyst lifting gas inlet, R12, reaction raw oil, R12A, a reaction raw oil inlet, R13, raw oil atomization steam, R14A, a lower regenerant inlet, R15, reaction supplementary steam, R15A, a reaction supplementary steam inlet, R17, a riser reaction zone, R18 and a fast fluidized bed reaction zone; R34A and spent agent return to the inlet of the reactor, R24A and upper regenerant inlet;
s10, a stripping section, S11 and a stripping component; s12, a stand pipe to be generated; S12A, a spent catalyst outlet (spent catalyst outlet); VS12, spent catalyst slide valve (spent catalyst slide valve); s13, stripping steam, S13A, a stripping steam inlet, D10, a sedimentation section, D11, a sedimentation cyclone separator, D12, hydrocarbon products, D12A and a hydrocarbon product outlet;
g10, regenerator, G11, catalyst regeneration gas, G11A, regeneration gas inlet, G12, upper regeneration zone, G12A, spent agent inlet, G13, lower regeneration zone, G14, lower regeneration riser (lower regenerant transfer pipe), G14A, lower regenerant outlet, G15, regenerator dilute phase zone, G16, regeneration cyclone, G17, post-char flue gas, G17A, flue gas outlet, G18, air, G18A, second regeneration gas inlet, G24, upper regeneration riser (upper regenerant transfer pipe), G24A, upper regenerant outlet; VG14, lower regenerant spool valve, VG24, upper regenerant spool valve;
TI, a temperature detector, TC and a temperature controller.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The method for preparing olefin by catalytic conversion of petroleum hydrocarbon adopts a catalytic conversion device shown in fig. 1, and is provided with a reactor R10 and a regenerator G10. The petroleum hydrocarbon is used as raw oil, and in specific implementation, the reaction raw oil can be at least one of vacuum wax oil, normal-pressure residual oil, hydrotreated wax oil, hydrotreated residual oil and crude oil;
the reactor R10 comprises a sedimentation section D10, a stripping section S10, a rapid fluidized bed reaction zone R18 and a riser reaction zone R17 which are communicated with each other from top to bottom; the top of the sedimentation section D10 is provided with a hydrocarbon product outlet D12A for leading out hydrocarbon products D12; the diameter of the rapid fluidized bed reaction zone R18 is smaller than that of the stripping section S10 and larger than that of the riser reaction zone R17, the rapid fluidized bed reaction zone R18 is partially arranged in the stripping section S10, the top outlet of the rapid fluidized bed reaction zone R18 is upwards communicated with the inlet D11 of the sedimentation cyclone separator in the sedimentation section D10, an annular space is formed between the shell of the stripping section S10 and the rapid fluidized bed reaction zone R18, the annular space is communicated with the middle part of the rapid fluidized bed reaction zone R18 through an annular space channel R34A, a stripping component S11 is arranged in the annular space, and stripping steam S13 is introduced into the stripping section S10 through a stripping steam inlet S13A to realize catalyst stripping; the lower part of the stripping section S10 is provided with a spent agent outlet S12A which is communicated with a spent agent inlet G12A of the upper regeneration zone G12 through a spent vertical pipe S12, and the spent vertical pipe S12 is provided with a spent catalyst slide valve VS12;
a rapid fluidized bed reaction zone R18 and a riser reaction zone R17 in the reactor R10, wherein the two reaction zones are used for setting the reactor R10 into an upper-lower partition reactor form with two paths of catalyst circulation and two times of heat supply, the diameter of the rapid fluidized bed reaction zone R18 is larger than that of the riser reaction zone R17, the riser reaction zone R17 is used for low-temperature catalytic cracking reaction, and the rapid fluidized bed reaction zone R18 is used for high-temperature propylene cracking reaction; the lower regenerant inlet R14A at the lower part of the riser reaction zone R17 is communicated with the lower regenerant outlet G14A of the regenerator G10 through a lower regeneration vertical pipe G14, a lower regenerated catalyst slide valve VG14 is arranged on the lower regeneration vertical pipe G14, the upper catalyst inlet R24A at the lower part, namely the upper part, of the riser reaction zone R17 is communicated with the upper regenerant outlet G24A of the regenerator G10 through an upper regeneration vertical pipe G24, and the upper regenerated catalyst slide valve VG24 is arranged on the upper regeneration vertical pipe G24; a reaction raw material oil inlet R12A is arranged at the lower part of a riser reaction zone R17 to introduce a reaction raw material R12 and raw material atomization steam R13, the reaction raw materials can be fed in layers (4 reaction raw material oil inlets are arranged in the embodiment), a reaction supplementary steam inlet R15A is also arranged below the reaction raw material oil inlet R12A at the lower part of the riser reaction zone R17 to introduce a reaction supplementary steam R15, and a catalyst lifting gas inlet R11A is arranged at the bottom of a reactor R10 to introduce a catalyst lifting gas R11;
the interior of the regenerator G10 is divided into a dilute phase zone G15 and a regeneration zone from top to bottom, a flue gas outlet G17A is arranged at the top of the dilute phase zone G15, flue gas G17 after the regenerator is burnt is discharged from the flue gas outlet G17A at the top of the regenerator G10, the regenerator G10 is regenerated by adopting two zones which are arranged in series up and down, an upper regeneration zone G13 and a lower regeneration zone G12 are arranged below the dilute phase zone G15, a to-be-regenerated agent firstly enters the upper regeneration zone G12, a lower regeneration agent outlet G14A is arranged in the lower regeneration zone G13, and an upper regeneration agent outlet G24A is arranged in the upper regeneration zone G12, so that semi-regeneration agent or carbon-containing catalyst is provided for a rapid fluidized bed reaction zone R18 through the upper regeneration zone G12, and a regeneration agent is provided for a riser reaction zone R17 through the lower regeneration zone G13; a dilute phase zone G15 of the regenerator G10 is internally provided with a regeneration cyclone separator G16, and catalyst regeneration gas G11 is introduced from a regeneration gas inlet G11A at the bottom of the regenerator G10; air G18 is introduced into regenerator G10 through a second regeneration gas inlet G18A in the lower portion of upper regeneration zone G12;
an annular gap channel R34A is arranged around a rapid fluidized bed reaction zone R18 of the reactor R10 and between the stripping sections, and a catalyst in the stripping section S10 returns to the upper reaction zone R18 through a spent agent return reactor inlet R34A of the channel, so that the catalyst density is improved, the reaction speed is reduced, and the activity of the catalyst is controlled; the catalyst level in the stripping section is controlled by a spent catalyst slide valve VS12, and the spent catalyst flow rate returned to the reaction section is controlled by the catalyst level in the stripping section;
in order to facilitate detection and control of the temperature of the riser reaction zone R17 and the fast fluidized bed reaction zone R18, both the riser reaction zone R17 and the fast fluidized bed reaction zone R18 are provided with a temperature detector TI and a temperature controller TC.
In the invention, the catalyst of the regenerator G10 respectively enters a riser reaction zone R17 and a rapid fluidized bed reaction zone R18, and gradual temperature rise in the reaction process is realized by a graded heat supply mode; the specific implementation process comprises the following steps:
(1) The preheated reaction raw material R12 is atomized by raw material atomization steam R13 and then enters a riser reaction zone R17 at the lower part of a reactor R10, a lower catalyst from a lower regeneration riser G14 to a regenerator upper regeneration zone G12 enters the riser reaction zone R17 from a lower regenerant inlet R14A, and is conveyed upwards to contact with the raw material under the action of catalyst lifting gas R11, and the reaction raw material R12 is subjected to catalytic cracking conversion under a mild condition in a catalyst environment to form an intermediate product mainly comprising C5-C12; the reaction temperature of the riser reaction zone R17 is 515-550 ℃, the reaction time is 1.0-2.5 s, and the catalyst-oil ratio is 5-15;
(2) After the reaction raw material R12 completes the low-temperature catalytic cracking reaction, then the product generated in the riser reaction zone R17 flows upwards to enter a rapid fluidized bed reaction zone R18 together with a catalyst, a new catalyst, namely, an upper catalyst introduced from a regenerator G10 through an upper regeneration vertical pipe G24 enters the rapid fluidized bed reaction zone R18, is conveyed to the rapid fluidized bed reaction zone R18 by a material flow from the riser reaction zone R17, the new catalyst further provides heat for the rapid fluidized bed reaction zone R18, the catalyst-oil ratio of the rapid fluidized bed reaction zone R18 is 5-20, a high-temperature cracking reaction condition with a higher severity is formed, and the product from the riser reaction zone continues to perform catalytic cracking and thermal cracking combined reaction, and is a low-carbon-number small molecular product such as ethylene, propylene and the like; the reaction temperature of the rapid fluidized bed reaction zone R18 is 550-580 ℃, the reaction time is 1.5-3.0 s, the weight hourly space velocity of the catalyst is 10 (1/H) to 35 (1/H), the absolute pressure of the reaction pressure is 0.20-0.26 MPa, the actual reaction temperature is controlled by the high-temperature catalyst amount entering the rapid fluidized bed reaction zone R18, and the catalyst-oil ratio of the rapid fluidized bed reaction zone R18 is controlled to be 5-20. The method comprises the steps of carrying out a first treatment on the surface of the
(3) The material flow after the reaction enters a sedimentation section D10 for gas-solid separation to obtain a hydrocarbon product D12, and the hydrocarbon product D12A is sent out to a subsequent treatment part; after being separated by a settling cyclone D11, the catalyst in the reacted material flow enters an upper regeneration zone G12 of the regenerator G10 through a spent riser S12A and a spent agent inlet G12A after being stripped in a stripping section S10, and is regenerated and recycled.
In practice, the hydrocarbon product D12 leaves the catalytic conversion device shown in FIG. 1 and is subjected to product fractionation; fractionation, etc. are well known to the engineering skilled person.
Example 1
The petroleum hydrocarbon is used as a reaction raw material for preparing propylene by catalytic conversion, the device and the process are shown in figure 1, and the implementation parameters are as follows:
the reaction raw material is decompressed wax oil, the density is 0.88, the hydrogen content is 13.2 percent (weight), the residual carbon is 4.0 percent, and the saturated hydrocarbon is 60 percent;
the preheating temperature of the raw oil is 220 ℃;
the reaction device is formed by arranging a sedimentation section and a regenerator in parallel, wherein the regenerator adopts a serial regeneration mode of a quick fluidized bed of a coke burning tank and a dense phase fluidized bed;
riser reaction zone R17 reaction conditions: the reaction temperature TC is controlled at 530 ℃, the average flow rate of gas is 6.5m/s, and the reaction time is 1.5s (seconds); the catalyst conveying gas is steam, the quantity is 5% of the reaction raw materials, and the raw material atomizing steam is 7% of the raw materials; the supplementary steam is 15% of the raw material, the catalyst (namely the lower regenerant) entering from the inlet of the lower regenerant is regenerant, the carbon content is 0.02%, and the temperature of the lower regenerant is 680 ℃;
rapid fluidized bed reaction zone R18 reaction conditions: the reaction temperature is controlled to 560 ℃, the catalyst entering from the upper regenerant inlet (namely the upper regenerant) is a semi-regenerant, the carbon content is 0.15%, the temperature is 690 ℃, the average flow rate of gas in a reaction zone is 3.5m/s, the catalyst space velocity is 15 (1/H), and the reaction time is 1.8 seconds;
the reaction process is as follows:
the reaction raw materials are atomized by steam and then enter a riser reaction zone, and heavy oil catalytic cracking conversion is carried out under the heat provided by a lower regenerant and a catalyst environment, so that the cracking conversion of heavy oil macromolecules into intermediate molecules is realized, intermediate component raw materials with the molecular weight of 80-200 are obtained as far as possible, and intermediate raw materials are provided for further conversion into propylene and propylene; the gas stream and the catalyst generated in the riser reaction zone continue to flow upwards into the high temperature reaction zone; the high-temperature catalyst from the regenerator, namely the upper catalyst, enters a rapid fluidized bed reaction zone, is upwards conveyed into the high-temperature reaction zone by gas from a low-temperature reaction zone, further provides heat for the high-temperature reaction zone, improves the reaction temperature in the high-temperature reaction zone, and realizes the conversion reaction of propylene by combining the catalytic reaction of intermediate components and the thermal reaction; the reactant flow of the high-temperature reaction zone is subjected to gas-solid separation in a settling section through a gas-solid separator, and the gas from which the catalyst is separated flows out of the settling section and enters a subsequent treatment system;
the catalyst to be regenerated is separated in the sedimentation section, and then enters a regenerator for catalyst regeneration after being stripped in the stripping section, and firstly enters an upper regeneration zone and then enters a lower regeneration zone, and the catalyst enters a reactor for recycling after being regenerated;
the regeneration of the catalyst, the gas-solid separation and the subsequent oil and gas treatment are common techniques, and are well known to the skilled person and will not be described again.
Comparative example 1
The difference from example 1 is that comparative example 1 is the same as example 1 with the slide valve VG24 closed, the riser reactor R17 reaction temperature is 560 c, the fast fluidized bed reactor R18 reaction temperature is 530 c, and the other fluidizing medium and fluidizing gas velocities are the same as example 1.
The results of example 1 and comparative example 1 are shown in table 1, with the comparative example being the closed state of the slide valve VG 24. From the results in Table 1, it can be seen.
Table 1 comparison of evaluation data of example 1 and comparative example 1
As can be seen from Table 1, the yields of ethylene and propylene are significantly improved, the yields of coke and dry gas are reduced (ethylene is subtracted), and the yields of lower olefins are significantly improved. Therefore, the cracking process is also illustrated to have fewer secondary side reactions, the utilization efficiency of the catalyst is improved, and the selectivity of the target product is increased.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (10)
1. An apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon, comprising: a reactor and a regenerator, wherein the reactor and the regenerator are arranged in a reactor,
the reactor comprises a sedimentation section, a stripping section, a rapid fluidized bed reaction zone and a riser reaction zone which are communicated with each other from top to bottom; the top of the settling section is provided with a hydrocarbon product outlet, the diameter of the rapid fluidized bed reaction zone is smaller than that of the stripping section and larger than that of the riser reaction zone, part or all of the rapid fluidized bed reaction zone is arranged in the stripping section, the top outlet of the rapid fluidized bed reaction zone is communicated with the settling section, an annular space is formed between the shell of the stripping section and the rapid fluidized bed reaction zone, the annular space is communicated with the middle part of the rapid fluidized bed reaction zone through an annular gap channel, a stripping member is arranged in the annular space, and the stripping section is provided with a spent catalyst outlet and a stripping steam inlet; the bottom of the riser reaction zone is provided with a catalyst lifting gas inlet, the lower part of the riser reaction zone is provided with a lower regenerant inlet, a reaction supplementary steam inlet and a reaction raw oil inlet from bottom to top, and the upper part or the upper part of the riser reaction zone is provided with an upper regenerant inlet;
the regeneration device comprises a regenerator, wherein the interior of the regenerator is divided into a dilute phase zone and a regeneration zone from top to bottom, a flue gas outlet is arranged at the top of the dilute phase zone, a spent catalyst inlet, an upper regenerant outlet and a lower regenerant outlet are arranged in the regeneration zone, the regeneration zone is respectively communicated with the spent catalyst outlet, the upper regenerant inlet and the lower regenerant inlet, and a regeneration gas inlet is arranged at the bottom of the regeneration zone.
2. The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 1, wherein said regeneration zone comprises an upper regeneration zone and a lower regeneration zone, said agent inlet to be regenerated being provided in said upper regeneration zone, said lower agent outlet and said regeneration gas inlet being provided in said lower regeneration zone.
3. The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 1, wherein the bottom of said upper regeneration zone is provided with a second regeneration gas inlet.
4. The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 1, wherein at least one, preferably 2, 4 or 6, reaction raw oil inlets are provided.
5. The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 1, wherein said spent catalyst outlet and said spent agent inlet are in communication via a spent riser, said upper regenerator outlet and said upper regenerator inlet are in communication via an upper regenerator riser, and said lower regenerator outlet and said lower regenerator inlet are in communication via a lower regenerator riser.
6. The apparatus for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 1, wherein a settling cyclone is provided inside the settling section; a regeneration cyclone separator is arranged in the dilute phase zone; slide valves are arranged on the stand pipe to be regenerated, the upper regeneration stand pipe and the lower regeneration stand pipe.
7. A process for the catalytic conversion of petroleum hydrocarbons to propylene, characterized in that the plant for the catalytic conversion of petroleum hydrocarbons to propylene according to any one of claims 1 to 6 comprises the following steps:
(1) The catalyst lifting gas enters from the bottom of the reactor, the regenerant is carried upwards by the catalyst lifting gas after entering from the lower part of the reactor, the reaction raw oil enters into the riser reaction zone and contacts with the regenerant to generate low-temperature catalytic cracking reaction to generate an intermediate product, the reaction temperature of the riser reaction zone is 515-550 ℃, the reaction time is 1.2-2.5 s, the catalyst-oil ratio is 5-15, and the reaction pressure is 0.20-0.26 MPa;
(2) The intermediate product and the catalyst flow upwards to enter the rapid fluidized bed reaction zone, the regenerant enters the rapid fluidized bed reaction zone through the upper regenerant inlet to perform high-temperature catalytic cracking reaction with the intermediate product, the reaction temperature of the rapid fluidized bed reaction zone is 550-580 ℃, the reaction time is 0.5-2.0 s, the reaction pressure is 0.20-0.26 MPa, and the catalyst-oil ratio is 5-20;
(3) And the reactant flow discharged from the rapid fluidized bed reaction zone enters the sedimentation section for gas-solid separation, hydrocarbon products obtained by separation are discharged from the sedimentation section, solid products, namely spent catalyst, are settled into the stripping section, enter the annular space after stripping, and then enter the regenerator for recycling after regeneration.
8. The method for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 7, wherein the average flow rate of gas in said riser reaction zone is 5.0m/s to 20m/s; the gas average flow rate of the rapid fluidized bed reaction zone is 1.8 m/s-5.0 m/s, and the catalyst weight hourly space velocity is 10 (1/H) -35 (1/H); preferably, the steam in the riser reaction zone accounts for 5-30% of the mass of the reaction raw materials, and the steam in the rapid fluidized bed reaction zone accounts for 15-50% of the mass of the reaction raw materials.
9. The method for producing propylene by catalytic conversion of petroleum hydrocarbon according to claim 7, wherein said reaction raw oil is one selected from the group consisting of vacuum wax oil, atmospheric residuum, coker wax oil, deasphalted oil and hydrotreated residuum.
10. The method for preparing propylene by catalytic conversion of petroleum hydrocarbon according to claim 7, wherein the temperature of the lower regenerant is 680 ℃ to 720 ℃ and the carbon content is lower than 0.10%; the temperature of the upper regenerant is 680-720 ℃, and the carbon content is lower than 0.3%.
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