Desulfurization, denitration and combustion-supporting triple-effect additive as well as preparation method and application thereof

Abstract

The invention provides a desulfurization, denitrification and combustion-supporting triple-effect additive as well as a preparation method and application thereof. The triple-effect additive comprises 30%-60% of magnesium oxide, 20%-50% of aluminum oxide, 8%-15% of cerium oxide, 2%-5% of vanadium pentoxide, 2%-10% of modified metal components in terms of oxide and 0.01%-0.1% of noble metal elements in terms of elementary substances. 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; the mass of the magnesium-aluminum matrix material is 5-30% of the total mass of the raw materials of the triple-effect additive; the magnesium-aluminum matrix material is obtained by mixing and crystallizing a second aluminum source and a second magnesium source which are 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 and application of the triple-effect auxiliary agent. The triple-effect auxiliary agent has catalytic cracking flue gas sulfur transfer, denitration and CO combustion-supporting effects.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum catalytic cracking materials, and in particular to a desulfurization, denitration and combustion-supporting triple-effect additive and a preparation method and application thereof. Background Art

[0002] In the crude oil processing process, catalytic cracking is the most important secondary processing technology currently used by refineries in my country, and it is also the core production unit of gasoline and diesel fractions. The atmospheric pollutants of the catalytic cracking unit mainly include SOx, NOx, CO and particulate matter, which mainly come from the flue gas generated when the regenerator is burned. Some nitrogen-containing compounds and sulfur-containing compounds in the catalytic cracking feedstock oil are converted into NOx and SOx during the production process, and finally discharged into the atmosphere with the regenerated flue gas, causing environmental pollution. During the catalytic cracking reaction, about 6% of the raw materials are converted into coke and deposited on the catalyst, making the catalyst inactive. In order to maintain or restore the activity of the catalyst, it is necessary to remove the carbon deposits on the catalyst. CO combustion improver plays a role in accelerating CO oxidation during the regeneration process of FCC catalyst. Adding CO combustion improver in the regenerator accelerates CO oxidation and reduces the CO content in the regenerated flue gas, which not only removes the carbon deposited on the catalyst, but also improves the activity and selectivity of the catalyst, thereby increasing the yield of light oil, eliminating the pollution of CO to the environment, and recovering heat, so that good economic benefits can be generated.

[0003] In terms of pollutant control in catalytic cracking units, CO emissions can be controlled below 0.05% by adding CO combustion aids and using CO incinerators; particulate matter emissions have been effectively controlled by improving the design of the regenerator cyclone separator and the three- and four-cyclone, using catalysts with high anti-wear indexes, and adding electrostatic dust removal and other technical means, but SOx and NOx emissions still cannot meet the requirements of existing environmental protection indicators. However, as the degree of crude oil deterioration increases and the processing ratio of sulfur-containing / high-sulfur crude oil increases, it is bound to cause an increase in SOx and NOx emissions from catalytic cracking units. Under the current environmental protection requirements, its emissions are strictly controlled, so the application of flue gas desulfurization and denitrification technology has become a general trend. The method of adding sulfur and nitrogen emission reduction aids and CO combustion aids in the catalytic cracking unit can achieve the goal of reducing SOx, NOx and CO emissions in catalytic cracking flue gas without stopping the operation or making changes.

[0004] In the catalytic cracking regenerator, in order to make CO burn efficiently and convert it into CO2, the FCC regenerator usually requires secondary combustion, but these additives will cause NO XThe emission volume has increased significantly. Therefore, CO combustion aids must usually be used in combination with denitrifiers, or additives that have both the effects of reducing NOx and CO combustion aids must be used. In terms of catalytic cracking flue gas desulfurization and denitrification and other multifunctional aspects, CN111420687A discloses a FCC regenerated flue gas NOx reduction and sulfur transfer dual-functional additive and a preparation method thereof. The additive uses a catalytic cracking balance agent modified with MgF2 as a carrier, and loads Pb, Sr and a Group VIII metal by an in-situ isomerization impregnation method. CN110787834A discloses a catalytic cracking flue gas desulfurization and denitrification additive and a preparation method thereof, which is mainly prepared by impregnation, pulping, spray drying and roasting with carriers such as alumina, matrices such as kaolin, active components such as alkali metals and rare earths, binders, etc. CN106345488A discloses a copper-manganese-cerium composite oxide FCC regeneration flue gas combustion-supporting denitrification agent and its preparation method, which uses alumina as a carrier, and uses the coexisting copper-manganese-cerium composite oxide as an active component, the active component is loaded on the carrier, and then through thermal decomposition and high-temperature activation, an agent with dual functions of supporting CO combustion and reducing NOx emissions is obtained. CN102962061A discloses a multifunctional catalyst for removing NOx and SOx from catalytic cracking regeneration flue gas and its preparation, the catalyst is made by impregnating the carrier microsphere alumina with rare earth desulfurization impregnation liquid, rare earth denitrification impregnation liquid, and precious metal salt, drying, baking, and roasting. CN1480246 discloses a sulfur transfer denitrification combustion-supporting three-effect agent and its preparation method and use, the three-effect agent includes an adsorbent of a spinel composite oxide, cerium dioxide and vanadium pentoxide as oxidation catalysts, and cerium fluoride as a structural additive, and the oxidation catalyst and the structural additive are dispersed in the adsorbent. Most catalytic cracking units use flue gas sulfur transfer additives, denitrification agents and CO combustion aids. Many of these units use two or even three of these functional additives at the same time. Since these additives have single functions and complicated addition processes, the use of certain functional additives is restricted when emissions meet standards, resulting in waste of resources and environmental pollution. Summary of the invention

[0005] In order to solve the above problems, the purpose of the present invention is to provide a desulfurization, denitration and combustion-supporting three-effect additive and its preparation method and application. The additive has the functions of sulfur transfer, denitration and CO combustion-supporting in catalytic cracking flue gas.

[0006] In order to achieve the above object, the present invention provides a desulfurization and denitration combustion-supporting triple-effect additive, which comprises, based on the total mass of the triple-effect additive being 100%, 30%-60% of magnesium oxide, 20%-50% of aluminum oxide, 8%-15% of cerium oxide, 2%-5% of vanadium pentoxide, 2%-10% of modified metal components calculated as oxides, and 0.01%-0.1% of precious metal elements calculated as single substances;

[0007] 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 triple-effect additive on a dry basis;

[0008] 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.

[0009] According to a specific embodiment of the present invention, the mass proportion of magnesium oxide in the triple-effect additive is generally 30%-60%, and can be specifically 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.

[0010] According to a specific embodiment of the present invention, the mass proportion of alumina in the triple-effect additive is generally 20%-50%, and can be specifically 20%, 25%, 30%, 35%, 40%, 45%, 50% and the like, as well as a range with any two of the above specific values ​​as endpoints.

[0011] According to a specific embodiment of the present invention, the mass proportion of cerium oxide in the triple-effect additive is generally 8%-15%, and specifically can be 8%, 9%, 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.

[0012] According to a specific embodiment of the present invention, the mass proportion of the vanadium pentoxide in the triple-effect additive is generally 2%-5%, and can be specifically 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0013] According to a specific embodiment of the present invention, the mass proportion of the modified metal component in the triple-effect additive calculated as oxide is generally 2%-10%, for example, it can be 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0014] According to a specific embodiment of the present invention, the mass proportion of the precious metal element in the triple-effect additive as a single substance is generally 0.01%-0.1%, for example, it can be 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10% and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0015] According to a specific embodiment of the present invention, the first magnesium source may include a magnesium salt and / or magnesium oxide.

[0016] According to a specific embodiment of the present invention, the first aluminum source may be pseudo-boehmite.

[0017] According to a specific embodiment of the present invention, the metal element in the modified metal component can be selected from non-rare earth metal elements in the following groups: one or a combination of two or more of group IB, group IIB, group IIIB, group IVB, group VB, group VIB, group VIIB. Further, the metal element in the modified metal component can include one or a combination of two or more of Cu, Zn, Ti, Zr, W, and Mn, for example, Ti and / or W.

[0018] According to a specific embodiment of the present invention, the noble metal element may include Pd and / or Pt, etc.

[0019] 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 desulfurization, denitration, and combustion-supporting triple-effect additive, the wear strength of the desulfurization, denitration, and combustion-supporting triple-effect additive can be improved.

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

[0021] According to a specific embodiment of the present invention, the mass of the magnesium-aluminum matrix material on a dry basis is generally 5%-30% of the total mass of the raw materials of the triple-effect additive on a dry basis, for example, 5%, 10%, 15%, 20%, 25%, 30% and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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 0.05-0.5:1, and can further be 0.05-0.25:1, for example, 0.05:1, 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] In the preparation method of the above-mentioned magnesium-aluminum matrix material, the crystallization time is 10-72h, for example 10h-24h, and specifically can be 10h, 15h, 20h, 24h, 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] In the above method for preparing the magnesium-aluminum matrix material, the surfactant may include hexadecyltrimethylammonium bromide and / or hexadecyltrimethylammonium chloride.

[0038] 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.

[0039] 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 particle strength and wear strength in the subsequent preparation of the desulfurization, denitration and combustion-supporting triple-effect additive.

[0040] The above-mentioned 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 materials of the desulfurization, denitration and combustion-supporting triple-effect additive. By adopting the magnesium-aluminum matrix material, on the one hand, the structural optimization of the desulfurization, denitration and combustion-supporting triple-effect additive can be achieved, the pore structure of the desulfurization, denitration and combustion-supporting triple-effect additive can be enriched, and the adsorption-desorption sulfur effect of the desulfurization, denitration and combustion-supporting triple-effect additive can be further improved; on the other hand, the viscosity of the system of peptized alumina and magnesium-containing substances in the preparation process of the desulfurization, denitration and combustion-supporting triple-effect additive can be reduced, the solid content of the raw material colloid can be increased, and the product performance and production efficiency can be improved.

[0041] The present invention also provides a method for preparing the above-mentioned desulfurization, denitration and combustion-supporting triple-effect additive, which comprises:

[0042] S1, mixing a first aluminum source, a cerium source, a modified metal source, a vanadium source and an acidic substance for peptization treatment to obtain a peptized product;

[0043] 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 calcining to obtain a combined carrier;

[0044] S3, immersing the combined carrier in a solution of a noble metal source, washing with alkali, and drying to obtain the triple-effect auxiliary agent.

[0045] In the preparation method of the above-mentioned desulfurization and denitration combustion-supporting triple-effect additive, the cerium source may include one or more combinations 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 lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0046] In the preparation method of the above-mentioned desulfurization and denitration combustion-supporting triple-effect additive, the vanadium source may include ammonium metavanadate and / or vanadium oxide (VO x ).

[0047] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, the modified metal source is used to provide the metal element in the modified metal component, and the modified metal source may include a soluble salt of the metal element in the modified metal component, such as chloride salts.

[0048] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, the noble metal source is used to provide noble metal elements, and the noble metal source can be a soluble salt of the noble metal element (Pd, Pt), such as chloride salt.

[0049] 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. No additional binder needs to be added during the preparation process, and the raw material composition is simple and the cost is low.

[0050] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, 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.

[0051] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, 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.

[0052] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, the acidic substance used in S1 can be an inorganic acid, specifically, can include one or a combination of two or more of hydrochloric acid, nitric acid, formic acid and acetic acid.

[0053] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, 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 0.10-0.60:1, and can further be 0.10-0.40:1; 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, 0.56:1, 0.57:1, 0.58:1, 0.59:1, 0.60:1 and other specific values, as well as ranges with any two of the above specific values ​​as endpoints.

[0054] In the preparation method of the above-mentioned desulfurization and denitration combustion-supporting triple-effect additive, 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.

[0055] In the above-mentioned method for preparing the desulfurization, denitration and combustion-supporting triple-effect additive, the peptized product obtained in S1 may be in the form of a colloid.

[0056] In the preparation method of the above-mentioned desulfurization, denitration and combustion-supporting triple-effect additive, in S2, the mixing time of the peptized product obtained in S1 with the first magnesium source and the magnesium-aluminum matrix material can be 0.5h-1h. The mixing method can be beating mixing.

[0057] In the preparation method of the above-mentioned desulfurization and denitration combustion-supporting triple-effect additive, 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 field. The combined carrier obtained after spray drying can be in the form of microspheres, and the average particle size of the microspheres can be 70-120 microns.

[0058] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, in S2, the roasting temperature can be controlled to be 300-500°C, for example, it can be specific values ​​such as 300°C, 350°C, 400°C, 450°C, 500°C, and a range with any two of the above-mentioned specific values ​​as endpoints.

[0059] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, in S2, the roasting time can be controlled to be 0.5h-2h, for example, it can be specific values ​​such as 0.5h, 1.0h, 1.5h, 2.0h, and a range with any two of the above-mentioned specific values ​​as endpoints.

[0060] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple agent, in S3, the volume of the solution of the precious metal source is generally 1.5-5 times the total volume of the combined carrier, for example, it can be 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0061] In the preparation method of the above-mentioned desulfurization and denitration combustion-supporting triple-effect additive, in S3, the impregnation process can load the soluble precious metal salt solution into the combined carrier obtained in S2. The impregnation method can be excessive impregnation. In some specific embodiments, the impregnation time is generally 10-60min, for example, it can be 10min, 20min, 30min, 40min, 50min, 60min and other specific values ​​and a range with any two of the above specific values ​​as endpoints. There is no special requirement for the impregnation temperature, which can be room temperature.

[0062] In the preparation method of the above-mentioned desulfurization, denitrification and combustion-supporting triple-effect additive, in S3, the alkaline washing process may include rinsing the combined carrier impregnated with the precious metal source with an alkaline solution, or slurrying and contacting the combined carrier impregnated with the precious metal source in an alkaline solution.

[0063] In some specific embodiments, the alkaline solution may include a solution of alkaline ammonium salt, such as ammonia water, ammonium carbonate, ammonium bicarbonate, or a combination of two or more thereof.

[0064] In some specific embodiments, the concentration of the alkaline solution can be 0.5mol / L-3mol / L, for example, it can be 0.5mol / L, 1.0mol / L, 1.5mol / L, 2.0mol / L, 2.5mol / L, 3.0mol / L, 3.5mol / L, 4.0mol / L, 4.5mol / L, 5.0mol / L and other specific values, and a range with any two of the above specific values ​​as endpoints.

[0065] In some specific embodiments, the volume of the alkaline solution can be 1.5-5 times the volume of the combined support impregnated with the precious metal source, for example, it can be 1.5 times, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, and other specific values, as well as a range with any two of the above specific values ​​as endpoints.

[0066] In some specific embodiments, the alkali washing time (the contact time between the alkaline solution and the composite support impregnated with the noble metal source) can be 10-60 min, for example, it can be 10 min, 20 min, 30 min, 40 min, 50 min, 60 min, etc., and a range with any two of the above specific values ​​as endpoints. There is no special requirement for the impregnation temperature, which can be room temperature. There is no special requirement for the alkali washing temperature, which can be room temperature.

[0067] In some specific embodiments, the alkali-washed combined carrier can be filtered, dried and / or calcined to form the desulfurization, denitrification and combustion-supporting triple-effect additive.

[0068] The present invention also provides the application of the above-mentioned desulfurization, denitration and combustion-supporting triple-effect additive in the catalytic cracking process. The desulfurization, denitration and combustion-supporting triple-effect additive can significantly reduce the NOx and Sox content in the catalytic cracking regeneration flue gas, and has the function of CO combustion-supporting, effectively avoiding tail combustion caused by excessive CO concentration in the regeneration flue gas; at the same time, the desulfurization, denitration and combustion-supporting triple-effect additive has no adverse effect on the distribution of FCC products, has a simple preparation process, and is convenient for industrial application.

[0069] The beneficial effects of the present invention include:

[0070] 1. The desulfurization and denitrification combustion-supporting triple-effect additive provided by the present invention is a kind of precious metal-containing, which can reduce the SO x and NO x Compared with the existing desulfurization, denitrification and combustion-supporting additives, the three-effect additive of the present invention has better performance in reducing SO in catalytic cracking regeneration flue gas. x 、NO x The three-effect additive has no adverse effect on the distribution of FCC products, and has simple preparation process, low cost and convenient industrial application.

[0071] 2. The present invention introduces magnesium-aluminum matrix materials into the raw materials of the desulfurization, denitration and combustion-supporting triple-effect additive 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 desulfurization, denitration and combustion-supporting triple-effect additive, 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 desulfurization, denitration and combustion-supporting triple-effect additive, enrich the pore structure in the additive, optimize the additive structure, and improve the desulfurization, denitration and combustion-supporting triple-effect additive to SO x The adsorption and desorption effects of NO x desorption effect and combustion-supporting effect on CO. DETAILED DESCRIPTION

[0072] 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.

[0073] In the following preparation examples, embodiments and comparative examples, the element contents in the samples were determined by X-ray fluorescence analysis.

[0074] The preparation examples of the present invention are used to illustrate the magnesium-aluminum matrix material and the preparation method thereof used in the present invention. The origin and specifications of the raw materials used in the preparation examples are as follows:

[0075] Pseudo-boehmite (alumina mass content is 62%): industrial product, Shanxi Aluminum Plant.

[0076] Hydrochloric acid, nitric acid, magnesium oxide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, etc. are commercially available reagents and are of analytical grade.

[0077] The examples of the present invention are used to illustrate the desulfurization, denitration, combustion-supporting triple-effect additive and its preparation method in the present invention. The origin and specifications of the raw materials used in the examples and comparative examples are as follows:

[0078] Pseudo-boehmite (alumina content is 62%): industrial product, Shanxi Aluminum Plant.

[0079] Magnesium oxide: industrial product, MgO content not less than 98%, Hebei Meishen Technology Co., Ltd.

[0080] Hydrochloric acid, nitric acid, formic acid, cerium nitrate, ammonium metavanadate, titanium chloride, tungsten hexachloride, platinum chloride, etc. are commercially available reagents and are of analytical grade.

[0081] Preparation Example 1

[0082] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0083] Take 161 grams of pseudo-boehmite, add 505 grams of deionized water, add 10 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 40°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 20 grams of magnesium oxide, add 50 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 1.2 grams of hexadecyltrimethylammonium bromide, beat and mix for 30 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0084] Preparation Example 2

[0085] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0086] Take 161 grams of pseudo-boehmite, add 339 grams of deionized water, add 15 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 50°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 30 grams of magnesium oxide, add 45 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 2.6 grams of hexadecyltrimethylammonium bromide, beat and mix for 30 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0087] Preparation Example 3

[0088] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0089] Take 161 grams of pseudo-boehmite, add 239 grams of deionized water, add 15 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 60°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 50 grams of magnesium oxide, add 75 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 4.5 grams of hexadecyltrimethylammonium chloride, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0090] Preparation Example 4

[0091] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0092] Take 161 grams of pseudo-boehmite, add 239 grams of deionized water, add 15 grams of nitric acid with a mass concentration of 65%-68% under continuous stirring, heat to 60°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 80 grams of magnesium oxide, add 187 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 9 grams of hexadecyltrimethylammonium chloride, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0093] Preparation Example 5

[0094] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0095] Take 161 grams of pseudo-boehmite, add 239 grams of deionized water, add 20 grams of nitric acid with a mass concentration of 65%-68% under continuous stirring, heat to 80°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 60 grams of magnesium oxide, add 140 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 5 grams of hexadecyltrimethylammonium chloride, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0096] Preparation Example 6

[0097] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0098] Take 161 grams of pseudo-boehmite, add 339 grams of deionized water, add 25 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 80°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 50 grams of magnesium oxide, add 120 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 6 grams of hexadecyltrimethylammonium chloride, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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.

[0099] Preparation Example 7

[0100] This preparation example provides a magnesium-aluminum matrix material, and the preparation method thereof includes:

[0101] Take 161 grams of pseudo-boehmite, add 257 grams of deionized water, add 15 grams of nitric acid with a mass concentration of 65%-68% under continuous stirring, heat to 75°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 60 grams of magnesium oxide, add 137 grams of deionized water, mix well and add to the peptized pseudo-boehmite slurry, then add 6 grams of hexadecyltrimethylammonium chloride, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry; transfer the magnesium aluminum colloidal slurry to a crystallization reactor for crystallization reaction, react 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] Example 1

[0103] This embodiment provides a desulfurization, denitration and combustion-supporting triple-effect additive, and the preparation method thereof comprises:

[0104] Take 1306 grams of pseudo-boehmite, 606 grams of cerium nitrate, 713 grams of titanium chloride and 189 grams of ammonium metavanadate, add 7557 grams of deionized water, add 111 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, and heat to 40°C for 30 minutes for peptization treatment; take 600 grams of magnesium oxide, add 900 grams of deionized water, mix well, and add to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source, and modified metal source after the peptization treatment, and then add 3214 grams of magnesium aluminum matrix material slurry obtained in the above-mentioned Preparation Example 5 (dry magnesium aluminum matrix material The raw material colloid is spray-dried and cured and calcined at 300°C for 2h to obtain the composite carrier M1. 100g (by dry weight) of the composite carrier M1 is weighed, 200g of deionized water is added, 12mL of PdCl2 solution with a mass content of 10g / L of the single precious metal element Pd is added, and the mixture is stirred for 30 minutes. The composition is filtered to obtain the composition impregnated with the precious metal element, and the filter cake is rinsed with 0.5mol / L ammonia water and dried to obtain a desulfurization, denitrification and combustion-supporting triple-effect additive.

[0105] The mass percentages of the components in the desulfurization, denitration and combustion-supporting triple-effect additive are: 26% by mass of magnesium oxide, 51% by mass of aluminum oxide, 8% by mass of cerium dioxide, 4.9% by mass of vanadium pentoxide, 10% by mass of metal components in terms of oxides, and 0.1% by mass of precious metal elements in terms of single substances.

[0106] The desulfurization and denitration combustion three-effect additive sample is recorded as S1. The physical and chemical properties of the sample are shown in Table 1, and the reaction performance is shown in Table 2.

[0107] Example 2

[0108] This embodiment provides a desulfurization, denitration and combustion-supporting triple-effect additive, and the preparation method thereof comprises:

[0109] Take 968 grams of pseudo-boehmite, 757 grams of cerium nitrate, 428 grams of titanium chloride and 151 grams of ammonium metavanadate, add 7254 grams of deionized water, add 117 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, and heat to 50°C for 60 minutes for peptization treatment; take 1200 grams of magnesium oxide, add 1800 grams of deionized water, mix well, and add to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source, and modified metal source after the peptization treatment, and then add 2143 grams of magnesium aluminum matrix material slurry (magnesium aluminum matrix material) obtained in the above-mentioned Preparation Example 1 The dry basis weight is 20% of the dry basis weight of the feed), mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray dried and cured and calcined at 400°C for 1h to obtain the composite carrier M2, 100 grams (by dry basis weight) of the composite carrier M2 is weighed, 150 grams of deionized water is added, 9 mL of PdCl2 solution with a mass content of 10 g / L of the single precious metal element Pd is added, stirred for 60 minutes, filtered to obtain the composition impregnated with the precious metal element, and then the filter cake is rinsed with 1.0 mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple-effect additive.

[0110] The mass percentage of each component in the desulfurization, denitration and combustion-supporting triple-effect additive is: 46wt% of magnesium oxide, 34wt% of aluminum oxide, 10wt% of cerium dioxide, 3.92wt% of vanadium pentoxide, 6wt% of metal components calculated as oxides, and 0.08wt% of precious metal elements calculated as single substances.

[0111] The desulfurization and denitration combustion three-effect additive 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.

[0112] Example 3

[0113] This embodiment provides a desulfurization, denitration and combustion-supporting triple-effect additive, and the preparation method thereof comprises:

[0114] Take 1452 grams of pseudo-boehmite, 743 grams of cerium chloride, 451 grams of tungsten hexachloride and 114 grams of ammonium metavanadate, add 6420 grams of deionized water, add 105 grams of nitric acid with a mass concentration of 65%-68% under continuous stirring, and heat to 60°C for 60 minutes for peptization treatment; take 1200 grams of magnesium oxide, add 1800 grams of deionized water, mix well, and add to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source, and modified metal source after the peptization treatment, and then add 1071 grams of magnesium aluminum matrix material slurry (magnesium aluminum matrix material) obtained in the above-mentioned Preparation Example 4 The dry basis weight is 10% of the dry basis weight of the feed), and the mixture is stirred evenly to form a raw material colloid; the raw material colloid is spray dried and cured and calcined at 450°C for 0.5h to obtain a composite carrier M3, 100g (by dry basis weight) of the composite carrier M3 is weighed, 175g of deionized water is added, 6mL of a PdCl2 solution with a mass content of 10g / L of the single precious metal element Pd is added, and the mixture is stirred for 30 minutes, and the composition impregnated with the precious metal element is obtained by filtering, and the filter cake is rinsed with 0.5mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0115] The mass percentages of the components in the desulfurization, denitration and combustion-supporting triple-effect additive are: 45wt% of magnesium oxide, 35wt% of aluminum oxide, 12wt% of cerium dioxide, 2.95wt% of vanadium pentoxide, 5wt% of metal components calculated as oxides, and 0.05wt% of precious metal elements calculated as single substances.

[0116] The desulfurization and denitration combustion three-effect additive 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.

[0117] Example 4

[0118] This embodiment provides a desulfurization, denitration and combustion-supporting triple-effect additive, and the preparation method thereof comprises:

[0119] Take 1355 grams of pseudo-boehmite, 803 grams of cerium chloride, 180 grams of tungsten hexachloride and 77 grams of ammonium metavanadate, add 5720 grams of deionized water, add 210 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, and heat to 70°C for 30 minutes for peptization treatment; take 1350 grams of magnesium oxide, add 2025 grams of deionized water, mix well, and add to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source, and modified metal source after the peptization treatment, and then add 1071 grams of magnesium aluminum matrix material slurry (magnesium aluminum matrix material) obtained in the above-mentioned Preparation Example 7 The dry basis weight is 10% of the dry basis weight of the feed), mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried and cured and calcined at 500°C for 1h to obtain a composite carrier M4, 100g (by dry basis weight) of the composite carrier M4 is weighed, 250g of deionized water is added, 7mL of a PdCl2 solution with a mass content of 5g / L of the single precious metal element Pd is added, stirred for 60 minutes, filtered to obtain a composition impregnated with precious metal elements, and then the filter cake is rinsed with 1.0mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0120] The mass percentage of each component in the desulfurization, denitration and combustion-supporting triple-effect additive is: 53wt% of magnesium oxide, 32wt% of aluminum oxide, 12.97wt% of cerium dioxide, 2wt% of vanadium pentoxide, 2wt% of metal components calculated as oxides, and 0.03wt% of precious metal elements calculated as single substances.

[0121] The desulfurization and denitration combustion three-effect additive 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.

[0122] Example 5

[0123] The present embodiment provides a desulfurization and denitrification combustion-supporting triple-effect additive, and the preparation method thereof comprises: taking 919 grams of pseudo-boehmite, 929 grams of cerium chloride, 713 grams of titanium chloride and 115 grams of ammonium metavanadate, adding 5863 grams of deionized water, adding 324 grams of formic acid with a mass concentration of 88% under continuous stirring, heating to 80°C and maintaining for 30 minutes for peptization treatment; taking 1440 grams of magnesium oxide, adding 2250 grams of deionized water, mixing evenly, and adding to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source and modified metal source after the peptization treatment, and then adding 536 grams of magnesium aluminum matrix obtained in the above-mentioned preparation example 6 The material slurry (the dry basis weight of the magnesium-aluminum matrix material is 5% of the dry basis weight of the feed) is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried and cured and calcined at 300°C for 2h to obtain the composite carrier M5, 100g (by dry basis weight) of the composite carrier M5 is weighed, 200g of deionized water is added, 3mL of PdCl2 solution with a mass content of 5g / L of the single precious metal element Pd is added, the mixture is stirred for 30 minutes, and the composition impregnated with the precious metal element is obtained by filtering, and the filter cake is rinsed with 1.5mol / L ammonia water and dried to obtain a desulfurization, denitrification and combustion-supporting triple-effect additive.

[0124] The mass percentages of the components in the desulfurization, denitration and combustion-supporting triple-effect additive are: 51wt% of magnesium oxide, 21wt% of aluminum oxide, 15wt% of cerium dioxide, 2.99wt% of vanadium pentoxide, 10wt% of metal components calculated as oxides, and 0.01wt% of precious metal elements calculated as single substances.

[0125] The desulfurization and denitration combustion three-effect additive 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.

[0126] Example 6

[0127] The present embodiment provides a desulfurization and denitration combustion-supporting triple-effect additive, and the preparation method thereof comprises: taking 823 grams of pseudo-boehmite, 908 grams of cerium nitrate, 428 grams of titanium chloride, 180 grams of tungsten hexachloride and 114 grams of ammonium metavanadate, adding 5300 grams of deionized water, adding 152 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heating to 60°C and maintaining for 50 minutes for peptization treatment; taking 1500 grams of magnesium oxide, adding 2250 grams of deionized water, mixing evenly, and adding to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source and modified metal source after the peptization treatment, and then adding 107 1 gram of magnesium-aluminum matrix material slurry (the dry basis weight of the magnesium-aluminum matrix material is 10% of the dry basis weight of the feed) is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried and cured and calcined at 400°C for 1h to obtain the composite carrier M6, 100 grams (by dry basis weight) of the composite carrier M6 is weighed, 230 grams of deionized water is added, 12 mL of a PdCl2 solution with a mass content of 5 g / L of the single precious metal element Pd is added, stirred for 30 minutes, filtered to obtain the composition impregnated with the precious metal element, and then the filter cake is rinsed with 1.5 mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0128] The mass percentages of the components in the desulfurization, denitration and combustion-supporting triple-effect additive are: 55wt% of magnesium oxide, 22wt% of aluminum oxide, 12wt% of cerium dioxide, 2.95wt% of vanadium pentoxide, 8wt% of metal components calculated as oxides, and 0.05wt% of precious metal elements calculated as single substances.

[0129] The desulfurization and denitration combustion three-effect additive 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.

[0130] Example 7

[0131] The present embodiment provides a desulfurization and denitration combustion-supporting triple-effect additive, and the preparation method thereof comprises: taking 774 grams of pseudo-boehmite, 757 grams of cerium nitrate, 285 grams of titanium chloride, 180 grams of tungsten hexachloride and 116 grams of ammonium metavanadate, adding 5214 grams of deionized water, adding 151 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heating to 60°C and maintaining for 40 minutes for peptization treatment; taking 1650 grams of magnesium oxide, adding 2475 grams of deionized water, mixing evenly, and adding to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source and modified metal source after the peptization treatment, and then adding 107 obtained in the above-mentioned preparation example 3; 1 gram of magnesium-aluminum matrix material slurry (the dry basis weight of the magnesium-aluminum matrix material is 10% of the dry basis weight of the feed) is mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried and cured and calcined at 450°C for 2h to obtain the composite carrier M7, 100 grams (by dry basis weight) of the composite carrier M7 is weighed, 300 grams of deionized water is added, 16 mL of a PdCl2 solution with a mass content of 5 g / L of the single precious metal element Pd is added, stirred for 30 minutes, filtered to obtain the composition impregnated with the precious metal element, and then the filter cake is rinsed with 1.5 mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0132] The mass percentage of each component in the desulfurization, denitration and combustion-supporting triple-effect additive is: 61wt% of magnesium oxide, 20wt% of aluminum oxide, 10wt% of cerium dioxide, 2.93wt% of vanadium pentoxide, 6wt% of metal components in terms of oxides, and 0.07wt% of precious metal elements in terms of single substances.

[0133] The desulfurization and denitration combustion three-effect additive 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.

[0134] Example 8

[0135] The present embodiment provides a desulfurization and denitrification combustion-supporting triple-effect additive, and the preparation method thereof comprises: taking 1694 grams of pseudo-boehmite, 833 grams of cerium nitrate, 285 grams of titanium chloride, 180 grams of tungsten hexachloride and 114 grams of ammonium metavanadate, adding 5139 grams of deionized water, adding 178 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heating to 50°C and maintaining for 40 minutes for peptization treatment; taking 660 grams of magnesium oxide, adding 990 grams of deionized water, mixing evenly, and adding to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source and modified metal source after the peptization treatment, and then adding 260 grams of the above-mentioned preparation example 3 obtained. 79 grams of magnesium-aluminum matrix material slurry (the dry basis weight of the magnesium-aluminum matrix material is 25% of the dry basis weight of the feed) are mixed and stirred evenly to form a raw material colloid; the raw material colloid is spray-dried and cured and calcined at 500°C for 1 hour to obtain a composite carrier M8, 100 grams (by dry basis weight) of the composite carrier M8 is weighed, 300 grams of deionized water is added, 12 mL of a PdCl2 solution with a mass content of 5 g / L of the single precious metal element Pd is added, the mixture is stirred for 60 minutes, and the composition impregnated with the precious metal element is obtained by filtering, and the filter cake is rinsed with 2 mol / L ammonia water and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0136] The mass percentage of each component in the desulfurization, denitration and combustion-supporting triple-effect additive is: 32.5wt% of magnesium oxide, 47.5wt% of aluminum oxide, 11wt% of cerium dioxide, 2.95wt% of vanadium pentoxide, 6wt% of metal components calculated as oxides, and 0.05wt% of precious metal elements calculated as single substances.

[0137] The desulfurization and denitration combustion three-effect additive 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.

[0138] Comparative Example 1

[0139] The present comparative example provides a desulfurization and denitration combustion-supporting triple-effect auxiliary agent, and the preparation method thereof comprises: taking 1355 grams of pseudo-boehmite, 833 grams of cerium nitrate, 722 grams of tungsten hexachloride and 114 grams of ammonium metavanadate, adding 14888 grams of deionized water, adding 189 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heating to 50°C and maintaining for 40 minutes for peptization treatment; taking 1500 grams of magnesium oxide, adding 2250 grams of deionized water, mixing evenly, and adding the above-mentioned peptization-treated pseudo-boehmite, cerium source, vanadium source, modified metal The raw material colloid is spray dried and cured and calcined at 500°C for 1h to obtain the composite carrier M9. 100g (by dry weight) of the composite carrier M9 is weighed, 200g of deionized water is added, 12mL of a PdCl2 solution with a mass content of 5g / L of the single precious metal element Pd is added, the mixture is stirred for 60 minutes, and the composition impregnated with the precious metal element is obtained by filtering. The filter cake is then rinsed with 1mol / L ammonia water and dried to obtain a desulfurization, denitrification and combustion-supporting triple-effect additive.

[0140] The mass percentage of each component in the desulfurization, denitration and combustion-supporting triple-effect additive is: 50wt% of magnesium oxide, 28wt% of aluminum oxide, 11wt% of cerium dioxide, 2.95wt% of vanadium pentoxide, 8wt% of metal components calculated as oxides, and 0.05wt% of precious metal elements calculated as single substances.

[0141] The desulfurization, denitration, combustion-supporting triple-effect additive 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 desulfurization, denitration, combustion-supporting triple-effect additive.

[0142] Comparative Example 2

[0143] This comparative example provides a desulfurization, denitrification and combustion-supporting three-effect additive

[0144] (1) Take 161 grams of pseudo-boehmite, add 239 grams of deionized water, add 15 grams of hydrochloric acid with a mass concentration of 36%-38% under continuous stirring, heat to 60°C and keep for 1 hour for peptization treatment to obtain peptized pseudo-boehmite slurry; take 50 grams of magnesium oxide, add 75 grams of deionized water, mix well and add to the above-mentioned peptized pseudo-boehmite slurry, beat and mix for 60 minutes to obtain magnesium aluminum colloidal slurry, the mass ratio of magnesium oxide to aluminum oxide in the material is 0.5:1.

[0145] (2) 1452 g of pseudo-boehmite, 743 g of cerium chloride, 451 g of tungsten hexachloride and 114 g of ammonium metavanadate were added to 6420 g of deionized water, and 105 g 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 60 minutes for peptization treatment; 1200 g of magnesium oxide was added to 1800 g of deionized water, and the mixture was mixed evenly and then added to the mixed slurry containing pseudo-boehmite, cerium source, vanadium source and modified metal source after the peptization treatment, and then 1071 g of magnesium aluminum colloidal slurry (1071 g of magnesium aluminum colloidal slurry) obtained in the above-mentioned Preparation Example 4 was added. The dry basis weight is 10% of the dry basis weight of the feed), and the mixture is stirred evenly to form a raw material colloid; the raw material colloid is spray dried and cured and calcined at 450°C for 0.5h to obtain a composite carrier M3, 100g (by dry basis weight) of the composite carrier M3 is weighed, 175g of deionized water is added, 6mL of a PdCl2 solution with a mass content of 10g / L of the single precious metal element Pd is added, and the mixture is stirred for 30 minutes, and the composition impregnated with the precious metal element is obtained by filtering, and the filter cake is rinsed with 0.5mol / L ammonia water, and dried to obtain a desulfurization, denitrification and combustion-supporting triple agent.

[0146] The mass percentages of the components in the desulfurization, denitration and combustion-supporting triple-effect additive are: 45wt% of magnesium oxide, 35wt% of aluminum oxide, 12wt% of cerium dioxide, 2.95wt% of vanadium pentoxide, 5wt% of metal components calculated as oxides, and 0.05wt% of precious metal elements calculated as single substances.

[0147] The desulfurization, denitration and combustion-supporting triple-effect additive 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 desulfurization, denitration and combustion-supporting triple-effect additive, this comparative example uses non-crystallized magnesium-aluminum colloidal slurry instead of magnesium-aluminum matrix material as the additive raw material.

[0148] Test Example 1

[0149] This test example provides the physical and chemical property test and reaction performance test of the desulfurization, denitrification and combustion-supporting triple-effect additive prepared in the above embodiments and comparative examples.

[0150] (1) Testing the colloidal solid content of the desulfurization, denitration and combustion-supporting triple-effect additives before spraying and the specific surface area (m 2 / g, test standard: NB / SH / T0959 Determination of specific surface area of ​​catalytic cracking catalyst (static nitrogen adsorption capacity method), wear index (w%, test standard: NB / SH / T 0964 Determination of wear index of catalytic cracking catalyst (straight tube method), the results are shown in Table 1.

[0151] Table 1 Colloidal solid content, surface area and wear index of desulfurization and denitrification combustion-supporting triple-effect additives

[0152]

[0153] (2) Performance evaluation of the desulfurization, denitration and combustion-supporting triple-effect additives of the embodiments and comparative examples:

[0154] 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 to analyze the content of each component.

[0155] The steps are as follows:

[0156] (1) Filling the reactor. First, fill the bottom of the reactor with asbestos mesh, the middle with quartz sand, and the top with the desulfurization, denitrification, and combustion-supporting three-effect additive sample to be evaluated, and finally connect the reactor to the pipeline;

[0157] (2) Open the gas circuit and circuit, check the air tightness of the device, and set the parameters;

[0158] (3) Evaluation of desulfurization performance: Use N2 as the protective gas and increase the temperature. When the temperature reaches the set value (700°C), keep the temperature constant for 10 minutes, then change the gas to a mixed gas (SO2 400ppm, 10% O2, N2), turn on the flue gas analyzer, and collect reaction data. After the reaction is completed, turn off the mixed gas, turn on N2, cool down to the set value (500°C), 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. Its desulfurization performance can be calculated according to the following formula:

[0159] w=(c-c0) / c

[0160] In the formula: c is the SO2 content in the flue gas without adding the desulfurization, denitrification and combustion-supporting triple additive; c0 is the SO2 content in the reaction process after adding the desulfurization, denitrification and combustion-supporting triple additive.

[0161] (4) Evaluation of denitrification and combustion-supporting performance: Use N2 as the protective gas and raise the temperature. When the temperature reaches the set value (700°C), keep the temperature constant for 10 minutes, then ventilate to a mixed gas (NO 1000ppm, 4% CO, N2), use a flue gas analyzer to measure the NOx content in the outlet flue gas, and collect reaction data. After the reaction is completed, turn off the mixed gas, turn on N2, cool down to the set value (600°C), keep the temperature constant for 10 minutes, ventilate to a mixed gas (4% CO, 1% O2, N2), turn on the CO detector, and collect reaction data. When the reaction is completed, switch the gas to N2 and cool to room temperature.

[0162] Its denitrification performance can be calculated according to the following formula:

[0163] w=(c-c0) / c

[0164] In the formula: c is the NO content in the flue gas without adding the desulfurization, denitrification and combustion-supporting triple additive; c0 is the NO content in the reaction process after adding the desulfurization, denitrification and combustion-supporting triple additive.

[0165] Its CO combustion-supporting performance can be calculated according to the following formula:

[0166] w=(c-c0) / c

[0167] Where: c is the CO content in the flue gas after the reaction is completed when the desulfurization, denitrification and combustion-supporting triple-effect additive is not added; c0 is the CO content after the reaction is completed with the addition of the desulfurization, denitrification and combustion-supporting triple-effect additive.

[0168] The SOx desulfurization performance of the three-effect additive is expressed by the concentration change rate of SO2 in the reaction mixture before and after the reaction, and the reduction regeneration performance is expressed by the ratio of sulfur generated from hydrogen sulfide to sulfur absorbed by the three-effect additive during the oxidation sulfur absorption process.

[0169] The above performance test results are shown in Table 2.

[0170] Table 2 Desulfurization, denitrification and combustion-supporting performance of the three-effect desulfurization, denitrification and combustion-supporting additive

[0171]

[0172] It can be seen from Table 1 and Table 2 that, when the precious metal content is the same or similar, the combustion-supporting performance of the additives of Example 3, Example 7, and Example 8 is at least not lower than the combustion-supporting performance of the additives of Comparative Example 1 and Comparative Example 2, especially in Example 7, Example 8, and Comparative Example 1 with the same precious metal content, the combustion-supporting performance of the additives of Example 7 and Example 8 is significantly improved relative to the combustion-supporting performance of the additive of Comparative Example 1; and the desulfurization performance and denitration performance of the additives of all embodiments are higher than the desulfurization and denitration performance of the additives of Comparative Example 1 and Comparative Example 2. The above results illustrate that the present invention can increase the solid content of the colloidal system formed by the raw materials of the desulfurization, denitration, and combustion-supporting three-effect additive by adding magnesium-aluminum matrix material during the preparation of the desulfurization, denitration, and combustion-supporting three-effect additive, thereby increasing the specific surface area and wear resistance of the desulfurization, denitration, and combustion-supporting three-effect additive. The desulfurization performance, denitration performance, and combustion-supporting performance of the desulfurization, denitration, and combustion-supporting three-effect additive obtained in the catalytic cracking process are significantly improved.

Claims

1. A desulfurization, denitration and combustion-supporting triple-effect additive, taking the total mass of the triple-effect additive as 100%, the triple-effect additive comprises: 30%-60% magnesium oxide, 20%-50% aluminum oxide, 8%-15% cerium oxide, 2%-5% vanadium pentoxide, 2%-10% modified metal components calculated as oxides, 0.01%-0.1% noble metal elements calculated as single substances; 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 triple-effect additive 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 triple-effect additive 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 triple-effect additive according to claim 1, wherein: The second magnesium source includes magnesium oxide; The second aluminum source includes pseudo-boehmite.

4. The triple-effect additive 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 0.05-0.5:1; 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 triple-effect additive 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. The triple-effect additive according to claim 1, wherein: The metal element in the modified metal component is selected from the non-rare earth metal elements in the following groups: one or a combination of two or more of the IB group, the IIB group, the IIIB group, the IVB group, the VB group, the VIB group, and the VIIB group; Preferably, the metal element in the modified metal component includes one or a combination of two or more of Cu, Zn, Ti, Zr, W, and Mn.

7. The triple benefit additive according to claim 1, wherein: The noble metal element includes Pd and / or Pt.

8. A method for preparing the desulfurization, denitration and combustion-supporting triple-effect additive according to any one of claims 1 to 7, the preparation method comprising: S1, mixing a first aluminum source, a cerium source, a modified metal 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 calcining to obtain a combined carrier; S3, immersing the combined carrier in a solution of a noble metal source, washing with alkali, and drying to obtain the triple-effect auxiliary agent.

9. The preparation method according to claim 8, 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.

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

11. The preparation method according to claim 8, wherein: The temperature of the peptization treatment is 40-80° C., and the time of the peptization treatment is 0.5 h-1 h.

12. The preparation method according to claim 8, 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 0.10-0.60:

1.

13. Use of the desulfurization, denitration and combustion-supporting triple-effect additive according to any one of claims 1 to 7 in a catalytic cracking process.

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