CN112745893B

CN112745893B - Method for regenerating spent catalyst, method and device for desulfurizing sulfur-containing hydrocarbon

Info

Publication number: CN112745893B
Application number: CN201911047818.8A
Authority: CN
Inventors: 朱丙田; 侯栓弟; 朱振兴; 张同旺; 毛俊义; 张哲民; 刘凌涛; 韩颖; 邹亢
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: 2019-10-30
Filing date: 2019-10-30
Publication date: 2022-11-15
Anticipated expiration: 2039-10-30
Also published as: CN112745893A

Abstract

The invention relates to the field of desulfurization of sulfur-containing hydrocarbon raw materials, and discloses a method for regenerating a spent catalyst, a method for desulfurizing sulfur-containing hydrocarbon and a device. The method comprises the following steps: introducing the spent catalyst from the sulfur-containing hydrocarbon desulfurization unit into a regeneration unit comprising a first regeneration zone and a second regeneration zone for regeneration; the spent catalyst is firstly regenerated in the first regeneration zone and then enters the second regeneration zone for second regeneration, wherein the oxygen content of the feed gas in the first regeneration zone is controlled to be 6-12% by volume, and the oxygen content of the feed gas in the second regeneration zone is controlled to be higher than that of the feed gas in the first regeneration zone.

Description

Method for regenerating spent catalyst, method and device for desulfurizing sulfur-containing hydrocarbon

Technical Field

The invention relates to the field of desulfurization of sulfur-containing hydrocarbon raw materials, in particular to a method for regenerating a spent catalyst, a method for desulfurizing sulfur-containing hydrocarbon, a device for desulfurizing sulfur-containing hydrocarbon and a method for desulfurizing by using the device.

Background

In order to protect the environment, countries around the world have set increasingly stringent standards for gasoline sulfur content.

The adsorption desulfurization (S Zorb) technology is a technology for producing ultra-low sulfur clean gasoline, can economically reduce the sulfur content in the gasoline to 10 micrograms/gram or lower, has prominent technical advantages in the production of clean gasoline, and has better market prospect in market application.

Most of the existing S Zorb adsorbents are desulfurization adsorbents prepared by using silicon/aluminum materials as carriers and zinc/nickel as active components, and the adsorption activity is reduced due to the formation of carbon deposit and zinc sulfide in the reaction process, so that the regeneration reduction is needed to recover the activity of the adsorbents.

However, with continuous cyclic regeneration of the S Zorb adsorbent, there are problems that the S Zorb adsorbent tends to be crushed (reduced in strength) and reduced in activity, resulting in a reduction in desulfurization efficiency and an increase in consumption.

CN108014766A proposes a two-stage regeneration method of desulfurization adsorbent. Under the condition of primary regeneration, the spent agent is promoted to contact with a first regeneration gas, and the obtained gas-solid mixture is subjected to gas-solid separation treatment to form a primary regeneration agent; and under secondary regeneration conditions, promoting the primary regenerant to contact a second regeneration gas to form the regenerant. Although the method can effectively reduce the formation of zinc silicate in the regenerant, the spent regenerant contains coke rich in hydrogen elements, so that local hot spots are easily caused once the oxygen distribution is uneven in the first-stage coking process, the oxidation of sulfur elements in the catalyst is promoted, and the possibility of generating zinc silicate is further caused.

Moreover, changes in refinery crude oil can affect changes in the operation of subsequent processing units. In the S Zorb gasoline desulfurization process, the change of the gasoline raw material composition can affect the change of the coke content on the catalyst, the change of the coke content on the catalyst can cause the change of the scorching temperature, and the catalyst regeneration operation needs to be correspondingly adjusted according to the situation.

Disclosure of Invention

The invention aims to provide a sulfur-containing hydrocarbon desulfurization method and a sulfur-containing hydrocarbon desulfurization device, aiming at solving the problem of high consumption of a catalyst in a sulfur-containing hydrocarbon desulfurization unit.

In order to achieve the above object, a first aspect of the present invention provides a method for regenerating a spent catalyst, the method comprising: introducing spent catalyst from a sulfur-containing hydrocarbon desulfurization unit into a regeneration unit comprising a first regeneration zone and a second regeneration zone for regeneration; the spent catalyst is firstly regenerated in the first regeneration zone and then enters the second regeneration zone for second regeneration, and the feeding gas enters the first regeneration zone in two ways of upstream and downstream according to the flow direction of the solid phase material flow in the first regeneration zone; the amount of the feed gas entering from upstream to the feed gas entering from downstream is such that the volume ratio of the oxygen input of the two is 0.5-1:1;

wherein the oxygen content of the feed gas in the first regeneration zone is controlled to be 6 to 12 vol%, and the oxygen content of the feed gas in the second regeneration zone is controlled to be higher than the oxygen content of the feed gas in the first regeneration zone.

In a second aspect, the present invention provides a process for the desulfurization of sulfur-containing hydrocarbons, which process comprises:

(1) Introducing hydrogen and a sulfur-containing hydrocarbon raw material into a sulfur-containing hydrocarbon desulfurization unit to contact with a catalyst for desulfurization reaction to obtain a spent catalyst and a desulfurization material flow;

(2) Regenerating the spent catalyst;

wherein the regeneration operation in step (2) is carried out by the method described in the foregoing first aspect.

In a third aspect, the present invention provides an apparatus for desulfurizing a sulfur-containing hydrocarbon, the apparatus comprising a sulfur-containing hydrocarbon desulfurization unit and a regeneration unit,

the sulfur-containing hydrocarbon desulfurization unit comprises a desulfurization reactor, a reactor receiver, a lock hopper and a reducer, wherein the reactor receiver and the reducer are communicated through the lock hopper, and the reactor receiver and the reducer are respectively communicated with the upper part and the lower part of the desulfurization reactor;

the regeneration unit comprises a regenerator receiver, a regenerator feed tank, a second regenerator and a first regenerator, the lock hopper is communicated with the first regenerator through the regenerator feed tank, and the first regenerator is communicated with the regenerator receiver through the second regenerator;

an upper gas distributor and a lower gas distributor are arranged in the regeneration section of the first regenerator.

In a fourth aspect, the present invention provides a process for desulphurisation of a sulphur-containing hydrocarbon, the process being carried out in an apparatus as described in the preceding third aspect, the process comprising:

(2) Regenerating the spent catalyst;

wherein the regeneration operation in step (2) is carried out by the method of the first aspect;

the operation of introducing hydrogen and the sulfur-containing hydrocarbon feedstock into the sulfur-containing hydrocarbon desulfurization unit for contact with the catalyst comprises: introducing hydrogen and a sulfur-containing hydrocarbon raw material into a desulfurization reactor to contact with a catalyst so as to perform desulfurization reaction, and introducing the obtained spent catalyst into a regeneration unit from a reactor receiver, a lock hopper and a regenerator feed tank in sequence; and

the operation of regenerating the spent catalyst comprises the following steps: introducing the spent catalyst from the regenerator feed tank into a first regenerator and a second regenerator in sequence for regeneration, and then recycling the regenerated catalyst obtained after regeneration back to the sulfur-containing hydrocarbon desulfurization unit through a regenerator receiver, a lock hopper and a reducer in sequence.

Compared with the prior art, the method and the device provided by the invention can obviously reduce the consumption of the catalyst and reduce the running cost of the device.

Preferably, the heat exchanger arranged in the first regeneration zone has the functions of heat extraction and heating, and can effectively solve the problems of temperature reduction and even regeneration flameout caused by less heat release of the first regeneration zone due to low carbon content on the spent catalyst.

In addition, the method and the device provided by the invention can effectively realize the stable scorching of the catalyst to remove hydrogen elements in a low-temperature environment, and the oxidation reaction of zinc sulfide to generate sulfur dioxide under a high-temperature scorching condition, thereby avoiding the overhigh water pressure during the high-temperature removal of the sulfur elements, inhibiting the generation of zinc silicate, improving the activity and strength of the catalyst, and greatly reducing the consumption of the catalyst.

Drawings

FIG. 1 is a schematic diagram of an apparatus for desulfurization of sulfur-containing hydrocarbons provided by the present invention;

FIG. 2 is a schematic diagram of the structure of a sulfur-containing hydrocarbon desulfurization unit provided by the present invention;

fig. 3 is a schematic structural diagram of a first regenerator in a regeneration unit provided by the present invention.

FIG. 4 is a partial schematic view of a heat exchanger tube in a first regenerator of a regeneration unit provided by the present invention.

Description of the reference numerals

1. Desulfurization reactor 2, reactor receiver

3. Lock hopper 4, reduction device

5. Regenerator receiver 6, regenerator feed tank

7. Riser 8, second regenerator

9. First regenerator 30, heat exchanger tubes

31. Tube array baffle

101. Material input pipe 102 and catalyst input pipe

103. Catalyst discharge pipe 104 and reactor reaction section

105. Expanding section 106 and member of reactor

107. Settling section 111, cone section of the reactor

112. Dipleg 113, dipleg outlet

91. Lower gas distributor 92 and upper gas distributor

931. Lower heat exchanger 932, upper heat exchanger

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the first aspect of the present invention provides a method for regenerating a spent catalyst, the method comprising: introducing spent catalyst from a sulfur-containing hydrocarbon desulfurization unit into a regeneration unit comprising a first regeneration zone and a second regeneration zone for regeneration; the spent catalyst is firstly regenerated in the first regeneration zone and then enters the second regeneration zone for second regeneration, and the feeding gas enters the first regeneration zone in two ways of upstream and downstream according to the flow direction of the solid phase material flow in the first regeneration zone; in the first regeneration zone, the feed gas entering from upstream and the feed gas entering from downstream are in such quantities that the volumetric ratio of the oxygen input of the two is between 0.5 and 1:1;

Preferably, the oxygen content of the feed gas in the second regeneration zone is controlled to be in the range of from 15 to 21 volume%.

Preferably, the operating conditions in the first regeneration zone comprise: the bed temperature is 310-390 ℃, the pressure is 0.1-0.5MPa, and the apparent gas velocity is 0.05-0.3m/s.

Preferably, the operating conditions in the second regeneration zone include: the bed temperature is 490-530 deg.C, the pressure is 0.1-0.5MPa, and the apparent gas velocity is 0.2-0.4m/s.

According to the invention, in the first regeneration zone, the feeding gas enters the first regeneration zone in two ways of upstream and downstream according to the flowing direction of the solid phase flow; in the first regeneration zone, the feed gas entering from upstream and the feed gas entering from downstream are in such quantities that the volumetric ratio of the oxygen input of the two is between 0.5 and 1:1, i.e. the feed gas entering from upstream to the feed gas entering from downstream such that the volumetric ratio of oxygen entering from upstream to oxygen entering from downstream is between 0.5 and 1:1.

in the present invention, the oxygen feed amount refers to the volume of oxygen carried into the first regeneration zone by the feed gas entering the first regeneration zone.

Preferably, in the present invention, the feed gas is a mixture of oxygen and other inert gases not participating in the reaction, such as nitrogen.

In order to maintain the temperature of the first regeneration in the first regeneration zone, it is preferable that a heat exchange unit capable of heat extraction and heating is provided in the first regeneration zone.

According to a preferred embodiment, in the present invention, when the carbon content on the spent catalyst is M wt%, the heat exchange unit in the first regeneration zone performs the function of heating and heat removal, and specifically, when the carbon content on the spent catalyst is higher than or equal to M wt%, the heat exchange unit performs the function of heat removal; the heat exchange unit performs a heating function when the carbon content on the spent catalyst is less than M wt%, which may be, for example, 1.2 to 1.5.

The method for regenerating the spent catalyst provided by the invention has the advantages that the catalyst is respectively regenerated in the two regeneration areas, the spent catalyst is firstly contacted with gas with low oxygen content in the first regeneration area, and the reaction conditions are controlled to ensure that coke on the deactivated catalyst participates in the reaction to form a primary regenerated catalyst; in the second regeneration zone, the once regenerated catalyst after the first regeneration zone is burnt is continuously contacted with oxygen-containing gas, so that zinc sulfide in the catalyst reacts with coke, sulfur elements on the catalyst are removed, and the regenerated catalyst is formed.

As previously mentioned, a second aspect of the invention provides a process for the desulfurization of sulfur-containing hydrocarbons, the process comprising:

(2) Regenerating the spent catalyst;

Preferably, the sour hydrocarbon feedstock is selected from at least one of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel and gas oil, more preferably gasoline and/or diesel. The gasoline, kerosene, diesel and gas oil fractions are full fractions and/or partially narrow fractions thereof (i.e., the distillation range of the gasoline, kerosene, diesel and gas oil fractions is broad and the sulfur-containing hydrocarbon feedstock may be all of them, or a fraction of a portion of the distillation range).

Preferably, the sulfur content of the sulfur-containing hydrocarbon feedstock is greater than or equal to 50 μ g/g, more preferably greater than or equal to 100 μ g/g, for example the sulfur content of the sulfur-containing hydrocarbon feedstock is in the range of from 100 to 1500 μ g/g.

In the present invention, the catalyst may be a conventional catalyst used in the art, and particularly, in order to obtain relatively good activity and less catalyst consumption, it is preferable that the catalyst is a catalyst capable of generating sulfur dioxide and zinc oxide during regeneration after completion of desulfurization reaction.

Preferably, according to the method of the second aspect of the present invention, in the step (1), the operating conditions of the desulfurization reaction include: the temperature is 350-440 ℃, the molar ratio of hydrogen to sulfur-containing hydrocarbon feedstock is 0.1-1:1, the weight hourly space velocity is 0.1-5h ^-1 The reaction pressure is 1.0-3.0MPa.

Preferably, before the spent catalyst is regenerated, the spent catalyst is subjected to gas stripping.

Preferably, the stripping is performed in a regenerator feed tank.

Preferably, the stripping operation conditions include: the bed temperature is 200-400 deg.C, the pressure is 0.1-0.2MPa, and the apparent gas velocity of stripping gas is 0.05-0.3m/s. Preferably, the fluidizing gas subjected to said stripping is nitrogen.

As described above, the third aspect of the present invention provides an apparatus for desulfurizing a sulfur-containing hydrocarbon, comprising a sulfur-containing hydrocarbon desulfurization unit and a regeneration unit,

In the present invention, the device preferably further comprises conduits and valves that enable the various components of the device to be in communication.

Preferably, according to the apparatus of the third aspect of the present invention, the desulfurization reactor comprises a reactor reaction section, a reactor settling section and a reactor expanding section connecting the reactor reaction section and the reactor settling section, the reactor settling section is further provided with a member having a funnel-shaped structure, the top of the member is open, the upper cross section of the cone portion is large, the lower cross section of the cone portion is small, and the lower side of the cone portion is connected with a dipleg.

Preferably, according to the apparatus of the third aspect of the present invention, the outlet of the dipleg is arranged in the dense bed of the desulfurization reactor.

Preferably, according to the device of the third aspect of the invention, the angle of the baffles constituting the conical part of the member to the horizontal is not less than 30 °, preferably 40 ° to 60 °.

In the present invention, it is preferable that the baffle plate forming the tapered portion is formed of at least one plate material by welding.

To reduce the effect of the flow of the gas stream in the settling zone on the settling of the particles above the openings in the elements, the baffles forming the cone section are preferably 100-300mm high dams.

In the present invention, the specific shape of the upper opening of the cone portion of the member is not particularly limited, and may be, for example, circular, square, and triangular.

Preferably, according to the apparatus of the third aspect of the present invention, the number of the members is at least one, and the ratio of the sum of the cross-sectional areas of the upper openings of the cone portions of the respective members to the maximum cross-sectional area of the settling section of the reactor is 0.05 to 0.5:1, more preferably 0.1 to 0.3:1. therefore, the device is used for blocking rising particles, changing the non-uniformity of gas flow of gas-solid fluid on the radial section of the settling space, reducing the non-uniformity of force applied to the particles on the radial section of the settling space, reducing the drag force applied to the particles in a local area, promoting the particles to settle, and collecting the particles to return to the reaction section of the reactor.

Preferably, the desulfurization reactor further comprises a material input pipe, a catalyst input pipe and a catalyst discharge pipe, and a filter is arranged at the top of the settling zone, wherein the material input pipe is positioned at the bottom of the desulfurization reactor and is used for feeding the sulfur-containing hydrocarbon raw material into a reactor reaction section of the desulfurization reactor to perform desulfurization reaction with the catalyst. The catalyst inlet is preferably disposed in a lower sidewall of the reactor section for introducing catalyst into the reactor section.

Preferably, according to the apparatus of the third aspect of the present invention, the upper gas distributor provided in the regeneration section of the first regenerator is a pipe distributor composed of a main pipe and a branch pipe.

Preferably, according to the apparatus of the third aspect of the present invention, the gas nozzles are arranged on the branch pipes of the pipe distributor, and the openings of the gas nozzles face downwards (so as to avoid the particle materials falling into the pipes during the operation or when the gas is stopped).

Preferably, the tubular distributor is provided with at least two gas inlets so that the gas is distributed uniformly within the tubular distributor.

Preferably, according to the apparatus of the third aspect of the present invention, a heat exchanger capable of heat extraction and heating is further provided in the first regenerator.

Preferably, according to the apparatus of the third aspect of the present invention, the heat exchanger axially passes through an upper gas distributor provided in the regeneration section of the first regenerator.

According to a preferred embodiment, the heat exchanger is a shell and tube heat exchanger, the heat exchanger is divided into an upper heat exchanger and a lower heat exchanger, the upper heat exchanger and the lower heat exchanger are connected through a pipeline, and the connecting pipeline penetrates through the upper gas distributor. The upper heat exchanger and the lower heat exchanger are respectively provided with a valve body communicated with a high-temperature heat exchange medium phase inlet and outlet pipeline and a low-temperature heat exchange medium phase inlet and outlet pipeline, so that the heat extraction and heating of the catalyst bed layer of the first regenerator are automatically realized.

Preferably, the heat exchange medium of the heat exchanger is liquid with phase change, and when the heat extraction function of the heat exchanger is realized, the heat exchange medium entering the heat exchanger is further preferably in a gas-liquid two-phase state; when the heating function of the heat exchanger is realized, the heat exchange medium entering the heat exchanger is preferably high-temperature gas phase, and the heat exchange medium is more preferably water.

Preferably, the temperature of the heat exchange medium at the inlet of the heat exchanger is 300-500 ℃ when the heat exchanger realizes the heating function.

Preferably, tube array baffles are arranged on the outer sides of the tubes of the heat exchanger, and the included angle between the plane of each tube array baffle and the horizontal plane is preferably 45-70 degrees. The baffles of adjacent tubes are further preferably arranged in a staggered mode, so that the guiding effect of the baffles on particles is improved, the large bubbles in a bed layer are crushed, the gas-solid contact efficiency is improved, and the heat exchange effect of the heat exchanger is enhanced. The ratio of the overlapping length of the baffles of adjacent tubes of the heat exchanger in the horizontal plane projection to the distance between the adjacent tubes is preferably 0.1-0.25:1.

according to the present invention, in order to further reduce the hydrogen element content of the spent catalyst and reduce the water yield in the subsequent regeneration, preferably, the gas stripping effect of the spent catalyst before regeneration is increased, and further preferably, the temperature and the operation gas velocity of the catalyst in the feed tank of the regenerator (before the spent catalyst enters the first regenerator) are increased, and the air inlet temperature of the feed tank of the regenerator is preferably 300 to 400 ℃.

According to the device of the invention, the second regenerator can be a conventional fluidized bed regenerator provided with a heat exchanger for heat extraction, and has no special requirement for the second regenerator, and the inner cavity of the second regenerator can be divided into a reaction section, an expanding section and a settling space from bottom to top by referring to the conventional regenerator known in the field as long as the two-stage coking of the catalyst can be realized, wherein a gas distributor for introducing into the regenerator and the heat exchanger for heat extraction are arranged in the reaction section, and at least one stage of cyclone separator is arranged in the settling space.

According to the device of the invention, the lock hopper is used for changing the environment of the adsorbent in the conveying process of the adsorbent, and the spent catalyst and the regenerated catalyst share one lock hopper for saving space. When the lock hopper is used for conveying the spent catalyst, changing the spent catalyst from a high-pressure environment of a reactor receiver to a low-pressure environment, and stopping conveying the regenerated catalyst of the lock hopper at the moment; when the lock hopper is used for conveying the regenerated catalyst, the regenerated catalyst can be changed from a low-pressure atmosphere to a high-pressure environment, and the conveying of the spent catalyst of the lock hopper needs to be stopped.

According to the device, the reactor receiver, the reducer, the lock hopper, the regenerator feed tank and the regenerator receiver are conventional reaction tank bodies, and are provided with gas and solid feed inlets, and pipelines and valves which are communicated with each other.

The device according to the present invention, wherein there is no special requirement for the structure and connection manner of the desulfurization reactor, the reactor receiver, the lock hopper, the reducer, the regenerator feed tank, and the regenerator receiver, can be obtained by referring to the conventional fluidized bed device known in the art, and the detailed description thereof is omitted.

Preferred embodiments of the sulfur-containing hydrocarbon desulfurization apparatus and method of the present invention are provided below in conjunction with fig. 1, fig. 2, fig. 3, and fig. 4.

The device of the invention comprises a sulfur-containing hydrocarbon desulfurization unit and a regeneration unit,

the sulfur-containing hydrocarbon desulfurization unit comprises a desulfurization reactor 1, a reactor receiver 2, a lock hopper 3 and a reducer 4, wherein the reactor receiver 2 and the reducer 4 are communicated through the lock hopper 3, and the reactor receiver 2 and the reducer 4 are respectively communicated with the upper part and the lower part of the desulfurization reactor 1;

the regeneration unit comprises a regenerator receiver 5, a regenerator feed tank 6, a second regenerator 8 and a first regenerator 9, the lock hopper 3 is communicated with the first regenerator 9 through the regenerator feed tank 6, the regenerator feed tank 6 is connected with the first regenerator 9 through a riser 7, and the first regenerator 9 is communicated with the regenerator receiver 5 through the second regenerator 8.

Preferably, the desulfurization reactor 1 comprises a reactor reaction section 104, a reactor settling section 107 and a reactor expanding section 105 connecting the reactor reaction section 104 and the reactor settling section 107, the reactor settling section 107 is also provided with a member 106 with a funnel-shaped structure, the top of the member 106 is open, the upper cross section of the cone part 111 is large, the lower cross section of the cone part 111 is small, and the lower part of the cone part 111 is connected with a dipleg 112;

an upper gas distributor 92 and a lower gas distributor 91 are arranged in the regeneration section of the first regenerator 9.

Preferably, the dipleg outlet 113 of the dipleg 112 is arranged in the dense bed of the desulfurization reactor 1.

Preferably, the angle of the baffles constituting the cone portion 111 of the member to the horizontal is not less than 30 °, preferably 40 ° to 60 °.

Preferably, the number of the members is at least one, and the ratio of the sum of the cross-sectional areas of the upper openings of the tapered portion 111 of each of the members to the cross-sectional area of the reactor settling section 107 (i.e., the maximum cross-sectional area of the reactor settling section) is 0.05 to 0.5:1, more preferably 0.1 to 0.3:1.

preferably, the desulfurization reactor 1 further comprises a material input pipe 101, a catalyst input pipe 102, a catalyst discharge pipe 103 and a filter arranged at the top of the settling zone, wherein the material input pipe 101 is located at the bottom of the desulfurization reactor 1 and is used for feeding a sulfur-containing hydrocarbon raw material into a reactor reaction section 104 of the desulfurization reactor 1 to perform desulfurization reaction with a catalyst. A catalyst input tube 102 is disposed on a lower sidewall of the reactor reaction section 104 for feeding catalyst into the reactor reaction section 104.

Preferably, the upper gas distributor 92 provided in the regeneration section of the first regenerator 9 is a tubular distributor consisting of main tubes and branch tubes.

Preferably, the branch pipe of the pipe distributor is provided with a gas nozzle, and the opening of the gas nozzle faces downwards.

Preferably, a heat exchanger capable of heat extraction and heating is further arranged in the first regenerator 9.

Preferably, the heat exchanger passes axially through an upper gas distributor provided in the regeneration section of the first regenerator.

Preferably, the heat exchanger is a shell and tube heat exchanger, which is divided into an upper heat exchanger 932 and a lower heat exchanger 931, which are connected by a pipe, and the connecting pipe passes through the upper gas distributor 92. The upper heat exchanger 932 and the lower heat exchanger 931 are respectively communicated with the heat exchange medium inlet and outlet pipes, and the heat exchangers are disposed above the lower gas distributor 91.

Preferably, a tube array baffle 31 is arranged outside the heat exchanger tube array 30 of the heat exchanger, and the included angle (also called an inclined angle) between the plane of the tube array baffle 31 and the horizontal plane is preferably 45-70 degrees. The baffles of adjacent tubes are further preferably arranged in a staggered mode, so that the guiding effect of the baffles on particles is improved, the large bubbles in a bed layer are crushed, the gas-solid contact efficiency is improved, and the heat exchange effect of the heat exchanger is enhanced. The ratio of the overlapping length of the baffles of adjacent tubes of the heat exchanger projected on the horizontal plane to the space between the adjacent tubes is preferably 0.1-0.25:1.

as mentioned above, in a fourth aspect, the present invention provides a process for the desulfurization of sulfur-containing hydrocarbons, which process is carried out in an apparatus as defined in the third aspect, which process comprises:

(2) Regenerating the spent catalyst;

wherein the regeneration operation in the step (2) is performed by the method of the first aspect;

the operation of introducing hydrogen and the sulfur-containing hydrocarbon feedstock into a sulfur-containing hydrocarbon desulfurization unit in contact with a catalyst comprises: introducing hydrogen and a sulfur-containing hydrocarbon raw material into a desulfurization reactor to contact with a catalyst so as to perform desulfurization reaction, and introducing the obtained spent catalyst into a regeneration unit from a reactor receiver, a lock hopper and a regenerator feed tank in sequence; and

Preferably, the method according to the fourth aspect of the present invention, further comprises: in the desulfurization reactor, the material flow participating in the desulfurization reaction sequentially flows through a reactor reaction section, a reactor expanding section and a reactor settling section, and at least part of catalyst in the material flow participating in the desulfurization reaction returns to the reactor reaction section for the desulfurization reaction after being blocked and/or collected by a component in the reactor settling section.

Preferably, in the method of the fourth aspect of the present invention, the operating conditions of the desulfurization reaction include: the temperature is 350-440 ℃, the molar ratio of hydrogen to sulfur-containing hydrocarbon feedstock is 0.1-0.5:1, the weight hourly space velocity is 0.1-0.5h ^-1 The reaction pressure is 2.0-3.0MPa.

Preferably, in the method according to the fourth aspect of the present invention, the spent catalyst is subjected to stripping before the spent catalyst is subjected to the regeneration.

Preferably, the stripping operation conditions include: the bed temperature is 200-400 deg.C, the pressure is 0.1-0.2MPa, and the apparent gas velocity of stripping gas is 0.05-0.3m/s. .

The following apparatus, in conjunction with fig. 1 and 2, provides a preferred embodiment of the sulfur-containing hydrocarbon desulfurization process of the present invention:

the method comprises the following steps:

(2) Regenerating the spent catalyst;

the operation of introducing hydrogen and the sulfur-containing hydrocarbon feedstock into a sulfur-containing hydrocarbon desulfurization unit in contact with a catalyst comprises: introducing hydrogen and a sulfur-containing hydrocarbon raw material into a desulfurization reactor 1 to contact with a catalyst for desulfurization reaction, and introducing the obtained spent catalyst into a regeneration unit from a reactor receiver 2, a lock hopper 3, a regenerator feed tank 6 and a riser 7 in sequence; and

the operation of regenerating the spent catalyst comprises the following steps: the spent catalyst from the regenerator feed tank 6 is introduced into a first regenerator 9 and a second regenerator 8 in sequence for regeneration, and the regenerated catalyst obtained after regeneration is recycled to the sulfur-containing hydrocarbon desulfurization unit from a regenerator receiver 5, a lock hopper 3 and a reducer 4 in sequence.

Preferably, the method further comprises: in the desulfurization reactor 1, the material flow participating in the desulfurization reaction sequentially flows through a reactor reaction section 104, a reactor expanding section 105 and a reactor settling section 107, and at least part of the catalyst in the material flow participating in the desulfurization reaction returns to the reactor reaction section 104 for the desulfurization reaction after being blocked and/or collected by a member 106 in the reactor settling section 107.

Another more preferred embodiment of the sulfur-containing hydrocarbon desulfurization process of the present invention is provided below in conjunction with the apparatus shown in fig. 1, 2, and 3 to further illustrate the process of the fourth aspect of the present invention.

The method comprises the following steps:

(1) Introducing a catalyst into a reactor reaction section 104 in a desulfurization reactor 1 through a catalyst input pipe 102, allowing a mixture of sulfur-containing hydrocarbon oil and hydrogen to enter the reactor reaction section 104 from a material input pipe 101 of the desulfurization reactor 1, and contacting the mixture with the catalyst under desulfurization reaction conditions to perform desulfurization reaction, wherein part of catalyst particles in a material flow participating in the desulfurization reaction rise to a reactor settling section 107 along with reaction oil gas, and return to the reactor reaction section 104 for continuous desulfurization reaction through blocking and/or collection of a component 106, and the oil gas is separated by a filter and enters a subsequent separation system;

(2) The deactivated spent catalyst is conveyed to a lock hopper 3 from a reactor receiver 2 through a catalyst discharge pipe 103, the spent catalyst entering the lock hopper 3 is conveyed to a regenerator feed tank 6 after being depressurized to a low-pressure state, and the spent catalyst in the regenerator feed tank 6 is conveyed to a first regenerator 9 through a riser 7 after being stripped;

the spent catalyst entering the first regenerator 9 contacts with oxygen-containing feed gas entering the upper gas distributor 92 and the lower gas distributor 91 to generate a coking reaction, wherein a heat exchange medium entering a heat exchanger in the first regenerator 9 can automatically regulate and control whether the entering heat exchange medium is a high-temperature medium or a low-temperature medium according to the change of the coking temperature of the first regenerator 9, and the coked spent catalyst forms a primary regenerated catalyst and enters the second regenerator 8;

in the second regenerator 8, the primary regenerated catalyst contacts with the entering oxygen-containing feed gas to react to form a regenerated catalyst, then the regenerated catalyst is conveyed to the regenerator receiver 5, subjected to gas stripping in the regenerator receiver 5 and conveyed to the lock hopper 3, the regenerant entering the lock hopper 3 is pressurized to a high-pressure state and conveyed to the reducer 4, and then enters the desulfurization reactor 1 for recycling.

The present invention will be described in detail below by way of examples.

In the following examples, the raw materials are all commercially available unless otherwise specified;

in the following examples, the composition and related properties of the feed gasoline employed are shown in table 1;

in the following examples, the catalyst used was FCAS-R09, a catalyst produced by the medium petrochemical catalyst company, the composition of which is shown in Table 2, and some of the properties of which are shown in Table 3.

In the following examples, the parameters involved were tested by the following methods:

(1) The sulfur content is determined by an off-line chromatographic analysis method by adopting a GC6890-SCD instrument of Agelan company;

(2) Motor Octane Number (MON) and Research Octane Number (RON) of the raw gasoline before desulfurization reaction and the product gasoline after desulfurization reaction are respectively measured by GB/T503-1995 and GB/T5487-1995;

(3) Measuring the contents of zinc sulfate and zinc silicate by an XRD method;

(4) Calculating hydrogen consumption by measuring the change of hydrogen in and out of the reactor; the catalyst consumption is calculated by adopting a method of the ratio of fresh catalyst supplemented into the device in unit time to the processed amount of the raw material.

In the present invention, the reactor filter pressure drop increase means a difference between the reactor filter pressure drop and the pressure drop when the apparatus is not supplied with air, unless otherwise specified; the treatment capacity of the raw material gasoline is 142.5t/h.

TABLE 1

Make up of	Analyzing data	Properties of	Analyzing data
				Sulfur content/. Mu.g/g	410.6	Induction period/min	922
Mercaptan sulfur content/ng. (μ L) ^-1	10.2	Distillation range/. Degree.C	/
				Hydrogen sulfide content/ng. (μ L) ^-1	0	Initial boiling point/. Degree.C	38.5
Octane number (RON/MON)	92.4/80.2	10% by weight	55.5
				Group composition volume/%)	/	50% by weight	97.2
Saturated hydrocarbons	54.0	90% by weight	155.2
				Olefins	21.2	End point/. Degree.C	185.0
Aromatic hydrocarbons	24.8	Density (20 ℃ C.)/kg.m ^-3	735.6
						Actual gum/mg. (mL) ^-1	0.34
		Refractive index (20 ℃ C.)	1.4143

TABLE 2

Catalyst component	Content/weight%
		ZnO	50
ZnAl ₂ O ₄	18
		ZnSO ₄	0
Zn ₂ SiO ₄	0
		Alumina carrier	Balance of

TABLE 3

Properties of	Analyzing data
		Apparent density/kg/m ³	1000
Abrasion index/weight%	6
		Screening composition/weight%	/
0～40μm	16
		40～80μm	60
>80μm	24

Example 1

Desulfurization was carried out using the sulfur-containing hydrocarbon desulfurization apparatus shown in FIG. 1.

Wherein, in the sulfur-containing hydrocarbon desulfurization unit:

a desulfurization reactor: 3 components are arranged in the sedimentation section of the reactor, openings of the components are circular, the included angle between a baffle of a cone part of the components and the horizontal plane is 50 degrees, the components are provided with a surrounding baffle with the height of 200mm at the cone part, the ratio of the opening above the cone part of the components to the cross sectional area of the sedimentation section of the reactor is 0.2, and the sedimentation section of the reactor is provided with a cyclone separator;

a first regenerator: an upper gas distributor and a lower gas distributor are arranged in the regeneration section, the upper gas distributor is a tubular distributor, the branch pipe is provided with a nozzle with an opening facing downwards, the included angle a between the central line of the nozzle and the vertical line is 30 degrees, and the first regenerator is provided with a heat exchanger; the heat exchanger tube is provided with tube baffles, and the inclination angle of the tube baffles is 50 degrees.

The method for adsorbing and desulfurizing the sulfur-containing hydrocarbon in the embodiment specifically comprises the following steps:

(1) Introducing gasoline and hydrogen into a reactor reaction section in a desulfurization reactor to contact with a catalyst for desulfurization reaction, wherein the desulfurization reaction conditions comprise that: the reaction temperature is 410 ℃, the pressure is 2.8MPa, the molar ratio of hydrogen to gasoline is 0.3, and the reaction weight hourly space velocity is 4h ^-1 ；

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and lock hopper to a regenerator feed tank, the conditions of the regenerator feed tank comprising: taking nitrogen as fluidizing gas, wherein the inlet gas preheating temperature is 400 ℃, the bed layer temperature is 350 ℃, the pressure is 0.13MPa, and the apparent gas velocity of gas stripping is 0.2m/s;

(3) Introducing the spent catalyst from the regenerator feed tank into a first regenerator and a second regenerator in sequence for regeneration to obtain a regenerated catalyst;

wherein the operating conditions of the first regenerator include: the inlet gas of the upper gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 6 volume percent, the inlet gas of the lower gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 10 volume percent, the volume ratio of the inlet oxygen of the upper gas distributor to the inlet oxygen of the lower gas distributor is 0.8, the apparent gas velocity of the reactor is 0.25m/s, the bed temperature is 350 ℃, the pressure is 0.13MPa, and the heat exchanger of the first regenerator performs the heat extraction function;

the operating conditions of the second regenerator include: preheating 150 ℃ air with the oxygen content of 15 volume percent as regeneration gas, wherein the bed temperature is 520 ℃, the pressure is 0.13MPa, and the apparent gas velocity of the reactor is 0.28m/s;

(4) And recycling the regenerated catalyst obtained after regeneration to the desulfurization reactor for use through a regenerator receiver, a lock hopper and a reducer in sequence.

In order to maintain the activity of the catalyst, 250kg of fresh catalyst needs to be added into the desulfurization reactor every 5 days, so that the desulfurization reaction can be continuously operated. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

Example 2

Desulfurization was carried out using the same sulfur-containing hydrocarbon desulfurization apparatus as in example 1, except that:

in the sulfur-containing hydrocarbon desulfurization unit:

a desulfurization reactor: 3 components are arranged in the settling section of the reactor, openings of the components are square, the included angle between a baffle plate of a cone part of the components and the horizontal plane is 40 degrees, the components are provided with a surrounding baffle with the height of 100mm on the cone part, and the ratio of the opening above the cone part of the components to the cross sectional area of the settling section of the reactor is 0.1; the settling section of the reactor is provided with a cyclone separator;

a first regenerator: an upper gas distributor and a lower gas distributor are arranged in the regeneration section, the upper gas distributor is a tubular distributor, branch pipes are provided with nozzles with openings facing downwards, the included angle a between the central line of each nozzle and the vertical line is 10 degrees, and the first regenerator is provided with a heat exchanger; the heat exchanger tube is provided with tube baffles, and the inclination angle of the tube baffles is 50 degrees.

(1) Introducing gasoline and hydrogen into a reactor reaction section in a desulfurization reactor to contact with a catalyst for desulfurization reaction, wherein the desulfurization reaction conditions comprise: the reaction temperature is 350 ℃, the pressure is 2.0MPa, the molar ratio of hydrogen to gasoline is 0.1, and the reaction weight hourly space velocity is 2h ^-1 ；

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and the lock hopper to a regenerator feed tank under conditions comprising: taking nitrogen as fluidizing gas, wherein the inlet gas preheating temperature is 400 ℃, the bed layer temperature is 350 ℃, the pressure is 0.13MPa, and the apparent gas velocity of stripping gas is 0.2m/s;

wherein the regeneration conditions of the first regenerator include: the inlet air of the upper gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 8 volume percent, the inlet air of the lower gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 10 volume percent, and the volume ratio of the inlet oxygen of the upper gas distributor to the inlet oxygen of the lower gas distributor is 0.5; the apparent gas velocity of the reactor is 0.1m/s, the bed temperature is 310 ℃, the pressure is 0.13MPa, and the heat exchanger of the first regenerator performs the heat extraction function;

the regeneration conditions of the second regenerator include: preheating 150 ℃ air with 16 volume percent of oxygen content as regeneration gas, wherein the bed temperature is 500 ℃, the pressure is 0.13MPa, and the apparent gas velocity of the reactor is 0.3m/s;

(4) And circulating the regenerated catalyst obtained after regeneration to the desulfurization reactor for use through a regenerator receiver, a lock hopper and a reducer in sequence.

In order to maintain the activity of the catalyst, 375kg of fresh catalyst was added to the desulfurization reactor every 5 days so that the desulfurization reaction could be continuously performed. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

Example 3

in the sulfur-containing hydrocarbon desulfurization unit:

the inclination angle of the tube baffles on the heat exchanger tubes in the first regenerator is 70 degrees.

(1) Introducing gasoline and hydrogen into a reactor reaction section in a desulfurization reactor to contact with a catalyst for desulfurization reaction, wherein the desulfurization reaction conditions comprise: the reaction temperature is 440 ℃, the pressure is 3.0MPa, the molar ratio of hydrogen to gasoline is 0.9, and the reaction weight hourly space velocity is 10h ^-1 ；

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and lock hopper to a regenerator feed tank, the conditions of the regenerator feed tank comprising: taking nitrogen as fluidizing gas, wherein the inlet air preheating temperature is 300 ℃, the bed layer temperature is 260 ℃, the pressure is 0.13MPa, and the apparent gas velocity of stripping gas is 0.3m/s;

(3) Introducing the spent catalyst from a regenerator feed tank into a first regenerator and a second regenerator in sequence for regeneration to obtain a regenerated catalyst;

wherein the regeneration conditions of the first regenerator include: the inlet air of the upper gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 12 volume percent, the inlet air of the lower gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 12 volume percent, and the volume ratio of the inlet oxygen of the upper gas distributor to the inlet oxygen of the lower gas distributor is 1; the apparent gas velocity of the reactor is 0.2m/s, the temperature is 380 ℃, the pressure is 0.13MPa, and the heat exchanger of the first regenerator performs the heat extraction function;

the regeneration conditions of the second regenerator include: preheating 150 ℃ air with the oxygen content of 21 volume percent as regeneration gas, wherein the temperature is 490 ℃, the pressure is 0.5MPa, and the apparent gas velocity of the reactor is 0.4m/s;

In order to maintain the activity of the catalyst, 375kg of fresh catalyst is added to the desulfurization reactor every 5 days so that the desulfurization reaction can be continuously performed. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

Example 4

Desulfurization was carried out using the same sulfur-containing hydrocarbon desulfurization apparatus as in example 2, except that:

in the sulfur-containing hydrocarbon desulfurization unit:

a desulfurization reactor: the ratio of the upper opening of the conical part of the member to the cross-sectional area of the settling section of the reactor was 0.4;

a first regenerator: the included angle a between the central line of the nozzle and the vertical line is 50 degrees; the tube baffles on the heat exchanger tubes in the first regenerator were inclined at an angle of 45 °.

(1) Introducing gasoline and hydrogen into a reactor reaction section in a desulfurization reactor to contact with a catalyst for desulfurization reaction, wherein the desulfurization reaction conditions comprise: the reaction temperature is 410 ℃, the pressure is 2.8MPa, the molar ratio of hydrogen to gasoline is 0.3, and the reaction weight hourly space velocity is 5h ^-1 ；

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and lock hopper to a regenerator feed tank, the conditions of the regenerator feed tank comprising: taking nitrogen as fluidizing gas, wherein the inlet air preheating temperature is 300 ℃, the bed layer temperature is 300 ℃, the pressure is 0.13MPa, and the apparent gas velocity of gas stripping is 0.2m/s;

wherein the regeneration conditions of the first regenerator include: the inlet air of the upper gas distributor is a mixture of air and nitrogen preheated to 100 ℃, the oxygen content is 9 volume percent, the inlet air of the lower gas distributor is a mixture of air and nitrogen preheated to 100 ℃, the oxygen content is 12 volume percent, and the volume ratio of the inlet oxygen of the upper gas distributor to the inlet oxygen of the lower gas distributor is 1; the apparent gas velocity of the reactor is 0.3m/s, the temperature is 390 ℃, the pressure is 0.13MPa, and the heat exchanger of the first regenerator performs the heat extraction function;

the regeneration conditions of the second regenerator include: preheating 150 ℃ air with oxygen content of 16 volume percent as regeneration gas, wherein the temperature is 530 ℃, the pressure is 0.13MPa, and the apparent gas velocity is 0.28m/s;

In order to maintain the activity of the catalyst, 500kg of fresh catalyst was added to the desulfurization reactor every 5 days so that the desulfurization reaction could be continuously performed. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

Comparative example 1

the apparatus of this comparative example was provided with only one regenerator, which had the same configuration as the second regenerator in example 1; and no member was provided in the desulfurization reactor in this comparative example.

The method for the adsorptive desulfurization of sulfur-containing hydrocarbon in this comparative example is as follows:

(1) Introducing gasoline and hydrogen into a reactor reaction section in a desulfurization reactor to contact with a catalyst for desulfurization reaction, wherein the desulfurization reaction conditions comprise: the reaction temperature is 410 ℃, the pressure is 2.8MPa, the molar ratio of hydrogen to gasoline is 0.3, and the reaction weight hourly space velocity is 4h ^-1 ；

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and lock hopper to a regenerator feed tank, the conditions of the regenerator feed tank comprising: taking nitrogen as fluidizing gas, wherein the inlet air preheating temperature is 400 ℃, the bed layer temperature is 350 ℃, the pressure is 0.13MPa, and the apparent gas velocity of gas stripping is 0.05m/s;

(3) Introducing the spent catalyst from a regenerator feed tank into a regenerator for regeneration to obtain a regenerated catalyst;

the regeneration conditions of the regenerator include: preheating 150 ℃ air with oxygen content of 21 volume percent as regeneration gas, wherein the temperature is 520 ℃, the pressure is 0.13MPa, and the apparent gas velocity is 0.28m/s;

In order to maintain the activity of the catalyst, 870kg of fresh catalyst was added to the desulfurization reactor every 5 days so that the desulfurization reaction could be continuously performed. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

Comparative example 2

the configurations of the first regenerator and the second regenerator in the apparatus of this comparative example were the same as those of the second regenerator in example 1, that is, the feed gas in the first regenerator was introduced from only one place; and no member was provided in the desulfurization reactor in this comparative example.

(2) Introducing spent catalyst in the desulfurization reactor from the reactor receiver and lock hopper to a regenerator feed tank, the conditions of the regenerator feed tank comprising: taking nitrogen as fluidizing gas, wherein the inlet gas preheating temperature is 400 ℃, the bed layer temperature is 350 ℃, the pressure is 0.13MPa, and the apparent gas velocity of stripping gas is 0.2m/s;

wherein the operating conditions of the first regenerator include: the inlet gas of the gas distributor is a mixture of air and nitrogen preheated to 150 ℃, the oxygen content is 9 volume percent, the gas apparent gas velocity is 0.2m/s, the bed layer temperature is 350 ℃, the pressure is 0.13MPa, and the heat exchanger of the first regenerator performs the heat extraction function;

the operating conditions of the second regenerator include: preheating 150 ℃ air with the oxygen content of 15 volume percent as regeneration gas, wherein the bed temperature is 530 ℃, the pressure is 0.13MPa, and the gas apparent gas velocity is 0.28m/s;

In order to maintain the activity of the catalyst, 750kg of fresh catalyst needs to be added into the desulfurization reactor every 5 days, so that the desulfurization reaction can be continuously operated. The properties of the product gasoline, catalyst consumption, hydrogen consumption and regenerated catalyst composition results after 3 months of operation according to the above method are shown in table 4.

TABLE 4

From the results, the method and the device for desulfurizing the sulfur-containing hydrocarbon provided by the invention have the advantages that the generation amount of zinc silicate in the regenerant is obviously reduced, the catalyst consumption is obviously reduced, the actual hydrogen consumption is obviously reduced, the sulfur content of the product gasoline is obviously reduced, the octane number is obviously improved, and the pressure drop increase of a reactor filter is small.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method for regenerating a spent catalyst, the method comprising: introducing spent catalyst from a sulfur-containing hydrocarbon desulfurization unit into a regeneration unit comprising a first regeneration zone and a second regeneration zone for regeneration; the spent catalyst is firstly regenerated in the first regeneration zone and then enters the second regeneration zone for second regeneration, and the feeding gas enters the first regeneration zone in two ways of upstream and downstream according to the flow direction of the solid phase material flow in the first regeneration zone; the amount of the feed gas entering from upstream to the feed gas entering from downstream is such that the volume ratio of the oxygen input of the two is 0.5-1:1;

wherein the oxygen content of the feed gas in the first regeneration zone is controlled to be in the range of 6 to 12 volume percent and the oxygen content of the feed gas in the second regeneration zone is controlled to be in the range of 15 to 21 volume percent.

2. The method of claim 1, wherein the operating conditions in the first regeneration zone comprise: the bed temperature is 310-390 ℃, the pressure is 0.1-0.5MPa, and the apparent gas velocity is 0.05-0.3m/s.

3. The process of claim 1 or 2, wherein the operating conditions in the second regeneration zone comprise: the bed temperature is 490-530 deg.C, the pressure is 0.1-0.5MPa, and the apparent gas velocity is 0.2-0.4m/s.

4. A process according to claim 1 or 2, wherein a heat exchange unit capable of heat extraction and heating is provided in the first regeneration zone.

5. A method for desulfurizing a sulfur-containing hydrocarbon, the method comprising:

(2) Regenerating the spent catalyst;

wherein the regeneration operation in step (2) is carried out by the method according to any one of claims 1 to 4.

6. The method of claim 5, wherein the operating conditions of the desulfurization reaction comprise: the temperature is 350-440 ℃, the molar ratio of hydrogen to sulfur-containing hydrocarbon feedstock is 0.1-1:1, the weight hourly space velocity is 0.1 to 5h ^-1 The reaction pressure is 1.0-3.0MPa.

7. The process of claim 5 or 6, wherein the spent catalyst is stripped prior to the regeneration of the spent catalyst.

8. The process of claim 5 or 6, wherein the stripping operation conditions comprise: the bed temperature is 200-400 deg.C, the pressure is 0.1-0.2MPa, and the apparent gas velocity of stripping gas is 0.05-0.3m/s.

9. A sulfur-containing hydrocarbon desulfurization device is characterized in that the device comprises a sulfur-containing hydrocarbon desulfurization unit and a regeneration unit,

the sulfur-containing hydrocarbon desulfurization unit comprises a desulfurization reactor (1), a reactor receiver (2), a lock hopper (3) and a reducer (4), wherein the reactor receiver (2) and the reducer (4) are communicated through the lock hopper (3), and the reactor receiver (2) and the reducer (4) are respectively communicated with the upper part and the lower part of the desulfurization reactor (1);

the regeneration unit comprises a regenerator receiver (5), a regenerator feed tank (6), a second regenerator (8) and a first regenerator (9), the lock hopper (3) is communicated with the first regenerator (9) through the regenerator feed tank (6), and the first regenerator (9) is communicated with the regenerator receiver (5) through the second regenerator (8);

an upper gas distributor and a lower gas distributor are arranged in the regeneration section of the first regenerator (9).

10. The device according to claim 9, wherein the desulfurization reactor (1) comprises a reactor reaction section (104), a reactor settling section (107) and a reactor expanding section (105) connecting the reactor reaction section (104) and the reactor settling section (107), a member (106) with a funnel-shaped structure is further arranged in the reactor settling section (107), the top of the member (106) is open, the upper cross section of a cone part (111) is large, the lower cross section of the cone part is small, and a dipleg (112) is connected below the cone part (111).

11. The apparatus of claim 10, wherein the outlet of the dipleg (112) is arranged in a dense bed of the desulfurization reactor (1).

12. The device according to claim 10, wherein the baffles constituting the conical portion (111) of the member are at an angle of not less than 30 ° to the horizontal.

13. The device according to claim 12, wherein the baffles constituting the conical part (111) of the member are angled 40 ° -60 ° from the horizontal.

14. An apparatus according to any one of claims 10-13, wherein the number of said members is at least one, and the ratio of the cross-sectional area of the upper opening of the cone portion (111) of each of said members to the cross-sectional area of the reactor settling section (107) is 0.05-0.5:1.

15. the apparatus of claim 14, wherein the number of said members is at least one, and the ratio of the cross-sectional area of the upper opening of the cone portion (111) to the cross-sectional area of the reactor settling section (107) of each of said members is 0.1-0.3:1.

16. the apparatus according to any of claims 10-13, wherein the upper gas distributor provided in the regeneration section of the first regenerator (9) is a tube distributor consisting of main tubes and branch tubes.

17. The apparatus according to claim 16, wherein the branch pipe of the pipe distributor is provided with a gas nozzle, preferably the opening of the gas nozzle faces downwards.

18. The apparatus according to any of claims 10-13, wherein a heat exchanger capable of heat extraction and heating is further arranged in the first regenerator (9).

19. The apparatus of claim 18 wherein the heat exchanger passes axially through an upper gas distributor provided within the regeneration section of the first regenerator.

20. A process for the desulfurization of sulfur-containing hydrocarbons, which is carried out in an apparatus according to any one of claims 9 to 19, comprising:

(2) Regenerating the spent catalyst;

wherein the regeneration operation in step (2) is carried out by the method of any one of claims 1 to 5;

the operation of introducing hydrogen and the sulfur-containing hydrocarbon feedstock into a sulfur-containing hydrocarbon desulfurization unit in contact with a catalyst comprises: introducing hydrogen and a sulfur-containing hydrocarbon raw material into a desulfurization reactor (1) to contact with a catalyst to perform desulfurization reaction, and introducing the obtained spent catalyst into a regeneration unit from a reactor receiver (2), a lock hopper (3) and a regenerator feed tank (6) in sequence; and

the operation of regenerating the spent catalyst comprises the following steps: and (2) introducing the spent catalyst from the regenerator feed tank (6) into a first regenerator (9) and a second regenerator (8) in sequence for regeneration, and then circulating the regenerated catalyst obtained after regeneration back to the sulfur-containing hydrocarbon desulfurization unit through a regenerator receiver (5), a lock hopper (3) and a reducer (4) in sequence.

21. The method of claim 20, wherein the method further comprises: in the desulfurization reactor (1), the stream participating in the desulfurization reaction sequentially flows through a reactor reaction section (104), a reactor expanding section (105) and a reactor settling section (107), and at least part of the catalyst in the stream participating in the desulfurization reaction returns to the reactor reaction section (104) for the desulfurization reaction after being blocked and/or collected by a member (106) in the reactor settling section (107).