CN111233608A - Naphtha-containing raw material conversion method - Google Patents

Naphtha-containing raw material conversion method Download PDF

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CN111233608A
CN111233608A CN201811446192.3A CN201811446192A CN111233608A CN 111233608 A CN111233608 A CN 111233608A CN 201811446192 A CN201811446192 A CN 201811446192A CN 111233608 A CN111233608 A CN 111233608A
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catalyst
fluidized bed
bed reactor
naphtha
regenerated
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赵银峰
叶茂
刘中民
唐海龙
王静
张今令
张涛
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02Preparation 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
    • C07C4/06Catalytic processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application discloses a method for converting a naphtha-containing feedstock, comprising the steps of: a) after the raw material containing naphtha and the catalyst are in contact reaction in a riser reactor, introducing the raw material into a fluidized bed reactor, and separating the raw material and the catalyst through an expansion section of the fluidized bed reactor to obtain product gas I and the catalyst subjected to pre-deposited carbon; the pre-deposited catalyst descends to the reaction section of the fluidized bed reactor; b) 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 descended into a regenerator to be regenerated, and then a regenerated catalyst is obtained; c) returning to said riser reactor via said regenerated catalyst. The method is used for naphtha catalytic cracking and has the advantage of adjustable product types.

Description

Naphtha-containing raw material conversion method
Technical Field
The invention relates to a method 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, the technology of preparing propylene through propane dehydrogenation and the like, the sources of ethylene and propylene are increasingly abundant. This requires that the naphtha catalytic cracking technology requires higher tunable property to meet the market demand change. This application is fine has solved this problem.
Disclosure of Invention
In accordance with one aspect of the present application, a process for converting a naphtha containing feedstock to lower olefins, aromatics and high quality gasoline is provided. The method is used for naphtha catalytic cracking and has the advantage of adjustable product types.
To achieve the above objects, the present application provides a method for converting a naphtha-containing feedstock into lower olefins, aromatic hydrocarbons and high-quality gasoline, the method comprising the steps of: 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 feed inlet of the fluidized bed reactor to react with the catalyst, the generated products enter the product gas outlet pipeline, the catalyst descends to enter a fluidized bed reactor steam stripping section, after steam stripping, the catalyst enters a regenerator through a to-be-regenerated inclined tube and a riser, and the regenerated catalyst enters the riser reactor through the regenerator steam stripping section and a regenerated inclined tube; the product gas enters a separation system through a product gas outlet pipeline to obtain different products.
In the above scheme, the conditions of the riser reactor are as follows: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 MPa in terms of gauge pressure, and the gas-phase linear speed is 3-10 m/s; fluidized bed reactor conditions: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 Pa in terms of gauge pressure, the gas phase linear speed is 0.5-1.5 m/s, and the mass space velocity is 0.5-2 h-1
The mass ratio of the carbon content of the regenerated catalyst is lower than 0.2 percent.
The method for converting a naphtha-containing feedstock is characterized by comprising the steps of:
a) after the raw material containing naphtha and the catalyst are in contact reaction in a riser reactor, introducing the raw material into a fluidized bed reactor, and separating the raw material and the catalyst through an expansion section of the fluidized bed reactor to obtain product gas I and the catalyst subjected to pre-deposited carbon; the pre-deposited catalyst descends to the reaction section of the fluidized bed reactor;
b) 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 descended into a regenerator to be regenerated, and then a regenerated catalyst is obtained;
c) 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 olefin comprises ethylene, propylene, butylene.
Optionally, the aromatic hydrocarbon comprises benzene, toluene, xylene.
Optionally, the conditions of the riser reactor: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 MPa in terms of gauge pressure, and the gas-phase linear speed is 3-10 m/s;
the fluidized bed reactor conditions: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 Pa in terms of gauge pressure, the gas phase linear velocity is 0.5-1.5 m/s, and the total mass space velocity of the methanol and/or naphtha is 0.5-2 h-1. Wherein, the ratio of methanol and naphtha can be adjusted at will.
Optionally, the upper limit of the reaction temperature in the riser reactor is selected from 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, 710 ℃ or 720 ℃; the lower limit is selected from 580 deg.C, 590 deg.C, 600 deg.C, 610 deg.C, 620 deg.C, 630 deg.C, 640 deg.C, 650 deg.C, 660 deg.C, 670 deg.C, 680 deg.C, 690 deg.C, 700 deg.C or 710 deg.C.
Optionally, the upper limit of the reaction pressure in the riser reactor, in terms of gauge pressure, is selected from 0.02MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, or 0.3 MPa; the lower limit is selected from 0.01MPa, 0.02MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.15MPa, 0.2MPa or 0.25 MPa.
Optionally, the upper limit of the linear velocity of the gas phase in the riser reactor is selected from 3m/s, 4m/s, 5m/s, 6m/s, 7m/s, 8m/s, 9m/s or 10 m/s; the lower limit is selected from 2m/s, 3m/s, 4m/s, 5m/s, 6m/s, 7m/s, 8m/s or 9 m/s.
Optionally, the upper limit of the reaction temperature in the fluidized bed reactor is selected from 590 ℃, 600 ℃, 610 ℃, 620 ℃, 630 ℃, 640 ℃, 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃, 700 ℃, 710 ℃ or 720 ℃; the lower limit is selected from 580 deg.C, 590 deg.C, 600 deg.C, 610 deg.C, 620 deg.C, 630 deg.C, 640 deg.C, 650 deg.C, 660 deg.C, 670 deg.C, 680 deg.C, 690 deg.C, 700 deg.C or 710 deg.C.
Optionally, the upper limit of the reaction pressure in the fluidized bed reactor, in terms of gauge pressure, is selected from 0.02MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.15MPa, 0.2MPa, 0.25MPa, or 0.3 MPa; the lower limit is selected from 0.01MPa, 0.02MPa, 0.05MPa, 0.08MPa, 0.1MPa, 0.15MPa, 0.2MPa or 0.25 MPa.
Optionally, the upper limit of the gas phase linear velocity in the fluidized bed reactor is selected from 1m/s or 1.5 m/s; the lower limit is selected from 0.5m/s or 1 m/s.
Optionally, the upper limit of the total mass space velocity in the fluidized bed reactor is selected from 1h-1、1.5h-1Or 2h-1(ii) a The lower limit is selected from 0.5h-1、1h-1Or 1.5h-1
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, step a) comprises: contacting and reacting raw materials containing naphtha and a catalyst in a riser to obtain a material flow which comprises the pre-reacted catalyst and a product gas I and flows upwards to a fluidized bed reactor; the method comprises the steps of separating material flows of a catalyst and a product gas I in an expansion section of a fluidized bed reactor, enabling the product gas I to enter a product gas outlet pipeline, and enabling the pre-reacted catalyst to descend to a reaction section of the fluidized bed reactor.
Optionally, step b) comprises: inputting raw materials containing naphtha and methanol from the bottom of the fluidized bed reactor, ascending to a reaction section of the fluidized bed reactor to contact with the pre-reacted catalyst to obtain product gas II and a catalyst to be regenerated; the product gas II ascends to the expansion section of the fluidized bed reactor and enters a product gas outlet pipeline; the catalyst to be regenerated descends to a stripping section of the fluidized bed reactor and enters a regenerator for regeneration through a to-be-regenerated inclined pipe and a riser.
Optionally, step c) comprises: the regenerated catalyst returns to the riser reactor through the regenerator stripping section and the regeneration inclined tube.
Optionally, the carbon content of the regenerated catalyst is lower than 0.5% by mass.
Optionally, the carbon content of the regenerated catalyst is lower than 0.2% by mass.
Optionally, the carbon content of the regenerated catalyst is lower than 0.1% by mass.
Optionally, the catalyst is a microsphere catalyst containing naphtha catalytic cracking activity; the diameter of the microspherical catalyst is 30-300 mu m.
Optionally, the weight content of the molecular sieve in the microspherical catalyst is 10-50%.
Optionally, the upper limit of the weight content of 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 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.
Optionally, the distillation range of the naphtha is between 20 and 200 ℃.
As an embodiment, the method includes the following steps: raw materials containing naphtha enter a riser reactor to contact with a catalyst, generated product I and catalyst material flow enter a fluidized bed reactor to be separated in an expanding section, the product I enters a product gas outlet pipeline, the catalyst enters a fluidized bed reactor reaction section, the raw materials containing naphtha and/or methanol enter the fluidized bed reactor reaction section through a fluidized bed reactor feed inlet to react with the catalyst, generated product II enters a product gas outlet pipeline, the catalyst descends into a fluidized bed reactor steam stripping section, after steam stripping, the catalyst enters a regenerator through a to-be-regenerated inclined tube and a riser, and the regenerated catalyst enters the riser reactor through a regenerator steam stripping section and a regeneration inclined tube; the product gas enters a separation system through a product gas outlet pipeline to obtain a product containing olefin, aromatic hydrocarbon and gasoline.
Alternatively, the process, the quality yield of olefins, aromatics and gasoline can be modulated.
Optionally, the mass yield of the olefin is 42-72%, the mass yield of the aromatic hydrocarbon is 16-24%, and the mass yield of the gasoline is 6-21%.
The beneficial effects that this application can produce include:
1) the device riser reactor and the fluidized bed reactor can simultaneously and independently carry out catalytic cracking reaction of naphtha.
2) The method can regulate and control the component content of the product in a larger range by adjusting the feeding proportion of the riser reactor and the fluidized bed reactor.
3) The application provides a conversion method of naphtha-containing raw materials, products are low-carbon olefin, light aromatic hydrocarbon and high-quality gasoline, and the proportion of the products can be adjusted. The method comprises the steps that raw materials including naphtha simultaneously enter a riser reactor and a fluidized bed reactor, and reaction products are converged at an outlet at the top of the fluidized bed reactor and then enter a separation system to obtain low-carbon olefin, light aromatic hydrocarbon and high-quality gasoline; the catalyst enters the fluidized bed reactor from the regenerator through the riser reactor, and returns to the regenerator for regeneration after the catalytic cracking is finished. The method improves the modulation range of the naphtha catalytic cracking product and improves the capability of the device for resisting the market fluctuation risk.
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 20.
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 catalytic cracking activity of naphtha", said catalyst being prepared according to the method of patent CN 200710118286.3.
The analysis method in the examples of the present application is as follows:
product analysis was performed using agilent gas chromatography.
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the olefin yield, the aromatic hydrocarbon yield, and the methane yield were calculated on the basis of mass:
olefin yield ═ product mass flow rate (olefin mass content in product)/(product mass flow rate + coke formation); aromatics yield ═ product mass flow rate)/(product mass flow rate + coke rate in the product; methane yield (mass methane content in product × (product mass flow rate)/(product mass flow rate + coke formation).
FIG. 1 is a diagram of an apparatus for use in a process for converting a naphtha-containing feedstock to lower olefins and aromatics, the process comprising the steps of: raw materials including naphtha enter a riser reactor 2 to contact with a catalyst, generated products and catalyst material flow enter an expanding section 14 of a fluidized bed reactor to be separated, the products enter a product gas outlet pipeline, the catalyst enters a reaction section 15 of the fluidized bed reactor, the raw materials including the naphtha or/and methanol enter the reaction section of the fluidized bed reactor through a feed inlet 4 of the fluidized bed reactor to react with the catalyst, the generated products enter the product gas outlet pipeline, the catalyst descends to enter a stripping section 16 of the fluidized bed reactor, the catalyst enters a regenerator 9 through a to-be-regenerated inclined tube 13 and a riser 20 after being stripped, and the regenerated catalyst enters the riser reactor 2 through a regenerator stripping section 19 and a regeneration inclined tube 12; the product gas enters a separation system through a product gas outlet pipeline to obtain different products. ,
example 1
In the apparatus shown in FIG. 1, the catalyst is a microspherical catalyst 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. Raw materials including naphtha enter a riser reactor to contact with a catalyst, generated products and catalyst material flow enter an expanding section of a fluidized bed reactor to be separated, the products enter a product gas outlet pipeline, the catalyst enters a reaction section of the fluidized bed reactor, the raw materials including the naphtha or/and methanol enter the reaction section of the fluidized bed reactor through a feed inlet of the fluidized bed reactor to react with the catalyst, the generated products enter the product gas outlet pipeline, the catalyst descends to enter a stripping section of the fluidized bed reactor, after stripping, the catalyst enters a regenerator through a to-be-regenerated inclined tube and a riser, and the regenerated catalyst enters the riser reactor through the stripping section of the regenerator and the regenerated inclined tube. 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 mass fraction of the carbon content of the regenerated catalyst is less than 0.1 percent. The composition of the naphtha is shown in Table 1. 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 on-line chromatography, the olefin mass yield is 54 percent, the BTX mass yield is 23 percent, and the high-quality gasoline mass yield is 15 percent.
TABLE 1 naphtha composition
Composition (wt%) Naphtha (IBP-150 ℃ C.) Naphtha (IBP-180 degree)
N-alkanes 41 35
Isoalkanes 24 29
Cycloalkanes 15 28
Aromatic hydrocarbons 14 7
Example 2
The catalyst was microspheres containing naphtha catalytic cracking activity, with a molecular sieve content of 30% by weight and a particle size range of 50-150 microns, according to the conditions and procedures described in example 1. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. 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. Maintaining the catalyst circulation amountThe fluidized bed reactor is 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
The catalyst was microspheres containing naphtha catalytic cracking activity, with a molecular sieve content of 30% by weight and a particle size range of 50-150 microns, according to the conditions and procedures described in example 1. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. 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 by on-line chromatography, the mass yield of olefin is 72%, the mass yield of BTX is 16%, and the mass yield of high-quality gasoline is 6%.
Example 4
The catalyst was microspheres containing naphtha catalytic cracking activity, with a molecular sieve content of 30% by weight and a particle size range of 50-150 microns, according to the conditions and procedures described in example 1. The mass fraction of the carbon content of the regenerated catalyst is less than 0.5 percent. 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 was 700 ℃, 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 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 on-line chromatography, the mass yield of olefin is 42%, the mass yield of BTX is 24%, and the mass yield of high-quality gasoline is 21%.
Example 5
The catalyst was stone-containing according to the conditions and procedures described in example 1The naphtha catalytic cracking active microsphere, 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. 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 was 700 ℃, 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 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 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 10%, 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 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 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 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 0.3. Riser reactionConditions of the apparatus: 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 (10)

1. A process for converting a naphtha containing feedstock comprising the steps of:
a) after the raw material containing naphtha and the catalyst are in contact reaction in a riser reactor, introducing the raw material into a fluidized bed reactor, and separating the raw material and the catalyst through an expansion section of the fluidized bed reactor to obtain product gas I and the catalyst subjected to pre-deposited carbon; the pre-deposited catalyst descends to the reaction section of the fluidized bed reactor;
b) 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 descended into a regenerator to be regenerated, and then a regenerated catalyst is obtained;
c) 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.
2. The method of claim 1, wherein the conditions of the riser reactor are: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 MPa in terms of gauge pressure, and the gas-phase linear speed is 3-10 m/s;
the fluidized bed reactor conditions: the reaction temperature is 580-720 ℃, the reaction pressure is 0.01-0.3 Pa in terms of gauge pressure, the gas-phase linear speed is 0.5-1.5 m/s, and the total mass space velocity of naphtha and/or methanol is 0.5-2 h-1
3. The method according to claim 1, wherein the mass ratio of the feeding amounts of the riser reactor and the fluidized bed reactor is 1: 9-9: 1.
4. The method of claim 1, wherein step a) comprises: contacting and reacting raw materials containing naphtha and a catalyst in a riser to obtain a material flow which comprises the pre-reacted catalyst and a product gas I and flows upwards to a fluidized bed reactor; the method comprises the steps of separating material flows of a catalyst and a product gas I in an expansion section of a fluidized bed reactor, enabling the product gas I to enter a product gas outlet pipeline, and enabling the pre-reacted catalyst to descend to a reaction section of the fluidized bed reactor.
5. The method of claim 1, wherein step b) comprises: inputting raw materials containing naphtha and methanol from the bottom of the fluidized bed reactor, ascending to a reaction section of the fluidized bed reactor to contact with the pre-reacted catalyst to obtain product gas II and a catalyst to be regenerated; the product gas II ascends to the expansion section of the fluidized bed reactor and enters a product gas outlet pipeline; the catalyst to be regenerated descends to a stripping section of the fluidized bed reactor and enters a regenerator for regeneration through a to-be-regenerated inclined pipe and a riser.
6. The method of claim 1, wherein step c) comprises: the regenerated catalyst returns to the riser reactor through the regenerator stripping section and the regeneration inclined tube.
7. The method according to claim 1, wherein the regenerated catalyst has a carbon content of less than 0.5% by mass.
8. The method of claim 1, wherein the catalyst is a microsphere catalyst comprising naphtha catalytic cracking activity; the diameter of the microspherical catalyst is 30-300 mu m.
9. The method of claim 1, wherein the microspheroidal catalyst has a diameter of 50 to 150 μm.
10. The method according to claim 1, wherein the naphtha boiling range is between 20 and 200 ℃.
CN201811446192.3A 2018-11-29 2018-11-29 Naphtha-containing raw material conversion method Pending CN111233608A (en)

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