Process for the utilization of catalytic cracking catalyst sludge

Abstract

The application provides a method for utilizing catalytic cracking catalyst sludge, which utilizes the sludge to prepare a catalytic cracking anti-vanadium additive, and comprises the following steps: (1) beating the catalytic cracking catalyst sludge; (2) performing a first modification and activation treatment on the sludge by using an acid for a period of time; (3) mixing an aluminum source and / or a magnesium source, aging at 80-120 DEG C, and drying and washing to obtain a medium and large pore matrix; and (4) mixing and beating the medium and large pore silicon aluminum matrix, a binder and clay, and performing spray drying and washing. The method can utilize the sludge to prepare an anti-metal additive with higher heavy oil cracking performance.

Description

Technical Field

[0001] This invention belongs to the field of waste utilization technology, and relates to a method for utilizing catalytic cracking catalyst residue and the application of the active silicon-aluminum material prepared therefrom. Background Technology

[0002] Catalytic cracking catalyst residue is a waste residue mainly composed of Al2O3 and SiO2, obtained from wastewater generated during the production of catalytic cracking catalysts after sedimentation, filtration, and slag cutting. Currently, this residue is mainly disposed of directly without reuse, resulting in a waste of resources such as Si and Al. Utilizing it using industrially feasible and cost-effective technologies could not only alleviate the environmental governance burden on enterprises but also reduce production costs and improve economic efficiency.

[0003] Zhang Zhimin (Research on the technology of recycling catalyst residue for catalytic cracking, Qilu Petrochemical, 2011, 39(3): 219-222) took advantage of the high content of silicon, aluminum and other substances in the catalyst residue to directly use the catalyst residue as the raw material for synthesizing molecular sieves. However, this method will affect the crystallinity of the molecular sieve.

[0004] Existing methods for preparing molecular sieves using slag can achieve the secondary use of slag, but they also cause fluctuations in the quality of the molecular sieves, limiting their application. Summary of the Invention

[0005] The purpose of this invention is to provide a novel method for utilizing catalytic cracking catalyst residue, which involves producing vanadium-resistant additives for catalytic cracking from the residue. The residue is obtained from wastewater generated during the production of the catalytic cracking catalyst through sedimentation, filtration, and slag cutting.

[0006] This invention provides a method for utilizing the slag residue from catalytic cracking catalysts, comprising the following steps:

[0007] (1) Pulverize the catalytic cracking catalyst residue to obtain a slurry with a solid content of 5-15% by weight;

[0008] (2) Add acid to the slurry obtained in step (1) to adjust the pH value to 1-5, and react at 30°C or above to obtain activated slurry;

[0009] (3) The activated slurry is mixed with an aluminum source and / or a magnesium source. Preferably, the pH of the resulting mixture is 8 to 11. The mixture is aged at 80°C or higher, dried, and washed to obtain a medium- to macroporous matrix.

[0010] (4) Mix the macroporous matrix, binder and clay, slurry, spray dry and wash to obtain catalytic cracking anti-metal additive.

[0011] One technical solution, based on the dry weight of the catalytic cracking catalyst slag, wherein the catalytic cracking catalyst slag (hereinafter referred to as slag) contains 10-50% by weight of Al2O3, 30-70% by weight of SiO2, 2-15% by weight of Na2O and 1-15% by weight of RE2O3.

[0012] According to any of the above technical solutions, in step (1), the particle size of the slurry obtained after pulping is controlled within the range of D(V,0.5)≤8μm (e.g., 1~8μm) and D(V,0.9)≤20μm (e.g., 2-20μm). D(V,0.9) refers to the volume of particles with a diameter smaller than this value accounting for 90% of the total volume of all particles in the sample, and D(V,0.5) refers to the volume of all particles with a diameter smaller than this value accounting for 50% of the total volume of all particles. The particle size distribution is analyzed using a laser particle size analyzer, as per standard NB / SH / T0951-2017.

[0013] According to any of the above technical solutions, the pulping can be carried out by high-speed stirring or by shearing with a shearing machine, as is well known to those skilled in the art.

[0014] According to any of the above technical solutions, the acid in step (2) can be an organic acid and / or an inorganic acid, such as one or more of formic acid, acetic acid, and oxalic acid, and such as one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

[0015] According to any of the above technical solutions, in step (2), acid is added to the slurry obtained in step (1) to adjust the pH value to 1-5, for example, 1.5-4 or 2-3. Then, the reaction is carried out at a temperature above 30°C, for example, 30°C-90°C, 30-99°C, or 60-90°C, and the reaction time is preferably 1-8 hours, for example, the reaction can be carried out by stirring for 1-8 hours or 3-5 hours. This allows the slurry residue after pulping to undergo a primary modification and activation treatment using acid.

[0016] According to any of the above technical solutions, the aluminum source in step (3) is one or more of Al(NO3)3, AlCl3, Al2(SO4)3, boehmite, and aluminum sol.

[0017] According to any of the above technical solutions, the magnesium source in step (3) is one or more of magnesium oxide, magnesium hydroxide, metallic magnesium, magnesium chloride, magnesium carbonate, and magnesium nitrate.

[0018] According to any of the above technical solutions, in step (3), the activated slag slurry is mixed with an aluminum source and / or a magnesium source. Preferably, the pH value of the resulting mixture is 8 to 11, for example, 9 to 11.

[0019] According to any of the above technical solutions, the aging in step (3) is carried out at an aging temperature of 80°C or above, for example, 80 to 120°C; the aging time is preferably 2 to 12 hours.

[0020] According to any of the above technical solutions, the product after aging in step (3) is dried and washed to obtain a mesoporous matrix. The washing can be done with water. After washing, the mesoporous matrix can be further dried.

[0021] According to any of the above technical solutions, preferably, the mesoporous matrix contains 0.01-3% by weight Na2O, 30-60% by weight (e.g., 35-55% by weight) Al2O3, 25-40% by weight (e.g., 25-35% by weight) SiO2, 2-15% by weight (e.g., 4-10% by weight) RE2O3 and 5-25% by weight (e.g., 10-25% by weight) MgO.

[0022] According to any of the above technical solutions, the specific surface area (BET method) of the mesoporous matrix is ​​150-300 m². 2 / g for example 200-300m 2 / g.

[0023] According to any of the above technical solutions, the pore volume of the mesoporous matrix obtained by the water droplet method is 0.5 to 0.8 mL / g.

[0024] According to any of the above technical solutions, the pore size distribution is measured by the low-temperature nitrogen adsorption capacity method and calculated by the BJH method. In the medium- and macroporous matrix, the pore volume of medium- and macroporous pores with a pore size greater than 10 nm accounts for no less than 40%, for example, 45-80%, of the total pore volume. The pore volume of medium- and macroporous pores with a pore size (diameter) greater than 10 nm refers to the pore volume of pores with a pore size greater than 10 nm and not exceeding 100 nm. The total pore volume refers to the pore volume of pores with a pore diameter greater than 0 and not exceeding 100 nm.

[0025] According to any of the above technical solutions, the clay in step (4) is one or more of kaolin, rettoite, diatomite, montmorillonite, bentonite and sepiolite.

[0026] In one embodiment, step (4) includes: mixing clay, binder, and water to form a slurry; adding an inorganic acid to adjust the pH to 2.5–4.0 to obtain a first slurry; mixing the first slurry and the aforementioned mesoporous matrix to obtain a second slurry; and spray-drying, calcining, and washing the obtained second slurry. For example, the calcination temperature can be 400–550°C, and the calcination time can be 1–4 hours. The additive obtained in this embodiment has better anti-metal contamination effects, for example, it can have better gasoline selectivity after metal contamination.

[0027] According to any of the above technical solutions, preferably, based on dry weight, the catalytic cracking anti-metal additive contains 10-40% by weight, for example, 15-35% by weight, clay, 20-40% by weight, for example, 22-35% by weight, binder, and 40-70% by weight of the mesoporous matrix.

[0028] The present invention further provides a mesoporous matrix material containing 0.01–3 wt% Na₂O, 30–60 wt% Al₂O₃, 25–40 wt% SiO₂, 2–15 wt% RE₂O₃, and 5–25 wt% MgO. The specific surface area of ​​the mesoporous matrix material is preferably 150–300 m² / s. 2 / g, the preferred pore volume for the water droplet method is 0.5-0.8 mL / g, and the proportion of macropores with a pore size greater than 10 nm is more than 40%.

[0029] In one embodiment, the mesoporous matrix material is prepared according to the method including steps (1) to (3) of any of the above technical solutions.

[0030] The present invention provides a method for utilizing catalytic cracking catalyst residue, which can be used to prepare a mesoporous and macroporous matrix material with good performance. This material can then be used to prepare a catalytic cracking additive resistant to metal contamination. The additive obtained by this method exhibits good resistance to vanadium contamination. For example, when mixed with the main catalytic cracking catalyst after vanadium contamination, it can achieve higher gasoline yield, higher conversion rate, and lower heavy oil yield. The catalytic cracking additive resistant to metal contamination prepared by this method has stable quality. Detailed Implementation

[0031] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0032] The 1# slag used has a solid content of 25% by weight, and based on the dry weight of the slag, it contains 9.0% by weight of Na2O, 23.0% by weight of Al2O3, 48.0% by weight of SiO2, and 9.2% by weight of RE2O3. It comes from Sinopec Catalyst Co., Ltd., and is waste slag obtained from wastewater generated in the production of catalytic cracking catalysts through sedimentation, filtration, and slag cutting operations.

[0033] Kaolin was produced by Suzhou Kaolin Company and has a solid content of 72% by weight.

[0034] The pseudoboehmite was produced by Aluminum Corporation of China and had a solid content of 62.0% by weight.

[0035] The aluminum oxide content in the aluminum sol is 21.5% by weight;

[0036] The hydrochloric acid was produced by Beijing Chemical Plant, and its specification was analytical grade with a mass concentration of 36%.

[0037] Magnesium oxide is produced by Beijing Chemical Plant and is of analytical grade.

[0038] Aluminum sulfate solution: 90g Al2O3 / L, produced by Qilu Branch of Sinopec Catalyst Co., Ltd.

[0039] Magnesium chloride solution: 100g MgO / L, produced by Sinopec Catalyst Co., Ltd., Qilu Branch;

[0040] Sodium aluminate solution: 105g Al2O3 / L, produced by Qilu Branch of Sinopec Catalyst Co., Ltd.

[0041] The specific surface area was analyzed using the NB / SH / T 0959-2017 method, and the pore size distribution was analyzed using the BJH method based on the adsorption data obtained under these conditions.

[0042] The composition of the samples was determined by X-ray fluorescence spectroscopy (XRF).

[0043] The apparent bulk density of catalytic cracking catalysts was determined according to NB / SH / T 0954-2017.

[0044] The pore volume of catalytic cracking catalyst was determined using the water droplet method according to NB / SH / T 0955-2017.

[0045] The wear index of catalytic cracking catalyst was determined using NB / SH / T 0964-2017.

[0046] Example 1 of medium- and macroporous matrix preparation

[0047] The glue residue No. 1 was mixed with deionized water under high-speed stirring to obtain glue residue slurry, wherein D(V,0.5) was 3.7 micrometers and D(V,0.9) was 8.2 micrometers;

[0048] Hydrochloric acid was added to adjust the pH of the slurry to 2, and the mixture was stirred at 90°C for 4 hours to obtain the activated slurry with a concentration of 100 g / L based on oxides (total amount of sodium oxide, aluminum oxide, silicon oxide and rare earth oxide, of which rare earth oxide is calculated as RE2O3).

[0049] The activated slurry was mixed with sodium aluminate solution, magnesium chloride solution, and aluminum sulfate solution in a volume ratio of 5:2:1:1. The resulting mixture had a pH of 9.1. The mixture was reacted at 120℃ for 4 hours, and after drying and washing, a mesoporous matrix MA-1 was obtained. Analysis showed that MA-1 had a specific surface area of ​​218 m². 2 / g, with medium and macropores larger than 10nm accounting for 78.3%, and the pore volume by water drop method is 0.78ml / g; by weight percentage, Na2O content is 0.16%, Al2O3 content is 48.9%, SiO2 content is 27.3%, MgO content is 12.1%, and RE2O3 content is 5.6%.

[0050] Example 2 of medium- and large-pore matrix preparation

[0051] The slurry, consisting of slag #1, was homogenized with deionized water under high-speed stirring. The resulting slurry had a density (D(V,0.5)) of 2.6 micrometers and a density (D(V,0.9)) of 5.9 micrometers.

[0052] Hydrochloric acid was added to adjust the pH of the slurry to 2.5, and the mixture was stirred at 90°C for 4 hours to obtain an activated slurry. The concentration of the activated slurry, calculated as oxides, was 100 g / L.

[0053] The activated slurry was mixed with sodium aluminate solution, magnesium chloride solution, and aluminum sulfate solution in a volume ratio of 13:3:3:1. The pH of the mixture was 10.5. The mixture was reacted at 100℃ for 4 hours. After drying and washing, the mesoporous matrix MA-2 was obtained, with a specific surface area of ​​271.2 m². 2 / g, with 76.1% being mesopores and macropores larger than 10nm, and a water droplet pore volume of 0.67ml / g. By weight percentage, the content of Na2O is 0.8%, Al2O3 is 38.2%, SiO2 is 34.1%, MgO is 17.1%, and RE2O3 is 6.1%.

[0054] Example 3 of medium- and macroporous matrix preparation

[0055] The slurry, consisting of slag #1, was homogenized with deionized water under high-speed stirring. The resulting slurry had a density (D(V,0.5)) of 3.1 micrometers and a density (D(V,0.9)) of 7.2 micrometers.

[0056] Hydrochloric acid was added to adjust the pH of the slurry to 2.6, and the mixture was stirred at 90°C for 4 hours to obtain an activated slurry with an oxide concentration of 100 g / L.

[0057] The activated residue was mixed with sodium aluminate solution, magnesium chloride solution, and aluminum sulfate solution in a volume ratio of 11:3:4.5:3. The pH of the mixture was 10.9. The mixture was reacted at 90℃ for 4 hours, and after drying and washing, a mesoporous matrix MA-3 was obtained. Analysis showed that the specific surface area of ​​MA-3 was 201.3 m². 2 / g, with pore size greater than 10nm, mesopores and macropores accounting for 49.6%, and water droplet pore volume of 0.52ml / g; percentage content: Na2O content is 0.3%, Al2O3 content is 41.6%, SiO2 content is 25.8%, MgO content is 21.5%, and RE2O3 content is 4.9%.

[0058] Example 1 of the preparation of antivanadium additive

[0059] Add 0.83 kg of kaolin, 1.61 kg of pseudoboehmite, and 0.7 kg of [unspecified substance] to 10 kg of deionized water.

[0060] The aluminum sol was stirred for 120 minutes, and hydrochloric acid was added to adjust the pH to 3.0. Stirring was continued for 60 minutes to obtain a slurry. 4.06 kg of the above-mentioned macroporous matrix MA-1 was added to the first slurry and stirred for 60 minutes to obtain a second slurry. The second slurry was then...

[0061] The microspheres were obtained by spray drying at a tower outlet temperature of 220℃, calcining at 450℃ for 2 hours, washing twice (each washing was done at a water:additive ratio of 10:1 by weight), and drying. They were denoted as M-1.

[0062] Examples of vanadium-resistant additive preparation 2-4

[0063] Examples 2, 3, and 4 were prepared using the same method as Example 1, except that Examples 2, 3, and 4 were prepared with different contents of macroporous matrices MA-1, MA-2, and MA-3, respectively, and were designated as M-2, M-3, and M-4.

[0064] Example 5 of the preparation of antivanadium additive

[0065] The amount and type of raw materials used in the preparation were the same as in Example 2. The difference was that the mesoporous matrix material was directly mixed with deionized water, kaolin, alumina and alumina sol and stirred for 120 min. After adding hydrochloric acid to adjust the pH to 3.0, the mixture was stirred for 60 min and spray-dried at a tower outlet temperature of 220℃. After calcination at 450℃ for 2 h, the mixture was washed twice (each time with a water:additive weight ratio of 10:1) and dried to obtain microspheres, which were designated as M-5.

[0066] The formulations and properties of the vanadium-resistant additives in Examples 1-5 are shown in Table 1.

[0067] Matrix preparation comparative example 1

[0068] The slurry was prepared by mixing the No. 1 glue residue with deionized water under high-speed stirring. The particle size distribution (D(V,0.5)) was 3.5 micrometers, and the particle size distribution (D(V,0.9)) was 8.0 micrometers.

[0069] The slurry was directly mixed with sodium aluminate solution, magnesium chloride solution, and aluminum sulfate solution in the same dry basis feeding ratio as in Example 1. The pH of the mixture was 12.5. The mixture was reacted at 120°C for 4 hours, and then dried and washed to obtain matrix DMA-1. Analysis showed that the specific surface area of ​​DMA-1 was 162 m². 2 / g, with a pore size greater than 10nm, the proportion of mesopores and macropores is 15.2%, the pore volume by water drop method is 0.26ml / g, the Na2O content is 0.21 wt%, the Al2O3 content is 47.2 wt%, the SiO2 content is 28.8 wt%, the MgO content is 11.2 wt%, and the RE2O3 content is 6.1 wt%.

[0070] Comparative Example 2 of Matrix Preparation

[0071] The slurry, consisting of slag #1, was homogenized with deionized water under high-speed stirring. The resulting slurry had a density (D(V,0.5)) of 2.6 micrometers and a density (D(V,0.9)) of 5.9 micrometers.

[0072] Hydrochloric acid was added to adjust the pH of the slurry to 2.5, and the mixture was stirred at 90°C for 4 hours to obtain activated slurry. The concentration of the modified slurry was 100 g / L.

[0073] The activated residue was mixed with sodium aluminate solution and aluminum sulfate solution in a volume ratio of 13:3:1 and reacted at 100℃ for 4 hours. After drying and washing, matrix DMA-2 was obtained. Analysis showed a specific surface area of ​​149 m². 2 / g, with mesopores and macropores larger than 10nm accounting for 21.8%. The pore volume by water droplet method is 0.31ml / g; the weight percentage content is as follows: Na2O content is 0.8%, Al2O3 content is 42.6%, SiO2 content is 46.4%, and RE2O3 content is 7.8%.

[0074] Matrix preparation comparative example 3

[0075] The slag 1# was mixed with deionized water under high-speed stirring to form a homogeneous slurry with a density (D(V,0.5)) of 2.6 micrometers and a density (D(V,0.9)) of 5.9 micrometers. The resulting slag slurry was then mixed with hydrochloric acid to adjust the pH to 2.6. The slurry was stirred at 90°C for 4 hours to obtain an activated slag slurry with an oxide concentration of 100 g / L.

[0076] The activated residue was mixed with sodium aluminate solution and aluminum sulfate solution in a volume ratio of 11:3:3 and reacted at 90℃ for 4 hours. After drying and washing, matrix DMA-3 was obtained. Analysis showed that the specific surface area of ​​DMA-3 was 122.9 m². 2 / g, with a pore size greater than 10nm, the proportion of mesopores and macropores is 9.6%, and the pore volume by water droplet method is 0.23ml / g; weight percentage content: Na2O content is 0.8%, Al2O3 content is 54.1%, SiO2 content is 36.4%, and RE2O3 content is 5.6%.

[0077] Comparative Example 1 for the Preparation of Vanadium-Resistant Additives

[0078] Following the method of Example 1, the auxiliary agent DM-1 was prepared using matrix DMA-1.

[0079] Comparative Example 2 for the Preparation of Vanadium-Resistant Additives

[0080] Add 1.6 kg of kaolin, 2.02 kg of pseudoboehmite and 0.47 kg of aluminum sol to 10 kg of deionized water and stir for 120 min. Add hydrochloric acid to adjust the pH to 3.0 and continue stirring for 60 min to obtain the first slurry.

[0081] 2.6 kg of the above matrix DMA-2 and 4.3 L of magnesium chloride solution were added to the first slurry and stirred for 30 minutes. The mixture was then spray-dried at a tower outlet temperature of 220°C and calcined at 450°C for 2 hours. After washing twice (each wash was performed at a water:solvent ratio of 10:1), the mixture was dried to obtain microspheres, which were designated as DM-2.

[0082] Preparation of vanadium-resistant additives: Comparative Example 3

[0083] Add 1.6 kg of kaolin, 2.02 kg of pseudoboehmite and 0.47 kg of aluminum sol to 10 kg of deionized water and stir for 120 min. Add hydrochloric acid to adjust the pH to 3.0 and continue stirring for 60 min to obtain the first slurry.

[0084] 2.45 kg of the above matrix DMA-3 and 0.55 kg of magnesium oxide were added to the first slurry and stirred for 30 minutes. The mixture was then spray-dried at a tower outlet temperature of 220°C and calcined at 450°C for 2 hours. After washing twice (each wash was performed at a water:agent ratio of 10:1), the mixture was dried to obtain microspheres, which were designated as DM-3.

[0085] The formulations and properties of the vanadium-resistant additives in Comparative Examples 1–4 are shown in Table 2.

[0086] Table 1

[0087] Additive number M-1 M-2 M-3 M-4 M-5 High-age soil 12 32 23 23 32 luminite 20 25 25 25 25 Aluminum Sol 3 3 2 2 3 Matrix MA-1 65 40 40 Matrix MA-2 50 Matrix MA-3 50 Pore ​​volume, mL / g 0.48 0.42 0.44 0.45 0.44 Apparent density, g / mL 0.66 0.71 0.67 0.68 0.68 Wear index, % / h 2.8 1.1 2.1 2.6 2.5

[0088] Table 2

[0089] Additive number DM-1 DM-2 DM-3 High-age soil 32 23 23 luminite 25 25 25 Aluminum Sol 3 2 2 Matrix DMA-1 40 Matrix DMA-2 41.4 Matrix DMA-3 39.3 Magnesium source 8.6 (Magnesium Chloride) 10.7 (Magnesium Oxide) Pore ​​volume, mL / g 0.35 0.32 0.33 Apparent density, g / mL 0.78 0.7 0.77 Wear index, % / h 5.1 3.9 6.7

[0090] In Tables 1 and 2, the proportions of kaolin, bauxite, alumina sol, matrix MA-1 to MA-3, and matrix DMA-1 to DMA-3 are dry weight ratios.

[0091] Examples 1-5

[0092] The additives prepared in Examples 1 to 5 were uniformly mixed with the main agent CAT-N (trade name CGP-1, manufactured by China Petrochemical Catalyst Co., Ltd.) at a weight ratio of 1:9, and then subjected to 4000ppm vanadium contamination.

[0093] Method of contamination: After introducing heavy metal V into the catalyst mixture via the Michell impregnation method, the catalyst mixture with introduced heavy metal V is then loaded into a D-100 unit (small fixed fluidized bed) and treated on the D-100 unit according to the following steps:

[0094] (a) Heating to 600°C at a heating rate of 20°C / min under a nitrogen atmosphere;

[0095] (b) Heat to 780°C at a heating rate of 1.5°C / min, and then maintain the temperature at 780°C. During the temperature maintenance process, change the treatment atmosphere according to the following steps.

[0096] (i) Treat for 10 minutes in an atmosphere containing 40% by volume nitrogen (of which 5% by volume propylene) and 60% by volume water vapor.

[0097] (ii) Treat for 10 minutes in an atmosphere containing 40% by volume nitrogen (pure nitrogen, propylene-free) and 60% by volume water vapor.

[0098] (iii) Treat for 10 minutes in an atmosphere containing 40% by volume air (containing 4000 ppm SO2) and 60% by volume water vapor.

[0099] (iv) Treat with an atmosphere containing 40% by volume nitrogen and 60% by volume water vapor for 10 minutes; then repeat steps (i)-(iv) in the aforementioned order once each, then repeat step (i) to end the cycle contamination step.

[0100] The catalysts were aged at 800℃ for 4 hours in a 100% volume water vapor atmosphere to obtain the aged catalysts, which were named CAT-M1, CAT-M2, CAT-M3, CAT-M4, and CAT-M5 in sequence.

[0101] Comparative Example 1

[0102] The main agent does not contain anti-metal additives.

[0103] The main agent CAT-N was contaminated with 4000ppm vanadium and then aged at 800℃ for 4 hours in a 100% volume water vapor atmosphere, and was denoted as CAT-NM.

[0104] Comparative Examples 2-4

[0105] The additives prepared in comparative examples 1 to 3 were uniformly mixed with the main agent CAT-N at a weight ratio of 1:9, and then subjected to 4000ppm vanadium contamination (the vanadium content after contamination was 4000ppm by mass). They were then aged at 800℃ in a 100% volume water vapor atmosphere for 4 hours to obtain aged CAT-DM1, CAT-DM2, and CAT-DM3.

[0106] Response evaluation

[0107] The mixtures of the aged vanadium-contaminated catalytic cracking catalysts and additives CAT-M1, CAT-M2, CAT-M3, CAT-M4, CAT-M5, CAT-DM1, CAT-DM2, CAT-DM3, and the contaminated main agent CAT-N were evaluated in an ACE unit under the following conditions: reaction temperature 520℃, and reaction weight hourly space velocity 8 h⁻¹. -1 The ratio of agent to oil was 8 by weight. The properties of the raw oil are shown in Table 3, and the results are shown in Table 4.

[0108] Conversion rate = Gasoline yield + LPG yield + Dry gas yield + Coke yield

[0109] Total liquid yield = Gasoline yield + LPG yield + Diesel yield

[0110] Table 3 Properties of Feed Oil

[0111]

[0112] Table 4 Evaluation Results

[0113]

[0114] As can be seen from the results in Table 4, compared with the comparative examples, the catalysts mixed with the vanadium-resistant additives of Examples 1-5 of the present invention have significantly improved conversion rates, higher gasoline yields, and significantly lower heavy oil yields.

[0115] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0116] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0117] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for utilizing catalytic cracking catalyst residue, comprising the following steps: (1) The catalytic cracking catalyst residue is slurried to obtain a slurry with a solid content of 5-15% by weight; the particle size of the slurry is D(V,0.5)≤8μm, D(V,0.9)≤20μm; (2) Add acid to the slurry obtained in step (1) to adjust the pH value of the slurry to 1~5, and carry out the reaction at 30℃ or above, with a reaction temperature of 30℃~90℃ and a reaction time of 1~8h to obtain activated slurry. (3) The activated slurry is mixed with an aluminum source and a magnesium source, aged at above 80°C, dried, and washed to obtain a mesoporous matrix; the aging temperature is 80°C to 120°C and the aging time is 2 h to 12 h; the mesoporous matrix contains 0.01% to 3% Na2O, 30% to 60% Al2O3, 25% to 40% SiO2, 2% to 15% RE2O3 and 5% to 25% MgO; The specific surface area of ​​the mesoporous matrix is ​​150 m². 2 / g~300m 2 / g, wherein the water droplet pore volume of the mesoporous matrix is ​​0.5 mL / g ~ 0.8 mL / g; The nitrogen adsorption capacity method was used to measure the volume of the medium- and macroporous matrix. The volume of pores with a diameter greater than 10 nm accounted for no less than 40% of the total pore volume. The volume of medium- and macroporous pores with a diameter greater than 10 nm refers to the volume of pores with a diameter greater than 10 nm and not exceeding 100 nm. The total pore volume refers to the volume of pores with a diameter greater than 0 nm and not exceeding 100 nm. The pore size distribution was calculated using the BJH method. (4) Mix the macroporous matrix, binder and clay, slurry, spray dry and wash to obtain catalytic cracking anti-metal additive.

2. The method according to claim 1, wherein, In step (2), the pH value is 1.5~4.

3. The method according to claim 1, wherein, In step (2), the acid is an organic acid and / or an inorganic acid.

4. The method according to claim 3, wherein, In step (2), the organic acid is one or more of formic acid, acetic acid, and oxalic acid, and the inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.

5. The method according to claim 1, wherein, In step (3), the pH value of the mixture formed by mixing the activated slag slurry with the aluminum source and the magnesium source is 8~11.

6. The method according to claim 5, wherein, In step (3), the pH value of the mixture formed by mixing the activated slag slurry with the aluminum source and the magnesium source is 9~11.

7. The method according to claim 1, wherein, The aluminum source is Al(NO3)3, AlCl3, or Al2(SO4). 3、 One or more of the following: boehmite, aluminum sol; The magnesium source is one or more of magnesium oxide, magnesium hydroxide, metallic magnesium, magnesium chloride, magnesium carbonate, and magnesium nitrate. The clay is one or more of the following: kaolin, rettoite, diatomite, montmorillonite, bentonite, and sepiolite.

8. The method according to claim 1, wherein, Based on the dry weight of the resin residue, the resin residue contains 10% to 50% by weight of Al2O3, 30% to 70% by weight of SiO2, 2% to 15% by weight of Na2O, and 1% to 15% by weight of RE2O3.

9. The method according to claim 1, wherein, The mesoporous matrix contains 0.01% to 3% Na₂O, 35% to 55% Al₂O₃, 25% to 35% SiO₂, 4% to 10% RE₂O₃, and 10% to 25% MgO. The specific surface area of ​​the mesoporous matrix is ​​200 m². 2 / g ~300m 2 / g; According to the low-temperature nitrogen adsorption capacity method, the pore volume of the mesoporous matrix with a pore size greater than 10 nm accounts for 45-80% of the total pore volume.

10. The method according to claim 1, wherein, Based on dry weight, the catalytic cracking anti-metal additive contains 10% to 40% by weight of clay, 20% to 40% by weight of binder, and 40% to 70% by weight of the mesoporous matrix.

11. The method according to claim 10, wherein, Based on dry weight, the catalytic cracking anti-metal additive contains 15% to 35% clay, 22% to 35% binder, and 40% to 70% of the mesoporous matrix.

12. The method according to claim 1, wherein, Step (4) includes: mixing clay, binder and water to form a slurry, adding inorganic acid to adjust the pH value to 2.5~4.0 to obtain a first slurry; mixing the first slurry and the mesoporous matrix to obtain a second slurry; spray drying the second slurry, calcining and washing it.

13. A mesoporous matrix material containing 0.01 wt% to 3 wt% Na₂O, 30 wt% to 60 wt% Al₂O₃, 25 wt% to 40 wt% SiO₂, 2 wt% to 15 wt% RE₂O₃, and 5 wt% to 25 wt% MgO; wherein the mesoporous matrix material has a specific surface area of ​​150 m². 2 / g ~300m 2 / g, the pore volume of the water droplet method is 0.5 mL / g ~ 0.8 mL / g, and the proportion of mesoporous and macroporous pores with a pore size greater than 10 nm is more than 40%; the mesoporous and macroporous matrix material is prepared according to the method including steps (1) to (3) of any one of claims 1 to 12.

14. The application of the mesoporous matrix material of claim 13 in vanadium-resistant additives for catalytic cracking.

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