阅读说明：本技术 一种处理含钒废催化剂的方法 (Method for treating vanadium-containing waste catalyst ) 是由 黄绵延 常耀超 黄明星 葛启明 王为振 高崇 刘会超 于 2020-12-22 设计创作，主要内容包括：本发明提供了一种处理含钒废催化剂的方法,包括以下步骤：A)将脱油废催化剂球磨,得到粉状废催化剂；B)将所述粉状废催化剂进行混料,得到混合物料；C)将所述混合物料进行造粒,干燥后得到混合物料颗粒；D)将所述混合物料颗粒冷固后于沸腾炉中焙烧,得到钠化熟料。本申请提供的方法实现了在沸腾炉中钠化焙烧,强化了钠化添加剂与含钒废催化剂之间、冷固颗粒与空气之间的接触,改善了钠化焙烧的化学反应动力学条件,提高了钠化熟料中钒的浸出率,钠化熟料的钒浸出率能够达到95％以上,解决了回转窑温度不易控制、易结窑的问题,有利于生产的组织和实施；钠化焙烧时利用了废催化剂中碳硫氧化所产生的自热,降低了生产成本。(The invention provides a method for treating vanadium-containing waste catalyst, which comprises the following steps: A) ball-milling the deoiled waste catalyst to obtain a powdery waste catalyst; B) mixing the powdery waste catalyst to obtain a mixed material; C) granulating the mixed material, and drying to obtain mixed material particles; D) and (3) roasting the mixed material particles in a fluidized bed furnace after the mixed material particles are cooled and solidified to obtain the sodium-modified clinker. The method provided by the application realizes sodium modification roasting in a fluidized bed furnace, strengthens the contact between a sodium modification additive and the vanadium-containing waste catalyst and between cold solid particles and air, improves the chemical reaction kinetic conditions of the sodium modification roasting, improves the leaching rate of vanadium in the sodium modification clinker, solves the problems that the temperature of a rotary kiln is difficult to control and the rotary kiln is easy to form, and is beneficial to production organization and implementation; during sodium roasting, the self-heating generated by carbon-sulfur oxidation in the waste catalyst is utilized, and the production cost is reduced.)

1. A method for treating vanadium-containing waste catalyst comprises the following steps:

A) ball-milling the deoiled waste catalyst to obtain a powdery waste catalyst;

B) sequentially carrying out primary mixing and secondary mixing on the powdery waste catalyst to obtain a mixed material; the additive of the primary mixed material is a sodium additive, and the additive of the secondary mixed material is an adhesive and water;

C) granulating the mixed material, and drying to obtain mixed material particles;

D) and (3) roasting the mixed material particles in a fluidized bed furnace after the mixed material particles are cooled and solidified to obtain the sodium-modified clinker.

2. The method as claimed in claim 1, wherein, in step A), the particle size D90 of the powdery spent catalyst is not less than 0.147 mm; in the step C), the diameter D90 of the mixed material particles is 3-5 mm.

3. The method of claim 1, wherein the sodium treatment additive is Na₂CO₃The addition amount of the sodium treatment additive is 20 to 40 weight percent of the powdery waste catalyst; the binder is a mixture of water glass and sodium bentonite, and the modulus of the water glass is 3.0-3.5; the adding amount of the water glass is 1 to 5 weight percent of the powdery waste catalyst, and the adding amount of the sodium bentonite is 1 to 4 weight percent of the powdery waste catalyst; the primary mixing time is 10-30 min; and the secondary mixing time is 10-30 min.

4. The method according to claim 1, wherein the drying is carried out in low-temperature hot air at a temperature of 100-150 ℃ for 1-2 h; the temperature of the cold solidification is room temperature, and the time is 2-4 h.

5. The method according to claim 1, wherein the roasting temperature is 600-800 ℃ and the roasting time is 0.5-2 h.

6. The method of claim 1, wherein the hood arrangement density of the fluidized bed furnace is 50 to 100/m²。

7. The method as claimed in claim 1, wherein the height of the discharge opening of the fluidized bed furnace is 1200 to 1800 mm.

8. The method according to claim 1, wherein the hearth angle of the fluidized bed furnace is 15-20 °.

9. The method of claim 1, wherein the hearth of the fluidized bed furnace is provided with a slag discharge port.

10. The method as claimed in claim 1, wherein the fluidized bed treatment capacity of the fluidized bed furnace is 20-30 t/(m)²·d)。

Technical Field

The invention relates to the technical field of solid waste treatment, in particular to a method for treating vanadium-containing waste catalyst.

Background

The hydrogenation catalyst is widely applied to the petrochemical industry, and the demand of the petrochemical industry for the hydrogenation catalyst is gradually increased year by year. After the hydrogenation catalyst is used for a long time, the problem of heavy metal deposition and inactivation can occur, and then the hydrogenation catalyst is discarded. Currently, about 12 million tons of hydrogenation catalyst are scrapped every year around the world. The waste hydrogenation catalyst belongs to dangerous solid waste and seriously pollutes the environment; but the vanadium content in the waste catalyst is higher, and the waste catalyst belongs to high-quality secondary resources, so that the development of the harmless treatment and comprehensive recycling technology of the vanadium-containing waste catalyst has important significance.

Sodium roasting is an effective method for treating vanadium-containing minerals and is industrially realized by adopting a high-temperature rotary kiln. The method has the basic principle that vanadium-containing minerals are converted into soluble sodium salts through high-temperature roasting, and vanadium is recovered through methods such as leaching and the like. The high-temperature roasting process determines the conversion rate of the soluble sodium salt, so that the optimization of the high-temperature roasting process is the key for improving the recovery rate of vanadium. The existing sodium treatment roasting process for treating the waste hydrogenation catalyst has a series of problems: firstly, the powdery material is easily influenced by factors such as material density, particle nonuniformity and friction force, so that the contact between the waste catalyst and the sodium treatment additive is insufficient, the sodium treatment roasting reaction is insufficient, and the conversion rate of soluble sodium salt is influenced; secondly, the existing sodium treatment roasting process needs proper temperature, but the temperature of the rotary kiln is difficult to control; if the temperature is lower, the conversion rate of the soluble sodium salt is low, so that the recovery rate of vanadium is lower; if the temperature is higher, the materials are easy to sinter, and vanadium is wrapped by a glass phase, so that the leaching rate of the sodium-modified clinker is reduced; finally, different from vanadium-containing waste, the waste hydrogenation catalyst contains a certain amount of carbon and sulfur, and in the sodium treatment roasting process of the waste catalyst, the carbon and sulfur are subjected to oxidation reaction to release a large amount of heat, so that local overheating is easily generated, the vanadium leaching rate is influenced, the ring formation of a rotary kiln is also caused, and the smooth production is seriously influenced. In view of the foregoing, there is currently a lack of a process for treating spent hydroprocessing catalysts.

Disclosure of Invention

The invention aims to provide a method for treating vanadium-containing waste catalyst, which can improve the leaching rate of vanadium in sodium-modified clinker and ensure that the production is smoothly carried out.

In view of the above, the present application provides a method for treating vanadium-containing waste catalyst, comprising the following steps:

A) ball-milling the deoiled waste catalyst to obtain a powdery waste catalyst;

B) sequentially carrying out primary mixing and secondary mixing on the powdery waste catalyst to obtain a mixed material; the additive of the primary mixed material is a sodium additive, and the additive of the secondary mixed material is an adhesive and water;

C) granulating the mixed material, and drying to obtain mixed material particles;

D) and (3) roasting the mixed material particles in a fluidized bed furnace after the mixed material particles are cooled and solidified to obtain the sodium-modified clinker.

Preferably, in the step A), the particle size D90 of the powdery waste catalyst is less than or equal to 0.147 mm; in the step C), the diameter D90 of the mixed material particles is 3-5 mm.

Preferably, the sodium additive is Na₂CO₃The addition amount of the sodium treatment additive is 20 to 40 weight percent of the powdery waste catalyst; the binder is a mixture of water glass and sodium bentonite, and the modulus of the water glass is3.0 to 3.5; the adding amount of the water glass is 1 to 5 weight percent of the powdery waste catalyst, and the adding amount of the sodium bentonite is 1 to 4 weight percent of the powdery waste catalyst; the primary mixing time is 10-30 min; and the secondary mixing time is 10-30 min.

Preferably, the drying is carried out in low-temperature hot air, the temperature of the low-temperature hot air is 100-150 ℃, and the time is 1-2 hours; the temperature of the cold solidification is room temperature, and the time is 2-4 h.

Preferably, the roasting temperature is 600-800 ℃, and the roasting time is 0.5-2 h.

Preferably, the arrangement density of the blast caps of the fluidized bed furnace is 50 to 100/m²。

Preferably, the height of the discharge opening of the fluidized bed furnace is 1200-1800 mm.

Preferably, the hearth angle of the fluidized bed furnace is 15-20 degrees.

Preferably, a slag discharging port is arranged at the bottom of the boiling furnace.

Preferably, the fluidized bed treatment capacity of the fluidized bed furnace is 20-30 t/(m)²·d)。

The application provides a method for treating vanadium-containing waste catalyst, which comprises the steps of firstly ball-milling deoiled waste catalyst, then sequentially carrying out primary mixing and secondary mixing on the obtained powdery waste catalyst, then carrying out granulation and cold solidification, and roasting in a fluidized bed furnace to obtain sodium-modified clinker. In the process, firstly, the powdery waste catalyst is subjected to primary mixing and secondary mixing in sequence, so that the strength of particles is ensured, meanwhile, the cold-solidification granulation process is used for preparing particles with certain strength at low temperature, can be used for boiling roasting, strengthens the contact between the vanadium-containing waste catalyst and a sodium treatment additive, solves the problem of uneven contact between solid phases in the boiling roasting process, improves the mass transfer condition of sodium treatment roasting, increases the conversion rate of soluble sodium salt, and improves the leaching rate of vanadium; furthermore, the fluidized bed furnace sodium salt roasting enables the vanadium-containing waste catalyst particles to be heated uniformly, heat transfer is uniform, and chemical reaction is facilitated, so that the leaching rate of vanadium is finally improved, and production is smoothly carried out.

Drawings

FIG. 1 is a schematic flow chart of the method for treating vanadium-containing waste catalyst of the present invention.

Detailed Description

For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.

In view of the recycling requirement and the current situation that the leaching rate of the vanadium-containing waste catalyst is low and the smooth production is influenced, the application provides a method for treating the vanadium-containing waste catalyst, the method adopts a granulation-sodium treatment roasting process to realize sodium treatment roasting in a fluidized bed furnace, the granulation method is adopted to strengthen the contact between the waste catalyst and powder, the fluidized bed roasting process is adopted to increase the contact area between cold-solidified particles and air, and the dynamic condition of chemical reaction is improved, so that the conversion rate of soluble sodium salt is improved, and the leaching rate of vanadium in the produced sodium treatment clinker can reach more than 95%. The flow schematic diagram of the method for treating the vanadium-containing waste catalyst is shown in figure 1, and comprises the steps of ball milling, primary mixing, secondary mixing, granulation, low-temperature solidification and sodium modification roasting, and specifically, the method for treating the vanadium-containing waste catalyst comprises the following steps:

A) ball-milling the deoiled waste catalyst to obtain a powdery waste catalyst;

B) sequentially carrying out primary mixing and secondary mixing on the powdery waste catalyst to obtain a mixed material; the additive of the primary mixed material is a sodium additive, and the additive of the secondary mixed material is an adhesive and water;

C) granulating the mixed material, and drying to obtain mixed material particles;

D) and (3) roasting the mixed material particles in a fluidized bed furnace after the mixed material particles are cooled and solidified to obtain the sodium-modified clinker.

In the process of treating the vanadium-containing waste catalyst, the deoiling waste catalyst is ball-milled to obtain the powdery waste catalyst; the ball milling is a ball milling process well known to those skilled in the art, and the specific embodiment of the ball milling is not particularly limited in this application, and in the specific embodiment, the ball milling is high energy ball milling, and the particle size of the powdery waste catalyst obtained after the ball milling reaches D90 ≤ 0.147 mm.

According to the invention, the powdery waste catalyst is sequentially subjected to primary mixing and secondary mixing to obtain a mixed material, wherein the additive of the primary mixing is a sodium additive, and the additive of the secondary mixing is a binder and water; more specifically, the sodium additive is Na₂CO₃The sodium treatment additive is added in an amount of 20 to 40 wt% of the powdery waste catalyst, and more specifically, the sodium treatment additive is added in an amount of 20, 22, 26, 28, 30, 32, 35, 38, or 40 wt%; the binder is water glass (Na)₂O·nSiO₂) With sodium bentonite (Na)_x(H₂O)₄·(Al_2-xMg_0.83)·Si₄O₁₀·(OH)₂) The modulus of the water glass is 3.0-3.5; the adding amount of the water glass is 1 to 5 weight percent of the powdery waste catalyst, the adding amount of the sodium bentonite is 1 to 4 weight percent of the powdery waste catalyst, more specifically, the adding amount of the water glass is 1, 2, 3, 4 or 5 weight percent, and the adding amount of the sodium bentonite is 1, 2, 3 or 4 weight percent of the powdery waste catalyst. The sodium silicate and the sodium bentonite are adopted as the composite binder, the sodium silicate can be solidified at room temperature, and the compressive strength of the particles can be remarkably improved by the sodium silicate; the curing mechanism of the water glass is the coexistence of chemical curing and physical curing, the chemical curing is to absorb carbon dioxide to generate sodium carbonate, and the physical curing is to generate the high-modulus water glass by water loss, so that the chemical curing reaction can supplement a sodium additive, the room-temperature curing can promote the chemical curing, and the water glass is prevented from being rapidly dehydrated to generate the physical curing at high temperature; the granules need certain compressive strength and certain falling strength, so that certain sodium bentonite is added, and after the granules enter the furnace, the strength of the granules is improved along with the heating and roasting, so that the premature cracking and pulverization of the granules are avoided; mixing materialsThe increase of the medium binder is beneficial to increasing the roasting utilization rate of the raw materials in a fluidized bed furnace in the pelletizing process, and prevents the small particles from raising dust and the large particles from sinking to the bottom due to uneven powder granularity. If the addition amount of the binder water glass is insufficient, the compressive strength of the granules is insufficient, and if the binder sodium bentonite is not added or the content is out of the range, the falling strength of the granules is poor. The primary mixing time is 10-30 min; and the secondary mixing time is 10-30 min. The mixing is performed in a mixing device including, but not limited to, a mill mixer, a coulter mixer, a screw mixer, etc., and the application is not particularly limited thereto.

The obtained mixed material is granulated and dried to obtain mixed material particles; water was sprayed simultaneously during the above granulation process. The granulating machine comprises, but is not limited to, a disk granulating machine, a rotary drum granulating machine or a rolling granulating machine, and is used for granulating the mixed material to obtain mixed material particles meeting certain standards. The particle diameter D90 of the mixed material particles is 3-5 mm.

After granulation, the granules are dried, in this case, low-speed hot air is blown by an air blower to dry the granules, and then the granules are solidified at room temperature to obtain solidified granules. The temperature of the hot air is 100-150 ℃, the drying time is 1-2 h, the cold setting temperature is natural room temperature, and the cold setting time is 2-4 h. Air circulation can be increased by a fan or the like during the particle freezing process to accelerate drying, as required. The method adopts a cold-solidification granulation process, prepares particles with certain strength at low temperature, can be used for boiling roasting, strengthens the contact between the vanadium-containing waste catalyst and the sodium treatment additive, solves the problem of uneven contact between solid phases in the boiling roasting process, improves mass transfer conditions of the sodium treatment roasting, increases the conversion rate of soluble sodium salt, and increases the leaching rate of vanadium. The free falling strength of the cooled and solidified particles from 1 meter is not less than 8 times, the compressive strength is not less than 9MPa, and the bursting temperature is not less than 800 ℃.

According to the invention, the cold-solidified material particles are finally roasted in a fluidized bed furnace to obtain sodium saltAnd (3) clinker. Fluidized roasting is a solid fluidized roasting technology, and the main equipment of the fluidized roasting technology is a fluidized bed furnace. In the fluidized bed furnace, the air is blown into the furnace from bottom to top by the air blower, and when the air passes through the material layer, the material particles form a pseudo-fluid state, so that the contact area between the air and the material is greatly increased, and the reaction rate between a gas phase and a solid phase is improved, therefore, the roasting strength is high, the temperature of a bed layer is uniform, and the problems that the high-temperature roasting of the rotary kiln is easy to be locally overheated and the temperature in the kiln is difficult to control can be effectively solved. The boiling roasting is used for enhancing the dynamic condition of gas-solid reaction, however, the sodium treatment roasting reaction mainly takes solid phase waste catalyst and solid phase sodium treatment additive, and the boiling roasting process has the problem that the solid phase particles are not contacted sufficiently and are difficult to react. Therefore, on one hand, the cold solidification granulation mode is adopted to solve the problem of uneven powder granularity, and on the other hand, partial parameters of the fluidized bed furnace are improved: the arrangement density of blast caps of the fluidized bed furnace is 50 to 100/m²(ii) a The height of a discharge port of the fluidized bed furnace is 1200-1800 mm; the hearth angle of the fluidized bed furnace is 15-20 degrees; a slag discharging port is formed at the bottom of the fluidized bed furnace; the fluidized bed treatment capacity of the fluidized bed furnace is 20-30 t/(m)²D). As the particles with larger mass are used as raw materials for boiling roasting, the density of the blast cap is increased, the better fluidization quality, pressure stabilization and flow equalization effect of the particles can be ensured, and the influence of uneven air distribution caused by the side wall effect is greatly reduced; the slag discharge port at the bottom of the furnace is convenient for discharging materials which cannot be blown out. In the boiling roasting process, the heat source is arranged in the particles, and from the macroscopic view, the heat source is uniform and dispersed due to the fluidization of the particles, so that the temperature is easy to control; from the microscopic view, the interior of each particle is uniformly heated, the heat transfer condition is good, and the chemical reaction is favorably carried out.

Compared with the rotary kiln sodium salt roasting, the fluidized bed furnace is easy to control the reaction temperature, can solve the problem that the rotary kiln is easy to overheat and solidify, and is beneficial to improving the leaching rate of vanadium; under the condition of the same volume, the capacity of a single device of the fluidized bed furnace is larger, and the heat exchange coil is arranged in the fluidized bed furnace, so that the heat utilization rate is higher.

The method for treating the vanadium-containing waste catalyst provided by the invention adopts a granulation-sodium treatment roasting process, realizes sodium treatment roasting in a fluidized bed furnace, strengthens the contact between the waste catalyst and powder materials by adopting the granulation method, increases the contact area between cold-solidified particles and air by adopting the fluidized bed roasting process, and improves the dynamic conditions of chemical reaction, thereby improving the conversion rate of soluble sodium salt, and the vanadium leaching rate of the produced sodium treatment clinker can reach more than 95%.

For further understanding of the present invention, the method for treating vanadium-containing catalyst provided by the present invention is described in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.

Example 1

(1) Taking 500kg of deoiled vanadium-containing waste catalyst, wherein the raw material is columnar particles with the length of 5-15 mm, and the raw material components are shown in table 1; putting the raw materials into a high-energy ball mill to grind until the particle size D90 of the waste catalyst is 0.147 mm;

TABLE 1 data sheet of the composition of vanadium-containing spent catalyst components

Substance(s)	V2O5	Mo	Ni	Co	Fe	C	S	P	Al2O3	Hydrocarbons of oils
											Content (%)	16.30	2.02	6.82	0.15	1.38	15.49	9.61	0.30	19.58	12.53

(2) Mixing the powdery waste catalyst obtained in the step (1) with 40 percent (mass percentage, the same below) of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles; testing the free falling strength and the compressive strength of the cold-set particles of 1 meter to be 9.7 times and 9.5MPa respectively;

(5) the fluidized bed furnace in the prior art is improved, the furnace bottom of the improved fluidized bed furnace is provided with a slag discharge port, and a blast cap is arrangedThe density is 80 pieces/m²The height of a discharge opening is 1600mm, and the hearth angle of the fluidized bed furnace is 20 degrees; adding the cold-cured particles obtained in the step (4) into the fluidized bed furnace for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Example 2

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 30 percent of Na₂CO₃(150kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into an improved fluidized bed furnace in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Example 3

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 5 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 4 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles; testing the free falling strength and the compressive strength of the cold setting particles of 1 meter to be 10.9 times and 9.9MPa respectively;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Example 4

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 1 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 1 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles; the 1m free falling strength and the compressive strength of the cold-set particles are respectively tested to be 8.1 times and 9.1 MPa;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Example 5

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 800 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Example 6

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 2 hours, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 1

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 60 percent of Na₂CO₃(300kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles; the 1m free falling strength and the compressive strength of the cold-set particles are respectively tested to be 9.3 times and 10.2 MPa;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 2

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 10 percent of Na₂CO₃(50kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into the fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, the temperature is 750 ℃, and the material is stirred once every 10min in the roasting process to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 3

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40% of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for grinding and mixing for 30 min;

(3) putting the powdery mixed material obtained in the step (2) into a fluidized bed furnace used in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is about 750 ℃, so as to obtain sodium-modified clinker; cooling the obtained sodium-modified clinker, and ball-milling until D90 is 0.147 mm;

(4) and (4) taking 500g of the ball-milled sodium-modified clinker obtained in the step (3) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 4

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water, and grinding and mixing for 15min for the second time to obtain a mixed material; in the step, the mixed material cannot be agglomerated and further cannot be granulated when the water adding amount is less than 20%, and the mixed material drips when the water adding amount is more than 30%; therefore, in comparative example 4, the amount of water added was selected to be 25%;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and continuously and naturally drying the obtained dry particles in the air for 4 h; the 1m free falling strength of the tested particles is only 1.8 times, the compression resistance of the particles is poor, and the particles can be fractured by hands;

(5) adding the particles obtained in the step (4) into a fluidized bed furnace used in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 5

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding 2% of sodium bentonite and 7% of water by mass, and carrying out secondary grinding and mixing for 15min to obtain a mixed material, wherein water glass is not added in the step;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and continuously and naturally drying the obtained dry particles in the air for 4 h; the 1m free falling strength of the tested particles is 8.5 times, but the compressive strength of the particles is poor, and the particles can be flattened by slight force;

(5) adding the particles obtained in the step (4) into a fluidized bed furnace used in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 6

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3% of the total mass and water accounting for 7% of the total mass, and carrying out secondary grinding and mixing for 15min to obtain a mixed material, wherein sodium bentonite is not added in the step;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and continuously and naturally drying the obtained dry particles in the air for 4 h; the compression strength of the particles is good and can reach 9.2MPa, but no sodium bentonite exists, the material cohesiveness is poor, and the free falling strength of the tested particles is low at 1m and is only 3.5 times;

(5) adding the particles obtained in the step (4) into a fluidized bed furnace used in the embodiment to carry out sodium treatment roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium treatment clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 7

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) are added into a mill type mixer at the same time for primary milling and mixing, and the milling and mixing time is 15min; then adding water glass accounting for 8 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 7 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the example 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 8

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) adding the cold-cured particles obtained in the step (4) into a fluidized bed furnace used in the embodiment 1 for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 850 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

Comparative example 9

(1) 500kg of deoiled vanadium-containing waste catalyst which is the same as that in the example 1 is taken and put into a high-energy ball mill for grinding until the particle size D90 of the waste catalyst is 0.147 mm;

(2) mixing the powdery waste catalyst obtained in the step (1) with 40 percent of Na₂CO₃(200kg) simultaneously adding into a grinding type mixer for primary grinding and mixing, wherein the grinding and mixing time is 15 min; then adding water glass accounting for 3 percent of the total mass of the powdery waste catalyst, sodium bentonite accounting for 2 percent of the total mass of the powdery waste catalyst and water accounting for 7 percent of the total mass of the powdery waste catalyst, and carrying out secondary grinding and mixing for 15min to obtain a mixed material;

(3) adding the mixed material obtained in the step (2) into a disc granulator, and spraying water at the same time to prepare mixed material particles, wherein the particle size of the mixed material particles is controlled to be D90-3 mm;

(4) paving the mixed material particles obtained in the step (3), blowing hot air at 150 ℃ for 1h to dry the mixed material particles, and naturally cooling the obtained dry particles in the air for 4h to obtain cooled particles;

(5) the conventional fluidized bed furnace is adopted, and the density of a blast cap is 40/m²The height of the discharge opening is 1000m, the hearth angle is 12 degrees, and the bottom of the furnace is not provided with a slag discharge opening; adding the cold-cured particles obtained in the step (4) into the fluidized bed furnace for sodium-modified roasting, wherein the roasting time is 1h, and the temperature is 750 ℃, so as to obtain sodium-modified clinker; the obtained sodium-modified clinker still has certain granularity, and after the clinker is cooled, the clinker is ball-milled until D90 is 0.147mm, and powdery sodium-modified clinker is obtained;

(6) and (3) taking 500g of the powdery sodium-modified clinker obtained in the step (5) for water immersion at the temperature of 60 ℃ for 30min, wherein the liquid-solid ratio is 2.5: 1.

In order to eliminate accidental errors, the water leaching tests in the above examples were performed three times, the vanadium content in the water leaching residue was analyzed, the vanadium leaching rate was calculated, and the obtained data were averaged and summarized in table 2.

TABLE 2 Process differences and Effect data tables for examples and comparative examples

(1) In the embodiments 1-6, the sodium-modified clinker prepared by applying the process disclosed by the invention has good solubility, and the vanadium leaching rate can reach more than 95%; in example 2, the amount of the sodium treatment additive is reduced by 10%, and the vanadium leaching rate is slightly reduced, but still can reach the 95% standard; in examples 3 and 4, the particle strength was changed by slightly increasing or decreasing the amount of the binder, but the vanadium leaching rate was hardly affected; in example 5, the vanadium leaching rate can be increased by 1.2% by increasing the roasting temperature at 50 ℃; in example 6, the roasting time is increased by 1h, and although the vanadium leaching rate is slightly increased, the increase amplitude is small;

(2) in comparative examples 1 and 2, substantially the same process as in example 1 was used except that Na was changed₂CO₃The amount of (c) added; the result shows that when the using amount of the sodium carbonate is increased to 60 percent, the vanadium leaching rate is almost unchanged; when the using amount of sodium carbonate is reduced to 10%, the vanadium leaching rate is obviously reduced; the reason was analyzed as follows: the vanadium leaching rate in comparative example 1 is unchanged compared to example 1, indicating that there is an excess of sodium carbonate, so 200kg of Na under the process conditions proposed in this application are present₂CO₃The dosage of sodium carbonate required by the sodium salt roasting of the waste catalyst can be met; the sodium carbonate in a proper range is alkaline in the aqueous solution, and when the using amount of the sodium carbonate is less than 200kg, the solution is acidic, which shows that the conversion rate of vanadate is insufficient due to the insufficient using amount of the sodium carbonate, so that the leaching rate is low;

(3) in comparative example 3, the process used was substantially the same as in example 1, but without powder granulation, the spent catalyst + Na was used directly₂CO₃Adding the mixed material into the improved fluidized bed furnace provided by the invention for sodium salt roasting; comparative example 3The leaching result shows that the leaching slag rate is high, the vanadium leaching rate is only 84.32%, and the leaching rate has a larger difference compared with the vanadium leaching rate in the embodiment; the reason was analyzed as follows: the main reason of low vanadium leaching rate is incomplete sodium roasting reaction caused by insufficient contact among powder materials, and further insufficient conversion rate of soluble sodium salt; in addition, in the process of implementing the comparative example, a large amount of dust is generated in the powder material in the fluidized bed furnace and is taken away by flue gas, so that the loss of raw materials is caused, in the examples 1-6, the contact between the waste catalyst and the sodium treatment additive is strengthened through granulation, so that the mass transfer is facilitated, the sodium treatment roasting reaction is complete, and therefore the conversion rate of soluble sodium salt and the leaching rate of vanadium are both obviously improved;

(4) in comparative examples 4, 5 and 6, the process is basically the same as that of example 1, but water, sodium bentonite and water glass are respectively adopted as binders for granulation, and the vanadium leaching rate of the obtained sodium-modified clinker is far lower than that of example 1 and is not more than 90 percent; the reason was analyzed as follows: the three binders cannot ensure the strength of the particles, the particles are extruded and collided in the roasting process, and the temperature in the furnace is rapidly increased after the materials are added, so that the particles are cracked and pulverized, the sodium additive cannot effectively contact with the catalyst, a large amount of powder is taken away by smoke, the raw material loss is caused, and a dust removal system is damaged; therefore, comparative examples 4 to 6 illustrate the necessity of using water glass and sodium bentonite as the composite binder;

(5) in comparative example 7, the process used was substantially the same as in example 1, but the binder usage was increased, the water glass and bentonite were increased by 5% respectively, the leaching residue rate was increased, and the vanadium leaching rate was slightly decreased because the binder would wrap up vanadate, thus preventing vanadium leaching;

(6) in comparative example 8, the process used is substantially the same as in example 1, but the roasting temperature is increased by 100 ℃ to 850 ℃, and the vanadium leaching rate is rather reduced; the reason was analyzed as follows: the vanadium-containing mineral is wrapped by the glass phase due to the over-high temperature, so that the calcine leaching is difficult;

(7) in comparative example 9, the process is completely the same as that of example 1, but the sodium treatment roasting is carried out by using a conventional fluidized bed furnace, and the vanadium leaching rate is far lower than that of the novel fluidized bed furnace provided by the application; the reason was analyzed as follows: when the particles are roasted in a conventional fluidized bed furnace, the particles are poor in fluidization and uneven in roasting; in the process of implementing the comparative example, the conventional fluidized bed furnace is difficult to control the fluidization quality, and if the wind pressure is small, the particles are difficult to fluidize; if the air pressure is large, a 'slug' phenomenon can be generated, the air pressure fluctuation is severe, materials can be deposited at the bottom of a bed layer, slagging is easy to cause, a fan is impacted, and the abrasion of the wall surface can be aggravated; in the conventional fluidized bed furnace roasting process, the retention time of furnace materials is short, the reaction is insufficient, and the vanadium leaching effect is poor.

In conclusion, the cold-setting granulation is simple and easy to implement, can strengthen the contact between the waste catalyst and the sodium treatment additive, is beneficial to mass transfer and heat transfer, improves the dynamic condition of the sodium treatment roasting process, and improves the sodium salt conversion rate of the vanadium-containing mineral in the sodium treatment clinker, so that the produced sodium treatment clinker has good solubility, and the leaching rate of vanadium can reach more than 95%.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.