CN111334676A

CN111334676A - Treatment method of spent rare earth-containing catalyst

Info

Publication number: CN111334676A
Application number: CN202010211936.4A
Authority: CN
Inventors: 刘俊峰; 张建国; 王义军; 石浩
Original assignee: Hebei Tianlan Environmental Protection Technology Co Ltd
Current assignee: Hebei Tianlan Environmental Protection Technology Co Ltd
Priority date: 2020-03-24
Filing date: 2020-03-24
Publication date: 2020-06-26

Abstract

The invention belongs to the technical field of catalyst treatment, and particularly relates to a treatment method of a spent rare earth-containing catalyst. A method of treating a spent rare earth-containing catalyst comprising the steps of: (1) reacting the spent rare earth-containing catalyst with an alkaline solution, and filtering to obtain a vanadium-containing solution and a first filter cake; (2) reacting the first filter cake with sulfuric acid and a reduction auxiliary agent, and filtering to obtain a second filter cake and a first filtrate; (3) reacting the second filter cake with sulfuric acid and a reduction auxiliary agent, and filtering to obtain a second filtrate; (4) mixing the first filtrate and the second filtrate, adding a precipitator for precipitation, and filtering to obtain filtrate containing aluminum and nickel; (5) and (4) adding sulfide into the filtrate containing aluminum and nickel in the step (4), and filtering to obtain nickel sulfide and filtrate containing aluminum sulfate.

Description

Treatment method of spent rare earth-containing catalyst

Technical Field

The invention belongs to the technical field of catalyst treatment, and particularly relates to a treatment method of a spent rare earth-containing catalyst.

Background

Regarding the recovery treatment of the catalyst, the following patent documents are disclosed:

CN107012331A discloses a method for recovering vanadium from molybdenum-containing vanadium spent catalyst, which is characterized by comprising the following steps:

s101: adding ammonium salt into the waste catalyst solution containing molybdenum and vanadium, uniformly mixing, fully precipitating, and filtering to obtain filter residue ammonium metavanadate and precipitated vanadium mother liquor;

s102: adsorbing the vanadium precipitation mother liquor by adopting acrylonitrile chelate resin, and separating to obtain vanadium-loaded resin and adsorption tail liquor;

s103: and desorbing the vanadium-loaded resin to obtain vanadium-containing desorption liquid and vanadium-poor resin.

CN108467939A discloses a method for recovering nickel and molybdenum from waste nickel-molybdenum catalyst, which is characterized by comprising the following steps:

(1) carrying out low-temperature oxidation roasting on the waste nickel-molybdenum catalyst to be treated at one stage, burning off carbon and sulfur deposition substances on the waste catalyst, and simultaneously converting valuable metal sulfides in the waste catalyst into valuable metal oxides;

(2) mixing the primary roasting material obtained in the step (1) with sodium carbonate according to a molar ratio of 1: 1.1-1.2, and then carrying out secondary alkali roasting at high temperature to convert the valuable metal oxide into soluble sodium salt;

(3) leaching the second-stage roasting material obtained in the step (2) by hot water at the temperature of 80-95 ℃, and filtering ore pulp after leaching to obtain leaching residue and leaching liquid;

(4) washing the leaching residue obtained in the step (3) to be neutral, then placing the leaching residue into a sulfuric acid solution with the mass fraction of 20-30% for acid leaching, directly evaporating and crystallizing the nickel sulfate solution obtained by acid leaching, and carrying out liquid-solid separation to obtain a nickel sulfate product;

(5) purifying the leachate obtained in the step (3) to remove impurities, and carrying out solid-liquid separation to obtain filter residue and alkaline filtrate containing molybdenum and aluminum, carrying out second-stage roasting on the filter residue and the first-stage roasting material obtained in the step (1), and carrying out centralized treatment on the filtrate;

(6) adding a barium compound into the alkaline filtrate containing molybdenum and aluminum obtained in the step (5), wherein the molar ratio of the barium compound to the molybdenum is 2.5-3.5: 1, reacting at the temperature of 80-90 ℃ for 45-70 min to obtain a sodium aluminate crude liquid and barium molybdate precipitate, and performing liquid-solid separation to obtain a deeply purified sodium aluminate solution;

(7) and (4) preparing the purified sodium aluminate solution obtained in the step (6) into aluminum hydroxide micro powder by adopting a chemical neutralization precipitation method, and calcining to obtain an aluminum oxide product.

The above patent relates to a method for treating a molybdenum-vanadium-containing waste catalyst and recovering nickel and molybdenum from the waste nickel-molybdenum catalyst, and discloses a method for separating vanadium, nickel and aluminum from the catalyst containing vanadium, nickel and aluminum and effectively recovering and utilizing the above three elements.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method which can separate vanadium, nickel and aluminum from a catalyst containing vanadium, nickel and aluminum and effectively recycle the three elements.

A method of treating a spent rare earth-containing catalyst comprising the steps of:

(1) reacting the spent rare earth-containing catalyst with an alkaline solution, and filtering to obtain a vanadium-containing solution and a first filter cake;

(2) taking the first filter cake in the step (1), reacting with sulfuric acid and a reduction auxiliary agent, and filtering to obtain a second filter cake and a first filtrate containing rare earth, aluminum and nickel;

(3) reacting the second filter cake in the step (2) with sulfuric acid and a reduction auxiliary agent, and filtering to obtain silicon slag and a second filtrate containing rare earth, aluminum and nickel;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator for precipitation, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel;

(5) and (4) adding sulfide into the filtrate containing aluminum and nickel in the step (4), and filtering to obtain nickel sulfide and filtrate containing aluminum sulfate.

Preferably, the alkaline solution in the above (1) is at least one of a sodium hydroxide solution, a sodium carbonate solution and a sodium bicarbonate solution;

preferably, the concentration of the alkaline solution is 0.1-2 mol/L.

(1) And the volume mass ratio of the alkaline solution to the spent rare earth-containing catalyst is 1: 1-4: 1, the temperature is 20-90 ℃, and the time is 0.5-6 hours.

(2) The reducing auxiliary agents in the step (3) comprise at least one of hydrogen peroxide, sodium sulfite and sodium bisulfite.

(2) In the method, the mass ratio of the total volume of the sulfuric acid and the reduction additive to the first filter cake is 1: 1-6: 1, and the reaction conditions are as follows: stirring for 2-24 hours at 20-100 ℃; the concentration of the sulfuric acid is 0.1-6 mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8-1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

or (2), soaking the first filter cake in a hydrochloric acid solution for 8-48 hours, and then taking the three raw materials according to the mass ratio of the total volume of the sulfuric acid and the reduction auxiliary agent to the first filter cake being 1: 1-6: 1, and reacting under the following conditions: stirring for 4-12 hours at 20-100 ℃; the concentration of the sulfuric acid is 0.1-6 mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8-1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst.

(3) In the method, the mass ratio of the total volume of the sulfuric acid and the reduction additive to the second filter cake is 1: 1-6: 1, and the reaction conditions are as follows: stirring for 2-24 hours at 20-100 ℃; the concentration of the sulfuric acid is 0.1-6 mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8-1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

or (3), soaking the second filter cake in a hydrochloric acid solution for 8-48 hours, and then taking the three raw materials according to the mass ratio of the total volume of the sulfuric acid and the reduction auxiliary agent to the second filter cake of 1: 1-6: 1, and reacting under the following conditions: stirring for 4-12 hours at 20-100 ℃; the concentration of the sulfuric acid is 0.1-6 mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8-1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst.

The precipitant is at least one of oxalic acid, ammonium sulfate, ammonium bisulfate, sodium sulfate, sodium bisulfate, potassium sulfate, potassium bisulfate, sodium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water;

preferably, the precipitant is or contains oxalic acid; the temperature is 20-100 ℃ during precipitation, the stirring time is 0.5-2 hours, and the mixture is kept stand for 0.5-2 hours;

preferably, the precipitant is at least one of ammonium sulfate, ammonium bisulfate, sodium sulfate, sodium bisulfate, potassium sulfate, potassium bisulfate, sodium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, and does not contain oxalic acid;

the conditions for precipitation were: stirring for 0.5-2 hours at 20-40 ℃, and standing for 0.5-2 hours;

preferably, the molar weight of the precipitator is 1-4 times of the theoretical reaction amount of the rare earth.

Further, synthesizing the filtrate containing aluminum and nickel in the step (4) into a molecular sieve or preparing an aluminum product;

when preparing an aluminum product: adding an alkaline substance into the filtrate containing the aluminum sulfate to adjust the pH value to 4.2-9.0 to prepare aluminum hydroxide;

or, when preparing the aluminum product: adding a fluorine-containing compound into the filtrate containing aluminum sulfate to prepare sodium fluoroaluminate or potassium fluoroaluminate;

or reacting the filtrate containing aluminum sulfate with an ammonium sulfate solution to prepare aluminum ammonium sulfate.

The alkaline substance is at least one of sodium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate;

the fluorine-containing compound is at least one of hydrogen fluoride, ammonium fluoride, sodium fluoride and potassium fluoride.

The temperature for preparing the aluminum hydroxide is 20-40 ℃, and the stirring time is 0.5-2 hours;

the temperature for preparing the sodium fluoroaluminate and the potassium fluoroaluminate is 60-100 ℃, and the time is 2-8 hours.

The invention has the beneficial effects that:

(1) the energy consumption is low, the invention carries out the complete leaching process by the energy generated by the mutual reaction of all the raw materials, and the consumed energy is very little;

(2) the recovery rate is high, and the recovery rates of vanadium, nickel and aluminum respectively reach 92-96%, 85-90% and 94-98%;

(3) the added value of the product is high, and the product of nickel sulfide, vanadium-containing solution and aluminum sulfate-containing filtrate can be further refined to obtain high-quality aluminum, nickel and vanadium;

(4) the method has the advantages of simple equipment, large treatment capacity and basically harmless production, and provides a scheme for easily realizing industrial large-scale production for the treatment of the catalyst.

Detailed Description

The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.

Example 1

(1) reacting the spent rare earth-containing catalyst with a sodium hydroxide solution, and filtering to obtain a vanadium-containing solution and a first filter cake;

the volume-mass ratio of the sodium hydroxide solution to the spent rare earth-containing catalyst is 1:3, and the concentration of the sodium hydroxide solution is 1.2 mol/L; the reaction temperature is 60 ℃, and the reaction time is 4 hours;

(2) reacting the first filter cake in the step (1) with sulfuric acid and a reduction auxiliary agent hydrogen peroxide, and filtering to obtain a second filter cake and a first filtrate containing rare earth, aluminum and nickel;

the mass concentration of the hydrogen peroxide is 30 percent;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the first filter cake is 1:4, and the reaction conditions are as follows: stirring for 20 hours at 80 ℃; the concentration of the sulfuric acid is 4mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(3) reacting the second filter cake in the step (2) with sulfuric acid and a reduction auxiliary agent hydrogen peroxide, and filtering to obtain silicon slag and a second filtrate containing rare earth, aluminum and nickel;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the second filter cake is 1:4, and the reaction conditions are as follows: stirring for 20 hours at 80 ℃; the concentration of the sulfuric acid is 4mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator oxalic acid, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel; precipitating at the temperature of 80 ℃, stirring for 0.5-2 hours, and standing for 1.5 hours; the molar weight of the precipitator oxalic acid is 2 times of the theoretical reaction quantity of the rare earth;

(5) and (4) adding sodium sulfide into the filtrate containing aluminum and nickel in the step (4), and filtering to obtain nickel sulfide and filtrate containing aluminum sulfate.

Example 1B

The difference from example 1A is that in (5), potassium sulfide is added to the filtrate containing aluminum and nickel in (4), and filtration is performed to obtain nickel sulfide and a filtrate containing aluminum sulfate.

Example 1C

Different from the embodiment 1A, in (5), hydrogen sulfide is added into the filtrate containing aluminum and nickel in (4), and the filtrate is filtered to obtain nickel sulfide and filtrate containing aluminum sulfate.

Example 1D

The difference from the example 1A is that in the step (2), the first filter cake is placed in a hydrochloric acid solution (with the mass concentration of 36-38%) to be soaked for 40 hours, and then the three raw materials are taken according to the mass ratio of the total volume of the sulfuric acid and the reduction auxiliary agent to the first filter cake of 1:4, and are reacted under the following conditions: stirring for 10 hours at 80 ℃; the concentration of the sulfuric acid is 4mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst. The rest is the same as in example 1A.

Example 1E

The difference from the example 1A is that in (3), the second filter cake is soaked in hydrochloric acid for 40 hours, and then the mass ratio of the total volume of the sulfuric acid and the reduction assistant to the second filter cake is 1: 1:1, taking the three raw materials in the proportion, and reacting under the following conditions: stirring for 8 hours at 80 ℃; the concentration of the sulfuric acid is 3mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst. The rest is the same as in example 1A.

Example 1F

The difference from the embodiment 1A is that in (1), the invalid rare earth-containing catalyst reacts with the sodium carbonate solution, and the vanadium-containing solution and the first filter cake are obtained after filtration;

the volume-mass ratio of the sodium carbonate solution to the spent rare earth-containing catalyst is 1:3, and the concentration of the sodium carbonate solution is 0.8 mol/L; the reaction temperature is 70 ℃, and the reaction time is 2 hours; the remaining steps were the same as in example 1A.

Example 1G

the volume mass ratio of the sodium bicarbonate solution to the spent rare earth-containing catalyst is 1:3, and the concentration of the sodium bicarbonate solution is 0.8 mol/L; the reaction temperature is 60 ℃, and the reaction time is 3 hours; the remaining steps were the same as in example 1A.

Example 1H

The difference from example 1A is that in (2) and (3), the reduction assistant is sodium sulfite, and the rest is the same as example 1A.

Example 1I

The difference from example 1A is that in (2) and (3), the reducing assistant is sodium bisulfite, and the rest is the same as example 1A.

Example 1J

The difference from the embodiment 1A is that in the step (4), the first filtrate and the second filtrate in the steps (2) and (3) are mixed, then precipitator ammonium sulfate is added, and filtration is carried out, so as to obtain rare earth precipitation and filtrate containing aluminum and nickel; the temperature during precipitation is 30 ℃, the stirring time is 1.5 hours, and the mixture is kept stand for 1.5 hours; the molar weight of the ammonium sulfate as the precipitant is 2 times of the theoretical reaction amount of the rare earth.

Example 1K

The difference from the embodiment 1A is that in the step (4), the first filtrate and the second filtrate in the steps (2) and (3) are mixed, then precipitator ammonium bisulfate is added, and filtration is carried out, so as to obtain rare earth precipitation and filtrate containing aluminum and nickel; the temperature during precipitation is 30 ℃, the stirring time is 1.5 hours, and the mixture is kept stand for 2 hours; the molar weight of the precipitator ammonium bisulfate is 3 times of the theoretical reaction quantity of the rare earth.

Example 1L

The difference from the embodiment 1A is that in the step (4), the first filtrate and the second filtrate in the steps (2) and (3) are mixed, then precipitator sodium bicarbonate is added, and filtration is carried out, so as to obtain rare earth precipitation and filtrate containing aluminum and nickel; the temperature during precipitation is 35 ℃, the stirring time is 1.5 hours, and the mixture is kept stand for 1.2 hours; the molar weight of the precipitator sodium bicarbonate is 2 times of the theoretical reaction quantity of the rare earth.

Example 2A

(1) - (4) the same as in example 1, except that in example 1, (4) the following steps are followed:

adding sodium hydroxide into the filtrate containing the aluminum sulfate to adjust the pH value to 7.5 to prepare the aluminum hydroxide, wherein the temperature for preparing the aluminum hydroxide is 30 ℃, and the stirring time is 1.5 hours.

Example 2B

and adding ammonia water into the filtrate containing the aluminum sulfate to adjust the pH value to 8.0 to prepare the aluminum hydroxide, wherein the temperature for preparing the aluminum hydroxide is 30 ℃, and the stirring time is 1.5 hours.

Example 2C

adding sodium carbonate into the filtrate containing the aluminum sulfate to adjust the pH value to 7.2 to prepare the aluminum hydroxide.

The temperature for preparing the aluminum hydroxide is 30 ℃, and the stirring time is 1.5 hours.

Example 2D

adding sodium bicarbonate into the filtrate containing the aluminum sulfate to adjust the pH value to 7.5 to prepare the aluminum hydroxide. The temperature for preparing the aluminum hydroxide is 30 ℃, and the stirring time is 1.5 hours.

Example 3A

adding fluorine-containing compound hydrogen fluoride into the filtrate containing aluminum sulfate to prepare sodium fluoroaluminate or potassium fluoroaluminate; the reaction temperature was 80 ℃ and the reaction time was 6 hours.

Example 3B

adding ammonium fluoride into the filtrate containing aluminum sulfate to prepare sodium fluoroaluminate or potassium fluoroaluminate; the reaction temperature was 70 ℃ and the reaction time was 5 hours.

Example 3C

adding sodium fluoride into the filtrate containing aluminum sulfate to prepare sodium fluoroaluminate; the reaction temperature was 80 ℃ and the reaction time was 6 hours.

Example 3D

adding fluorine-containing compound potassium fluoride into the filtrate containing aluminum sulfate to prepare potassium fluoroaluminate; the reaction temperature was 80 ℃ and the reaction time was 5 hours.

Example 4

the volume-mass ratio of the sodium hydroxide solution to the spent rare earth-containing catalyst is 1:4, and the concentration of the sodium hydroxide solution is 0.8 mol/L; the temperature is 70 ℃, and the time is 1.5 hours;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the first filter cake is 1:4, and the reaction conditions are as follows: stirring for 20 hours at 80 ℃; the concentration of the sulfuric acid is 3mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the second filter cake is 1:4, and the reaction conditions are as follows: stirring for 18 hours at 70 ℃; the concentration of the sulfuric acid is 3mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator to precipitate oxalic acid, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel; the temperature during precipitation is 80 ℃, the stirring time is 1.5 hours, and the mixture is kept stand for 1 hour; the molar weight of the precipitator oxalic acid is 3 times of the theoretical reaction quantity of the rare earth;

Example 5

the volume-mass ratio of the sodium hydroxide solution to the spent rare earth-containing catalyst is 1:3, and the concentration of the sodium hydroxide solution is 0.9 mol/L; the temperature is 70 ℃, and the time is 1.5 hours;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the first filter cake is 1:5, and the reaction conditions are as follows: stirring for 15 hours at 80 ℃; the concentration of the sulfuric acid is 4mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the second filter cake is 1:4, and the reaction conditions are as follows: stirring for 16 hours at 70 ℃; the concentration of the sulfuric acid is 0.8mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.9 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator to precipitate oxalic acid, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel; the temperature for precipitation is 80 ℃, the stirring time is 1.5 hours, and the mixture is kept stand for 1.5 hours; the molar weight of the precipitator oxalic acid is 3 times of the theoretical reaction quantity of the rare earth;

Example 6

the volume mass ratio of the sodium hydroxide solution to the spent rare earth-containing catalyst is 1:1, and the concentration of the sodium hydroxide solution is 0.1 mol/L; the temperature is 20 ℃ and the time is 6 hours;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the first filter cake is 1:4, and the reaction conditions are as follows: stirring for 2 hours at 20 ℃; the concentration of the sulfuric acid is 0.1mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator oxalic acid, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel; the temperature for precipitation is 80 ℃, the stirring time is 0.5 hour, and the mixture is kept stand for 1.5 hours; the molar weight of the precipitator oxalic acid is 2 times of the theoretical reaction quantity of the rare earth;

Example 7

the volume-mass ratio of the sodium hydroxide solution to the spent rare earth-containing catalyst is 1:4, and the concentration of the sodium hydroxide solution is 2 mol/L; the temperature is 90 ℃ and the time is 6 hours;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the first filter cake is 1:6, and the reaction conditions are as follows: stirring for 10 hours at 100 ℃; the concentration of the sulfuric acid is 6mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.2 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

the mass ratio of the total volume of the sulfuric acid and the reducing auxiliary agent hydrogen peroxide to the second filter cake is 1:4, and the reaction conditions are as follows: stirring for 20 hours at 80 ℃; the concentration of the sulfuric acid is 6mol/L, and the sum of the molar weight of the sulfuric acid added twice is 1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

(4) mixing the first filtrate and the second filtrate in the steps (2) and (3), adding a precipitator oxalic acid, and filtering to obtain rare earth precipitate and filtrate containing aluminum and nickel; the temperature for precipitation is 80 ℃, the stirring time is 0.8 hour, and the mixture is kept stand for 1.5 hours; the molar weight of the precipitator oxalic acid is 2 times of the theoretical reaction quantity of the rare earth;

The metal recoverable by the method in the above embodiment is detected, and the results are as follows:

table 1 recovery of vanadium (%)

Table 2 recovery of Nickel (%)

	Recovery rate		Recovery rate		Recovery rate		Recovery rate
								Example 1A	89.4	Example 1G	87.2	Example 2A	87.3	Example 3C	88.3
Example 1B	88.7	Example 1H	88.5	Example 2B	89.6	Example 3D	89.2
								Example 1C	89.2	Example 1I	87.9	Example 2C	87.2	Example 4	87.4
Example 1D	85.4	Example 1J	86.5	Example 2D	88.8	Example 5	87.6
								Example 1E	85.1	Example 1K	89.1	Example 3A	89.1	Example 6	88.3
Example 1F	86.8	Example 1L	88.4	Example 3B	87.7	Example 7	88.6

TABLE 3 recovery of aluminum (%)

	Recovery rate		Recovery rate		Recovery rate		Recovery rate
								Example 1A	97.2	Example 1G	96.9	Example 2A	94.9	Example 3C	96.4
Example 1B	97.8	Example 1H	97.4	Example 2B	95.3	Example 3D	97.5
								Example 1C	96.9	Example 1I	97.2	Example 2C	96.1	Example 4	97.7
Example 1D	94.4	Example 1J	96.6	Example 2D	97.2	Example 5	97.3
								Example 1E	94.8	Example 1K	95.8	Example 3A	96.6	Example 6	96.5
Example 1F	97.6	Example 1L	95.4	Example 3B	97.8	Example 7	97.2

The data in the table show that the method provided by the invention has a remarkable separation effect when used for separating vanadium, nickel and aluminum from the spent catalyst containing vanadium, nickel and aluminum, and the recovery rates of vanadium, nickel and aluminum respectively reach 92-96%, 85-90% and 94-98%.

Claims

1. A method of treating a spent rare earth-containing catalyst comprising the steps of:

2. The method of treating a spent rare earth-containing catalyst according to claim 1,

(1) the alkaline solution in the step (a) is at least one of a sodium hydroxide solution, a sodium carbonate solution and a sodium bicarbonate solution;

preferably, the concentration of the alkaline solution is 0.1-2 mol/L.

3. The method of treating a spent rare earth-containing catalyst according to claim 1,

4. The method of treating a spent rare earth-containing catalyst according to claim 1,

5. The method of treating a spent rare earth-containing catalyst according to claim 1,

6. The method of treating a spent rare earth-containing catalyst according to claim 1,

(3) in the method, the mass ratio of the total volume of the sulfuric acid and the reduction auxiliary agent to the second filter cake is 1 (1-6) to 1, and the reaction conditions are as follows: stirring for 2-24 hours at 20-100 ℃; the concentration of the sulfuric acid is 0.1-6 mol/L, and the sum of the molar weight of the sulfuric acid added twice is 0.8-1.5 times of the theoretical acid consumption of rare earth, aluminum and nickel in the spent rare earth-containing catalyst;

7. The method of treating a spent rare earth-containing catalyst according to claim 1,

8. The spent rare earth-containing catalyst treatment process of claim 1 wherein the aluminum-and nickel-containing filtrate of (4) is synthesized into a molecular sieve or an aluminum product is produced;

9. The method of treating a spent rare earth-containing catalyst according to claim 8,

10. The method of treating a spent rare earth-containing catalyst according to claim 8,