CN118308146B - A catalytic conversion method and system for producing light olefins and light aromatics from crude oil - Google Patents
A catalytic conversion method and system for producing light olefins and light aromatics from crude oilInfo
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- CN118308146B CN118308146B CN202310029158.0A CN202310029158A CN118308146B CN 118308146 B CN118308146 B CN 118308146B CN 202310029158 A CN202310029158 A CN 202310029158A CN 118308146 B CN118308146 B CN 118308146B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
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Abstract
本发明提供了一种原油生产低碳烯烃和轻芳烃的催化转化方法，包括：S1、原油进行闪蒸，得到轻馏分油和重馏分油；将所述轻馏分油与第一催化剂在下行床反应器中接触，得到第一半再生剂；S2、将第二催化剂和所述第一半再生剂分别从底部和中部引入提升管反应器；并且将所述重馏分油从底部引入所述提升管反应器中与所述第二催化剂和所述第一半再生剂依次接触，进行第二催化转化反应，得到第二油剂混合物；S3、将所述第二油剂混合物导入催化剂分离装置进行分离；S4、将第三油剂混合物再进行气固分离。本发明还提供了一种催化转化系统。通过上述技术方案，本发明提高了原油生产低碳烯烃和轻芳烃的产率。
The present invention provides a catalytic conversion method for producing light olefins and light aromatics from crude oil, comprising: S1, flashing crude oil to obtain light distillate oil and heavy distillate oil; contacting the light distillate oil with a first catalyst in a downer reactor to obtain a first semi-regenerated agent; S2, introducing a second catalyst and the first semi-regenerated agent into a riser reactor from the bottom and middle, respectively; and introducing the heavy distillate oil from the bottom into the riser reactor to sequentially contact the second catalyst and the first semi-regenerated agent to perform a second catalytic conversion reaction to obtain a second oil-agent mixture; S3, introducing the second oil-agent mixture into a catalyst separation device for separation; S4, further subjecting the third oil-agent mixture to gas-solid separation. The present invention also provides a catalytic conversion system. Through the above technical solution, the present invention improves the yield of light olefins and light aromatics produced from crude oil.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalytic conversion method and a catalytic conversion system for producing low-carbon olefin and light aromatic hydrocarbon from crude oil.
Background
Crude oil is a complex mixture of various hydrocarbons. At present, a refinery mainly converts crude oil into fuels such as gasoline, kerosene, diesel oil and the like, and simultaneously byproducts such as ethylene, propylene and BTX (benzene, toluene and xylene are called BTX for short). The annual growth rate of the demand for vehicle fuels has been gradually reduced in recent years, and fuels such as gasoline, kerosene, and diesel have tended to have an excessive capacity. However, petrochemical products such as ethylene, propylene and BTX have very wide applications, and the demand has been increasing in recent years. Therefore, a petroleum refining method for reducing the yield of fuels such as gasoline, kerosene, diesel oil and the like and improving the yield of petrochemical products such as ethylene, propylene, BTX and the like is developed.
For example, CN106029610a discloses an integrated process and plant for converting crude oil into petrochemical products. The integrated process in which the facilities include a crude distillation unit, a hydrocracking unit, an aromatization unit, and an olefin synthesis unit includes crude distillation, hydrocracking, aromatization, and olefin synthesis. .
However, there is a need to further increase the yields of ethylene, propylene and light aromatics from crude oil.
Disclosure of Invention
The invention aims to further improve the yield of ethylene, propylene and light aromatic hydrocarbon prepared from crude oil.
The invention provides a catalytic conversion method for producing light olefins and light aromatics from crude oil, which comprises the following steps of S1, carrying out flash evaporation on crude oil to obtain light distillate and heavy distillate, enabling the light distillate to be in contact with a first catalyst in a down-bed reactor to carry out a first catalytic conversion reaction, carrying out first gas-solid separation on the obtained first oil catalyst mixture to obtain first reaction oil gas and a first half of regeneration catalyst, S2, respectively introducing a second catalyst and the first half of regeneration catalyst into a riser reactor from the bottom and the middle, and enabling the heavy distillate to be in contact with the second catalyst and the first half of regeneration catalyst in sequence, carrying out a second catalytic conversion reaction to obtain a second oil catalyst mixture, S3, introducing the second oil catalyst mixture into a catalyst separation device to carry out separation to obtain a second to-be-regenerated catalyst and a third oil catalyst mixture, S4, carrying out gas-solid separation on the third oil catalyst mixture to obtain the second to-be-regenerated catalyst and the first to-be-regenerated catalyst, and S4, and taking the second to-be-regenerated catalyst and S5 to take part in the first catalytic conversion reaction, and the first to take part in the first to be in the first catalytic conversion step.
The invention also provides a catalytic conversion system for producing light olefins and light aromatics from crude oil, which comprises a crude oil flash tank, a descending reactor, a riser reactor, a settler and a regenerator, wherein a top discharge port of the crude oil flash tank is communicated with an oil gas inlet at the upper end of the descending reactor, a bottom discharge port of the crude oil flash tank is communicated with a lower oil gas inlet of the riser reactor, a first gas-solid separator is arranged at the lower end of the descending reactor, a solid outlet of the first gas-solid separator is communicated with a first half of regenerator inlet at the middle part of the riser reactor, a settler separator and a catalyst separator are arranged in the settler, the settler separator is divided into a first settling zone at the upper part and a second settling zone at the lower part, a material inlet of the catalyst separator is communicated with the upper end of the riser reactor, the catalyst separator is also provided with a first material outlet arranged in the first settling zone and a second material settling zone arranged in the second settling zone, the first stripper is also connected with the second stripper zone, the second stripper is also connected with the second stripper zone, the regenerator partition plate divides the regenerator into a first regeneration zone and a second regeneration zone, a first to-be-regenerated catalyst conveying connection is arranged between the first stripper and the first regeneration zone, a second to-be-regenerated catalyst conveying connection is arranged between the second stripper and the second regeneration zone, a first regenerated catalyst conveying connection is arranged between the first regeneration zone and the descending reactor, a second regenerated catalyst conveying connection is arranged between the second regeneration zone and the lifting pipe reactor, a second stripper is arranged at the lower part of the second sedimentation zone, and a first stripper is arranged in the first to-be-regenerated catalyst conveying connection.
According to the technical scheme, the crude oil is subjected to flash evaporation separation, the obtained light distillate oil reacts with the first catalyst of the light oil catalyst, and the heavy distillate oil reacts with the second catalyst rich in the heavy oil catalyst and the first half of the regenerant in sequence, so that the partition conversion of the light distillate oil and the heavy distillate oil is realized, the relay of the primary cracking reaction and the secondary cracking reaction of the heavy distillate oil is facilitated, and the yields of the light olefins and the light aromatics are improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
Fig. 1 is a schematic structural view of a catalytic conversion system according to an embodiment of the present invention.
Description of the reference numerals
In fig. 1, reference numerals are explained as follows:
1-crude oil flash tank 2-catalyst distributor 3-downgoing reactor
4-First gas-solid separator 5-riser reactor 6-catalyst separator
7-First settling zone 8-first stripper 9-second settling zone
10-Second stripper 11-first regeneration zone 12-second regeneration zone
101-Crude oil 102-light distillate 103-heavy distillate
104-Remixed light fraction 105-first reaction oil gas 106-first semi-regenerant
107-Pre-lift gas 108-second oil mixture delivery pipe
109. 115-Stripping gas 110, 116-stripping baffle 111-settler baffle
112-Second spent agent delivery pipe 113, 118-oil and gas pipeline
114. 117-First spent agent delivery tube
119-Cyclone 120-gas collection chamber 121-reaction oil gas
122-Main air 123-regenerator separator 124-first catalyst transfer pipe
125-Second catalyst transfer tube 126, 127-cyclone 128-plenum
129-Regenerated flue gas
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a catalytic conversion method for producing light olefins and light aromatics from crude oil, which comprises the following steps of S1, carrying out flash evaporation on the crude oil to obtain light distillate and heavy distillate, enabling the light distillate to be in contact with a first catalyst in a down-bed reactor to carry out a first catalytic conversion reaction, carrying out first gas-solid separation on the obtained first oil catalyst mixture to obtain first reaction oil gas and a first half of regeneration catalyst, S2, respectively introducing a second catalyst and the first half of regeneration catalyst into a riser reactor from the bottom and the middle, and introducing the heavy distillate into the riser reactor from the bottom to be in contact with the second catalyst and the first half of regeneration catalyst in sequence to carry out a second catalytic conversion reaction to obtain a second oil catalyst mixture, S3, introducing the second oil catalyst mixture into a catalyst separation device to carry out separation to obtain a second to-be-regenerated catalyst and a third oil catalyst mixture, S4, carrying out gas-solid separation on the third oil catalyst mixture to obtain the first to-be-regenerated catalyst and S5, and carrying out the second catalytic conversion reaction to take part in the first to be in the first step of the first catalytic conversion reaction, and the first to take part in the first to be regenerated step 1.
In the invention, part of oil gas is carried in the first half regenerated catalyst generated in the down-flow reactor, heavy distillate oil in the lower part of the riser reactor contacts with the second catalyst to carry out the first stage of the second catalytic conversion reaction, and then the heavy distillate oil contacts with the first half regenerated catalyst in the upper part of the riser reactor to carry out the second stage of the second catalytic conversion reaction with the first half regenerated catalyst, namely relay performance of the catalytic conversion reaction can be realized.
Wherein, optionally, for convenience, the separation of the first spent catalyst and the second spent catalyst is performed, the particle size and density of the second catalyst are both larger than those of the first catalyst.
The catalyst comprises a first catalyst, a second catalyst, a third catalyst, a fourth catalyst and a fifth catalyst, wherein the first catalyst comprises 60-100 mass% of a light oil catalyst and 0-40 mass% of a heavy oil catalyst, and the second catalyst comprises 0-40 mass% of a light oil catalyst and 60-100 mass% of a heavy oil catalyst.
Preferably, the first catalyst contains 80-100% by mass of a light oil catalyst and 0-20% by mass of a heavy oil catalyst, and the second catalyst contains 0-20% by mass of a light oil catalyst and 80-100% by mass of a heavy oil catalyst.
Wherein, optionally, the heavy oil catalyst comprises an unmodified Y-type molecular sieve or a modified Y-type molecular sieve, clay, and a binder.
Wherein, optionally, based on the total weight of the heavy oil catalyst, the content of the unmodified Y-type molecular sieve or the modified Y-type molecular sieve is 10-80%, preferably 30-60%, the content of clay is 10-80%, preferably 15-60%, and the content of the binder is 10-30%, preferably 10-20%.
Wherein, optionally, the particle size range of the heavy oil catalyst is 60-250 μm, preferably 80-200 μm, and the particle density is 1200-160 kg/m 3, preferably 1300-1500 kg/m 3.
The clay is selected from various clays which can be used as catalyst components, such as kaolin, montmorillonite, bentonite, etc. The binder is selected from one or two or three of silica sol, alumina sol and pseudo-boehmite, wherein the preferred binder is a double-aluminum binder of alumina sol and pseudo-boehmite.
Wherein optionally the light oil catalyst comprises an unmodified ZSM-5 molecular sieve or a modified ZSM-5 molecular sieve, clay and a binder.
Wherein, optionally, based on the total weight of the catalyst, the content of the unmodified ZSM-5 molecular sieve or the modified ZSM-5 molecular sieve is 10-60%, preferably 20-50%, the content of clay is 10-80%, preferably 20-70%, and the content of the binder is 10-30%, preferably 10-20%.
Wherein, optionally, the particle size range of the light oil catalyst is 10-100 μm, preferably 30-80 μm, and the particle density is 800-1200 kg/m 3, preferably 900-1100 kg/m 3.
The clay is selected from various clays which can be used as catalyst components, such as kaolin, montmorillonite, bentonite, etc. The binder is selected from one or two or three of silica sol, alumina sol and pseudo-boehmite, wherein the preferred binder is a double-aluminum binder of alumina sol and pseudo-boehmite.
Wherein, optionally, the first regeneration and the second regeneration are respectively carried out in a first regeneration zone and a second regeneration zone of the regenerator, wherein the first regeneration zone and the second regeneration zone are arranged in parallel, and the first regeneration zone and the second regeneration zone adopt complete regeneration.
The regeneration conditions of the first regeneration zone and the second regeneration zone respectively and independently comprise a regeneration temperature of 670-730 ℃, preferably 690-710 ℃, a catalyst distribution density of 30-350 kg/m 3, preferably 80-250 kg/m 3, and a main air residence time of 0.5-15 s, preferably 2-10 s.
Wherein, optionally, the reaction temperature of the downlink reactor is 620-700 ℃, preferably 640-680 ℃, the catalyst-to-oil ratio is 10-50, preferably 20-30, and the reaction time is 0.1-5 seconds, preferably 0.5-3 seconds.
The reaction temperature of the riser reactor is 520-620 ℃, preferably 540-600 ℃, the catalyst-to-oil ratio is 2-25, preferably 3-20, and the reaction time is 1-15 seconds, preferably 2-10 seconds.
Wherein, optionally, the inlet of the first half of the regenerant on the riser reactor is 30-70%, preferably 40-60% of the total height of the riser reactor from the bottom of the riser reactor.
Wherein, optionally, the temperature cutting point of the light distillate and the heavy distillate is any temperature between 250 ℃ and 400 ℃, preferably any temperature between 280 ℃ and 350 ℃.
The method preferably further comprises the steps of separating a remixed light fraction from the first reaction oil gas and/or the third reaction oil gas, introducing the remixed light fraction from the top of the downlink reactor for remixing, wherein the initial distillation point of the remixed light fraction is any temperature between 10 and 40 ℃, and the final distillation point is any temperature between 50 and 80 ℃.
Wherein optionally the process further comprises introducing a pre-lift gas to the bottom of the riser reactor, said pre-lift gas may be selected from one or more of steam, nitrogen, dry gas, preferably steam.
The invention also provides a catalytic conversion system for producing light olefins and light aromatics from crude oil, which comprises a crude oil flash tank, a descending reactor, a riser reactor, a settler and a regenerator, wherein a top discharge port of the crude oil flash tank is communicated with an oil gas inlet at the upper end of the descending reactor, a bottom discharge port of the crude oil flash tank is communicated with a lower oil gas inlet of the riser reactor, a first gas-solid separator is arranged at the lower end of the descending reactor, a solid outlet of the first gas-solid separator is communicated with a first half of regenerator inlet at the middle part of the riser reactor, a settler separator and a catalyst separator are arranged in the settler, the settler separator is divided into a first settling zone at the upper part and a second settling zone at the lower part, a material inlet of the catalyst separator is communicated with the upper end of the riser reactor, the catalyst separator is also provided with a first material outlet arranged in the first settling zone and a second settling zone arranged in the second settling zone, the first stripper is also connected with the second settling zone, the second stripper is also connected with the second settling zone, the regenerator partition plate divides the regenerator into a first regeneration zone and a second regeneration zone, a first to-be-regenerated catalyst conveying connection is arranged between the first stripper and the first regeneration zone, a second to-be-regenerated catalyst conveying connection is arranged between the second stripper and the second regeneration zone, a first regenerated catalyst conveying connection is arranged between the first regeneration zone and the descending reactor, a second regenerated catalyst conveying connection is arranged between the second regeneration zone and the lifting pipe reactor, a second stripper is arranged at the lower part of the second sedimentation zone, and a first stripper is arranged in the first to-be-regenerated catalyst conveying connection.
Wherein the downgoing reactor is selected from one or more of an equal diameter downgoing reactor and a variable diameter downgoing reactor, and the riser reactor is selected from one or more of an equal diameter riser reactor and a variable diameter riser reactor.
Wherein, optionally, the catalyst separation device separates the first catalyst from the second catalyst based on the particle size and density difference of the first catalyst and the particle size and density difference of the second catalyst.
As an embodiment of the first regenerated catalyst transfer connection between the first regeneration zone and the downgoing reactor, a first catalyst inlet is also provided in the upper part of the downgoing reactor, which may be used for introducing fresh first catalyst or for introducing regenerated first catalyst. As an embodiment of the second regenerated catalyst transfer connection between the second regeneration zone and the riser reactor, the lower part of the riser reactor is further provided with a second catalyst inlet, which may be used for introducing fresh second catalyst or for introducing regenerated second catalyst.
The catalyst separators are optionally one or more of cyclone type quick separators, three-leaf type quick separators, ejection type quick separators, U-shaped pipe type quick separators, wall-attached cutting type quick separators and the like, preferably cyclone type quick separators, the number of the catalyst separators in each settler is one or more, and a plurality of the catalyst separators are in serial connection and/or parallel connection.
As a particularly preferred embodiment of the present invention, referring to fig. 1, the top of the down-flow reactor 3 is provided with a catalyst distributor 2 for dispersing the first catalyst from the first regeneration zone 11 to have a better fluidization state, the bottom of the down-flow reactor 3 is provided with a first gas-solid separator 4, and the catalyst outlet of the first gas-solid separator 4 is connected with the middle part of the riser reactor 5 due to the separation of the first reaction oil-gas 105 and the first half-regenerant, and the down-flow reactor 3 is selected from one or more of a constant diameter down-flow reactor and a variable diameter down-flow reactor. In the present invention, the bottom of the riser 5 is connected to the second regeneration zone 12 through a second catalyst delivery pipe 125, and the middle of the riser reactor 5 is connected to the first gas-solid separator 4 at the bottom of the downgoing reactor 3 through a first half of a regenerant delivery pipe 106, where the height of the connection point from the bottom of the riser reactor is 30 to 70%, preferably 40 to 60% of the total height of the riser reactor. the top of the riser reactor 5 is connected to the catalyst separator 6 inside the settler by a second reaction oil mixture transfer pipe 108. The catalyst separator 6 is positioned in the interior of the settler, the settler is divided into an upper first settling zone 7 and a lower second settling zone 9 by a settler baffle 111, a first spent agent outlet of the catalyst separator 6 is positioned in the first settling zone 7, a second spent agent outlet is positioned in the second settling zone 9, the first settling zone 7 is communicated with the first stripper 8, so that the first spent agent is introduced into the first regeneration zone 11 for regeneration through a first spent agent conveying pipe 117 after being stripped in the first stripper 8, and the second settling zone 9 is communicated with the second stripper 10, so that the second spent agent is introduced into the second regeneration zone 12 for regeneration through a second spent agent conveying pipe 112 after being stripped in the second stripper 10. The catalyst separator 6 is selected from one or more of a cyclone type quick separator, a three-blade type quick separator, an ejection type quick separator, a U-shaped pipe type quick separator, a wall-attached cutting type quick separator and the like, and is preferably a cyclone type quick separator. The interior of the settler is also provided with a cyclone 119 for separating catalyst entrained in the reaction oil gas, and the obtained reaction oil gas 121 is led out of the device. The catalyst delivery rate can be regulated by a valve on the catalyst delivery tube. In the present invention, a first regeneration zone 11 and a second regeneration zone 12 are disposed in the regenerator, the first regeneration zone 11 and the second regeneration zone 12 are disposed in parallel, a partition 123 is disposed therebetween to separate the two catalysts, and the first regeneration zone 11 and the second regeneration zone 12 are completely regenerated. Cyclone separators 126 and 127 are arranged at the upper parts of the first regeneration zone 11 and the second regeneration zone 12, and are used for separating catalyst carried in the regenerated flue gas, and the obtained regenerated flue gas 129 is led out of the device. The first regeneration zone 11 is connected with the catalyst distributor 2 at the top of the downgoing reactor 3 through a first catalyst conveying pipe 124, the regeneration zone 12 is connected with the bottom of the riser reactor 5 through a second catalyst conveying pipe 125, and the conveying speed of the catalyst can be adjusted through a valve on the catalyst conveying pipe.
As a particularly preferred embodiment of the present invention, referring to fig. 1, crude oil 101 is preheated to 250 to 400 ℃ and then introduced into crude oil flash tank 1, and is split into light distillate 102 and heavy distillate 103 under the conditions of a temperature of 250 to 400 ℃, preferably 280 to 350 ℃, and a pressure of 0.1 to 0.3mpa, preferably 0.12 to 0.2mpa, wherein the temperature cut point of light distillate 102 and heavy distillate 103 is any temperature between 250 to 400 ℃, preferably any temperature between 280 to 350 ℃. The obtained light distillate 102 is sprayed into a following reactor 3 through a nozzle, and the reaction temperature is 620-700 ℃, preferably 640-680 ℃, the catalyst-oil ratio is 10-50, preferably 20-30, the reaction time is 0.1-5 seconds, preferably 0.5-3 seconds, the obtained light distillate is in contact reaction with the first catalyst introduced into the catalyst distributor 2 through the first catalyst conveying pipe 124, the generated first oil mixture is separated through the first gas-solid separator 4, the obtained first reaction oil gas 105 is led out of the device, and the obtained first half of the regenerant is led into the middle part of the riser reactor 5 through the first half of the regenerant conveying pipe 106. The heavy distillate 103 is sprayed into the bottom of the riser reactor 5 through a nozzle, the reaction temperature is 520-620 ℃, preferably 540-600 ℃, the catalyst-oil ratio is 2-25, preferably 3-20, the reaction time is 1-15 seconds, preferably 2-10 seconds, the heavy distillate is contacted and reacted with a second catalyst introduced into the bottom of the riser reactor 5 through a second regenerant conveying pipe 125, then the heavy distillate is contacted and reacted with a first half of regenerant introduced into the middle part of the riser reactor 5, the obtained second reaction oil mixture is introduced into a catalyst separator 6 and separated into a first to-be-regenerated agent and a second to-be-regenerated agent, the first to-be-regenerated agent is introduced into a first stripper 8 through a first settling zone 7 for stripping, the stripped first to-be-regenerated agent is introduced into a first regeneration zone 11 through a first to-be-regenerated agent conveying pipe 117, and the regenerated first catalyst is introduced into a catalyst distributor 2 at the top of the down-stream reactor 3 through a first catalyst conveying pipe 124. The second spent agent is introduced into the second stripper 10 through the second settling zone 9 for stripping, the stripped second spent agent is introduced into the second regeneration zone 12 through the second spent agent delivery pipe 112 for regeneration, and the regenerated second catalyst is introduced into the bottom of the riser reactor 5 through the second catalyst delivery pipe 125. And the main wind 122 is respectively led into the first regeneration zone 11 and the second regeneration zone 12, and is respectively completely regenerated with the first to-be-regenerated agent and the second to-be-regenerated agent, and the generated regenerated flue gas 129 is led out of the device. The regeneration temperature of the first regeneration zone and the second regeneration zone is 670-730 ℃, preferably 690-710 ℃, the catalyst density is 30-350 kg/m 3, preferably 80-250 kg/m 3, and the main air residence time is 0.5-15 s, preferably 2-10 s. The reaction oil and gas 105 and 121 enter a subsequent product separation system. In a product separation system, the catalytic cracking products are separated into fuel gas, ethylene, ethane, propylene, propane, carbon tetrahydrocarbon, light gasoline, heavy gasoline, diesel oil and slurry oil, and the light gasoline is introduced into the top of a downstream reactor 3 to be in contact reaction with the first catalyst.
The invention is illustrated in further detail by the following examples.
Three catalysts, GOR-II, RAG-6 and DMMC-2, were used in the examples and comparative examples, and were commercially available from Qilu corporation, petrochemical catalyst, china. The specific properties of the three catalysts are shown in Table 1. Wherein GOR-II is a catalyst containing 40 wt% of Y molecular sieve, RAG-6 is a catalyst containing 35 wt% of ZSM-5 molecular sieve, DMMC-2 is a catalyst containing 25 wt% of Y molecular sieve and 15 wt% of ZSM-5 molecular sieve. The catalyst was aged at 800 ℃ for 17 hours under 100% steam conditions prior to the test. The feedstock oils used in the examples and comparative examples were all Yangzhou crude oils, the specific properties of which are shown in Table 2. In examples and comparative examples, first, the Yangzhou crude oil was separated to obtain light distillate and heavy distillate, and properties of the light distillate and heavy distillate are shown in Table 3. Light gasoline fractions were also used as recycle materials in the examples and comparative examples, and the compositions and properties thereof are shown in Table 4.
TABLE 1 composition and Properties of the catalysts
| Catalyst | GOR-II | RAG-6 | DMMC-2 |
| Chemical composition,% (w) | |||
| Al2O3 | 57.5 | 51.2 | 48.1 |
| SiO2 | 36.1 | 43.1 | 46 |
| BET total analysis | |||
| BET total area/(m 2·g-1) | 181.000 | 197.000 | 102.491 |
| Micropore area/(m 2·g-1) | 104.000 | 98.000 | 49.601 |
| Total pore volume/(cm 3·g-1) | 0.2240 | 0.1500 | 0.1057 |
| Micropore volume/(cm 3·g-1) | 0.0340 | 0.0450 | 0.0259 |
| Particle Density/(kg/m 3) | 1352 | 965 | 987 |
| Particle size distribution,% (w) | |||
| 0-20μm | 0.1 | 0.5 | 0.1 |
| 0-40μm | 5.1 | 32.6 | 17 |
| 0-80μm | 20.3 | 87.3 | 70.9 |
| 0-105μm | 50.6 | 98.5 | 87.8 |
| >105μm | 49.4 | 1.5 | 12.2 |
TABLE 2 composition and Properties of Yangzhou crude oil
| Project | Yangzhou crude oil |
| Density (20 ℃ C.)/(kg/m 3) | 848.8 |
| Carbon residue mass fraction/% | 3.46 |
| Elemental mass composition/% | |
| C | 85.94 |
| H | 13.56 |
| S | 0.20 |
| N | 0.14 |
| Mass group composition/% | |
| Saturated hydrocarbons | 65.1 |
| Aromatic hydrocarbons | 26.3 |
| Colloid | 8.4 |
| Asphaltenes | 0.2 |
| Metal mass composition/(mg/kg) | |
| Fe | 1.4 |
| Ni | 9.9 |
| V | 0.1 |
| Na | 3.0 |
| Ca | 0.8 |
| Distillation range/° C | |
| Initial point of distillation | 40 |
| 10v% | 164.2 |
| 30v% | 330.3 |
| 50v% | 435.5 |
| 70v% | 574.1 |
| 85v% | 716.7 |
TABLE 3 composition and Properties of light and heavy distillate
TABLE 4 chemical composition and Properties of light gasoline fraction
| Project | Light gasoline |
| Density (20 ℃ C.)/(kg/m 3) | 635.1 |
| Elemental mass composition/% | |
| Carbon (C) | 84.76 |
| Hydrogen gas | 15.24 |
| Sulfur/(μg/g) | 46.29 |
| Nitrogen/(μg/g) | 32 |
| Distillation range/° C | |
| Initial point of distillation | 12 |
| 10v% | 18 |
| 30v% | 30 |
| 50v% | 35 |
| 70v% | 57 |
| 90v% | 59 |
| End point of distillation | 60 |
| Mass group composition/% | |
| Alkanes | 37.19 |
| Olefins | 62.49 |
| Cycloalkane (CNS) | 0.32 |
| Aromatic hydrocarbons | 0 |
Example 1
The test was performed on the apparatus shown in fig. 1. The apparatus comprises a downgoing reactor and a riser reactor. The diameter of the descending reactor is 15mm, the length is 2500mm, the inner diameter of the riser reactor is 16mm, and the length is 3200mm. The preheated light distillate oil is introduced into a downlink reactor to be in contact reaction with a first catalyst rich in RAG-6 catalyst, the obtained first reaction oil mixture is separated by a separation device, the obtained first reaction oil gas is led out of the device, a first half of regenerant is introduced into a position, which is 1500mm away from the bottom of a riser reactor, the heavy distillate oil is preheated and then introduced into the bottom of the riser reactor to be in contact reaction with a second catalyst rich in GOR-II catalyst, then the preheated heavy distillate oil is contacted with the first half of regenerant and then is continuously reacted, the generated second reaction oil mixture is introduced into a catalyst separator to be separated, the first to-be-regenerated catalyst rich in RAG-6 catalyst and the second to-be-regenerated catalyst rich in GOR-II catalyst are obtained, the two catalysts are introduced into a stripper through a settling zone to be stripped, the stripped to-be-regenerated agents are respectively introduced into different regeneration zones, and the regenerated catalysts are introduced into the reactor to be recycled. The reaction conditions and results are shown in Table 5.
Example 2
The process of example 1 was followed except that the light gasoline fraction was introduced as a feed to the top of the downgoing reactor along with the light distillate. The mass ratio of the light gasoline fraction to the light distillate oil is 0.2:1. The reaction conditions and results are shown in Table 5.
Comparative example 1
Unlike example 1, the apparatus used in this comparative example had only one riser reactor. The inner diameter of the riser reactor is 16mm and the length is 3200mm. The preheated Yangzhou crude oil is introduced into a riser reactor and contacted with DMMC-2 catalyst, the obtained oil mixture is separated through a separation device, the obtained reaction oil gas is led out of a device, the spent catalyst is led into a stripper for stripping through a settling zone, the stripped spent catalyst is respectively led into a regeneration zone for regeneration, and the regenerated catalyst is led into the riser reactor for recycling. The reaction conditions and results are shown in Table 5.
Comparative example 2
The procedure of example 1 was followed except that the catalyst used in the downgoing reactor and the riser reactor was a mixed catalyst of RAG-6 catalyst and GOR-II catalyst in a mass ratio of 1:1. The reaction conditions and results are shown in Table 5.
TABLE 5 reaction conditions and results for examples 1-2 and comparative examples 1-2
As can be seen from Table 5, the method and apparatus of the present invention can improve the yields of lower olefins such as ethylene and propylene.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (14)
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| CN102690682A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Catalytic cracking method and catalytic cracking device for producing propylene |
| CN114426877A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | A method for producing light olefins and BTX by catalytic cracking of crude oil |
| CN115161060A (en) * | 2021-04-02 | 2022-10-11 | 上海河图工程股份有限公司 | Catalytic cracking method and device for producing more low-carbon olefins |
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| CN110194967B (en) * | 2018-05-29 | 2021-07-23 | 青岛京润石化设计研究院有限公司 | Catalytic reaction regeneration method for producing more propylene |
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| CN114426877A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | A method for producing light olefins and BTX by catalytic cracking of crude oil |
| CN115161060A (en) * | 2021-04-02 | 2022-10-11 | 上海河图工程股份有限公司 | Catalytic cracking method and device for producing more low-carbon olefins |
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