CN114752405B

CN114752405B - Heavy naphtha desulfurizer with high space velocity and high activity and preparation method thereof

Info

Publication number: CN114752405B
Application number: CN202210219398.2A
Authority: CN
Inventors: 李选志; 曹晓玲; 潘喜强; 王瑞
Original assignee: Xi'an Origin Chemical Technologies Co ltd
Current assignee: Xi'an Origin Chemical Technologies Co ltd
Priority date: 2022-03-08
Filing date: 2022-03-08
Publication date: 2022-11-01
Anticipated expiration: 2042-03-08
Also published as: CN114752405A

Abstract

The invention discloses a heavy naphtha desulfurizer with high airspeed and high activity and a preparation method thereof, wherein the desulfurizer comprises the following components: 30-50% of activated alumina, 5-20% of molecular sieve, 20-40% of first active metal element, 10-30% of second active metal element and 1-5% of auxiliary agent; the method comprises the following steps: 1. uniformly mixing an oxide containing active metal elements and a carrier raw material to obtain dry powder; 2. drying the powder to prepare pellets to obtain a desulfurizer A; 3. soaking the mixed salt solution containing the active metal elements in the desulfurizer A in the same volume to obtain a desulfurizer B; 4. activating; 5. and (5) surface oxidation treatment. The invention designs the carrier, the active substance and the auxiliary agent, and improves the adsorption capacity and the sulfur capacity of the desulfurizer; the invention enhances the activation degree, improves the processing capacity and the desulfurization precision of the desulfurizer and meets the requirements of storage, transportation and production of the desulfurizer by controlling the adding form of the active components step by step and combining the activation and the surface oxidation treatment.

Description

Heavy naphtha desulfurizer with high space velocity and high activity and preparation method thereof

Technical Field

The invention belongs to the field of petrochemical engineering catalytic purificant, and particularly relates to a heavy naphtha desulfurizer with high space velocity and high activity and a preparation method thereof.

Background

Naphtha is a product of primary or secondary processing of crude oil or other oil products in refining enterprises, and is the most important raw material for producing high-octane gasoline, aromatic hydrocarbon and hydrogen through catalytic reforming or isomerization due to high potential content of aromatic hydrocarbon and low content of nitrogen and sulfur in naphtha. Especially in recent years, domestic demands for clean gasoline, benzene, toluene, xylene and other chemical raw materials are vigorous, and naphtha processing devices are promoted to be larger and larger, so that the demand for naphtha raw materials is continuously increased, and the contradiction between supply and demand is increasingly prominent. In order to solve the problem of shortage of raw materials, the refining enterprises carry out hydrocracking and catalytic cracking treatment on heavy diesel oil, wax oil or mixed diesel wax oil, and the obtained heavy naphtha is used as the raw material. However, the raw material used for hydrocracking or catalytic cracking has complex sources, various forms of sulfur and high content, so that the sulfur content in heavy naphtha obtained after hydrocracking or catalytic cracking is seriously exceeded, and the olefin can react with hydrogen sulfide to generate organic sulfur such as mercaptan or thioether due to the existence of a small amount of olefin in the heavy naphtha. Analysis has determined that naphtha generally has a total sulfur content of about 5 μ g^-1In which H₂The S content is about 3. Mu.g.g^-1The content of organic sulfur such as mercaptan and thioether is about 2 μ g^-1To achieveTo over 40% of the total sulfur. The presence of these sulfur can be a serious hazard to the processing of heavy naphtha. The literature data show that when heavy naphtha is used as the feedstock for catalytic reforming or isomerization, the sulfur content in the oil is 1 mug g^-1When the activity of the reforming catalyst is affected, the liquid yield and hydrogen yield of C5 or more are lowered, and when the sulfur content in the oil is 1.5. Mu.g.g^-1During the process, the activity of the reforming catalyst is reduced by about 20%, the service cycle of the catalyst is shortened, and the sulfur content in the liquid product exceeds the standard. At present, it is widely accepted by researchers and industry that only heavy naphthas have a total sulfur content of less than 0.5 μ g^-1The requirements of the catalytic reforming or isomerization unit for the feedstock are met, and the sulfur in the heavy naphtha must be removed.

The fixed bed dry desulfurization technology is also applied to the naphtha desulfurization process due to the advantages of simple flow, convenient application and the like. In the 'application of heavy naphtha desulfurization technology', such as strong light irradiation and the like, znO desulfurizer is adopted to remove sulfide in heavy naphtha, the ZnO desulfurizer is suitable for use at a high temperature of more than 250 ℃, and when the ZnO desulfurizer is used under the condition of naphtha desulfurization process at a temperature of between 130 and 180 ℃, the sulfur capacity is low, and the service cycle of the desulfurizer is short.

Chinese patent CN110791308A discloses a normal temperature liquid hydrocarbon desulfurizer, in order to increase the sulfur capacity of ZnO at low temperature, cuO is added in the desulfurizer. The preparation method comprises the following steps: firstly, mixing a copper salt solution and a zinc salt solution, then neutralizing and precipitating with an alkali solution to obtain a copper-zinc composite precipitate, then neutralizing and precipitating an aluminum salt with the alkali solution to obtain an alumina gel carrier, mixing the copper-zinc composite precipitate with the alumina gel carrier, then washing, drying and grinding to obtain powder, adding metal copper or nickel powder and a binder into the powder, mixing, kneading and molding to obtain the desulfurizer. The desulfurizer adopts a two-step neutralization coprecipitation method to prepare an active component and a carrier respectively, the preparation process is complex, and the operation difficulty is increased; and the sediment needs a large amount of clear water for washing, which causes waste of water resources. In the desulfurizer, metal powder of copper or nickel is used for removing mercaptan and elemental sulfur, and the capability of removing organic sulfur is very limited due to stable properties of metal simple substances at low temperature.

The above solid desulfurizing agents all use ZnO as an active material, but since heavy naphtha usually contains Cl^-And Cl^-And Zn²⁺Reaction to form ZnCl with low volatility₂And the ZnO-containing desulfurizer is transferred to the downstream along with the oil product to cause catalyst poisoning or pipeline blockage in the later working section, and the damage occurs in the industry, so that huge economic loss is caused to enterprises, and the ZnO-containing desulfurizer is rarely used in the naphtha desulfurization process.

The Wangjian et al introduces the experiment of removing hydrogen sulfide in naphtha by iron oxide desulfurizer in "evaluation of using effect of naphtha desulfurizer", and the result shows that the iron oxide desulfurizer can only remove the hydrogen sulfide in naphtha to 5 mug. G^-1On the left and right sides, the desulfurization precision can not meet the requirement, and the desulfurizer is easy to harden and argillize when meeting water, which affects the service life.

Chinese patent 104923158A discloses a process for preparing desulfurizer for oil products, which is prepared by mixing activated carbon modified by hydrochloric acid with zinc, iron and manganese composite oxides, and is mainly used for removing sulfides in gasoline and diesel oil. However, in the preparation process of the desulfurizer, a large amount of water is needed for washing after the active carbon is modified by strong acid, which causes waste of water resources and environmental pollution. The active carbon desulfurization mainly takes physical adsorption as a main part, the optimal use temperature is required to be not higher than 50 ℃, and meanwhile, oxygen is beneficial to active carbon desulfurization, so that when the active carbon desulfurization agent is used, a certain amount of oxygen is required to be contained in raw materials, and the use range of the active carbon desulfurization agent is limited. When the active carbon desulfurizer of the patent is used for gasoline and diesel oil desulfurization, the content of the active carbon desulfurizer in oil products can be 150 mug^-1To a total sulfur removal of 10. Mu.g.g^-1Hereinafter, the desulfurization accuracy is low, the sulfur capacity is low, and it is not suitable for use at a temperature of 130 ℃ or higher.

At present, metal oxides are mostly used as active components in industrial solid desulfurizing agents, the metal oxides have good removing effect on hydrogen sulfide, but have poor removing capability on organic sulfur such as mercaptan, thioether and the like, and when the metal oxides are applied to the desulfurization process of heavy naphtha, the total sulfur content in the purified heavy naphtha is over standard, so that subsequent catalyst poisoning and product quality reduction are caused, and the normal operation of production is influenced.

In addition, with the continuous enlargement of the demand of the heavy naphtha, the annual desulfurization purification treatment capacity of the heavy naphtha is also continuously improved, and the device is used for high-load production.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a heavy naphtha desulfurizer with high space velocity and high activity aiming at the defects of the prior art. The desulfurizer adopts a carrier formed by coupling activated alumina and a molecular sieve, improves the adsorption effect on sulfides, and forms more surface lattice defect ions in the activation process by combining the synergistic effect of an active substance and an auxiliary agent which are formed by compounding a first active metal element and a second active metal element, thereby promoting the combination of metal ions and sulfides, improving the desulfurization precision and the sulfur capacity, and prolonging the service life of the desulfurizer.

In order to solve the technical problems, the invention adopts the technical scheme that: the heavy naphtha desulfurizer with high space velocity and high activity is characterized by comprising the following components in percentage by mass: 30-50% of activated alumina, 5-20% of molecular sieve, 20-40% of first active metal element, 10-30% of second active metal element and 1-5% of auxiliary agent; the desulfurizing agent is activated and then has a liquid air speed of up to 16h^-1In the process, hydrogen sulfide, mercaptans and sulfides in the heavy naphtha are removed to not more than 0.1ppmwt.

The heavy naphtha desulfurizer carrier is formed by coupling activated alumina and a molecular sieve, exerts the advantages of high specific surface area of alumina, large aperture, uniform pore channels of the molecular sieve and orderly arranged pore structures, thereby having strong adsorption effect on polar molecules such as hydrogen sulfide, mercaptan, thioether and the like, and enhances the rapid diffusion and adsorption capacity of sulfides in the heavy naphtha in the desulfurizer pore channels.

The active substance of the heavy naphtha desulfurizer is compounded by a first active metal element and a second active metal element, under the synergistic action of an auxiliary agent, sulfides in the heavy naphtha react with the compounded metal element ions to generate metal sulfides, and the metal sulfides are adsorbed and deposited in a pore channel of the desulfurizer to be removed, wherein the first active metal element is a main body of the desulfurizer and plays an important role in improving the sulfur capacity of the desulfurizer and enhancing the adaptability to oil products and process conditions, the second active metal element is not only an active substance of the desulfurizer but also a structure enhancing substance of the desulfurizer, and after being added, the second active metal element and the first active metal element form more surface lattice defect ions in the activation process, so that the combination of the metal ions and the sulfides is promoted, and the desulfurization precision is improved; meanwhile, the addition of the second active metal element also reduces the activation temperature of the desulfurizer, shortens the activation time, improves the activation degree, increases the strength of the desulfurizer, improves the thermodynamic stability of the desulfurizer, prevents coking, delays the reduction trend of the surface area of the desulfurizer, and further prolongs the service life of the desulfurizer.

The heavy naphtha desulfurizer of the invention is also added with an additive which is usually an alkali metal additive, the alkali metal additive is utilized to play a role in conditioning the desulfurizer, meanwhile, the alkaline constitution of the desulfurizer improves the rapid adsorption reaction capability of weakly acidic sulfides such as hydrogen sulfide and mercaptan on the surface of the desulfurizer, shortens the reaction time of the sulfides and metal active elements, improves the reaction airspeed of the desulfurizer, and prevents active components from losing due to the generation of sulfate by active substances caused by the acidification of the surface of the desulfurizer.

The heavy naphtha desulfurizer of the invention can exert high activity performance at large space velocity after activation treatment, metal active oxides in the desulfurizer form zero-valent lattice defect metal ions in an activated state in the activation process, the desulfurization reaction activation energy of the metal ions is low, the reaction induction period is short, the desulfurization reaction is rapid, and especially, the heavy naphtha desulfurizer has stronger removal capability on organic sulfur such as mercaptan, thioether and the like, so that when the heavy naphtha treatment capacity is increased (the space velocity is increased), sulfides in oil can be adsorbed and removed when the retention time of the sulfides in the desulfurizer on the surface is shortened, and higher desulfurization precision is kept. The desulfurization reaction mechanism of the desulfurizing agent is shown as follows:

the mechanism of activation of the desulfurizing agent is: MO + H₂→M⁰+H₂O

Desulfurization mechanism of the desulfurizing agent:

M⁰+H₂S→MS+H₂

M⁰+RSR`+H₂→MS+RH+R`H

M⁰+RSH→MS+RH

in the formula: MO represents a metal oxide;

M⁰represents a metal ion in an activated state after activation;

MS represents a metal sulfide;

RSR' represents a thioether;

RSH represents a thiol;

RH and R' H represent alkane.

In addition, the activated desulfurizing agent and the sulfide do not have H during the reaction₂O is generated, H is avoided₂O pollutes the heavy naphtha, and is more beneficial to purifying the heavy naphtha.

The heavy naphtha desulfurizer with high space velocity and high activity is characterized in that an aluminum source of the active alumina is pseudo-boehmite or/and aluminum hydroxide. The pseudo-boehmite or the aluminum hydroxide can form the gamma-Al with high specific surface and large aperture through high-temperature decomposition₂O₃The method is favorable for the diffusion of the liquid phase heavy naphtha raw material and realizes better desulfurization effect.

The heavy naphtha desulfurizer with high space velocity and high activity is characterized in that the molecular sieve is one or two of 5A, 13X and mordenite. The optimized molecular sieve has uniform pore channels and regular pore structure arrangement, has extremely strong adsorption effect on polar molecules such as hydrogen sulfide, mercaptan, thioether and the like, and enhances the adsorption and diffusion capacity of sulfide on the desulfurizer.

The heavy naphtha desulfurizer with the large space velocity and the high activity is characterized in that the first active metal element is copper or/and nickel.

The heavy naphtha desulfurizer with high space velocity and high activity is characterized in that the second active metal element comprises one or two of cerium, lanthanum and cobalt.

The heavy naphtha desulfurizer with high space velocity and high activity is characterized in that the assistant is alkali metal oxide K₂O or/and Na₂And (O). The alkali metal oxide is selected as the regulating assistant, so that the alkalinity of the desulfurizer is enhanced, the rapid adsorption reaction capability of weakly acidic sulfides such as hydrogen sulfide and mercaptan on the surface of the desulfurizer is improved, and the activity loss caused by sulfate generated by the surface acidification of the desulfurizer is effectively prevented.

In addition, the invention also discloses a method for preparing the large space velocity high activity heavy naphtha desulfurizer, which comprises the following steps:

selecting an oxide and a salt containing a first active metal element as a raw material of the first active metal element, selecting an oxide and a salt containing a second active metal element as a raw material of the second active metal element, fully and uniformly mixing the oxide containing the first active metal element, the oxide containing the second active metal element, an aluminum source of active alumina and a molecular sieve raw powder to obtain a mixed powder, spraying an auxiliary agent raw material aqueous solution into the mixed powder, stirring until the mixed powder is fully wetted, and then placing the mixed powder in the shade for drying or baking to obtain a dry powder;

step two, adding a sol agent into the dry powder obtained in the step one, preparing small balls with the diameter phi of 2mm to 3mm in a sugar coater, and then sequentially curing the small balls at normal temperature for 12h to 24h, drying at 100 ℃ to 120 ℃ for 8h to 12h, and roasting at 400 ℃ to 500 ℃ for 4h to 6h to obtain a desulfurizer A;

step three, heating the mixed salt solution containing the salt of the first active metal element and the salt containing the second active metal element selected in the step one to 30-50 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume manner, standing the mixture for 2-4 hours, and then drying the mixture for 8-12 hours at 100-120 ℃ and roasting the mixture for 4-6 hours at 350-450 ℃ in sequence to obtain a desulfurizer B;

filling the desulfurizer B obtained in the third step into a fixed bed tubular reactor, introducing hydrogen-nitrogen mixed gas with the hydrogen volume fraction of 10-20%, and then carrying out programmed heating to 300-400 ℃ for activation for 4-6 h;

and step five, cooling the desulfurizer B activated in the step four to 25-45 ℃ by adopting nitrogen, then adding oxygen into the nitrogen for surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain the heavy naphtha desulfurizer with high space velocity and high activity.

The preparation method of the desulfurizer comprises the steps of mixing partial raw materials of active components, namely oxides, carrier raw materials and auxiliary raw materials to form small balls, oxidizing, drying and roasting to obtain the desulfurizer A, then carrying out equal-volume impregnation with the rest raw materials of the active components, namely salt solution, standing, drying and roasting to obtain the desulfurizer B, then introducing hydrogen-nitrogen mixed gas for heating and activating, and adding oxygen for surface oxidation treatment to obtain the desulfurizer. In the process, the first active metal element and the second active metal element are added into the desulfurizer in two forms in two steps, so that the content of the active metal elements on the surface of the desulfurizer is improved, the surface active sites of the desulfurizer are increased, and the processing capacity of the desulfurizer on heavy naphtha is enhanced while the dispersion degree of the active metal elements is fully improved; secondly, activating the active metal oxide in the desulfurizer B into metal ions with zero valence state by a hydrogen activation mode, reducing reaction active energy and reaction induction period, shortening desulfurization reaction time, increasing heavy naphtha treatment capacity and improving desulfurization precision; thirdly, the activated desulfurizer B is subjected to surface oxidation treatment to obtain the desulfurizer, so that a thin metal oxide protective film is formed on the surface of the desulfurizer, the desulfurizer can still keep more than 90% of activation degree when contacting with air at normal temperature, and the requirements of long-time storage and transportation and large-scale industrial production of the desulfurizer are met.

The preparation method is characterized in that, in the first step, the mass ratio of the oxide to the salt in the raw material containing the first active metal element is 3 to 5:1, the mass ratio of the oxide to the salt in the raw material containing the second active metal element is 3-5: 1.

the preparation method is characterized in that the auxiliary raw material in the first step is alkali metal carbonate potassium carbonate or/and sodium carbonate, the sol agent in the second step is silica sol or alumina sol with the mass concentration of 10-20%, and the salt containing the first active metal element and the salt containing the second active metal element in the third step are both nitrate or/and acetate.

The preparation method is characterized in that the activation degree of the large space velocity high activity heavy naphtha desulfurizer in the step five is more than 90%.

Compared with the prior art, the invention has the following advantages:

1. the heavy naphtha desulfurizer takes the coupling substance of the activated alumina and the molecular sieve as a carrier, exerts the advantages of high specific surface area and large aperture of the alumina, the rule of the molecular sieve and strong adsorption effect of rich pore channels on polar molecules such as hydrogen sulfide, mercaptan, thioether and the like, and enhances the rapid diffusion and adsorption capacity of sulfides in the heavy naphtha in the pore channels of the desulfurizer.

2. The heavy naphtha desulfurizer of the invention adopts alkali metal oxide as the adjusting assistant, changes the acidity and alkalinity of the desulfurizer, enhances the rapid adsorption reaction capability of the heavy naphtha desulfurizer on weakly acidic sulfides such as hydrogen sulfide, mercaptan and the like, simultaneously prevents the activity loss caused by sulfate generated by the surface acidification of the desulfurizer, and further improves the desulfurization effect of the desulfurizer.

3. According to the heavy naphtha desulfurizer disclosed by the invention, the first active metal element and the second active metal element which are active components are added into the desulfurizer in two steps in different forms, so that the dispersion degree of the active metal elements on the surface of the desulfurizer is improved, the surface active sites of the desulfurizer are increased, meanwhile, the activation temperature of the desulfurizer is reduced due to the addition of the second active metal element, more lattice defect ions are formed by the active metal elements in the activation process, the activation degree is improved, the sulfur capacity and the thermodynamic stability of the desulfurizer are enhanced, and the service life of the desulfurizer is prolonged.

4. The preparation method of the desulfurizer adopts a hydrogen activation mode to process active metal oxide into activated metal ions, effectively reduces the activation energy of desulfurization reaction, shortens the reaction induction period, and acceleratesThe reaction rate of sulfide and metal ions is increased, the desulfurization capability of the desulfurizer under the condition of high space velocity is enhanced, and the desulfurization precision and activity of the desulfurizer are improved; meanwhile, H does not exist when the activated desulfurizing agent reacts with sulfide₂O is generated, H is avoided₂O pollutes the heavy naphtha, and is more beneficial to purifying the heavy naphtha.

5. According to the preparation method of the desulfurizer, the activated desulfurizer is subjected to oxidation treatment, and the thin-layer metal oxide protective film is formed on the surface of the desulfurizer, so that the activation degree of the desulfurizer in contact with air at normal temperature is improved, large-scale production and long-term storage and transportation of the desulfurizer are facilitated, the desulfurizer can be directly used without activation after being filled, the use effect is not influenced, the start-up time is saved, and the economic benefit of an enterprise is improved.

The technical solution of the present invention is further described in detail by examples below.

Detailed Description

Example 1

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 30% of active alumina, 20% of 5A molecular sieve, 30% of copper, 15% of cobalt and Na₂O 5％。

The preparation method of the heavy naphtha desulfurizer of the embodiment comprises the following steps:

step one, fully and uniformly mixing 462g of pseudo-boehmite, 200g of 5A molecular sieve raw powder, 281g of copper oxide and 143g of cobalt oxide to obtain mixed powder, dissolving 85g of sodium carbonate into an aqueous solution by using deionized water, uniformly spraying the aqueous solution into the mixed powder, stirring the mixed powder until the mixed powder is fully wetted, and then placing the mixed powder at 100 ℃ for drying to obtain dry powder;

step two, adding 10 mass percent of alumina sol into the dry powder obtained in the step one, rolling the mixture in a sugar-coating machine to prepare small balls with the diameter phi of 2mm to 3mm, and then sequentially curing the small balls for 12 hours at normal temperature, drying the small balls for 12 hours at 100 ℃, and roasting the small balls for 6 hours at 400 ℃ to obtain a desulfurizer A;

step three, dissolving 220g of copper nitrate and 116g of cobalt nitrate into deionized water to form a mixed salt solution, heating to 30 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume, standing for 4 hours, and then drying at 100 ℃ for 12 hours and roasting at 350 ℃ for 6 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 10% of hydrogen at the flow rate of 800mL/min, and then carrying out temperature programming to 300 ℃ at the heating rate of 20 ℃/h for constant temperature activation for 6h;

and step five, introducing nitrogen at the flow rate of 800mL/min to reduce the temperature of the activated desulfurizer B in the step four to 25 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 1% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high activity and large space velocity, wherein the heavy naphtha desulfurizer is marked as TL-1.

The TL-1 prepared in the example was tested to have an activation of 92.8%.

Example 2

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 50% of activated alumina, 5% of 13X molecular sieve, 20% of nickel, 20% of cerium and K₂O 5％。

step one, mixing 769g of aluminum hydroxide, 50g of 13X molecular sieve raw powder, 212g of nickel oxide and 205g of cerium oxide uniformly to obtain mixed powder, dissolving 51g of potassium carbonate into an aqueous solution by using deionized water, uniformly spraying the aqueous solution into the mixed powder, stirring until the mixed powder is fully wet, and drying at 100 ℃ to obtain dry powder;

step two, adding alumina sol with the mass concentration of 15% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 24 hours, drying the small balls at 120 ℃ for 8 hours and roasting the small balls at 500 ℃ for 4 hours to obtain a desulfurizer A;

step three, dissolving 103g of nickel nitrate and 78g of cerium nitrate into deionized water to form a mixed salt solution, heating to 50 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume manner, standing for 4 hours, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 20% of hydrogen at the flow rate of 1000mL/min, and then carrying out temperature programming to 400 ℃ at the heating rate of 10 ℃/h for constant-temperature activation for 4h;

and step five, introducing nitrogen at the flow rate of 600mL/min to reduce the temperature of the activated desulfurizer B in the step four to 45 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 0.5% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-2.

The TL-2 prepared in the example was tested to have an activation level of 93.1%.

Example 3

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 40% of activated alumina, 7% of mordenite molecular sieve, 40% of copper, 10% of lanthanum and K₂O 3％。

step one, 615g of pseudo-boehmite, 70g of mordenite raw powder, 417g of copper oxide and 98g of lanthanum oxide are fully and uniformly mixed to obtain mixed powder, 44g of potassium carbonate is dissolved into an aqueous solution by adopting deionized water and then is uniformly sprayed into the mixed powder to be stirred until the mixed powder is fully wet, and then the mixed powder is placed at 100 ℃ for drying to obtain dry powder;

step two, adding aluminum sol with the mass concentration of 20% into the dry powder obtained in the step one, rolling the mixture in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 18 hours, drying the small balls at 110 ℃ for 10 hours and roasting the small balls at 450 ℃ for 5 hours to obtain a desulfurizer A;

step three, dissolving 196g of nickel nitrate and 39g of lanthanum nitrate into deionized water to form a mixed salt solution, heating to 40 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume, standing for 3 hours, and then drying at 110 ℃ for 10 hours and roasting at 400 ℃ for 5 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 15% of hydrogen at the flow rate of 1000mL/min, and then carrying out temperature programming to 350 ℃ at the heating rate of 10 ℃/h for constant temperature activation for 5h;

and step five, introducing nitrogen at the flow rate of 600mL/min to reduce the temperature of the activated desulfurizer B in the step four to 35 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 0.75% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-3.

The TL-3 prepared in the example was tested to have an activation of 92.3%.

Example 4

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 40% of active alumina, 7% of 5A molecular sieve, 20% of nickel, 10% of cobalt, 20% of cerium and Na₂O 3％。

step one, fully and uniformly mixing 615g of aluminum hydroxide, 70g of 5A molecular sieve raw powder, 203g of nickel oxide, 102g of cobalt oxide and 197g of cerium oxide to obtain mixed powder, then dissolving 51g of sodium carbonate into an aqueous solution by using deionized water, uniformly spraying the aqueous solution into the mixed powder, stirring the solution till the solution is fully wet, and then placing the solution in the shade for drying to obtain dry powder;

step two, adding silica sol with the mass concentration of 10% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 24 hours, drying the small balls at 100 ℃ for 8 hours and roasting the small balls at 450 ℃ for 6 hours to obtain a desulfurizer A;

dissolving 62g of nickel nitrate, 62g of cobalt nitrate and 93g of cerium nitrate into deionized water to form a mixed salt solution, heating to 40 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume, standing for 4 hours, and then drying at 100 ℃ for 12 hours and roasting at 400 ℃ for 5 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 12.5 percent of hydrogen at the flow rate of 1000mL/min, and then carrying out programmed heating to 400 ℃ at the heating rate of 10 ℃/h for constant-temperature activation for 4h;

and step five, introducing nitrogen at the flow rate of 600mL/min to reduce the temperature of the activated desulfurizer B in the step four to 25 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 0.5% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-4.

The TL-4 prepared in the example was tested to have an activation level of 94.2%.

Example 5

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 30% of activated alumina, 12.5% of mordenite molecular sieve, 20% of copper, 20% of nickel, 16.5% of lanthanum and K₂O 1％。

step one, 462g of aluminum hydroxide, 125g of mordenite molecular sieve raw powder, 200g of copper oxide, 203g of nickel oxide and 155g of lanthanum oxide are fully and uniformly mixed to obtain mixed powder, then 15g of potassium carbonate is dissolved into an aqueous solution by adopting deionized water and then is uniformly sprayed into the mixed powder to be stirred until the mixed powder is fully wet, and then the mixed powder is placed in the shade for drying to obtain dry powder;

step two, adding silica sol with the mass concentration of 10% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 12 hours, drying the small balls at 100 ℃ for 12 hours and roasting the small balls at 500 ℃ for 4 hours to obtain a desulfurizer A;

step three, dissolving 125g of copper acetate, 120g of nickel acetate and 75g of lanthanum acetate in deionized water to form a mixed salt solution, heating to 30 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume manner, standing for 2 hours, drying at 100 ℃ for 12 hours, and roasting at 350 ℃ for 6 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 10% of hydrogen at the flow rate of 900mL/min, and then carrying out temperature programming to 300 ℃ at the heating rate of 15 ℃/h for constant temperature activation for 6h;

and step five, introducing nitrogen at the flow rate of 700mL/min to reduce the temperature of the activated desulfurizer B in the step four to 25 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 0.5% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-5.

The TL-5 prepared in the example was tested to have an activation of 95.8%.

Example 6

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 50% of activated alumina, 9% of 5A molecular sieve, 10% of copper, 10% of nickel, 20% of cerium and Na₂O 1％。

step one, fully and uniformly mixing 500g of pseudo-boehmite, 269g of aluminum hydroxide, 90g of 5A molecular sieve raw powder, 94g of copper oxide, 95g of nickel oxide and 184g of cerium oxide to obtain mixed powder, dissolving 17g of sodium carbonate into an aqueous solution by using deionized water, uniformly spraying the aqueous solution into the mixed powder, stirring the aqueous solution until the mixed powder is fully wetted, and then placing the mixed powder at 100 ℃ for drying to obtain dry powder;

step two, adding silica sol with the mass concentration of 15% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 24 hours, drying the small balls at 120 ℃ for 8 hours and roasting the small balls at 500 ℃ for 4 hours to obtain a desulfurizer A;

step three, dissolving 73g of copper nitrate, 78g of nickel nitrate and 116g of cerium nitrate into deionized water to form a mixed salt solution, heating to 50 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equal volume, standing for 4 hours, and then drying at 120 ℃ for 8 hours and roasting at 450 ℃ for 4 hours in sequence to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 20% of hydrogen at the flow rate of 800mL/min, and then raising the temperature to 400 ℃ at the temperature raising rate of 15 ℃/h by a program for constant-temperature activation for 4h;

and step five, introducing nitrogen at the flow rate of 700mL/min to reduce the temperature of the activated desulfurizer B in the step four to 45 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 0.75% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-6.

The TL-6 prepared in the example was tested to have an activation of 95.6%.

Example 7

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 30% of activated alumina, 10% of 13X molecular sieve, 10% of mordenite molecular sieve, 20% of copper, 10% of nickel, 10% of cerium, 5% of cobalt and Na₂O 2.5％，K₂O 2.5％。

step one, fully and uniformly mixing 462g of aluminum hydroxide, 100g of 13X molecular sieve raw powder, 100g of mordenite molecular sieve raw powder, 208g of copper oxide, 106g of nickel oxide, 53g of cobalt oxide and 102g of cerium oxide to obtain mixed powder, then uniformly spraying 43g of sodium carbonate and 37g of potassium carbonate into the mixed powder after dissolving into a mixed aqueous solution by adopting deionized water, stirring until the mixture is fully wetted, and then placing in the shade for drying to obtain dry powder;

step two, adding silica sol with the mass concentration of 20% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 12 hours, drying the small balls at 100 ℃ for 12 hours and roasting the small balls at 500 ℃ for 4 hours to obtain a desulfurizer A;

dissolving 103g of copper nitrate, 52g of nickel nitrate, 26g of cobalt nitrate and 39g of cerium nitrate into deionized water to form a mixed salt solution, heating to 40 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the second step in an equal volume manner, standing for 4 hours, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 4 hours to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 10% of hydrogen at the flow rate of 800mL/min, and then carrying out temperature programming to 350 ℃ at the heating rate of 15 ℃/h for constant temperature activation for 6h;

and step five, introducing nitrogen at the flow rate of 800mL/min to reduce the temperature of the activated desulfurizer B in the step four to 45 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the rate of 1% per hour of volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain a heavy naphtha desulfurizer with high activity and large space velocity, wherein the heavy naphtha desulfurizer is marked as TL-7.

The TL-7 prepared in the examples was tested to have an activation level of 96.5%.

Example 8

The heavy naphtha desulfurizer of the embodiment comprises the following components in percentage by mass: 30% of activated alumina, 7% of mordenite molecular sieve, 10% of copper, 20% of nickel, 15% of cobalt, 15% of lanthanum and Na₂O 3％。

step one, 462g of pseudo-boehmite, 70g of mordenite molecular sieve raw powder, 100g of copper oxide, 203g of nickel oxide, 153g of cobalt oxide and 141g of lanthanum oxide are fully and uniformly mixed to obtain mixed powder, 51g of sodium carbonate is dissolved into an aqueous solution by adopting deionized water and then is uniformly sprayed into the mixed powder to be stirred until the mixed powder is fully wet, and then the mixed powder is dried at 100 ℃ to obtain dry powder;

step two, adding silica sol with the mass concentration of 20% into the dry powder obtained in the step one, rolling the powder in a sugar coating machine to form small balls with the diameter phi of 2mm to 3mm, and then sequentially maintaining the small balls at normal temperature for 18 hours, drying the small balls at 120 ℃ for 10 hours and roasting the small balls at 500 ℃ for 6 hours to obtain a desulfurizer A;

dissolving 68g of copper acetate, 120g of nickel acetate, 90g of cobalt acetate and 68g of lanthanum nitrate into deionized water to form a mixed salt solution, heating to 40 ℃, then soaking the mixed salt solution on the desulfurizer A obtained in the second step in an equal volume, standing for 4 hours, drying at 120 ℃ for 8 hours, and roasting at 450 ℃ for 6 hours to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor with the diameter of 60 multiplied by 1000mm (the diameter is multiplied by the length), introducing hydrogen-nitrogen mixed gas with the volume fraction of 15% of hydrogen at the flow rate of 1000mL/min, and then carrying out temperature programming to 400 ℃ at the heating rate of 20 ℃/h for constant-temperature activation for 4h;

and step five, introducing nitrogen at the flow rate of 600mL/min to reduce the temperature of the activated desulfurizer B in the step four to 25 ℃ at the speed of 50 ℃/h, then adding oxygen into the nitrogen at the mixing speed of 0.5% per hour in volume fraction to carry out surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out the heavy naphtha desulfurizer with high air speed and high activity, wherein the heavy naphtha desulfurizer is marked as TL-6.

The TL-8 prepared in the examples was tested to have an activation level of 97.1%.

Comparative example 1

This comparative example was carried out only according to the procedure of step one and step two of example 1, and the desulfurizing agent obtained was designated as DB-1.

Comparative example 2

The desulfurizing agent of the comparative example consists of the following components in percentage by mass: gamma-Al₂O₃30 percent, 13X type molecular sieve 10 percent, copper oxide 45 percent and nickel oxide 15 percent.

The preparation method of the desulfurizing agent of the comparative example is as follows: 450g of copper oxide powder, 150g of zinc oxide powder and 300g of gamma-Al₂O₃Adding 100g of 13X type molecular sieve raw powder, 30g of carboxymethyl cellulose and 600mL of water into a material grinding machine, uniformly mixing and kneading for 20min to obtain a material to be extruded, then placing the material to be extruded into a double-screw rod extruder for extrusion molding to obtain a material with the diameter of phi 3mm multiplied by 5mm (the diameter multiplied by the length), drying the material at 110 ℃ for 12h, and roasting at 450 ℃ for 4h to obtain a naphtha desulfurizer which is recorded as DB-2.

Comparative example 3

Adopts a liquid hydrocarbon described in Chinese patent with publication number CN110791308AThe normal temperature desulfurizer and the preparation method prepare the desulfurizer of the comparative example, and the desulfurizer comprises the following components by mass percent: 40% of copper oxide, 35% of zinc oxide, 1% of copper powder, 1% of nickel powder and gamma-Al₂O₃15 percent, 4 percent of bentonite and 4 percent of kaolin.

The preparation method of the desulfurizing agent of this comparative example included the following steps:

step one, preparing Zn (NO) according to the proportion that the mass fraction of corresponding oxides in the desulfurizer is 40 percent and 35 percent respectively₃)₂And Cu (NO)₃)₂The concentration of zinc salt in the copper-zinc mixed solution is 0.34mol/L, the concentration of copper salt is 0.30mol/L, then under the condition of water bath at 40 ℃, the ammonium bicarbonate solution is dripped into the copper-zinc mixed solution and stirred at the stirring speed of 400r/min, the total dripping time is 1h, the molar ratio of ammonium bicarbonate in the dripped ammonium bicarbonate solution to metal cations in the copper-zinc mixed solution is 1.8;

step two, weighing the calculated amount of AlCl according to the proportion that the mass fraction of the oxides in the desulfurizer is 15 percent₃Preparing a 0.4mol/L salt solution, then dropwise adding 10% ammonium bicarbonate into the salt solution under the conditions that the water bath temperature is 80 ℃ and the stirring speed is 400r/min, wherein the molar ratio of the salt to the alkali is 1:2.2, continuously keeping the temperature and stirring for 1h after the dropwise adding is finished, then closing the stirring and heating, and aging for 2h to obtain the aluminum sol;

step three, slowly pouring the aluminum sol obtained in the step three into the copper-zinc composite oxide precipitate, stirring for 1h at the water bath temperature of 40 ℃ at the speed of 400r/min, stopping reaction, performing suction filtration, washing with clear water, naturally drying and oxidizing completely, and grinding to obtain desulfurizer raw powder;

step four, respectively weighing kaolin and bentonite as binders according to the mass fraction of the desulfurizer of 4%, simultaneously weighing copper powder and nickel powder as promoters according to the mass fraction of the desulfurizer of 1%, uniformly mixing the promoters with the desulfurizer raw powder obtained in the step three, adding water, kneading for 30min, extruding and molding by using a single screw extruder, naturally airing at room temperature, placing the mixture into a drying room after curing, and drying and activating at 260 ℃ on the nitrogen atmosphere to obtain a finished product desulfurizer, which is recorded as DB-3.

Comparative example 4

The desulfurizer of the comparative example is prepared by adopting the preparation method of the oil desulfurizer disclosed in the Chinese patent with the publication number of CN1049158A, and the concrete steps are as follows:

the method comprises the following steps: soaking activated carbon in 10% dilute hydrochloric acid by mass for 2h, washing with clear water until the pH is =7, and drying at 120 ℃ for 8h;

step two: uniformly mixing 40% of zinc oxide, 10% of manganese oxide, 10% of iron oxide and 40% of carbon, adding a hydroxymethyl cellulose aqueous solution with the mass concentration of 3%, kneading and extruding to obtain a bar-shaped object with the diameter of phi 3mm multiplied by 10 mm;

step three: and drying the strip-shaped objects at 100 ℃ for 8h and roasting the dried strip-shaped objects at 250 ℃ for 4h to obtain the active carbon loaded zinc, manganese and iron desulfurizer which is marked as DB-4.

Evaluation tests of examples 1 to 8 of the present invention and comparative examples 1 to 4

Respectively weighing 50mL of the heavy naphtha desulfurizer with large space velocity and high activity in the embodiments 1 to 6 and the desulfurizer prepared in the comparative examples 1 to 4 according to the original granularity, filling the weighed materials into a middle constant temperature area of a stainless steel reactor with phi 40mm multiplied by 600mm (diameter multiplied by length), filling two ends of the stainless steel reactor with inert ceramic balls with phi 3mm, and connecting the stainless steel reactor into a desulfurization device for performance evaluation test: (1) test raw materials: 15.5 mu g is added to heavy naphtha produced by hydrocracking^-1Hydrogen sulfide, 4.75. Mu.g.g^-1And 3.2. Mu.g.g.of methyl mercaptan^-1Methyl ethyl sulfide of (5); (2) test conditions: simulating the desulfurization process conditions of heavy naphtha in an industrial device, namely the desulfurization temperature is 130-150 ℃, and the pressure is 0.1-0.25 MPa; analyzing the sulfur content at the outlet shape of the stainless steel reactor every 1h in the evaluation process, and when the total sulfur content at the outlet of the stainless steel reactor exceeds 0.5 mu g^-1When the sulfur content is determined to be penetrated, the desulfurization test is stopped, and the desulfurizing agent is taken out and analyzed.

The sulfur capacity of the desulfurizer is measured according to HG/T2513-2014 & lt & gt Zinc oxide desulfurizerStandard execution of sulfur capacity determination method; the analysis of the morphological sulfur is carried out on an Agilent liquid chromatography sulfur special analyzer, and the lower limit of the analyzer analysis is 0.01 mu g^-1(ii) a The evaluation and test results are shown in tables 1 and 2 below, wherein the test conditions in table 1 correspond to: the desulfurization temperature is 145 ℃, the pressure is 0.15MPa, and the feeding airspeed is 8h^-1Table 2 corresponds to the test conditions: and (3) desulfurization temperature: 145 ℃, 0.15MPa of pressure and 8h of space velocity of feeding^-1。

TABLE 1

TABLE 2

The "-" in Table 2 indicates that the total sulfur content in the reactor outlet oil just after the start of the desulfurization test exceeded 0.5. Mu.g.g^-1No sulfur capacity test was performed.

It can be known from the combination of table 1 and table 2 that, compared with the desulfurizing agents prepared in comparative examples 1 to 4, the heavy naphtha desulfurizing agents with high space velocity and high activity in the embodiments 1 to 8 of the invention have good effect of removing sulfides, and have strong ability of removing mercaptan and thioether; at a feeding airspeed of 8h^-1When the total sulfur at the outlet is less than 0.1 mug g^-1The sulfur capacity is up to 15.4%, and when the feeding space velocity is increased to 16h^-1In addition to slight decrease of sulfur capacity, the desulfurizing agent still has strong capability of removing sulfides such as hydrogen sulfide, mercaptan and thioether, and the total sulfur at the outlet can also reach 0.1 mug.g^-1Below, far exceeding the heavy naphtha outlet total sulfur content < 0.5 mug g^-1The index value shows the technical advantages of the desulfurizer of the invention of large airspeed, high activity and high sulfur capacity, and has very high popularizationAnd (4) application value.

Meanwhile, as can be seen from the test data of comparative examples 1 to 4, the desulfurizing agents of comparative examples 1 to 4 have certain desulfurizing capacity at low space velocity, but have poor desulfurizing precision and low sulfur capacity; and at 16h^-1The desulfurization capability under large space velocity is worse, and the requirement of the technical index of the heavy naphtha desulfurization process can not be met at all.

The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.

Claims

1. The heavy naphtha desulfurizer with high space velocity and high activity is characterized by comprising the following components in percentage by mass: 30-50% of activated alumina, 5-20% of molecular sieve, 20-40% of first active metal element, 10-30% of second active metal element and 1-5% of auxiliary agent; the first active metal element is copper or/and nickel element, and the second active metal element comprises one or two of cerium, lanthanum and cobalt element; the desulfurizing agent is activated and has a liquid hourly space velocity of up to 16h^-1In the process, removing hydrogen sulfide, mercaptan and thioether in the heavy naphtha to be not more than 0.1ppmwt;

the heavy naphtha desulfurizer is prepared by the method comprising the following steps:

step two, adding a sol agent into the dry powder obtained in the step one, making small balls with the diameter of phi 2mm to 3mm in a sugar coating machine, and then curing the small balls at the normal temperature for 12h to 24h, drying at 100-120 ℃ for 8h to 12h, and baking at 400-500 ℃ for 4h to 6h to obtain a desulfurizer A;

step three, heating the mixed salt solution containing the salt containing the first active metal element and the salt containing the second active metal element selected in the step one to 30-50 ℃, soaking the mixed salt solution on the desulfurizer A obtained in the step two in an equivoluminal manner, standing for 2h-4h, drying at 100-120 ℃ for 8h-12h, and roasting at 350-450 ℃ for 4h-6h to obtain a desulfurizer B;

step four, filling the desulfurizer B obtained in the step three into a fixed bed tubular reactor, introducing hydrogen-nitrogen mixed gas with the hydrogen volume fraction of 10-20%, and then carrying out temperature programming to 300-400 ℃ for activation for 4-6 h;

and step five, cooling the desulfurizer B activated in the step four to 25-45 ℃ by adopting nitrogen, then adding oxygen into the nitrogen to perform surface oxidation treatment until the volume fraction of the oxygen in the nitrogen is 20%, and taking out to obtain the heavy naphtha desulfurizer with high air speed and high activity.

2. The heavy naphtha desulfurizer with high space velocity and high activity as claimed in claim 1, wherein the aluminum source of the active alumina is pseudoboehmite or/and aluminum hydroxide.

3. The heavy naphtha desulfurizing agent with high space velocity and high activity according to claim 1, wherein the molecular sieve is one or two of 5A, 13X and mordenite.

4. The desulfurizing agent for heavy naphtha as claimed in claim 1, wherein the assistant is alkali metal oxide K₂O or/and Na₂O。

5. The desulfurizing agent for heavy naphtha at a high space velocity and high activity according to claim 1, wherein in the first step, the mass ratio of the oxide to the salt in terms of the mass of the first active metal element in the raw material containing the first active metal element is 3 to 5:1, the mass ratio of the oxide to the salt in the raw material containing the second active metal element is 3 to 5:1.

6. the heavy naphtha desulfurizer with high space velocity and high activity according to claim 1, wherein the auxiliary raw material in the first step is alkali carbonate potassium carbonate or/and sodium carbonate, the sol agent in the second step is silica sol or alumina sol with a mass concentration of 10% -20%, and the salt containing the first active metal element and the salt containing the second active metal element in the third step are both nitrate or/and acetate.

7. The desulfurizing agent for high-space-velocity high-activity heavy naphtha as claimed in claim 1, wherein the degree of activation of the desulfurizing agent for high-space-velocity high-activity heavy naphtha in step five is greater than 90%.