Sulfur transfer aids, methods of making and using the same

Abstract

This invention provides a sulfur transfer aid, its preparation method, and its application. The sulfur transfer aid comprises 30%-70% magnesium oxide, 15%-60% aluminum oxide, 10%-15% cerium oxide, and 2%-5% vanadium pentoxide. The magnesium oxide is provided by a first magnesium source and a magnesium-aluminum matrix material, and the aluminum oxide is provided by a first aluminum source and a magnesium-aluminum matrix material. On a dry basis, the mass of the magnesium-aluminum matrix material is 5%-30% of the total mass of the raw materials of the sulfur transfer aid. The magnesium-aluminum matrix material is obtained by crystallizing a mixture of a second magnesium source and a second aluminum source after sol-treatment, and the magnesium-aluminum matrix material comprises magnesium oxide and aluminum oxide in a mass ratio of 0.2-0.8:1. This invention also provides a preparation method for the above-mentioned sulfur transfer aid and its application in catalytic cracking processes. This sulfur transfer aid can efficiently desulfurize and is suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of petroleum catalytic cracking materials technology, and in particular to a sulfur transfer aid, its preparation method and application. Background Technology

[0002] Fluidized catalytic cracking (FCC) is the most important deep-processing technology for heavy oil to lighten its products, yielding many high-value products such as gasoline, diesel, and liquefied petroleum gas (LPG). The catalytic cracking catalyst is a porous microsphere composed of molecular sieves, an active matrix, and a silica-alumina binder. During catalytic cracking, the FCC catalyst repeatedly undergoes reaction, stripping, and regeneration within the reactor and regenerator. In the FCC riser reactor, approximately 45%-55% of the sulfur in the feedstock is converted into H2S and discharged with the cracked gas, while 35%-45% remains in the liquid product. The remaining 5%-10% of sulfur is deposited on the coke of the catalyst to be regenerated. Upon entering the regenerator, the sulfur on the coke is oxidized to SO2. X It is discharged with the regenerated flue gas.

[0003] Methods for controlling sulfur emissions from FCC regeneration flue gas mainly include crude oil pretreatment, flue gas scrubbing desulfurization, and sulfur transfer technology. Due to limitations in source and cost, refineries are not highly selective in their crude oil selection. Although catalytic hydrogenation of feedstock and flue gas scrubbing desulfurization are widely applicable and economical, suitable for processing high-sulfur crude oil, they require increased equipment investment costs and have high energy consumption. In contrast, the addition of sulfur transfer agents can be easily achieved using existing equipment, without additional equipment investment, and has low operating costs. Under current environmental requirements, when SO₂ in the catalytic cracking regeneration flue gas... x Concentration below 1000 mg / m 3 In some cases, using a sulfur transfer agent alone can achieve the required emission standards for flue gas, which is simpler and more economical than using wet desulfurization. When SO₂ in the flue gas... x When the content is higher, a combination of sulfur transfer agent and wet desulfurization process or wet desulfurization process alone can be used to improve the operating efficiency of the equipment.

[0004] The working principle of the sulfur transfer agent is to mechanically mix the sulfur transfer agent with the catalytic cracking catalyst, and then mix them together between the riser reactor and the regenerator. The SO₂ produced during the regeneration of coke is then transferred to the reactor. X The sulfur transfer agent reacts to promote the oxidation of SO2 to SO3, forming stable metal sulfates. These sulfates, along with the regenerated catalyst, are recycled to the riser reactor. In the reducing atmosphere of the reactor, the previously formed sulfates are reduced to H2S, while the sulfur transfer agent is regenerated, returning to its original metal oxide form. This re-entrainment is then recycled to the regenerator for the next SO2 oxidation process. x Oxidative adsorption reaction. This portion of H2S, along with the H2S generated from the cracking reaction, is transported to the sulfur recovery unit and converted into sulfur through the Claus process.

[0005] To enhance the ability of sulfur transfer agents to oxidize SO2 to SO3 and further improve their performance, transition metal components such as Fe, V, and Ni, or rare earth metals such as Ce and La, are introduced into the catalyst. This significantly improves the adsorption rate, adsorption capacity, and reduction and regeneration capacity of the sulfur transfer agent.

[0006] CN103861436 discloses a mixed-phase catalytic cracking flue gas sulfur transfer agent, its preparation method, and its application. By utilizing a composite structure formed by titanium-magnesium structural materials and magnesium-aluminum spinel structural materials, the desulfurization effect and service life of the sulfur transfer agent are greatly enhanced, and the composition range of the sulfur transfer agent is broadened.

[0007] CN101905168A discloses a catalytic cracking additive for increasing propylene production, which functions as a sulfur transfer agent. This additive not only increases propylene production but also acts as a sulfur transfer agent to remove SOx from flue gas. Due to the chemical inertness of magnesium aluminum spinel, the active component ZSM-5 can be incorporated into the matrix, thus creating a dual-functional additive.

[0008] However, the preparation process of magnesium aluminum spinel is relatively complex, and the magnesium oxide content in magnesium aluminum spinel is low (generally 28%), which greatly reduces the sulfur adsorption effect of sulfur transfer agents. Compared with sulfur transfer agents with high magnesium oxide content, its sulfur transfer effect is reduced.

[0009] Currently, commercially available sulfur transfer agents are typically magnesium-aluminum oxide complexes containing the metallic elements vanadium and cerium. MgO is the active component for SO2 adsorption, forming stable MgSO4. CeO2 is a highly efficient SO2 oxidation promoter, but it does not contribute to the reduction of MgSO4. V2O5 is a redox promoter, which accelerates the SO2 oxidation rate in the regenerator and the reduction of sulfate to H2S in the reactor, allowing the sulfur transfer agent to quickly regain its activity.

[0010] However, existing sulfur transfer aids suffer from drawbacks such as viscous preparation systems, low colloidal solids content, poor wear resistance, and unsatisfactory desulfurization effects. To address these shortcomings, there is a need for a sulfur transfer agent suitable for industrial production that offers high desulfurization efficiency, low cost, and simple preparation for catalytic cracking regenerated flue gas. Summary of the Invention

[0011] To address the aforementioned problems, the present invention aims to provide a sulfur transfer aid, its preparation method, and its application. This sulfur transfer aid is characterized by high desulfurization efficiency, low cost, and simple preparation, making it suitable for industrial production.

[0012] To achieve the above objectives, the present invention provides a sulfur transfer aid, which comprises, based on the total mass of the sulfur transfer aid as 100%, 30%-70% magnesium oxide, 15%-60% aluminum oxide, 10%-15% cerium oxide, and 2%-5% vanadium pentoxide.

[0013] Wherein, the magnesium oxide is provided by a first magnesium source and a magnesium-aluminum matrix material, and the alumina is provided by a first aluminum source and the magnesium-aluminum matrix material; the magnesium-aluminum matrix material, on a dry basis, accounts for 5%-30% of the total dry basis mass of the raw materials of the sulfur transfer aid.

[0014] The magnesium-aluminum matrix material is obtained by mixing a second magnesium source with a second aluminum source after sol-gel treatment and then crystallizing the mixture. The magnesium-aluminum matrix material includes magnesium oxide and aluminum oxide in a mass ratio of 0.2-0.8:1.

[0015] According to a specific embodiment of the present invention, the mass percentage of magnesium oxide in the sulfur transfer aid is generally 30%-70%, specifically it can be 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc., and a range with any two of the above specific values ​​as endpoints.

[0016] According to a specific embodiment of the present invention, the mass percentage of alumina in the sulfur transfer aid is generally 15%-60%, for example 18%-60% or 20%-60%, and can specifically be 15%, 16%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc., and a range with any two of the above specific values ​​as endpoints.

[0017] According to a specific embodiment of the present invention, the mass percentage of cerium oxide in the sulfur transfer aid is generally 10%-15%, specifically 10%, 11%, 12%, 13%, 14%, 15%, etc., and a range with any two of the above specific values ​​as endpoints.

[0018] According to a specific embodiment of the present invention, the mass percentage of vanadium pentoxide in the sulfur transfer aid is generally 2%-5%, specifically 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc., and a range with any two of the above specific values ​​as endpoints.

[0019] According to a specific embodiment of the present invention, the first magnesium source may include magnesium salts and / or magnesium oxide.

[0020] According to a specific embodiment of the present invention, the first aluminum source may include pseudoboehmite.

[0021] According to a specific embodiment of the present invention, the second magnesium source may include magnesium oxide. In some specific embodiments, the second magnesium source may be ultrafine magnesium oxide, wherein the D(0.9) particle size of the ultrafine magnesium oxide is less than or equal to 2 μm. By using ultrafine magnesium oxide to prepare a magnesium-aluminum matrix material, and then using the magnesium-aluminum matrix material to prepare a sulfur transfer aid, the wear strength of the sulfur transfer aid can be improved.

[0022] According to a specific embodiment of the present invention, the second aluminum source may include boehmite.

[0023] According to a specific embodiment of the present invention, on a dry basis, the mass of the magnesium-aluminum matrix material is 5%-30% of the total mass of the raw materials of the sulfur transfer aid, for example, specific values ​​such as 5%, 10%, 15%, 20%, 25%, 30%, etc., and a range with any two of the above specific values ​​as endpoints.

[0024] According to a specific embodiment of the present invention, the magnesium-aluminum matrix material contains magnesium oxide and aluminum oxide in a mass ratio of 0.2-0.8:1. In some specific embodiments, the mass ratio of magnesium oxide to aluminum oxide in the magnesium-aluminum matrix material can be specific values ​​such as 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, etc., or a range with any two of the above specific values ​​as endpoints.

[0025] According to a specific embodiment of the present invention, the second aluminum source can be first subjected to a sol-gel treatment and then mixed with the second magnesium source; the second magnesium source and the sol-gel treated second aluminum source can form a colloidal system after mixing. Specifically, the preparation method of the magnesium-aluminum matrix material may include: mixing a slurry of the second aluminum source with an acidic substance for sol-gel treatment, then mixing the sol-gel treated slurry of the second aluminum source with a slurry of the second magnesium source to obtain a magnesium-aluminum colloidal slurry, crystallizing it, and obtaining the magnesium-aluminum matrix material.

[0026] In the above-mentioned method for preparing magnesium-aluminum matrix material, the second aluminum source combines with hydrogen ions (from acidic substances) in the liquid environment and dissociates into smaller microcrystalline aluminum sources. The hydroxyl groups of the microcrystalline aluminum sources then combine with at least part of the second magnesium source and undergo crystallization treatment to form a stable magnesium-aluminum matrix material with a crystalline structure.

[0027] In some specific implementations, the mixing time between the slurry of the second aluminum source and the slurry of the second magnesium source after sol-solution treatment can be controlled to be 0.5h-1h, and the mixing method can be pulping and mixing.

[0028] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the acidic substance can be an inorganic acid, specifically including one or more of hydrochloric acid, nitric acid, formic acid and acetic acid.

[0029] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the mass of the second aluminum source is based on alumina, and the mass ratio of the acidic substance to the second aluminum source is usually controlled to be 0.10-0.5:1, for example, 0.10-0.25:1. Specifically, it can be 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1, 0.50:1, etc., as well as a range with any two of the above specific values ​​as endpoints.

[0030] In the above-mentioned method for preparing magnesium-aluminum matrix materials, when the acidic substance is an inorganic acid, a commercially available inorganic acid solution can be used, and the mass ratio of the acidic substance to the second aluminum source can also be the ratio of the mass of the commercially available inorganic acid solution to the mass of the second aluminum source. Specifically, when the acidic substance includes hydrochloric acid, the mass ratio of hydrochloric acid to the second aluminum source is the mass ratio of a 35-38% hydrochloric acid solution to the second aluminum source calculated as alumina; when the acidic substance includes nitric acid, the mass ratio of nitric acid to the second aluminum source is the mass ratio of an 88% nitric acid solution to the second aluminum source calculated as alumina; when the acidic substance includes formic acid, the mass ratio of formic acid to the second aluminum source is the mass ratio of an 88% formic acid solution to the second aluminum source calculated as alumina; when the acidic substance includes acetic acid, the mass ratio of acetic acid to the second aluminum source is the mass ratio of a 99% acetic acid solution to the second aluminum source calculated as alumina.

[0031] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the temperature of the sol-gel treatment is usually controlled at 40-80℃, for example, specific values ​​such as 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, and a range with any two of the above specific values ​​as endpoints.

[0032] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the time for the sol-gel treatment is usually controlled to be more than 1 hour, for example, 1 hour to 3 hours.

[0033] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the crystallization temperature is usually controlled to be 50-95℃, for example, specific values ​​such as 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, etc., and a range with any two of the above specific values ​​as endpoints.

[0034] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the crystallization time is 10-72h, for example, it can be a specific value such as 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 72h, or a range with any two of the above specific values ​​as endpoints.

[0035] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the crystallization method can be one of static crystallization, dynamic crystallization, or intermittent dynamic crystallization.

[0036] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the slurry of the second aluminum source can be formed by mixing the second aluminum source with water. The solid content of the slurry of the second aluminum source (the solid content mentioned in this invention refers to the mass content of solids) can be 0.15-0.25, for example, specific values ​​such as 0.15, 1.6, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, etc., and a range with any two of the above specific values ​​as endpoints.

[0037] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the slurry of the second magnesium source can be formed by mixing the second magnesium source with water. The solid content of the slurry of the second magnesium source is 0.2-0.4 (i.e., 20%-40%), for example, it can be a specific value such as 0.2, 0.25, 0.3, 0.35, 0.4, or a range with any two of the above specific values ​​as endpoints.

[0038] In the above-mentioned method for preparing the magnesium-aluminum matrix material, the raw materials for the magnesium-aluminum matrix material may further include a surfactant, which is added to the uncrystallized magnesium-aluminum colloidal slurry. That is, the method for preparing the magnesium-aluminum matrix material may include: mixing a slurry of a second aluminum source with an acidic substance for sol-gel treatment; then mixing the sol-gel treated slurry of the second aluminum source with a slurry of a second magnesium source to obtain a magnesium-aluminum colloidal slurry; mixing the magnesium-aluminum colloidal slurry with a surfactant; and crystallizing to obtain the magnesium-aluminum matrix material.

[0039] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the surfactant may include hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium chloride.

[0040] In the above-mentioned method for preparing magnesium-aluminum matrix materials, the ratio of the mass of the surfactant to the total mass of the raw materials of magnesium-aluminum matrix materials on a dry basis can be controlled to be 0.01-0.05:1, for example, it can be a specific value such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, or any two of the above specific values ​​as endpoints.

[0041] In the above-mentioned preparation method of magnesium-aluminum matrix materials, the dispersion effect of magnesium-aluminum colloids can be improved by adding surfactants. Surfactants can micellize in aqueous solutions, reduce the interfacial tension between two phases, and make the liquid and solid exist stably in water, exhibiting emulsification and dispersion effects. This effectively reduces the particle size of the magnesium-aluminum matrix material and avoids adverse effects on its particle strength and wear strength during subsequent preparation of sulfur transfer aids.

[0042] The magnesium-aluminum matrix material provided by this invention can replace part of the aluminum source and part of the magnesium source in the raw materials of the sulfur transfer aid. By using the magnesium-aluminum matrix material, on the one hand, the structure of the sulfur transfer aid can be optimized, giving it a certain mesoporous pore size and enriching its pore structure, thereby further improving the adsorption-desorption sulfur effect; on the other hand, it can reduce the viscosity of the system of colloidal alumina and magnesium-containing substances during the preparation of the sulfur transfer aid, increase the colloidal solid content of the raw materials, and improve product performance and production efficiency.

[0043] The present invention also provides a method for preparing the above-mentioned sulfur transfer aid, the method comprising:

[0044] S1. The first aluminum source, cerium source, vanadium source and acidic substance are mixed and subjected to sol-gel treatment to obtain sol-gel product;

[0045] S2. The sol product obtained in S1 is mixed with the first magnesium source and magnesium-aluminum matrix material to form a raw material colloid, dried, and calcined to obtain the sulfur transfer aid.

[0046] In the above-mentioned method for preparing sulfur transfer aids, the cerium source may include one or more of cerium chloride, cerium nitrate, cerium dioxide, compounds and / or mixtures of cerium and rare earth elements other than cerium. In some specific embodiments, the rare earth elements other than cerium may specifically include elements other than cerium in the lanthanide series, such as one or more of lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0047] In the above-mentioned method for preparing sulfur transfer aids, the vanadium source may include ammonium metavanadate and / or vanadium oxide (VO₂O₃). x ).

[0048] The above-mentioned preparation method of the present invention can improve the bonding effect by utilizing the bonding effect of aluminum-magnesium colloid and magnesium-aluminum matrix material formed by aluminum source and magnesium source. No additional binder needs to be added during the preparation process, and the raw material composition is simple and low cost.

[0049] In the above-mentioned method for preparing sulfur transfer aid, in S1, the temperature of the sol-gel treatment can be controlled to be 40-80℃, for example, specific values ​​such as 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, and a range with any two of the above specific values ​​as endpoints.

[0050] In the above-mentioned method for preparing sulfur transfer aid, in S1, the time of the sol-gel treatment can be controlled to be 0.5h-1h, for example, it can be a specific value such as 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, or any two of the above specific values ​​as endpoints.

[0051] In the above-mentioned method for preparing sulfur transfer aid, the acidic substance used in S1 can be an inorganic acid, specifically including one or more of hydrochloric acid, nitric acid, formic acid and acetic acid.

[0052] In the above-mentioned method for preparing the sulfur transfer aid, in S1, the mass of the first aluminum source is based on alumina, and the mass ratio of the acidic substance to the first aluminum source is 0.10-0.70:1, further can be 0.10-0.50:1, and even further can be 0.10-0.25:1; for example, the mass ratio of the acidic substance to the first aluminum source can be specific values ​​such as 0.10:1, 0.15:1, 0.20:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1, 0.45:1, 0.50:1, 0.55:1, 0.60:1, 0.65:1, 0.66:1, 0.67:1, 0.68:1, 0.69:1, 0.70:1, etc., and a range with any two of the above specific values ​​as endpoints.

[0053] In the above-mentioned method for preparing the sulfur transfer aid, when the acidic substance is an inorganic acid, a commercially available inorganic acid solution can be used, and the mass ratio of the acidic substance to the first aluminum source can also be the ratio of the mass of the commercially available inorganic acid solution to the mass of the first aluminum source. Specifically, when the acidic substance includes hydrochloric acid, the mass ratio of hydrochloric acid to the first aluminum source is the mass ratio of a 35-38% hydrochloric acid solution to the first aluminum source calculated as alumina; when the acidic substance includes nitric acid, the mass ratio of nitric acid to the first aluminum source is the mass ratio of an 88% nitric acid solution to the first aluminum source calculated as alumina; when the acidic substance includes formic acid, the mass ratio of formic acid to the first aluminum source is the mass ratio of an 88% formic acid solution to the first aluminum source calculated as alumina; when the acidic substance includes acetic acid, the mass ratio of acetic acid to the first aluminum source is the mass ratio of a 99% acetic acid solution to the first aluminum source calculated as alumina.

[0054] In the above-mentioned method for preparing sulfur transfer aids, the sol product obtained in S1 can be in colloidal form.

[0055] In the above-mentioned method for preparing sulfur transfer aid, in step S2, the mixing time between the sol-gel product obtained in step S1 and the first magnesium source and magnesium-aluminum matrix material can be 0.5 h to 1 h. The mixing method can be pulping.

[0056] In the above method for preparing the sulfur transfer aid, in step S2, the drying process is used to promote molding and can be spray drying. The spray drying process can use conventional conditions and parameters in the art. The average particle size of the particles obtained by spray drying can be 90-100 μm.

[0057] In the above-mentioned method for preparing sulfur transfer aid, in step S2, the calcination temperature can be controlled to be 300-600℃, for example, it can be a specific value such as 300℃, 350℃, 400℃, 450℃, 500℃, 550℃, 600℃, or a range with any two of the above specific values ​​as endpoints.

[0058] In the above-mentioned method for preparing sulfur transfer aid, in step S2, the calcination time can be controlled to be 0.5h-4h, for example, it can be a specific value such as 0.5h, 1.0h, 1.5h, 2.0h, 2.5h, 3.0h, 3.5h, 4.0h, or a range with any two of the above specific values ​​as endpoints.

[0059] This invention also provides the application of the above-mentioned sulfur transfer aid in catalytic cracking processes. By adding a magnesium-aluminum matrix material during the preparation of the sulfur transfer aid, the solid content of the colloidal system formed by the raw materials of the sulfur transfer aid can be increased, thereby improving the specific surface area and wear resistance of the sulfur transfer aid. The resulting sulfur transfer aid exhibits significantly improved desulfurization and reduction performance in catalytic cracking processes. Specifically, the above-mentioned sulfur transfer aid can be applied to the flue gas regeneration process in catalytic cracking as a sulfur transfer aid for catalytic cracking regenerated flue gas. This sulfur transfer aid can promote the conversion of sulfur oxides in flue gas regeneration into stable metal salts, and then sequentially into hydrogen sulfide and sulfur. The sulfur transfer aid can also be regenerated in a reducing atmosphere and reused. In some specific embodiments, the desulfurization rate of the catalytic cracking process using the above-mentioned sulfur transfer aid can reach over 89%, and the reduction rate can reach over 91%.

[0060] The beneficial effects of this invention are as follows:

[0061] 1. This invention introduces a magnesium-aluminum matrix material into the raw materials of the sulfur transfer aid to replace part of the aluminum source and part of the magnesium source. On the one hand, this reduces the viscosity of the raw material colloid during the preparation of the sulfur transfer aid, increases the solid content of the raw material colloid, reduces production energy consumption, and improves product qualification rate and production efficiency. On the other hand, it can improve the wear resistance of the sulfur transfer aid, enrich the pore structure in the sulfur transfer aid, optimize the aid structure, and improve the sulfur transfer aid's resistance to SO₂. x The adsorption and desorption effects of (sulfur oxides).

[0062] 2. The sulfur transfer aid provided by this invention has strong wear resistance, high reactivity, high desulfurization efficiency, simple preparation method, low cost, and is suitable for industrial production. Detailed Implementation

[0063] In order to provide a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention will now be described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.

[0064] In the following examples and comparative examples, the elemental content in the samples was determined by X-ray fluorescence analysis.

[0065] The origin and specifications of the raw materials used in the following examples and comparative examples are as follows:

[0066] Magnesium chloride, magnesium nitrate, magnesium oxide, ammonium metavanadate, cerium dioxide, cerium chloride, cerium nitrate, hexadecyltrimethylammonium bromide, and hexadecyltrimethylammonium chloride are commercially available reagents of analytical grade.

[0067] Boehmite (alumina content 62%): Industrial product, Shanxi Aluminum Plant.

[0068] Example 1

[0069] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0070] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 505 g of deionized water, and 10 g of hydrochloric acid with a mass concentration of 36%-38% was added under continuous stirring. The mixture was heated to 40°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 20 g of magnesium oxide was added to 50 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 1.2 g of hexadecyltrimethylammonium bromide was added, and the mixture was stirred for 30 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 50°C for 72 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.2:1.

[0071] (2) Preparation of sulfur transfer aid: Take 161 g of boehmite, 50 g of cerium nitrate and 5 g of ammonium metavanadate, add 263 g of deionized water, add 10 g of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 40℃ and keep for 30 minutes for gelation treatment; take 56 g of magnesium oxide, add 168 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 67 g of magnesium-aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium-aluminum matrix material is 10% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 300℃ for 6 h to obtain sulfur transfer aid.

[0072] The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 30 wt%, aluminum oxide 58 wt%, cerium dioxide 10 wt%, and vanadium pentoxide 2 wt%.

[0073] The sulfur transfer aid sample is designated as S1. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0074] Example 2

[0075] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0076] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 339 g of deionized water, and 15 g of hydrochloric acid with a mass concentration of 36%-38% was added under continuous stirring. The mixture was heated to 50°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 30 g of magnesium oxide was added to 45 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 2.6 g of hexadecyltrimethylammonium bromide was added, and the mixture was stirred for 30 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 95°C for 10 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.3:1.

[0077] (2) Preparation of sulfur transfer aid: Take 98g of boehmite, 61g of cerium nitrate and 6g of ammonium metavanadate, add 179g of deionized water, add 10g of nitric acid with a mass concentration of 65%-68% under continuous stirring, heat to 50℃ and keep for 60 minutes for gelation treatment; take 80g of magnesium oxide, add 240g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 100g of magnesium-aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium-aluminum matrix material is 15% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100μm, and cure and calcine at 350℃ for 2h to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 44.5 wt%, aluminum oxide 41 wt%, cerium dioxide 12 wt%, and vanadium pentoxide 2.5 wt%.

[0078] The sulfur transfer aid sample is designated as S2. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0079] Example 3

[0080] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0081] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 239 g of deionized water, and 15 g of hydrochloric acid with a mass concentration of 36%-38% was added under continuous stirring. The mixture was heated to 60°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 50 g of magnesium oxide was added to 75 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 4.5 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 80°C for 24 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.5:1.

[0082] (2) Preparation of sulfur transfer aid: Take 48 g of boehmite, 76 g of cerium nitrate and 13 g of ammonium metavanadate, add 119 g of deionized water, add 20 g of formic acid with a mass concentration of 88% under continuous stirring, heat to 60℃ and keep for 60 minutes for gelation treatment; take 100 g of magnesium oxide, add 300 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 100 g of magnesium aluminum matrix material slurry prepared in step (1) (the mass of magnesium aluminum matrix material is 15% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 400℃ for 1 h to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 57.5 wt%, aluminum oxide 22.5 wt%, cerium dioxide 15 wt%, and vanadium pentoxide 5 wt%.

[0083] The sulfur transfer aid sample is designated as S3. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0084] Example 4

[0085] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0086] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 239 g of deionized water, and 15 g of nitric acid with a mass concentration of 65%-68% was added under continuous stirring. The mixture was heated to 60°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 80 g of magnesium oxide was added to 187 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 9 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 90°C for 24 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.8:1.

[0087] (2) Preparation of sulfur transfer aid: Take 45g of boehmite, 54g of cerium chloride and 8g of ammonium metavanadate, add 160g of deionized water, add 10g of formic acid with a mass concentration of 88% under continuous stirring, heat to 70℃ and maintain for 60 minutes for gelation treatment; take 100g of magnesium oxide, add 300g of deionized water, mix evenly and add to the above gelation-treated boehmite slurry, then add 133g of the magnesium-aluminum matrix material slurry prepared in step (1) (the dry basis mass of the magnesium-aluminum matrix material is 20% of the total dry basis mass of the auxiliary raw materials), mix and stir evenly to form a raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100μm, and cure and calcine at 500℃ for 30 minutes to obtain the sulfur transfer aid. The mass percentage of each component in the sulfur transfer aid is: magnesium oxide 66wt%, aluminum oxide 18wt%, cerium dioxide 13wt%, and vanadium pentoxide 3wt%.

[0088] The sulfur transfer aid sample is designated as S4. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0089] Example 5

[0090] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0091] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 239 g of deionized water, and 20 g of nitric acid with a mass concentration of 65%-68% was added under continuous stirring. The mixture was heated to 80°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 60 g of magnesium oxide was added to 140 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 5 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 90°C for 18 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.6:1.

[0092] (2) Preparation of sulfur transfer aid: Take 39 g of boehmite, 54 g of cerium chloride and 8 g of ammonium metavanadate, add 190 g of deionized water, add 5 g of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 80℃ and keep for 60 minutes for gelation treatment; take 124 g of magnesium oxide, add 186 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 67 g of magnesium aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium aluminum matrix material is 10% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 600℃ for 30 minutes to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 68 wt%, aluminum oxide 16 wt%, cerium dioxide 13 wt%, and vanadium pentoxide 3 wt%.

[0093] The sulfur transfer aid sample is designated as S5. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0094] Example 6

[0095] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0096] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 339 g of deionized water, and 25 g of hydrochloric acid with a mass concentration of 36%-38% was added under continuous stirring. The mixture was heated to 80°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 50 g of magnesium oxide was added to 120 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 6 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 95°C for 48 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.5:1.

[0097] (2) Preparation of sulfur transfer aid: Take 152 g of boehmite, 41 g of cerium chloride and 8 g of ammonium metavanadate, add 249 g of deionized water, add 10 g of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 80℃ and keep for 60 minutes for gelation treatment; take 60 g of magnesium oxide, add 90 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 67 g of magnesium aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium aluminum matrix material is 10% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 350℃ for 60 minutes to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 35 wt%, aluminum oxide 52 wt%, cerium dioxide 10 wt%, and vanadium pentoxide 3 wt%.

[0098] The sulfur transfer aid sample is designated as S6. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0099] Example 7

[0100] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0101] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 257 g of deionized water, and 15 g of nitric acid with a mass concentration of 65%-68% was added under continuous stirring. The mixture was heated to 75°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 60 g of magnesium oxide was added to 137 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 6 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 95°C for 18 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.6:1.

[0102] (2) Preparation of sulfur transfer aid: Take 71 g of boehmite, 41 g of cerium chloride and 8 g of ammonium metavanadate, add 190 g of deionized water, add 5 g of formic acid with a mass concentration of 88% under continuous stirring, heat to 60℃ and keep for 60 minutes for gelation treatment; take 100 g of magnesium oxide, add 150 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 100 g of magnesium aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium aluminum matrix material is 15% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 400℃ for 30 minutes to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 59 wt%, aluminum oxide 28 wt%, cerium dioxide 10 wt%, and vanadium pentoxide 3 wt%.

[0103] The sulfur transfer aid sample is designated as S7. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0104] Example 8

[0105] This embodiment provides a sulfur transfer aid, the preparation method of which is as follows:

[0106] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 278 g of deionized water, and 10 g of nitric acid with a mass concentration of 65%-68% was added under continuous stirring. The mixture was heated to 60°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 60 g of magnesium oxide was added to 130 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 8 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 90°C for 24 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.6:1.

[0107] (2) Preparation of sulfur transfer aid: Take 53 g of boehmite, 50 g of cerium chloride and 6 g of ammonium metavanadate, add 190 g of deionized water, add 6 g of nitric acid with a mass concentration of 88% under continuous stirring, heat to 70℃ and keep for 60 minutes for gelation treatment; take 108 g of magnesium oxide, add 162 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 100 g of magnesium aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium aluminum matrix material is 15% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 400℃ for 30 minutes to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 63 wt%, aluminum oxide 22.5 wt%, cerium dioxide 12 wt%, and vanadium pentoxide 2.5 wt%.

[0108] The sulfur transfer aid sample is designated as S8. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2.

[0109] Comparative Example 1

[0110] This comparative example provides a sulfur transfer aid, prepared by the following method:

[0111] Preparation of the sulfur transfer aid: 73 g of boehmite, 50 g of cerium chloride, and 6 g of ammonium metavanadate were added to 200 g of deionized water. Under continuous stirring, 6 g of 88% nitric acid was added, and the mixture was heated to 70°C and maintained for 60 minutes for sol-gel treatment. 126 g of magnesium oxide was added to 155 g of deionized water, mixed thoroughly, and then added to the sol-gel treated boehmite slurry. The mixture was stirred thoroughly to form a raw material colloid. The raw material colloid was spray-dried to obtain particles with an average particle size of 90-100 μm. The particles were then cured and calcined at 400°C for 30 minutes to obtain the sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 63 wt%, aluminum oxide 22.5 wt%, cerium dioxide 12 wt%, and vanadium pentoxide 2.5 wt%.

[0112] The sulfur transfer aid sample is designated D1. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2. Compared to the preparation methods of the above embodiments, this comparative example did not add magnesium-aluminum matrix materials during the preparation of the sulfur transfer aid.

[0113] Comparative Example 2

[0114] This comparative example provides a sulfur transfer aid, prepared by the following method:

[0115] (1) Preparation of magnesium-aluminum matrix material: Take 161 g of boehmite, add 339 g of deionized water, and add 15 g of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring. Heat to 50℃ and maintain for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. Take 30 g of magnesium oxide, add 45 g of deionized water, mix evenly, and add to the above solubilized boehmite slurry. Then add 2.6 g of hexadecyltrimethylammonium bromide, mix and stir for 30 minutes to obtain a magnesium-aluminum colloidal slurry for later use. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.3:1.

[0116] (2) Preparation of sulfur transfer aid: Take 98g of boehmite, 61g of cerium nitrate and 6g of ammonium metavanadate, add 179g of deionized water, add 10g of nitric acid with a mass concentration of 65%-68% under continuous stirring, heat to 50℃ and keep for 60 minutes for gelation treatment; take 80g of magnesium oxide, add 240g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 100g of magnesium-aluminum colloidal slurry prepared in step (1) (the dry basis mass of magnesium-aluminum colloidal slurry is 15% of the total dry basis mass of the auxiliary raw materials), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100μm, and cure and calcine at 350℃ for 2h to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 44.5 wt%, aluminum oxide 41 wt%, cerium dioxide 12 wt%, and vanadium pentoxide 2.5 wt%.

[0117] The sulfur transfer aid sample is designated D2. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2. Compared to the preparation methods of the above embodiments, this comparative example uses an uncrystallized magnesium-aluminum colloidal slurry instead of the magnesium-aluminum matrix material as the raw material for the sulfur transfer aid.

[0118] Comparative Example 3

[0119] This comparative example provides a sulfur transfer aid, prepared by the following method:

[0120] (1) Preparation of magnesium-aluminum matrix material: 161 g of boehmite was added to 239 g of deionized water, and 20 g of nitric acid with a mass concentration of 65%-68% was added under continuous stirring. The mixture was heated to 80°C and kept at that temperature for 1 hour for solubilization treatment to obtain a solubilized boehmite slurry. 60 g of magnesium oxide was added to 140 g of deionized water, mixed evenly, and then added to the solubilized boehmite slurry. 5 g of hexadecyltrimethylammonium chloride was added, and the mixture was stirred for 60 minutes to obtain a magnesium-aluminum colloidal slurry. The magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction at 70°C for 4 hours to obtain the magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in this material is 0.6:1.

[0121] (2) Preparation of sulfur transfer aid: Take 39 g of boehmite, 54 g of cerium chloride and 8 g of ammonium metavanadate, add 190 g of deionized water, add 5 g of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 80℃ and keep for 60 minutes for gelation treatment; take 124 g of magnesium oxide, add 186 g of deionized water, mix evenly and add to the above gelation treatment of mixed slurry containing boehmite, cerium source and vanadium source, and then add 67 g of magnesium aluminum matrix material slurry prepared in step (1) (the dry basis mass of magnesium aluminum matrix material is 10% of the total dry basis mass of the auxiliary raw material), mix and stir evenly to form raw material colloid; spray dry the raw material colloid to obtain particles with an average particle size of 90-100 μm, and cure and calcine at 600℃ for 30 minutes to obtain sulfur transfer aid. The mass percentages of the components in this sulfur transfer aid are: magnesium oxide 68 wt%, aluminum oxide 16 wt%, cerium dioxide 13 wt%, and vanadium pentoxide 3 wt%.

[0122] The sulfur transfer aid sample is designated D3. The physicochemical properties of the sample are shown in Table 1, and the reactivity is shown in Table 2. Compared to the magnesium-aluminum matrix material preparation method of this invention, this comparative example shortens the crystallization time during the preparation of the magnesium-aluminum matrix material.

[0123] Test Example 1

[0124] (1) The solid content of the colloidal material before spraying (i.e. the solid content of the raw material colloid) of the sulfur transfer aids in each embodiment and each comparative example was measured, as well as the specific surface area (test standard: NB / SH / T0959 Determination of specific surface area of ​​catalytic cracking catalyst by static nitrogen adsorption capacity method) and wear index (test standard: NB / SH / T 0964 Determination of wear index of catalytic cracking catalyst by straight tube method) of each sulfur transfer aid sample. The results are shown in Table 1.

[0125] Table 1

[0126]

[0127] (2) The desulfurization performance of the sulfur transfer aids in each embodiment and comparative example was evaluated using the following methods:

[0128] Nitrogen, used as a protective gas and diluent, is mixed with the reactant gas and then introduced into the reactor. The reaction takes place in a fixed bed. After cooling, the products are directly introduced into a flue gas analyzer and an H2S detector to analyze the content of each component.

[0129] The operation steps are as follows:

[0130] 1) Filling the reactor. First, fill the bottom of the reactor with asbestos mesh, then fill the middle with quartz sand, and finally fill the top layer with the sulfur transfer agent sample to be evaluated. Finally, connect the reactor to the pipeline.

[0131] 2) Open the air and electrical circuits, check the airtightness of the device, and set the parameters;

[0132] 3) Use N2 as a protective gas and heat the gas. Once the temperature reaches the set value (700℃), maintain the temperature for 10 minutes, then switch to a mixed gas (SO2 400ppm, 10% O2, N2). Turn on the flue gas analyzer and collect reaction data. After the reaction is complete, turn off the mixed gas, turn on N2, cool down to the set value (500℃), maintain the temperature for 10 minutes, then switch to a mixed gas (H2, N2). Turn on the H2S detector and collect reaction data. When the reaction is complete, switch the gas back to N2 and cool to room temperature.

[0133] Sulfur transfer agent SO x Desulfurization performance is expressed as the rate of change in the volume concentration of SO2 in the reaction mixture before and after the reaction. Reduction and regeneration performance is expressed as the ratio of the volume concentration of sulfur generated to hydrogen sulfide to the sulfur absorbed by the sulfur transfer aid during the oxidation and sulfur absorption process. The test results are summarized in Table 2.

[0134] Table 2. Desulfurization and reduction performance of sulfur transfer aids

[0135]

[0136] As can be seen from Tables 1 and 2, this invention, by adding a magnesium-aluminum matrix material and controlling the preparation conditions of the magnesium-aluminum matrix material during the preparation of the sulfur transfer aid, can increase the solid content of the colloidal system formed by the raw materials of the sulfur transfer aid, thereby improving the specific surface area and wear resistance of the sulfur transfer aid. The resulting sulfur transfer aid exhibits significantly improved desulfurization and reduction performance in catalytic cracking processes.

Claims

1. A sulfur transfer aid, comprising, based on 100% of its total mass, the sulfur transfer aid: Magnesium oxide 30%-70%, aluminum oxide 15%-58%, cerium oxide 10%-15%, vanadium pentoxide 2%-5%; The magnesium oxide is provided by a first magnesium source and a magnesium-aluminum matrix material, and the alumina is provided by a first aluminum source and the magnesium-aluminum matrix material; the magnesium-aluminum matrix material, on a dry basis, constitutes 5%-30% of the total dry basis mass of the raw materials for the sulfur transfer aid. The magnesium-aluminum matrix material is obtained by mixing a second magnesium source with a second aluminum source after sol-solution treatment and then crystallizing the mixture. The magnesium-aluminum matrix material includes magnesium oxide and aluminum oxide in a mass ratio of 0.2-0.8:

1.

2. The sulfur transfer aid according to claim 1, wherein, The first magnesium source includes magnesium salts and / or magnesium oxide; The first aluminum source includes boehmite.

3. The sulfur transfer aid according to claim 1, wherein, The second magnesium source includes magnesium oxide; The second aluminum source includes boehmite.

4. The sulfur transfer aid according to claim 1, wherein, The preparation method of the magnesium-aluminum matrix material includes: mixing a slurry of a second aluminum source with an acidic substance for sol-gel treatment, then mixing the sol-gel treated slurry of the second aluminum source with a slurry of a second magnesium source to obtain a magnesium-aluminum colloidal slurry, crystallizing it, and obtaining the magnesium-aluminum matrix material.

5. The sulfur transfer aid according to claim 4, wherein, The mass of the second aluminum source is calculated as alumina, and the mass ratio of the acidic substance to the second aluminum source is 0.10-0.5:

1.

6. The sulfur transfer aid according to claim 4, wherein, The temperature of the gelation treatment is 40-80℃, and the time of the gelation treatment is more than 1 hour.

7. The sulfur transfer aid according to claim 4, wherein, The crystallization temperature is 50-95℃, and the crystallization time is 10-72h.

8. The sulfur transfer aid according to claim 4, wherein, The raw materials for the magnesium-aluminum matrix material also include surfactants, which are added to the uncrystallized magnesium-aluminum colloidal slurry.

9. The sulfur transfer aid according to claim 8, wherein, The surfactant includes hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium chloride.

10. The sulfur transfer aid according to claim 8, wherein, The ratio of the mass of the surfactant to the total mass of the raw materials of the magnesium-aluminum matrix material on a dry basis is 0.01-0.05:

1.

11. A method for preparing the sulfur transfer aid according to any one of claims 1-10, the method comprising: S1. The first aluminum source, cerium source, vanadium source and acidic substance are mixed and subjected to sol-gel treatment to obtain sol-gel product; S2. The sol product obtained in S1 is mixed with the first magnesium source and magnesium-aluminum matrix material to form a raw material colloid, dried, and calcined to obtain the sulfur transfer aid.

12. The preparation method according to claim 11, wherein, The cerium source includes one or more of cerium chloride, cerium nitrate, cerium dioxide, and compounds and / or mixtures of cerium and rare earth elements other than cerium.

13. The preparation method according to claim 11, wherein, The vanadium source includes ammonium metavanadate and / or vanadium oxide.

14. The preparation method according to claim 11, wherein, In S1, the temperature of the sol-gel treatment is 40-80℃, and the time of the sol-gel treatment is 0.5h-1h.

15. The preparation method according to claim 11, wherein, In S1, the mass of the first aluminum source is based on aluminum oxide, and the mass ratio of the acidic substance to the first aluminum source is 0.10-0.70:

1.

16. The application of the sulfur transfer aid according to any one of claims 1-10 in a catalytic cracking process.

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