A method for staged utilization of spent catalytic cracking / catalytic cracking catalyst

Abstract

The application provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst. The method comprises the following steps: screening the waste catalytic cracking / catalytic cracking catalyst according to particle size into two parts, taking the waste catalytic cracking / catalytic cracking catalyst with a particle size within a range from a first particle size threshold to a second particle size threshold as a first part of to-be-treated catalyst, and taking the remaining part as a second part of to-be-treated catalyst, wherein the first particle size threshold is less than or equal to the second particle size threshold, the first particle size threshold is greater than or equal to 45 mu m, and the second particle size threshold is less than or equal to 110 mu m; sequentially performing alkali treatment and acid treatment on the first part of to-be-treated catalyst to obtain a rejuvenated catalytic cracking / catalytic cracking catalyst; crushing the second part of to-be-treated catalyst and then performing acid immersion treatment to obtain a leaching solution and loose microspheres through solid-liquid separation; recycling metal by using the leaching solution; reacting the loose microspheres with a hydrofluoric acid solution, passing the generated gas into a sodium hydroxide solution, and removing the solid phase from the obtained product to obtain liquid sodium silicate.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of oil refining catalysts, and relates to a method for hierarchical utilization of spent catalytic cracking / catalytic cracking catalysts. BACKGROUND

[0002] Catalytic cracking / catalytic cracking is an important petroleum refining process, which converts heavy oil, crude oil into gasoline, diesel and other finished oil or ethylene, propylene and other basic chemical raw materials. At present, most of the industrial catalytic cracking / catalytic cracking devices use fast fluidized bed (riser) reactors, and use microspherical catalysts with an average particle size of 60-80 μm. With the long-term operation of the catalytic cracking / catalytic cracking equipment, the contents of heavy metals Ni, V and coke, alkali metals are continuously increased, which leads to the continuous decrease of the activity, selectivity and hydrothermal stability of the catalyst, and the decrease of the conversion rate. Usually, the activity balance cannot be obtained by adding fresh catalyst, and fresh catalyst needs to be replaced in time. 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, due to the high temperature and the poisoning effect of heavy metals, the activity of the catalyst is reduced and cannot meet the demand of the catalytic cracking / catalytic cracking reaction, so fresh catalyst is periodically supplemented and part of the deactivated catalyst is removed from the regenerator; the second source is that due to the collision or thermal collapse between the catalyst in the equipment and the high-speed flow (main air and raw oil), the container wall and the catalyst particles, fine particles with a particle size of less than 20 μm are produced, which cannot be collected by the first and second cyclone separators, but can be collected by the subsequent third cyclone separator. These spent catalysts are three-spin fine powder; the third source is the catalyst ultrafine powder collected in the flue gas desulfurization and denitration sludge during the flue gas purification process. The chemical composition of the spent catalytic cracking / catalytic cracking catalyst includes alumina, silica, 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] Item % ω(Al203), % [CAT] ω(SiO2), % [CAT] ω (RE2O3), % ω(Ni), μg / g ω(V), μg / g Spent catalyst 43.5 46.4 4.5 7200 2500

[0006] According to statistics, about 500,000 tons of spent catalytic cracking / catalytic cracking catalysts are produced worldwide every year, and continue to grow at a rate of 5% per year. At present, the most common way to treat spent catalytic cracking / catalytic cracking catalysts is to bury them. Since the spent catalytic cracking / catalytic cracking catalysts contain heavy metal elements such as Ni, V and rare earth, burying them will inevitably lead to a waste of a large amount of effective resources and cause pollution to the ecological environment.

[0007] In recent years, some researchers have studied the spent FCC / FCC catalyst and proposed some methods for reviving and recycling the elements of the spent catalyst. However, there are generally two problems: (1) the strength and fluidization performance of the reviving agent are poor; (2) the recycling methods mainly focus on the metal elements of the spent FCC / FCC catalyst, including rare earth, nickel, vanadium and alumina, and basically do not involve the recycling method of silicon. In summary, the current spent FCC / FCC catalyst treatment technology cannot achieve full utilization of the spent FCC / FCC catalyst.

[0008] In summary, there is still a need to study the spent FCC / FCC catalyst treatment technology to achieve full recycling of the spent FCC / FCC catalyst, maximize resource utilization, and improve economic and environmental benefits. SUMMARY

[0009] The purpose of the present application is to provide a technical solution that can achieve full recycling of the spent FCC / FCC catalyst. In order to achieve the above purpose, the present application provides the following technical solution.

[0010] The present application provides a method for grading utilization of spent FCC / FCC catalyst, wherein the method comprises:

[0011] The spent FCC / FCC catalyst is sieved according to particle size into two parts, the spent FCC / FCC catalyst with particle size in the range of the first particle size threshold-second particle size threshold is taken as the first part of the to-be-treated catalyst, and the remaining particle size of the spent FCC / FCC catalyst is taken as the second part of the to-be-treated catalyst; 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 greater than 110 μm;

[0012] The first part of the to-be-treated catalyst is sequentially subjected to alkali treatment and acid treatment to obtain the revived FCC / FCC catalyst;

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

[0014] The application provides a waste catalytic cracking / catalytic cracking catalyst grading utilization method, which classifies waste catalytic cracking / catalytic cracking catalysts according to particle size, and can effectively realize the revival of waste catalytic cracking / catalytic cracking catalysts in a specific particle size range through alkali treatment and acid treatment, and avoid the problems of poor strength and fluidity of the revival agent, and effectively realize the recovery of various main elements including silicon and metal elements in waste catalytic cracking / catalytic cracking catalysts with the remaining particle size through specific treatment, thereby completing the revival utilization and full element recovery of waste catalytic cracking / catalytic cracking catalysts, and realizing the full recovery utilization of waste catalytic cracking / catalytic cracking catalysts.

[0015] The waste catalytic cracking / catalytic cracking catalyst grading utilization method provided by the application sequentially performs alkali treatment and acid treatment on waste catalytic cracking / catalytic cracking catalysts in a specific particle size range to restore the activity of the waste catalytic cracking / catalytic cracking catalysts, the alkali treatment can expose the pores and surface of the waste catalytic cracking / catalytic cracking catalysts to make the heavy metals easily leached by the subsequent acid solution, and the acid treatment can clean the pores of the waste catalytic cracking / catalytic cracking catalysts and remove the heavy metals, so that the waste catalytic cracking / catalytic cracking catalysts in the specific particle size range can effectively restore the activity after being sequentially subjected to the alkali treatment and the acid treatment.

[0016] The waste catalytic cracking / catalytic cracking catalyst grading utilization method provided by the application performs acid leaching treatment on the waste catalytic cracking / catalytic cracking catalysts to leach the Ni, V, rare earth and Al components in the waste catalytic cracking / catalytic cracking catalysts into the leaching solution and obtain loose microspheres containing silicon, and then utilizes the loose microspheres to react with a hydrofluoric acid solution to generate silicon tetrafluoride gas, i.e., SiO2+4HF=SiF4(gas)+2H2O, so that the silicon enters the generated gas phase, and the gas phase is introduced into a sodium hydroxide solution to generate a liquid phase silicon product, i.e., SiF4+6NaOH=Na2SiO3+4NaF+3H2O.

[0017] According to the preferred embodiment of the waste catalytic cracking / catalytic cracking catalyst grading utilization method, 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 the preferred embodiment of the waste catalytic cracking / catalytic cracking catalyst grading utilization method, in the process of sequentially performing alkali treatment and acid treatment on the first part of the catalyst to be treated, the alkali used in the alkali treatment is sodium hydroxide.

[0020] According to the preferred embodiment of the waste catalytic cracking / catalytic cracking catalyst grading utilization method, in the process of sequentially performing alkali treatment and acid treatment on the first part of the catalyst to be treated, the acid used in the acid treatment is at least one of hydrochloric acid and nitric acid.

[0021] According to the preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic pyrolysis catalyst, wherein the first part of the spent catalyst to be treated is sequentially subjected to alkaline treatment and acid treatment, the method comprises:

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

[0023] mixing the alkaline-treated catalyst with water and an acid solution, treating at room temperature for 5-30 minutes, then performing solid-liquid separation and drying the separated solid phase, and calcining the dried product to obtain the rejuvenated catalytic cracking / catalytic pyrolysis catalyst;

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

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

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

[0027] Further, the mass ratio of the first part of the spent catalyst to be treated to the water used during the mixing of the alkaline-treated catalyst with water and an 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] Further, the mass of the acid in the acid solution is 0.1-5% of the mass of the first part of the spent catalyst to be treated, preferably 0.3-2%.

[0030] According to the preferred embodiment of the above-mentioned method for graded utilization of spent catalytic cracking / catalytic pyrolysis catalyst, wherein the second part of the spent catalyst to be treated is treated by the following method:

[0031] After the second part of the spent catalyst to be treated is crushed, it is subjected to hydrochloric acid leaching treatment using hydrochloric acid with a concentration of 1-3 mol / L (based on the volume of hydrochloric acid) at 60-120°C, and the leaching liquid and loose microspheres are obtained through solid-liquid separation;

[0032] The leaching liquid is used for metal recovery;

[0033] The loose microspheres are reacted with a hydrofluoric acid solution, the generated gas is introduced into a sodium hydroxide solution to react, and the product obtained by the reaction is subjected to solid phase removal 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 being 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 being 100%);

[0034] In the preferred embodiment, the waste catalytic cracking / catalytic cracking catalyst is subjected to hydrochloric acid leaching treatment at a specific temperature and a specific concentration, which realizes complete or nearly complete leaching of Ni, V, rare earth and Al components in the waste catalytic cracking / catalytic cracking catalyst into the leaching solution and obtains loose microspheres with high silicon content, large porosity and large silicon exposed surface area (wherein the silicon component is completely or nearly completely retained in the loose microspheres), and then the loose microspheres are mixed with a specific concentration of hydrofluoric acid, a large number of accessible silicon species in the loose microspheres react with the hydrofluoric acid to generate silicon tetrafluoride gas, so that the silicon is completely or nearly completely introduced into the generated gas phase, and then the gas phase is introduced into a sodium hydroxide solution to make the silicon tetrafluoride gas react with a specific concentration of sodium hydroxide solution to generate sodium fluoride and sodium silicate, and the reaction product is subjected to concentration and precipitation of 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 loose microspheres with very high silicon content (which can reach more than 98.5%), very high porosity (which can reach more than 0.9 cm 3 / g), and very large silicon exposed surface area, which lays a foundation for efficient and high-purity recovery of silicon; in summary, the efficient and high-purity recovery of silicon is realized by the combination of hydrochloric acid leaching treatment at a specific temperature and a specific concentration, treatment with a specific concentration of hydrofluoric acid solution, and treatment with a specific concentration of sodium hydroxide; the recovery rate of silicon can reach 95%; at the same time, the hydrochloric acid leaching treatment at a specific temperature and a specific concentration and the treatment with the hydrofluoric acid solution can completely or nearly completely leach the Ni, V, rare earth and Al components into the leaching solution, which lays a foundation for efficient recovery of the Ni, V, rare earth and Al components; the preferred technical solution simultaneously realizes efficient recovery of silicon and metals (the recovery rates of silicon and metals can both reach high levels);

[0035] Further, the mass content of SiO2 in the spent catalytic cracking / catalytic cracking catalyst is 40-50 wt%, the mass content of SiO2, Al2O3, RE2O3, Ni, V and no less than 99.5 wt%, based on the total mass of the spent catalytic cracking / catalytic cracking catalyst being 100%; further, the mass content of SiO2 in the spent catalytic cracking / catalytic cracking catalyst is 40-50 wt%, the mass content of Al2O3 is 40-50 wt%, the mass content of RE2O3 is 0.1-10 wt%, the mass content of Ni is 0.01-2 wt%, and the mass content of V is 0.01-2 wt%, based on the total mass of the spent catalytic cracking / catalytic cracking catalyst being 100%;

[0036] Further, the spent catalytic cracking / catalytic cracking catalyst is subjected to a crushing treatment before being subjected to the hydrochloric acid leaching treatment, and is treated into a material with a particle size of 1-15 μm before being subjected to the hydrochloric acid leaching treatment;

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

[0038] Further, the spent catalytic cracking / catalytic cracking catalyst is subjected to a crushing treatment before being subjected to the hydrochloric acid leaching treatment, and is treated into a material with a particle size of 1-15 μm before being subjected to the hydrochloric acid leaching treatment; 3

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

[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 being 100%);

[0041] Further, the temperature for the reaction of the loose microspheres with the hydrofluoric acid solution is 20-80℃;

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

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

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

[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 being 100%);

[0046] Further, the temperature for the reaction of the generated gas with the sodium hydroxide solution is 60-100℃;

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

[0048] Further, the reaction of the generated gas with the sodium hydroxide solution is carried out in a sealed high-pressure reactor.

[0049] Further, the method further comprises: removing the solid phase to obtain liquid sodium silicate, which is concentrated, adjusted with lye, and filtered again to obtain a sodium silicate solution product meeting the modulus and concentration requirements; further, the concentration is carried out at 85-105℃, and the concentration time is 1h; further, the lye adjustment adjusts the pH value to 12-13; further, the modulus of the sodium silicate solution product is 1.5-3.5; further, the SiO2 mass concentration in the sodium silicate solution product is 15-25wt%.

[0050] According to the preferred embodiment of the above-mentioned waste catalytic cracking / catalytic cracking catalyst grading utilization method, wherein the metal recovery using the leaching solution comprises:

[0051] The leaching solution is mixed with an oxalic acid solution and reacted by adjusting the pH value with lye to 1.6-2.3, and solid-liquid separation is carried out to obtain a rare earth oxalate precipitate and a first filtrate, realizing rare earth recovery;

[0052] The first filtrate is subjected to extraction recovery of vanadium to obtain a vanadium-rich extraction solution and an extraction residual liquid, realizing vanadium recovery;

[0053] The extraction residual liquid is reacted by adjusting the pH value with lye to 6-10, and solid-liquid separation is carried out to obtain a mixed precipitate of aluminum hydroxide and nickel hydroxide;

[0054] The mixed precipitate of aluminum hydroxide and nickel hydroxide is reacted by adding lye to adjust the pH value to 12-13, and solid-liquid separation is carried out to obtain a nickel hydroxide precipitate and a met alloaluminate solution, realizing recovery of nickel and aluminum;

[0055] In the preferred technical solution, the characteristics of aluminum hydroxide as an amphoteric compound, which is dissolved in strong acid and strong base conditions, are combined with specific processing to recover nickel and aluminum, specifically: adding alkali to the acid extraction residual liquid to adjust the pH value to 6-10, and nickel and aluminum are both in the form of hydroxide precipitate, when the alkalinity is further increased, the pH value is adjusted to 12-13, the nickel hydroxide is still a solid precipitate, and the aluminum hydroxide is dissolved into sodium metaaluminate solution under strong alkaline conditions, through filtration, solid-liquid separation, the separation and recovery of nickel and aluminum is realized;

[0056] Further, the metal recovery using the leaching solution also includes: the vanadium-rich extraction solution is obtained by evaporation, pyrolysis and roasting to obtain vanadium pentoxide;

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

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

[0059] Further, the extraction liquid used in the process of extracting and recovering vanadium from the first filtrate is an organic extraction liquid; more preferably, the extraction liquid can include but is not limited to at least one of (2-ethylhexyl) phosphonate, ethylhexyl phosphonic acid mono-2-ethylhexyl ester;

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

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

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

[0063] Further, the alkali used in the process of adjusting the pH value of the mixture of aluminum hydroxide and nickel hydroxide 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 the preferred embodiment of the above-mentioned waste catalytic cracking / catalytic cracking catalyst grading utilization method, the second part of the to-be-processed catalyst is crushed to 1-15 μm before subsequent processing;

[0065] Further, the second part of the to-be-processed catalyst is crushed to 5-10 μm before subsequent processing.

[0066] The application provides a waste catalytic cracking / catalytic cracking catalyst grading utilization method, which divides waste catalytic cracking / catalytic cracking catalyst into two parts according to particle size, and treats waste catalytic cracking / catalytic cracking catalyst in a specific particle size range with an alkali solution and an acid solution in sequence to recover catalytic activity and reuse the waste catalytic cracking / catalytic cracking catalyst as a catalytic cracking / catalytic cracking catalyst; the rest of the waste catalytic cracking / catalytic cracking catalyst is crushed and treated with an acid solution, an extractant, a hydrofluoric acid solution and a sodium hydroxide solution to recover metals and silicon in the waste catalyst, so that the waste catalytic cracking / catalytic cracking catalyst is fully recycled and utilized, resources are used to the maximum extent, and economic and environmental benefits are achieved. Compared with conventional waste catalytic cracking / catalytic cracking catalyst recycling or element recycling methods, the waste catalytic cracking / catalytic cracking catalyst grading utilization method has the following beneficial effects:

[0067] The technical scheme of the application adopts a grading utilization method, waste catalytic cracking / catalytic cracking catalyst in a specific particle size range is subjected to catalyst recovery, the fluidization property of the recovery agent is good, and the micro-reaction activity is more than 60%; the rest is subjected to comprehensive element recovery, including metal elements and silicon elements, and in the preferred technical scheme, the element recovery rate is more than 95%; and the method has the advantages of simple operation, low cost, high element recovery utilization rate and full recovery of waste catalytic cracking / catalytic cracking catalyst. DETAILED DESCRIPTION

[0068] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the application, the technical scheme of the application will be described in detail below, but it should not be understood as limiting the scope of the application.

[0069] The sources of the raw materials involved in the examples and comparative examples of the application are as follows:

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

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

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

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

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

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

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

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

[0078] Microreactor Activity Analysis: Microreactor activity index (MII) was determined using a catalyst microreactor activity evaluation device manufactured by Beijing Huiersanji Green Chemical Technology Co., Ltd. Dagang light diesel was used as the starting material for the microreactor test. The reaction temperature was 460°C, the reaction time was 70 seconds, and the diesel feed volume was 1.56 mL. Liquid products were analyzed using a GC-2014C gas chromatograph from Shimadzu, Japan.

[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-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 60-100μm was used as the first part of the catalyst to be treated, weighing 400g, and the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size (particle size <60μm and particle size >100μm) was used as the second part of the catalyst to be treated, weighing 600g.

[0082] The first part of the catalyst to be treated is added to 1600 g of deionized water, 400 g of a sodium hydroxide solution with a mass concentration of 2.5% of sodium hydroxide, heated to 80°C for 2 h, filtered and dried; the filtered and dried material is added to 1400 g of deionized water, 400 g of a hydrochloric acid solution with a mass concentration of 1% of hydrochloric acid, treated at room temperature for 15 min, filtered, dried, and calcined at 600°C for 2 h to obtain the rejuvenated catalytic cracking / catalytic cracking catalyst; the rejuvenated catalytic cracking / catalytic cracking catalyst is subjected to micro-reaction activity analysis, and the micro-reaction activity index thereof is 66%.

[0083] The second part of the catalyst to be treated is subjected to physical sand milling and crushing to obtain material A1 with an average particle size of 10 μm. The material is added to 1200 g of a hydrochloric acid solution with a concentration of 3 mol / L of hydrochloric acid, reacted at 100°C for 20 h, and the reaction product is subjected to solid-liquid separation to obtain a leaching solution in the liquid phase and material B1 in the solid phase; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst are dissolved into the leaching solution, and silicon remains in the material B1, which is a loose microsphere with a silicon content of 99 wt%, a porosity of 1.05 cm 3The leaching solution is added with 1300g oxalic acid solution with a concentration of 0.3mol / L, and the pH value is adjusted to 2 with 25wt% ammonia water to generate rare earth oxalate precipitate, and the rare earth is recovered by filtration to obtain the rare earth oxalate precipitate and the first filtrate; the rare earth recovery rate is 96% by analysis, and the purity of the obtained rare earth oxalate is 98%. The first filtrate is added with di(2-ethylhexyl) phosphate extractant (the volume ratio of di(2-ethylhexyl) phosphate extractant to the first filtrate is 2:1), and extraction is carried out for 60min to obtain a vanadium-rich extract and an extraction residue; the vanadium-rich extract is evaporated at 105°C until dry, and is calcined at 480°C to obtain vanadium pentoxide to realize the recovery of vanadium; the vanadium recovery rate is 96% by analysis, and the purity of the obtained vanadium pentoxide is 97%. The extraction residue (aqueous phase) is added with 2.5wt% sodium hydroxide solution to adjust the pH value to 8 to generate mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 13 and then filtered again, the precipitate is nickel hydroxide, the filtrate is sodium metaaluminate solution, and the nickel and aluminum are recovered; the nickel and aluminum recovery rates are 95% and 97% respectively by analysis, the purity of the obtained nickel hydroxide is 98.5%, and the purity of the obtained sodium metaaluminate is 99%. The material B1 is transferred into a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600g of 20wt% hydrofluoric acid solution is injected, and reaction is carried out at 60°C for 0.5h; the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1600g of 15wt% sodium hydroxide solution through a one-way valve, and reaction is carried out at 80°C for 1h; after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation to obtain solid sodium fluoride and sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, adjusted to a pH value of 12.5 with 2.5wt% sodium hydroxide lye, and then filtered to obtain a sodium silicate solution product with a modulus of 3 and a SiO2 mass concentration of 21wt%. The silicon recovery rate is 97% by analysis and calculation, and the purity of the obtained sodium silicate is 99.4%.

[0084] Example 2

[0085] The present embodiment provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0086] 1000g of dry base waste catalytic cracking / catalytic cracking catalyst is sieved according to particle size into two parts, the waste catalytic cracking / catalytic cracking catalyst with a particle size of 50-90μm is taken as the first part of the to-be-treated catalyst, with a weight of 500g, and the remaining waste catalytic cracking / catalytic cracking catalyst with a particle size of <50μm and >90μm is taken as the second part of the to-be-treated catalyst, with a weight of 500g.

[0087] The first part of the catalyst to be treated is added to 2500 g of deionized water, 500 g of a sodium hydroxide solution with a mass concentration of 1.5% of sodium hydroxide, heated to 90°C for 1 h, filtered and dried; the filtered and dried material is added to 1700 g of deionized water, 500 g of a nitric acid solution with a mass concentration of 0.5% of nitric acid, treated at room temperature for 20 min, filtered, dried, and calcined at 600°C for 2 h to obtain the rejuvenated catalytic cracking / catalytic cracking catalyst; the rejuvenated catalytic cracking / catalytic cracking catalyst is subjected to micro-reaction activity analysis, and the micro-reaction activity index thereof is 64%.

[0088] The second part of the catalyst to be treated is subjected to physical sand milling and crushing to obtain material A1 with an average particle size of 15 μm. The material is added to 1000 g of a hydrochloric acid solution with a concentration of 2.5 mol / L of hydrochloric acid, reacted at 100°C for 15 h, and the reaction product is subjected to solid-liquid separation to obtain a leaching solution in the liquid phase and material B1 in the solid phase; wherein the rare earth, vanadium, nickel, and aluminum elements in the waste catalytic cracking / cracking catalyst are dissolved into the leaching solution, and silicon remains in the material B1, which is a loose microsphere with a silicon content of 98.8 wt%, a porosity of 0.95 cm 3The leaching solution is added with 1100g oxalic acid solution with a concentration of 0.4mol / L, and the pH value is adjusted to 1.8 with 25wt% ammonia water to generate rare earth oxalate precipitate, and the rare earth oxalate precipitate and the first filtrate are obtained by filtration to realize rare earth recovery; the rare earth recovery rate is 95% by analysis, and the purity of the obtained rare earth oxalate is 97%. The first filtrate is added with ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid (the volume ratio of ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid to the first filtrate is 2.5:1), and extraction is performed for 50min to obtain vanadium-rich extraction liquid and extraction residual liquid; the vanadium-rich extraction liquid is evaporated at 100℃ until dry, and is calcined at 470℃ to obtain vanadium pentoxide to realize vanadium recovery; the vanadium recovery rate is 96% by analysis, and the purity of the obtained vanadium pentoxide is 97%. The extraction residual liquid (aqueous phase) is added with 2.5wt% sodium hydroxide solution to adjust the pH value to 9 to generate mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 12.5 and then filtered again, the precipitate is nickel hydroxide, and the filtrate is sodium metaaluminate solution to realize nickel and aluminum recovery; the nickel and aluminum recovery rates are 96% and 96% respectively by analysis, the purity of the obtained nickel hydroxide is 98%, and the purity of the obtained sodium metaaluminate is 99%. The material B1 is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 500g of 25wt% hydrofluoric acid solution is injected, and reaction is performed at 70℃ for 0.6h; the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1000g of 25wt% sodium hydroxide solution through a one-way valve, and reaction is performed at 90℃ for 1.5h; after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95℃ for 1h, adjusted to a pH value of 12.8 with 2.5wt% sodium hydroxide lye, and then filtered to obtain a sodium silicate solution product with a modulus of 2.8 and a SiO2 mass concentration of 22wt%; the silicon recovery rate is 96% by analysis and calculation, and the purity of the obtained sodium silicate is 98%.

[0089] Example 3

[0090] The present embodiment provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0091] 1000g of dry base waste catalytic cracking / catalytic cracking catalyst is sieved according to particle size into two parts, the waste catalytic cracking / catalytic cracking catalyst with a particle size of 55-110μm is taken as the first part of the to-be-treated catalyst with a weight of 600g, and the remaining waste catalytic cracking / catalytic cracking catalyst with a particle size of <55μm and >110μm is taken as the second part of the to-be-treated catalyst with a weight of 400g.

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

[0093] The second part of the catalyst to be treated is subjected to physical sand milling and crushing treatment to obtain material A1 with an average particle size of 5 μm. The material is added to 800 g of a hydrochloric acid solution with a concentration of 1.5 mol / L of hydrochloric acid, reacted at 90°C for 12 h, and the product obtained by the reaction is subjected to solid-liquid separation to obtain a leaching solution in liquid phase and material B1 in solid phase; wherein the rare earth, vanadium, nickel and aluminum elements in the waste catalytic cracking / cracking catalyst are dissolved into the leaching solution, and silicon remains in the material B1, the material B1 being a loose microsphere with a silicon content of 99.1 wt%, a porosity of 0.98 cm 3g, the total mass content of rare earth, aluminum, nickel, and vanadium is 0.9 wt%. Oxalic acid solution with a concentration of 0.5 mol / L is added to the leaching solution at 900 g, and ammonia water with a concentration of 25 wt% is used to adjust the pH value to 2.1, to generate a rare earth oxalate salt precipitate, and a first filtrate is obtained by filtration, to realize rare earth recovery; through analysis, the rare earth recovery rate is 96%, and the purity of the obtained rare earth oxalate salt is 97%. Ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid (the volume ratio of ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid to the first filtrate is 1.5:1) is added to the first filtrate, and extraction is performed for 70 min, to obtain a vanadium-rich extraction liquid and an extraction residual liquid; the vanadium-rich extraction liquid is evaporated at 98°C until dry, and is calcined at 490°C to obtain vanadium pentoxide, to realize vanadium recovery; through analysis, the vanadium recovery rate is 95%, and the purity of the obtained vanadium pentoxide is 97%. Sodium hydroxide solution with a concentration of 2.5 wt% is added to the extraction residual liquid (aqueous phase) to adjust the pH value to 10, to generate a mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, sodium hydroxide solution is continuously added to the precipitate and stirred to adjust the pH value to 12.8, and then the precipitate is filtered again, the precipitate is nickel hydroxide, the filtrate is sodium metaaluminate solution, to realize nickel and aluminum recovery; through analysis, the nickel and aluminum recovery rates are 95% and 96% respectively, the purity of the obtained nickel hydroxide is 97.5%, and the purity of the obtained sodium metaaluminate is 98%. The material B1 is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600 g of hydrofluoric acid solution with a concentration of 30 wt% is injected, and reaction is performed at 50°C for 0.3 h, the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 3600 g of sodium hydroxide solution with a concentration of 10 wt%, and reaction is performed at 70°C for 2 h, after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation, to obtain solid sodium fluoride and a crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 100°C for 1 h, the pH value is adjusted to 12.4 by sodium hydroxide lye with a concentration of 2.5 wt%, and then filtration is performed, to obtain a sodium silicate solution product with a modulus of 2 and a SiO2 mass concentration of 19 wt%. Through 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 grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0096] 1000g dry base waste FCC / crack catalyst (including 250g waste FCC / crack catalyst with particle size <45 μm, 350g waste FCC / crack catalyst with particle size >110 μm, and 400g waste FCC / crack catalyst with particle size 45 μm-110 μm) was not classified according to the particle size, 4000g deionized water was added, 1000g sodium hydroxide solution with a mass concentration of 2.5% was added, and the mixture was heated to 80°C for 2h, then filtered and dried; the filtered and dried material was added to 3500g deionized water, 1000g hydrochloric acid solution with a mass concentration of 1% was added, and the mixture was treated at room temperature for 15min, then filtered, dried, and calcined at 600°C for 2h to obtain the rejuvenated FCC / crack catalyst; micro-reaction activity analysis was performed on the rejuvenated FCC / crack catalyst, and the micro-reaction activity index of the rejuvenated FCC / crack catalyst was 52%.

[0097] Comparing the data of Example 1, it can be seen that the waste FCC / crack catalyst was not classified according to the particle size, and the rejuvenated FCC / crack catalyst obtained by alkali treatment + acid treatment has a low micro-reaction activity index, and the waste FCC / crack catalyst with particle size <45 μm and particle size >110 μm treated by alkali treatment + acid treatment can cause problems such as device agent running or poor fluidization.

[0098] Comparative Example 2

[0099] The present comparative example provides a waste FCC / crack catalyst classification utilization method, wherein the method comprises:

[0100] 1000g dry base waste FCC / crack catalyst was classified according to the particle size into two parts, the waste FCC / crack catalyst with particle size 60-100 μm was used as the first part of the to-be-treated catalyst with a weight of 400g, and the remaining waste FCC / crack catalyst with particle size <60 μm and particle size >100 μm was used as the second part of the to-be-treated catalyst with a weight of 600g.

[0101] The first part of the to-be-treated catalyst was added to 1400g deionized water, 400g hydrochloric acid solution with a mass concentration of 1% was added, and the mixture was treated at room temperature for 15min, then filtered, dried, and calcined at 600°C for 2h to obtain the rejuvenated FCC / crack catalyst; micro-reaction activity analysis was performed on the rejuvenated FCC / crack catalyst, and the micro-reaction activity index of the rejuvenated FCC / crack catalyst was 50%.

[0102] Comparing the data of Example 1, it can be seen that the waste FCC / crack catalyst was not classified according to the particle size, and the rejuvenated FCC / crack catalyst obtained by alkali treatment + acid treatment has a low micro-reaction activity index, and the waste FCC / crack catalyst with particle size <45 μm and particle size >110 μm treated by alkali treatment + acid treatment can cause problems such as device agent running or poor fluidization.

[0103] Comparative Example 3

[0104] The present comparative example provides a method for graded utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

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

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

[0107] Comparing the data of Example 1, it can be seen that the rejuvenated catalytic cracking / catalytic cracking catalyst obtained without acid treatment has a low micro-reaction activity index, which cannot meet the requirement of catalytic activity.

[0108] Comparative Example 4

[0109] The present comparative example provides a method for graded utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

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

[0111] The second part of the to-be-treated catalyst was directly added into 1200 g of hydrochloric acid solution with a concentration of 3 mol / L of HCl, reacted at 100°C for 20 h, and the product obtained by the reaction was subjected to solid-liquid separation to obtain leaching solution in liquid phase and material B1 in solid phase; wherein the rare earth, vanadium, nickel and aluminum elements in the waste catalytic cracking / catalytic cracking catalyst were dissolved into the leaching solution, and silicon was left in the material B1, which was a loose microsphere, with a silicon content of 67 wt%, a porosity of 0.65 cm 3The leaching solution is added with 1300g oxalic acid solution with a concentration of 0.3mol / L, and the pH value is adjusted to 2 with 25wt% ammonia water to form a rare earth oxalate precipitate, and the rare earth oxalate precipitate and the first filtrate are obtained by filtration to realize the recovery of rare earth; the recovery rate of rare earth is 89% through analysis, and the purity of the obtained rare earth oxalate is 97%. The first filtrate is added with di(2-ethylhexyl) phosphate extractant (the volume ratio of di(2-ethylhexyl) phosphate extractant to the first filtrate is 2:1), and extraction is carried out for 60min to obtain a vanadium-rich extract and an extraction residue; the vanadium-rich extract is evaporated at 105°C to dryness, and vanadium pentoxide is obtained by calcining at 480°C to realize the recovery of vanadium; the recovery rate of vanadium is 93% through analysis, and the purity of the obtained vanadium pentoxide is 98%. The extraction residue (aqueous phase) is added with 2.5wt% sodium hydroxide solution to adjust the pH value to 8 to form a mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 13 and then filtered again, the precipitate is nickel hydroxide, and the filtrate is sodium metaaluminate solution to realize the recovery of nickel and aluminum; the recovery rates of nickel and aluminum are 91% and 90% respectively through analysis, the purity of the obtained nickel hydroxide is 96.8%, and the purity of the obtained sodium metaaluminate is 97.2%. The material B1 is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600g of 20wt% hydrofluoric acid solution is injected, and reaction is carried out at 60°C for 0.5h; the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1600g of 15wt% sodium hydroxide solution through a one-way valve, and reaction is carried out at 80°C for 1h; after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95°C for 1h, the pH value is adjusted to 12.5 with 2.5wt% sodium hydroxide lye, and then filtered to obtain a sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 12wt%. Through 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 known that the second part of the catalyst to be treated is not physically sand milled and crushed for direct treatment, and the recovery rate of each component is relatively low.

[0113] Comparative Example 5

[0114] The present comparative example provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0115] 1000g dry base spent FCC / crack catalyst was divided into two parts according to particle size, the spent FCC / crack catalyst with particle size of 60-100 μm was used as the first part of the to-be-treated catalyst, with a weight of 400g, and the spent FCC / crack catalyst with the remaining particle size (particle size < 60 μm and particle size > 100 μm) was used as the second part of the to-be-treated catalyst, with a weight of 600g.

[0116] The second part of the to-be-treated catalyst was subjected to physical sand mill crushing treatment to obtain material A1 with an average particle size of 10 μm. The material was transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600g of hydrofluoric acid solution with a concentration of 20wt% was injected, and the reaction was carried out at 60℃ for 0.5h. The gas generated in the reaction was input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1600g of sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and the reaction was carried out at 80℃ for 1h. After the reaction was completed, the product in the reaction kettle (II) was subjected to solid-liquid separation to obtain solid sodium fluoride and a crude sodium silicate liquid. The crude sodium silicate liquid was concentrated at 105℃ for 1h, the pH value was adjusted to 12.5 by using sodium hydroxide lye with a sodium hydroxide concentration of 2.5wt%, and then filtration was performed to obtain a sodium silicate solution product with a modulus of 2.5 and a SiO2 mass concentration of 10wt%. Through 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 to-be-treated catalyst is not subjected to hydrochloric acid leaching treatment, and the silicon recovery rate is low.

[0118] Comparative Example 6

[0119] The present comparative example provides a method for graded utilization of spent FCC / crack catalyst, wherein the method comprises:

[0120] 1000g dry base spent FCC / crack catalyst was divided into two parts according to particle size, the spent FCC / crack catalyst with particle size of 60-100 μm was used as the first part of the to-be-treated catalyst, with a weight of 400g, and the spent FCC / crack catalyst with the remaining particle size (particle size < 60 μm and particle size > 100 μm) was used as the second part of the to-be-treated catalyst, with a weight of 600g.

[0121] The second part of the to-be-treated catalyst was directly added into 1200g of sulfuric acid solution with a concentration of 3mol / L H2SO4, and the reaction was carried out at 100℃ for 20h. The product obtained in the reaction was subjected to solid-liquid separation to obtain leaching liquid in liquid phase and material B1 in solid phase. Among them, the rare earth elements, vanadium, nickel and aluminum elements in the spent FCC / crack catalyst were dissolved into the leaching liquid, and silicon was left in the material B1. The material B1 was a loose microsphere, with a silicon content of 57wt% and a porosity of 0.58cm3 The leaching solution is added with 1300g oxalic acid solution with a concentration of 0.3mol / L, and the pH value is adjusted to 2 with ammonia water with a concentration of 25wt%, to generate rare earth oxalate precipitate, and the rare earth is recovered by filtration to obtain the rare earth oxalate precipitate and the first filtrate; the rare earth recovery rate is 60% by analysis, and the purity of the obtained rare earth oxalate is 97.5%. The first filtrate is added with di(2-ethylhexyl) phosphate extractant (the volume ratio of di(2-ethylhexyl) phosphate extractant to the first filtrate is 2:1), and the extraction is carried out for 60min to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated at 105℃ to dryness, and is calcined at 480℃ to obtain vanadium pentoxide to recover vanadium; the vanadium recovery rate is 53% by analysis, and the purity of the obtained vanadium pentoxide is 97%. The extraction residue (aqueous phase) is added with sodium hydroxide solution with a concentration of 2.5wt% to adjust the pH value to 8, to generate mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 13, and then filtered again, the precipitate is nickel hydroxide, and the filtrate is sodium metaaluminate solution, to recover nickel and aluminum; the nickel and aluminum recovery rates are 41% and 30% respectively by analysis, the purity of the obtained nickel hydroxide is 97%, and the purity of the obtained sodium metaaluminate is 96%. The material B1 is transferred to the polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600g hydrofluoric acid solution with a concentration of 20wt% is injected, and the reaction is carried out at 60℃ for 0.5h, the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1600g sodium hydroxide solution with a concentration of 15wt% through a one-way valve, and the reaction is carried out at 80℃ for 1h, after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95℃ for 1h, the pH value is adjusted to 12.5 with sodium hydroxide lye with a concentration of 2.5wt%, and then filtered to obtain sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 5wt%. The silicon recovery rate is 29% by analysis and calculation, and the purity of the obtained sodium silicate is 95%.

[0122] Compared with the data of Example 1, it can be known that the second part of the catalyst to be treated is not treated with hydrochloric acid but with other acids, and the recovery rate and purity of each component are low.

[0123] Comparative Example 7

[0124] The present comparative example provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0125] 1000g dry base spent FCC / crack catalyst is classified by particle size into two parts, the spent FCC / crack catalyst with particle size of 50-90 μm is used as the first part of the spent catalyst to be treated, with a weight of 500g, and the remaining spent FCC / crack catalyst with particle size of <50 μm and >90 μm is used as the second part of the spent catalyst to be treated, with a weight of 500g.

[0126] The first part of the spent catalyst to be treated is added to 2500g deionized water, 500g sodium hydroxide solution with a mass concentration of 1.5% of sodium hydroxide is added, heated to 90°C for 1h, filtered and dried; the filtered and dried material is added to 1700g deionized water, 500g nitric acid solution with a mass concentration of 0.5% of nitric acid is added, treated at room temperature for 20min, filtered, dried and calcined at 600°C for 2h to obtain the rejuvenated FCC / crack catalyst; the rejuvenated FCC / crack catalyst is subjected to micro-reactor activity analysis, and the micro-reactor activity index thereof is 64%.

[0127] The second part of the spent catalyst to be treated is subjected to physical sanding and crushing treatment to obtain material A1 with an average particle size of 15 μm. The material is added to 1000g hydrochloric acid solution with a concentration of 5mol / L of hydrochloric acid, reacted at 100°C for 15h, and the product obtained by the reaction is subjected to solid-liquid separation to obtain leaching solution in liquid phase and material B1 in solid phase; wherein the rare earth, vanadium, nickel and aluminum elements in the spent FCC / crack catalyst are dissolved into the leaching solution, and silicon remains in the material B1, the material B1 is a loose microsphere, the silicon content thereof is 92.5wt%, the porosity thereof is 0.75cm 3The leaching solution is added with 1100g oxalic acid solution with a concentration of 0.4mol / L, and the pH value is adjusted to 1.8 with ammonia water with a concentration of 25wt% to generate rare earth oxalate precipitate, and the rare earth is recovered by filtration to obtain the rare earth oxalate precipitate and the first filtrate; the rare earth recovery rate is 85% by analysis, and the purity of the obtained rare earth oxalate is 96%. The first filtrate is added with ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid (the volume ratio of ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid to the first filtrate is 2.5:1), and extraction is performed for 50min to obtain vanadium-rich extraction liquid and extraction residual liquid; the vanadium-rich extraction liquid is evaporated at 100°C to dryness, and vanadium pentoxide is obtained by calcining at 470°C to realize the recovery of vanadium; the vanadium recovery rate is 87% by analysis, and the purity of the obtained vanadium pentoxide is 97.5%. The extraction residual liquid (aqueous phase) is added with sodium hydroxide solution with a concentration of 2.5wt% to adjust the pH value to 9 to generate mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 12.5 and then filtered again, the precipitate is nickel hydroxide, the filtrate is sodium metaaluminate solution, and the nickel and aluminum are recovered; the nickel and aluminum recovery rates are 76% and 83% respectively by analysis, the purity of the obtained nickel hydroxide is 97%, and the purity of the obtained sodium metaaluminate is 98%. The material B1 is transferred to the polytetrafluoroethylene-lined high-pressure reaction kettle (I), 500g hydrogen fluoride solution with a concentration of 25wt% is injected, and reaction is performed at 70°C for 0.6h; the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 1000g sodium hydroxide solution with a concentration of 25wt% through a one-way valve, and reaction is performed at 90°C for 1.5h; after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation 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 value of 12.8 with sodium hydroxide lye with a concentration of 2.5wt%, and then filtered to obtain sodium silicate solution product with a modulus of 2.7 and a SiO2 mass concentration of 14wt%; the silicon recovery rate is 76% by analysis and calculation, and the purity of the obtained sodium silicate is 98%.

[0128] Compared with the data of Example 2, it can be known that the second part of the catalyst to be treated is subjected to acid leaching treatment using hydrochloric acid with a concentration not in the range of 1-3mol / L, and the recovery rate of each component is low.

[0129] Comparative Example 8

[0130] The present comparative example provides a method for grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0131] 1000g dry base spent FCC / crack catalyst was divided into two parts according to particle size, the spent FCC / crack catalyst with particle size of 55-110 μm was used as the first part of the spent catalyst to be treated, with a weight of 600g, and the remaining spent FCC / crack catalyst with particle size of <55 μm and >110 μm was used as the second part of the spent catalyst to be treated, with a weight of 400g.

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

[0133] The second part of the spent catalyst to be treated was subjected to physical sanding and crushing treatment to obtain material A1 with an average particle size of 5 μm; the material was added to 800g hydrochloric acid solution with a concentration of 1.5mol / L of hydrochloric acid, and reacted at 90°C for 12h; the product obtained by the reaction was subjected to solid-liquid separation to obtain leaching solution in liquid phase and material B1 in solid phase; wherein the rare earth, vanadium, nickel, and aluminum elements in the spent FCC / crack catalyst were dissolved into the leaching solution, and silicon was left in the material B1; the material B1 was a loose microsphere, with a silicon content of 99.1wt%, a porosity of 0.98cm 3The leaching solution is added with 900 g of oxalic acid solution with a concentration of 0.5 mol / L, and the pH value is adjusted to 2.1 by using ammonia water with a concentration of 25 wt% to generate a rare earth oxalate precipitate, and the rare earth oxalate precipitate and the first filtrate are obtained by filtration to realize the recovery of rare earth; the recovery rate of rare earth is 96% through analysis, and the purity of the obtained rare earth oxalate is 97%. The first filtrate is added with ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid (the volume ratio of ethylhexyl phosphonic acid mono-2-ethylhexyl ester extraction liquid to the first filtrate is 1.5:1), and extraction is performed for 70 min to obtain a vanadium-rich extraction liquid and an extraction residual liquid; the vanadium-rich extraction liquid is evaporated at 98°C to dryness and is calcined at 490°C to obtain vanadium pentoxide to realize the recovery of vanadium; the recovery rate of vanadium is 95% through analysis, and the purity of the obtained vanadium pentoxide is 97%. The extraction residual liquid (aqueous phase) is added with sodium hydroxide solution with a concentration of 2.5 wt% to adjust the pH value to 10 to generate a mixed precipitate of aluminum hydroxide and nickel hydroxide, and after filtration, the precipitate is continuously added with sodium hydroxide solution and stirred to adjust the pH value to 12.8 and then filtered again, the precipitate is nickel hydroxide, the filtrate is sodium metaaluminate solution, and the recovery of nickel and aluminum is realized; the recovery rates of nickel and aluminum are 95% and 96%, respectively, through analysis, the purity of the obtained nickel hydroxide is 97.5%, and the purity of the obtained sodium metaaluminate is 98%. The material B1 is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 6000 g of hydrofluoric acid solution with a concentration of 3 wt% is injected, reaction is performed at 50°C for 0.3 h, the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 3600 g of sodium hydroxide solution with a concentration of 10 wt%, reaction is performed at 70°C for 2 h, and after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation to obtain solid sodium fluoride and crude sodium silicate liquid; the crude sodium silicate liquid is concentrated at 100°C for 1 h, adjusted to a pH value of 12.4 by using sodium hydroxide lye with a concentration of 2.5 wt%, and then filtered to obtain a sodium silicate solution product with a modulus of 1.8 and a SiO2 mass concentration of 13 wt%. Through analysis and calculation, the recovery rate of silicon is 87%, and the purity of the obtained sodium silicate is 98.5%.

[0134] Compared with the data of Example 3, it can be known that the second part of the catalyst to be treated uses HF with a concentration not in 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 grading utilization of waste catalytic cracking / catalytic cracking catalyst, wherein the method comprises:

[0137] 1000g dry base spent FCC / crack catalyst was classified by particle size into two parts, the spent FCC / crack catalyst with particle size of 60-100 μm was used as the first part of the spent catalyst to be treated, 400g in weight, and the remaining spent FCC / crack catalyst with particle size of < 60 μm and > 100 μm was used as the second part of the spent catalyst to be treated, 600g in weight.

[0138] The first part of the spent catalyst to be treated was added to 1600g deionized water, 400g sodium hydroxide solution with mass concentration of 2.5% of sodium hydroxide was added, heated to 80°C for 2h, filtered and dried; the filtered and dried material was added to 1400g deionized water, 400g hydrochloric acid solution with mass concentration of 1% of hydrochloric acid was added, treated at room temperature for 15min, filtered, dried and calcined at 600°C for 2h to obtain the rejuvenated FCC / crack catalyst; the rejuvenated FCC / crack catalyst was subjected to micro-activity analysis, and the micro-activity index thereof was 66%.

[0139] The second part of the spent catalyst to be treated was subjected to physical sanding and crushing treatment to obtain material A1 with average particle size of 10 μm. The material was added to 1200g hydrochloric acid solution with concentration of 3mol / L, reacted at 100°C for 20h, and the product obtained by the reaction was subjected to solid-liquid separation to obtain leaching solution in liquid phase and material B1 in solid phase; wherein the rare earth, vanadium, nickel and aluminum elements in the spent FCC / crack catalyst were dissolved into the leaching solution, and silicon was left in the material B1, the material B1 was loose microspheres, the silicon content thereof was 99wt%, the porosity thereof was 1.05cm 3 / g, the total mass content of rare earth, aluminum, nickel and vanadium is 1wt%. Oxalic acid solution 1300g with oxalic acid concentration of 0.3mol / L is added to the leaching solution, and ammonia water with ammonia concentration of 25wt% is used to adjust the pH value to 2, to generate rare earth oxalate precipitate, and the rare earth oxalate precipitate and the first filtrate are obtained by filtration, to realize the recovery of rare earth; the recovery rate of rare earth is 96% through analysis, and the purity of the obtained rare earth oxalate is 98%. Bis(2-ethylhexyl) phosphate extractant (the volume ratio of bis(2-ethylhexyl) phosphate extractant to the first filtrate is 2:1) is added to the first filtrate, and extraction is carried out for 60min, to obtain vanadium-rich extract and extraction residue; the vanadium-rich extract is evaporated at 105℃ until dry, and is calcined at 480℃ to obtain vanadium pentoxide, to realize the recovery of vanadium; the recovery rate of vanadium is 96% through analysis, and the purity of the obtained vanadium pentoxide is 97%. Sodium hydroxide solution with sodium hydroxide concentration of 2.5wt% is added to the extraction residue (aqueous phase) to adjust the pH value to 8, to generate mixed precipitate of aluminum hydroxide and nickel hydroxide, after filtration, sodium hydroxide solution is continuously added to the precipitate and stirred to adjust the pH value to 13, and then the precipitate is filtered again, the precipitate is nickel hydroxide, the filtrate is sodium aluminate solution, to realize the recovery of nickel and aluminum; the recovery rates of nickel and aluminum are 95% and 97% respectively through analysis, the purity of the obtained nickel hydroxide is 98.5%, and the purity of the obtained sodium aluminate is 99%. Material B1 is transferred to a polytetrafluoroethylene-lined high-pressure reaction kettle (I), 600g of hydrofluoric acid solution with HF concentration of 20wt% is injected, and reaction is carried out at 60℃ for 0.5h, the gas generated in the reaction is input into another polytetrafluoroethylene-lined high-pressure reaction kettle (II) containing 8000g of sodium hydroxide solution with sodium hydroxide concentration of 3wt% through a one-way valve, and reaction is carried out at 80℃ for 1h, after the reaction is completed, the product in the reaction kettle (II) is subjected to solid-liquid separation, to obtain solid sodium fluoride and sodium silicate liquid; the crude sodium silicate liquid is concentrated at 95℃ for 1h, the pH value is adjusted to 12.5 by sodium hydroxide lye with sodium hydroxide concentration of 2.5wt%, and then filtration is carried out, to obtain sodium silicate solution product with modulus of 2.6 and SiO2 mass concentration of 12wt%. Through analysis and calculation, the silicon recovery rate is 87%, and the purity of the obtained sodium silicate is 98%.

[0140] Compared with the data of Example 1, it can be known that the gas generated in the second part of the process of treating the catalyst to be treated is introduced into a concentration not within the range of 5-40%, and the silicon component recovery rate is low.

Claims

1. A method for graded utilization of spent catalytic cracking / catalytic cracking catalysts, wherein: The method includes: Sieving the spent catalytic cracking / catalytic cracking catalyst into two parts according to particle size, using the spent catalytic cracking / catalytic cracking catalyst with a particle size between a first particle size threshold and a second particle size threshold as a first part of catalyst to be treated, and using the spent catalytic cracking / catalytic cracking catalyst with the remaining particle size as a second part of 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; sequentially subjecting the first portion of the catalyst to be treated to an alkali treatment and an acid treatment to obtain a revived catalytic cracking / catalytic cracking catalyst; The second portion 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 reaction product is removed to obtain liquid sodium silicate; Among them, metal recovery using leaching solution includes: The leachate is mixed with an oxalic acid solution and the pH value is adjusted to 1.6-2.3 with an alkaline solution for reaction. After solid-liquid separation, a rare earth oxalate precipitate and a first filtrate are obtained to achieve rare earth recovery. The concentration of oxalic acid in the oxalic acid solution is 0.1-0.5 mol / L. The first filtrate is subjected to extraction to recover vanadium, thereby obtaining a vanadium-rich extract and an extract residue, thereby achieving vanadium recovery; The pH value of the extraction residue is adjusted to 6-10 by using alkaline solution, and then reacted, and solid-liquid separation is performed to obtain a mixed precipitate of aluminum hydroxide and nickel hydroxide; Alkali solution is added to the mixed precipitate of aluminum hydroxide and nickel hydroxide to adjust the pH value to 12-13 for reaction, and solid-liquid separation is performed to obtain nickel hydroxide precipitate and metaaluminate solution, thereby realizing the recovery of nickel and aluminum; The vanadium-rich extract is evaporated to dryness, pyrolyzed and calcined to obtain vanadium pentoxide.

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.

3. The method according to claim 1, wherein The first particle size threshold is 60 μm, and the second particle size threshold is 100 μm.

4. The method according to claim 1, wherein In the process of sequentially subjecting the first portion 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 portion 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.

5. The method according to claim 1 or 4, wherein The first portion of the catalyst to be treated is subjected to an alkali treatment and an acid treatment in sequence, comprising: Mixing the first portion of the catalyst to be treated with water and an alkaline 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 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.

6. The method according to claim 5, wherein During the mixing of the first portion of the catalyst to be treated with water and the alkaline solution, the mass ratio of the first portion 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%; the mass of the alkali in the alkaline solution is 1-10% of the mass of the first portion of the catalyst to be treated; 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 alkali-treated catalyst with water and the acid solution is 1:3-1:6; the mass concentration of the acid in the acid solution is 0.15-3.5%; 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.

7. The method according to claim 6, wherein: The mass concentration of alkali in the alkali solution is 1-3%.

8. The method according to claim 6, wherein: The mass of the alkali in the alkali solution is 2-6% of the mass of the first part of the catalyst to be treated.

9. The method according to claim 6, wherein: The mass concentration of acid in the acid solution is 0.35-1.5%.

10. The method according to claim 6, wherein: The mass of the acid in the acid solution is 0.3-2% of the mass of the first part of the catalyst to be treated.

11. The method according to claim 1, wherein The second portion of 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 with a concentration of 1-3 mol / L, and a leachate 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. The solid phase of the reaction product is removed 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%.

12. The method according to claim 1 or 11, wherein: 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.

13. The method according to claim 1 or 11, wherein: The alkali solution used in the process of adjusting the pH value of the extraction residue to 6-10 includes at least one of sodium hydroxide solution, potassium hydroxide solution and ammonia water.

14. The method according to claim 1 or 11, wherein: 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.

15. The method according to claim 11, wherein The extracting liquid used in the process of extracting and recovering vanadium from the first filtrate is an organic extracting liquid.

16. The method according to claim 15, wherein The extract includes at least one of (2-ethylhexyl) phosphate and ethylhexyl mono-2-ethylhexyl phosphate.

17. The method according to claim 15, wherein: During the extraction and recovery of vanadium by the first filtrate, the volume ratio of the extract to the first filtrate is 1-3:

1.

18. The method according to claim 11, 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%.

19. The method according to claim 11, 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%.

20. The method according to claim 11, 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 a sodium hydroxide solution for reaction at a temperature of 60-100°C.

21. The method according to claim 11, wherein The method further comprises: removing the solid phase to obtain liquid sodium silicate, concentrating, adjusting with alkali solution and re-filtering to obtain a sodium silicate solution product meeting the modulus and concentration requirements.

22. The method according to claim 21, wherein The modulus of sodium silicate solution products is 1.5-3.

5.

23. The method according to claim 21, wherein The SiO2 mass concentration in the sodium silicate solution product is 15-25wt%.

24. The method according to claim 1 or 11, wherein The second part of the catalyst to be treated is crushed to 1-15 μm and then subjected to subsequent treatment.

25. The method according to claim 24, wherein The second part of the catalyst to be treated is crushed to 5-10 μm and then subjected to subsequent treatment.

26. The method according to claim 1, wherein 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%, and the mass content of SiO2, Al2O3, RE2O3, Ni and V is not less than 99.5wt%.

27. The method according to claim 26, wherein 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%.