Anti-scaling and nitrogen removal catalyst additive

Abstract

This invention discloses an anti-scaling and denitrifying catalytic additive, belonging to the field of catalyst technology, aiming to improve catalyst regeneration efficiency and flue gas purification performance in catalytic cracking (FCC) processes. Through special carrier pretreatment and active component loading technology, combined with the introduction of composite functional agents, this additive significantly improves the anti-scaling ability and denitrification efficiency of the flue gas regenerator compared to existing technologies. Using this additive in catalytic cracking regenerators not only reduces pollutant emissions in flue gas and protects the environment, but also extends catalyst lifespan, improving the economy and environmental friendliness of the refining process. The additive preparation method of this invention is scientific and cost-effective, and has important applications in promoting the green development of the refining industry.

Description

Technical Field

[0001] The invention relates to the technical field of catalysts, and in particular to an anti-fouling and nitrogen removal catalyst aid. Background Art

[0002] As a core process in the oil refining process, catalytic cracking (FCC) is used to lighten heavy oil and produce high value-added products such as liquefied petroleum gas, gasoline, and diesel. This technology occupies an important position in the global oil refining industry and is a key technology for improving the depth of crude oil processing and the yield of light oil. During the FCC process, the crude oil undergoes a cracking reaction under the action of the catalyst and generates a certain amount of coke, which will cover the surface of the catalyst and reduce the activity and selectivity of the catalyst. Therefore, the operating efficiency and environmental performance of the FCC unit depend to a large extent on the performance and regeneration efficiency of the catalyst.

[0003] In the FCC process, the reaction-regeneration system is the core component, including the reaction process between the feedstock oil and the catalyst, the separation process between the oil gas and the catalyst, the charring regeneration process of the catalyst, and the treatment process of the heat generated by the charring and the flue gas. The optimization of these processes is crucial to improving the overall performance of the FCC unit.

[0004] However, the conventional FCC process has some limitations, especially in flue gas treatment and catalyst regeneration. Nitrogen oxides (NOx) and sulfur oxides (SOx) in flue gas are the main pollutants, which not only cause serious damage to the environment but also pose a threat to human health. In addition, the formation of coke can lead to catalyst deactivation, requiring regular regeneration treatment. Traditional regeneration methods often have problems such as high energy consumption, low efficiency, and large catalyst loss.

[0005] China's invention patent CN103240098B discloses a catalyst composition and method for removing sulfur oxides and nitrogen oxides from flue gas, wherein the flue gas containing sulfur oxides and nitrogen oxides passes through a fluidized bed reactor having a denitrification oxide reducing agent, a catalyst and a calcium-based adsorbent therein to remove sulfur oxides and nitrogen oxides from the flue gas, wherein the catalyst comprises a fluidized catalytic cracking waste catalyst acting as a main catalyst and an auxiliary catalyst acting as an auxiliary catalyst. Since the removal of sulfur oxides and nitrogen oxides is carried out in one reactor and at the same temperature, the process is simple and the operating cost is relatively low; at the same time, the method also has the advantages of a wide reaction temperature range, the catalyst is not afraid of the scouring and wear of smoke dust and the pollution of impurities in fly ash. However, the denitration catalyst prepared by the invention still has the problems of poor denitration effect and easy fouling of the smoke exhaust fan. Summary of the invention

[0006] In order to solve these problems, the present invention proposes a method for preparing an anti-fouling and nitrogen removal catalyst additive. Through special carrier pretreatment and active component loading technology, the additive can be mixed with the main catalyst in the catalytic cracking regenerator, effectively reducing nitrogen oxide emissions in flue gas, while reducing fouling and loss, and improving the operating efficiency and environmental performance of the catalytic cracking regenerator.

[0007] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0008] A method for preparing an anti-fouling and nitrogen removal catalyst additive is as follows:

[0009] Step 1, carrier pretreatment: soaking the alumina material in 4-6 mol / L nitric acid solution for 2-4 hours, and then calcining the alumina to obtain a pretreated carrier;

[0010] Step 2, loading of active components: adding cerium salt, lanthanum salt, manganese salt, cobalt salt, iron salt, nickel salt, bismuth salt, zinc salt, titanium salt and zirconium salt into water by solution impregnation method, stirring with a magnetic stirrer for 5 to 10 minutes to completely dissolve them, and obtaining a salt solution; immersing the pretreated carrier obtained in step 1 in the salt solution, standing for 20 to 40 minutes, drying at 60 to 80°C for 5 to 10 hours, adding a functional agent and mixing evenly, and then placing in a muffle furnace for calcination, and obtaining an anti-scaling and nitrogen removal catalyst after natural cooling.

[0011] The weight proportions of the substances in step 2 are 7 to 9 parts of cerium salt, 2 to 4 parts of lanthanum salt, 1 to 2 parts of manganese salt, 0.5 to 2 parts of cobalt salt, 3 to 5 parts of iron salt, 0.2 to 1 parts of nickel salt, 0.5 to 1 parts of bismuth salt, 5 to 7 parts of zinc salt, 4 to 6 parts of titanium salt, 3 to 5 parts of zirconium salt, 180 to 220 parts of water, 30 to 50 parts of the pretreated carrier obtained in step 1, and 5 to 7 parts of functional agent.

[0012] The cerium salt is cerium nitrate; the lanthanum salt is lanthanum nitrate; the manganese salt is at least one of manganese sulfate, potassium permanganate, manganese chloride or manganese nitrate; the cobalt salt is cobalt nitrate; the iron salt is at least one of iron nitrate, iron oxalate, iron acetate or iron chloride; the nickel salt is at least one of nickel nitrate and nickel acetate; the bismuth salt is bismuth nitrate pentahydrate; the zinc salt is at least one of zinc acetate, zinc nitrate or zinc sulfate; the titanium salt is at least one of titanyl sulfate and titanium tetrachloride; the zirconium salt is at least one of zirconium oxychloride, zirconium nitrate and zirconium sulfate.

[0013] In the step 1, the calcination temperature is 500-700° C. and the calcination time is 2-5 hours.

[0014] In step 2, the calcination temperature is 500-700° C. and the calcination time is 4-8 hours.

[0015] The preparation method of the functional agent is as follows, in parts by weight:

[0016] 25-35 parts of isopropyl titanate and 80-120 parts of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 2-4 parts of activated carbon are calcined, and then placed at room temperature for 0.5-2 days and then uniformly mixed with 25-35 parts of water to form a dispersed solution; the temperature is controlled to be 60-70° C., 3-5 parts of a 4-6wt% aqueous solution of dodecyl ammonium sulfate and a dispersed solution are respectively added dropwise to the mixed solution at a speed of 4-6mL / min under stirring at 200-400rpm, and the pH is adjusted with dilute hydrochloric acid; 1-3 parts of indium chloride and 4-6 parts of germanium chloride are added to the reaction system, and a sodium hydroxide aqueous solution is added dropwise at the same time, and stirring is continued for 0.5-2 hours after the addition, and a solid is collected, and the solid is washed with water and anhydrous ethanol for 1-3 times respectively, and then dried in an oven at 50-70° C. for 20-40 hours, and crushed through a 200-500 mesh sieve to obtain a functional agent.

[0017] The calcination is carried out at 600-900° C. in a nitrogen atmosphere for 1-2 hours.

[0018] The pH value is adjusted to 1 to 3 by using 0.5 to 1 mol / L dilute hydrochloric acid.

[0019] The step of dripping the sodium hydroxide aqueous solution comprises dripping 1-3 mol / L sodium hydroxide aqueous solution until the pH value reaches 12-13.

[0020] An anti-scaling and nitrogen removal catalyst aid is prepared by adopting the preparation method.

[0021] The effects of each substance in the present invention are summarized as follows:

[0022] As a catalyst carrier, alumina material provides the necessary mechanical strength and chemical stability, and has a suitable pore structure to increase the dispersion of active components.

[0023] Nitric acid solution is used to pretreat the alumina support to increase its surface activity and improve its pore structure.

[0024] Compounds such as cerium nitrate, lanthanum nitrate, manganese chloride, cobalt nitrate, iron nitrate, nickel nitrate, bismuth nitrate pentahydrate, zinc acetate, titanium tetrachloride, and zirconium oxychloride are loaded on carriers as active components and are responsible for catalyzing specific chemical reactions such as denitrification and anti-scaling.

[0025] The salt solution is a solution formed by dissolving the above active components in water, and is used to impregnate the carrier to achieve uniform distribution of the active components.

[0026] Functional agent is a composite additive used to enhance the performance of the catalyst, including denitrification efficiency and anti-fouling ability.

[0027] Through the synergistic effect of these substances, the anti-fouling and nitrogen removal catalyst aid of the present invention can effectively remove nitrides in the catalytic cracking process, while reducing equipment fouling and improving catalytic efficiency and equipment operation cycle.

[0028] Compared with the prior art, it has the following beneficial effects:

[0029] 1) The catalyst promoter of the present invention achieves a high removal rate of NH3 and HCN in the regeneration device through special carrier treatment and selection of active components. It can scientifically regulate the combustion-supporting behavior under the premise of ensuring denitration, thereby ensuring the combustion-supporting effect, enhancing the denitration effect, and having significant benefits for environmental protection and emission control.

[0030] 2) The addition of the catalyst promoter of the present invention not only improves the denitrification efficiency, but also ensures no negative impact on the performance of the catalytic cracking main catalyst through a carefully designed formulation and carrier modification, avoiding undesirable catalytic behaviors such as dehydrogenation, coking, condensation, etc., thereby maintaining the stability of the catalytic cracking process and the consistency of product distribution.

[0031] 3) The catalyst promoter of the present invention does not use any components that are toxic or harmful to the device, the environment, and the human body, thereby ensuring the safety and environmental friendliness of the entire denitration process and meeting the current strict requirements for environmental protection and health and safety of industrial processes.

[0032] 4) The catalyst promoter of the present invention can be adjusted according to the specific conditions and needs of the device, and has high operational flexibility. At the same time, due to its efficient denitrification performance and positive impact on the catalytic cracking process, it can bring economic savings, such as reducing the amount of coke and dry gas, improving the long-term operation efficiency of the device, and thus reducing operating costs. DETAILED DESCRIPTION

[0033] Main sources of substances:

[0034] Alumina material: Zibo Yinghe Chemical Co., Ltd., item number: YH-1.

[0035] Activated carbon: Zhengzhou Haosen Environmental Protection Technology Co., Ltd., item number: YK101239.

[0036] Graphite: Dongguan Xinke New Materials Co., Ltd., item number: 007.

[0037] Fly ash: Lingshou County Chuangwei Mineral Products Processing Plant, item number: fmh1100.

[0038] The FCC waste catalyst is taken from a domestic heavy oil catalytic balance agent, where the specific surface area of ​​the balance agent is 90m 2 / g, pore volume 0.12cm 3 / g, metal Ni is 12000μg / g, V is 7500μg / g, Ca is 13000μg / g, Fe is 10000μg / g, and Cu is 50μg / g.

[0039] Example 1

[0040] A method for preparing an anti-fouling and nitrogen removal catalyst additive is as follows:

[0041] Step 1, carrier pretreatment: soak the alumina material in 5 mol / L nitric acid solution for 3 hours, then calcine the alumina at a temperature of 600° C. for 4 hours to obtain a pretreated carrier;

[0042] Step 2, loading of active components: 8g of cerium nitrate, 3g of lanthanum nitrate, 1.5g of manganese chloride, 1g of cobalt nitrate, 4g of iron nitrate, 0.5g of nickel nitrate, 0.8g of bismuth nitrate pentahydrate, 6g of zinc acetate, 5g of titanium tetrachloride, and 4g of zirconium oxychloride were added to 200g of water by solution impregnation method, and stirred with a magnetic stirrer for 8 minutes to completely dissolve them to obtain a salt solution; 40g of the pretreated carrier obtained in step 1 was immersed in the salt solution, allowed to stand for 30 minutes, dried at 70°C for 8 hours, 6g of functional agent was added and mixed evenly, and then placed in a muffle furnace for calcination at a temperature of 600°C for 6 hours, and an anti-scaling and nitrogen removal catalyst was obtained after natural cooling.

[0043] The preparation method of the functional agent is as follows:

[0044] 30g of isopropyl titanate and 100g of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 3g of activated carbon is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of indium chloride and 5g of germanium chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after being added dropwise until the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0045] Example 2

[0046] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0047] The preparation method of the functional agent is as follows:

[0048] 30g of isopropyl titanate and 100g of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 3g of graphite is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of indium chloride and 5g of germanium chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after being added dropwise until the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0049] Example 3

[0050] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0051] The preparation method of the functional agent is as follows:

[0052] 30g of isopropyl titanate and 100g of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 3g of fly ash is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of indium chloride and 5g of germanium chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after being added dropwise until the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0053] Example 4

[0054] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0055] The preparation method of the functional agent is as follows:

[0056] 30g of isopropyl titanate and 100g of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 3g of activated carbon is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of tin chloride and 5g of germanium chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after being added dropwise until the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0057] Example 5

[0058] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0059] The preparation method of the functional agent is as follows:

[0060] 30g of isopropyl titanate and 100g of anhydrous ethanol are mixed uniformly to obtain a mixed solution; 3g of activated carbon is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of indium chloride and 5g of antimony chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0061] Example 6

[0062] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0063] The preparation method of the functional agent is as follows:

[0064] 30g of isopropyl titanate and 100g of anhydrous ethanol are mixed uniformly to obtain a mixed solution; 3g of activated carbon is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2g of tin chloride and 5g of antimony chloride are added to the reaction system, and 2mol / L of sodium hydroxide aqueous solution is added dropwise at the same time, and the pH is continued to be stirred for 1 hour after being added dropwise until the pH is 12.5, and the solid is collected, and the solid is washed with water and anhydrous ethanol for 3 times respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0065] Comparative Example 1

[0066] The preparation method of an anti-fouling and nitrogen removal catalyst aid is basically the same as that of Example 1, the only difference being that the preparation method of the functional agent is different.

[0067] The preparation method of the functional agent is as follows:

[0068] 30g of isopropyl titanate and 100g of anhydrous ethanol are mixed uniformly to obtain a mixed solution; 3g of activated carbon is calcined in a nitrogen atmosphere at 800°C for 1.5 hours, and after being placed at room temperature for 1 day, it is uniformly mixed with 30g of water to form a dispersed solution; the temperature is controlled to be 65°C, 4g of a 5wt% aqueous solution of dodecyl ammonium sulfate and the dispersed solution are respectively added dropwise to the mixed solution at a speed of 5mL / min under stirring at 300rpm, and the pH is adjusted to 2 with 1mol / L dilute hydrochloric acid; 2mol / L of sodium hydroxide aqueous solution is then added dropwise until the pH reaches 12.5, and stirring is continued for 1 hour, solids are collected, the solids are washed 3 times with water and anhydrous ethanol respectively, and then dried in an oven at 60°C for 30 hours, crushed and sieved through a 400-mesh sieve to obtain a functional agent.

[0069] Comparative Example 2

[0070] A method for preparing an anti-fouling and nitrogen removal catalyst additive is as follows:

[0071] Step 1, carrier pretreatment: soak the alumina material in 5 mol / L nitric acid solution for 3 hours, then calcine the alumina at a temperature of 600° C. for 4 hours to obtain a pretreated carrier;

[0072] Step 2, loading of active components: 8g of cerium nitrate, 3g of lanthanum nitrate, 1.5g of manganese chloride, 1g of cobalt nitrate, 4g of iron nitrate, 0.5g of nickel nitrate, 0.8g of bismuth nitrate pentahydrate, 6g of zinc acetate, 5g of titanium tetrachloride, and 4g of zirconium oxychloride were added to 200g of water by solution impregnation method, and stirred with a magnetic stirrer for 8 minutes to completely dissolve them to obtain a salt solution; 40g of the pretreated carrier obtained in step 1 was immersed in the salt solution, allowed to stand for 30 minutes, dried at 70°C for 8 hours, 6g of activated carbon was added and mixed evenly, and then placed in a muffle furnace for roasting at a temperature of 600°C for 6 hours, and an anti-scaling and nitrogen removal catalyst was obtained after natural cooling.

[0073] Comparative Example 3

[0074] A method for preparing an anti-fouling and nitrogen removal catalyst additive is as follows:

[0075] Step 1, carrier pretreatment: soak the alumina material in 5 mol / L nitric acid solution for 3 hours, then calcine the alumina at a temperature of 600° C. for 4 hours to obtain a pretreated carrier;

[0076] Step 2, loading of active components: 8g of cerium nitrate, 3g of lanthanum nitrate, 1.5g of manganese chloride, 1g of cobalt nitrate, 4g of iron nitrate, 0.5g of nickel nitrate, 0.8g of bismuth nitrate pentahydrate, 6g of zinc acetate, 5g of titanium tetrachloride, and 4g of zirconium oxychloride were added to 200g of water by solution impregnation method, and stirred with a magnetic stirrer for 8 minutes to completely dissolve them to obtain a salt solution; 40g of the pretreated carrier obtained in step 1 was immersed in the salt solution, allowed to stand for 30 minutes, dried at 70°C for 8 hours, and then placed in a muffle furnace for calcination at a temperature of 600°C for 6 hours. After natural cooling, an anti-scaling and nitrogen removal catalyst additive was obtained.

[0077] Test Example 1

[0078] NH3 and HCN removal rate test

[0079] The evaluation test of the additive was carried out on a ф8×1mm small quartz tube fixed bed reactor. The loading amount of the reactor was 1.0g, the reaction temperature was 680℃, and the flow rate of each gas component used in the test was controlled by a gas mass flow controller. During the test, the additive was diluted with FCC catalyst, and the weight content of the additive in the FCC catalyst was controlled at 3%. 1.0g of the diluted additive was weighed and placed in a quartz tube reactor. The temperature was raised to 680℃ through Ar flow and then kept constant. After stabilization for 5 minutes, it was switched to the reaction mixed gas, and the mixed gas contained 1000mg / m SO2. 3 , NH3900mg / m 3 , CO6.5%(v), HCN150mg / m 3, O2 is 0.5% (v), the rest is Ar, and a portable flue gas detector is used for online detection to determine the NH3 and NO in the reaction tail gas. x The change of NH3 and HCN content in the flue gas before and after the reaction is used to indicate the removal performance of the additive. The removal rate of NH3 and HCN is calculated using the following formula:

[0080] Y=(C1-C2) / C1×100%

[0081] Where: Y is the NH3 or HCN removal rate (%);

[0082] C1 is the concentration of NH3 or HCN in the mixed gas before the reaction (mg / m 3 ;

[0083] C2 is the concentration of NH3 or HCN in the mixed gas after the reaction, mg / m 3 .

[0084] The test results are shown in Table 1.

[0085] Table 1

[0086] Experimental protocol <![CDATA[NH3 removal rate / %]]> HCN removal rate / % Example 1 94.6 92.5 Example 2 89.7 86.7 Example 3 88.4 85.9 Example 4 93.4 90.2 Example 5 93.8 90.5 Example 6 92.7 89.9 Comparative Example 1 90.0 86.8 Comparative Example 2 87.4 84.5 Comparative Example 3 85.6 82.7

[0087] Test Example 2

[0088] Testing of additives for product distribution

[0089] The effect of the additive prepared in Example 1 of the present invention on the product distribution was studied on an ACE device. The feed oil was 70% hydrogenated wax oil + 30 Daqing slag, the catalyst was FCC waste catalyst, and the additive addition amounts were 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, and 5.0wt%, respectively. After the additive treatment, the reaction temperature was 500°C, the catalyst-to-oil ratio was 8.0, and the blank experiment without the addition of the additive was used to test the effect of the additive on the product distribution. The test results are shown in Table 2.

[0090] Table 2

[0091]

[0092] Test Example 3

[0093] Micro-anti-activity test

[0094] In the micro-reactor activity evaluation device, the additive addition amount of Example 1 was 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, and 5.0wt%, and the effect of the additive treatment on the FCC catalyst activity was measured. It can be seen from Table 3 that at a content of less than 5wt%, the additive has no adverse effect on the FCC catalyst activity.

[0095] Table 3 Effect of additives on product distribution

[0096] project blank 1# 2# 3# 4# 5# Micro-anti-activity % 64.25 65.11 65.26 65.84 65.67 65.95

[0097] Test Example 4

[0098] Anti-fouling performance test method

[0099] To evaluate the ability of anti-fouling and denitrification catalyst additives to reduce the fouling of smoke turbine blades in actual flue gas environments, as well as the potential effect of extending the life of the equipment.

[0100] By simulating the actual flue gas environment, the anti-fouling effect of the anti-fouling and denitrifying catalytic additive within a certain period of time was tested, and by comparing with the control group without the additive, its effect on the scaling of the smoke exhaust fan blades was analyzed. The same smoke exhaust fan blade simulation test bench was prepared, and the anti-fouling and denitrifying catalytic additive was used, and no additive was used as a control group. Using a simulated flue gas generating device, simulated flue gas was generated according to the flue gas composition and flow rate of the catalytic cracking unit. The anti-fouling and denitrifying catalytic additive was added to the simulation system at a ratio of 3.0wt%. The smoke exhaust fan blade simulation test bench was turned on to allow the simulated flue gas to pass through the blades to simulate the actual working environment. After one year, the scaling thickness of the blades was measured using a scaling thickness measuring instrument.

[0101] Table 4

[0102] Experimental protocol Scaling thickness / mm Example 1 0.61 Example 2 0.72 Example 3 0.83 Example 4 0.71 Example 5 0.73 Example 6 0.77 Comparative Example 1 0.89 Comparative Example 2 1.21 Comparative Example 3 1.36 Control group 2.64

[0103] From test examples 1 to 4, it can be seen that the anti-fouling and nitrogen removal catalyst additive obtained in Example 1 of the present invention has the highest removal rate of NH3 and HCN and the smallest scale thickness. Compared with the blank experiment without additive, the product distribution does not change much, and at a content of less than 5wt%, the additive has no adverse effect on the FCC catalyst activity.

[0104] The activated carbon used in Example 1 as part of the functional agent performs better in improving the removal rate of NH3 and HCN and reducing scaling than the graphite in Example 2 and the fly ash in Example 3. The reason may be that the activated carbon has a highly developed pore structure, providing more surface area and active sites, which helps to more effectively adsorb and catalyze reactions, thereby improving the removal rate of NH3 and HCN. Activated carbon generally has higher purity and more uniform physical and chemical properties than graphite and fly ash, which helps to maintain the performance consistency of the catalytic promoter and improve the overall efficiency. The pore structure and surface characteristics of activated carbon may help to reduce the deposition of scaling materials such as dust and ammonium bisulfate on the smoke exhaust blades, thereby reducing scaling.

[0105] The functional agent in Example 1 uses indium chloride and germanium chloride as active ingredients. The specific chemical properties and electronic structures of these elements provide efficient active sites for the catalytic process, enhancing the adsorption and catalytic conversion capabilities of NH3 and HCN. Indium chloride may promote the removal of nitrogen and sulfur due to its good electron acceptance ability and appropriate metal-support interaction; germanium chloride may improve the thermal stability and anti-poisoning of the catalyst due to its regulation of the redox properties and electronic characteristics of the catalyst. This combination not only optimizes the path of the catalytic reaction and improves the conversion rate, but also enhances the structural stability of the catalyst, reduces the deposition of dust and ammonium bisulfate, thereby effectively preventing the scaling of the smoke machine blades and extending the operating cycle of the equipment. In addition, the synergistic effect of these active ingredients may also improve the reaction efficiency of the catalyst with pollutants in the flue gas, reduce the generation of by-products, maintain the stability of the product distribution, and have no adverse effect on the activity of the FCC catalyst.

Claims

1. A method for preparing an anti-fouling and nitrogen removal catalyst aid, characterized in that: Here’s how: Step 1, carrier pretreatment: soaking the alumina material in 4-6 mol / L nitric acid solution for 2-4 hours, and then calcining the alumina to obtain a pretreated carrier; Step 2, loading of active components: adding cerium salt, lanthanum salt, manganese salt, cobalt salt, iron salt, nickel salt, bismuth salt, zinc salt, titanium salt and zirconium salt into water by solution impregnation method, stirring with a magnetic stirrer for 5-10 minutes to completely dissolve them, and obtaining a salt solution; immersing the pretreated carrier obtained in step 1 in the salt solution, standing for 20-40 minutes, drying at 60-80°C for 5-10 hours, adding a functional agent and mixing evenly, and then calcining in a muffle furnace, and obtaining an anti-scaling and nitrogen removal catalyst after natural cooling; The weight proportions of the substances in step 2 are 7-9 parts of cerium salt, 2-4 parts of lanthanum salt, 1-2 parts of manganese salt, 0.5-2 parts of cobalt salt, 3-5 parts of iron salt, 0.2-1 parts of nickel salt, 0.5-1 parts of bismuth salt, 5-7 parts of zinc salt, 4-6 parts of titanium salt, 3-5 parts of zirconium salt, 180-220 parts of water, 30-50 parts of the pretreated carrier obtained in step 1, and 5-7 parts of functional agent; The preparation method of the functional agent is as follows, in parts by weight: 25-35 parts of isopropyl titanate and 80-120 parts of anhydrous ethanol are uniformly mixed to obtain a mixed solution; 2-4 parts of activated carbon are calcined, and then placed at room temperature for 0.5-2 days and then uniformly mixed with 25-35 parts of water to form a dispersed solution; the temperature is controlled to be 60-70°C, 3-5 parts of a 4-6wt% aqueous solution of dodecyl ammonium sulfate and a dispersed solution are respectively added dropwise to the mixed solution at a speed of 4-6mL / min under stirring at 200-400rpm, and the pH is adjusted with dilute hydrochloric acid; 1-3 parts of indium chloride and 4-6 parts of germanium chloride are added to the reaction system, and a sodium hydroxide aqueous solution is added dropwise at the same time, and stirring is continued for 0.5-2 hours after the addition, and a solid is collected, and the solid is washed with water and anhydrous ethanol for 1-3 times, respectively, and then dried in an oven at 50-70°C for 20-40 hours, and crushed through a 200-500 mesh sieve to obtain a functional agent.

2. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: The cerium salt is cerium nitrate; the lanthanum salt is lanthanum nitrate; the manganese salt is at least one of manganese sulfate, potassium permanganate, manganese chloride or manganese nitrate; the cobalt salt is cobalt nitrate; the iron salt is at least one of iron nitrate, iron oxalate, iron acetate or iron chloride; the nickel salt is at least one of nickel nitrate and nickel acetate; the bismuth salt is bismuth nitrate pentahydrate; the zinc salt is at least one of zinc acetate, zinc nitrate or zinc sulfate; the titanium salt is at least one of titanyl sulfate and titanium tetrachloride; the zirconium salt is at least one of zirconium oxychloride, zirconium nitrate and zirconium sulfate.

3. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: In the step 1, the calcination temperature is 500-700° C. and the calcination time is 2-5 hours.

4. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: In step 2, the calcination temperature is 500-700° C. and the calcination time is 4-8 hours.

5. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: The calcination is carried out at 600-900° C. in a nitrogen atmosphere for 1-2 hours.

6. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: The step of adjusting the pH value with dilute hydrochloric acid is to use 0.5-1 mol / L dilute hydrochloric acid to adjust the pH value to 1-3.

7. The method for preparing the anti-fouling and nitrogen removal catalyst aid according to claim 1, characterized in that: The step of dripping the sodium hydroxide aqueous solution comprises dripping 1-3 mol / L sodium hydroxide aqueous solution until the pH value is 12-13.

8. An anti-scaling and nitrogen removal catalyst aid, characterized in that: The method is prepared according to any one of claims 1 to 7.

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