Method for utilizing zeolite y synthesis filtrate

Abstract

The application belongs to the field of environmental protection technology, and relates to a utilization method of Y-type molecular sieve synthesis filtrate. The method utilizes a specific method to synthesize a silicon-aluminum matrix material, and then synthesizes an anti-metal additive, so that the Y-type molecular sieve synthesis filtrate can be utilized, and an anti-metal catalytic cracking additive with good anti-metal property can be obtained.

Description

TECHNICAL FIELD

[0001] The application relates to a method for preparing an anti-metal contamination additive by using a Y-type molecular sieve synthesis filtrate. BACKGROUND

[0002] A catalytic cracking catalyst is a catalyst with the largest consumption in the current oil refining industry, and its preparation process generally comprises the following steps: synthesizing NaY molecular sieve, modifying the molecular sieve, forming a gel from the synthesized molecular sieve, spray drying, and calcining. A large amount of waste water is generated in the multiple processes, and the waste water is subjected to operations such as sedimentation, filtration and slag cutting, and then waste slag mainly composed of Al2O3 and SiO2 is obtained. Utilization of the gel slag or gel slag source in waste water can not only reduce the environmental protection management pressure of enterprises, but also is beneficial to reducing the production cost of enterprises and improving the economic benefits.

[0003] Zhang Zhimin (Research on the Recycling Technology of Catalytic Cracking Catalyst Gel Slag, Qilu Petroleum Chemical Industry, 2011, 39(3): 219-222) directly uses the catalytic cracking catalyst gel slag as a raw material for synthesizing molecular sieve by taking advantage of the high content of silicon and aluminum in the catalyst gel slag, but the crystallinity of the molecular sieve is affected.

[0004] CN102442686B provides a preparation method of ZSM-5 molecular sieve, which comprises crystallizing a slurry containing a silicon source, an aluminum source, an alkali agent, a template agent and water under the crystallization conditions of generating ZSM-5 molecular sieve, wherein 0.1-20 wt% of the silicon source calculated based on SiO2 and 0.1-60 wt% of the aluminum source calculated based on Al2O3 in the catalyst gel slag, the rest of the aluminum source is a soluble aluminum salt, and the rest of the silicon source is at least one of silica gel, water glass solution, silica sol and silica gel. In the catalyst gel slag, the content of SiO2 is 20-60 wt%, the content of Al2O3 is 15-40 wt%, the content of Na2O is 0-30 wt%, and the content of rare earth oxide is 0-10 wt%. The method can fully utilize the colloidal substance formed by the silicon and aluminum compounds in the catalyst gel slag.

[0005] CN104261425A relates to a high-efficiency utilization method of a catalytic cracking catalyst gel slag, which comprises the following steps: firstly, activating the gel slag, and then synthesizing ultrafine Y-type molecular sieve by using a hydrothermal crystallization method under the action of a structure directing agent.

[0006] The above method synthesizes molecular sieve by using gel slag, which can realize the secondary utilization of the gel slag, but causes the quality fluctuation of the molecular sieve.

[0007] In the process of synthesizing NaY molecular sieve, the crystallization product is filtered to form a NaY molecular sieve filter cake and a NaY molecular sieve synthesis post-filtering filtrate, also referred to as a NaY mother liquor. This part of the filtrate is alkaline and contains free silicon oxide and suspended solids. After modification, the NaY molecular sieve is usually used for catalytic cracking. One modification method includes subjecting the NaY molecular sieve or the product of ammonium and / or rare earth exchange of the NaY molecular sieve to ultrastabilization treatment and the step of washing the ultrastabilization treatment, and the filtrate containing silicon oxide and aluminum oxide produced by the washing is referred to as the filtrate after the ultrastabilization modification of the molecular sieve. If the silicon and aluminum substances in the two filtrates are utilized, the amount of sludge generated can be reduced. However, the prior art is difficult to effectively utilize the two filtrates to synthesize a silicon and aluminum material with good metal contamination resistance.

[0008] CN106809854A provides a preparation method of a multi-level porous material, which uses an aluminum source, an alkali solution, and a NaY crystallization mother liquor and / or a water washing filtrate selected from the NaY crystallization mother liquor and / or the water washing filtrate, and the above-mentioned substances are mixed into a gel in a parallel flow manner, and a solid precipitate is obtained after aging, and then sodium is removed through acid mixing exchange. The mixing into a gel is performed at room temperature to 85℃, and the pH value in the mixing into a gel system is controlled to be 7-11, and the weight ratio of SiO2 to Al2O3 is 1:(1-9). The porous material obtained by using the method provided by the application has a mesoporous characteristic, small particle size, and better cracking performance. However, the effect of resisting metal contamination is not good. SUMMARY

[0009] The technical problem to be solved by the present application is to provide a method for reducing the sludge discharge of a catalytic cracking catalyst, which can controllably synthesize a medium and large pore silicon and aluminum matrix material suitable for resisting metal contamination under certain conditions by using wastewater containing a silicon source, an aluminum source and rare earth generated in the production of a molecular sieve, and then preparing an active anti-metal additive by using the silicon and aluminum matrix material.

[0010] The present application further provides a utilization method of the anti-metal additive, which is used by being mixed with a main agent, has higher metal resistance, and has higher catalyst activity after metal contamination.

[0011] In a first aspect, the present application provides a utilization method of a Y-type molecular sieve synthesis post-filtering filtrate, which comprises the following steps:

[0012] (1) adjusting the pH value of the filtrate after the ultrastabilization modification of the molecular sieve to 1-4 by using an acid to obtain the adjusted filtrate after the ultrastabilization modification of the molecular sieve;

[0013] (2) mixing the NaY molecular sieve synthesis post-filtering filtrate (NaY crystallization mother liquor) with the adjusted filtrate after the ultrastabilization modification of the molecular sieve and an acidic aluminum source, controlling the pH value of the mixture to be 2-6, for example, 3-6, and reacting at a reaction temperature of 30-90℃ for 1-12h to obtain a reaction slurry;

[0014] (3) filtering and washing the post-reaction slurry to obtain a silicon-aluminum matrix material;

[0015] (4) slurry-pulping the silicon-aluminum matrix material, adding an inorganic acid to modify the same, and obtaining a modified silicon-aluminum material;

[0016] (5) mixing and slurry-pulping the modified silicon-aluminum material with a clay slurry and a binder, spray-drying, optionally performing a first calcination, and washing to obtain microspheres;

[0017] (6) introducing rare earths into the microspheres by, for example, impregnation or exchange, after a second calcination at 550-700°C, and drying to obtain a metal catalytic cracking aid. The second calcination time is, for example, 1-4 h.

[0018] According to the present application, the solid content of the post-modification filtrate of the molecular sieve ultrastable is 0.5-2% by weight; and the dry basis chemical composition of the solid product obtained by drying includes 1-5% by weight of Na2O, 35-50% by weight of Al2O3, 40-55% by weight of SiO2, and 2-8% by weight of RE2O3.

[0019] According to an embodiment of the present application, the concentration of suspended solids in the post-modification filtrate of the molecular sieve ultrastable is 5000-15000 mg / L.

[0020] According to the present application, the post-modification filtrate of the molecular sieve ultrastable can be the filtrate produced by washing after hydrothermal ultrastable or silicon tetrachloride ultrastable modification; preferably, the filtrate produced by washing for the first time after hydrothermal ultrastable or silicon tetrachloride ultrastable gas phase modification.

[0021] According to an embodiment, the post-modification filtrate of the molecular sieve ultrastable is replaced by a dispersion liquid containing silicon oxide and aluminum oxide with a pH value of 1-4; according to an embodiment, the dispersion liquid containing silicon oxide and aluminum oxide has a solid content of 0.5-2% by weight; and the dry basis chemical composition of the solid product obtained by drying includes 1-5% by weight of Na2O, 35-50% by weight of Al2O3, 40-55% by weight of SiO2, and 2-8% by weight of RE2O3. The dispersion liquid can be obtained by mixing a silica sol and an alumina sol, or by mixing a water glass and an aluminum salt.

[0022] According to the present application, the acid in step (1) is an organic acid and / or an inorganic acid; the organic acid is, for example, one or more of formic acid, acetic acid, and oxalic acid; and the inorganic acid is, for example, one or more of hydrochloric acid, sulfuric acid, nitric acid, boric acid, and phosphoric acid.

[0023] According to the present application, the free SiO2 concentration in the post-synthesis filtrate of the NaY molecular sieve is 10-60 g / L, and the suspended solids content is 5000-15000 mg / L.

[0024] According to the present application, the acidic aluminum source is preferably one or more of Al(N03)3, AlCl3, Al2(S04)3, pseudoboehmite, and aluminum sol; the acidic aluminum source can be added by adding a dispersion of the acidic aluminum source.

[0025] Preferably, the alumina introduced by the acidic aluminum source accounts for 10-35 wt% of the total amount of alumina, silica, and rare earths introduced during the synthesis of the molecular sieve (including: the alumina, silica, and rare earths introduced by the filtrate after the ultrastable modification of the molecular sieve and the filtrate after the synthesis of the NaY molecular sieve, and the alumina introduced by the acidic aluminum source), wherein the rare earths are calculated as RE2O3.

[0026] In step (2), the mixture formed is reacted at a temperature of 30-90°C, such as 40-60°C or 45-55°C, for 1-12 h or 1.5-5 h or 1.5-3 h. The reaction can be carried out with stirring.

[0027] In step (3), the washing is well known to those skilled in the art, for example, water washing can be used. After washing, the material can also be optionally dried to obtain the silica-alumina matrix material.

[0028] According to the present application, the silica-alumina matrix material (also referred to as the silica-alumina material before modification) obtained in step (3) contains 0.01-3 wt% of Na20, 30-60 wt% of Al203, 25-65 wt% of Si02, and 0.1-5 wt%, such as 0.5-5 wt% or 1-5 wt%, of RE2O3. The silica-alumina matrix material has higher hydrothermal stability and good resistance to metal contamination.

[0029] In one embodiment, the silica-alumina matrix material contains 0.1-0.5 wt% of Na20, 30-50 wt%, such as 35-48 wt%, of Al203, 45-62 wt% of Si02, and 0.8-4 wt% of RE2O3.

[0030] In one embodiment, the silica-alumina matrix material contains 0.1-0.5 wt% of Na20, 30-50 wt%, such as 35-48 wt%, of Al203, 45-62 wt% of Si02, and 0.8-4 wt% of RE2O3.

[0031] According to the present application, in one embodiment, the particle size of the pulp after beating in step (4) is controlled to be D(V, 0.5)≤8 μm, D(V, 0.9)≤20 μm. The particle size distribution can be measured by laser particle size method; in the cumulative particle volume distribution from small to large particle diameter, the particle diameters corresponding to the cumulative volume of 50% and 90% of the total volume of particles are D(V, 0.5) and D(V, 0.9), respectively. The laser particle size method for measuring particle size distribution is described in standard NB / SH / T 0951-2017.

[0032] In one embodiment, the modification method in step (4) is as follows: the prepared silicon-aluminum material is beaten and then acid is added, the mass ratio of the added acid to the silicon-aluminum material on a dry basis is 0.01-0.1:1, and the inorganic acid in step (4) is one or more of hydrochloric acid, sulfuric acid, and nitric acid.

[0033] According to the present application, in step (5), the clay can be one or more of kaolin, rectorite, diatomite, montmorillonite, bentonite, and sepiolite; and the binder can be one or more of aluminum sol, silicon sol, silicon-aluminum composite sol, aluminum phosphate sol, and acidified pseudo-boehmite.

[0034] Preferably, the first calcination in step (5) can improve the structural stability of the additive, increase the yield, and improve the washing effect; the first calcination is preferably performed at a temperature of 250-450°C for 1-4 h.

[0035] In step (6), the calcination is performed at 550-700°C for 1-4 h to obtain calcined microspheres. Then, rare earth can be introduced into the calcined microspheres by impregnation or exchange. For example, the calcined microspheres can be mixed with a solution of a rare earth salt and stirred to perform over-impregnation or exchange. In one embodiment, the weight ratio of the solution of the rare earth salt to the calcined microspheres is 2-8:1, for example, 3-5:1, and the concentration of the solution of the rare earth salt is 1-20 wt% of RE2O3, for example, 2-12 wt%. Preferably, the amount of the introduced rare earth is such that the content of the rare earth in the obtained additive is 5-20 wt% of RE2O3 based on the dry weight of the additive.

[0036] In the second aspect of the present application, an anti-metal catalytic cracking additive is provided, which contains 10-40 wt% of clay on a dry basis, 10-40 wt% of a binder on a dry basis, 30-70 wt% of the modified silicon-aluminum material on a dry basis, and 5-20 wt% of RE2O3. The anti-metal catalytic cracking additive has good anti-metal pollution effect.

[0037] In still another aspect, the application provides use of the catalytic cracking catalyst additive of the application in catalytic cracking of heavy oil.

[0038] In a fourth aspect, the application provides a catalytic cracking catalyst comprising a main catalytic cracking catalyst and a metal-resistant catalytic cracking additive, wherein the metal-resistant catalytic cracking additive is the metal-resistant catalytic cracking additive described above or obtained by the method for utilizing the filtrate after filtering of Y-type molecular sieve synthesis.

[0039] According to the above technical solution, the main catalytic cracking catalyst contains Y-type molecular sieve, clay and binder. The Y-type molecular sieve may be one or more of REY molecular sieve, HY molecular sieve, REHY molecular sieve, USY molecular sieve, REUSY molecular sieve, phosphorus-containing REY molecular sieve, phosphorus-containing HY molecular sieve, phosphorus-containing REHY molecular sieve, phosphorus-containing USY molecular sieve, and phosphorus-containing REUSY molecular sieve.

[0040] In the main catalytic cracking catalyst, the clay may be one or more of kaolin, rectorite, diatomite, montmorillonite, bentonite and sepiolite.

[0041] In the main catalytic cracking catalyst, the binder may be one or more of aluminum sol, silicon sol, silicon-aluminum composite sol, aluminum phosphate sol and acidified pseudo-boehmite.

[0042] In a fifth aspect, the application provides a catalytic cracking method, which comprises the step of contacting heavy oil with the catalytic cracking catalyst, wherein the heavy oil contains contaminating metals such as one or more of Fe, Ni and V.

[0043] Optionally, the reaction conditions for contacting the heavy oil with the catalytic cracking catalyst include a temperature of 490-530℃ and a catalyst / oil ratio of 3-8 by weight.

[0044] The method for utilizing the filtrate after filtering of Y-type molecular sieve synthesis provided by the application can utilize NaY mother liquor and molecular sieve modification filtrate to prepare a silicon-aluminum matrix material with good metal contamination resistance and good hydrothermal stability, and then utilize the modified silicon-aluminum material to prepare a catalytic cracking additive. The catalytic cracking additive can have good metal contamination resistance. The method utilizes molecular sieve production waste liquid to prepare a metal contamination resistant additive, which can reduce the waste residue discharge amount of catalytic cracking catalyst production and reduce the raw material cost of metal-resistant catalytic cracking catalyst.

[0045] The catalytic cracking catalyst mixed with the metal-resistant additive of the application has good metal contamination resistance and can significantly improve the total liquid yield of heavy oil conversion and the gasoline yield of the catalytic cracking catalyst after metal contamination.

[0046] The catalytic cracking method provided by the application can be used for catalytic cracking conversion of heavy oil containing contaminating metals.

[0047] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0048] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0049] The hydrothermal ultrastable molecular sieve washing solution has a dry basis content of 23.6 g / L, and contains 3.3 wt% of Na2O, 43.2 wt% of Al2O3, 45.1 wt% of SiO2, and 5.2 wt% of RE2O3 based on the dry basis weight. The pH value is 5.7.

[0050] The NaY molecular sieve synthesis filtrate (referred to as NaY molecular sieve filtrate) has a free SiO2 concentration of 40 g / L and a suspended matter concentration of 13700 mg / L. The dry basis composition of the suspended matter contains 14.5 wt% of Na2O, 3.1 wt% of Al2O3, and 78.1 wt% of SiO2. The NaY molecular sieve filtrate is provided by SINOPEC Catalyst Co., Ltd.

[0051] The kaolin is produced by Suzhou Kaolin Co., Ltd. and has a solid content of 72 wt%;

[0052] The pseudoboehmite is produced by Shandong Branch of China Aluminum Co., Ltd. and has a solid content of 62.0 wt%;

[0053] The alumina content in the aluminum sol is 21.5 wt%;

[0054] The hydrochloric acid is produced by Beijing Chemical Plant and has a specification of analytical pure and a mass concentration of 36%;

[0055] The sulfuric acid is produced by Beijing Chemical Plant and has a specification of analytical pure and a mass concentration of 98%;

[0056] The phosphoric acid is produced by Beijing Chemical Plant and has a specification of analytical pure and a mass concentration of 85%;

[0057] The boric acid is produced by Beijing Chemical Plant and has a specification of analytical pure and a content of 99.99%;

[0058] The aluminum sulfate solution: 90 g Al2O3 / L produced by SINOPEC Catalyst Co., Ltd.

[0059] The specific surface area is analyzed by using the method of NB / SH / T 0959-2017.

[0060] The sample composition is determined by X-ray fluorescence spectroscopy (XRF);

[0061] The apparent bulk density of the catalytic cracking catalyst is determined according to NB / SH / T 0954-2017.

[0062] The pore volume of the catalytic cracking catalyst is determined according to NB / SH / T 0955-2017.

[0063] The attrition index of the catalytic cracking catalyst is determined according to NB / SH / T 0964-2017.

[0064] The filtrate suspended substance is measured according to GB11901.

[0065] The free silicon dioxide is measured according to GB / T 12149.

[0066] The solid content analysis method is as follows: the ratio of the solid weight after calcination at 850℃ for 1h to the solid weight before calcination, i.e., solid content = 100% x w (焙烧前) / w (焙烧前)

[0067] Silicon-aluminum material preparation example 1

[0068] Sulfuric acid (20 mass fraction %) is added to adjust the pH of the filtrate after the ultrastable modification of the molecular sieve to 3.7 to obtain an adjusted filtrate. The adjusted filtrate, NaY molecular sieve filtrate, and aluminum sulfate solution are mixed according to a volume ratio of 70:5:6, and the pH value of the mixture is 3.3. The mixture is stirred at a temperature of 50℃ for 2h to react. The slurry after the reaction is filtered, washed with deionized water according to a weight ratio of water:solid (dry basis) = 10:1, and the above washing is repeated once. The dried product is a silicon-aluminum matrix material GL-1, and the specific surface area of the silicon-aluminum matrix material GL-1 is 315m 2 / g. In terms of weight percentage content, the Na2O content of GL-1 is 0.22%, the Al2O3 content is 49.4%, the SiO2 content is 45.1%, and the RE2O3 content is 2.5%.

[0069] Silicon-aluminum material preparation example 2

[0070] Sulfuric acid (20 mass fraction %) is added to adjust the pH of the filtrate after the ultrastable modification of the molecular sieve to 2.7, and then mixed with the NaY synthesis filtrate and aluminum sulfate according to a volume ratio of 20:1:0.8. The pH value of the mixture is 3.1, and then the mixture is stirred at a temperature of 50℃ for 2h to react. The slurry after the reaction is filtered, washed with deionized water according to a weight ratio of water:solid (dry basis) = 10:1, and the above washing is repeated twice. The dried product is a silicon-aluminum matrix material GL-2, and the specific surface area of the silicon-aluminum matrix material GL-2 is 290m 2Na2O content of 0.57%, Al2O3 content of 43.4%, SiO2 content of 49.1%, and RE2O3 content of 3.2% in terms of weight percentage.

[0071] Silico-aluminum material preparation example 3

[0072] The pH of the filtrate after the ultrastable modification of the molecular sieve was adjusted to 2 by adding hydrochloric acid to obtain an adjusted filtrate. The adjusted filtrate, the NaY molecular sieve filtrate, and the aluminum sulfate solution were mixed in a volume ratio of 20:5:1, and the pH was 2.2. The mixture was stirred and reacted at a temperature of 50°C for 2h. The slurry after the reaction was filtered, washed with deionized water at a water:solid ratio of 10:1 (by weight), and then washed again according to the above washing process. The dried product was a silico-aluminum matrix material GL-3, which had a specific surface area of 321m 2 / g. In terms of weight percentage, the Na2O content of GL-3 was 0.31%, the Al2O3 content was 36.3%, the SiO2 content was 60.7%, and the RE2O3 content was 2.5%.

[0073] Silico-aluminum material preparation example 4

[0074] The pH of the filtrate after the ultrastable modification of the molecular sieve was adjusted to 2.7 by adding hydrochloric acid to obtain an adjusted filtrate. The adjusted filtrate, the NaY molecular sieve filtrate, and the aluminum sulfate solution were mixed in a volume ratio of 10:6:3, and the pH was controlled at 4.3. The mixture was stirred and reacted at a temperature of 50°C for 2h. The slurry after the reaction was filtered, washed with deionized water at a water:solid ratio of 10:1 (by weight), and then washed again according to the above washing process. The dried product was a silico-aluminum matrix material GL-4, which had a specific surface area of 284m 2 / g. In terms of weight percentage, the Na2O content of GL-4 was 0.16%, the Al2O3 content was 44.2%, the SiO2 content was 51.4%, and the RE2O3 content was 0.95%.

[0075] Anti-metal additive preparation example 1

[0076] The above GL-1 silico-aluminum matrix material 3.13Kg (solid content 80% by weight) was added to 7Kg of deionized water to make a slurry, with a D(V,0.5) of 3.7μm and a D(V,0.9) of 8.9μm. 0.1kg of hydrochloric acid was added to modify it to obtain a first slurry.

[0077] In 10Kg of deionized water, 1.11Kg of kaolin, 1.61Kg of pseudo-boehmite (referred to as alumina), and 0.7Kg of aluminum sol were added and stirred for 120min. Hydrochloric acid was added to adjust the pH to 3.0, and stirring was continued for 60min to obtain a second slurry.

[0078] The first slurry was added to the second slurry, stirred for 30 minutes, spray dried at an outlet temperature of 220°C, calcined in a muffle furnace at 300°C for 2 hours, washed with water to catalyst (weight ratio of water to calcined microspheres) = 10:1, and the washing was repeated twice to obtain the microspheres.

[0079] After the microspheres were calcined at 550°C for 2 hours, 1 kg of the microspheres (solid content 95% by weight) were added to 4 kg of deionized water in which 0.261 kg of cerium chloride hexahydrate (cerium oxide content 45% by weight) was dissolved, stirred for 30 minutes, filtered and dried to obtain the metal-resistant catalytic cracking aid M-1.

[0080] Table 1

[0081]

[0082]

[0083] In Table 1, the weight ratio is based on dry basis, and the cerium chloride is based on Ce2O3.

[0084] The dry basis weight is the weight of the solid product after calcination at 850°C for 1 hour.

[0085] Preparation of metal-resistant aids in Examples 2-7

[0086] Catalysts M-2-M-7 were prepared according to the method of Example 1, and the formulations are shown in Table 1. In Example 2, boric acid was added to the second slurry, and in Example 3, phosphoric acid was added to the second slurry.

[0087] The formulations of the metal-resistant aids are shown in Table 1, and the properties are shown in Table 2.

[0088] Table 2

[0089] Aid No. Pore volume, ml / g Bulk ratio (apparent bulk density), g / mL Wear index (AI), % / h M-1 0.56 0.61 2.6 M-2 0.51 0.67 2 M-3 0.47 0.71 1.7 M-4 0.50 0.69 1.6 M-5 0.45 0.74 1.2 M-6 0.38 0.77 1.9 M-7 0.51 0.63 2.2 D2M-2 0.48 0.63 4.7 D3M-3 0.49 0.60 5.2 D4M-1 0.57 0.57 6.9

[0090] Examples 1-7

[0091] The metal-resistant aids M-1-M-7 prepared in Examples 1-7 were mixed with the main agent CAT-N (a CMT catalytic cracking catalyst containing Y-type molecular sieves, a product of Sinopec Catalyst Co., Ltd.) at a weight ratio of 1:9, and then contaminated with 5000 ppm of nickel, 2000 ppm of iron and 3000 ppm of vanadium to obtain contaminated CAT-M1, CAT-M2, CAT-M3, CAT-M4, CAT-M5, CAT-M6 and CAT-M7.

[0092] Method of contamination: The catalyst mixture was introduced with heavy metals (Fe, Ni and V) by the Mitchell impregnation method, and then the catalyst with heavy metals introduced was charged into a D-100 device (a small fixed fluidized bed), and the following steps were carried out on the D-100 device:

[0093] (a) heating to 600°C at a temperature increase rate of 20°C / min under a nitrogen atmosphere;

[0094] (b) heating to 780°C at a temperature increase rate of 1.5°C / min, and then keeping the temperature at 780°C, and in the process of keeping the temperature, the treatment atmosphere was changed as follows:

[0095] (i) treating for 10 minutes with an atmosphere containing 40% by volume of nitrogen (containing 5% by volume of propylene in the nitrogen) and 60% by volume of water vapor,

[0096] (ii) treating for 10 minutes with an atmosphere containing 40% by volume of nitrogen (pure nitrogen without propylene) and 60% by volume of water vapor,

[0097] (iii) treating for 10 minutes with an atmosphere containing 40% by volume of air (containing 4000 ppm of SO2) and 60% by volume of water vapor,

[0098] (iv) treating for 10 minutes with an atmosphere containing 40% by volume of nitrogen and 60% by volume of water vapor; and then repeating steps (i)-(iv) each once in the order mentioned above, and then repeating step (i) to end the cycle of contamination.

[0099] Comparative Example 1

[0100] Main agent without adding anti-metal additives

[0101] The main agent CAT-N was contaminated with 5000 ppm of nickel, 2000 ppm of iron and 3000 ppm of vanadium according to Example 1 to obtain CAT-NM.

[0102] Comparative Example 2

[0103] The comparative silicon-aluminum material DGL-1 was prepared according to the method of Example 1 for preparing a silicon-aluminum material, wherein the hydrothermal ultrastable molecular sieve washing solution was directly used without adjusting the pH value, and the filter solution after synthesis of the NaY molecular sieve and aluminum sulfate were added into the stirred tank in parallel flow. The chemical composition of DGL-1 was as follows: the content of Na2O was 0.17% by weight, the content of Al2O3 was 47.1% by weight, the content of SiO2 was 47.0% by weight, the specific surface area was 222.7 m 2GL-1 was replaced by an equal amount of DGL-1 to prepare the metal-resistant additive according to the method of Example 1 of the anti-metal additive preparation, to obtain the additive D2M-2. Then mixed with the main agent CAT-N according to the method of Example 1, and contaminated with metals according to the pollution amount of Example 1, to obtain CAT-D2M2.

[0104] Comparative Example 3

[0105] Mesoporous material DGL-2 was prepared according to the method of Example 1 of the patent CN106809854A, and the pH was controlled at 10.8 during the preparation process. The chemical composition of the prepared material was Na2O content of 0.23 wt%, Al2O3 content of 51.4 wt%, and SiO2 content of 46.1 wt%. Then an equal amount of DGL-2 was used to replace GL-2 to prepare the additive according to the method of Example 3 of the anti-metal additive preparation, to obtain the additive D3M-3. Then mixed with the main agent CAT-N according to the method of Example 1, and contaminated with metals according to the pollution amount of Example 1, to obtain CAT-D3M3.

[0106] Comparative Example 4

[0107] The GL-1 obtained by the method of Example 1 of the anti-metal additive preparation was used to prepare the comparative example D4M-1 according to the method of Example 1 of the anti-metal additive preparation, except that the GL-1 was not modified with inorganic acid after being pulped during the preparation process. The comparative example D4M-1 prepared has poorer anti-wear performance than Example 1.

[0108] Test Example 1

[0109] CAT-M1 to CAT-M7 and CAT-NM, CAT-D2M2, CAT-D3M3 were pre-aged in a fixed bed aging device at 800℃ for 4 hours with 100% water vapor, and then evaluated in a small fixed bed reactor. The properties of the raw oil are shown in Table 3. The reaction temperature was 500℃, the agent to oil ratio (weight ratio) was 8, and the weight hourly space velocity was 8h -1 .

[0110] Wherein, the conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield;

[0111] Total liquid yield = liquefied gas yield + gasoline yield + diesel yield;

[0112] Coke selectivity = coke yield / conversion rate; the evaluation results are shown in Table 4.

[0113] Table 3 Properties of raw oil

[0114]

[0115] Table 4 Evaluation results

[0116]

[0117] The results in Table 4 show that, after being contaminated, the catalysts doped with the anti-metallic agent of the present application have significantly improved conversion rate and significantly reduced heavy oil yield compared with the catalysts without the doped agent.

[0118] The agent provided by the present application can have better anti-metallic contamination effect, and after being mixed with the main agent and contaminated by metal, can have higher gasoline yield and higher total liquid yield.

[0119] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0120] In addition, it should be noted that, in the above specific embodiments, various specific technical features can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0121] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should also be considered as disclosed by the present application.

Claims

1. A method for utilizing a Y-type molecular sieve synthesis filtrate, comprising the following steps: (1) adjusting the pH value of a molecular sieve ultrastable modified filtrate to 1-4 using an acid to obtain an adjusted molecular sieve ultrastable modified filtrate; the molecular sieve ultrastable modified filtrate has a solid content of 0.5-2 wt%, and the dry basis chemical composition of the solid product obtained by drying the filtrate includes 1-5 wt% Na 2 O, 35-50 wt% Al 2 O 3, 40-55 wt% SiO 2, and 2-8 wt% RE 2 O 3; (2) mixing a NaY molecular sieve synthesis post-filtration filtrate with the adjusted molecular sieve ultrastable modified filtrate and an acidic aluminum source, wherein the pH value of the formed mixture is controlled to be 2-6, and the mixture is reacted at a reaction temperature of 30-90 ℃ for 1-12 h to obtain a post-reaction slurry; the free SiO 2 concentration in the NaY molecular sieve synthesis post-filtration filtrate is 10-60 g / L, and the suspended solids content is 5000-15000 mg / L; the aluminum oxide introduced by the acidic aluminum source accounts for 10-35 wt% of the total amount of the molecular sieve ultrastable modified filtrate, the NaY molecular sieve synthesis post-filtration filtrate, and the aluminum oxide and silicon oxide and rare earth introduced by the acidic aluminum source, wherein the rare earth is calculated as RE 2 O 3; (3) filtering and washing the post-reaction slurry to obtain a silicon-aluminum matrix material; the obtained silicon-aluminum matrix material contains 0.01-3 wt% Na 2 O, 30-60 wt% Al 2 O 3, 25-65 wt% SiO 2, and 0.1-5 wt% RE 2 O 3; and the obtained silicon-aluminum matrix material includes drying; (4) slushing the silicon-aluminum matrix material and adding an inorganic acid modification to obtain a modified silicon-aluminum material; the mass ratio of the added acid to the silicon-aluminum matrix material on a dry basis is 0.01-0.1:1; (5) mixing and slushing the modified silicon-aluminum material with a clay slurry and a binder, spray drying, optionally first calcining, and washing to obtain microspheres; and (6) calcining the microspheres at 550-700 ℃ to introduce rare earth and drying. The molecular sieve ultrastable modified filtrate is a filtrate produced by hydrothermal ultrastabilization and silicon tetrachloride ultrastabilization and washing. The acid in step (1) is an organic acid and / or an inorganic acid. 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, and nitric acid. The acidic aluminum source is one or more of Al (NO 3) 3, AlCl 3, Al 2 (SO 4) 3, pseudo-boehmite, and aluminum sol. The silicon-aluminum matrix material obtained in step (3) contains 0.1-0.5 wt% Na 2 O, 30-50 wt% Al 2 O 3, 45-62 wt% SiO 2, and 0.8-4 wt% RE 2 O 3. The modification method in step (4) is to add an acid after slushing the prepared silicon-aluminum material; the inorganic acid in step (4) is one or more of hydrochloric acid, sulfuric acid, nitric acid, boric acid, and phosphoric acid; and the particle size of the slushed slurry in step (4) is controlled to be D (V, 0.5) ≤8 μm and D (V, 0.9) ≤20 μm.

2. The method of claim 1, wherein, ​ 3. The method of claim 1, wherein, ​ 4. The method of claim 3, wherein, ​ 5. The method of claim 1, wherein, ​ 6. The method of claim 1, wherein, ​ 7. The method of claim 1, wherein, ​ 8. The method of claim 1, wherein, The clay is one or more of kaolin, halloysite, diatomite, montmorillonite, bentonite and sepiolite; the binder is one or more of aluminum sol, silica sol, silica-aluminum composite sol, aluminum phosphate sol and acidified pseudo-boehmite.

9. An anti-metallic FCC aid, containing 10-40 wt% of clay on a dry basis, 10-40 wt% of binder on a dry basis, 30-70 wt% of the modified silica-aluminum material of claim 1 on a dry basis and 5-20 wt% of RE2O3, based on the dry weight of the anti-metallic FCC aid; the modified silica-aluminum material is prepared according to the method of any one of claims 1-8.

10. A catalytic cracking catalyst, comprising a main catalytic cracking catalyst and an anti-metallic FCC aid, the anti-metallic FCC aid being the anti-metallic FCC aid of claim 9 or the anti-metallic FCC aid prepared according to the method of any one of claims 1-8.

11. The catalytic cracking catalyst according to claim 10, characterized in that The main catalytic cracking catalyst contains Y-type molecular sieve, clay, binder; the Y-type molecular sieve is one or more of REY molecular sieve, HY molecular sieve, REHY molecular sieve, USY molecular sieve, REUSY molecular sieve, phosphorus-containing REY molecular sieve, phosphorus-containing HY molecular sieve, phosphorus-containing REHY molecular sieve, phosphorus-containing USY molecular sieve, phosphorus-containing REUSY molecular sieve; the clay is one or more of kaolin, halloysite, diatomite, montmorillonite, bentonite and sepiolite; the binder is one or more of aluminum sol, silica sol, silica-aluminum composite sol, aluminum phosphate sol and acidified pseudo-boehmite.

12. A catalytic cracking method, comprising the step of contacting and reacting heavy oil with the catalytic cracking catalyst of claim 10 or 11, the heavy oil containing contaminating metals, the contaminating metals being one or more of Fe, Ni and V.

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