阅读说明：本技术 一种催化汽油加氢深度脱硫的方法 (Method for deep desulfurization of catalytic gasoline by hydrogenation ) 是由 陶春风 滕明才 瞿滨 刘海星 杨先庆 于 2021-01-29 设计创作，主要内容包括：本发明公开了一种催化汽油加氢深度脱硫的方法,包括以下步骤：S1、将原料经过过滤后送入缓冲罐中,经过原料气体压缩机升压后送入预热炉并与氢气预混合构成混合气体进行预热到280℃,然后与脱硫后的输出气体进行换热并降温至245℃；S2、将加氢反应器内的床温控制在320℃,然后将步骤S1的混合气体送入加氢反应器内,先添加加氢催化剂,在加氢催化剂的作用下,发生烯烃饱和反应,同时发生有机硫化转换反应和有机氯的转化反应,使得有机硫化转化为无极硫,有机氯转化为无机氯被脱出；S3、然后在进入氧化锌脱硫反应器中,氧化锌与硫化氢发生脱硫反应,脱除原气体中的硫,从而得到硫含量低于1ppm的精制油。本发明提高脱氮效果。(The invention discloses a catalytic gasoline hydrogenation deep desulfurization method, which comprises the following steps: s1, filtering the raw materials, sending the filtered raw materials into a buffer tank, boosting the pressure of the raw materials by a raw material gas compressor, sending the raw materials into a preheating furnace, premixing the raw materials with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas and cooling the mixed gas to 245 ℃; s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed; s3, then, in a zinc oxide desulfurization reactor, performing desulfurization reaction on zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content lower than 1 ppm. The invention improves the denitrification effect.)

1. The catalytic gasoline hydrogenation deep desulfurization method is characterized by comprising the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, allowing the oil to enter a zinc oxide desulfurization reactor, and performing desulfurization reaction on zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, so as to obtain refined oil with the sulfur content of less than 1 ppm;

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, where the shaped carrier includes one or more of alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, graphene and zeolite, and the active metal element mixture is formed by mixing one or more of a group VIII metal element, a group iv metal complex containing a phenoxyimine ligand, and a catalytic slurry oil.

2. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 1, wherein the active metal element mixture comprises the following raw materials in parts by weight: 2-10 parts of VIII group metal element, 1-5 parts of IV group metal complex containing phenoxyl imine ligand and 15-20 parts of catalytic slurry oil.

3. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 2, characterized in that the shape of the molded carrier is that more than one through hole (2) is arranged inside the sphere (1), more than one extension part (3) is annularly distributed outside the sphere (1), more than one branch part (4) is arranged on the extension part (3), and the sphere (1), the extension part (3) and the branch part (4) form a snowflake shape.

4. The method for deep desulfurization by hydrogenation of gasoline according to claim 3, characterized in that the active metal element mixture is filled in the through holes (2).

5. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 1, wherein the operation regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h ^-1 -5.0h ^-1 。

6. The method for deep desulfurization by hydrogenation of gasoline according to claim 1, wherein in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98 g/m.

7. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 1, wherein the molded carrier uses graphene as a main raw material, and the graphene and other raw materials are mixed in parts as follows: 25-30 parts of graphene, 3-5 parts of aluminum oxide, 3-5 parts of silicon oxide, 3-5 parts of magnesium oxide, 3-5 parts of titanium oxide, 3-5 parts of zirconium oxide and 3-5 parts of amorphous silica-alumina.

8. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 7, wherein the molded carrier uses graphene as a main raw material, and the graphene and other raw materials are mixed in parts as follows: 26 parts of graphene, 4 parts of aluminum oxide, 4 parts of silicon oxide, 4 parts of magnesium oxide, 4 parts of titanium oxide, 4 parts of zirconium oxide and 4 parts of amorphous silica-alumina.

9. The method for deep desulfurization by hydrogenation of catalytic gasoline according to claim 7, characterized in that the processing steps of the shaped carrier are as follows: respectively crushing the graphene, the alumina, the silicon oxide, the magnesium oxide, the titanium oxide, the zirconium oxide and the amorphous silica-alumina, mixing and extruding for molding.

Technical Field

The invention relates to the technical field of desulfurization, in particular to a catalytic gasoline hydrogenation deep desulfurization method.

Background

With the rapid development of catalytic cracking heavy oil lightening in China, the catalytic light aromatic hydrocarbon is increased, and with the heavy and high-sulfuration of the raw material, the sulfur and olefin content of the catalytic light aromatic hydrocarbon is increased. Hydrofining is one of core technologies for processing sulfur-containing raw materials and producing clean energy, and through decades of research, development and industrial practice, the hydrofining technology in China is close to the advanced level in the world on the whole, occupies higher market share in China, and makes an important contribution to the development of the petrochemical industry. With the upgrading of market products, the national environmental protection requirements and standards are becoming stricter, and the severe requirements of catalysts and adsorbents in the deep processing procedure of light aromatic hydrocarbons on the contents of sulfur, nitrogen, oxygen and heavy metals are met, so that the hydrofining of the light aromatic hydrocarbons is performed to improve the quality and improve the stability.

However, in the existing hydrodesulfurization system, due to the problem of the catalyst, the later desulfurization effect is poor, the effective production period of the hydrodesulfurization system is increased, the processing capacity of the hydrodesulfurization system is also reduced, and the quality of the final aromatic hydrocarbon is affected, so that improvement is needed.

Disclosure of Invention

The invention aims to provide a catalytic gasoline hydrogenation deep desulfurization method, which aims to solve the problems that the desulfurization effect is poor, the effective production period of a hydrodesulfurization system is prolonged, and the processing capacity of the hydrodesulfurization system is reduced in the prior art.

In order to achieve the purpose, the invention provides the following technical scheme: a method for deep desulfurization of catalytic gasoline by hydrogenation comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, and then, in a zinc oxide desulfurization reactor, performing desulfurization reaction between zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content of less than 1 ppm.

Further, in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, the shaped carrier includes one or more of alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, graphene and zeolite, the active metal element mixture is composed of one or more of a group VIII metal element, a group iv metal complex containing a phenoxyimine ligand and a mixture of the group VIII metal element and the group iv metal complex containing the phenoxyimine ligand and the catalytic slurry oil;

the active metal element mixture comprises the following raw materials in parts by weight: 2-10 parts of VIII group metal element, 1-5 parts of IV group metal complex containing phenoxyl imine ligand and 15-20 parts of catalytic slurry oil.

Further, the shape of the molding carrier is a sphere, more than one through hole is arranged in the sphere, more than one extending part is annularly distributed outside the sphere, more than one branch part is arranged on the extending part, and the sphere, the extending part and the branch part form a snowflake shape.

Further, the active metal element mixture is filled into the through hole.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h < -1 > -5.0h < -1 >.

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 25-30 parts of graphene, 3-5 parts of aluminum oxide, 3-5 parts of silicon oxide, 3-5 parts of magnesium oxide, 3-5 parts of titanium oxide, 3-5 parts of zirconium oxide and 3-5 parts of amorphous silica-alumina.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 26 parts of graphene, 4 parts of aluminum oxide, 4 parts of silicon oxide, 4 parts of magnesium oxide, 4 parts of titanium oxide, 4 parts of zirconium oxide and 4 parts of amorphous silica-alumina.

Further, the processing steps of the molded carrier are as follows: respectively crushing the graphene, the alumina, the silicon oxide, the magnesium oxide, the titanium oxide, the zirconium oxide and the amorphous silica-alumina, mixing and extruding for molding.

The invention has the beneficial effects that: 1. the invention solves the problems that the original catalyst has high requirement on the initial reaction temperature and the desulfurization effect is poor due to low catalyst activity is compensated by increasing the operation temperature when the catalyst activity is reduced in the later period, and develops and produces the hydrogenation catalyst suitable for the raw material of the device through the technology, and the outstanding performance point of the hydrogenation catalyst is mainly to further reduce the activation energy of the reaction and can adapt to higher operation temperature in the later period, thereby breaking through the original operation bottleneck, prolonging the service life of the catalyst and improving the quality of aromatic hydrocarbon; 2. meanwhile, the feeding temperature is reduced from original 280 ℃ to 245 ℃, the initial reaction temperature is reduced from original 350 ℃ to 320 ℃, so that the safety is higher, 3, experiments prove that the catalyst has high activity and durability, the consumption and replacement frequency of the catalyst are reduced, and the operation period is prolonged; 4. the catalyst is high temperature resistant, and the temperature raising space for later activity reduction is large.

Drawings

FIG. 1 is a schematic cross-sectional view of the catalyst in the method for deep desulfurization by hydrogenation of gasoline in this example 3.

In the figure: a sphere 1; a through hole 2; an extension 3; a branch portion 4.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

Example 1:

the embodiment discloses a method for deep desulfurization of catalytic gasoline by hydrogenation, which comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, then the refined oil enters a zinc oxide desulfurization reactor to carry out desulfurization reaction between zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content lower than 1ppm,

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, where the shaped carrier includes one or more of alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, graphene and zeolite, and the active metal element mixture is formed by mixing one or more of a group VIII metal element, a group iv metal complex containing a phenoxyimine ligand, and a catalytic slurry oil.

Further, the active metal element mixture comprises the following raw materials in parts by weight: 2-10 parts of VIII group metal element, 1-5 parts of IV group metal complex containing phenoxyl imine ligand and 15-20 parts of catalytic slurry oil.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h^-1 -5.0h ^-1 。

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 25-30 parts of graphene, 3-5 parts of aluminum oxide, 3-5 parts of silicon oxide, 3-5 parts of magnesium oxide, 3-5 parts of titanium oxide, 3-5 parts of zirconium oxide and 3-5 parts of amorphous silica-alumina.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 26 parts of graphene, 4 parts of aluminum oxide, 4 parts of silicon oxide, 4 parts of magnesium oxide, 4 parts of titanium oxide, 4 parts of zirconium oxide and 4 parts of amorphous silica-alumina.

Further, the processing steps of the molded carrier are as follows: respectively crushing the graphene, the alumina, the silicon oxide, the magnesium oxide, the titanium oxide, the zirconium oxide and the amorphous silica-alumina, mixing and extruding for molding.

According to the invention, a novel hydrogenation catalyst suitable for the device is developed on the basis of the existing device through technology, and meanwhile, a method for improving the structure is adopted, the oil generated by cracking the hydrogenation feed is mixed with hydrogen, the mixture and the output discharge gas are subjected to heat exchange to 245 ℃, the mixture enters a hydrogenation reactor with the bed temperature of 320 ℃ and is subjected to a series of olefin saturation and desulfurization reactions under the action of the catalyst, the denitrification efficiency is finally improved, and the refined oil with the sulfur content lower than 1ppm is finally obtained.

Therefore, the invention has the following technical advantages:

1. the invention solves the problems that the original catalyst has high requirement on the initial reaction temperature and the desulfurization effect is poor due to low catalyst activity is compensated by increasing the operation temperature when the catalyst activity is reduced in the later period, and develops and produces the hydrogenation catalyst suitable for the raw material of the device through the technology, and the outstanding performance point of the hydrogenation catalyst is mainly to further reduce the activation energy of the reaction and can adapt to higher operation temperature in the later period, thereby breaking through the original operation bottleneck, prolonging the service life of the catalyst and improving the quality of aromatic hydrocarbon; 2. meanwhile, the feeding temperature is reduced from original 280 ℃ to 245 ℃, the initial reaction temperature is reduced from original 350 ℃ to 320 ℃, so that the safety is higher, 3, experiments prove that the catalyst has high activity and durability, the consumption and replacement frequency of the catalyst are reduced, and the operation period is prolonged; 4. the catalyst is high temperature resistant, and the temperature raising space for later activity reduction is large.

Example 2:

the embodiment discloses a method for deep desulfurization of catalytic gasoline by hydrogenation, which comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, then the refined oil enters a zinc oxide desulfurization reactor to carry out desulfurization reaction between zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content lower than 1ppm,

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, where the shaped carrier includes alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, and graphene, and the active metal element mixture is formed by mixing one or more elements of a group VIII metal element and a group iv metal complex containing a phenoxyimine ligand with the catalytic slurry oil.

Further, the active metal element mixture comprises the following raw materials in parts by weight: 5 parts of VIII group metal element, 1 part of IV group metal complex containing phenoxyimine ligand and 15 parts of catalytic slurry oil.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h ^-1 -5.0h ^-1 。

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Example 3:

the embodiment discloses a method for deep desulfurization of catalytic gasoline by hydrogenation, which comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, then the refined oil enters a zinc oxide desulfurization reactor to carry out desulfurization reaction between zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content lower than 1ppm,

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, the shaped carrier includes alumina, silica, and magnesia, and the active metal element mixture is formed by mixing one or more elements of a VIII group metal element, a iv group metal complex containing a phenoxyimine ligand, and a catalytic slurry oil.

Further, the active metal element mixture comprises the following raw materials in parts by weight: 6 parts of VIII group metal element, 2 parts of IV group metal complex containing phenoxyimine ligand and 16 parts of catalytic slurry oil.

Referring to fig. 1, the shaped carrier is a sphere 1, more than one through hole 2 is arranged inside the sphere 1, more than one extension part 3 is annularly distributed outside the sphere 1, more than one branch part 4 is arranged on the extension part 3, and the sphere 1, the extension part 3 and the branch part 4 form a snowflake shape.

Further, the active metal element mixture is filled into the through-hole 2.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h^-1 -5.0h ^-1 。

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Example 4:

the embodiment discloses a method for deep desulfurization of catalytic gasoline by hydrogenation, which comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, then the refined oil enters a zinc oxide desulfurization reactor to carry out desulfurization reaction between zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, thereby obtaining refined oil with the sulfur content lower than 1ppm,

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, where the shaped carrier includes one or more of alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, graphene and zeolite, and the active metal element mixture is formed by mixing one or more of a group VIII metal element, a group iv metal complex containing a phenoxyimine ligand, and a catalytic slurry oil.

Further, the active metal element mixture comprises the following raw materials in parts by weight: 8 parts of VIII group metal element, 3 parts of IV group metal complex containing phenoxyimine ligand and 16 parts of catalytic slurry oil.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h^-1 -5.0h ^-1 。

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 25 parts of graphene, 3 parts of aluminum oxide, 3 parts of silicon oxide, 3 parts of magnesium oxide, 3 parts of titanium oxide, 3 parts of zirconium oxide and 3 parts of amorphous silica-alumina.

Further, the processing steps of the molded carrier are as follows: respectively crushing the graphene, the alumina, the silicon oxide, the magnesium oxide, the titanium oxide, the zirconium oxide and the amorphous silica-alumina, mixing and extruding for molding.

Example 5:

the embodiment discloses a method for deep desulfurization of catalytic gasoline by hydrogenation, which comprises the following steps:

s1, filtering the raw material, sending the filtered raw material into a buffer tank, boosting the pressure of the raw material gas by a raw material gas compressor, sending the raw material gas into a preheating furnace, premixing the raw material gas with hydrogen to form mixed gas, preheating the mixed gas to 280 ℃, then exchanging heat with the desulfurized output gas, cooling the mixed gas to 245 ℃, and entering the next step;

s2, controlling the bed temperature in the hydrogenation reactor at 320 ℃, then sending the mixed gas obtained in the step S1 into the hydrogenation reactor, adding a hydrogenation catalyst, generating olefin saturation reaction under the action of the hydrogenation catalyst, and simultaneously generating organic vulcanization conversion reaction and organic chlorine conversion reaction, so that organic vulcanization is converted into electrodeless sulfur, and the organic chlorine is converted into inorganic chlorine and is removed;

s3, allowing the oil to enter a zinc oxide desulfurization reactor, and performing desulfurization reaction on zinc oxide and hydrogen sulfide to remove sulfur in the raw gas, so as to obtain refined oil with the sulfur content of less than 1 ppm;

in step S2, the hydrogenation catalyst includes a shaped carrier and an active metal element mixture filled on the shaped carrier, where the shaped carrier includes one or more of alumina, silica, magnesia, titania, zirconia, amorphous silica-alumina, graphene and zeolite, and the active metal element mixture is formed by mixing one or more of a group VIII metal element, a group iv metal complex containing a phenoxyimine ligand, and a catalytic slurry oil.

Further, the active metal element mixture comprises the following raw materials in parts by weight: 10 parts of VIII group metal element, 5 parts of IV group metal complex containing phenoxyimine ligand and 20 parts of catalytic slurry oil.

Further, the operating regulation requirement of the hydrogenation reactor in step S2 is: the reaction temperature is 320 ℃, and the volume space velocity is 2.0h^-1 -5.0h ^-1 。

Further, in step S2, the specific surface area of the hydrogenation catalyst is not less than 180 square meters per gram, the pore volume of the hydrogenation catalyst is not less than 0.29ml/g, the crushing strength of the hydrogenation catalyst is not less than 150N/cm, and the stacking density of the hydrogenation catalyst is 0.88-0.98g/m for carrying out the cultivation.

Further, the molding carrier takes graphene as a main raw material, and the parts of the graphene and other raw materials are as follows: 30 parts of graphene, 5 parts of aluminum oxide, 5 parts of silicon oxide, 5 parts of magnesium oxide, 5 parts of titanium oxide, 5 parts of zirconium oxide and 5 parts of amorphous silica-alumina.

Further, the processing steps of the molded carrier are as follows: respectively crushing the graphene, the alumina, the silicon oxide, the magnesium oxide, the titanium oxide, the zirconium oxide and the amorphous silica-alumina, mixing and extruding for molding.

Experimental data:

serial number	High temperature resistance detection of catalyst
		Example 1	Does not deform at the high temperature of 400 ℃ for half an hour
Example 2	Does not deform at the high temperature of 430 ℃ for half an hour
		Example 3	Does not deform at 450 ℃ for one hour
Example 4	Does not deform at the high temperature of 500 ℃ for one hour
		Example 5	Does not deform at the high temperature of 600 ℃ for one hour

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.