Method for graded utilization of waste catalytic cracking / catalytic cracking catalyst

Abstract

The invention provides a graded utilization method of a waste catalytic cracking / catalytic cracking catalyst. The method comprises the following steps: screening the waste catalytic cracking / catalytic cracking catalyst into two parts according to the particle size, taking the waste catalytic cracking / catalytic cracking catalyst with the particle size in a range from a first particle size threshold value to a second particle size threshold value as a first part to-be-treated catalyst, and taking the rest part as a second part to-be-treated catalyst, the first granularity threshold is smaller than or equal to the second granularity threshold and larger than or equal to 45 microns, and the second granularity threshold is smaller than or equal to 110 microns; sequentially carrying out alkali treatment and acid treatment on the first part of the to-be-treated catalyst to obtain a reactivated catalytic cracking / catalytic cracking catalyst; crushing the second part of the to-be-treated catalyst, carrying out acid leaching treatment, and carrying out solid-liquid separation to obtain a leaching solution and loose microspheres; the leaching liquid is used for metal recovery; reacting the loose microspheres with a hydrofluoric acid solution, introducing generated gas into a sodium hydroxide solution, and removing a solid phase from a product obtained by the reaction to obtain liquid sodium silicate.

Description

Technical Field

[0001] The invention belongs to the technical field of oil refining catalysts and relates to a method for graded utilization of waste catalytic cracking / catalytic cracking catalysts. Background Art

[0002] Catalytic cracking / catalytic cracking is an important oil refining process that converts heavy oil and crude oil into finished oil such as gasoline and diesel or basic chemical raw materials such as ethylene and propylene. At present, most industrial catalytic cracking / catalytic cracking units use fast fluidized bed (riser) reactors and use microsphere catalysts with an average particle size of 60-80μm. With the long-term operation of catalytic cracking / catalytic cracking equipment, the content of heavy metals Ni, V, coke, and alkali metals continues to increase, resulting in a continuous decrease in catalyst activity, selectivity, hydrothermal stability, and conversion rate. It is usually impossible to achieve activity balance by adding fresh catalyst. It is necessary to discharge the used catalyst from the equipment in a timely manner and replace it with fresh catalyst. The discharged catalyst is called spent catalytic cracking / catalytic cracking catalyst.

[0003] There are three main sources of spent catalytic cracking / catalytic cracking catalysts: the most important source is that during the operation of the catalytic cracking / catalytic cracking equipment, the catalyst activity is reduced due to the poisoning of high temperature and heavy metals and cannot meet the requirements of the catalytic cracking / catalytic cracking reaction. In order to maintain the catalyst in the equipment at a certain activity, fresh agents are regularly added and some deactivated catalysts are removed from the regenerator; the second is fine particles with a particle size of less than 20 μm generated by factors such as collision or thermal collapse between the catalyst and the high-speed logistics (main air and crude oil), container wall and catalyst particles in the equipment. These particles cannot be collected by the first and second stage cyclone separators, but can be collected by the subsequent third stage cyclone separator. These spent catalysts are the third cyclone fine powder; the third source is the ultrafine catalyst powder collected from the flue gas desulfurization and denitrification sludge during the flue gas purification process. The chemical composition of spent catalytic cracking / catalytic cracking catalysts includes aluminum oxide, silicon oxide, rare earth, nickel, vanadium, etc., and the typical content is shown in Table 1.

[0004] Table 1. Chemical composition of spent catalytic cracking / catalytic cracking catalyst

[0005] project <![CDATA[ω(Al2O3),%]]> <![CDATA[ω(SiO2),%]]> <![CDATA[ω(RE2O3),%]]> ω(Ni), μg / g ω(V), μg / g Waste Catalyst 43.5 46.4 4.5 7200 2500

[0006] According to statistics, the world produces about 500,000 tons of spent FCC / Cracking catalysts every year, and the amount continues to grow at an annual rate of 5%. At present, the most common way to deal with spent FCC / Cracking catalysts is to bury them. Since spent FCC / Cracking catalysts contain heavy metal elements such as Ni, V, and rare earths, burying them will inevitably lead to a large amount of waste of effective resources and cause pollution to the ecological environment.

[0007] In recent years, researchers have studied waste catalytic cracking / catalytic cracking catalysts and proposed some methods for resurrecting waste catalysts and recovering waste catalyst elements. However, the following problems are common: (1) poor strength and fluidization performance of the resurrection agent; (2) the focus is mainly on recovering the metal elements of the waste catalytic cracking / catalytic cracking catalysts, including rare earths, nickel, vanadium and alumina, and there is basically no method for recovering silicon. In short, the current waste catalytic cracking / catalytic cracking catalyst treatment technology cannot achieve full utilization of waste catalytic cracking / catalytic cracking catalysts.

[0008] In summary, there is still a need to study the treatment technology of waste catalytic cracking / catalytic cracking catalysts in order to achieve the full recovery and utilization of waste catalytic cracking / cracking catalysts, maximize the use of resources, and enhance both economic and environmental benefits. Summary of the invention

[0009] The object of the present invention is to provide a technical solution that can achieve the full recycling of spent catalytic cracking / catalytic cracking catalysts. In order to achieve the above object, the present invention provides the following technical solution.

[0010] The present invention provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0011] The spent catalytic cracking / catalytic cracking catalyst is screened into two parts according to the particle size, and the spent catalytic cracking / catalytic cracking catalyst with a particle size within the range of a first particle size threshold value and a second particle size threshold value is used as the first part of the catalyst to be treated, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size is used as the second part of the catalyst to be treated; wherein the first particle size threshold value is less than or equal to the second particle size threshold value, and the first particle size threshold value is not less than 45 μm, and the second particle size threshold value is not more than 110 μm;

[0012] The first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence to obtain a revived catalytic cracking / catalytic cracking catalyst;

[0013] The second part of the catalyst to be treated is crushed and then subjected to acid leaching treatment, and a leachate and loose microspheres are obtained through solid-liquid separation; the leachate is used to recover metals; the loose microspheres react with a hydrofluoric acid solution, and the generated gas is passed into a sodium hydroxide solution for reaction, and the solid phase of the product obtained by the reaction is removed to obtain liquid sodium silicate.

[0014] The method for graded utilization of waste catalytic cracking / catalytic cracking catalysts provided by the present invention grades the waste catalytic cracking / catalytic cracking catalysts according to particle size, and the waste catalytic cracking / catalytic cracking catalysts within a specific particle size range are subjected to alkali treatment and acid treatment to effectively realize their revival and avoid the problems of poor resurrection agent strength and fluidization performance, and the waste catalytic cracking / catalytic cracking catalysts of the remaining particle size are effectively recovered simultaneously through specific treatment of various major elements including silicon and metal elements, thereby completing the revival and utilization of the waste catalytic cracking / catalytic cracking catalysts and the recovery of all elements, and realizing the full recovery of the waste catalytic cracking / catalytic cracking catalysts.

[0015] The invention provides a method for graded utilization of waste catalytic cracking / catalytic cracking catalysts, which sequentially treats waste catalytic cracking / catalytic cracking catalysts within a specific particle size range with alkali and acid to restore their activity. The alkali treatment can expose the pores and surface of the waste catalytic cracking / catalytic cracking catalysts so that heavy metals can be easily leached out by subsequent acid solutions. The acid treatment can clean the pores of the waste catalytic cracking / catalytic cracking catalysts and remove heavy metals. The waste catalytic cracking / catalytic cracking catalysts within a specific particle size range can effectively restore their activity after sequentially treating with alkali and acid.

[0016] The invention provides a method for graded utilization of waste catalytic cracking / catalytic cracking catalysts, wherein the waste catalytic cracking / catalytic cracking catalysts are subjected to acid leaching treatment to leach Ni, V, rare earth and Al components in the waste catalytic cracking / catalytic cracking catalysts into a leachate and obtain loose silicon-containing microspheres, which are then reacted with a hydrofluoric acid solution to generate silicon tetrafluoride gas, SiO2+4HF=SiF4(gas)+2H2O, thereby achieving silicon entry into the generated gas phase, and the gas phase is passed into a sodium hydroxide solution to generate a liquid silicon product, SiF4+6NaOH=Na2SiO3+4NaF+3H2O.

[0017] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalyst, the first particle size threshold is 45-65 μm, and the second particle size threshold is 85-110 μm;

[0018] Further, the first particle size threshold is 60 μm, and the second particle size threshold is 100 μm.

[0019] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence, and the alkali used in the alkali treatment is sodium hydroxide.

[0020] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, the first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence, and the acid used in the acid treatment is at least one of hydrochloric acid and nitric acid.

[0021] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence, comprising:

[0022] Mixing the first part of the catalyst to be treated with water and an alkali solution, treating at 70-100° C. for 1-4 hours, then performing solid-liquid separation and drying the separated solid phase to obtain an alkali-treated catalyst;

[0023] The alkali-treated catalyst is mixed with water and an acid solution, treated at room temperature for 5-30 minutes, then solid-liquid separation is performed and the separated solid phase is dried, and the dried product is calcined to obtain a revived catalytic cracking / catalytic cracking catalyst;

[0024] Furthermore, during the mixing of the first part of the catalyst to be treated with water and the alkaline solution, the mass ratio of the first part of the catalyst to be treated to water is 1:3-1:6;

[0025] Further, the mass concentration of the alkali in the alkali solution is 0.5-5%, preferably 1-3%;

[0026] Further, the mass of the alkali in the alkali solution is 1-10% of the mass of the first part of the catalyst to be treated, preferably 2-6%;

[0027] Further, the ratio of the mass of the first part of the catalyst to be treated to the mass of the water used in the process of mixing the catalyst treated with alkali with water and acid solution is 1:3-1:6;

[0028] Further, the mass concentration of the acid in the acid solution is 0.15-3.5%, preferably 0.35-1.5%;

[0029] Furthermore, the mass of the acid in the acid solution is 0.1-5%, preferably 0.3-2%, of the mass of the first part of the catalyst to be treated.

[0030] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalyst, the second portion of the catalyst to be treated is treated in the following manner:

[0031] The catalyst to be treated in the second part is crushed and then subjected to hydrochloric acid leaching at 60-120° C. using hydrochloric acid having a HCl concentration of 1-3 mol / L (based on the volume of the hydrochloric acid), and a leaching solution and loose microspheres are obtained by solid-liquid separation;

[0032] Utilizing leachate for metal recovery;

[0033] The loose microspheres react with a hydrofluoric acid solution, and the generated gas is passed into a sodium hydroxide solution for reaction, and the solid phase is removed from the product obtained by the reaction to obtain liquid sodium silicate; wherein the mass concentration of HF in the hydrofluoric acid solution is 5-47% (based on the total mass of the hydrofluoric acid solution as 100%), and the mass concentration of sodium hydroxide in the sodium hydroxide solution is 5-40% (based on the total mass of the sodium hydroxide solution as 100%);

[0034] In the preferred embodiment, the waste catalytic cracking / catalytic cracking catalyst is subjected to acid leaching treatment with hydrochloric acid of a specific concentration at a specific temperature, so that the Ni, V, rare earth, and Al components in the waste catalytic cracking / catalytic cracking catalyst are completely or nearly completely leached into the leachate and loose microspheres with high silicon content, large porosity, and large silicon exposed surface area are obtained (wherein the silicon component is completely or nearly completely retained in the loose microspheres), and then the loose microspheres are mixed with hydrofluoric acid of a specific concentration, and a large number of accessible silicon species in the loose microspheres react deeply with the hydrofluoric acid to generate silicon tetrafluoride gas, so that the silicon completely or nearly completely enters the generated gas phase, and then the gas phase is introduced into a sodium hydroxide solution to react the silicon tetrafluoride gas with a sodium hydroxide solution of a specific concentration to generate sodium fluoride and sodium silicate, and the reaction product is concentrated to precipitate NaF solid, and then the solid phase is removed to obtain a high-purity liquid silicon product, i.e., a sodium silicate solution; the loose microspheres obtained in the preferred embodiment are a kind of product with a very high silicon content (which can reach more than 98.5%) and a very high porosity (which can reach 0.9 cm 3 / g or more), loose microspheres with large silicon exposed surface area, which lays the foundation for efficient and high-purity recovery of silicon; in summary, efficient and high-purity recovery of silicon is achieved through acid leaching with hydrochloric acid of a specific concentration at a specific temperature, treatment with a hydrofluoric acid solution of a specific concentration, and treatment with sodium hydroxide of a specific concentration, and the recovery rate of silicon can reach 95%; at the same time, the acid leaching with hydrochloric acid of a specific concentration at a specific temperature and treatment with a hydrofluoric acid solution can completely or almost completely leach Ni, V, rare earth, and Al components into the leachate, laying the foundation for efficient recovery of Ni, V, rare earth, and Al components; this preferred technical solution simultaneously realizes efficient recovery of silicon and metals (the recovery rates of silicon and metals can reach a relatively high level);

[0035] Further, based on the total mass of the waste catalytic cracking / catalytic cracking catalyst as 100%, the mass content of SiO2 in the waste catalytic cracking / catalytic cracking catalyst is 40-50wt%, and the mass content of SiO2, Al2O3, RE2O3, Ni, and V is not less than 99.5wt%; further, based on the total mass of the waste catalytic cracking / catalytic cracking catalyst as 100%, the mass content of SiO2 in the waste catalytic cracking / catalytic cracking catalyst is 40-50wt%, the mass content of Al2O3 is 40-50wt%, the mass content of RE2O3 is 0.1-10wt%, the mass content of Ni is 0.01-2wt%, and the mass content of V is 0.01-2wt%;

[0036] Furthermore, before the spent catalytic cracking / catalytic cracking catalyst is subjected to hydrochloric acid leaching treatment, it is crushed into a material with a particle size of 1-15 μm and then subjected to hydrochloric acid leaching treatment;

[0037] Further, the hydrochloric acid pickling treatment time is 4-24h;

[0038] Furthermore, the silicon oxide content of the loose microspheres is not less than 98.5wt% (based on the total mass of the loose microspheres as 100%), and the porosity is not less than 0.9cm 3 / g;

[0039] Furthermore, based on the total mass of the loose microspheres as 100%, the total mass content of rare earth, aluminum, nickel and vanadium in the loose microspheres is less than 1.5wt%;

[0040] Further, the mass concentration of HF in the hydrofluoric acid solution is 15-25% (based on the total mass of the hydrofluoric acid solution as 100%);

[0041] Further, the temperature of the reaction between the loose microspheres and the hydrofluoric acid solution is 20-80°C;

[0042] Further, the reaction time of the loose microspheres and the hydrofluoric acid solution is 0.1-1h;

[0043] Further, the reaction of the loose microspheres with the hydrofluoric acid solution is carried out under stirring conditions, and the stirring speed is 300-600 rpm;

[0044] Furthermore, the reaction of the loose microspheres and the hydrofluoric acid solution is carried out in a closed polytetrafluoroethylene-lined high-pressure reactor; wherein the total loading amount of the loose microspheres and the hydrofluoric acid solution in the polytetrafluoroethylene-lined high-pressure reactor is 1 / 5-1 / 3 of the volume of the reactor, and the pressure in the polytetrafluoroethylene-lined high-pressure reactor during the reaction of the loose microspheres and the hydrofluoric acid solution is 0.1-20MPa;

[0045] Further, the mass concentration of sodium hydroxide in the sodium hydroxide solution is 10-25% (based on the total mass of the sodium hydroxide solution as 100%);

[0046] Further, the temperature at which the generated gas is passed into the sodium hydroxide solution for reaction is 60-100°C;

[0047] Further, the generated gas is passed into the sodium hydroxide solution for a reaction time of 0.2-2h;

[0048] Furthermore, the generated gas is passed into a sodium hydroxide solution for reaction in a closed high-pressure reactor.

[0049] Furthermore, the method also includes: the liquid sodium silicate obtained by removing the solid phase is concentrated, adjusted with alkali solution and re-filtered to obtain a sodium silicate solution product that meets the modulus and concentration requirements; further, the concentration is carried out at 85-105° C., and the concentration time is 1 hour; further, the alkali solution adjustment adjusts the pH value to 12-13; further, the modulus of the sodium silicate solution product is 1.5-3.5; further, the mass concentration of SiO2 in the sodium silicate solution product is 15-25wt%.

[0050] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the metal recovery using the leaching solution comprises:

[0051] The leaching solution is mixed with the oxalic acid solution and the pH value is adjusted to 1.6-2.3 by using an alkali solution for reaction, and the oxalic acid rare earth salt precipitate and the first filtrate are obtained through solid-liquid separation to realize rare earth recovery;

[0052] The first filtrate is subjected to extraction to recover vanadium, thereby obtaining a vanadium-rich extract and an extraction residue, thereby achieving vanadium recovery;

[0053] The pH value of the extract residue is adjusted to 6-10 by using alkaline solution to react, and a mixed precipitate of aluminum hydroxide and nickel hydroxide is obtained by solid-liquid separation;

[0054] Adding alkaline solution to the mixed precipitate of aluminum hydroxide and nickel hydroxide to adjust the pH value to 12-13 for reaction, and performing solid-liquid separation to obtain nickel hydroxide precipitate and aluminate solution, thereby realizing the recovery of nickel and aluminum;

[0055] In this preferred technical solution, the characteristic of aluminum hydroxide as an amphoteric compound that can dissolve under strong acid and strong alkaline conditions is utilized in combination with specific treatment to recover nickel and aluminum. Specifically, alkaline solution is added to the acidic extraction residue to adjust the pH value to 6-10, and nickel and aluminum exist in the form of hydroxide precipitation. When the alkalinity is further increased and the pH value is adjusted to 12-13, nickel hydroxide is still a solid precipitate, and aluminum hydroxide is dissolved into sodium aluminate solution under strong alkaline conditions. The separation and recovery of nickel and aluminum are achieved by filtering and solid-liquid separation.

[0056] Furthermore, the metal recovery using the leaching solution also includes: evaporating the vanadium-rich extract to dryness, pyrolyzing, and roasting to obtain vanadium pentoxide;

[0057] Further, the concentration of oxalic acid in the oxalic acid solution is 0.1-0.5 mol / L (based on the volume of the oxalic acid solution);

[0058] Furthermore, the alkali solution used in the process of adjusting the pH value to 1.6-2.3 using alkali solution is ammonia water and / or sodium hydroxide solution;

[0059] Furthermore, the extracting liquid used in the process of extracting and recovering vanadium from the first filtrate is an organic extracting liquid; more preferably, the extracting liquid may include, but is not limited to, at least one of (2-ethylhexyl) phosphate and ethylhexyl mono-2-ethylhexyl phosphate;

[0060] Furthermore, in the process of extracting and recovering vanadium from the first filtrate, the volume ratio of the extract to the first filtrate is 1-3:1;

[0061] Furthermore, the extraction time of the first filtrate in the process of extracting and recovering vanadium is 30-90 minutes;

[0062] Furthermore, the alkali solution used in the process of adjusting the pH value of the extraction residue to 6-10 by using alkali solution can include but is not limited to at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water;

[0063] Furthermore, the alkali solution used in the process of adding alkali solution to the mixed precipitate of aluminum hydroxide and nickel hydroxide to adjust the pH value to 12-13 can include but is not limited to at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water.

[0064] According to a preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, the second part of the catalyst to be treated is crushed to 1-15 μm and then subjected to subsequent treatment;

[0065] Furthermore, the second part of the catalyst to be treated is crushed to 5-10 μm and then subjected to subsequent treatment.

[0066] The method for graded utilization of waste catalytic cracking / catalytic cracking catalysts provided by the present invention divides the waste catalytic cracking / catalytic cracking catalysts into two parts according to the particle size. The waste catalytic cracking / catalytic cracking catalysts within a specific particle size range are treated with alkaline solution + acid solution in sequence to restore the catalytic activity and are reused as catalytic cracking / cracking catalysts; the remaining waste catalytic cracking / cracking catalysts are crushed and treated with acid solution + extractant + hydrofluoric acid solution + sodium hydroxide solution to recover metals and silicon in the waste catalysts; thereby achieving full recycling of waste catalytic cracking / catalytic cracking catalysts, utilizing resources to the greatest extent, and having both economic and environmental benefits. The method for graded utilization of waste catalytic cracking / catalytic cracking catalysts provided by the present invention has the following beneficial effects compared with conventional methods for reviving and utilizing waste catalytic cracking / catalytic cracking catalysts or recovering elements:

[0067] The technical solution of the present invention adopts a graded utilization method, and the waste catalytic cracking / cracking catalyst within a specific particle size range is revived. The reviver has good fluidization properties and a micro-reaction activity of more than 60%. The remaining part is comprehensively recovered with all elements, including metal elements and silicon elements. In the preferred technical solution, the element recovery rate is more than 95%. The method is simple to operate, low in cost, and high in element recovery rate, and the waste catalytic cracking / cracking catalyst is fully recovered. DETAILED DESCRIPTION

[0068] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0069] Sources of raw materials involved in the examples and comparative examples of the present invention:

[0070] Waste catalytic cracking / cracking catalyst: industrial grade, provided by Lanzhou Petrochemical Company; taking the total mass of the waste catalytic cracking / catalytic cracking catalyst as 100%, the mass content of SiO2 in the waste catalytic cracking / catalytic cracking catalyst is 50wt%, the mass content of Al2O3 is 44wt%, the mass content of RE2O3 is 4.7wt%, the mass content of Ni is 0.8wt%, and the mass content of V is 0.5wt%.

[0071] Hydrofluoric acid solution: industrial grade, HF concentration 40wt%, density 1.15g / cm 3 .

[0072] Sodium hydroxide: industrial grade, purity 99wt%, density 2.13g / cm 3 .

[0073] Oxalic acid: industrial grade, purity 99.6wt%, density 1.77g / cm 3 .

[0074] Di(2-ethylhexyl) phosphate: industrial grade, purity 99wt%, density 1.13g / cm 3 .

[0075] Ethylhexyl phosphate mono-2-ethylhexyl ester: industrial grade, purity 99wt%, density 1.12g / cm 3 .

[0076] The present invention relates to the analysis method:

[0077] Analysis of elemental content of samples: XRF analysis was used for elemental analysis of solid samples, specifically using a ZSX Primus X-ray fluorescence spectrometer produced by Rigaku Corporation of Japan. The X-ray tube was an Rh target with good excitation efficiency for heavy and light elements. The current of the X-ray tube was 50mA, the voltage was 50kV, the field aperture diameter was 20mm, and the attenuation was 1. ICP analysis was used for elemental analysis of liquid samples, specifically using a Plasma2000 inductively coupled plasma-atomic emission spectrometer produced by China Iron and Steel Research Institute NAK Co., Ltd. The elemental content was determined after the analysis samples were diluted and fixed to volume.

[0078] Micro-reaction activity analysis: The catalyst micro-reaction activity evaluation device produced by Beijing Huier Sanji Green Chemical Technology Co., Ltd. was used to conduct micro-reaction test on the sample to be tested to determine the micro-reaction activity index of the sample to be tested. The reaction raw material used in the micro-reaction test was Dagang light diesel, the reaction temperature was 460℃, the reaction time was 70s, and the diesel oil intake was 1.56mL. The liquid product was analyzed using a GC-2014C gas chromatograph from Japan SHIMADZU Company.

[0079] Example 1

[0080] This embodiment provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0081] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0082] Add 1600g of deionized water and 400g of a sodium hydroxide solution with a mass concentration of 2.5% to the first part of the catalyst to be treated, heat to 80°C for 2h, filter and dry; add 1400g of deionized water and 400g of a hydrochloric acid solution with a mass concentration of 1% to the filtered and dried material, treat at room temperature for 15min, filter, dry, and calcine at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; perform micro-reaction activity analysis on the revived catalytic cracking / catalytic cracking catalyst, and obtain a micro-reaction activity index of 66%.

[0083] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 10 μm. The material was added to 1200 g of a hydrochloric acid solution with an HCl concentration of 3 mol / L, and reacted at 100°C for 20 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 99 wt% and a porosity of 1.05 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 1wt%. 1300g of oxalic acid solution with an oxalic acid concentration of 0.3mol / L is added to the leaching solution, and the pH value is adjusted to 2 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 96%, and the purity of the obtained oxalic acid rare earth salt is 98%. Di(2-ethylhexyl) phosphate extract (the volume ratio of di(2-ethylhexyl) phosphate extract to the first filtrate is 2:1) is added to the first filtrate, and extracted for 60min to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated to dryness at 105℃, and roasted at 480℃ to vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 96%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 8, thereby generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 13 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 95% and 97% respectively, the purity of the obtained nickel hydroxide is 98.5%, and the purity of the obtained sodium aluminate is 99%. Transfer material B1 to a polytetrafluoroethylene-lined autoclave (I), inject 600g of HF solution with a concentration of 20wt%, react at 60°C for 0.5h, and input the gas produced by the reaction into another polytetrafluoroethylene-lined autoclave (II) filled with 1600g of sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and react at 80°C for 1h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to pH 12.5 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 3 and a SiO2 mass concentration of 21wt%. After analysis and calculation, the silicon recovery rate is 97%, and the purity of the obtained sodium silicate is 99.4%.

[0084] Example 2

[0085] This embodiment provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0086] 1000g of dry-based spent catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size, and the spent catalytic cracking / catalytic cracking catalyst with a particle size of 50-90μm was used as the first part of the catalyst to be treated, weighing 500g, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <50μm and particle size >90μm) was used as the second part of the catalyst to be treated, weighing 500g.

[0087] Add 2500g of deionized water and 500g of a sodium hydroxide solution with a mass concentration of 1.5% to the first part of the catalyst to be treated, heat to 90°C for treatment for 1h, filter and dry; add 1700g of deionized water and 500g of a nitric acid solution with a mass concentration of 0.5% to the filtered and dried material, treat at room temperature for 20min, filter, dry, and calcine at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; perform micro-reaction activity analysis on the revived catalytic cracking / catalytic cracking catalyst, and obtain a micro-reaction activity index of 64%.

[0088] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 15 μm. The material was added with 1000 g of hydrochloric acid solution with an HCl concentration of 2.5 mol / L, and reacted at 100°C for 15 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 98.8 wt% and a porosity of 0.95 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 1.2wt%. 1100g of oxalic acid solution with an oxalic acid concentration of 0.4mol / L is added to the leaching solution, and the pH value is adjusted to 1.8 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 95%, and the purity of the obtained oxalic acid rare earth salt is 97%. Ethylhexyl phosphate mono-2-ethylhexyl ester extract (the volume ratio of ethylhexyl phosphate mono-2-ethylhexyl ester extract to the first filtrate is 2.5:1) is added to the first filtrate, and extraction is performed for 50min to obtain a vanadium-rich extract and an extract residue; the vanadium-rich extract is evaporated to dryness at 100°C, and roasted at 470°C to obtain vanadium pentoxide to achieve vanadium recovery; after analysis, the vanadium recovery rate is 96%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 9, generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 12.5 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 96% and 96% respectively, the purity of the obtained nickel hydroxide is 98%, and the purity of the obtained sodium aluminate is 99%. Transfer material B1 to a polytetrafluoroethylene-lined autoclave (I), inject 500g of HF solution with a concentration of 25wt%, react at 70°C for 0.6h, and input the gas produced by the reaction into another polytetrafluoroethylene-lined autoclave (II) filled with 1000g of sodium hydroxide solution with a concentration of 25wt% through a one-way valve, and react at 90°C for 1.5h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to a pH of 12.8 with sodium hydroxide lye with a concentration of 2.5wt% and filtered again to obtain a sodium silicate solution product with a modulus of 2.8 and a SiO2 mass concentration of 22wt%. After analysis and calculation, the silicon recovery rate is 96%, and the purity of the obtained sodium silicate is 98%.

[0089] Example 3

[0090] This embodiment provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0091] 1000g of dry-based spent catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The spent catalytic cracking / catalytic cracking catalyst with a particle size of 55-110μm was used as the first part of the catalyst to be treated, weighing 600g, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <55μm and particle size >110μm) was used as the second part of the catalyst to be treated, weighing 400g.

[0092] The first part of the catalyst to be treated was added with 1800g of deionized water and 600g of a sodium hydroxide solution with a mass concentration of 1% of sodium hydroxide, heated to 75°C for treatment for 3h, filtered and dried; the filtered and dried material was added with 2000g of deionized water and 600g of a hydrochloric acid + nitric acid solution with a mass concentration of 2% ((the mass ratio of hydrochloric acid to nitric acid is 1:1), treated at room temperature for 25min, filtered, dried, and calcined at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; the revived catalytic cracking / catalytic cracking catalyst was subjected to a micro-reaction activity analysis, and its micro-reaction activity index was obtained to be 67%.

[0093] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 5 μm. The material was added with 800 g of hydrochloric acid solution with a HCl concentration of 1.5 mol / L, and reacted at 90°C for 12 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 99.1 wt% and a porosity of 0.98 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 0.9wt%. 900g of oxalic acid solution with an oxalic acid concentration of 0.5mol / L is added to the leaching solution, and the pH value is adjusted to 2.1 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 96%, and the purity of the obtained oxalic acid rare earth salt is 97%. Ethylhexyl phosphate mono-2-ethylhexyl ester extract (the volume ratio of ethylhexyl phosphate mono-2-ethylhexyl ester extract to the first filtrate is 1.5:1) is added to the first filtrate, and extraction is performed for 70min to obtain a vanadium-rich extract and an extract residue; the vanadium-rich extract is evaporated to dryness at 98°C, and roasted at 490°C to obtain vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 95%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5wt% is added to the extract residue (aqueous phase) to adjust the pH value to 10, generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 12.8 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 95% and 96%, respectively, the purity of the obtained nickel hydroxide is 97.5%, and the purity of the obtained sodium aluminate is 98%. Transfer material B1 to a polytetrafluoroethylene lined autoclave (I), inject 600g of HF solution with a concentration of 30wt%, react at 50℃ for 0.3h, and input the gas produced by the reaction into another polytetrafluoroethylene lined autoclave (II) filled with 3600g of sodium hydroxide solution with a concentration of 10wt% through a one-way valve, and react at 70℃ for 2h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 100℃ for 1h, adjusted to pH 12.4 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 2 and a SiO2 mass concentration of 19wt%. After analysis and calculation, the silicon recovery rate is 97%, and the purity of the obtained sodium silicate is 98.3%.

[0094] Comparative Example 1

[0095] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0096] 1000g of dry-based waste catalytic cracking / catalytic cracking catalyst (including 250g of waste catalytic cracking / catalytic cracking catalyst with a particle size of less than 45μm, 350g of waste catalytic cracking / catalytic cracking catalyst with a particle size of more than 110μm, and 400g of waste catalytic cracking / catalytic cracking catalyst with a particle size of 45μm-110μm) is not classified by screening, 4000g of deionized water and 1000g of sodium hydroxide solution with a sodium hydroxide mass concentration of 2.5% are added, heated to 80°C for treatment for 2h, filtered and dried; 3500g of deionized water and 1000g of hydrochloric acid solution with a hydrochloric acid mass concentration of 1% are added to the filtered and dried material, treated at room temperature for 15min, filtered, dried, and calcined at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; a micro-reaction activity analysis is performed on the revived catalytic cracking / catalytic cracking catalyst, and its micro-reaction activity index is obtained to be 52%.

[0097] By comparing with the data of Example 1, it can be seen that the waste catalytic cracking / catalytic cracking catalysts are not classified according to particle size, and all are revived by alkali treatment + acid treatment. The revived catalytic cracking / catalytic cracking catalysts have a low micro-reaction activity index, and the waste catalytic cracking / catalytic cracking catalysts with a particle size of <45μm and a particle size of >110μm are revived by alkali treatment + acid treatment, which will cause problems such as catalyst leakage or poor fluidization in the device.

[0098] Comparative Example 2

[0099] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0100] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0101] The first part of the catalyst to be treated is added with 1400g of deionized water and 400g of a hydrochloric acid solution with a mass concentration of 1%, treated at room temperature for 15min, filtered, dried, and calcined at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; the revived catalytic cracking / catalytic cracking catalyst is subjected to a micro-reaction activity analysis, and its micro-reaction activity index is obtained to be 50%.

[0102] Compared with the data of Example 1, it can be seen that the spent catalytic cracking / catalytic cracking catalyst is not treated with alkali, and the revived catalytic cracking / catalytic cracking catalyst has a low micro-reaction activity index and cannot meet the catalytic activity requirements.

[0103] Comparative Example 3

[0104] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0105] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0106] The first part of the catalyst to be treated is added with 1600g of deionized water and 400g of a sodium hydroxide solution with a mass concentration of 2.5%, and heated to 80°C for 2h. The catalyst is filtered, dried, and calcined at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst. The revived catalytic cracking / catalytic cracking catalyst is subjected to a micro-reaction activity analysis, and its micro-reaction activity index is obtained to be 46%.

[0107] Compared with the data of Example 1, it can be seen that the spent catalytic cracking / catalytic cracking catalyst is not subjected to acid treatment, and the revived catalytic cracking / catalytic cracking catalyst has a low micro-reaction activity index and cannot meet the catalytic activity requirements.

[0108] Comparative Example 4

[0109] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0110] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0111] The second part of the catalyst to be treated is directly added to 1200g of 3mol / L hydrochloric acid solution without physical sand grinding treatment, and reacted at 100°C for 20h. The product obtained by the reaction is subjected to solid-liquid separation to obtain a liquid phase leaching liquid and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the spent catalytic cracking / cracking catalyst are dissolved in the leaching liquid, and silicon is retained in the material B1. The material B1 is a loose microsphere with a silicon content of 67wt% and a porosity of 0.65cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 33wt%. 1300g of oxalic acid solution with an oxalic acid concentration of 0.3mol / L is added to the leaching solution, and the pH value is adjusted to 2 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 89%, and the purity of the obtained oxalic acid rare earth salt is 97%. Di(2-ethylhexyl) phosphate extract (the volume ratio of di(2-ethylhexyl) phosphate extract to the first filtrate is 2:1) is added to the first filtrate, and extracted for 60min to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated to dryness at 105℃, and roasted at 480℃ to vanadium pentoxide to obtain vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 93%, and the purity of the obtained vanadium pentoxide is 98%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 8, generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 13 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 91% and 90% respectively, the purity of the obtained nickel hydroxide is 96.8%, and the purity of the obtained sodium aluminate is 97.2%. Transfer material B1 to a polytetrafluoroethylene-lined autoclave (I), inject 600g of HF solution with a concentration of 20wt%, react at 60°C for 0.5h, and input the gas produced by the reaction into another polytetrafluoroethylene-lined autoclave (II) filled with 1600g of sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and react at 80°C for 1h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to a pH of 12.5 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 12wt%. After analysis and calculation, the silicon recovery rate is 88%, and the purity of the obtained sodium silicate is 96%.

[0112] Compared with the data of Example 1, it can be seen that the second part of the catalyst to be treated is directly treated without physical sand grinding, and the recovery rate of each component is low.

[0113] Comparative Example 5

[0114] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0115] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0116] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 10 μm. The material was transferred to a polytetrafluoroethylene-lined autoclave (I), injected with 600g of HF solution with a concentration of 20wt%, and reacted at 60°C for 0.5h. The gas produced by the reaction was input into another polytetrafluoroethylene-lined autoclave (II) filled with 1600g of sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and reacted at 80°C for 1h. After the reaction, the product in the reactor (II) was separated into solid and liquid to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid was concentrated at 105°C for 1h, adjusted to a pH of 12.5 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and then filtered to obtain a sodium silicate solution product with a modulus of 2.5 and a SiO2 mass concentration of 10wt%. After analysis and calculation, the silicon recovery rate was 73%, and the purity of the obtained sodium silicate was 97%.

[0117] Compared with the data of Example 1, it can be seen that the second part of the catalyst to be treated was not subjected to hydrochloric acid leaching treatment, and the silicon recovery rate was low.

[0118] Comparative Example 6

[0119] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0120] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0121] The second part of the catalyst to be treated is directly added to 1200g of 3mol / L sulfuric acid solution of H2SO4 without physical sand grinding treatment, and reacted at 100°C for 20h. The product obtained by the reaction is subjected to solid-liquid separation to obtain a liquid phase leaching liquid and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the spent catalytic cracking / cracking catalyst are dissolved in the leaching liquid, and silicon is retained in the material B1. The material B1 is a loose microsphere with a silicon content of 57wt% and a porosity of 0.58cm3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 43wt%. 1300g of oxalic acid solution with an oxalic acid concentration of 0.3mol / L is added to the leaching solution, and the pH value is adjusted to 2 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 60%, and the purity of the obtained oxalic acid rare earth salt is 97.5%. Di(2-ethylhexyl) phosphate extract (the volume ratio of di(2-ethylhexyl) phosphate extract to the first filtrate is 2:1) is added to the first filtrate, and extracted for 60min to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated to dryness at 105℃, and roasted at 480℃ to vanadium pentoxide to obtain vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 53%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 8, thereby generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 13 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 41% and 30% respectively, the purity of the obtained nickel hydroxide is 97%, and the purity of the obtained sodium aluminate is 96%. Transfer material B1 to a polytetrafluoroethylene lined autoclave (I), inject 600g of HF solution with a concentration of 20wt%, react at 60℃ for 0.5h, and input the gas produced by the reaction into another polytetrafluoroethylene lined autoclave (II) filled with 1600g of sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and react at 80℃ for 1h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95℃ for 1h, adjusted to pH 12.5 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 5wt%. After analysis and calculation, the silicon recovery rate is 29%, and the purity of the obtained sodium silicate is 95%.

[0122] Compared with the data of Example 1, it can be seen that the second part of the catalyst to be treated is treated with other acids instead of hydrochloric acid, and the recovery rate and purity of each component are low.

[0123] Comparative Example 7

[0124] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0125] 1000g of dry-based spent catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size, and the spent catalytic cracking / catalytic cracking catalyst with a particle size of 50-90μm was used as the first part of the catalyst to be treated, weighing 500g, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <50μm and particle size >90μm) was used as the second part of the catalyst to be treated, weighing 500g.

[0126] Add 2500g of deionized water and 500g of a sodium hydroxide solution with a mass concentration of 1.5% to the first part of the catalyst to be treated, heat to 90°C for treatment for 1h, filter and dry; add 1700g of deionized water and 500g of a nitric acid solution with a mass concentration of 0.5% to the filtered and dried material, treat at room temperature for 20min, filter, dry, and calcine at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; perform micro-reaction activity analysis on the revived catalytic cracking / catalytic cracking catalyst, and obtain a micro-reaction activity index of 64%.

[0127] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 15 μm. The material was added with 1000 g of hydrochloric acid solution with a HCl concentration of 5 mol / L, and reacted at 100°C for 15 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 92.5 wt% and a porosity of 0.75 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 7.5wt%. 1100g of oxalic acid solution with an oxalic acid concentration of 0.4mol / L is added to the leaching solution, and the pH value is adjusted to 1.8 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 85%, and the purity of the obtained oxalic acid rare earth salt is 96%. Ethylhexyl phosphate mono-2-ethylhexyl ester extract (the volume ratio of ethylhexyl phosphate mono-2-ethylhexyl ester extract to the first filtrate is 2.5:1) is added to the first filtrate, and extraction is performed for 50min to obtain a vanadium-rich extract and an extract residue; the vanadium-rich extract is evaporated to dryness at 100°C, and roasted at 470°C to obtain vanadium pentoxide to achieve vanadium recovery; after analysis, the vanadium recovery rate is 87%, and the purity of the obtained vanadium pentoxide is 97.5%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 9, generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and stirred to adjust the pH value to 12.5, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 76% and 83% respectively, the purity of the obtained nickel hydroxide is 97%, and the purity of the obtained sodium aluminate is 98%. Transfer material B1 to a polytetrafluoroethylene lined autoclave (I), inject 500g of HF solution with a concentration of 25wt%, react at 70°C for 0.6h, and input the gas produced by the reaction into another polytetrafluoroethylene lined autoclave (II) filled with 1000g of sodium hydroxide solution with a concentration of 25wt% through a one-way valve, and react at 90°C for 1.5h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to pH 12.8 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 14wt%. After analysis and calculation, the silicon recovery rate is 76%, and the purity of the obtained sodium silicate is 98%.

[0128] Compared with the data of Example 2, it can be seen that the second part of the catalyst to be treated was acid-leached with hydrochloric acid concentration not in the range of 1-3 mol / L, and the recovery rate of each component was low.

[0129] Comparative Example 8

[0130] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0131] 1000g of dry-based spent catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The spent catalytic cracking / catalytic cracking catalyst with a particle size of 55-110μm was used as the first part of the catalyst to be treated, weighing 600g, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <55μm and particle size >110μm) was used as the second part of the catalyst to be treated, weighing 400g.

[0132] The first part of the catalyst to be treated was added with 1800g of deionized water and 600g of a sodium hydroxide solution with a mass concentration of 1% of sodium hydroxide, heated to 75°C for treatment for 3h, filtered and dried; the filtered and dried material was added with 2000g of deionized water and 600g of a hydrochloric acid + nitric acid solution with a mass concentration of 2% ((the mass ratio of hydrochloric acid to nitric acid is 1:1), treated at room temperature for 25min, filtered, dried, and calcined at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; the revived catalytic cracking / catalytic cracking catalyst was subjected to a micro-reaction activity analysis, and its micro-reaction activity index was obtained to be 67%.

[0133] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 5 μm. The material was added with 800 g of hydrochloric acid solution with a HCl concentration of 1.5 mol / L, and reacted at 90°C for 12 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 99.1 wt% and a porosity of 0.98 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 0.9wt%. 900g of oxalic acid solution with an oxalic acid concentration of 0.5mol / L is added to the leaching solution, and the pH value is adjusted to 2.1 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 96%, and the purity of the obtained oxalic acid rare earth salt is 97%. Ethylhexyl phosphate mono-2-ethylhexyl ester extract (the volume ratio of ethylhexyl phosphate mono-2-ethylhexyl ester extract to the first filtrate is 1.5:1) is added to the first filtrate, and extraction is performed for 70min to obtain a vanadium-rich extract and an extract residue; the vanadium-rich extract is evaporated to dryness at 98°C, and roasted at 490°C to obtain vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 95%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5wt% is added to the extract residue (aqueous phase) to adjust the pH value to 10, generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 12.8 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 95% and 96%, respectively, the purity of the obtained nickel hydroxide is 97.5%, and the purity of the obtained sodium aluminate is 98%. Transfer material B1 to a polytetrafluoroethylene lined autoclave (I), inject 6000g of hydrofluoric acid solution with a HF concentration of 3wt%, react at 50°C for 0.3h, and input the gas produced by the reaction into another polytetrafluoroethylene lined autoclave (II) filled with 3600g of sodium hydroxide solution with a sodium hydroxide concentration of 10wt% through a one-way valve, and react at 70°C for 2h. After the reaction, separate the product in the reactor (II) into solid and liquid to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 100°C for 1h, adjusted to a pH value of 12.4 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 1.8 and a SiO2 mass concentration of 13wt%. After analysis and calculation, the silicon recovery rate is 87%, and the purity of the obtained sodium silicate is 98.5%.

[0134] Comparison with the data of Example 3 shows that the HF concentration used in the second part of the catalyst to be treated is not within the range of 5-47%, and the recovery rate of the silicon component is low.

[0135] Comparative Example 9

[0136] This comparative example provides a method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein the method comprises:

[0137] 1000g of dry waste catalytic cracking / catalytic cracking catalyst was sieved into two parts according to particle size. The waste catalytic cracking / catalytic cracking catalyst with a particle size of 60-100μm was used as the first part of catalyst to be treated, weighing 400g, and the waste catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of catalyst to be treated, weighing 600g.

[0138] Add 1600g of deionized water and 400g of a sodium hydroxide solution with a mass concentration of 2.5% to the first part of the catalyst to be treated, heat to 80°C for 2h, filter and dry; add 1400g of deionized water and 400g of a hydrochloric acid solution with a mass concentration of 1% to the filtered and dried material, treat at room temperature for 15min, filter, dry, and calcine at 600°C for 2h to obtain a revived catalytic cracking / catalytic cracking catalyst; perform micro-reaction activity analysis on the revived catalytic cracking / catalytic cracking catalyst, and obtain a micro-reaction activity index of 66%.

[0139] The second part of the catalyst to be treated was subjected to physical sand milling to obtain material A1 with an average particle size of 10 μm. The material was added with 1200 g of hydrochloric acid solution with a HCl concentration of 3 mol / L, and reacted at 100°C for 20 hours. The product obtained by the reaction was subjected to solid-liquid separation to obtain a liquid phase leaching solution and a solid phase material B1; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst were dissolved in the leaching solution, and silicon remained in the material B1. The material B1 was a loose microsphere with a silicon content of 99 wt% and a porosity of 1.05 cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 1wt%. 1300g of oxalic acid solution with an oxalic acid concentration of 0.3mol / L is added to the leaching solution, and the pH value is adjusted to 2 with ammonia water with an ammonia concentration of 25wt%, generating oxalic acid rare earth salt precipitation, filtering to obtain oxalic acid rare earth salt precipitation and the first filtrate, realizing rare earth recovery; after analysis, the rare earth recovery rate is 96%, and the purity of the obtained oxalic acid rare earth salt is 98%. Di(2-ethylhexyl) phosphate extract (the volume ratio of di(2-ethylhexyl) phosphate extract to the first filtrate is 2:1) is added to the first filtrate, and extracted for 60min to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated to dryness at 105℃, and roasted at 480℃ to vanadium pentoxide, realizing vanadium recovery; after analysis, the vanadium recovery rate is 96%, and the purity of the obtained vanadium pentoxide is 97%. A sodium hydroxide solution with a sodium hydroxide concentration of 2.5 wt % is added to the extract residue (aqueous phase) to adjust the pH value to 8, thereby generating a mixed precipitate of aluminum hydroxide and nickel hydroxide. After filtering, sodium hydroxide solution is continuously added to the precipitate and the pH value is adjusted to 13 by stirring, and then filtered again. The precipitate is nickel hydroxide, and the filtrate is a sodium aluminate solution, thereby realizing the recovery of nickel and aluminum. Analysis shows that the recovery rates of nickel and aluminum are 95% and 97% respectively, the purity of the obtained nickel hydroxide is 98.5%, and the purity of the obtained sodium aluminate is 99%. Transfer material B1 to a polytetrafluoroethylene-lined autoclave (I), inject 600g of HF solution with a concentration of 20wt%, react at 60°C for 0.5h, and input the gas produced by the reaction into another polytetrafluoroethylene-lined autoclave (II) filled with 8000g of sodium hydroxide solution with a concentration of 3wt% sodium hydroxide through a one-way valve, and react at 80°C for 1h. After the reaction, separate the solid and liquid of the product in the reactor (II) to obtain solid sodium fluoride and sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to pH 12.5 with sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and filtered again to obtain a sodium silicate solution product with a modulus of 2.6 and a SiO2 mass concentration of 12wt%. After analysis and calculation, the silicon recovery rate is 87%, and the purity of the obtained sodium silicate is 98%.

[0140] Comparison with the data of Example 1 shows that the concentration of the gas generated during the treatment of the second part of the catalyst to be treated is not within the range of 5-40%, and the recovery rate of the silicon component is low.

Claims

1. A method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein: The method includes: The spent catalytic cracking / catalytic cracking catalyst is screened into two parts according to the particle size, and the spent catalytic cracking / catalytic cracking catalyst with a particle size between a first particle size threshold and a second particle size threshold is used as the first part of the catalyst to be treated, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size is used as the second part of the catalyst to be treated; wherein the first particle size threshold is less than or equal to the second particle size threshold, and the first particle size threshold is not less than 45 μm, and the second particle size threshold is not more than 110 μm; The first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence to obtain a revived catalytic cracking / catalytic cracking catalyst; The second part of the catalyst to be treated is crushed and then subjected to acid leaching treatment, and a leachate and loose microspheres are obtained through solid-liquid separation; the leachate is used to recover metals; the loose microspheres react with a hydrofluoric acid solution, and the generated gas is passed into a sodium hydroxide solution for reaction, and the solid phase of the product obtained by the reaction is removed to obtain liquid sodium silicate.

2. The method according to claim 1, wherein: The first particle size threshold is 45-65 μm, and the second particle size threshold is 85-110 μm; Preferably, the first particle size threshold is 60 μm and the second particle size threshold is 100 μm.

3. The method according to claim 1, wherein: In the process of sequentially subjecting the first part of the catalyst to be treated to an alkali treatment and an acid treatment, the alkali used in the alkali treatment is sodium hydroxide; and / or The first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence, and the acid used in the acid treatment is at least one of hydrochloric acid and nitric acid.

4. The method according to claim 1 or 3, wherein: The first part of the catalyst to be treated is subjected to alkali treatment and acid treatment in sequence, comprising: Mixing the first part of the catalyst to be treated with water and an alkali solution, treating at 70-100° C. for 1-4 hours, then performing solid-liquid separation and drying the separated solid phase to obtain an alkali-treated catalyst; The alkali-treated catalyst is mixed with water and an acid solution, treated at room temperature for 5-30 minutes, and then solid-liquid separation is performed and the separated solid phase is dried. The dried product is calcined to obtain a revived catalytic cracking / catalytic cracking catalyst.

5. The method according to claim 4, wherein: During the mixing of the first part of the catalyst to be treated with water and the alkaline solution, the mass ratio of the first part of the catalyst to be treated to water is 1:3-1:6; the mass concentration of the alkali in the alkaline solution is 0.5-5%, preferably 1-3%; the mass of the alkali in the alkaline solution is 1-10% of the mass of the first part of the catalyst to be treated, preferably 2-6%; and / or The ratio of the mass of the first part of the catalyst to be treated to the mass of the water used in the process of mixing the catalyst treated with alkali with water and acid solution is 1:3-1:6; the mass concentration of the acid in the acid solution is 0.15-3.5%, preferably 0.35-1.5%; the mass of the acid in the acid solution is 0.1-5% of the mass of the first part of the catalyst to be treated, preferably 0.3-2%.

6. The method according to claim 1, wherein: The second portion of the catalyst to be treated is treated in the following manner: The catalyst to be treated in the second part is crushed and then subjected to hydrochloric acid leaching at 60-120° C. using hydrochloric acid having a concentration of 1-3 mol / L (based on the volume of the hydrochloric acid), and a leaching solution and loose microspheres are obtained by solid-liquid separation; Utilizing leachate for metal recovery; The loose microspheres react with a hydrofluoric acid solution, and the generated gas is passed into a sodium hydroxide solution for reaction, and the solid phase is removed from the product obtained by the reaction to obtain liquid sodium silicate; wherein the mass concentration of HF in the hydrofluoric acid solution is 5-47%, and the mass concentration of sodium hydroxide in the sodium hydroxide solution is 5-40%.

7. The method according to claim 1 or 6, wherein: Metal recovery using leachate includes: The leaching solution is mixed with the oxalic acid solution and the pH value is adjusted to 1.6-2.3 by using an alkali solution for reaction, and the oxalic acid rare earth salt precipitate and the first filtrate are obtained through solid-liquid separation to realize rare earth recovery; The first filtrate is subjected to extraction to recover vanadium, thereby obtaining a vanadium-rich extract and an extraction residue, thereby achieving vanadium recovery; The pH value of the extract residue is adjusted to 6-10 by using alkaline solution to react, and a mixed precipitate of aluminum hydroxide and nickel hydroxide is obtained by solid-liquid separation; Adding alkaline solution to the mixed precipitate of aluminum hydroxide and nickel hydroxide to adjust the pH value to 12-13 for reaction, and performing solid-liquid separation to obtain nickel hydroxide precipitate and aluminate solution, thereby realizing the recovery of nickel and aluminum; Preferably, the method further comprises: evaporating the vanadium-rich extract to dryness, pyrolyzing, and roasting to obtain vanadium pentoxide; Preferably, the concentration of oxalic acid in the oxalic acid solution is 0.1-0.5 mol / L; Preferably, the alkali solution used in the process of adjusting the pH value to 1.6-2.3 by using alkali solution includes ammonia water and / or sodium hydroxide solution; Preferably, the alkali solution used in the process of adjusting the pH value of the extraction residue to 6-10 by using alkali solution includes at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water; Preferably, the alkali solution used in the process of adding alkali solution to the mixed precipitate of aluminum hydroxide and nickel hydroxide to adjust the pH value to 12-13 includes at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water.

8. The method according to claim 6, wherein: The extracting liquid used in the process of extracting and recovering vanadium from the first filtrate is an organic extracting liquid; Preferably, the extract may include, but is not limited to, at least one of (2-ethylhexyl) phosphate, ethylhexyl mono-2-ethylhexyl phosphate; Preferably, in the process of extracting and recovering vanadium from the first filtrate, the volume ratio of the extract to the first filtrate is 1-3:

1.

9. The method according to claim 6, wherein: The silicon oxide content of the loose microspheres is not less than 98.5wt% and the porosity is not less than 0.9cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium in the loose microspheres is less than 1.5wt%.

10. The method according to claim 6, wherein: The mass concentration of HF in the hydrofluoric acid solution is 15-25%; and / or The mass concentration of sodium hydroxide in the sodium hydroxide solution is 10-25%.

11. The method according to claim 6, wherein: The temperature of the reaction between the loose microspheres and the hydrofluoric acid solution is 20-80°C; and / or The generated gas is passed into the sodium hydroxide solution for reaction at a temperature of 60-100°C.

12. The method according to claim 6, wherein: The method further comprises: removing the solid phase to obtain the liquid sodium silicate, concentrating, adjusting with alkali solution and re-filtering to obtain a sodium silicate solution product that meets the requirements of modulus and concentration; Preferably, the modulus of the sodium silicate solution product is 1.5-3.5; Preferably, the SiO2 mass concentration in the sodium silicate solution product is 15-25wt%.

13. The method according to claim 1 or 6, wherein: The second part of the catalyst to be treated is crushed to 1-15 μm and then subjected to subsequent treatment; Preferably, the second portion of the catalyst to be treated is crushed to 5-10 μm before subsequent treatment.

14. The method according to claim 1, wherein: Taking the total mass of the waste catalytic cracking / catalytic cracking catalyst as 100%, the mass content of SiO2 in the waste catalytic cracking / catalytic cracking catalyst is 40-50wt%, and the mass content of SiO2, Al2O3, RE2O3, Ni and V is not less than 99.5wt%; Preferably, based on the total mass of the spent catalytic cracking / catalytic cracking catalyst as 100%, the mass content of SiO2 in the spent catalytic cracking / catalytic cracking catalyst is 40-50wt%, the mass content of Al2O3 is 40-50wt%, the mass content of RE2O3 is 0.1-10wt%, the mass content of Ni is 0.01-2wt%, and the mass content of V is 0.01-2wt%.