CN111233609B - Naphtha-containing raw material conversion device - Google Patents
Naphtha-containing raw material conversion device Download PDFInfo
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- CN111233609B CN111233609B CN201811447630.8A CN201811447630A CN111233609B CN 111233609 B CN111233609 B CN 111233609B CN 201811447630 A CN201811447630 A CN 201811447630A CN 111233609 B CN111233609 B CN 111233609B
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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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- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The application discloses a conversion device of raw materials containing naphtha includes: a reaction unit comprising a riser reactor and a fluidized bed reactor; the top of the riser reactor is connected with the top expanded section of the fluidized bed reactor through a pipeline; introducing the pre-deposited carbon catalyst obtained by the riser reactor into the fluidized bed reactor; introducing raw materials containing naphtha and/or methanol into the fluidized bed reactor to contact and react with the pre-carbon deposition catalyst; and a regeneration unit comprising a regenerator; the reaction unit is connected with the regeneration unit through a pipeline, and a circulating system is formed; inputting the catalyst to be regenerated output from the reaction unit into a regeneration unit for regeneration to obtain a regenerated catalyst; the regenerated catalyst is fed into the reaction unit. The problem of improve the adjustable degeneration of naphtha catalytic cracking technique is solved, the device is arranged in naphtha catalytic cracking, has the advantage that the product kind is adjustable.
Description
Technical Field
The invention relates to a device for converting a raw material containing naphtha into low-carbon olefin, aromatic hydrocarbon and high-quality gasoline, belonging to the field of catalysis.
Background
Naphtha is one of the most important raw materials for producing ethylene and propylene. The naphtha high-temperature steam cracking is a huge petrochemical industry for preparing chemical products such as ethylene, propylene and the like. There are billions of tons of naphtha used to produce ethylene and propylene each year, with the production accounting for over 50% of the total ethylene and propylene production. Through the development of many years, the steam cracking technology reaches a high level, the conversion rate is high, and the yield of the product can reach a high level through one-time reaction. But the disadvantages are also obvious, the selectivity is poor, a large amount of methane is generated in the product, the reaction temperature is high, and the energy consumption is high. Its potential for development is already small. For this reason, a catalytic cracking technique using a catalyst to lower the cracking temperature has been vigorously developed. The existing naphtha catalytic cracking technology is mainly carried out by a riser reactor, so that the yield of ethylene and propylene is improved. But the relative adjustability range is small.
With the application of technologies such as the technology of preparing olefin from coal through methanol and the technology of preparing propylene through propane dehydrogenation, the sources of ethylene and propylene are increasingly rich. Therefore, naphtha catalytic cracking technology is required to have higher adjustable denaturation to meet the change of market demand. This application is fine has solved this problem.
Disclosure of Invention
According to an aspect of the application, a device for converting naphtha-containing raw materials into low-carbon olefins, aromatic hydrocarbons and high-quality gasoline is provided, the problem of improving the adjustable property of a naphtha catalytic cracking technology is solved, and the device is used for naphtha catalytic cracking and has the advantage of adjustable product types.
In order to solve the above problems, the technical scheme adopted by the application is as follows: a device for converting raw materials containing naphtha into low-carbon olefins, aromatic hydrocarbons and high-quality gasoline mainly comprises a riser reactor 2, a fluidized bed reactor 3 and a regenerator 9. The fluidized bed reactor 3 comprises a reactor expanding section 14, a reaction section 15 and a reactor steam stripping section 16, the regenerator 9 comprises a regenerator expanding section 17, a regeneration section 18 and a regenerator steam stripping section 19, a catalyst outlet at the top of the riser reactor 9 is connected with the fluidized bed reactor expanding section 14, a product gas outlet 7 is arranged at the top of the fluidized bed reactor, the bottom end of the fluidized bed reactor steam stripping section 16 is connected with the regenerator expanding section 17 through a to-be-regenerated inclined pipe 13 and a riser 20, and the bottom end of the regenerator steam stripping section 19 is connected with the riser reactor 2 through a regeneration inclined pipe 12.
Alternatively, the fluidized bed reactor 3 is a bubbling fluidized bed reactor or a turbulent fluidized bed reactor.
Optionally, the fluidized bed reactor 3 has a catalyst bed layer with a certain height in the reaction section 15, and the naphtha feedstock is fed at the bottom of the reaction section 15.
Optionally, a gas-solid separation device is arranged inside the fluidized bed reactor 3.
Alternatively, regenerator 9 is a bubbling fluidized bed regenerator or a turbulent fluidized bed regenerator.
The device comprises a riser reactor and a fluidized bed reactor, wherein the fluidized bed reactor is a bubbling fluidized bed reactor or a turbulent fluidized bed reactor. The riser reactor and the fluidized bed reactor can simultaneously or separately carry out the catalytic cracking reaction of naphtha. The content of the product components can be regulated and controlled in a larger range by adjusting the feeding proportion of the riser reactor and the fluidized bed reactor.
The apparatus for converting a naphtha-containing feedstock is characterized by comprising:
a reaction unit comprising a riser reactor and a fluidized bed reactor; the top of the riser reactor is connected with a pipeline of an expansion section of the fluidized bed reactor; introducing the pre-deposited carbon catalyst obtained by the riser reactor into the fluidized bed reactor; introducing a raw material containing naphtha and/or methanol into the fluidized bed reactor to contact and react with the pre-deposited carbon catalyst; and
a regeneration unit including a regenerator;
the reaction unit is connected with the regeneration unit through a pipeline, and a circulating system is formed; and the catalyst to be regenerated output by the reaction unit is input into a regeneration unit for regeneration, and the regenerated catalyst is input into the reaction unit.
Optionally, the output products of the riser reactor and fluidized bed reactor include olefins, aromatics, and gasoline.
Optionally, a naphtha containing feedstock is input through the bottom of the riser reactor.
Alternatively, a feedstock containing naphtha and/or methanol is fed through the bottom of the fluidized bed reactor.
Optionally, a raw material containing naphtha is input through the bottom of the riser reactor, is in contact reaction with the catalyst in the riser reactor, is introduced into the fluidized bed reactor, and is separated through the expanded section of the fluidized bed reactor to obtain a product gas I and the catalyst subjected to pre-carbon deposition; the pre-deposited catalyst descends to the reaction section of the fluidized bed reactor;
inputting raw materials containing naphtha and/or methanol from the bottom of the fluidized bed reactor, ascending to a reaction section of the fluidized bed reactor to contact with the carbon deposited catalyst to obtain product gas II and a catalyst to be regenerated; the catalyst to be regenerated is subjected to downward regeneration in a regenerator to obtain a regenerated catalyst;
returning the regenerated catalyst to the riser reactor;
wherein, the product gas I and the product gas II are mixed and output, and are separated to obtain olefin, aromatic hydrocarbon and gasoline.
Optionally, the content of the molecular sieve in the microspherical catalyst is 10-50%.
Optionally, the upper limit of the content of the molecular sieve in the microspherical catalyst is selected from 20%, 30%, 40% or 50%; the upper limit is selected from 10%, 20%, 30% or 40%.
Optionally, the diameter of the microspherical catalyst is preferably 30-300 μm.
Optionally, the diameter of the microspherical catalyst is preferably 50-150 μm.
Optionally, the catalyst is a microspherical catalyst containing a ZSM-5 molecular sieve.
Optionally, the forming of the microspheroidal catalyst comprises: and (3) spray drying and forming the slurry containing the molecular sieve and the binder.
Alternatively, the regenerated catalyst is fed from the bottom of the riser reactor, ascends to the top of the riser reactor, is fed to the expanded section of the fluidized bed reactor, then descends in the fluidized bed reactor, and is fed to the regeneration unit.
Optionally, a naphtha containing feedstock is introduced through the bottom of the riser reactor and contacts the catalyst in the riser reactor;
a feedstock comprising naphtha and/or methanol is introduced through the bottom of the fluidized bed reactor and contacted with the catalyst introduced into the fluidized bed reactor.
Alternatively, the mass ratio of naphtha and methanol in the naphtha and/or methanol-containing feedstock fed to the fluidized bed reactor may be arbitrarily adjusted.
Optionally, the mass ratio of the feeding amounts of the riser reactor and the fluidized bed reactor is 1: 9-9: 1.
Optionally, the mass ratio of the feed rates of the riser reactor and the fluidized bed reactor is 1:9, 1:7, 1:5, 1:3, 1:1, 3:1, 5:1, 9:1, and ranges between any two ratios.
Optionally, the fluidized bed reactor is a bubbling fluidized bed reactor or a turbulent fluidized bed reactor.
Optionally, the fluidized bed reactor comprises an expansion section I, a reaction section I and a stripping section I, wherein a gas-solid separation device is arranged in the fluidized bed reactor, and a product gas outlet is arranged at the top of the fluidized bed reactor.
Optionally, the reaction section I of the fluidized bed reactor comprises a catalyst bed.
Optionally, the height-diameter ratio of the catalyst bed layer is 0.3-10.
Optionally, the height-diameter ratio of the catalyst bed layer is 2-8.
Alternatively, the upper limit of the aspect ratio of the catalyst bed is selected from 0.5, 1, 2, 3, 5, 8, 9 or 10; the lower limit is selected from 0.3, 0.5, 1, 2, 3, 5, 8 or 9.
Optionally, the regenerator is a bubbling fluidized bed regenerator or a turbulent fluidized bed regenerator.
Optionally, the regenerator comprises an expansion section II, a regeneration section I and a stripping section II, and the top of the regenerator is provided with a flue gas outlet;
the steam stripping section I of the riser reactor is connected with the expanding section II of the regenerator through a to-be-grown inclined pipe and a riser I;
and the stripping section II of the regenerator is connected with a bottom pipeline of the riser reactor through a regeneration inclined pipe.
Optionally, a feed inlet I is arranged at the bottom of the riser reactor;
a reaction section I of the fluidized bed reactor is provided with a feed inlet II;
a gas inlet I is arranged at a stripping section I of the fluidized bed reactor;
and the bottom of the lifting pipe I is provided with an air inlet II.
Alternatively, feed I inputs a naphtha-containing feedstock.
Alternatively, feed II inputs a feedstock containing naphtha and/or methanol.
Alternatively, the mass ratio of naphtha to methanol in the naphtha and/or methanol-containing feedstock may be arbitrarily adjusted.
Alternatively, the gas inlet I inputs a gas which does not participate in the reaction, such as water vapor, nitrogen gas, and the like.
Alternatively, the gas inlet II inputs a gas which does not participate in the reaction, such as water vapor, nitrogen gas, and the like.
As an embodiment, the device comprises
The bottom of the riser reactor is provided with a feed inlet of the riser reactor;
the fluidized bed reactor comprises an expansion section I, a reaction section I and a steam stripping section I, wherein a gas-solid separation device is arranged in the fluidized bed reactor, and a product gas outlet is formed in the top of the fluidized bed reactor; the bottom of the stripping section I of the fluidized bed reactor is provided with an air inlet;
the regenerator comprises an expansion section II, a regeneration section I and a stripping section II, and the top of the regenerator is provided with a flue gas outlet; the regeneration section I is provided with a regeneration air inlet, and the bottom of the stripping section II is provided with an air inlet;
the top catalyst outlet of the riser reactor is connected with the pipeline of the expanded section of the fluidized bed reactor, the bottom end of the steam stripping section of the fluidized bed reactor is connected with the pipeline of the expanded section of the regenerator through a to-be-regenerated inclined pipe and the riser, and the bottom end of the steam stripping section of the regenerator is connected with the pipeline of the riser reactor through a regenerated inclined pipe.
Optionally, the quality yield of the olefin in the product gas is 42-72%, the quality yield of the aromatic hydrocarbon is 16-24%, and the quality yield of the high-quality gasoline is 6-21%.
The beneficial effects that this application can produce include:
the device provided by the application comprises a riser reactor and a fluidized bed reactor, wherein the fluidized bed reactor is a bubbling fluidized bed reactor or a turbulent fluidized bed reactor. The riser reactor and the fluidized bed reactor can simultaneously or separately carry out the catalytic cracking reaction of naphtha. The content of the product components can be regulated and controlled in a larger range by adjusting the feeding proportion of the riser reactor and the fluidized bed reactor.
Drawings
Fig. 1 is a schematic flow diagram of the apparatus of the present application.
List of parts and reference numerals:
1: riser reactor feed inlet, 2: riser reactor, 3: fluidized bed reactor, 4: feed inlet of fluidized bed reactor, 5: gas inlet of stripping section of fluidized bed reactor, 6: riser inlet, 7: product gas outlet line, 8: flue gas outlet line, 9: regenerator, 10: regeneration air inlet, 11: regenerator stripping section gas inlet, 12: regenerated inclined tube, 13: tube to be grown, 14: fluidized bed reactor expansion section, 15: fluidized bed reactor reaction section, 16: fluidized bed reactor stripping section, 17: regenerator expansion section, 18: regenerator regeneration section, 19: regenerator stripping section, 20: a riser.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the examples, the catalyst was "microspheres containing naphtha catalytic cracking activity" prepared according to the method of patent CN 200710118286.3.
The analytical methods in the examples of the present application are as follows:
product analysis was performed using gas chromatography.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the yields of olefins, aromatics and methane were calculated on the basis of mass:
olefin yield (olefin mass content in product x product mass flow rate)/(product mass flow rate + coke formation); aromatic hydrocarbons (BTX) yield ═ (mass content of aromatic hydrocarbons in the product × (product mass flow rate)/(product mass flow rate + coke rate); methane yield (mass methane content in product: product mass flow rate)/(product mass flow rate + coke formation).
According to an embodiment of the present application, there is provided a naphtha-containing feedstock conversion apparatus, comprising
A reaction unit comprising a riser reactor and a fluidized bed reactor; a naphtha-containing feedstock is input through the bottom of the riser reactor; a feedstock containing naphtha and/or methanol is input through the bottom of the fluidized bed reactor;
and a regeneration unit comprising a regenerator;
the reaction unit and the regeneration unit are connected through pipelines and form a circulating system.
Example 1
In the device shown in fig. 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 30%, and the particle size range is 50-150 micrometers. Raw materials including naphtha enter a riser reactor to contact with a catalyst, generated products and catalyst material flow enter a fluidized bed reactor to be separated in an expanding section, the products enter a product gas outlet pipeline, the catalyst enters a fluidized bed reactor reaction section, the raw materials including the naphtha or/and methanol enter the fluidized bed reactor reaction section through a fluidized bed reactor feed inlet to react with the catalyst, the generated products enter the product gas outlet pipeline, the catalyst descends to enter a fluidized bed reactor stripping section, after stripping, the catalyst enters a regenerator through a to-be-regenerated inclined tube and a riser, and the regenerated catalyst enters a regenerator through the regenerator stripping section and a regeneration inclined tubeAnd then enters a riser reactor. The product gas enters a separation system through a product gas outlet pipeline to obtain different products. The catalyst circulation amount is controlled by a plug valve or a slide valve. The composition of the naphtha is shown in Table 1. The height/diameter ratio of the catalyst bed layer in the reaction section of the fluidized bed reactor was 5. Conditions of the riser reactor: the reaction temperature is 700 ℃, the reaction pressure is 0.01MPa in terms of gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature is 690 ℃, the reaction pressure is 0.01MPa in gauge pressure, the gas-phase linear speed is 1m/s, and the mass ratio of naphtha to methanol is 2. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 1: 1. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 1h -1 . The product gas is analyzed by online chromatography, the mass yield of the olefin is 54 percent, the mass yield of the BTX is 23 percent, and the mass yield of the high-quality gasoline is 15 percent.
TABLE 1 naphtha composition
| Composition (wt%) | Naphtha (IBP-150 ℃ C.) | Naphtha (IBP-180 degree) |
| N-alkanes | 41 | 35 |
| Isoalkanes | 24 | 29 |
| |
15 | 28 |
| |
14 | 7 |
Example 2
According to the conditions and steps described in example 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 30%, and the particle size range is 50-150 micrometers. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height/diameter ratio of the catalyst bed layer in the reaction zone of the fluidized bed reactor was 0.3. Conditions of the riser reactor: the reaction temperature is 680 ℃, the reaction pressure is 0.01MPa in gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature was 670 ℃, the reaction pressure was 0.01MPa in gauge pressure, the gas linear velocity was 1m/s, and the mass ratio of naphtha to methanol was 10. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 9: 1. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 0.5h -1 . The product gas is analyzed by on-line chromatography, the mass yield of olefin is 45%, the mass yield of BTX is 18%, and the mass yield of high-quality gasoline is 13%.
Example 3
According to the conditions and steps described in example 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 30%, and the particle size range is 50-150 microns. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height-diameter ratio of the catalyst bed layer in the reaction section of the fluidized bed reactor was 10. Conditions of the riser reactor: the reaction temperature is 680 ℃, the reaction pressure is 0.01MPa in terms of gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature was 670 ℃, the reaction pressure was 0.01MPa in gauge pressure, the gas linear velocity was 1m/s, and the mass ratio of naphtha to methanol was 0.5. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 1: 9. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 1.5h -1 . The product gas is analyzed through an on-line chromatographic method,the olefin mass yield is 72 percent, the BTX mass yield is 16 percent, and the high-quality gasoline mass yield is 6 percent.
Example 4
According to the conditions and steps described in example 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 30%, and the particle size range is 50-150 microns. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height/diameter ratio of the catalyst bed layer in the reaction section of the fluidized bed reactor was 5. Conditions of the riser reactor: the reaction temperature is 720 ℃, the reaction pressure is 0.01MPa in gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature is 700 ℃, the reaction pressure is 0.01MPa in gauge pressure, the gas phase linear speed is 1m/s, and the mass ratio of naphtha to methanol is 50. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 1: 1. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 1.0h -1 . The product gas is analyzed by online chromatography, the mass yield of the olefin is 42 percent, the mass yield of the BTX is 24 percent, and the mass yield of the high-quality gasoline is 21 percent.
Example 5
According to the conditions and steps described in example 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 30%, and the particle size range is 50-150 microns. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height-diameter ratio of the catalyst bed layer in the reaction section of the fluidized bed reactor is 2. Conditions of the riser reactor: the reaction temperature is 720 ℃, the reaction pressure is 0.01MPa in gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature is 700 ℃, the reaction pressure is 0.01MPa in gauge pressure, the gas phase linear speed is 1m/s, and the mass ratio of naphtha to methanol is 1. The mass ratio of the naphtha feeding amount of the riser reactor to the fluidized bed reactor is 1: 1. The catalyst circulation quantity is kept stable, and the total mass airspeed of the fluidized bed reactor is 1.0h -1 . The product gas is analyzed by on-line chromatography, the mass yield of olefin is 61%, the mass yield of BTX is 19%, and the mass yield of high-quality gasoline is 9%.
Example 6
According to example 1According to the conditions and the steps, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 10%, and the particle size range is 50-150 micrometers. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height/diameter ratio of the catalyst bed layer in the reaction zone of the fluidized bed reactor was 0.3. Conditions of the riser reactor: the reaction temperature is 680 ℃, the reaction pressure is 0.01MPa in gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature was 670 ℃, the reaction pressure was 0.01MPa in gauge pressure, the gas linear velocity was 1m/s, and the mass ratio of naphtha to methanol was 10. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 9: 1. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 0.5h -1 . The product gas is analyzed by on-line chromatography, the mass yield of olefin is 42%, the mass yield of BTX is 17%, and the mass yield of high-quality gasoline is 15%.
Example 7
According to the conditions and steps described in example 1, the catalyst is microspheres containing naphtha catalytic cracking activity, the weight content of the molecular sieve in the catalyst is 50%, and the particle size range is 50-150 micrometers. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. The height-diameter ratio of the catalyst bed layer in the reaction section of the fluidized bed reactor was 0.3. Conditions of the riser reactor: the reaction temperature is 680 ℃, the reaction pressure is 0.01MPa in terms of gauge pressure, and the gas-phase linear speed is 3 m/s; fluidized bed reactor conditions: the reaction temperature was 670 ℃, the reaction pressure was 0.01MPa in gauge pressure, the gas linear velocity was 1m/s, and the mass ratio of naphtha to methanol was 10. The mass ratio of the feeding amount of the riser reactor to the feeding amount of the fluidized bed reactor is 9: 1. The catalyst circulation quantity is kept stable, and the mass space velocity of the fluidized bed reactor is 0.5h -1 . The product gas is analyzed by on-line chromatography, the olefin mass yield is 78%, the BTX mass yield is 22%, and the high-quality gasoline mass yield is 11%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. A process for the conversion of naphtha, said process being carried out using a naphtha-containing feedstock conversion unit, said naphtha-containing feedstock conversion unit comprising:
a reaction unit comprising a riser reactor and a fluidized bed reactor; the top of the riser reactor is connected with a pipeline of an expansion section I of the fluidized bed reactor;
inputting raw materials containing naphtha through the bottom of the riser reactor, introducing the obtained product gas I and the catalyst subjected to pre-carbon deposition into an expansion section I of the fluidized bed reactor, and outputting the product gas I; the pre-deposited catalyst descends to a reaction section I of the fluidized bed reactor;
inputting raw materials containing naphtha and methanol from the bottom of the fluidized bed reactor, ascending to a reaction section I of the fluidized bed reactor to contact with the pre-deposited catalyst to obtain a product gas II and a catalyst to be regenerated, and outputting the product gas II; the catalyst to be regenerated is subjected to downward regeneration in a regenerator to obtain a regenerated catalyst;
the regenerated catalyst returns to the riser reactor;
wherein, the product gas I and the product gas II are mixed and output, and are separated to obtain olefin, aromatic hydrocarbon and gasoline; and
a regeneration unit including a regenerator;
the reaction unit is connected with the regeneration unit through a pipeline, and a circulating system is formed; inputting the catalyst to be regenerated output by the reaction unit into a regeneration unit for regeneration to obtain a regenerated catalyst; inputting the regenerated catalyst from the bottom of the riser reactor, ascending to the top of the riser reactor, inputting to the expansion section of the fluidized bed reactor, then descending in the fluidized bed reactor, and inputting to the regeneration unit;
the mass ratio of the feeding amounts of the riser reactor and the fluidized bed reactor is 1: 1-9: 1;
the catalyst is a microspherical catalyst containing a ZSM-5 molecular sieve; the content of the molecular sieve in the microspherical catalyst is 10-50%; the diameter of the microspherical catalyst is 50-150 mu m;
the quality yield of olefin in the product gas is 42-72%, the quality yield of aromatic hydrocarbon is 16-24%, and the quality yield of high-quality gasoline is 6-21%.
2. The conversion process of claim 1, wherein the fluidized bed reactor is a bubbling fluidized bed reactor or a turbulent fluidized bed reactor.
3. The conversion process of claim 1, wherein the fluidized bed reactor further comprises a stripping section I, a gas-solid separation device is arranged in the stripping section I, and a product gas outlet is arranged at the top of the stripping section I.
4. The conversion process of claim 1, characterized in that the reaction section I of the fluidized bed reactor comprises a catalyst bed; the height-diameter ratio of the catalyst bed layer is 0.3-10.
5. The conversion process of claim 4, wherein the catalyst bed has a height to diameter ratio of 2 to 8.
6. The conversion process of claim 1, wherein the regenerator is a bubbling fluidized bed regenerator or a turbulent fluidized bed regenerator.
7. The conversion method according to claim 1, wherein the regenerator comprises an expansion section II, a regeneration section I and a stripping section II, and a flue gas outlet is arranged at the top of the regenerator;
the steam stripping section I of the fluidized bed reactor is connected with the expanding section II of the regenerator through a to-be-regenerated inclined pipe and a riser I;
and the stripping section II of the regenerator is connected with a bottom pipeline of the riser reactor through a regeneration inclined pipe.
8. The conversion process according to claim 4, characterized in that the bottom of the riser reactor is provided with a feed inlet I;
a reaction section I of the fluidized bed reactor is provided with a feeding hole II;
a gas inlet I is arranged at a stripping section I of the fluidized bed reactor;
and the bottom of the lifting pipe I is provided with an air inlet II.
9. The transformation method according to claim 1, comprising
The bottom of the riser reactor is provided with a feed inlet of the riser reactor;
the fluidized bed reactor also comprises a steam stripping section I, wherein a gas-solid separation device is arranged in the steam stripping section I, and a product gas outlet is formed in the top of the steam stripping section I; the bottom of a stripping section I of the fluidized bed reactor is provided with an air inlet;
the regenerator comprises an expansion section II, a regeneration section I and a stripping section II, and the top of the regenerator is provided with a flue gas outlet;
the regeneration section I is provided with a regeneration air inlet, and the bottom of the stripping section II is provided with an air inlet;
the top catalyst outlet of the riser reactor is connected with the pipeline of the expanded section of the fluidized bed reactor, the bottom end of the steam stripping section of the fluidized bed reactor is connected with the pipeline of the expanded section of the regenerator through a to-be-regenerated inclined pipe and the riser, and the bottom end of the steam stripping section of the regenerator is connected with the pipeline of the riser reactor through a regeneration inclined pipe.
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| WO2024108507A1 (en) * | 2022-11-24 | 2024-05-30 | 中国科学院大连化学物理研究所 | Circulating fluidized bed reaction regeneration device and use method |
| WO2024108506A1 (en) * | 2022-11-24 | 2024-05-30 | 中国科学院大连化学物理研究所 | Naphtha and methanol based aromatic hydrocarbon preparation and olefin co-production fluidized bed device and method |
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