CN111763069A - Waste FCC catalyst ceramic membrane support and preparation method and application thereof - Google Patents
Waste FCC catalyst ceramic membrane support and preparation method and application thereof Download PDFInfo
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Abstract
A ceramic membrane support for waste FCC catalyst and a preparation method and application thereof belong to the technical field of waste water purification. The preparation method of the waste FCC catalyst ceramic membrane support comprises the following steps: and molding and sintering the mixed raw materials. The sintering comprises heating to 1150-1240 ℃ and then preserving heat for 1-3 h. The feedstock comprises spent FCC catalyst and a forming aid. The mass of the forming auxiliary agent is 3-10% of that of the waste FCC catalyst. The waste FCC catalyst ceramic membrane support body has the advantages of high mechanical strength, porosity of 30-50%, pore diameter of 1-5 mu m and good permeability. Because the waste FCC catalyst contains some heavy metals, such as nickel, iron, vanadium and oxides thereof, the waste FCC catalyst is a good ozone catalyst, and the waste FCC catalyst has a large specific surface area, the ceramic membrane support body made of the waste FCC catalyst can be applied to ozone purification of waste water.
Description
Technical Field
The application relates to the technical field of wastewater purification, in particular to a waste FCC catalyst ceramic membrane support body and a preparation method and application thereof.
Background
The FCC catalyst (Fluid Catalytic Cracking) catalyst is an important substance in crude oil production, and since the reaction activity of the FCC catalyst inevitably decreases after being used for a period of time along with heavy metal pollution deactivation, carbon deposition deactivation and hydrothermal deactivation in the crude oil production process, the requirements of crude oil production cannot be met, and the waste FCC catalyst in the device needs to be removed regularly.
And the waste FCC catalyst contains trace amount of heavy metals or oxides such as nickel, vanadium and the like, and causes environmental pollution if the waste FCC catalyst is not treated properly, which adds extra treatment cost to enterprises.
About 16 million tons of waste FCC catalysts are generated every year, building materials such as landfill and cement manufacturing are basically used as treatment means, the utilization degree is low, and a large amount of resources are wasted.
Disclosure of Invention
The application provides a waste FCC catalyst ceramic membrane support body, a preparation method and an application thereof, which have a better ozone catalysis function.
The embodiment of the application is realized as follows:
in a first aspect, the present application provides a method for preparing a spent FCC catalyst ceramic membrane support, comprising: and molding and sintering the mixed raw materials.
The sintering comprises heating to 1150-1240 ℃ and then preserving heat for 1-3 h.
The feedstock comprises spent FCC catalyst and a forming aid.
The mass of the forming auxiliary agent is 3-10% of that of the waste FCC catalyst.
Optionally, the heating rate is 0.5-3 ℃/min during heating.
In the technical scheme, the waste FCC catalyst, the forming aid and the sintering aid are subjected to heat preservation at 1150-1240 ℃ for 1-3 hours to prepare the waste FCC catalyst ceramic membrane support with high mechanical strength, porosity of 30-50%, pore diameter of 1-5 mu m and good permeability. Because the waste FCC catalyst contains some heavy metals, such as nickel, iron, vanadium and oxides thereof, the waste FCC catalyst is a good ozone catalyst, and the waste FCC catalyst has a large specific surface area, the ceramic membrane support body made of the waste FCC catalyst can be applied to ozone purification of waste water.
Meanwhile, the waste FCC catalyst is used as the raw material, so that waste materials can be changed into valuable materials, the cost is low, and the preparation method is simple and convenient.
With reference to the first aspect, in a first possible example of the first aspect of the present application, the forming aid includes a first component and a second component, and a mass ratio of the first component to the second component is 1:5 to 5: 1;
the first component comprises any one or more of PVA, PEG, cellulose, starch and dextrin;
the second component comprises any one or more of hydraulic oil, engine oil, tung oil, white oil and glycerol.
In the above example, the first component is used to bind the spent FCC catalyst particles to form a ceramic membrane support; the second component is used for improving the lubricity of the raw materials and enabling the raw materials to be easier to form.
In a second possible example of the first aspect of the present application in combination with the first aspect, the above-mentioned manner of molding includes extrusion molding.
In the above examples, since the raw material has good lubricity, extrusion molding is easy.
In a third possible example of the first aspect of the present application in combination with the first aspect, the feedstock further includes a sintering aid, and the mass of the sintering aid is 0.1 to 3% of the mass of the spent FCC catalyst.
Optionally, the sintering aid comprises any one or more of alumina, kaolin, cordierite and talc.
In the above example, the sintering aid has a lower melting point than the spent FCC catalyst and is in a liquid phase at a high temperature, which can lower the sintering temperature of the raw material, and at the same time, the sintering aid is distributed among the particles of the spent FCC catalyst, which can bond the particles of the spent FCC catalyst, thereby improving the strength of the ceramic membrane support.
In a fourth possible example of the first aspect of the present application in combination with the first aspect, the above raw material comprises water, and the mass of the water is 0.1 to 20% of the mass of the spent FCC catalyst.
Optionally, the mass of water is 10-15% of the mass of the spent FCC catalyst.
In a fifth possible example of the first aspect of the present application in combination with the first aspect, the spent FCC catalyst is prepared by a pretreatment.
Optionally, the pretreatment comprises subjecting the spent FCC catalyst to a hydrothermal reaction.
In the above example, the hydrothermal reaction can solidify heavy metals in the spent FCC catalyst and retain the catalytic activity and high specific surface area of the spent FCC catalyst.
In a second aspect, the present application provides a waste FCC catalyst ceramic membrane support prepared according to the above method for preparing a waste FCC catalyst ceramic membrane support.
In the technical scheme, the waste FCC catalyst ceramic membrane support prepared by the preparation method of the waste FCC catalyst ceramic membrane support has stable performance, and has better permeability, mechanical strength and ozone catalytic performance.
In a first possible example of the second aspect of the present application in combination with the second aspect, the porosity of the spent FCC catalyst ceramic membrane support is 30 to 50% and the pore diameter is 1 to 5 μm.
In a second possible example of the second aspect of the present application in combination with the second aspect, the mechanical strength of the spent FCC catalyst ceramic membrane support is 20 to 50 MPa.
Optionally, the pure water flux of the waste FCC catalyst ceramic membrane support is 5-10 m3/m2/h/bar。
In a third aspect, the present application provides a use of the above-mentioned waste FCC catalyst ceramic membrane support for purifying waste water, wherein ozone is passed through the waste FCC catalyst ceramic membrane support, and contaminants clogged in the waste FCC catalyst ceramic membrane support are removed by oxidation of the ozone under catalysis of the waste FCC catalyst in the waste FCC catalyst ceramic membrane support.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is an electron micrograph of spent FCC catalyst particles obtained by pretreatment according to example 1 of the present application;
fig. 2 is an electron microscope image of the spent FCC catalyst ceramic membrane support prepared in example 1 of the present application.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. 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.
The spent FCC catalyst itself is a catalyst having a high specific surface area and a large contact area with the reactants. Meanwhile, the inventor finds that some heavy metals of nickel, iron, vanadium and oxides thereof contained in the waste FCC catalyst are good ozone catalysts, and after the waste FCC catalyst is made into a ceramic membrane support body, the waste FCC catalyst can realize self-cleaning through the own ozone catalytic function. When the conventional inorganic membrane is polluted, a cleaning agent is needed to realize cleaning.
The following description is made in detail for the waste FCC catalyst ceramic membrane support, the preparation method and the application thereof according to the embodiments of the present application:
the application provides a preparation method of a waste FCC catalyst ceramic membrane support, which comprises the following steps: pretreating the waste FCC catalyst and preparing the ceramic membrane support of the waste FCC catalyst.
Since the waste FCC catalyst contains some heavy metals, if the waste FCC catalyst is directly used, the heavy metals therein may be dissolved out, thereby bringing new contaminants into the wastewater being purified.
The pretreatment method comprises the following steps:
carrying out hydrothermal reaction on the waste FCC catalyst at 120-180 ℃, cooling to room temperature after 2-4 reaction, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst. The cleaning agent is deionized water during washing.
The drying temperature is 100 deg.C and the drying time is 30 min.
The leaching toxicity of heavy metals such as nickel, vanadium and the like in the waste FCC catalyst obtained after pretreatment is respectively as low as ppb level, which is far lower than the requirement of <5mg/L in GB5085.3-2007 'hazardous waste identification Standard leaching toxicity identification'.
Compared with other heavy metal curing methods, such as calcination curing method or acid digestion. The pretreatment method has low treatment energy consumption, and most importantly, can stably solidify the heavy metal and keep the original specific surface area and catalytic performance of the waste FCC catalyst.
The method for preparing the waste FCC catalyst ceramic membrane support comprises the following steps:
and uniformly mixing the pretreated waste FCC catalyst particles and a forming auxiliary agent to prepare a raw material, and sintering after forming.
The forming auxiliary agent comprises a first component and a second component, the first component comprises one or more of PVA, PEG, cellulose, starch and dextrin, and the first component is used for bonding the waste FCC catalyst particles to form the ceramic membrane support.
In one embodiment of the present application, the first component is PVA. In some other embodiments of the present application, the first component may also be PEG, cellulose, starch, or dextrin, or a mixture of PVA and PEG, or a mixture of PEG and cellulose, or a mixture of PVA and starch, or a mixture of PEG and dextrin, or a mixture of PVA, PEG and cellulose, or a mixture of PVA, PEG and starch, or a mixture of PVA, PEG, cellulose, starch and dextrin.
The second component comprises any one or more of hydraulic oil, engine oil, tung oil, white oil and glycerol, and is used for improving the lubricity of the raw materials and enabling the raw materials to be easier to form.
In one embodiment of the present application, the second component is hydraulic oil. In some other embodiments of the present application, the second component may also be an engine oil, a tung oil, a white oil or glycerol, or a mixture of a hydraulic oil and an engine oil, or a mixture of a hydraulic oil and a tung oil, or a mixture of a hydraulic oil, an engine oil and a white oil, or a mixture of a hydraulic oil, an engine oil, a tung oil, a white oil and a glycerol.
The mass of the forming auxiliary agent is 3-10% of that of the waste FCC catalyst, and the mass ratio of the first component to the second component is 1: 5-5: 1.
In one embodiment of the present application, the mass of the first component is 1.5% of the mass of the spent FCC catalyst and the mass of the second component is 1.5% of the mass of the spent FCC catalyst. In some other embodiments herein, the mass of the first component may also be 1.6%, 2%, 3%, 4%, 5%, 7%, or 8% of the mass of the spent FCC catalyst, and the mass of the second component may also be 1.6%, 2%, 3%, 4%, 5%, 7%, or 8% of the mass of the spent FCC catalyst.
Besides the forming auxiliary agent, the raw material also comprises a sintering auxiliary agent, the sintering auxiliary agent has a lower melting point than the waste FCC catalyst and is in a liquid phase at a high temperature, so that the sintering temperature of the raw material can be reduced, and meanwhile, the sintering auxiliary agent is distributed among the particles of the waste FCC catalyst, so that the particles of the waste FCC catalyst can be bonded, and the strength of the prepared ceramic membrane support body is improved.
The sintering aid comprises any one or more of alumina, kaolin, cordierite and talcum powder.
In one embodiment of the present application, the sintering aid is alumina. In some other embodiments of the present application, the sintering aid may also be kaolin, cordierite or talc, or a mixture of alumina and kaolin, or a mixture of kaolin and cordierite, or a mixture of cordierite and talc, or a mixture of alumina, kaolin and cordierite, or a mixture of kaolin, cordierite and talc.
The mass of the sintering aid is 0.1-3% of the mass of the waste FCC catalyst.
In one embodiment of the present application, the mass of the sintering aid is 1% of the mass of the spent FCC catalyst. In other embodiments herein, the mass of the sintering aid may also be 0.1%, 0.2%, 0.5%, 0.8%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, or 3% of the mass of the spent FCC catalyst.
Also included in the feedstock herein is water, wherein the water may be deionized water or other treated or untreated water.
In one embodiment of the present application, the mass of water is 10% of the mass of the spent FCC catalyst. In other embodiments herein, the mass of water may also be 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20% of the mass of the spent FCC catalyst.
The forming method comprises extrusion forming, compression molding and other forming modes capable of forming the ceramic membrane support.
The shape of the ceramic membrane support is not limited in the present application, and may be a sheet, a segment, a tube, a multi-channel, or the like.
The sintering comprises raising the temperature to 1150-1240 ℃ at a rate of 0.5-3 ℃/min and then preserving the heat for 1-3 h.
Optionally, the heating rate is 1-3 ℃/min;
optionally, the heating rate is 1-2 ℃/min.
In one embodiment of the present application, the temperature rise rate may be 1.5 ℃/min. In some other embodiments of the present application, the temperature increase rate can be 0.5 ℃/min, 1 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 0.5-1.5 ℃/min, 1-2 ℃/min, 2.5-3 ℃/min, 0.5-2.5 ℃/min, 1-3 ℃/min, or 1-1.5 ℃/min.
Optionally, heating to 1150-1230 ℃;
optionally, the temperature is raised to 1180 ℃.
In one embodiment of the present application, the temperature may be raised to 1180 ℃. In other embodiments of the present application, the temperature may be increased to 1150 ℃, 1160 ℃, 1170 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃ or 1230 ℃.
Optionally, the heat preservation time is 1.5-2.5 h;
optionally, the incubation time is 2 h.
In one embodiment of the present application, the incubation time may be 2 hours. In other embodiments of the present application, the incubation time may also be 1.5h, 1.7h, 2.1h, 2.4h, 2.7h, or 3 h.
The application also provides a waste FCC catalyst ceramic membrane support body which is prepared by the preparation method of the waste FCC catalyst ceramic membrane support body.
The waste FCC catalyst ceramic membrane support prepared by the method has stable performance, and has better permeability, mechanical strength and ozone catalytic performance.
Wherein the porosity of the ceramic membrane support body of the waste FCC catalyst is 30-50%, the aperture is 1-5 mu m, and the specific surface area is 15-50 g/cm2The mechanical strength is 20 to 50MPa, and the pure water flux is 5 to 10m3/m2/h/bar。
The application also provides an application of the waste FCC catalyst ceramic membrane supporter in the purification of wastewater, ozone is introduced into the waste FCC catalyst ceramic membrane supporter, and pollutants blocked in the waste FCC catalyst ceramic membrane supporter are removed by ozone oxidation under the catalysis of the waste FCC catalyst in the waste FCC catalyst ceramic membrane supporter.
Hereinafter, a spent FCC catalyst ceramic membrane support, a method for preparing the same, and applications thereof according to the present invention will be described in further detail with reference to examples.
Example 1
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 2
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 150 ℃, cooling to room temperature after reacting for 2h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 5 parts by weight of PEG, 5 parts by weight of engine oil, 3 parts by weight of kaolin and 20 parts by weight of deionized water, extruding and molding, heating to 1150 ℃ at the heating rate of 3 ℃/min, preserving heat for 3 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 3
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 180 ℃, cooling to room temperature after reacting for 4 hours, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA and starch, 1.5 parts by weight of hydraulic oil and white oil, 0.1 part by weight of kaolin, talcum powder and 0.1 part by weight of deionized water, extruding and molding, heating to 1240 ℃ at the heating rate of 1.5 ℃/min, preserving heat at the temperature for 1h, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 4
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1 part by weight of PEG and cellulose, 3 parts by weight of hydraulic oil and glycerol, 1 part by weight of cordierite and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at a heating rate of 1.5 ℃/min, preserving heat at the temperature for 2 hours, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 5
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 150 ℃, cooling to room temperature after reacting for 3.5h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 3 parts by weight of cellulose, 1 part by weight of glycerol, 1 part by weight of alumina and talcum powder and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 6
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1150 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 7
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1230 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 8
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 3 parts by weight of PVA, 3 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 9
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 5 parts by weight of PVA, 5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 10
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 4 parts by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Example 11
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Comparative example 1
The present application provides a support for a ceramic membrane of a spent FCC catalyst and a method for preparing the same, which comprises the steps of:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1100 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Comparative example 2
The present application provides a support for a ceramic membrane of a spent FCC catalyst and a method for preparing the same, which comprises the steps of:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1250 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Comparative example 3
The present application provides a support for a ceramic membrane of a spent FCC catalyst and a method for preparing the same, which comprises the steps of:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1 part by weight of PVA, 1 part by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Comparative example 4
The embodiment of the application provides a waste FCC catalyst ceramic membrane support and a preparation method thereof, which comprises the following steps:
1. pretreatment of spent FCC catalyst
Carrying out hydrothermal reaction on the waste FCC catalyst at 120 ℃, cooling to room temperature after reacting for 3h, mixing with water, and sequentially stirring, filtering, washing and drying at room temperature to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 6 parts by weight of PVA, 6 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at a heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to form the waste FCC catalyst ceramic membrane support body.
Comparative example 5
The present application provides a support for a ceramic membrane of a spent FCC catalyst and a method for preparing the same, which comprises the steps of:
1. pretreatment of spent FCC catalyst
Sintering the waste FCC catalyst for 2 hours at 1250 ℃ to obtain the pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of waste FCC catalyst particles obtained by pretreatment, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to form the waste FCC catalyst ceramic membrane support body.
Comparative example 6
The present application provides a support for a ceramic membrane of a spent FCC catalyst and a method for preparing the same, which comprises the steps of:
1. pretreatment of spent FCC catalyst
Carrying out heavy metal curing treatment on the waste FCC catalyst by adopting an acid digestion method in CN109821859A to obtain a pretreated waste FCC catalyst;
2. preparation of waste FCC catalyst ceramic membrane support
Uniformly mixing 100 parts by weight of pretreated waste FCC catalyst particles, 1.5 parts by weight of PVA, 1.5 parts by weight of hydraulic oil, 1 part by weight of alumina and 10 parts by weight of deionized water, extruding and molding, heating to 1180 ℃ at the heating rate of 1.5 ℃/min, preserving heat for 2 hours at the temperature, and cooling to room temperature to obtain the waste FCC catalyst ceramic membrane support.
Test example 1
The mechanical strength, pore size distribution, porosity, specific surface area and pure water flux of the ceramic supports for spent FCC catalysts prepared in examples 1, 6 to 11 and comparative examples 1 to 6 were measured, respectively, as shown in table 1.
TABLE 1 mechanical Strength, pore size distribution, porosity, specific surface area and pure Water flux of the spent FCC catalyst ceramic Membrane support
As can be seen from Table 1, the mechanical strength of the ceramic support of the waste FCC catalyst increases with the increase of the sintering temperature, and the specific surface area decreases with the increase of the sintering temperature (see the comparison of examples 1 and 6 to 7 and comparative examples 1 to 2);
when the mass of the forming auxiliary agent is 3-10% of that of the waste FCC catalyst, the porosity of the prepared waste FCC catalyst ceramic membrane support is 30-50%, the aperture is 1-5 mu m, the mechanical strength is 20-50 Mpa, and the ceramic membrane support cannot be formed when too much or too little forming auxiliary agent is added (the comparison of examples 1 and 8-9 and comparative examples 3-4 shows);
when the mass of the sintering aid is 0.1-3% of the mass of the waste FCC catalyst, the prepared waste FCC catalyst ceramic membrane support has the porosity of 30-50%, the pore diameter of 1-5 mu m and the specific surface area of 15-50 g/cm2The mechanical strength is 20-50 Mpa, the aperture, the porosity and the specific surface area of the ceramic membrane support body are reduced due to excessive sintering aids, and the strength of the ceramic membrane support body is reduced due to the fact that the sintering aids are not added. (comparative examples 1, 10 to 11).
The sintering temperature, the amount of the forming aid and the amount of the sintering aid have great influence on the mechanical strength, the pore diameter, the porosity, the specific surface area and the permeability of the ceramic membrane support of the waste FCC catalyst. Wherein the porosity of the obtained product is 30-50%, the pore diameter is 1-5 mu m, and the specific surface area is 15-50 g/cm2And the mechanical strength of the ceramic membrane support body is 20-50 MPa.
Test example 2
The metal content (%) and the solid hazardous waste impregnation liquid (ppm) in the waste FCC catalyst particles obtained by the pretreatment in examples 1 to 3 and comparative examples 5 to 6 were respectively detected by ICP, as shown in tables 2 and 3, wherein the control group was the waste FCC catalyst particles without pretreatment.
TABLE 2 Metal content of spent FCC catalyst particles
TABLE 3 specific surface area of spent FCC catalyst particles and solid hazardous spent impregnation
As can be seen from tables 2 and 3, the pretreatment of the present application can better solidify the heavy metals in the waste FCC catalyst, the leaching danger of the heavy metals is far lower than the national standard, and the Ni and Fe in the waste FCC catalyst are retained2O3And V, and the specific surface area is not greatly changed, fromWhile retaining the catalytic activity of the spent FCC catalyst. While the specific surface area of the waste FCC catalyst can be reduced by adopting a calcination and solidification method, the Ni and Fe in the waste FCC catalyst can be reduced by adopting an acid digestion method2O3And a V content.
Test example 3
The waste FCC catalyst ceramic membrane support bodies of example 1 and comparative examples 5 to 6 were prepared into a waste FCC catalyst ceramic membrane module, the waste FCC catalyst ceramic membrane module was placed in a reaction tank, a clean water chamber was formed in the middle of the waste FCC catalyst ceramic membrane module, organic pollutants in the sewage in the reaction tank were decomposed by ozone oxidation under the action of an ozone catalyst, clean water was introduced into the clean water chamber through membrane pores of the waste FCC catalyst ceramic membrane module and collected, and the flux and the pressure difference of the sewage in the waste FCC catalyst ceramic membrane module prepared from the waste FCC catalyst ceramic membrane support bodies of example 1 and comparative examples 5 to 6 were measured, as shown in table 4.
TABLE 4 Sewage flux and Membrane pressure differential of ceramic Membrane modules of spent FCC catalysts
As can be seen from table 4, the catalytic activity and the high specific surface area of the waste FCC catalyst can be maintained by using the hydrothermal method to cure the heavy metal, so that the ceramic membrane support of the waste FCC catalyst has good ozone catalytic performance, and self-cleaning is achieved. The specific surface area and catalytic activity of the ceramic membrane support of the waste FCC catalyst can be reduced by adopting a calcination curing method and an acid digestion method, so that the ceramic membrane support of the waste FCC catalyst basically has no ozone catalytic performance any more.
Test example 3
Electron micrographs of the waste FCC catalyst particles obtained by the pretreatment of example 1 and the ceramic membrane support of the waste FCC catalyst obtained by the pretreatment of example 2 were respectively measured and shown in fig. 1 and 2.
To sum up, the intensity of the useless FCC catalyst ceramic membrane supporter of this application directly influences the result of use of later stage ceramic membrane water treatment process. The heavy metal ozone catalytic reaction is a surface reaction, and the size of the specific surface area can directly influence the catalytic effect. The principle of using the waste FCC catalyst ceramic membrane support body for ozone catalytic water treatment is as follows: the waste FCC catalyst ceramic membrane support body is made into a ceramic membrane component and is placed in a reaction tank, a clear water chamber is formed in the middle of the ceramic membrane component, organic pollutants in sewage in the reaction tank are oxidized and decomposed by ozone under the action of an ozone catalyst, and clear water enters the clear water chamber through membrane holes of the ceramic membrane component and is collected. The aperture and the pore space of the FCC ceramic membrane represent the specific surface area on one hand, and directly influence the interception and treatment effects on pollutants with different molecular weights, and the efficiency and the pressure drop of the ozone catalysis process on the other hand. The selection and content of the sintering aid, the selection and content of the forming aid, the sintering temperature and the hydrothermal treatment of the waste FCC catalyst ceramic membrane support body synergistically influence the aperture, the pore, the specific surface area and the mechanical property of a waste FCC ceramic membrane substrate, further synergistically influence the use effect and the catalytic effect of the ceramic membrane water treatment, the interception and treatment effect on pollutants with different molecular weights and the efficiency and the pressure drop of the ozone catalysis process. The sintering temperature is increased, liquid phase components among waste FCC particles are more in the sintering process, the particle bonding effect is good, the mechanical property of the ceramic membrane is favorably improved, but the specific surface area of the waste FCC ceramic is reduced (air hole blockage) and the heavy metal is coated in a large amount of air inlet holes and cannot play a catalytic function, the sintering temperature is reduced due to the increase of the adding amount of the sintering aid, the specific surface area is further influenced, and meanwhile, the sintering energy consumption can be reduced. The forming auxiliary agent is oil, hydraulic oil, engine oil, tung oil, white oil, glycerol and the like, PVA, PEG, cellulose, starch and dextrin are oxidized (i.e. burnt) at the sintering temperature, and the oxidized process of the forming auxiliary agent can affect the aperture, the pore, the specific surface area and the mechanical property. The hydrothermal reaction also synergistically affects the specific surface area, retains the specific surface area of the waste FCC catalyst and the heavy metals on the surface, thereby retaining the catalytic activity.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for preparing a support body for a ceramic membrane of a spent FCC catalyst, the method comprising: molding and sintering the mixed raw materials;
the sintering comprises heating to 1150-1240 ℃ and then preserving heat for 1-3 h;
the raw materials comprise a waste FCC catalyst and a forming auxiliary agent;
the mass of the forming auxiliary agent is 3-10% of that of the waste FCC catalyst;
optionally, the heating rate is 0.5-3 ℃/min during heating.
2. The method for preparing a waste FCC catalyst ceramic membrane support according to claim 1, wherein the forming aid comprises a first component and a second component, and the mass ratio of the first component to the second component is 1:5 to 5: 1;
the first component comprises any one or more of PVA, PEG, cellulose, starch and dextrin;
the second component comprises any one or more of hydraulic oil, engine oil, tung oil, white oil and glycerol.
3. The method of preparing a spent FCC catalyst ceramic membrane support according to claim 2, wherein the forming means comprises extrusion.
4. The method for preparing a waste FCC catalyst ceramic membrane support according to claim 1, wherein the raw material further comprises a sintering aid, and the mass of the sintering aid is 0.1-3% of the mass of the waste FCC catalyst;
optionally, the sintering aid comprises any one or more of alumina, kaolin, cordierite and talc.
5. The method for preparing a waste FCC catalyst ceramic membrane support according to claim 1, wherein the raw material comprises water, and the mass of the water is 0.1 to 20% of the mass of the waste FCC catalyst;
optionally, the mass of the water is 10-15% of the mass of the spent FCC catalyst.
6. The method for preparing a ceramic membrane support for a spent FCC catalyst according to any one of claims 1 to 5, wherein the spent FCC catalyst is prepared by pretreatment;
optionally, the pre-treatment comprises subjecting the spent FCC catalyst to a hydrothermal reaction.
7. A waste FCC catalyst ceramic membrane support prepared by the method according to any one of claims 1 to 6.
8. The support for a waste FCC catalyst ceramic membrane according to claim 7, wherein the support for a waste FCC catalyst ceramic membrane has a porosity of 30 to 50% and a pore diameter of 1 to 5 μm.
9. The support according to claim 7, wherein the support has a mechanical strength of 20 to 50 MPa;
optionally, the pure water flux of the waste FCC catalyst ceramic membrane support is 5-10 m3/m2/h/bar。
10. Use of the waste FCC catalyst ceramic membrane support according to any one of claims 7 to 9, wherein ozone is introduced into the waste FCC catalyst ceramic membrane support, and pollutants blocked in the waste FCC catalyst ceramic membrane support are removed by oxidation with ozone under the catalysis of the waste FCC catalyst in the waste FCC catalyst ceramic membrane support.
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