Sulfur transfer auxiliary agent and preparation method and application thereof

Abstract

The invention provides a sulfur transfer additive as well as a preparation method and application thereof. The sulfur transfer aid comprises 30%-70% of magnesium oxide, 15%-60% of aluminum oxide, 10%-15% of cerium oxide and 2%-5% of vanadium pentoxide. The magnesium oxide is provided by the first magnesium source and the magnesium-aluminum matrix material, and the aluminum oxide is provided by the first aluminum source and the 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 additive; the magnesium-aluminum matrix material is obtained by mixing and crystallizing a second magnesium source and a second aluminum source subjected to peptizing treatment, and the magnesium-aluminum matrix material comprises magnesium oxide and aluminum oxide in a mass ratio of (0.2-0.8): 1. The invention also provides a preparation method of the sulfur transfer auxiliary agent and application of the sulfur transfer auxiliary agent in a catalytic cracking process. The sulfur transfer additive can efficiently desulfurize and is suitable for industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum catalytic cracking materials, and in particular to a sulfur transfer additive and a preparation method and application thereof. Background Art

[0002] Fluidized catalytic cracking (FCC) is the most important deep processing operation process for lightening heavy oil. Through catalytic cracking, many high-value products such as gasoline, diesel and liquefied petroleum gas can be obtained. Catalytic cracking catalyst is a porous microsphere composed of molecular sieve, active matrix, silicon-aluminum binder, etc. In the catalytic cracking process, the FCC catalyst repeatedly undergoes reaction, stripping and regeneration in the reactor and regenerator. In the FCC riser reactor, about 45%-55% of the sulfur contained in the crude oil is converted into H2S and discharged with the cracked gas, while 35%-45% remains in the liquid product, and 5%-10% of the sulfur is deposited on the coke of the catalyst to be regenerated. After entering the regenerator, the sulfur on the coke is oxidized to generate SO X Exhaust with regenerated flue gas.

[0003] The main methods for controlling sulfur emissions from FCC regeneration flue gas include crude oil pretreatment, flue gas scrubbing and desulfurization, and sulfur transfer technology. Due to source and cost constraints, refineries are not very selective for crude oil. Although crude oil catalytic hydrogenation and flue gas scrubbing and desulfurization are highly applicable and economical, and suitable for processing high-sulfur crude oil, they require increased equipment investment costs and high energy consumption. The addition of sulfur transfer agents can be easily achieved using existing equipment measures, without the need for additional equipment investment, and with low operating costs. Under current environmental protection requirements, when SO in catalytic cracking regeneration flue gas x Concentration below 1000mg / m 3 When the flue gas contains SO 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 device.

[0004] The working principle of sulfur transfer agent is to mechanically mix sulfur transfer agent with catalytic cracking catalyst and mix them together between the riser reactor and the regenerator. SO generated during regeneration of coke X It reacts with the sulfur transfer agent to promote the oxidation of SO2 to SO3, forming stable metal sulfates, which are circulated to the riser reactor together with the regenerated catalyst. In the reducing atmosphere of the reactor, the previously generated sulfates are reduced to H2S, and the sulfur transfer agent is regenerated and restored to the original metal oxide form, and then circulated to the regenerator for the next SO x Oxidation adsorption reaction. This part of H2S is transported to the sulfur recovery unit together with the H2S generated by the cracking reaction and converted into sulfur recovery through the Claus process.

[0005] In order 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, Ni, etc. or rare earth metals such as Ce and La are introduced into the catalyst, which greatly improves the adsorption rate, adsorption amount and reduction regeneration ability of the sulfur transfer agents.

[0006] CN103861436 discloses a mixed crystal phase catalytic cracking flue gas sulfur transfer agent and its preparation method and application. The composite structure is formed by using titanium magnesium structural material and magnesium aluminum spinel structural material, which greatly enhances the desulfurization effect and service life of the sulfur transfer agent and broadens the composition range of the sulfur transfer agent.

[0007] CN101905168A discloses a catalytic cracking propylene production enhancing agent with sulfur transfer agent function. The agent not only has the function of increasing propylene production, but also can simultaneously act as a sulfur transfer agent to remove SOx from flue gas. Since magnesium aluminum spinel is chemically inert, the active component of ZSM-5 can be added to the matrix, i.e., an agent with dual functions.

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

[0009] Currently, commercial sulfur transfer agents are usually magnesium-aluminum oxide complexes containing the metal elements vanadium and cerium, in which MgO is the active component that adsorbs SO2, forming stable MgSO4; CeO2 is a very efficient SO2 oxidation promoter, but it does not contribute to the reduction of MgSO4. V2O5 is a redox promoter, which firstly accelerates the oxidation rate of SO2 in the regenerator; secondly, it accelerates the rate of sulfate reduction to H2S in the reactor, so that the sulfur transfer agent can quickly recover its activity.

[0010] However, the existing sulfur transfer aids have the disadvantages of viscous preparation system, low colloid solid content, poor wear strength and unsatisfactory desulfurization effect. In view of the above disadvantages, it is necessary to provide a catalytic cracking regeneration flue gas sulfur transfer agent suitable for industrial production with high desulfurization efficiency, low price and simple preparation. Summary of the invention

[0011] In order to solve the above problems, the present invention aims to provide a sulfur transfer aid and its preparation method and application. The sulfur transfer aid has the characteristics of high desulfurization efficiency, low price and simple preparation, and is suitable for industrial production.

[0012] In order to achieve the above object, the present invention provides a sulfur transfer aid, which comprises, based on the total mass of the sulfur transfer aid being 100%, 30%-70% of magnesium oxide, 15%-60% of aluminum oxide, 10%-15% of cerium oxide, and 2%-5% of vanadium pentoxide;

[0013] 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 the magnesium-aluminum matrix material; the mass of the magnesium-aluminum matrix material on a dry basis is 5%-30% of the total mass of the raw materials of the sulfur transfer aid on a dry basis;

[0014] The magnesium-aluminum matrix material is obtained by mixing a second magnesium source with a second aluminum source after peptization treatment and then crystallizing the mixture. The magnesium-aluminum matrix material comprises 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 proportion of magnesium oxide in the sulfur transfer aid is generally 30%-70%, and can be specifically 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

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

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

[0018] According to a specific embodiment of the present invention, the mass proportion of the vanadium pentoxide in the sulfur transfer aid is generally 2%-5%, and can be specifically 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and the like, as well as 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 a magnesium salt and / or magnesium oxide.

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

[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, and the particle size D(0.9) 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 pseudo-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 material of the sulfur transfer aid, for example, 5%, 10%, 15%, 20%, 25%, 30% and other specific values, 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 0.2: 1, 0.3: 1, 0.4: 1, 0.5: 1, 0.6: 1, 0.7: 1, 0.8: 1 and other specific values, as well as 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 peptization treatment and then mixed with the second magnesium source; the second magnesium source can form a colloidal system after being mixed with the second aluminum source subjected to peptization treatment. Specifically, the method for preparing the magnesium-aluminum matrix material may include: mixing a slurry of the second aluminum source with an acidic substance for peptization treatment, then mixing the slurry of the second aluminum source after peptization treatment with the slurry of the second magnesium source to obtain a magnesium-aluminum colloidal slurry, and crystallizing to obtain the magnesium-aluminum matrix material.

[0026] In the above-mentioned method for preparing the magnesium-aluminum matrix material, the second aluminum source combines with hydrogen ions (from acidic substances) in the liquid environment and dissociates into smaller particles of microcrystalline aluminum source. The hydroxyl groups of the microcrystalline aluminum source 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 embodiments, the mixing time of the slurry of the second aluminum source after peptization treatment and the slurry of the second magnesium source can be controlled to be 0.5h-1h, and the mixing method can be slurry mixing.

[0028] In the above-mentioned method for preparing the magnesium-aluminum matrix material, the acidic substance may be an inorganic acid, specifically, may include one or a combination of two or more of hydrochloric acid, nitric acid, formic acid and acetic acid.

[0029] In the above-mentioned method for preparing the magnesium-aluminum matrix material, 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 usually controlled to be 0.10-0.5:1, for example, 0.10-0.25:1, and specifically 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 and other specific values, as well as a range with any two of the above-mentioned specific values ​​as endpoints.

[0030] In the preparation method of the above-mentioned magnesium-aluminum matrix material, 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 hydrochloric acid solution with a mass concentration of 35-38% to the mass ratio of the second aluminum source calculated as aluminum oxide; when the acidic substance includes nitric acid, the mass ratio of nitric acid to the second aluminum source is the mass ratio of a nitric acid solution with a mass concentration of 88% to the mass ratio of the second aluminum source calculated as aluminum oxide; when the acidic substance includes formic acid, the mass ratio of formic acid to the second aluminum source is the mass ratio of a formic acid solution with a mass concentration of 88% to the mass ratio of the second aluminum source calculated as aluminum oxide; when the acidic substance includes acetic acid, the mass ratio of acetic acid to the second aluminum source is the mass ratio of an acetic acid solution with a mass concentration of 99% to the mass ratio of the second aluminum source calculated as aluminum oxide.

[0031] In the preparation method of the above-mentioned magnesium-aluminum matrix material, the temperature of the peptization treatment is usually controlled to be 40-80°C, for example, specific values ​​such as 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, and a range with any two of the above-mentioned specific values ​​as endpoints.

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

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

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

[0035] In the above-mentioned method for preparing the magnesium-aluminum matrix material, the crystallization method may be static crystallization, dynamic crystallization or intermittent dynamic crystallization.

[0036] In the above-mentioned method for preparing the magnesium-aluminum matrix material, 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 in the present invention is the mass content of the solid) can be 0.15-0.25, for example, 0.15, 1.6, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25 and other specific values ​​and ranges with any two of the above specific values ​​as endpoints.

[0037] In the above-mentioned method for preparing the magnesium-aluminum matrix material, 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 0.2, 0.25, 0.3, 0.35, 0.4 and other specific values, and 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 material of the magnesium-aluminum matrix material may further include a surfactant, and the surfactant is added to the uncrystallized magnesium-aluminum colloidal slurry. That is, the method for preparing the magnesium-aluminum matrix material may include: mixing the slurry of the second aluminum source with an acidic substance for peptization treatment, then mixing the peptized second aluminum source slurry with the second magnesium source slurry 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 method for preparing the magnesium-aluminum matrix material, the surfactant may include hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium chloride.

[0040] In the preparation method of the above-mentioned magnesium-aluminum matrix material, 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 can be controlled to be 0.01-0.05:1, for example, it can be specific values ​​such as 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, and a range with any two of the above-mentioned specific values ​​as endpoints.

[0041] In the above-mentioned method for preparing the magnesium-aluminum matrix material, the dispersion effect of the magnesium-aluminum colloid can be improved by adding a surfactant. The surfactant can form micelles in the aqueous solution, reduce the interfacial tension between the two phases, and make the liquid and solid exist stably in the water, showing the effects of emulsification and dispersion, thereby effectively reducing the particle size of the magnesium-aluminum matrix material, avoiding adverse effects on its particle strength and wear strength in the subsequent preparation of the sulfur transfer additive.

[0042] The magnesium-aluminum matrix material provided by the present invention can replace part of the aluminum source and part of the magnesium source in the raw material of the sulfur transfer aid. By adopting the magnesium-aluminum matrix material, on the one hand, the structure of the sulfur transfer aid can be optimized, so that the sulfur transfer aid has a certain mesopore diameter, enriches the pore structure of the sulfur transfer aid, and further improves the adsorption-desorption effect of the sulfur transfer aid; on the other hand, the viscosity of the system of peptized alumina and magnesium-containing substances in the preparation process of the sulfur transfer aid can be reduced, the solid content of the raw material colloid can be increased, and the product performance and production efficiency can be improved.

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

[0044] S1, mixing a first aluminum source, a cerium source, a vanadium source and an acidic substance for peptization treatment to obtain a peptized product;

[0045] S2, mixing the peptized product obtained in S1 with the first magnesium source and the magnesium-aluminum matrix material to form a raw material colloid, drying, and roasting to obtain the sulfur transfer aid.

[0046] In the preparation method of the above sulfur transfer aid, 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 element other than cerium may specifically include elements other than cerium in the lanthanide series, such as lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. A combination of one or more of.

[0047] In the preparation method of the above sulfur transfer aid, the vanadium source may include ammonium metavanadate and / or vanadium oxide (VO x ).

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

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

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

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

[0052] In the preparation method of the above-mentioned sulfur transfer aid, in S1, the mass of the first aluminum source is calculated as 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 further can be 0.10-0.25:1; for example, the mass ratio of the acidic substance to the first aluminum source 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, 0.55:1, 0.60:1, 0.65:1, 0.66:1, 0.67:1, 0.68:1, 0.69:1, 0.70:1 and other specific values, as well as ranges with any two of the above specific values ​​as endpoints.

[0053] In the preparation method of the above 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 hydrochloric acid solution with a mass concentration of 35-38% to the first aluminum source calculated as aluminum oxide; when the acidic substance includes nitric acid, the mass ratio of nitric acid to the first aluminum source is the mass ratio of a nitric acid solution with a mass concentration of 88% to the first aluminum source calculated as aluminum oxide; when the acidic substance includes formic acid, the mass ratio of formic acid to the first aluminum source is the mass ratio of a formic acid solution with a mass concentration of 88% to the first aluminum source calculated as aluminum oxide; when the acidic substance includes acetic acid, the mass ratio of acetic acid to the first aluminum source is the mass ratio of an acetic acid solution with a mass concentration of 99% to the first aluminum source calculated as aluminum oxide.

[0054] In the above method for preparing the sulfur transfer aid, the peptized product obtained in S1 may be in a colloid form.

[0055] In the above method for preparing the sulfur transfer aid, in S2, the peptized product obtained in S1 and the first magnesium source and the magnesium-aluminum matrix material can be mixed for 0.5 h to 1 h, and the mixing method can be slurry mixing.

[0056] In the above-mentioned method for preparing the sulfur transfer aid, in S2, the drying is used to promote molding, and spray drying can be used. The spray drying process can adopt 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 preparation method of the above-mentioned sulfur transfer aid, in S2, the calcination temperature can be controlled to be 300-600°C, for example, it can be specific values ​​such as 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, and a range with any two of the above-mentioned specific values ​​as endpoints.

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

[0059] The present invention also provides the use of the above-mentioned sulfur transfer aid in a catalytic cracking process. 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 sulfur transfer aid raw material can be increased, thereby increasing the specific surface area and anti-wear ability of the sulfur transfer aid. The desulfurization performance and reduction performance of the sulfur transfer aid obtained in the catalytic cracking process are significantly improved. Specifically, the above-mentioned sulfur transfer aid can be applied to the flue gas regeneration process in the catalytic cracking process as a catalytic cracking regeneration flue gas sulfur transfer aid. The sulfur transfer aid can promote the conversion of sulfur oxides in flue gas regeneration into stable metal salts, and then successively 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 more than 89%, and the reduction rate can reach more than 91%.

[0060] The beneficial effects of the present invention are:

[0061] 1. The present invention introduces a magnesium-aluminum matrix material into the raw material of the sulfur transfer aid to replace part of the aluminum source and part of the magnesium source. On the one hand, it can reduce the viscosity of the raw material colloid in the preparation process of the sulfur transfer aid, increase the solid content of the raw material colloid, reduce production energy consumption, and improve the 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 additive structure, and improve the sulfur transfer aid to SO x (Sulfur oxides) adsorption and desorption effect.

[0062] 2. The sulfur transfer additive provided by the present invention has strong anti-wear ability, high reaction activity, high desulfurization efficiency, simple preparation method, low cost, and is suitable for industrial production. DETAILED DESCRIPTION

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

[0064] In the following examples and comparative examples, the element contents in the samples were 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, hexadecyltrimethylammonium chloride, etc. are commercially available reagents of analytical grade;

[0067] Pseudo-boehmite (alumina mass content is 62%): industrial product, Shanxi Aluminum Plant.

[0068] Example 1

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

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

[0071] (2) Preparation of sulfur transfer aid: 161 g of pseudo-boehmite, 50 g of cerium nitrate and 5 g of ammonium metavanadate are added to 263 g of deionized water, and 10 g of hydrochloric acid with a mass concentration of 36%-38% is added under continuous stirring, and the temperature is raised to 40°C and maintained for 30 minutes for peptization treatment; 56 g of magnesium oxide is added to 168 g of deionized water, and the mixture is mixed evenly and then added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 67 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 10% of the total dry basis mass of the raw material of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 300°C for 6 hours to obtain a sulfur transfer aid.

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

[0073] The sulfur transfer agent sample is denoted as S1. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0074] Example 2

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

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

[0077] (2) Preparation of sulfur transfer aid: 98 g of pseudo-boehmite, 61 g of cerium nitrate and 6 g of ammonium metavanadate are added to 179 g of deionized water, and 10 g of nitric acid with a mass concentration of 65%-68% is added under continuous stirring, and the temperature is raised to 50°C and maintained for 60 minutes for peptization treatment; 80 g of magnesium oxide is added to 240 g of deionized water, mixed evenly, and then added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 100 g of the magnesium aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium aluminum matrix material is 15% of the total dry basis mass of the raw material of the additive), and the raw material colloid is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray dried to obtain particles with an average particle size of 90-100 μm, and cured and calcined at 350°C for 2 hours to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 44.5wt% of magnesium oxide, 41wt% of aluminum oxide, 12wt% of cerium dioxide, and 2.5wt% of vanadium pentoxide.

[0078] The sulfur transfer agent sample is recorded as S2. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0079] Example 3

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

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

[0082] (2) Preparation of sulfur transfer aid: Take 48 grams of pseudo-boehmite, 76 grams of cerium nitrate and 13 grams of ammonium metavanadate, add 119 grams of deionized water, add 20 grams of formic acid with a mass concentration of 88% under continuous stirring, and heat to 60°C for 60 minutes for peptization treatment; Take 100 grams of magnesium oxide, add 300 grams of deionized water, mix well, and add to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then add 100 grams of magnesium aluminum matrix material slurry prepared in step (1) (the mass of magnesium aluminum matrix material is 15% of the total mass of the raw material of the additive on a dry basis), mix and stir well to form a 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°C for 1 hour to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 57.5wt% of magnesium oxide, 22.5wt% of aluminum oxide, 15wt% of cerium dioxide, and 5wt% of vanadium pentoxide.

[0083] The sulfur transfer agent sample is recorded as S3. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0084] Example 4

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

[0086] (1) Preparation of magnesium-aluminum matrix material: 161 grams of pseudo-boehmite was added to 239 grams of deionized water, and 15 grams of nitric acid with a mass concentration of 65%-68% was added under continuous stirring, and the temperature was raised to 60°C and maintained for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; 80 grams of magnesium oxide was added to 187 grams of deionized water, and the mixture was added to the peptized pseudo-boehmite slurry, and then 9 grams of hexadecyltrimethylammonium chloride was added, and the mixture was beaten and stirred for 60 minutes to obtain magnesium-aluminum colloidal slurry; the magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction, and the reaction was carried out at 90°C for 24 hours to obtain a magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in the material is 0.8:1.

[0087] (2) Preparation of sulfur transfer aid: 45 g of pseudo-boehmite, 54 g of cerium chloride and 8 g of ammonium metavanadate are added to 160 g of deionized water, and 10 g of formic acid with a mass concentration of 88% is added under continuous stirring, and the temperature is raised to 70°C and maintained for 60 minutes for peptization treatment; 100 g of magnesium oxide is added to 300 g of deionized water, and the mixture is mixed and added to the pseudo-boehmite slurry after the peptization treatment, and then 133 g of the magnesium aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium aluminum matrix material is 20% of the total dry basis mass of the raw material of the additive), and the mixture is mixed and stirred to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 500°C for 30 minutes to obtain a sulfur transfer aid. The mass percentage of each component in the sulfur transfer aid is: 66 wt% of magnesium oxide, 18 wt% of aluminum oxide, 13 wt% of cerium dioxide, and 3 wt% of vanadium pentoxide.

[0088] The sulfur transfer agent sample is recorded as S4. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0089] Example 5

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

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

[0092] (2) Preparation of sulfur transfer aid: 39 g of pseudo-boehmite, 54 g of cerium chloride and 8 g of ammonium metavanadate are added to 190 g of deionized water, and 5 g of hydrochloric acid with a mass concentration of 36%-38% is added under continuous stirring, and the temperature is raised to 80°C and maintained for 60 minutes for peptization treatment; 124 g of magnesium oxide is added to 186 g of deionized water, and the mixture is mixed evenly and then added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 67 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 10% of the total dry basis mass of the raw materials of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 600°C for 30 minutes to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 68wt% of magnesium oxide, 16wt% of aluminum oxide, 13wt% of cerium dioxide, and 3wt% of vanadium pentoxide.

[0093] The sulfur transfer agent sample is recorded as S5. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0094] Example 6

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

[0096] (1) Preparation of magnesium-aluminum matrix material: 161 grams of pseudo-boehmite was taken, 339 grams of deionized water was added, 25 grams of hydrochloric acid with a mass concentration of 36%-38% was added under continuous stirring, and the temperature was raised to 80°C and maintained for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; 50 grams of magnesium oxide was taken, 120 grams of deionized water was added, and the mixture was evenly mixed and added to the peptized pseudo-boehmite slurry, and 6 grams of hexadecyltrimethylammonium chloride was added, and the mixture was beaten and stirred for 60 minutes to obtain magnesium-aluminum colloidal slurry; the magnesium-aluminum colloidal slurry was transferred to a crystallization reactor for crystallization reaction, and the reaction was carried out at 95°C for 48 hours to obtain a magnesium-aluminum matrix material. The mass ratio of magnesium oxide to aluminum oxide in the material is 0.5:1.

[0097] (2) Preparation of sulfur transfer aid: 152 g of pseudo-boehmite, 41 g of cerium chloride and 8 g of ammonium metavanadate are added to 249 g of deionized water, and 10 g of hydrochloric acid with a mass concentration of 36%-38% is added under continuous stirring, and the temperature is raised to 80°C and maintained for 60 minutes for peptization treatment; 60 g of magnesium oxide is added to 90 g of deionized water, mixed evenly, and then added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 67 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 10% of the total dry basis mass of the raw material of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and cured and calcined at 350°C for 60 minutes to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 35wt% of magnesium oxide, 52wt% of aluminum oxide, 10wt% of cerium dioxide, and 3wt% of vanadium pentoxide.

[0098] The sulfur transfer agent sample is recorded as S6. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0099] Example 7

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

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

[0102] (2) Preparation of sulfur transfer aid: 71 g of pseudo-boehmite, 41 g of cerium chloride and 8 g of ammonium metavanadate are added to 190 g of deionized water, and 5 g of formic acid with a mass concentration of 88% is added under continuous stirring, and the temperature is raised to 60° C. and maintained for 60 minutes for peptization treatment; 100 g of magnesium oxide is added to 150 g of deionized water, and the mixture is mixed evenly and added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 100 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 15% of the total dry basis mass of the raw material of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 400° C. for 30 minutes to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 59wt% of magnesium oxide, 28wt% of aluminum oxide, 10wt% of cerium dioxide, and 3wt% of vanadium pentoxide.

[0103] The sulfur transfer agent sample is recorded as S7. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0104] Example 8

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

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

[0107] (2) Preparation of sulfur transfer aid: 53 g of pseudo-boehmite, 50 g of cerium chloride and 6 g of ammonium metavanadate are added to 190 g of deionized water, and 6 g of nitric acid with a mass concentration of 88% is added under continuous stirring, and the temperature is raised to 70°C and maintained for 60 minutes for peptization treatment; 108 g of magnesium oxide is added to 162 g of deionized water, and the mixture is mixed evenly and added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 100 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 15% of the total dry basis mass of the raw material of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 400°C for 30 minutes to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 63wt% of magnesium oxide, 22.5wt% of aluminum oxide, 12wt% of cerium dioxide, and 2.5wt% of vanadium pentoxide.

[0108] The sulfur transfer agent sample is recorded as S8. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0109] Comparative Example 1

[0110] This comparative example provides a sulfur transfer aid, and the preparation method is as follows:

[0111] Preparation of sulfur transfer aid: 73 grams of pseudo-boehmite, 50 grams of cerium chloride and 6 grams of ammonium metavanadate are taken, 200 grams of deionized water are added, 6 grams of nitric acid with a mass concentration of 88% is added under continuous stirring, and the temperature is raised to 70°C and maintained for 60 minutes for peptization treatment; 126 grams of magnesium oxide is taken, 155 grams of deionized water are added, and after mixing evenly, the mixture is added to the pseudo-boehmite slurry after the peptization treatment, and mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 400°C for 30 minutes to obtain a sulfur transfer aid. The mass percentage of each component in the sulfur transfer aid is: 63wt% of magnesium oxide, 22.5wt% of aluminum oxide, 12wt% of cerium dioxide, and 2.5wt% of vanadium pentoxide.

[0112] The sulfur transfer aid sample is recorded as D1. The sample physical and chemical properties are shown in Table 1, and the reaction performance is shown in Table 2. Compared with the preparation method of the above embodiment, this comparative example does not add magnesium aluminum matrix material during the preparation of the sulfur transfer aid.

[0113] Comparative Example 2

[0114] This comparative example provides a sulfur transfer aid, and the preparation method is as follows:

[0115] (1) Preparation of magnesium-aluminum matrix material: 161 grams of pseudo-boehmite is added to 339 grams of deionized water, and 15 grams of hydrochloric acid with a mass concentration of 36%-38% is added under continuous stirring, and the temperature is raised to 50°C and maintained for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; 30 grams of magnesium oxide is added to 45 grams of deionized water, and the mixture is mixed evenly and added to the peptized pseudo-boehmite slurry, and then 2.6 grams of hexadecyltrimethylammonium bromide is added, and the mixture is beaten and stirred for 30 minutes to obtain magnesium-aluminum colloidal slurry for standby use. The mass ratio of magnesium oxide to aluminum oxide in the material is 0.3:1.

[0116] (2) Preparation of sulfur transfer aid: 98 g of pseudo-boehmite, 61 g of cerium nitrate and 6 g of ammonium metavanadate are added to 179 g of deionized water, and 10 g of nitric acid with a mass concentration of 65%-68% is added under continuous stirring, and the temperature is raised to 50°C and maintained for 60 minutes for peptization treatment; 80 g of magnesium oxide is added to 240 g of deionized water, and the mixture is mixed evenly and added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 100 g of magnesium aluminum colloidal slurry prepared in step (1) is added (the dry basis mass of magnesium aluminum colloidal slurry is 15% of the total dry basis mass of the raw materials of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 350°C for 2 hours to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 44.5wt% of magnesium oxide, 41wt% of aluminum oxide, 12wt% of cerium dioxide, and 2.5wt% of vanadium pentoxide.

[0117] The sulfur transfer aid sample is recorded as D2. The sample physical and chemical properties are shown in Table 1, and the reaction performance is shown in Table 2. Compared with the preparation method of the above embodiment, in the process of preparing the sulfur transfer aid, the present comparative example uses non-crystallized magnesium aluminum colloidal slurry instead of magnesium aluminum matrix material as the aid raw material.

[0118] Comparative Example 3

[0119] This comparative example provides a sulfur transfer aid, and the preparation method is as follows:

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

[0121] (2) Preparation of sulfur transfer aid: 39 g of pseudo-boehmite, 54 g of cerium chloride and 8 g of ammonium metavanadate are added to 190 g of deionized water, and 5 g of hydrochloric acid with a mass concentration of 36%-38% is added under continuous stirring, and the temperature is raised to 80°C and maintained for 60 minutes for peptization treatment; 124 g of magnesium oxide is added to 186 g of deionized water, and the mixture is mixed evenly and then added to the mixed slurry containing pseudo-boehmite, cerium source and vanadium source after the peptization treatment, and then 67 g of the magnesium-aluminum matrix material slurry prepared in step (1) is added (the dry basis mass of the magnesium-aluminum matrix material is 10% of the total dry basis mass of the raw materials of the additive), and the mixture is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried to obtain particles with an average particle size of 90-100 μm, and the particles are cured and calcined at 600°C for 30 minutes to obtain a sulfur transfer aid. The mass percentages of the components in the sulfur transfer aid are: 68wt% of magnesium oxide, 16wt% of aluminum oxide, 13wt% of cerium dioxide, and 3wt% of vanadium pentoxide.

[0122] The sulfur transfer aid sample is recorded as D3. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2. Compared with the preparation method of the magnesium-aluminum matrix material of the present invention, this comparative example shortens the crystallization time in the preparation process of the magnesium-aluminum matrix material.

[0123] Test Example 1

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

[0125] Table 1

[0126]

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

[0128] Nitrogen is used as a protective gas and a diluent, and then mixed with the reaction gas and enters the reactor together. The reaction is carried out in a fixed bed. After cooling, the product directly enters the flue gas analyzer and H2S detector to analyze the content of each component.

[0129] The steps are as follows:

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

[0131] 2) Open the gas circuit and circuit, check the air tightness of the device, and set the parameters;

[0132] 3) Use N2 as the protective gas and raise the temperature. When the temperature reaches the set value (700℃), keep the temperature constant for 10 minutes, change the gas to a mixed gas (SO2 400ppm, 10% O2, N2), turn on the flue gas analyzer, and collect reaction data. When the reaction is completed, turn off the mixed gas, turn on N2, cool down to the set value (500℃), keep the temperature constant for 10 minutes, change the gas to a mixed gas (H2, N2), turn on the H2S detector, and collect reaction data. When the reaction is completed, switch the gas to N2 and cool to room temperature.

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

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

[0135]

[0136] As can be seen from Table 1 and Table 2, the present invention can increase the solid content of the colloidal system formed by the sulfur transfer aid raw material by adding the magnesium aluminum matrix material during the preparation process of the sulfur transfer aid and controlling the preparation conditions of the magnesium aluminum matrix material, thereby increasing the specific surface area and anti-wear ability of the sulfur transfer aid. The desulfurization performance and reduction performance of the sulfur transfer aid obtained in the catalytic cracking process are significantly improved.

Claims

1. A sulfur transfer aid, based on the total mass of the sulfur transfer aid being 100%, the sulfur transfer aid comprises: Magnesium oxide 30%-70%, aluminum oxide 15%-60%, 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 aluminum oxide is provided by a first aluminum source and the magnesium-aluminum matrix material; the mass of the magnesium-aluminum matrix material on a dry basis is 5%-30% of the total mass of the raw materials of the sulfur transfer aid on a dry basis; The magnesium-aluminum matrix material is obtained by mixing a second magnesium source with a second aluminum source after peptization treatment and then crystallizing the mixture. The magnesium-aluminum matrix material comprises 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 comprises magnesium salt and / or magnesium oxide; The first aluminum source includes pseudo-boehmite.

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

4. The sulfur transfer aid according to claim 1, wherein The preparation method of the magnesium-aluminum matrix material comprises: mixing a slurry of a second aluminum source with an acidic substance for peptization treatment, then mixing the peptized second aluminum source slurry with a second magnesium source slurry to obtain a magnesium-aluminum colloidal slurry, and crystallizing to obtain the magnesium-aluminum matrix material; Preferably, the mass of the second aluminum source is calculated as aluminum oxide, and the mass ratio of the acidic substance to the second aluminum source is 0.10-0.5:1; Preferably, the temperature of the peptization treatment is 40-80°C, and the time of the peptization treatment is more than 1 hour; Preferably, the crystallization temperature is 50-95° C., and the crystallization time is 10-72 h.

5. The sulfur transfer aid according to claim 4, wherein The raw material of the magnesium-aluminum matrix material also includes a surfactant, which is added to the uncrystallized magnesium-aluminum colloidal slurry; Preferably, the surfactant comprises cetyltrimethylammonium bromide and / or cetyltrimethylammonium chloride; Preferably, 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.

6. A method for preparing the sulfur transfer aid according to any one of claims 1 to 5, comprising: S1, mixing a first aluminum source, a cerium source, a vanadium source and an acidic substance for peptization treatment to obtain a peptized product; S2, mixing the peptized product obtained in S1 with the first magnesium source and the magnesium-aluminum matrix material to form a raw material colloid, drying, and roasting to obtain the sulfur transfer aid.

7. The preparation method according to claim 6, wherein: The cerium source includes one or a combination of two or more of cerium chloride, cerium nitrate, cerium dioxide, a compound and / or a mixture of cerium and a rare earth element other than cerium.

8. The preparation method according to claim 6, wherein: The vanadium source includes ammonium metavanadate and / or vanadium oxide.

9. The preparation method according to claim 6, wherein: In S1, the temperature of the peptization treatment is 40-80°C, and the time of the peptization treatment is 0.5h-1h.

10. The preparation method according to claim 6, wherein: In S1, the mass of the first aluminum source is calculated as aluminum oxide, and the mass ratio of the acidic substance to the first aluminum source is 0.10-0.70:

1.

11. Use of the sulfur transfer aid according to any one of claims 1 to 5 in a catalytic cracking process.

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