CN112316743A - Preparation method of low-cost low-density catalytic functional ceramic membrane - Google Patents

Preparation method of low-cost low-density catalytic functional ceramic membrane Download PDF

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CN112316743A
CN112316743A CN202011142609.4A CN202011142609A CN112316743A CN 112316743 A CN112316743 A CN 112316743A CN 202011142609 A CN202011142609 A CN 202011142609A CN 112316743 A CN112316743 A CN 112316743A
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ceramic membrane
low
density
mixture
preparation
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CN112316743B (en
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马军
张瑛洁
杨智伟
程喜全
王凯
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Shandong Zhong'ou Membrane Technology Research Co ltd
Harbin Institute of Technology Weihai
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Shandong Zhong'ou Membrane Technology Research Co ltd
Harbin Institute of Technology Weihai
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores

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Abstract

A preparation method of a low-cost low-density catalytic functional ceramic membrane relates to a preparation method of a ceramic membrane. The invention aims to solve the problems of low strength, easy deformation of pore diameter, poor chemical stability, easy pollution, difficult cleaning, short service life, complex preparation process of an inorganic ceramic membrane, high preparation cost, high density, uneven pore diameter distribution, loss of catalyst particles in the using and backwashing processes and heavy metal pollution of a water body of the existing organic membrane material. The method comprises the following steps: firstly, preparing high-efficiency catalytic active particles; secondly, preparing a ceramic membrane raw material; standing and ageing, and then performing pugging treatment; fourthly, molding; and fifthly, drying and sintering to obtain the low-cost low-density catalytic functional ceramic membrane. The low-cost low-density catalytic functional ceramic membrane prepared by the method is suitable for treating sewage.

Description

Preparation method of low-cost low-density catalytic functional ceramic membrane
Technical Field
The invention relates to a preparation method of a ceramic membrane.
Background
With the continuous growth of the population in China and the continuous development of industrialization, the water pollution caused by industrialization has serious influence on the lives of residents. For part of small-molecule, difficult-to-degrade and highly toxic environmental pollutants, the traditional coagulation-clarification-filtration-sterilization mode of a water plant is difficult to completely remove. In recent years, membrane separation technology, catalytic degradation technology, advanced oxidation technology and the like have the characteristics of high efficiency, wide application and the like, are widely concerned, can replace the traditional water treatment mode technology or can be used as a preposed technology of the traditional mode, and therefore have wide application prospects in the aspect of water body pollution, particularly treatment of pollutants difficult to degrade. However, the current membrane material market is mainly an organic polymer membrane material, and the organic membrane material has low strength, easy deformation of pore diameter, poor chemical stability, easy pollution, difficult cleaning and short service life. Thus resulting in higher operating costs.
In recent years, ceramic membrane materials have attracted attention in the field of water treatment. The ceramic membrane material has excellent performance, high strength, good chemical stability, acid and alkali corrosion resistance and oxidation resistance, and can be used under the conditions of high-concentration potassium permanganate and ozone; meanwhile, the membrane can be back-flushed at high pressure without damaging the membrane structure, and the service life is long; in addition, the porous ceramic membrane material can load metal catalyst particles, and the surface of the loaded ceramic membrane can directly catalyze the advanced oxidation process, so that the water treatment efficiency is improved. However, commonly used ceramic membrane materials such as Al2O3、TiO2、ZrO2The preparation process of the powder is complex, the preparation cost is high, the sintering temperature is high in the sintering process, the sintering time is long, and the prepared ceramic membrane has higher density and uneven pore size distribution compared with an organic membrane material; the existing catalyst loading technology is mainly to directly dope, and catalyst particles are not mixedIs easy to combine with membrane material, and the catalyst particles can be lost in the using and back washing processes, thereby causing the heavy metal pollution of water body. Therefore, ceramic membrane materials are difficult to be widely used in the field of water treatment.
Disclosure of Invention
The invention aims to solve the problems that the existing organic membrane material has low strength, easy deformation of pore diameter, poor chemical stability, easy pollution, difficult cleaning, short service life, complex preparation process of the inorganic ceramic membrane, high preparation cost, large density, uneven pore diameter distribution and loss of catalyst particles in the using and backwashing processes, which cause heavy metal pollution of a water body, and provides a preparation method of a low-cost low-density catalytic functional ceramic membrane.
A preparation method of a low-cost low-density catalytic functional ceramic membrane is completed according to the following steps:
firstly, preparing high-efficiency catalytic active particles:
taking a metal organic framework compound as a carrier, fixing transition metal particles in the carrier by a solvothermal method, and grinding and sieving by using a ball mill to obtain high-efficiency catalytic active particles;
secondly, preparing ceramic membrane raw materials:
adding ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol into a mixer, and mixing to obtain a mixture;
in the second step, the mass ratio of ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol in the mixture is (85-90): 10-15): 75-85): 3-8;
the ceramic membrane raw material powder in the mixture in the step two is diatomite and Al2O3Mixture of powders of diatomaceous earth and Al2O3The mass ratio of the powder is (25-30) to (70-75);
standing and ageing the mixture, and pugging the mixture by a vacuum pug mill to obtain mixed pug;
fourthly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
and fifthly, placing the ceramic membrane blank in a hot air drying box for drying, and then placing in a muffle furnace for gradient temperature rise sintering to obtain the low-cost low-density catalytic functional ceramic membrane.
The principle and the advantages of the invention are as follows:
firstly, the invention uses diatomite as a ceramic membrane raw material, wherein the diatomite is siliceous rock which is formed by piling up silicate remains after the death of diatoms for tens of thousands of years and mainly comprises amorphous SiO2The catalyst has the advantages that the catalyst is composed of a special porous structure, and the special structure enables the catalyst to have low density, large specific surface area and relative incompressibility, and meanwhile, the catalyst has a stabilizing effect on active ingredients and can well load catalyst particles; at present, China has found that the total storage capacity of more than four hundred million tons of diatomite in more than 70 places of a diatomite ore bed can obviously reduce the preparation cost of a ceramic membrane and solve the problems of high density and uneven pore size distribution of a ceramic membrane material by using diatomite as a ceramic membrane raw material; and the diatomite contains a small part of Fe2O3、CaO、K2O、TiO2Impurities, impurity elements, etc. can generate liquid phase or react with Al in the sintering process2O3Solid solution is formed, which is beneficial to the mass transfer and bonding of aggregate particles and can reduce the sintering temperature and the sintering time;
secondly, the low-cost low-density catalytic functional ceramic membrane prepared by the method has large specific surface area, high catalytic activity and long service life, the prepared ceramic membrane forms a bicontinuous phase structure, and the density of the ceramic membrane is 1.6g/cm3～1.7g/cm3Porosity of about 40% and density of Al only2O3The porosity of the ceramic membrane is improved by more than 10 percent, the aperture is about 0.1 mu m, the aperture size is uniform, the water permeability is excellent, the bonding strength of the supported catalyst is high, and no heavy metal is leached after long-time testing; tests show that the membrane has turbidity removal rate of over 99 percent, Chemical Oxygen Demand (COD) removal rate of over 95 percent, ammonia nitrogen removal rate of over 99 percent and total phosphorus removal rate of over 92 percent, and under the condition of the same catalyst particle addition and oxidant dosage, each index is only Al compared with aggregate2O3The performance of the ceramic membrane is improved by 15 percent.
The low-cost low-density catalytic functional ceramic membrane prepared by the method is suitable for treating sewage.
Drawings
FIG. 1 is an SEM image of a low-cost, low-density catalytic functional ceramic film prepared according to example one;
FIG. 2 shows Al prepared in comparative example one2O3SEM pictures of ceramic membranes;
FIG. 3 is a schematic view of a ceramic membrane water treatment apparatus.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of a low-cost low-density catalytic functional ceramic membrane, which is completed by the following steps:
firstly, preparing high-efficiency catalytic active particles:
taking a metal organic framework compound as a carrier, fixing transition metal particles in the carrier by a solvothermal method, and grinding and sieving by using a ball mill to obtain high-efficiency catalytic active particles;
secondly, preparing ceramic membrane raw materials:
adding ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol into a mixer, and mixing to obtain a mixture;
in the second step, the mass ratio of ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol in the mixture is (85-90): 10-15): 75-85): 3-8;
the ceramic membrane raw material powder in the mixture in the step two is diatomite and Al2O3Mixture of powders of diatomaceous earth and Al2O3The mass ratio of the powder is (25-30) to (70-75);
standing and ageing the mixture, and pugging the mixture by a vacuum pug mill to obtain mixed pug;
fourthly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
and fifthly, placing the ceramic membrane blank in a hot air drying box for drying, and then placing in a muffle furnace for gradient temperature rise sintering to obtain the low-cost low-density catalytic functional ceramic membrane.
The principle and advantages of the embodiment are as follows:
first, in the present embodiment, diatomaceous earth, which is a siliceous rock formed by stacking dead siliceous remains of diatoms for tens of thousands of years and mainly composed of amorphous SiO, is used as a raw material for ceramic membranes2The catalyst has the advantages that the catalyst is composed of a special porous structure, and the special structure enables the catalyst to have low density, large specific surface area and relative incompressibility, and meanwhile, the catalyst has a stabilizing effect on active ingredients and can well load catalyst particles; at present, China has found that the total storage capacity of more than four hundred million tons of diatomite in more than 70 places of a diatomite ore bed can obviously reduce the preparation cost of a ceramic membrane and solve the problems of high density and uneven pore size distribution of a ceramic membrane material by using diatomite as a ceramic membrane raw material; and the diatomite contains a small part of Fe2O3、CaO、K2O、TiO2Impurities, impurity elements, etc. can generate liquid phase or react with Al in the sintering process2O3Solid solution is formed, which is beneficial to the mass transfer and bonding of aggregate particles and can reduce the sintering temperature and the sintering time;
secondly, the low-cost low-density catalytic functional ceramic membrane prepared by the embodiment has large specific surface area, high catalytic activity and long service life, the prepared ceramic membrane forms a bicontinuous phase structure, and the density of the ceramic membrane is 1.6g/cm3～1.7g/cm3Porosity of about 40% and density of Al only2O3The porosity of the ceramic membrane is improved by more than 10 percent, the aperture is about 0.1 mu m, the aperture size is uniform, the water permeability is excellent, the bonding strength of the supported catalyst is high, and no heavy metal is leached after long-time testing; tests show that the membrane has turbidity removal rate of over 99 percent, Chemical Oxygen Demand (COD) removal rate of over 95 percent and ammonia nitrogen removal rate of 99 percentThe total phosphorus removal rate is more than 92 percent, and under the condition of the same catalyst particle addition and oxidant dosage, each index is only Al compared with the aggregate2O3The performance of the ceramic membrane is improved by 15 percent.
The low-cost low-density catalytic functional ceramic membrane prepared by the embodiment is suitable for treating sewage.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the metal organic framework compound in the step one is UiO-66 or NH2-UiO-66. Other steps are the same as in the first embodiment.
The UiO-66 of the embodiment is synthesized by the following steps:
firstly, 5g of ZrCl4Adding into 200mL of DMF (N, N-dimethylformamide), adding 40mL of concentrated hydrochloric acid with mass fraction of 37%, and performing ultrasonic treatment for 20 min;
adding 400mL of DMF and 4.92g of terephthalic acid after the ultrasonic treatment is finished, and performing ultrasonic treatment for 20min to obtain a reaction solution;
thirdly, heating the reaction solution in a water bath at 90 ℃ for 10 hours to generate layering, naturally cooling to room temperature, and pouring out supernatant to obtain solid matters;
fourthly, using DMF as a cleaning agent, centrifugally cleaning the solid substance for 15min at the centrifugal speed of 8000r/min, and then pouring out the supernatant to obtain the solid substance cleaned by the DMF;
centrifugally cleaning the solid substance washed by the DMF for 2 times by using absolute ethyl alcohol as a cleaning agent, wherein the speed of each centrifugal cleaning is 8000r/min, and the time of each centrifugal cleaning is 15min to obtain the solid substance washed by the absolute ethyl alcohol;
sixthly, putting the solid matter cleaned by the absolute ethyl alcohol into a drying oven with the temperature of 60 ℃ for drying for 10 hours, and then putting the solid matter into a vacuum drying oven with the temperature of 70 ℃ for drying for 48 hours to obtain UiO-66.
NH according to the present embodiment2-UiO-66 is synthesized by the following steps:
firstly, 5g of ZrCl4Adding into 200mL of DMF (N, N-dimethylformamide), adding 40mL of concentrated hydrochloric acid with mass fraction of 37%, and performing ultrasonic treatment for 20 min;
adding 400mL of DMF and 5.36g of 2-amino terephthalic acid after the ultrasonic treatment is finished, and performing ultrasonic treatment for 20min to obtain a reaction solution;
thirdly, heating the reaction solution in a water bath at 90 ℃ for 10 hours to generate layering, naturally cooling to room temperature, and pouring out supernatant to obtain solid matters;
fourthly, using DMF as a cleaning agent, centrifugally cleaning the solid substance for 15min at the centrifugal speed of 8000r/min, and then pouring out the supernatant to obtain the solid substance cleaned by the DMF;
centrifugally cleaning the solid substance washed by the DMF for 2 times by using absolute ethyl alcohol as a cleaning agent, wherein the speed of each centrifugal cleaning is 8000r/min, and the time of each centrifugal cleaning is 15min to obtain the solid substance washed by the absolute ethyl alcohol;
sixthly, putting the solid matter cleaned by the absolute ethyl alcohol into a drying oven with the temperature of 60 ℃ for drying for 10 hours, and then putting the solid matter into a vacuum drying oven with the temperature of 70 ℃ for drying for 48 hours to obtain NH2-UiO-66。
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the transition metal particles in the step one are La (NO)3)3、Ce(NO3)3、Cu(NO3)2、Fe(NO3)3、Cr(NO3)3And Co (NO)3)2One or a mixture of several of them. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the first step, a metal organic framework compound is used as a carrier, transition metal particles are fixed in the carrier by a solvothermal method, and then are ground and sieved by a ball mill to obtain high-efficiency catalytic active particles; the method comprises the following steps:
dissolving transition metal particles into ethylene glycol to obtain a mixed solution;
the concentration of the transition metal particles in the step I is 1 mmol/L-10 mmol/L;
the transition metal particles in the step (I) are La(NO3)3、Ce(NO3)3、Cu(NO3)2、Fe(NO3)3、Cr(NO3)3And Co (NO)3)2One or a mixture of several of them;
adjusting the pH value of the mixed solution to 7-8, adding a metal organic framework compound, and performing ultrasonic oscillation to obtain a reaction solution;
the concentration of the metal-organic framework compound in the reaction solution is 1 g/L-5 g/L;
the power of the ultrasonic oscillation in the second step is 180W-200W, and the time of the ultrasonic oscillation is 20 min-40 min;
thirdly, placing the reaction liquid into a reaction kettle, heating the reaction kettle to 180-200 ℃ at the heating rate of 3-5 ℃/min, and reacting for 8-10 h at the temperature of 180-200 ℃ to obtain a reaction product;
fourthly, grinding the reaction product by using a ball mill, and then sieving to obtain high-efficiency catalytic active particles;
the particle size of the high-efficiency catalytic active particles in the step (iv) is less than 300 meshes. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the particle size of the diatomite in the step two is 120 meshes, and Al is2O3The particle size of the powder was 500 mesh. The other steps are the same as those in the first to fourth embodiments.
The diatomite described in the embodiment is refined diatomite subjected to acid washing and presintering, wherein SiO is2The content is more than 85 percent, and the aluminum alloy contains Al2O3、Fe2O3、CaO、K2O、TiO2And the like.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the binder in the second step is hydroxypropyl methyl cellulose; and the pore-forming agent in the second step is graphite powder or starch. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the second step, ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol are added into a mixer to be mixed for 20-40 min, and the rotating speed of the mixer is 40-60 r/min. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the standing and staling time in the third step is 40 to 48 hours; the frequency of pugging treatment is 2-3 times. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and step five, placing the ceramic membrane blank in a hot air drying box at the temperature of 40-45 ℃ for drying for 2-3 h, and then heating to 55-65 ℃ for drying for 8-10 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: and fifthly, heating the muffle furnace from room temperature to 250-300 ℃ at the heating rate of 2-4 ℃/min, roasting at 250-300 ℃ for 1-1.5 h, heating from 250-300 ℃ to 780-820 ℃ at the heating rate of 2-4 ℃/min, heating from 780-820 ℃ to 1100-1150 ℃ at the heating rate of 1 ℃/min, and roasting at 1100-1150 ℃ for 3.5-4.5 h to obtain the low-cost low-density catalytic functional ceramic membrane. The other steps are the same as those in the first to ninth embodiments.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The first embodiment is as follows: a preparation method of a low-cost low-density catalytic functional ceramic membrane is completed according to the following steps:
firstly, preparing high-efficiency catalytic active particles:
(ii) 0.87g of La (NO)3)3·6H2O and 0.87g Ce (NO)3)3·6H2Dissolving O in 100mL of glycol to obtain a mixed solution;
adjusting the pH value of the mixed solution to 7, adding 0.2g of UiO-66, and performing ultrasonic oscillation to obtain a reaction solution;
the power of ultrasonic oscillation in the first step is 180W, and the time of ultrasonic oscillation is 30 min;
thirdly, placing the reaction liquid in a reaction kettle, heating the reaction kettle to 200 ℃ at the heating rate of 3 ℃/min, and reacting for 10 hours at the temperature of 200 ℃ to obtain a reaction product;
fourthly, grinding the reaction product by using a ball mill, and then sieving to obtain high-efficiency catalytic active particles;
the particle size of the high-efficiency catalytic active particles in the first step is less than 300 meshes;
secondly, preparing ceramic membrane raw materials:
adding ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol into a mixer, and uniformly mixing for 30min at the rotating speed of 60r/min to obtain a mixture;
the mass ratio of the ceramic membrane raw material powder, the high-efficiency catalytic active particles, the binder, the pore-forming agent, the water and the glycerol in the mixture in the step two is 90:15:10:10:80: 5;
the ceramic membrane raw material powder in the mixture in the step two is diatomite and Al2O3Mixture of powders of diatomaceous earth and Al2O3The mass ratio of the powder is 1: 1;
the particle size of the diatomite in the step two is 120 meshes, and Al is2O3The particle size of the powder is 500 meshes;
the binder in the second step is hydroxypropyl methyl cellulose;
the pore-forming agent in the second step is starch;
standing and ageing the mixture for 48 hours, and pugging for 3 times by using a vacuum pug mill to obtain mixed pug;
fourthly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
fifthly, firstly placing the ceramic membrane blank in a hot air drying box with the temperature of 40 ℃ for drying for 2h, then heating to 60 ℃ for drying for 10h, then placing in a muffle furnace, heating the muffle furnace from room temperature to 300 ℃ at the heating rate of 4 ℃/min, then roasting at 300 ℃ for 1h, then heating from 300 ℃ to 800 ℃ at the heating rate of 2 ℃/min, then heating from 800 ℃ to 1150 ℃ at the heating rate of 1 ℃/min, and then roasting at 1150 ℃ for 4h to obtain the low-cost low-density catalytic functional ceramic membrane.
Fig. 1 is an SEM image of a low-cost low-density catalytic functional ceramic membrane prepared in example one.
As can be seen from fig. 1, the low-cost low-density catalytic functional ceramic membrane substrate prepared in the first embodiment has a large number of micropores, which are caused by the natural special porous structure of the diatomite, in addition to the pores generated by the stacking of the pore-forming agent and the powder. The porous structure increases the specific surface area and porosity of the ceramic membrane material added with the diatomite, and has better adsorption and load performance and excellent strength and density.
Comparative example one: al (Al)2O3The ceramic membrane is prepared by the following steps:
firstly, mixing Al2O3Adding the powder, the binder, the pore-forming agent, water and glycerol into a mixer, and uniformly mixing for 30min at the rotating speed of 60r/min to obtain a mixture;
al in the mixture in the step one2O3The mass ratio of the powder to the binder to the pore-forming agent to the water to the glycerol is 90:10:10:80: 5;
the binder in the first step is hydroxypropyl methyl cellulose;
the pore-forming agent in the first step is starch;
al described in step one2O3The particle size of the powder is 500 meshes;
standing and ageing the mixture for 48 hours, and pugging for 3 times by using a vacuum pug mill to obtain mixed pug;
thirdly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
fourthly, firstly, the ceramic membrane blank is put into hot air with the temperature of 40 DEG CDrying in a drying oven for 2h, heating to 60 deg.C, drying for 10h, placing in a muffle furnace, heating from room temperature to 300 deg.C at a heating rate of 4 deg.C/min, calcining at 300 deg.C for 1h, heating from 300 deg.C to 800 deg.C at a heating rate of 2 deg.C/min, heating from 800 deg.C to 1300 deg.C at a heating rate of 1 deg.C/min, and calcining at 1300 deg.C for 4h to obtain Al2O3A ceramic membrane.
FIG. 2 shows Al prepared in comparative example one2O3SEM image of ceramic membrane.
As can be seen from FIG. 2, Al2O3Powder particles in the ceramic membrane are bonded and accumulated to generate a porous structure, the porosity of the porous material is low, meanwhile, the surface of coarse particles is smooth, and the loading capacity of catalyst particles is poor.
Comparative example two: catalyst-supporting Al2O3The ceramic membrane is prepared by the following steps:
firstly, preparing high-efficiency catalytic active particles:
(ii) 0.87g of La (NO)3)3·6H2O and 0.87g Ce (NO)3)3·6H2Dissolving O in 100mL of glycol to obtain a mixed solution;
adjusting the pH value of the mixed solution to 7, adding 0.2g of UiO-66, and performing ultrasonic oscillation to obtain a reaction solution;
the power of ultrasonic oscillation in the first step is 180W, and the time of ultrasonic oscillation is 30 min;
thirdly, placing the reaction liquid in a reaction kettle, heating the reaction kettle to 200 ℃ at the heating rate of 3 ℃/min, and reacting for 10 hours at the temperature of 200 ℃ to obtain a reaction product;
fourthly, grinding the reaction product by using a ball mill, and then sieving to obtain high-efficiency catalytic active particles;
the particle size of the high-efficiency catalytic active particles in the first step is less than 300 meshes;
secondly, preparing ceramic membrane raw materials:
mixing Al2O3Powder, high-efficiency catalytic active particles, binder, pore-forming agent, water and sweetAdding the oil into a mixer, and uniformly mixing for 30min at the rotating speed of 60r/min to obtain a mixture;
al in the mixture in the second step2O3The mass ratio of the powder to the high-efficiency catalytic active particles to the binder to the pore-forming agent to the water to the glycerol is 90:15:10:10:80: 5;
the binder in the second step is hydroxypropyl methyl cellulose;
the pore-forming agent in the second step is starch;
al described in step two2O3The particle size of the powder is 500 meshes;
standing and ageing the mixture for 48 hours, and pugging for 3 times by using a vacuum pug mill to obtain mixed pug;
fourthly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
fifthly, firstly placing the ceramic membrane blank in a hot air drying box with the temperature of 40 ℃ for drying for 2h, then heating to 60 ℃ for drying for 10h, then placing in a muffle furnace, heating the muffle furnace from room temperature to 300 ℃ at the heating rate of 4 ℃/min, then roasting at 300 ℃ for 1h, then heating from 300 ℃ to 800 ℃ at the heating rate of 2 ℃/min, then heating from 800 ℃ to 1150 ℃ at the heating rate of 1 ℃/min, and then roasting at 1150 ℃ for 4h to obtain the catalyst-loaded Al2O3A ceramic membrane.
The low-cost low-density catalytic functional ceramic membrane prepared in the first embodiment and the Al prepared in the first comparative embodiment2O3Ceramic membranes and catalyst-loaded Al prepared in comparative example two2O3The density, porosity and pore size of the ceramic films are listed in table 1;
TABLE 1
Figure BDA0002738452630000091
Low-cost low-density catalytic functional ceramic membrane prepared in example one and Al prepared in comparative example one are used respectively2O3Ceramic membranes and Supported catalysts prepared in comparative example IIAl of the agent2O3The ceramic membrane is used for treating raw sewage, and the treatment result is shown in table 2;
the sewage raw water: the source is bathing water wastewater in the Weihai school district of Harbin Industrial university; cutting the prepared ceramic membrane into membranes with the sizes of 45mm multiplied by 5mm multiplied by 200mm, wherein through holes in the membrane are square holes with the sizes of 2mm multiplied by 2 mm; the sewage is encapsulated by epoxy resin and treated by a device shown in figure 3. Chemical Oxygen Demand (COD), ammonia nitrogen, total phosphorus and turbidity of water before and after treatment are measured by adopting a 5B-3B (V8) type intelligent multi-parameter measuring instrument produced by the continuous Hua technology, and the data are shown in Table 2;
TABLE 2
Figure BDA0002738452630000092
Figure BDA0002738452630000101
The low-cost low-density catalytic functional ceramic membrane prepared in the first embodiment is immersed in water for 240 hours, and the metal in the water is tested, so that the result shows that the water does not contain heavy metal, and the combination strength of the carrier loaded high-efficiency catalytic active particles is high.
The low-cost low-density catalytic functional ceramic membrane prepared in the first embodiment can be reused, and the turbidity removal rate of the second time sewage treatment by using the low-cost low-density catalytic functional ceramic membrane prepared in the first embodiment is more than 99%, the Chemical Oxygen Demand (COD) removal rate is more than 95%, the ammonia nitrogen removal rate is more than 99%, and the total phosphorus removal rate is more than 92%; after the continuous operation for 48 hours, the turbidity removal rate can still reach more than 97 percent through tests, the Chemical Oxygen Demand (COD) removal rate is more than 90 percent, the ammonia nitrogen removal rate is more than 95 percent, and the total phosphorus removal rate is more than 90 percent.
In conclusion, the invention has the advantages that part of alumina in the conventional alumina ceramic membrane is replaced by cheap and easily-obtained diatomite without adding MgO and TiO2CaO, etc., which can be sintered at 1150 deg.C, andcompared with the alumina ceramic membrane, the raw material cost and the production cost can be saved by more than 30 percent, and the prepared ceramic membrane has small density and high porosity, and the density is only Al2O3About 65 percent of the ceramic membrane, the porosity is improved by more than 10 percent, the water permeability is excellent, the rejection rate is high, the sintering temperature is low, the time is short, active catalyst particles are loaded, the advanced oxidation reaction can be carried out on the membrane layer, and pollutants can be effectively degraded. Due to the fact that the diatomite is added to serve as a ceramic membrane aggregate component, the diatomite has a microporous structure which can well support the catalyst, and no heavy metal is leached out after long-time testing. Tests show that the membrane has turbidity removal rate of over 99 percent, Chemical Oxygen Demand (COD) removal rate of over 95 percent, ammonia nitrogen removal rate of over 99 percent and total phosphorus removal rate of over 92 percent, and under the condition of the same catalyst particle addition and oxidant dosage, each index is only Al compared with aggregate2O3The performance of the ceramic membrane is improved by 15 percent.

Claims (10)

1. A preparation method of a low-cost low-density catalytic functional ceramic membrane is characterized in that the preparation method of the low-cost low-density catalytic functional ceramic membrane is completed according to the following steps:
firstly, preparing high-efficiency catalytic active particles:
taking a metal organic framework compound as a carrier, fixing transition metal particles in the carrier by a solvothermal method, and grinding and sieving by using a ball mill to obtain high-efficiency catalytic active particles;
secondly, preparing ceramic membrane raw materials:
adding ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol into a mixer, and mixing to obtain a mixture;
in the second step, the mass ratio of ceramic membrane raw material powder, high-efficiency catalytic active particles, a binder, a pore-forming agent, water and glycerol in the mixture is (85-90): 10-15): 75-85): 3-8;
the ceramic membrane raw material powder in the mixture in the step two is diatomite and Al2O3Mixture of powders of diatomaceous earth and Al2O3The mass ratio of the powder is (25-30) to (70-75);
standing and ageing the mixture, and pugging the mixture by a vacuum pug mill to obtain mixed pug;
fourthly, forming the mixed pug into a flat membrane by using a ceramic tube extruding machine to obtain a ceramic membrane blank;
and fifthly, placing the ceramic membrane blank in a hot air drying box for drying, and then placing in a muffle furnace for gradient temperature rise sintering to obtain the low-cost low-density catalytic functional ceramic membrane.
2. The method according to claim 1, wherein the metal organic framework compound in step one is UiO-66 or NH2-UiO-66。
3. The method according to claim 1, wherein the transition metal particles in step one are La (NO)3)3、Ce(NO3)3、Cu(NO3)2、Fe(NO3)3、Cr(NO3)3And Co (NO)3)2One or a mixture of several of them.
4. The preparation method of a low-cost low-density catalytic functional ceramic membrane according to claim 1, wherein in the step one, a metal organic framework compound is used as a carrier, transition metal particles are fixed in the carrier by a solvothermal method, and then are ground and sieved by a ball mill to obtain high-efficiency catalytic active particles; the method comprises the following steps:
dissolving transition metal particles into ethylene glycol to obtain a mixed solution;
the concentration of the transition metal particles in the step I is 1 mmol/L-10 mmol/L;
the transition metal particles in the step (I) are La (NO)3)3、Ce(NO3)3、Cu(NO3)2、Fe(NO3)3、Cr(NO3)3And Co (NO)3)2One or a mixture of several of them;
adjusting the pH value of the mixed solution to 7-8, adding a metal organic framework compound, and performing ultrasonic oscillation to obtain a reaction solution;
the concentration of the metal-organic framework compound in the reaction solution is 1 g/L-5 g/L;
the power of the ultrasonic oscillation in the second step is 180W-200W, and the time of the ultrasonic oscillation is 20 min-40 min;
thirdly, placing the reaction liquid into a reaction kettle, heating the reaction kettle to 180-200 ℃ at the heating rate of 3-5 ℃/min, and reacting for 8-10 h at the temperature of 180-200 ℃ to obtain a reaction product;
fourthly, grinding the reaction product by using a ball mill, and then sieving to obtain high-efficiency catalytic active particles;
the particle size of the high-efficiency catalytic active particles in the step (iv) is less than 300 meshes.
5. The method according to claim 1, wherein the diatomaceous earth in step two has a particle size of 120 mesh and Al2O3The particle size of the powder was 500 mesh.
6. The method according to claim 1, wherein the binder in step two is hydroxypropyl methylcellulose; and the pore-forming agent in the second step is graphite powder or starch.
7. The method according to claim 1, wherein in the second step, the ceramic membrane raw material powder, the high efficiency catalytic active particles, the binder, the pore-forming agent, water and glycerol are mixed in a mixer at a rotation speed of 40 r/min-60 r/min for 20 min-40 min.
8. The method for preparing a low-cost low-density catalytic functional ceramic membrane according to claim 1, wherein the standing and aging time in step three is 40-48 hours; the frequency of pugging treatment is 2-3 times.
9. The method for preparing a low-cost low-density catalytic functional ceramic membrane according to claim 1, wherein in the step five, the ceramic membrane blank is dried in a hot air drying oven at a temperature of 40-45 ℃ for 2-3 h, and then heated to 55-65 ℃ for 8-10 h.
10. The preparation method of a low-cost low-density catalytic functional ceramic membrane according to claim 1, wherein in the fifth step, the muffle furnace is heated from room temperature to 250-300 ℃ at a heating rate of 2-4 ℃/min, then the ceramic membrane is roasted at 250-300 ℃ for 1-1.5 h, then the temperature is increased from 250-300 ℃ to 780-820 ℃ at a heating rate of 2-4 ℃/min, then the temperature is increased from 780-820 ℃ to 1100-1150 ℃ at a heating rate of 1 ℃/min, and then the ceramic membrane is roasted at 1100-1150 ℃ for 3.5-4.5 h, so as to obtain the low-cost low-density catalytic functional ceramic membrane.
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