CN110342910B - Method for preparing ceramic hollow fiber membrane from FCC (fluid catalytic cracking) waste catalyst and ceramic hollow fiber membrane - Google Patents
Method for preparing ceramic hollow fiber membrane from FCC (fluid catalytic cracking) waste catalyst and ceramic hollow fiber membrane Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/025—Aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
Abstract
The invention relates to the technical field of resource utilization of solid wastes, in particular to a method for preparing a ceramic hollow fiber membrane by using an FCC (fluid catalytic cracking) waste catalyst and the ceramic hollow fiber membrane. The method comprises the following steps: sintering the fiber membrane blank at high temperature to remove the organic polymer and solidify heavy metal in the fiber membrane blank into spinel; the fiber membrane blank is obtained by molding the casting membrane slurry; the casting film slurry is obtained by mixing pretreated FCC dead catalyst powder and alumina powder in a polymer solution containing organic polymers; the pretreatment method of the FCC spent catalyst powder comprises the following steps: dipping the ground FCC spent catalyst powder in a metal curing agent solution. The invention can recover resources and reduce the preparation cost of the ceramic hollow fiber membrane while solidifying heavy metals to thoroughly solve the environmental pollution caused by FCC waste catalyst; the product does not cause secondary pollution to the environment when being discarded, and has good economic benefit and environmental protection benefit.
Description
Technical Field
The invention relates to the technical field of resource utilization of solid wastes, in particular to a method for preparing a ceramic hollow fiber membrane by using an FCC (fluid catalytic cracking) waste catalyst and the ceramic hollow fiber membrane.
Background
Catalytic Cracking (FCC) is the most important secondary processing process in the oil refining industry, the processing capacity of catalytic cracking in China currently exceeds 1.5 million tons, the catalyst usage accounts for more than 86% of the catalyst usage in the oil refining industry, nearly 20 million tons of FCC waste catalysts are generated every year, 2016, the FCC waste catalysts are listed in the national hazardous waste record, and the processes of production, storage, transportation, disposal and the like of the FCC catalysts are strictly regulated. At present, the waste FCC catalyst is usually buried, so that heavy metal pollution is caused, and resources are greatly wasted. How to pretreat the FCC spent catalyst, solidify heavy metals and prepare high value-added products, and the product abandons without causing secondary pollution to the environment is always a key concern.
In the prior art, the waste FCC catalyst is prepared into mullite, molecular sieve, rubber composite materials, baking-free bricks, catalysts for other reactions and the like, but the existing technology for recycling the waste FCC catalyst mostly has secondary pollution, low product added value and small market driving force, and the technology is weak in basic research as other reaction catalysts and cannot thoroughly solve the problems of heavy metal pollution and the like, so that a green and recycling technology for recycling the waste FCC catalyst is urgently needed.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing a ceramic hollow fiber membrane by using an FCC spent catalyst, which is used for solving the technical problems of secondary pollution and low added value of products in the resource treatment process in the prior art.
The second purpose of the invention is to provide a ceramic hollow fiber membrane prepared by the preparation method, the cost of raw materials is low, and meanwhile, the metal component in the waste catalyst is utilized to reduce the roasting temperature, so that the production cost is further reduced, and the ceramic hollow fiber membrane has good environmental protection benefit and market effect.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for preparing a ceramic hollow fiber membrane from FCC spent catalyst, comprising the steps of:
sintering the fiber membrane blank at high temperature to remove the organic polymer and solidify heavy metal in the fiber membrane blank into spinel;
the fiber membrane blank is obtained by molding the casting membrane slurry; the casting film slurry is obtained by mixing pretreated FCC dead catalyst powder and alumina powder in a polymer solution containing organic polymers;
the pretreatment method of the FCC spent catalyst powder comprises the following steps: dipping the ground FCC spent catalyst powder in a metal curing agent solution.
According to the invention, the heavy metal in the FCC spent catalyst can be preliminarily cured by dipping the FCC spent catalyst in the metal curing agent solution, so that heavy metal pollution and the like caused by heavy metal loss are avoided. And sintering the fiber membrane obtained by molding the casting membrane slurry at high temperature to enable the heavy metal to be deeply solidified into spinel.
In addition, the FCC spent catalyst and the alumina powder are mixed for spinning, and the obtained ceramic hollow fiber membrane product has high added value.
The invention recovers the resources while solidifying the heavy metals to thoroughly solve the environmental pollution caused by the FCC dead catalyst, reduces the preparation cost of the ceramic hollow fiber membrane and obtains the product with high added value; and the product does not cause secondary pollution to the environment when being discarded, and has good economic benefit and environmental protection benefit.
In some embodiments of the invention, the mass ratio of the pretreated spent FCC catalyst powder to the alumina powder is (1-8): 9-2, or (3-6): 7-4.
As in the different embodiments, the mass ratio of spent FCC catalyst powder to alumina powder may be 1: 9, 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, 8: 2 etc.
In some embodiments of the invention, the polymer solution consists essentially of an organic polymer, an organic solvent, and an additive.
For example, the organic polymer may be polyether sulfone, the organic solvent may be N-methyl-2-pyrrolidone, and the additive may be polyvinylpyrrolidone, etc.
Specifically, the polymer solution mainly comprises polyether sulfone, N-methyl-2-pyrrolidone and polyvinylpyrrolidone.
Optionally, the polymer solution mainly comprises the following components in parts by weight: 15-25 parts of polyether sulfone, 70-80 parts of N-methyl-2-pyrrolidone and 1-10 parts of polyvinylpyrrolidone. Preferably, the polymer solution mainly comprises the following components in parts by weight: 18-22 parts of polyether sulfone, 72-78 parts of N-methyl-2-pyrrolidone and 3-7 parts of polyvinylpyrrolidone. Further preferably, the polymer solution mainly comprises the following components in parts by weight: 21 parts of polyether sulfone, 75 parts of N-methyl-2-pyrrolidone and 4 parts of polyvinylpyrrolidone.
In some embodiments of the present invention, the metal curing agent solution has a metal curing agent mass concentration of 3 to 15%.
In a preferred embodiment of the present invention, the solvent in the metal hardener solution includes any one or more of ethyl xanthate and silicate, and preferably includes ethyl xanthate and silicate.
Optionally, the ethyl xanthate comprises either or both of potassium ethyl xanthate and sodium ethyl xanthate, preferably sodium ethyl xanthate.
Optionally, the silicate comprises either or both of potassium silicate and sodium silicate, preferably sodium silicate.
In some embodiments of the invention, the solute in the metal curative solution comprises sodium ethylxanthate and sodium silicate.
In some embodiments of the invention, the mass ratio of the sodium ethyl xanthate to the sodium silicate is 2-3: examples of the ratio of 7 to 8 include 1: 4, 1: 3, and 1: 2.5.
Optionally, the time of the impregnation treatment is 5-24 h.
Optionally, the particle size of the ground FCC spent catalyst powder is less than or equal to 1.5 μm. In actual operation, the FCC spent catalyst is ground to a particle size of less than or equal to 1.5 μm and then subjected to impregnation treatment and the like.
After the impregnation treatment, the FCC spent catalyst powder is collected by filtration or the like, and then dried. The drying conditions can be selected as follows: drying at 30-70 deg.C.
In some embodiments of the invention, the sum of the mass of FCC spent catalyst powder and alumina powder in the casting film slurry is 50 to 90%, preferably 60 to 80% of the casting film slurry.
Before forming, the casting film slurry is vacuumized for 0.6-1.2h to remove residual bubbles.
In some embodiments of the present invention, the method for forming the fibrous membrane comprises the steps of:
adding a gelling agent into the casting film slurry, pressurizing to 0.2-0.5bar, extruding to obtain a fiber wet film, and gelling and curing to obtain a fiber film blank.
Optionally, the wet fiber membrane is immersed into an external coagulating bath through a dry spinning process of 5-30cm, and is subjected to gelling and solidification for more than 24 hours to form a fiber membrane blank.
Preferably, the fiber membrane blank is immersed in water and dried before sintering treatment. Immersing the fiber membrane blank in water to replace residual organic solvent, and naturally drying.
In a preferred embodiment of the present invention, the method of sintering treatment includes: heating to 750 + -10 deg.C, maintaining the temperature for 0.5-2h, heating to 950 deg.C and 1300 deg.C, maintaining the temperature for 0.5-7h, and cooling.
As in the specific embodiment, after the temperature is maintained at 750 + -10 ℃ for 0.5-2h, the temperature can be raised to 950 ℃, 980 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and so on. For example, the temperature can be raised to 1000-1300 ℃ for sintering treatment; more preferably, the sintering treatment may be carried out by raising the temperature to 1000-1200 ℃.
During sintering, the temperature is raised to 750 +/-10 ℃ and kept, volatile substances and organic polymers can be removed, and the influence of the organic polymers on the sintering process of the ceramic hollow fiber membrane in the further temperature raising process is avoided.
The raw materials of the invention are matched with the pretreated FCC dead catalyst and alumina, and the roasting temperature can be partially reduced on the premise of ensuring the product performance, thereby reducing the production energy consumption and taking the product performance and low energy consumption into consideration.
The cooling method preferably comprises the following steps: cooling to 400 +/-10 ℃ at the cooling rate of 1-10 ℃/min, and then naturally cooling.
In a preferred embodiment of the present invention, the atmosphere for sintering is air.
Preferably, the temperature rise rate of the sintering is 1-10 ℃/min.
The invention adopts the FCC spent catalyst as the raw material, and the metal component in the FCC spent catalyst can reduce the sintering temperature of the ceramic hollow fiber membrane and reduce the production cost.
By adopting the sintering conditions, the degree of deep curing of heavy metal in the FCC spent catalyst into spinel can be increased, secondary pollution to the environment can not be caused when the product is abandoned, and the method has good environmental protection benefit.
The invention also provides the ceramic hollow fiber membrane prepared by the method.
The ceramic hollow fiber membrane prepared by the method has the advantages of large specific surface area, high strength and good water permeability.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the heavy metal curing of the FCC spent catalyst is combined with the preparation of the ceramic hollow fiber membrane, so that resources are recovered while the heavy metal is cured to thoroughly solve the environmental pollution of the FCC spent catalyst, the preparation cost of the ceramic hollow fiber membrane is reduced, and a product with a high added value is obtained;
(2) according to the invention, the sintering process is optimized, so that heavy metal can be deeply solidified into spinel, secondary pollution to the environment can not be caused when the product is abandoned, and good economic benefit and environmental protection benefit are achieved;
(3) the ceramic hollow fiber membrane prepared by the method has the advantages of large specific surface area, high strength and good water permeability.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a method for preparing a ceramic hollow fiber membrane by pretreating FCC spent catalyst, which comprises the following steps:
(1) grinding and crushing the FCC spent catalyst until the particle size is less than or equal to 1.5 mu m to obtain FCC spent catalyst powder; then dipping the FCC waste catalyst powder in a metal curing agent solution with solute mass percent of 7% for 10 hours, filtering and collecting the dipped FCC waste catalyst powder, putting the FCC waste catalyst powder in an oven to dry at 70 ℃, and primarily curing heavy metals in the waste catalyst; wherein the solute in the metal curing agent solution is sodium silicate; the FCC spent catalyst is the FCC spent catalyst with the metal contents of Ni, V and Sb of 0.79 percent, 0.52 percent and 0.27 percent respectively;
(2) mixing the pretreated FCC spent catalyst powder in the step (1) with alumina powder according to a mass ratio of 3: 7, adding the mixture into a polymer solution, and uniformly mixing to obtain casting film slurry; wherein the sum of the mass of the FCC spent catalyst powder and the mass of the alumina powder accounts for 70 percent of the casting film slurry;
the polymer solution is formed by mixing polyethersulfone, N-methyl-2-pyrrolidone and polyvinylpyrrolidone in a mass ratio of 21: 75: 4;
(3) introducing the casting film slurry obtained in the step (2) into a slurry tank of a spinning device, vacuumizing for 1h to remove residual bubbles, introducing a conventional gelling agent, injecting nitrogen gas to 0.25bar, extruding the casting film slurry after vacuumizing into a spinning nozzle, immersing a wet fiber film extruded from the spinning nozzle into an external solidification bath through a dry spinning process of 15cm, and gelling and solidifying for more than 24h to form a ceramic hollow fiber film blank;
(4) replacing residual organic solvent in deionized water for the ceramic hollow fiber membrane blank obtained in the step (3), naturally drying the ceramic hollow fiber membrane blank, and sintering in a high-temperature furnace with air as sintering atmosphere;
the sintering step comprises: heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, heating to 1300 ℃ at the heating rate of 2 ℃/min, sintering for 3h, cooling to 400 ℃ at the cooling rate of 5 ℃/min, and naturally cooling to obtain the ceramic hollow fiber membrane.
Example 2
This example refers to the preparation of example 1, with the only difference that: in the step (4), the sintering step includes: heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, heating to 1200 ℃ at the heating rate of 2 ℃/min, sintering for 3h, cooling to 400 ℃ at the cooling rate of 5 ℃/min, and naturally cooling to obtain the ceramic hollow fiber membrane.
Example 3
This example refers to the preparation of example 1, with the only difference that: in the step (4), the sintering step includes: heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, heating to 1150 ℃ at the heating rate of 2 ℃/min, sintering for 3h, cooling to 400 ℃ at the cooling rate of 5 ℃/min, and naturally cooling to obtain the ceramic hollow fiber membrane.
Example 4
This example refers to the preparation of example 1, with the only difference that: in the step (4), the sintering step includes: heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, heating to 1100 ℃ at the heating rate of 2 ℃/min, sintering for 3h, cooling to 400 ℃ at the cooling rate of 5 ℃/min, and naturally cooling to obtain the ceramic hollow fiber membrane.
Example 5
The embodiment provides a method for preparing a ceramic hollow fiber membrane by pretreating FCC spent catalyst, which comprises the following steps:
(1) grinding and crushing the FCC spent catalyst until the particle size is less than or equal to 1.5 mu m to obtain FCC spent catalyst powder; then dipping the FCC waste catalyst powder in a metal curing agent solution with the mass fraction of solute being 7% for 10 hours, filtering and collecting the dipped FCC waste catalyst powder, putting the FCC waste catalyst powder in an oven to dry at 70 ℃, and primarily curing heavy metals in the waste catalyst; the solute in the metal curing agent solution is sodium ethyl xanthate and sodium silicate in a mass ratio of 1: 4; the FCC spent catalyst is the FCC spent catalyst with the metal contents of Ni, V and Sb of 0.79 percent, 0.52 percent and 0.27 percent respectively;
(2) mixing the pretreated FCC spent catalyst powder in the step (1) with alumina powder according to a mass ratio of 3: 7, adding the mixture into a polymer solution, and uniformly mixing to obtain casting film slurry; wherein the sum of the mass of the FCC spent catalyst powder and the mass of the alumina powder accounts for 70 percent of the casting film slurry;
the polymer solution is formed by mixing polyethersulfone, N-methyl-2-pyrrolidone and polyvinylpyrrolidone in a mass ratio of 21: 75: 4;
(3) introducing the casting film slurry obtained in the step (2) into a slurry tank of a spinning device, vacuumizing for 1h to remove residual bubbles, introducing a conventional gelling agent, injecting nitrogen gas to 0.25bar, extruding the casting film slurry after vacuumizing into a spinning nozzle, immersing a wet fiber film extruded from the spinning nozzle into an external solidification bath through a dry spinning process of 15cm, and gelling and solidifying for more than 24h to form a ceramic hollow fiber film blank;
(4) replacing residual organic solvent in deionized water for the ceramic hollow fiber membrane blank obtained in the step (3), naturally drying the ceramic hollow fiber membrane blank, and sintering in a high-temperature furnace with air as sintering atmosphere;
the sintering step comprises: heating to 750 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 1.5h, heating to 1200 ℃ at the heating rate of 2 ℃/min, sintering for 3h, cooling to 400 ℃ at the cooling rate of 5 ℃/min, and naturally cooling to obtain the ceramic hollow fiber membrane.
Example 6
This example refers to the preparation of example 5, with the only difference that: in the step (2), the mass ratio of the FCC spent catalyst powder after pretreatment in the step (1) to the alumina powder was 1: 9.
Example 7
This example refers to the preparation of example 5, with the only difference that: in the step (2), the mass ratio of the FCC waste catalyst powder after pretreatment in the step (1) to the alumina powder was 4: 1.
Comparative example 1
Comparative example 1 the preparation process of example 1 was referenced, with the following differences: directly and uniformly mixing alumina powder and polymer solution to obtain casting film slurry, and then carrying out the same steps of casting film and sintering; wherein the mass of the alumina powder accounts for 70% of the casting film slurry.
Experimental example 1
In order to comparatively illustrate the performance of the ceramic hollow fiber membranes prepared in the examples and comparative examples of the present invention, the performance of the ceramic hollow fiber membranes prepared in the examples 1 to 4 and 7 of the present invention and comparative example 1 was measured, and the test results are shown in table 1. Wherein the pressure in the pure water flux test is 0.5 bar.
TABLE 1 Performance test results for different ceramic hollow fiber membranes
| Numbering | Pure water flux (L/m)2·h) | Porosity (%) | Pore size distribution |
| Example 1 | 5100 | 30.1 | 82nm～1μm |
| Example 2 | 5125 | 31 | 90nm～1μm |
| Example 3 | 5080 | 29.5 | 85nm～1μm |
| Example 4 | 5010 | 27 | 60nm～1μm |
| Example 5 | 5150 | 31.5 | 80nm～1μm |
| Example 6 | 5200 | 32 | 85nm～1μm |
| Example 7 | 4955 | 25 | 50nm～1μm |
| Comparative example 1 | 5120 | 30.2 | 80nm～1μm |
As can be seen from table 1 above, the indexes of the ceramic hollow fiber membrane prepared by the preparation method of the present invention are close to those of comparative example 1, which indicates that it is feasible to prepare the ceramic hollow fiber membrane by using the FCC waste catalyst as a raw material, and the calcination temperature can be partially reduced on the premise of ensuring the product performance, thereby reducing the production energy consumption.
Experimental example 2
In order to comparatively illustrate the influence of the curing agent on the performance of the ceramic hollow fiber membrane prepared in each example of the present invention, the heavy metal content of the metal curing agent solution after the FCC spent catalyst powder impregnation treatment using the metal curing agent solutions of examples 2 and 5 of the present invention was measured, and the test results are shown in table 2.
TABLE 2 heavy metal content in Metal curative solution after treatment under different curative conditions
| Kind of curing agent | Ni(mg/L) | V(mg/L) | Sb(mg/L) |
| Sodium silicate | 0.26 | 0.95 | 1.08 |
| Sodium ethyl xanthate and sodium silicate (1: 4) | 0.23 | 0.82 | 1.05 |
As can be seen from table 2 above, the sodium ethylxanthate and sodium silicate used as curing agents have stronger ability to cure heavy metals in FCC spent catalyst.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (17)
1. The method for preparing the ceramic hollow fiber membrane by the FCC spent catalyst is characterized by comprising the following steps:
sintering the fiber membrane blank at high temperature to remove the organic polymer and solidify heavy metal in the fiber membrane blank into spinel;
the fiber membrane blank is obtained by molding the casting membrane slurry; the casting film slurry is obtained by mixing pretreated FCC dead catalyst powder and alumina powder in a polymer solution containing organic polymers;
the pretreatment method of the FCC spent catalyst powder comprises the following steps: dipping the ground FCC waste catalyst powder in a metal curing agent solution;
wherein the mass ratio of the pretreated FCC spent catalyst powder to the alumina powder is (1-8): 9-2;
the method for sintering treatment comprises the following steps: heating to 750 +/-10 ℃ and preserving heat for 0.5-2h, then heating to 950 + 1300 ℃ and preserving heat for 0.5-7h, and cooling; the temperature rise rate of the sintering is 1-10 ℃/min; the cooling comprises the following steps: cooling to 400 +/-10 ℃ at the cooling rate of 1-10 ℃/min, and then naturally cooling.
2. The method for preparing a ceramic hollow fiber membrane from the spent FCC catalyst according to claim 1, wherein the mass ratio of the pretreated spent FCC catalyst powder to the alumina powder is (3 to 6): 7 to 4.
3. The method of preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 1, wherein the solute in the metal curative solution includes either or both of ethyl xanthate and silicate.
4. The method of preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 3, wherein the ethyl xanthate comprises either or both of potassium ethyl xanthate and sodium ethyl xanthate.
5. The method of preparing a ceramic hollow fiber membrane from FCC spent catalyst according to claim 4, wherein the ethyl xanthate is sodium ethyl xanthate.
6. The method of preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 3, wherein the silicate comprises either or both of potassium silicate and sodium silicate.
7. The method of preparing a ceramic hollow fiber membrane from FCC spent catalyst according to claim 6, wherein the silicate is sodium silicate.
8. The method for preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 7, wherein the mass ratio of sodium ethylxanthate to sodium silicate is 2-3: 7 to 8.
9. The method for preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 3, wherein the mass concentration of the metal curing agent is 3 to 15%.
10. The method for preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 1, wherein the impregnation treatment time is 5-24 hours;
the particle size of the ground FCC spent catalyst powder is less than or equal to 1.5 mu m.
11. The method of preparing a ceramic hollow fiber membrane from an FCC spent catalyst according to claim 1, wherein the polymer solution mainly comprises an organic polymer, an organic solvent and an additive.
12. The method for preparing a ceramic hollow fiber membrane from an FCC spent catalyst as claimed in claim 11, wherein the polymer solution mainly comprises the following components in parts by weight: 15-25 parts of polyether sulfone, 70-80 parts of N-methyl-2-pyrrolidone and 1-10 parts of polyvinylpyrrolidone.
13. The method of producing ceramic hollow fiber membrane from FCC spent catalyst according to any of claims 1 to 12, wherein the sum of the mass of FCC spent catalyst powder and alumina powder in the casting membrane slurry is 50-90% of the casting membrane slurry.
14. The method for preparing a ceramic hollow fiber membrane by FCC dead catalyst as claimed in claim 1, wherein the gelling agent is added to the casting slurry, pressurized to 0.2-0.5bar, extruded to obtain a wet fiber membrane, and gelled and solidified to obtain a fiber membrane blank.
15. The method for preparing a ceramic hollow fiber membrane from an FCC dead catalyst as claimed in claim 14, wherein the wet fiber membrane is immersed in an external coagulation bath through a dry spinning process of 5-30cm, and is subjected to gelation and solidification for 24 hours or more to form a fiber membrane blank.
16. The method of preparing a ceramic hollow fiber membrane from FCC spent catalyst according to claim 1, wherein the sintering process comprises: after the temperature is kept at 750 +/-10 ℃ for 0.5-2h, the temperature is raised to 1000-1300 ℃ for 0.5-7h, and the temperature is reduced.
17. A ceramic hollow fiber membrane produced by the method for producing a ceramic hollow fiber membrane from an FCC spent catalyst according to any one of claims 1 to 16.
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