CN115678608B

CN115678608B - Deep desulfurization method and system for gasoline

Info

Publication number: CN115678608B
Application number: CN202110875400.7A
Authority: CN
Inventors: 徐莉; 王文寿; 刘玉良; 毛安国; 汪燮卿
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-07-30
Filing date: 2021-07-30
Publication date: 2024-03-12
Anticipated expiration: 2041-07-30
Also published as: CN115678608A

Abstract

The present disclosure relates to a method for deep desulfurization of gasoline, the method comprising: s1, feeding sulfur-containing gasoline and a hydrogen donor into the bottom of a fluidized bed reactor which comprises a first fluidized bed reaction zone, a first fixed bed reaction zone and a sedimentation separation zone from bottom to top, and contacting with an adsorbent fed from the middle lower part of the first fluidized bed reaction zone to obtain a first mixed material; s2, lifting the first mixed material into a first fixed bed reaction zone, contacting with a first desulfurization catalyst filled in the first fixed bed reaction zone, and performing a first adsorption desulfurization reaction to obtain a first reaction oil; s3, lifting the first reaction oil to a sedimentation separation area for oil-agent separation to obtain reaction oil gas and spent adsorbent; wherein the mass airspeed in the fluidized bed reactor is 1-10 h ^‑1 The temperature is 250-600 ℃ and the pressure is 0.1-4.0 MPa. The method realizes the synergistic effect of the fixed bed and the fluidized bed in one reactor, and the operation period can reach more than 3 years.

Description

Deep desulfurization method and system for gasoline

Technical Field

The application relates to the technical field of clean fuels, in particular to a deep desulfurization method and system for gasoline.

Background

With the increasing importance of people's living standard and environmental protection, the standard requirements of all countries in the world on clean fuels are higher and higher, the restrictions on sulfur content in fuels are also stricter, the international European V standard requires that the sulfur content of gasoline be lower than 10 mug/g, and the national V standard in China also requires that the sulfur content of motor gasoline be lower than 10 mug/g. Because all the gasoline produced by refineries can leave the factory after deep desulfurization, various technologies for deeply removing sulfur content in hydrocarbon oil are developed at home and abroad in a dispute.

The traditional hydrocarbon oil desulfurization is mainly carried out by adopting a hydrodesulfurization method, wherein selective hydrodesulfurization is the main mode for removing thiophene sulfides at present. US4334982, US6126814 are processes that only promote thiophene hydrogenation without saturating the olefin by controlling the reactivity of the catalyst to achieve deep desulfurization at low octane number losses. Another hydrodesulfurization method is a deep hydrodesulfurization method for recovering the octane number, which is to set up a second stage reactor to promote the cracking, isomerization and alkylation reaction of hydrocarbons with low octane number (such as normal paraffins) while the gasoline is subjected to deep desulfurization and olefin saturation, thereby achieving the purpose of recovering the octane number.

In addition, adsorption to remove sulfur compounds from fuel is one of the desulfurization technologies that have been frequently used in recent years. The S Zorb technology can be directly used for full-component desulfurization of catalytic cracking gasoline, and has the characteristics of high desulfurization efficiency, low hydrogen consumption, low octane number loss, low operation energy consumption and the like. The patent of US7427581, US6869522 and US6274533 disclose that under the proper pressure, temperature and hydrogen-bearing technological conditions, a fluidized bed reactor is adopted to make raw oil contact with S Zorb patent adsorbent to implement desulfurization reaction, so that sulfur in the raw material is converted and stored on the adsorbent to produce the product gasoline with very low sulfur content, the carrier of the adsorbent is the mixture of zinc oxide, silica and alumina, and the loaded active component is one or several of reduced metals including cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin and vanadium. The pressure is 0.10 to 10.34MPa, the temperature is 37.3 to 537.7 ℃ and the weight hourly space velocity is 0.5 to 50h ^-1 And under the condition of hydrogen, capturing sulfur in the gasoline by using the adsorbent, and fluidizing and conveying the sulfur-containing adsorbent to another fluidized bed for burning sulfur for regeneration, and then returning to be recycled. The technology can produce low-sulfur gasoline on the basis of lower octane number loss at present, but the strength of the adsorbent is also found to be poor in the use process, and various spinel compounds can be generated on the adsorbent in the regeneration process to deactivate the adsorbent, so that the operation cost is increased.

Disclosure of Invention

The present disclosure is directed to a method for desulfurizing and refining fuel oil. In particular to a process method for realizing ultra-low sulfur clean fuel production by using desulfurization catalyst and adsorbent in a reactor.

In order to achieve the above object, the present disclosure provides a method for deep desulfurization of gasoline, the method comprising:

s1, feeding sulfur-containing gasoline and a hydrogen donor into the bottom of a fluidized bed reactor which comprises a first fluidized bed reaction zone, a first fixed bed reaction zone and a sedimentation separation zone from bottom to top, and contacting with an adsorbent fed from the middle lower part of the first fluidized bed reaction zone to obtain a first mixed material;

s2, lifting the first mixed material into the first fixed bed reaction zone, contacting with a first desulfurization catalyst filled in the first fixed bed reaction zone, and performing a first adsorption desulfurization reaction to obtain a first reaction oil;

s3, lifting the first reaction oil to the sedimentation separation area for oil-solution separation to obtain reaction oil gas and spent adsorbent;

wherein the mass airspeed in the fluidized bed reactor is 1-10 h ^-1 The temperature is 250-600 ℃ and the pressure is 0.1-4.0 MPa.

Optionally, the fluidized bed reactor comprises at least two fluidized bed reaction zones and at least two fixed bed reaction zones, wherein the fluidized bed reaction zones and the fixed bed reaction zones are arranged at intervals.

Preferably, the fluidized bed reactor comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top; the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone are respectively filled with a first desulfurization catalyst, a second desulfurization catalyst and a third desulfurization catalyst, and the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst are identical or different from each other.

Optionally, the mass space velocity in the fluidized bed reactor is 1-10 h ^-1 Preferably 2 to 6 hours ^-1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 250-600 ℃, preferably 320-440 ℃; the pressure is 0.1 to 5.0MPa, preferably 1.5 to 3.5MPa.

Optionally, the gasoline comprises one or more of catalytic cracking gasoline, coker gasoline and straight run gasoline; preferably, the sulfur content of the gasoline is greater than 50 micrograms/gram; preferably, the sulfur content of the gasoline is greater than 100 micrograms/gram.

Optionally, the volume ratio of the hydrogen donor to the sulfur-containing gasoline is 0.01-1000; the hydrogen donor is selected from at least one of hydrogen, hydrogen-containing gas and hydrogen donor; optionally, the volume fraction of hydrogen in the hydrogen-containing gas is greater than 30 vol%; optionally, the hydrogen donor is at least one selected from tetrahydronaphthalene, decalin and indane.

Optionally, the adsorbent is selected from at least one of activated carbon, an oxide of an active metal, a hydroxide of an active metal, and an oxide of an active metal supported on an inorganic oxide, clay, or molecular sieve; preferably, the adsorbent is a mixture of zinc oxide, aluminum oxide and silicon oxide; further preferably, the adsorbent comprises 50 to 90 wt% zinc oxide, 2 to 30wt% silicon oxide and 5 to 30wt% aluminum oxide, based on the weight of the adsorbent; the particle size of the adsorbent is 5-500 mu m, preferably 20-50 mu m; specific surface area of 20-50 m ² Per gram, the total pore volume is 0.01 to 0.35cc/g.

Alternatively, the first desulfurization catalyst comprises 20 to 80 wt% of an active metal element, 2 to 10 wt% of a molecular sieve, 20 to 50 wt% of an inorganic oxide, and 10 to 50 wt% of clay, based on the weight of the first desulfurization catalyst; the second desulfurization catalyst comprises 20-80 wt% of active metal elements, 2-10 wt% of molecular sieve, 20-50 wt% of inorganic oxide and 10-50 wt% of clay based on the weight of the second desulfurization catalyst; the third desulfurization catalyst comprises 20-80 wt% of active metal elements, 2-10 wt% of molecular sieve, 20-50 wt% of inorganic oxide and 10-50 wt% of clay based on the weight of the third desulfurization catalyst; optionally, the active metal component is selected from at least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium; optionally, the molecular sieve comprises one or more of a large pore molecular sieve, a medium pore molecular sieve and a small pore molecular sieve.

Optionally, the method further comprises: carrying out first regeneration and first reduction on the to-be-regenerated adsorbent to obtain regenerated adsorbent; optionally, the first regeneration is performed under a regeneration atmosphere; the regeneration atmosphere is an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas is 5-50% by volume; the conditions for the first regeneration include: the temperature is 300-800 ℃, preferably 400-550 ℃; the pressure is 0.1-0.3 MPa, preferably 0.1-0.18 MPa; optionally, the first reduction is performed under a reducing atmosphere; the reducing atmosphere is hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas is 30-100% by volume; the conditions for the first reduction include: the temperature is 300-600 ℃, preferably 350-450 ℃; the pressure is 0.1 to 4.0MPa, preferably 1 to 3MPa.

Optionally, the method further comprises: when the sulfur content of the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst is larger than the first working sulfur capacity, performing second regeneration and second reduction on the first desulfurization adsorbent, the second desulfurization catalyst and the third desulfurization catalyst; the first working sulfur capacity is any one value in the range of 5 to 50 weight percent; optionally, the second regeneration is performed under a regeneration atmosphere; the regeneration atmosphere is an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas is 5-50% by volume; the conditions for the second regeneration include: the temperature is 300-800 ℃, preferably 400-550 ℃; the pressure is 0.1-0.3 MPa, preferably 0.1-0.18 MPa; optionally, the second reduction is performed under a reducing atmosphere; the reducing atmosphere is hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas is 30-100% by volume; the conditions for the second reduction include: the temperature is 300-600 ℃, preferably 350-450 ℃; the pressure is 0.1 to 4.0MPa, preferably 1.5 to 3.0MPa.

The present disclosure also provides a system for deep desulfurization of gasoline, the system comprising a fluidized bed reactor, a regenerator, and a lock hopper; the fluidized bed reactor is connected with an adsorbent receiver, the regenerator is connected with a spent agent receiver, and the adsorbent purging hopper is connected with a first receiver and a second receiver;

the fluidized bed reactor is provided with a raw oil inlet, a hydrogen donor inlet, an adsorbent inlet, an oil gas outlet and a spent agent outlet; the lock hopper is provided with a first receiver inlet, a second receiver inlet and a third material outlet, the first receiver is provided with a first material inlet and a first material outlet, and the second receiver is provided with a second material inlet and a second material outlet; the regenerator is provided with a spent agent inlet and a regenerant outlet;

the adsorbent inlet of the fluidized bed reactor is communicated with the outlet of the adsorbent receiver, the inlet of the adsorbent receiver is communicated with the third material outlet of the lock hopper, the inlet of the lock hopper is communicated with the first material outlet of the first receiver, and the first material inlet of the first receiver is communicated with the spent agent outlet of the fluidized bed reactor; the to-be-regenerated agent inlet of the regenerator is communicated with the outlet of the to-be-regenerated agent receiver, the inlet of the to-be-regenerated agent receiver is communicated with the third material outlet of the lock hopper, and the regeneration agent outlet of the regenerator is communicated with the inlet of the second receiver;

the fluidized bed reactor is internally provided with a first fluidized bed reaction zone, a first fixed bed reaction zone and a sedimentation separation zone from bottom to top in sequence, and a pore canal is arranged in the first fixed bed reaction zone.

Through above-mentioned technical scheme, this disclosure has following technical effect compared with prior art:

(1) The method realizes the synergistic effect of the fixed bed and the fluidized bed in one reactor, fully utilizes different reaction mechanisms of the desulfurization catalyst and the adsorbent, ensures that sulfur removed by the reaction is immediately adsorbed and taken away, drives the desulfurization reaction to be continuously carried out, realizes the effect of deep desulfurization, and has low octane number loss and high product liquid yield. The sulfur content in the gasoline product is lower than 10 mug/g, the desulfurization rate reaches more than 98%, the octane number loss of the gasoline is less than 0.5, and the liquid yield of the gasoline product is higher than 99.5%.

(2) The method provided by the disclosure separates the desulfurization catalyst and the adsorbent, and adopts different regeneration modes respectively, so that substances such as spinel and the like which reduce the activity of the catalyst are avoided from being generated by the reaction of active components on the two catalysts.

(3) By adopting the method provided by the disclosure, unnecessary cyclic regeneration and reduction of the desulfurization catalyst are avoided, the energy consumption and the hydrogen consumption are reduced, and the processing cost is reduced.

(4) The method provided by the disclosure has a running period of more than 3 years.

Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:

fig. 1 is a schematic flow chart of a method for refining fuel oil provided by the present disclosure.

Fig. 2 is a schematic diagram of a fluidized bed combined with fixed bed reactor provided by the present disclosure.

Fig. 3 is a cross-sectional view of a fixed bed in a reactor provided by the present disclosure.

Fig. 4 is a top view of a fixed bed in a reactor provided by the present disclosure.

Description of the reference numerals

1. Pipeline 2, fluidized bed reactor 3, pipeline

4. Transfer agent horizontal tube 5, first receiver 6 and pipeline

7. Lock hopper 8, line 9, line

10. Spent agent receiver 11, line 12, line

13. Regenerator 14, line 15, line

16. A second receiver 17, a pipeline 18, a pipeline

19. Adsorbent receiver 20, line 21, feedstock

22. Adsorbent 23, first fluidized bed reaction zone 24, first fixed bed reaction zone

25. A second fluidized bed reaction zone 26, a second fixed bed reaction zone 27, and a third fluidized bed reaction zone

28. Third fixed bed reaction zone 29, spent adsorbent 30, reaction oil and gas

31. Ascending channel 32, desulfurization catalyst

Detailed Description

The following describes specific embodiments of the present disclosure in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.

The present disclosure provides a method for deep desulfurization of gasoline, the method comprising:

The method comprises the steps of introducing sulfur-containing gasoline raw materials and hydrogen donor from the bottom of a fluidized bed reactor, enabling the sulfur-containing gasoline raw materials and the hydrogen donor to pass through a fixed bed reaction zone from bottom to top together with an adsorbent introduced from the middle lower part of the fluidized bed reactor, enabling the sulfur-containing gasoline raw materials and the hydrogen donor to contact with a desulfurization catalyst in the fixed bed reaction zone, enabling sulfur to be released and timely captured by the adsorbent, completing separation of oil gas and the adsorbent in a settling separation zone at the top of the reactor, enabling separated reaction products and hydrogen to enter a subsequent separation part for treatment, enabling separated spent adsorbent particles to enter a regenerator after being blown by a hopper, and enabling the separated spent adsorbent particles to contact with regenerated gas for regeneration. The regenerated adsorbent enters the reactor for recycling after being purged. The method fully utilizes the synergistic effect of the desulfurization catalyst and the adsorbent, so that sulfur removed by the reaction is immediately absorbed and taken away, the desulfurization reaction is driven to continuously proceed, the sulfur content is reduced to not more than 10 mug/g, the desulfurization rate reaches more than 98%, the octane number loss of the gasoline is less than 0.5, and the gasoline yield is higher than 99.5%.

In a preferred embodiment of the present disclosure, the fluidized bed reactor comprises at least two fluidized bed reaction zones and at least two fixed bed reaction zones, which are disposed at a distance from each other.

Further preferably, the fluidized bed reactor comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top; the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone are respectively filled with a first desulfurization catalyst, a second desulfurization catalyst and a third desulfurization catalyst, and the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst are identical or different from each other. And sequentially lifting the first mixed material to the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone, contacting with the filled first desulfurization catalyst, second desulfurization catalyst and third desulfurization catalyst, and carrying out adsorption desulfurization reaction.

According to the present disclosure, the mass space velocity in the fluidized bed reactor may be 1 to 10 hours ^-1 Preferably 2 to 6 hours ^-1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature may be 250 to 600 ℃, preferably 320 to 440 ℃; the pressure may be 0.1 to 5.0MPa, preferably 1.5 to 3.5MPa.

According to the present disclosure, the gasoline may include one or more of catalytic cracking gasoline, coker gasoline, and straight run gasoline; preferably, the sulfur content of the gasoline is greater than 50 micrograms/gram; further preferably, the sulfur content of the gasoline is greater than 100 micrograms/gram.

According to the present disclosure, the volume ratio of the hydrogen donor to the sulfur-containing gasoline may be 0.01 to 1000; the hydrogen donor may be selected from at least one of hydrogen gas, hydrogen-containing gas, and hydrogen donor; optionally, the volume fraction of hydrogen in the hydrogen-containing gas is greater than 30 vol%; optionally, the hydrogen donor is at least one selected from tetrahydronaphthalene, decalin and indane.

The adsorbent used in the present disclosure is an adsorbent having a strong adsorption effect on inorganic sulfur, and the adsorbent may be selected from at least one of activated carbon, an oxide of an active metal, a hydroxide of an active metal, and an oxide of an active metal supported on an inorganic oxide, clay, or a molecular sieve; preferably, the adsorbent is a mixture of zinc oxide, aluminum oxide and silicon oxide; further preferably, the adsorbent may include 50 to 90 wt% zinc oxide, 2 to 30wt% silicon oxide, and 5 to 30wt% aluminum oxide, based on the weight of the adsorbent; the particle size of the adsorbent may be 5 to 500 μm, preferably 20 to 50 μm; the specific surface area can be 20-50 m ² And/g, the total pore volume may be from 0.01 to 0.35cc/g. The adsorbent of the present disclosure can be reused according to actual operation conditions.

The desulfurization catalyst used in the present disclosure is a catalyst that can react with sulfides in gasoline in a hydrogen environment, which can break sulfur-carbon bonds of sulfides in the feedstock. The desulfurization catalysts used in the present disclosure may be formed in various shapes, such as spheres, stripes or clover, and the average particle size thereof is related to the diameter of the reactor, and is generally 1 to 6mm, preferably 3 to 5mm, for example.

According to the present disclosure, the first desulfurization catalyst may include 20 to 80 wt% of an active metal element, 2 to 10 wt% of a molecular sieve, 20 to 50 wt% of an inorganic oxide, and 10 to 50 wt% of clay, based on the weight of the first desulfurization catalyst; the second desulfurization catalyst may comprise 20 to 80 wt% of an active metal element, 2 to 10 wt% of a molecular sieve, 20 to 50 wt% of an inorganic oxide, and 10 to 50 wt% of clay, based on the weight of the second desulfurization catalyst; the third desulfurization catalyst may comprise 20 to 80 wt% of an active metal element, 2 to 10 wt% of a molecular sieve, 20 to 50 wt% of an inorganic oxide, and 10 to 50 wt% of clay, based on the weight of the third desulfurization catalyst; optionally, the active metal component is selected from at least one of cobalt, nickel, copper, iron, manganese, molybdenum, tungsten, silver, tin, vanadium; optionally, the molecular sieve comprises one or more of a large pore molecular sieve, a medium pore molecular sieve and a small pore molecular sieve.

According to the present disclosure, the method may further include: carrying out first regeneration and first reduction on the to-be-regenerated adsorbent to obtain regenerated adsorbent; alternatively, the first regeneration may be performed under a regeneration atmosphere; the regeneration atmosphere may be an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas may be 5 to 50% by volume; the conditions of the first regeneration may include: the temperature is 300-800 ℃, preferably 400-550 ℃; the pressure is 0.1-0.3 MPa, preferably 0.1-0.18 MPa; optionally, the first reduction is performed under a reducing atmosphere; the reducing atmosphere may be a hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas may be 30 to 100% by volume; the conditions of the first reduction may include: the temperature is 300-600 ℃, preferably 350-450 ℃; the pressure is 0.1 to 4.0MPa, preferably 1 to 3MPa.

According to the present disclosure, the method may further include: when the sulfur content of the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst is larger than the first working sulfur capacity, performing second regeneration and second reduction on the first desulfurization adsorbent, the second desulfurization catalyst and the third desulfurization catalyst; the first working sulfur capacity may be any value in the range of 5 to 50 wt%; alternatively, the second regeneration may be performed under a regeneration atmosphere; the regeneration atmosphere may be an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas may be 5 to 50% by volume; the conditions for the second regeneration may include: the temperature is 300-800 ℃, preferably 400-550 ℃; the pressure is 0.1-0.3 MPa, preferably 0.1-0.18 MPa; alternatively, the second reduction may be performed under a reducing atmosphere; the reducing atmosphere may be a hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas may be 30 to 100% by volume; the conditions of the second reduction may include: the temperature is 300-600 ℃, preferably 350-450 ℃; the pressure is 0.1 to 4.0MPa, preferably 1.5 to 3.0MPa.

The present disclosure also provides a system for deep desulfurization of gasoline, the system comprising a fluidized bed reactor 2, a regenerator 13 and a lock hopper 7; the fluidized bed reactor 2 is connected with an adsorbent receiver 19, the regenerator 13 is connected with a spent agent receiver 10, and the adsorbent purge hopper 7 is connected with a first receiver 5 and a second receiver 16;

the fluidized bed reactor 2 is provided with a raw oil inlet, a hydrogen donor inlet, an adsorbent inlet, an oil gas outlet and a spent agent outlet; the lock hopper 7 is provided with a first receiver inlet, a second receiver inlet and a third material outlet, the first receiver 5 is provided with a first material inlet and a first material outlet, and the second receiver 16 is provided with a second material inlet and a second material outlet; the regenerator 13 is provided with a spent agent inlet and a regenerant outlet;

the adsorbent inlet of the fluidized bed reactor 2 is communicated with the outlet of the adsorbent receiver 19, the inlet of the adsorbent receiver 19 is communicated with the third material outlet of the lock hopper 7, the inlet of the lock hopper 7 is communicated with the first material outlet of the first receiver 5, and the first material inlet of the first receiver 5 is communicated with the spent agent outlet of the fluidized bed reactor 2; the spent agent inlet of the regenerator 13 is communicated with the outlet of the spent agent receiver 10, the inlet of the spent agent receiver 10 is communicated with the third material outlet of the lock hopper 7, and the regenerator agent outlet of the regenerator 13 is communicated with the inlet of the second receiver 16;

the fluidized bed reactor 2 is internally provided with a first fluidized bed reaction zone, a first fixed bed reaction zone and a sedimentation separation zone from bottom to top in sequence, the first fixed bed reaction zone is internally provided with a pore canal, preferably, the fluidized bed reactor 2 is internally provided with at least two fluidized bed reaction zones and at least two fixed bed reaction zones, and the fluidized bed reaction zones and the fixed bed reaction zones are arranged at intervals.

In one embodiment of the present disclosure, as shown in fig. 1, preheated sulfur-containing gasoline and hydrogen donor enter from the bottom of a fluidized bed reactor 2 through a pipeline 1, pass through a fixed bed layer in the reactor from bottom to top together with an adsorbent introduced by a pipeline 20 at the lower part of the reactor, contact a desulfurization catalyst in the bed layer, enter a settling separation section at the top of the reactor through the reacted oil gas and the adsorbent, undergo oil-agent separation, and the desulfurized oil-gas mixture is sent to a subsequent product separation and stabilization system through a pipeline 3 for treatment. The spent adsorbent is sent from a reactor upper transfer agent transverse pipe 4 to a first receiver 5, is sent to a lock hopper 7 through a pipeline 6 after being stripped in the first receiver 5, is converted into a low-pressure inactive atmosphere from a high-pressure hydrogen environment after being replaced by nitrogen, and is sent to a combustion furnace through a pipeline 8. The adsorbent is then transported via line 9 to a spent receiver 10 where the spent is lifted by lift gas via line 11 into a regenerator 13. The oxygen-containing gas enters the regenerator from the bottom of the regenerator through a pipeline 12, the adsorbent after regeneration is obtained after the to-be-regenerated agent contacts the oxygen-containing gas in the regenerator 13 for sulfur burning, and the sulfur-containing flue gas is separated from the regenerant at the top of the regenerator and then is conveyed to a sulfur production system or is subjected to alkali elution to remove SO through a pipeline 14 _x The regenerant is fed from the regenerator via line 15 toIn the second receiver 16, the mixture is lifted by nitrogen and conveyed to the lock hopper 7 through a pipeline 17, the mixture is stripped and replaced by hydrogen in the lock hopper 7, the mixture is boosted and then is converted into a high-pressure hydrogen environment, the mixture is conveyed to the reactor feeder 19 through a pipeline 18 and conveyed to the fluidized bed reactor 2 through a pipeline 20, and the continuous desulfurization reaction is realized.

The present disclosure is further illustrated in detail by the following examples. The starting materials used in the examples are all available commercially.

Wherein the desulfurization catalyst used in the examples comprises Ni as an active component and gamma-Al ₂ O ₃ As a carrier. The preparation method comprises the following steps: preparing commercially available nickel nitrate hexahydrate (Beijing chemical reagent Co., purity is greater than 98.5%) into solution with certain concentration, adding into the same volume of oil to form carrier gamma-Al ₂ O ₃ Pellets (average particle diameter: 3 mm) were immersed and stirred at room temperature, dried at 120℃for 4 hours, and baked at 750℃for 6 hours. The desulfurization catalysts obtained in the way that the percentage of Ni in the catalyst was 25%, 20% and 15% were designated DSC-1, DSC-2 and DSC-3, respectively.

The desulfurization adsorbent used in the examples contained ZnO as an active ingredient. The preparation method comprises the following steps: mixing 1.40 kg of pseudo-boehmite (obtained from Shandong aluminum factory and containing 1.82 kg of dry basis) and 2.10 kg of expanded perlite (obtained from Shandong aluminum factory and containing 2.06 kg of dry basis) under stirring, adding 8.2 kg of deionized water, uniformly mixing, adding 360 ml of 30wt% hydrochloric acid (obtained from chemical pure Beijing chemical factory) to make pH value of the slurry be 2.3, stirring and acidifying for 1 hour, and heating to 80 ℃ for aging for 2 hours. After the temperature was lowered, 3.36 kg of zinc oxide powder (Headhorse Co., 99.7% pure) was added and stirred for 1 hour to obtain a mixture slurry. Spray drying with Niro Bowen Nozzle TowerTM model spray dryer at 8.5-9.5 MPa, inlet temperature below 500 deg.C and outlet temperature of about 150 deg.C. The microspheres obtained by spray drying were dried at 180℃for one hour and then calcined at 635℃for 1 hour to give a desulfurization adsorbent, designated as DAS-1, having an average particle diameter of 50. Mu.m.

The desulfurization adsorbent FCAS-R09 used in the comparative example was commercially available and was manufactured by Nanjing, inc.

TABLE 1

Example 1

The process shown in fig. 1 was used to conduct a small-scale test for deep desulfurization of catalytically cracked gasoline. The fluidized bed reactor of the embodiment comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top, wherein desulfurization catalyst DSC-1 is filled in each of the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone, the adsorbent DAS-1 and gasoline hydrogen are mixed and then enter from the bottom of the fluidized bed reactor, and the separated spent adsorbent is regenerated and reduced to obtain regenerated adsorbent; the regenerated adsorbent is returned to the fluidized bed reactor. The properties of the raw gasoline are shown in Table 1, and the operating conditions and the product properties are shown in Table 2.

Comparative example 1

This comparative example conducted a small-sized desulfurization test on catalytically cracked gasoline. The fluidized bed reactor of the comparative example comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top, wherein desulfurization catalyst DSC-1 is filled in each of the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone, and gasoline hydrogen enters from the bottom of the fluidized bed reactor. The properties of the raw gasoline are shown in Table 1, and the operating conditions and the product properties are shown in Table 2.

Comparative example 2

In the comparative example, a small desulfurization test is carried out on the catalytic cracking gasoline, a fixed bed reaction zone is not arranged in the fluidized bed reactor of the comparative example, the adsorbent DAS-1 and gasoline hydrogen are mixed and then enter from the bottom of the fluidized bed reactor, and the separated adsorbent to be regenerated is regenerated and reduced to obtain a regenerated adsorbent; the regenerated adsorbent is returned to the fluidized bed reactor. The properties of the raw gasoline are shown in Table 1, and the operating conditions and the product properties are shown in Table 2.

Example 2

The process shown in fig. 1 was used to conduct a small-scale test for deep desulfurization of catalytically cracked gasoline. The fluidized bed reactor of the embodiment comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top, wherein a desulfurization catalyst DSC-1 is filled in the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone, and an adsorbent DAS-1 enters from the bottom of the reactor together after being mixed with gasoline hydrogen. The properties of the raw gasoline are shown in Table 1, the operating conditions are shown in Table 3, the desulfurization adsorbent is not regenerated, and the properties of the product after 10 hours of continuous reaction are shown in Table 3.

Comparative example 3

The comparative example adopts an adsorbent FCAS-R09 to carry out a small desulfurization test on the catalytic cracking gasoline, the reactor of the comparative example is a fixed bed reactor, the adsorbent FCAS-R09 is filled in the reactor, and gasoline and hydrogen are mixed and then enter from the bottom of the reactor. The properties of the raw gasoline are shown in Table 1, the operating conditions are shown in Table 3, the adsorbent is not regenerated, and the properties of the product after 10 hours of continuous reaction are shown in Table 3.

Example 3

The process shown in fig. 1 was used to conduct a small-scale test for deep desulfurization of catalytically cracked gasoline. The fluidized bed reactor of the embodiment comprises a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone and a sedimentation separation zone from bottom to top, wherein desulfurization catalysts DSC-1, DSC-2 and DSC-3 are respectively filled in the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone from top to bottom, the adsorbent DAS-1 and gasoline hydrogen are mixed and then enter from the bottom of the reactor, and the separated spent adsorbent is regenerated and reduced to obtain a regenerated adsorbent; the regenerated adsorbent is returned to the fluidized bed reactor. The properties of the raw gasoline are shown in Table 1, the operating conditions are the same as those of Table 3, and the properties of the product are shown in Table 3.

TABLE 2

TABLE 3 Table 3

From the data in tables 2 and 3, it can be seen that the sulfur content in the product of example 1 was 3. Mu.g/g, the sulfur content in the product of comparative example 1 was 35. Mu.g/g, and the sulfur content in the product of comparative example 2 was 435.2. Mu.g/g, comparing example 1 with comparative examples 1-2; the olefin content in the product of example 1 was 25.82w%, the olefin content in the product of comparative example 1 was 19.34w%, and the olefin content in the product of comparative example 2 was 27.86w%; from this, it can be seen that the sulfur content and the olefin content in the product of example 1 were significantly reduced. Comparing example 1 with example 2, the desulfurization adsorbent of example 2 had a sulfur content of 4 μg/g and an olefin content of 25.62w% without regeneration, and it was found that deep desulfurization and continuous desulfurization could be achieved by regenerating and recycling the desulfurization adsorbent. Comparing example 1 with example 3, the sulfur content of the product of example 3 is 2 μg/g, and the olefin content is 27.58w%, it can be seen that the desulfurization catalyst packed in the fixed bed layer can be adjusted according to actual needs in order to obtain the best desulfurization effect.

Therefore, the method fully utilizes different reaction mechanisms of the desulfurization catalyst and the adsorbent, achieves the effect of realizing deep desulfurization, and has low octane number loss and high product liquid yield.

The preferred embodiments of the present disclosure have been described in detail above, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.

In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations are not described further in this disclosure in order to avoid unnecessary repetition.

Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.

Claims

1. A method for deep desulfurization of gasoline, the method comprising:

the adsorbent is selected from at least one of active carbon, an oxide of an active metal, a hydroxide of an active metal, and an oxide of an active metal supported on an inorganic oxide, clay, or molecular sieve;

the first desulfurization catalyst takes Ni as an active component and gamma-Al ₂ O ₃ As a carrier;

wherein the mass in the fluidized bed reactorAirspeed of 1-10 h ^-1 The temperature is 250-600 ℃ and the pressure is 0.1-4.0 MPa.

2. The process of claim 1, wherein the fluidized bed reactor comprises at least two fluidized bed reaction zones and at least two fixed bed reaction zones, the fluidized bed reaction zones and the fixed bed reaction zones being spaced apart from one another.

3. The method of claim 2, wherein the fluidized bed reactor comprises, from bottom to top, a first fluidized bed reaction zone, a first fixed bed reaction zone, a second fluidized bed reaction zone, a second fixed bed reaction zone, a third fluidized bed reaction zone, a third fixed bed reaction zone, and a sedimentation separation zone; the first fixed bed reaction zone, the second fixed bed reaction zone and the third fixed bed reaction zone are respectively filled with a first desulfurization catalyst, a second desulfurization catalyst and a third desulfurization catalyst, and the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst are identical or different from each other.

4. The method of claim 1, wherein the mass space velocity in the fluidized bed reactor is 2-6 h ^-1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 320-440 ℃; the pressure is 1.5-3.5 MPa.

5. The method of claim 1, wherein,

the gasoline comprises one or more of catalytic cracking gasoline, coker gasoline and straight-run gasoline.

6. The method of claim 5 wherein the sulfur content of the gasoline is greater than 50 micrograms/gram.

7. The method of claim 6 wherein the sulfur content of the gasoline is greater than 100 micrograms/gram.

8. The method of claim 1, wherein,

the volume ratio of the hydrogen donor to the sulfur-containing gasoline is 0.01-1000;

the hydrogen donor is selected from at least one of hydrogen gas, hydrogen-containing gas and hydrogen donor.

9. The method of claim 8, wherein the volume fraction of hydrogen in the hydrogen-containing gas is greater than 30 vol%;

the hydrogen donor is at least one selected from tetrahydronaphthalene, decalin and indane.

10. The method of claim 1, wherein,

the adsorbent is a mixture of zinc oxide, aluminum oxide and silicon oxide;

the adsorbent comprises, by weight, 50-90% of zinc oxide, 2-30% of silicon oxide and 5-30% of aluminum oxide; the particle size of the adsorbent is 5-500 mu m; specific surface area of 20-50 m ² And/g, the total pore volume is 0.01-0.35 cc/g.

11. The method of claim 10, wherein the adsorbent has a particle size of 20-50 μm.

12. The method of claim 1, wherein the method further comprises:

and carrying out first regeneration and first reduction on the to-be-regenerated adsorbent to obtain the regenerated adsorbent.

13. The method of claim 12, wherein the first regeneration is performed under a regeneration atmosphere; the regeneration atmosphere is an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas is 5-50% by volume; the conditions for the first regeneration include: the temperature is 300-800 ℃; the pressure is 0.1-0.3 MPa;

the first reduction is performed under a reducing atmosphere; the reducing atmosphere is hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas is 30-100% by volume; the conditions for the first reduction include: the temperature is 300-600 ℃; the pressure is 0.1-4.0 MPa.

14. The method of claim 13, wherein the conditions of the first regeneration comprise: the temperature is 400-550 ℃; the pressure is 0.1-0.18 MPa;

the conditions for the first reduction include: the temperature is 350-450 ℃; the pressure is 1-3 MPa.

15. A method according to claim 3, wherein the method further comprises:

when the sulfur content of the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst is larger than the working sulfur capacity, performing second regeneration and second reduction on the first desulfurization catalyst, the second desulfurization catalyst and the third desulfurization catalyst; the working sulfur capacity is any value in the range of 5-50 wt%.

16. The method of claim 15, wherein the second regeneration is performed under a regeneration atmosphere; the regeneration atmosphere is an oxygen-containing gas; the volume fraction of oxygen in the oxygen-containing gas is 5-50% by volume; the conditions for the second regeneration include: the temperature is 300-800 ℃; the pressure is 0.1-0.3 MPa;

the second reduction is performed under a reducing atmosphere; the reducing atmosphere is hydrogen-containing gas; the volume fraction of hydrogen in the hydrogen-containing gas is 30-100% by volume; the conditions for the second reduction include: the temperature is 300-600 ℃; the pressure is 0.1-4.0 MPa.

17. The method of claim 16, wherein the conditions of the second regeneration comprise: the temperature is 400-550 ℃; the pressure is 0.1-0.18 MPa;

the conditions for the second reduction include: the temperature is 350-450 ℃; the pressure is 1.5-3.0 MPa.

18. A system for a method for deep desulfurization of gasoline as claimed in any one of claims 1 to 17, characterized in that it comprises a fluidized bed reactor (2), a regenerator (13) and a lock hopper (7); the fluidized bed reactor (2) is connected with an adsorbent receiver (19), the regenerator (13) is connected with a spent agent receiver (10), and the lock hopper (7) is connected with a first receiver (5) and a second receiver (16);

the fluidized bed reactor (2) is provided with a raw oil inlet, a hydrogen donor inlet, an adsorbent inlet, an oil gas outlet and a spent agent outlet; the lock hopper (7) is provided with a first receiver inlet, a second receiver inlet and a third material outlet, the first receiver (5) is provided with a first material inlet and a first material outlet, and the second receiver (16) is provided with a second material inlet and a second material outlet; the regenerator (13) is provided with a spent agent inlet and a regenerant outlet;

the adsorbent inlet of the fluidized bed reactor (2) is communicated with the outlet of the adsorbent receiver (19), the inlet of the adsorbent receiver (19) is communicated with the third material outlet of the lock hopper (7), the inlet of the lock hopper (7) is communicated with the first material outlet of the first receiver (5), and the first material inlet of the first receiver (5) is communicated with the spent agent outlet of the fluidized bed reactor (2); the to-be-regenerated agent inlet of the regenerator (13) is communicated with the outlet of a to-be-regenerated agent receiver (10), the inlet of the to-be-regenerated agent receiver (10) is communicated with the third material outlet of the lock hopper (7), and the regeneration agent outlet of the regenerator (13) is communicated with the inlet of the second receiver (16);

the fluidized bed reactor (2) is internally provided with a first fluidized bed reaction zone, a first fixed bed reaction zone and a sedimentation separation zone from bottom to top in sequence, and a pore canal is arranged in the first fixed bed reaction zone.