CN114956784A - Ceramic membrane and preparation method thereof - Google Patents

Ceramic membrane and preparation method thereof Download PDF

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CN114956784A
CN114956784A CN202210523672.5A CN202210523672A CN114956784A CN 114956784 A CN114956784 A CN 114956784A CN 202210523672 A CN202210523672 A CN 202210523672A CN 114956784 A CN114956784 A CN 114956784A
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ceramic membrane
bottom slag
polyvinyl alcohol
household garbage
sintering
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CN114956784B (en
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唐圆圆
刘越
吕中
徐喆
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/135—Combustion residues, e.g. fly ash, incineration waste
    • C04B33/1355—Incineration residues
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/1305—Organic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/131—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C04B33/1328—Waste materials; Refuse; Residues without additional clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/24—Manufacture of porcelain or white ware
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Environmental & Geological Engineering (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention discloses a ceramic membrane and a preparation method thereof, wherein the preparation method of the ceramic membrane comprises the following steps: mixing: burning the bottom slag and Al of the domestic garbage 2 O 3 Mixing and grinding an organic solvent, a binder, and a pore former to form a mixture; pressing: pressing the mixture into flakes; and (3) sintering: sintering the thin sheet at 900-1050 ℃ to obtain the ceramic membrane. The preparation method of the ceramic membrane is to burn the bottom slag and Al in life 2 O 3 As a raw material, the preparation cost of the ceramic membrane is low, and experiments show that when the molar weight ratio of silicon to aluminum in the mixture is 2:1, the proportion of the bottom slag of the household incineration waste in the whole mass of the ceramic membrane can reach 81%, and the utilization rate of the bottom slag of the household incineration waste is higherHigh in efficiency, can effectively solve the problem of recycling the bottom slag of the household garbage incineration and greatly reduces the production cost of the ceramic membrane.

Description

Ceramic membrane and method for producing same
Technical Field
The invention relates to the technical field of ceramic membrane preparation, in particular to a ceramic membrane and a preparation method thereof.
Background
The ceramic membrane has excellent coagulation, precipitation and interception capabilities, has the advantages of easiness in cleaning, stable performance, high mechanical strength, acid and alkali corrosion resistance, strong heat resistance and the like, and is widely applied to food and beverage industries and industrial filtration.
In the related art, pure chemical or industrial reagents are used as raw materials for preparing the ceramic membrane, but the pure substances have high cost and low sintering activity, and generally the sintering temperature is required to be more than 1500 ℃, so that the ceramic membrane is high in preparation energy consumption and production cost.
Disclosure of Invention
The embodiment of the invention discloses a ceramic membrane and a preparation method thereof.
In order to achieve the above object, in a first aspect, an embodiment of the present invention discloses a method for preparing a ceramic film, including the following steps:
mixing: burning the bottom slag and Al of the domestic garbage 2 O 3 Mixing and grinding an organic solvent, a binder, and a pore former to form a mixture;
pressing: pressing the mixture into flakes;
and (3) sintering: and sintering the thin sheet at 900-1050 ℃ to obtain the ceramic membrane.
According to the preparation method of the ceramic membrane provided by the embodiment of the invention, the household garbage is burnt to obtain the bottom slag and Al 2 O 3 The organic solvent, the adhesive and the pore-forming agent are mixed and ground, and are pressed to form a sheet so as to be convenient for sintering, in the sintering process at the temperature of 900-1050 ℃, the organic solvent, the adhesive and the pore-forming agent are decomposed to generate gas, so that dense holes are generated on the surface and inside of the sintered ceramic membrane, ions can be intercepted on the surface of the ceramic membrane when the ceramic membrane is applied to wastewater filtration, and meanwhile, the ceramic membrane can intercept ions on the surface of the ceramic membrane because of the fact that the ceramic membrane is pressed to form the sheet so as to be convenient for sinteringThe ceramic membrane has a certain adsorption effect on metal ions under the action of surface charges, and the interception effect on the metal ions is further improved. Because the bottom slag of the household garbage incineration is used as the raw material, the preparation cost of the ceramic membrane is low. In addition, compared with the method of preparing the ceramic membrane by using pure substances (the pure substances can comprise alumina and silicon oxide) as raw materials and using the household garbage incineration bottom slag as the raw materials, the sintering temperature is lower, the ceramic membrane can be sintered at the temperature below 1050 ℃ to form the ceramic membrane, and the energy conservation in the process of preparing the ceramic membrane is realized.
Since the general incineration bottom slag contains more silicon and less aluminum, if the aluminum content is less, the pore diameter of the prepared ceramic membrane is too small, and the filtering efficiency of the ceramic membrane is low, in this embodiment, Al is added 2 O 3 The content of silicon and aluminum is balanced, so that the prepared ceramic membrane has better and proper aperture and higher filtering efficiency.
As an alternative embodiment, in the embodiment of the first aspect of the present invention, before the step of mixing, the preparation method further comprises the steps of:
and (3) component analysis: analyzing the components of the household garbage incineration bottom slag to obtain the molar weight of silicon and aluminum in the household garbage incineration bottom slag;
weighing Al 2 O 3 : weighing Al 2 O 3 So that the molar weight of silicon in the bottom slag of the household garbage incineration and the Al 2 O 3 The ratio of the sum of the molar weight of the medium aluminum is 1: 1-3: 1.
The molar weight of silicon and aluminum in the household garbage incineration bottom slag is obtained by analyzing the components of the household garbage incineration bottom slag, so that the added Al can be obtained by calculation 2 O 3 Such that the ratio of the molar amount of silicon to the sum of the molar amounts of aluminum is 1:1 to 3: 1. The ratio of the molar weight of silicon to the molar weight of aluminum is controlled to be 1: 1-3: 1, and the ratio of silicon to aluminum is controlled to be in a reasonable range, so that the prepared ceramic membrane can have a proper pore diameter. When the ratio of the molar amount of silicon to the sum of the molar amounts of aluminumWhen the ratio is less than 1:1, namely the molar quantity of silicon is too small and the molar quantity of aluminum is too large, the prepared ceramic membrane has small aperture, small pure water flux and low filtration efficiency. When the ratio of the sum of the molar weight of silicon and the molar weight of aluminum is more than 3:1, namely the molar weight of silicon is too large and the molar weight of aluminum is too small, the prepared ceramic membrane has too large pore diameter, can not effectively intercept some ions and has poor filtering effect.
As an alternative embodiment, in the embodiment of the first aspect of the present invention, before the step of mixing, the preparation method further comprises the steps of:
grinding: and grinding the household garbage incineration bottom slag until the particle size of the particles of the household garbage incineration bottom slag is smaller than 325 meshes.
The household garbage incineration bottom slag is ground until the particle size of particles of the household garbage incineration bottom slag is smaller than 325 meshes, so that the household garbage incineration bottom slag particles are fine and can be uniformly mixed with other components in the mixing step, and the structural uniformity of the sintered ceramic membrane is improved.
As an alternative embodiment, in the embodiment of the first aspect of the present invention, the Al 2 O 3 Is gamma-Al 2 O 3 The method also comprises the following steps before the mixing step:
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 600 ℃ to 650 ℃ to form gamma-Al 2 O 3 。
Due to gamma-Al 2 O 3 Has the advantages of porosity, large surface area, good adsorption performance, good thermal stability and the like, thus utilizing the gamma-Al 2 O 3 The prepared ceramic membrane also has the advantages of porosity and better filtering performance.
As an alternative embodiment, in an embodiment of the first aspect of the present invention, the organic solvent comprises at least one of methanol, ethanol, formaldehyde, acetaldehyde; alternatively, the first and second electrodes may be,
the adhesive comprises at least one of a polyvinyl alcohol solution, a carboxymethyl cellulose solution and a polyethylene glycol solution; alternatively, the first and second electrodes may be,
the pore-forming agent is calcium carbonate.
The organic solvent can improve the dissolution of each component, the adhesive effect is realized through the adhesive, and the pore-forming agent enables the prepared ceramic membrane to have porosity so as to realize the filtering effect.
As an alternative implementation, in the embodiment of the first aspect of the present invention, when the adhesive includes a polyvinyl alcohol solution, the mixing step further includes:
preparing a polyvinyl alcohol solution: adding deionized water into polyvinyl alcohol particles, and stirring at 80-100 ℃ until the polyvinyl alcohol particles are dissolved to prepare a polyvinyl alcohol solution, wherein the polyvinyl alcohol solution contains 5-10 wt% of polyvinyl alcohol.
The polyvinyl alcohol particles are dissolved at 80-100 ℃ to form a polyvinyl alcohol solution, and the polyvinyl alcohol solution can be ensured to have proper viscosity by limiting the mass percentage of polyvinyl alcohol in the polyvinyl alcohol solution to 5-10 wt%.
As an alternative embodiment, in the embodiment of the first aspect of the present invention, the mass of the polyvinyl alcohol solution is greater than that of the bottom slag from incineration of domestic garbage and the Al 2 O 3 10 wt% of the sum of the masses.
By limiting the mass of the polyvinyl alcohol solution to be larger than that of the bottom slag and Al in the incineration of the household garbage 2 O 3 The amount of the polyvinyl alcohol is 10 wt% of the total mass of the polyvinyl alcohol and the polyvinyl alcohol solution, and the adhesive effect of the polyvinyl alcohol solution can be fully realized. Illustratively, the quality of the polyvinyl alcohol solution is household garbage incineration bottom slag and Al 2 O 3 10 wt%, 20 wt%, 30 wt% of the sum of the masses of (A), (B), (C), and the like.
As an alternative embodiment, in an embodiment of the first aspect of the present invention, before the step of compressing, the preparation method comprises the steps of:
and (3) drying: drying the mixture at 60-70 ℃.
The mixture is dried at a lower temperature before the pressing step, so that the organic solvent in the mixture can be removed, and the phenomenon that the organic solvent is evaporated too fast to influence the forming of the ceramic membrane and the aperture of the ceramic membrane is avoided during sintering.
As an alternative embodiment, in the embodiment of the first aspect of the present invention, in the step of pressing, the pressure of the pressing is 20MPa to 30MPa, and the pressure holding time is 1min to 3 min. By controlling the pressing pressure to be 20 MPa-30 MPa, the pressed thin sheet can be ensured not to crack. When the pressure is more than 30MPa, the pressure is too high, which easily causes the sheet to crack, and when the pressure is less than 20MPa, the pressure is too low, which makes the press molding difficult. By controlling the pressure maintaining time to be 1-3 min, the pressed sheet can be ensured not to crack.
In a second aspect, the present invention also discloses a ceramic film prepared by the method of the first aspect. The ceramic membrane has low cost and excellent filtering effect.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the ceramic membrane and the preparation method thereof provided by the embodiment, the domestic garbage is burnt to obtain the bottom slag and Al 2 O 3 The organic solvent, the adhesive and the pore-forming agent are mixed and ground, and are pressed to form a sheet, so that the sheet is convenient to sinter, the organic solvent, the adhesive and the pore-forming agent are decomposed to generate gas in the sintering process at the temperature of 900-1050 ℃, dense holes are generated on the surface and inside of the sintered ceramic membrane, ions can be intercepted on the surface of the ceramic membrane when the ceramic membrane is applied to wastewater filtration, and meanwhile, the ceramic membrane has a certain adsorption effect on metal ions due to the effect of surface charges of the ceramic membrane, so that the interception effect on the metal ions is further improved. Because the bottom slag of the household garbage incineration is used as the raw material, the preparation cost of the ceramic membrane is low. In addition, compared with the method of preparing the ceramic membrane by using pure substances (the pure substances can comprise alumina and silicon oxide) as raw materials and using the household garbage incineration bottom slag as the raw materials, the sintering temperature is lower, the ceramic membrane can be sintered at the temperature below 1050 ℃ to form the ceramic membrane, and the energy conservation in the process of preparing the ceramic membrane is realized.
Because the life burns the bottom slagGenerally, the content of silicon is high, the content of aluminum is low, and if the content of aluminum is low, the pore diameter of the prepared ceramic membrane is too small, and the filtering efficiency of the ceramic membrane is low 2 O 3 The content of silicon and aluminum is balanced, so that the prepared ceramic membrane has better and proper pore diameter and higher filtering efficiency.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a scanning electron microscope image of a ceramic film according to one embodiment of the present invention;
FIG. 2 is a scanning electron micrograph of a ceramic film according to the second embodiment;
FIG. 3 is a graph showing the separation effect of the ceramic membrane provided in the second embodiment on metal ions in a single metal component solution;
FIG. 4 is a graph showing the separation effect of the ceramic membrane provided in the second embodiment on metal ions in the mixed metal component solution;
FIG. 5 shows the permeation flux and the pair Cr of the ceramic membrane provided in the second embodiment in six-cycle filtration 3+ The separation effect map of (1);
FIG. 6 is a scanning electron micrograph of a ceramic film according to the third embodiment;
FIG. 7 is a scanning electron micrograph of a ceramic film according to the fourth embodiment;
FIG. 8 is a scanning electron micrograph of a ceramic film according to the first comparative example;
FIG. 9 is a graph showing Cr pairs of ceramic films provided in examples one to four and comparative example one 3+ A separation result graph;
FIG. 10 is a Cu-pair ceramic film for the ceramic films provided in the first to fourth examples and the first comparative example 2+ A separation result graph;
fig. 11 is a graph showing a comparison of pure water flux of the ceramic membranes of the second embodiment and the first comparative example.
Detailed Description
In the present invention, the terms "upper", "lower", "left", "right", "front", "rear", "top", "bottom", "inner", "outer", "center", "vertical", "horizontal", "lateral", "longitudinal", and the like indicate an orientation or positional relationship based on the orientation or positional relationship shown in the drawings. These terms are used primarily to better describe the invention and its embodiments and are not intended to limit the indicated devices, elements or components to a particular orientation or to be constructed and operated in a particular orientation.
Moreover, some of the above terms may be used to indicate other meanings besides the orientation or positional relationship, for example, the term "on" may also be used to indicate some kind of attachment or connection relationship in some cases. The specific meanings of these terms in the present invention can be understood according to specific situations by those of ordinary skill in the art.
Furthermore, the terms "mounted," "disposed," "provided," "connected," and "connected" are to be construed broadly. For example, it may be a fixed connection, a removable connection, or a unitary construction; can be a mechanical connection, or an electrical connection; may be directly connected, or indirectly connected through intervening media, or may be in internal communication between two devices, elements or components. The specific meanings of the above terms in the present invention can be understood by those of ordinary skill in the art according to specific situations.
Furthermore, the terms "first," "second," and the like, are used primarily to distinguish one device, element, or component from another (the specific nature and configuration may be the same or different), and are not used to indicate or imply the relative importance or number of the indicated devices, elements, or components. "plurality" means two or more unless otherwise specified.
The rapid industrialization and urbanization of today, as well as certain illegal discharges, lead to the discharge of waste waters containing large amounts of heavy metals (e.g. lead, chromium, nickel, copper, etc.) into the environment, posing a threat to the ecosystem and to human health.
For example, the tanning industry produces about 3X 10 of products each year 8 Ton of Cr-containing 3+ Wastewater of (2), low concentration of Cr 3+ High concentration of Cr causing diabetes or coronary artery disease 3+ Can cause diseases such as weight loss, anemia, renal failure, liver dysfunction, etc. If Cr is present 3+ Is oxidized into Cr 6+ More serious consequences can result.
In the manufacturing industries of batteries, paints, fertilizers, automobile parts and the like, wastewater containing heavy metals such as copper, lead, nickel and the like, especially Cu in large amount is generated 2+ The wastewater of (1), copper is a neurotoxic substance, excessive Cu 2+ Enter fish and aquatic products through the action of biological accumulation, and then can be ingested into human body, if too much Cu is ingested 2+ It may lead to Alzheimer's disease, dyslexia, or nausea. Lead and nickel are highly toxic at very low concentrations. Therefore, there is a need for filtering industrial wastewater to separate heavy metal ions in the wastewater.
In the research of the technology for filtering and separating industrial wastewater, the inventor synthesizes a ceramic membrane by using silicon oxide and aluminum oxide as raw materials to separate heavy metal ions in the industrial wastewater, however, the pure material synthesized ceramic membrane has a very high price and is difficult to satisfy economic benefits at the same time when the industrial wastewater is filtered and separated. The inventor finds that the household garbage is mainly treated by burning, and a large amount of household garbage burning bottom slag is accumulated along with the gradual increase of the burning amount of the household garbage, and the inventor finds that the household garbage burning bottom slag contains a large amount of silicon and aluminum. Therefore, the inventor researches a method for preparing a ceramic membrane by using the bottom slag of the household garbage incineration so as to separate heavy metals in industrial wastewater through the ceramic membrane and realize the consideration of economic benefits and environmental protection.
The embodiment of the invention provides a preparation method of a ceramic membrane, which comprises the following steps:
mixing: burning the bottom slag and Al of the domestic garbage 2 O 3 Mixing and grinding an organic solvent, a binder, and a pore former to form a mixture;
pressing: pressing the mixture into flakes;
and (3) sintering: sintering the thin sheet at 900-1050 ℃ to obtain the ceramic membrane.
According to the preparation method of the ceramic membrane provided by the embodiment of the invention, the bottom slag and Al of the household garbage are incinerated 2 O 3 The organic solvent, the adhesive and the pore-forming agent are mixed and ground, and are pressed to form a thin sheet, so that the thin sheet is convenient to sinter, and in the sintering process at the temperature of 900-1050 ℃, the organic solvent, the adhesive and the pore-forming agent are decomposed to generate gas, so that dense holes are generated on the surface and inside of the sintered ceramic membrane, and ions, especially heavy metal ions, in the waste water can be efficiently filtered when the ceramic membrane is applied to waste water filtration. In addition, when the ceramic membrane filters wastewater, the metal ions generate a bridging effect at the inlet of the pores of the ceramic membrane, so that the metal ions smaller than the pore diameter can be effectively separated, and the separation rate is improved. After a period of filtration, the surface of the ceramic membrane is polluted due to concentration polarization, so that particles are accumulated on the surface of the ceramic membrane, and the separation rate is improved.
Because the main component of the domestic incineration bottom slag is SiO 2 And Al 2 O 3 Silicate and aluminosilicate can be formed after sintering, and cations are needed to neutralize crystals due to the particularity of the crystal structure of the silicate and aluminosilicate, so that ion exchange can be carried out when metal cations are filtered, the crystal structure is stabilized, and the separation rate of heavy metals from the ceramic membrane is improved.
In addition, the surface of the ceramic membrane is electronegative, so that the ceramic membrane has an adsorption effect on metal cations, and meanwhile, solutes in some wastewater are deposited in pores due to electrostatic adsorption, so that the separation rate of metal ions is further improved.
Compared with the method for preparing the ceramic membrane by using pure substances (the pure substances can comprise alumina and silicon oxide) as raw materials and using the household garbage incineration bottom slag as the raw materials, the household garbage incineration bottom slag also comprises a plurality of metal oxides and other substances, so that the household garbage incineration bottom slag is a mixed system of a plurality of components, the sintering temperature is lower, the ceramic membrane can be sintered at the temperature below 1050 ℃, and the energy is saved in the process of preparing the ceramic membrane.
Since the general incineration bottom slag contains more silicon and less aluminum, if the aluminum content is less, the pore diameter of the prepared ceramic membrane is too small, and the filtering efficiency of the ceramic membrane is low, in this embodiment, Al is added 2 O 3 The content of silicon and aluminum is balanced, so that the prepared ceramic membrane has better and proper pore diameter and higher filtering efficiency.
Optionally, before the step of mixing, the preparation method further comprises the steps of:
and (3) component analysis: analyzing the components of the household garbage incineration bottom slag to obtain the molar weight of silicon and aluminum in the household garbage incineration bottom slag;
weighing Al 2 O 3 : weighing Al 2 O 3 So that the molar weight of silicon in the bottom slag of the household garbage incineration, the bottom slag of the household garbage incineration and Al 2 O 3 The ratio of the sum of the molar weight of the medium aluminum is 1: 1-3: 1.
The molar weight of silicon and aluminum in the household garbage incineration bottom slag is obtained by analyzing the components of the household garbage incineration bottom slag, so that the added Al can be obtained by calculation 2 O 3 In such an amount that the ratio of the molar amount of silicon to the molar amount of aluminum is 1:1 to 3: 1. The ratio of the molar weight of silicon to the molar weight of aluminum is controlled to be 1: 1-3: 1, and the ratio of silicon to aluminum is controlled to be in a reasonable range, so that the prepared ceramic membrane can have a proper pore diameter. When the ratio of the molar weight of silicon to the molar weight of aluminum is less than 1:1, namely the molar weight of silicon is too small and the molar weight of aluminum is too large, the pore diameter of the prepared ceramic membrane is small,the pure water flux is small, and the filtration efficiency is low. When the ratio of the molar weight of silicon to the molar weight of aluminum is greater than 3:1, that is, the molar weight of silicon is too large and the molar weight of aluminum is too small, the prepared ceramic membrane has too large pore diameter, can not effectively intercept some ions, and has poor filtering effect. In addition, experiments show that when the molar weight ratio of silicon to aluminum in the mixture is 2:1, the ratio of the bottom slag of the household garbage incineration to the mass of the whole ceramic membrane can reach 81%, the utilization rate of the bottom slag of the household garbage incineration is high, the problem of recycling the bottom slag of the household garbage incineration can be effectively solved, and the production cost of the ceramic membrane is greatly reduced.
Alternatively, the components of the bottom slag from the incineration of the household garbage can be analyzed by using an X-ray fluorescence spectrum, and of course, the components of the bottom slag from the incineration of the household garbage can be analyzed by using other component analysis methods.
The ratio of the molar amount of silicon to the molar amount of aluminum is 1:1 to 3:1 inclusive, and illustratively, the ratio of the molar amount of silicon to the molar amount of aluminum is 1:1, 1:1.5, 1:2, 1:2.5, 1:3, and the like.
Optionally, prior to the step of mixing, the preparation method further comprises the steps of:
grinding: and grinding the domestic garbage incineration bottom slag until the particle size of the domestic garbage incineration bottom slag particles is smaller than 325 meshes.
The household garbage incineration bottom slag is ground until the particle size of household garbage incineration bottom slag particles is smaller than 325 meshes, the particles of the household garbage incineration bottom slag are fine, and the household garbage incineration bottom slag particles can be uniformly mixed with other components in the mixing step, so that the structural uniformity of the sintered ceramic membrane is improved.
Alternatively, Al 2 O 3 Is gamma-Al 2 O 3 The method also comprises the following steps before the mixing step:
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 600 ℃ to 650 ℃ to form gamma-Al 2 O 3 . Due to gamma-Al 2 O 3 Has the advantages of porosity, large surface area, good adsorption performance, good thermal stability and the like, thus utilizing the gamma-Al 2 O 3 The prepared ceramic membrane also has the advantages of porosity and better filtering performance.
In the preparation of gamma-Al 2 O 3 In the step (2), the temperature rising rate of boehmite sintered in a muffle furnace can be 5-10 ℃/min, and the sintering time can be 2-3 h. It should be noted that the temperature rising rate of boehmite sintering in the muffle furnace is 5 ℃/min to 10 ℃/min, including any point value in the temperature rising rate range, for example, the temperature rising rate may be 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, etc., and the sintering time is 2h to 3h including any point value in the time range, for example, the sintering time is 2h, 2.5h, 3h, etc.
Optionally, the organic solvent comprises at least one of methanol, ethanol, formaldehyde, acetaldehyde; or the adhesive comprises at least one of a polyvinyl alcohol solution, a carboxymethyl cellulose solution and a polyethylene glycol solution; alternatively, the pore former is calcium carbonate. The organic solvent can improve the dissolution of each component, the adhesive effect is realized through the adhesive, and the pore-forming agent enables the prepared ceramic membrane to have porosity so as to realize the filtering effect. When calcium carbonate is used as a pore-forming agent, the calcium carbonate and SiO in the bottom slag of the incineration of the household garbage 2 And Al 2 O 3 A chemical reaction occurs, the reaction formula is as follows:
2CaCO 3 +Al 2 O 3 +SiO 2 →Ca 2 Al 2 O 7 +2CO 2
wherein, calcium in the calcium carbonate can play a grafting role, and compared with the method of adopting starch as a pore-forming agent, the prepared ceramic membrane is not easy to crack and has better forming effect. Furthermore, CaCO 3 、Al 2 O 3 、SiO 2 CO is produced when a chemical reaction occurs 2 Gas, thereby making the ceramic membrane have porosity to form better filtering effect. Optionally, when the adhesive comprises a polyvinyl alcohol solution, the mixing step further comprises:
preparing a polyvinyl alcohol solution: adding deionized water into the polyvinyl alcohol particles, and stirring at 80-100 ℃ until the polyvinyl alcohol particles are dissolved to prepare a polyvinyl alcohol solution, wherein the polyvinyl alcohol solution contains 5-10 wt% of polyvinyl alcohol.
The polyvinyl alcohol particles are dissolved at 80-100 ℃ to form a polyvinyl alcohol solution, and the polyvinyl alcohol solution can be ensured to have proper viscosity by limiting the mass percentage of polyvinyl alcohol in the polyvinyl alcohol solution to 5-10 wt%.
The dissolution temperature of the polyvinyl alcohol particles may be any value from 80 ℃ to 100 ℃, for example, the dissolution temperature of the polyvinyl alcohol particles is 80 ℃, 90 ℃, 100 ℃, etc., and the mass percentage of the polyvinyl alcohol in the polyvinyl alcohol solution is 5 wt% to 10 wt%, including any value within the range, for example, the mass percentage of the polyvinyl alcohol in the polyvinyl alcohol solution is 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, etc.
Optionally, the mass of the polyvinyl alcohol solution is larger than that of the bottom slag and Al generated by burning the household garbage 2 O 3 10 wt% of the sum of the masses. By limiting the mass of the polyvinyl alcohol solution to be larger than that of the bottom slag and Al in the incineration of the household garbage 2 O 3 The amount of the polyvinyl alcohol is 10 wt% of the total mass of the polyvinyl alcohol and the polyvinyl alcohol solution, and the adhesive effect of the polyvinyl alcohol solution can be fully realized. Illustratively, the quality of the polyvinyl alcohol solution is household garbage incineration bottom slag and Al 2 O 3 10 wt%, 20 wt%, 30 wt% of the sum of the masses of (A), (B), (C), and the like.
Optionally, before the step of pressing, the preparation method comprises the steps of:
and (3) drying: the mixture is dried at 60-70 ℃.
The mixture is dried at a lower temperature before the pressing step, so that the organic solvent in the mixture can be removed, and the phenomenon that the organic solvent is evaporated too fast to influence the forming of the ceramic membrane and the aperture of the ceramic membrane is avoided during sintering.
Note that the drying of the mixture at 60 to 70 ℃ includes any point within the drying temperature, and the drying temperature is, for example, 60 ℃, 65 ℃, 70 ℃, or the like.
Optionally, in the step of pressing, the pressure of pressing is 20MPa to 30MPa, and the pressure maintaining time is 1min to 3 min. The pressure of pressing is controlled to be 20 MPa-30 MPa, so that the pressed sheet can be ensured not to crack. When the pressure is more than 30MPa, the pressure is too high, which easily causes the sheet to crack, and when the pressure is less than 20MPa, the pressure is too low, which makes the press molding difficult. By controlling the pressure maintaining time to be 1-3 min, the pressed sheet can be ensured not to crack.
Note that the pressing pressure is 20MPa to 30MPa inclusive of any point value in the pressure range, and exemplarily, the pressing pressure is 20MPa, 23MPa, 25MPa, 28MPa, 30MPa, or the like. The time for holding the pressure for 1min to 3min includes any point value within the time range, and exemplarily, the time for holding the pressure is 1min, 2min, 3min, or the like.
Optionally, the step of sintering comprises:
and (3) putting the slices into a muffle furnace, and sintering at 900-1050 ℃ for 2-4 h at a heating rate of less than 10 ℃/min to obtain the ceramic membrane. By controlling the sintering at the heating rate of less than 10 ℃/min, the ceramic film can be prevented from cracking due to the excessively high heating rate. By controlling the sintering time to be 2-4 h, the organic solvent, the adhesive and the pore-forming agent can be fully volatilized, so that the ceramic membrane has uniform and dense pores, the filtering performance is improved, and meanwhile, the forming effect of the ceramic membrane can be ensured. When the sintering time is longer than 4 hours, the ceramic film is easy to crack due to overlong sintering time, and when the sintering time is shorter than 2 hours, the ceramic film forming effect is poor.
The sintering time 2h to 4h includes any value in the time range, for example, the sintering time is 2h, 3h, 4h, and the like.
The embodiment of the invention also discloses a ceramic membrane which is prepared by the preparation method of the ceramic membrane. The ceramic membrane has low cost and excellent filtering effect.
The technical solution of the present invention will be further described with reference to the following embodiments and the accompanying drawings.
Example one
The embodiment of the invention discloses a preparation method of a ceramic membrane, which comprises the following steps:
grinding: crushing the household garbage incineration bottom slag by a crusher and grinding the household garbage incineration bottom slag by a planetary grinder, and screening the household garbage incineration bottom slag by using a 325-mesh filter screen to obtain uniform and fine household garbage incineration bottom slag particles.
And (3) component analysis: carrying out X-ray fluorescence spectrum analysis on the domestic waste incineration bottom slag to obtain the molar weight of silicon and aluminum in the domestic waste incineration bottom slag;
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 650 ℃ for 3h at a sintering rate of 5 ℃/min to obtain gamma-Al 2 O 3 。
Weighing gamma-Al 2 O 3 : weighing a certain amount of gamma-Al 2 O 3 So that the molar quantity of the silicon of the bottom slag from the incineration of the household garbage, the bottom slag from the incineration of the household garbage and gamma-Al 2 O 3 The ratio of the sum of the molar amounts of aluminum in (a) is 2: 1.
Preparing a polyvinyl alcohol solution: adding 5g of 1788 type polyvinyl alcohol particles into 95g of deionized water, and magnetically stirring for 1h at 80 ℃ to obtain a polyvinyl alcohol solution with the mass percent of 5 wt%.
Mixing: the ground household garbage incineration bottom slag and gamma-Al are mixed 2 O 3 Adding into a mortar, adding absolute ethyl alcohol, 5 wt% polyvinyl alcohol solution and calcium carbonate, grinding and mixing uniformly to obtain a mixture. Wherein the added polyvinyl alcohol solution with the weight percent of 5 percent is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 The added calcium carbonate accounts for 10 wt% of the total mass of the slag, and the mass of the added calcium carbonate is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 10 wt% of the sum of the masses.
And (3) drying: drying the mixture at 60-70 deg.c.
Pressing: the dried mixture was subjected to tableting in an electric tableting machine using a die having a diameter of 22mm under a pressure of 20MPa for 1min to obtain a sheet.
And (3) sintering: and sintering the thin sheet in a muffle furnace at the temperature rise rate of 5 ℃/min for 3h at 900 ℃ to obtain the ceramic membrane.
As shown in fig. 1, this example also discloses a ceramic film prepared by the above method.
Example two
The embodiment of the invention discloses a preparation method of a ceramic membrane, which comprises the following steps:
grinding: crushing the household garbage incineration bottom slag by a crusher and grinding the household garbage incineration bottom slag by a planetary grinder, and screening the household garbage incineration bottom slag by using a 325-mesh filter screen to obtain uniform and fine household garbage incineration bottom slag particles.
And (3) component analysis: carrying out X-ray fluorescence spectrum analysis on the domestic waste incineration bottom slag to obtain the molar weight of silicon and aluminum in the domestic waste incineration bottom slag;
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 650 ℃ for 3h at a sintering rate of 5 ℃/min to obtain gamma-Al 2 O 3 。
Weighing gamma-Al 2 O 3 : weighing a certain amount of gamma-Al 2 O 3 So that the molar quantity of the silicon of the bottom slag of the household garbage incineration is equal to that of the bottom slag of the household garbage incineration and the gamma-Al 2 O 3 The ratio of the sum of the molar amounts of aluminum in (a) is 2: 1.
Preparing a polyvinyl alcohol solution: adding 5g of 1788 type polyvinyl alcohol particles into 95g of deionized water, and magnetically stirring for 1h at 80 ℃ to obtain a polyvinyl alcohol solution with the mass percent of 5 wt%.
Mixing: the ground household garbage incineration bottom slag and gamma-Al are mixed 2 O 3 Adding into a mortar, adding absolute ethyl alcohol, 5 wt% polyvinyl alcohol solution and calcium carbonate, grinding and mixing uniformly to obtain a mixture. Wherein the added polyvinyl alcohol solution with the weight percent of 5 percent is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 The mass of the calcium carbonate is 10 wt% of the total mass of the slag and the gamma-Al, and the mass of the added calcium carbonate is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 10 wt% of the sum of the masses.
And (3) drying: drying the mixture at 60-70 deg.c.
Pressing: the dried mixture was subjected to tableting in an electric tableting machine using a die having a diameter of 22mm under a pressure of 20MPa for 1min to obtain a sheet.
And (3) sintering: and sintering the thin sheet in a muffle furnace at the temperature rise rate of 5 ℃/min at 950 ℃ for 3 hours to obtain the ceramic membrane.
As shown in fig. 2, this example also discloses a ceramic film prepared by the above method for preparing a ceramic film.
Tests show that the ceramic membrane has the aperture of 0.5-1.5 mu m, the porosity of 40-50 percent and the pure water flux of 215-322 kg/m under the pressure of 0.3bar 2 H. Therefore, the ceramic membrane has a small aperture, can be applied to filtering heavy metal ions in wastewater, and has high porosity, so that the ceramic membrane can realize high separation rate and high filtering efficiency.
The ceramic membrane is used for testing the separation rate of metal ions in a single-component metal ion solution, and specifically, the ceramic membrane is used for testing the separation rate of Cu with the initial concentration of 100mg/L 2+ Solution, initial concentration of Pb of 100mg/L 2+ Solution, initial concentration of Cr 100mg/L 3+ Solution, initial concentration of 100mg/L Ni 2+ Filtering the solution at 0.3bar pressure with Cu 2+ 、Pb 2 + 、Cr 3+ 、Ni 2+ The results of the separation ratio test are shown in FIG. 3, and it is clear from FIG. 3 that the ceramic membrane is applied to Cu 2+ 、Pb 2+ 、Cr 3+ All have better separation rate, especially for Pb 2+ The separation rate of (A) can reach 99%.
The ceramic membrane is used for testing the separation rate of metal ions in metal ion solutions with various components, and specifically, the ceramic membrane is used for testing the separation rate of Cu-containing solution with the initial concentration of 100mg/L 2+ 、Pb 2+ 、Cr 3+ 、Ni 2+ The mixed solution of (3) was filtered under a pressure of 0.3bar, Cu 2+ 、Pb 2+ 、Cr 3+ 、Ni 2+ The results of the separation ratio test of (A) are shown in FIG. 4, and it is understood from FIG. 4 that the ceramic membrane is opposed to Cu 2 + 、Pb 2+ The separation rate of the chromium-containing chromium alloy can reach 100 percent, and the chromium-containing chromium alloy is used for treating the chromium 3+ The separation rate of (A) was 87.94%, showing that the ceramic membrane has a high Cu content 2+ 、Pb 2+ 、Cr 3+ All have very good separation effect on Ni 2+ The separation rate of (2) can also reach 67.93%. In addition, the separation rate of the ceramic membrane to the metal ions in the metal ion solutions with multiple components is higher than that of the metal ion solution with a single component, because the multiple metal ions can compete or compete for adsorption during filtration, and the competition among the metal ions brings a synergistic effect for separation, so that the separation rate is improved.
To test the reusability of the ceramic membranes, 100mg/L Cr was coupled through the ceramic membranes 3+ Performing six-round circulation filtration on the solution, wherein after each filtration, the ceramic membrane is cleaned by hydrochloric acid and ultrapure water, and the six-round circulation filtered Cr is subjected to six-round circulation filtration 3+ The separation rate and the pure water flux were measured, and the results are shown in FIG. 5.
As can be seen from FIG. 5, after six cycles of filtration, Cr was filtered 3+ The separation rate can reach 97.31%, and the permeation flux can still reach 200L/m 2 H, therefore, the ceramic membrane still has better separation effect and permeation flux after being repeatedly used for 6 times.
EXAMPLE III
The third embodiment of the invention discloses a preparation method of a ceramic membrane, which comprises the following steps:
grinding: crushing the household garbage incineration bottom slag by a crusher and grinding the household garbage incineration bottom slag by a planetary grinder, and screening the household garbage incineration bottom slag by using a 325-mesh filter screen to obtain uniform and fine household garbage incineration bottom slag particles.
Component analysis: adopting X-ray fluorescence spectrum analysis on the domestic waste incineration bottom slag to obtain the molar weight of silicon and aluminum in the domestic waste incineration bottom slag;
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 650 ℃ for 3h at a sintering rate of 5 ℃/min to obtain gamma-Al 2 O 3 。
Weighing gamma-Al 2 O 3 : weighing a certain amount of gamma-Al 2 O 3 So that the molar quantity of the silicon of the bottom slag of the household garbage incineration is equal to that of the bottom slag of the household garbage incineration and the gamma-Al 2 O 3 Aluminum in (1)The ratio of the sum of the molar amounts of (b) is 2: 1.
Preparing a polyvinyl alcohol solution: adding 5g of 1788 type polyvinyl alcohol particles into 95g of deionized water, and magnetically stirring for 1h at 80 ℃ to obtain a polyvinyl alcohol solution with the mass percent of 5 wt%.
Mixing: burning the ground household garbage to obtain bottom slag and gamma-Al 2 O 3 Adding into a mortar, adding absolute ethyl alcohol, 5 wt% polyvinyl alcohol solution and calcium carbonate, grinding and mixing uniformly to obtain a mixture. Wherein the added polyvinyl alcohol solution with the weight percent of 5 percent is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 The mass of the calcium carbonate is 10 wt% of the total mass of the slag and the gamma-Al, and the mass of the added calcium carbonate is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 10 wt% of the sum of the masses.
And (3) drying: drying the mixture at 60-70 deg.c.
Pressing: the dried mixture was subjected to tableting in an electric tableting machine using a die having a diameter of 22mm under a pressure of 20MPa for 1min to obtain a sheet.
And (3) sintering: and sintering the thin sheet in a muffle furnace at the temperature rise rate of 5 ℃/min for 3 hours at 1000 ℃ to obtain the ceramic membrane.
As shown in fig. 6, this example also discloses a ceramic film prepared by the above method for preparing a ceramic film.
Example four
The fourth embodiment of the invention discloses a preparation method of a ceramic membrane, which comprises the following steps:
grinding: crushing the household garbage incineration bottom slag by a crusher and grinding the household garbage incineration bottom slag by a planetary grinder, and screening the household garbage incineration bottom slag by using a 325-mesh filter screen to obtain uniform and fine household garbage incineration bottom slag particles.
And (3) component analysis: carrying out X-ray fluorescence spectrum analysis on the domestic waste incineration bottom slag to obtain the molar weight of silicon and aluminum in the domestic waste incineration bottom slag;
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 650 ℃ for 3h at a sintering rate of 5 ℃/min to obtain gamma-Al 2 O 3 。
Weighing gamma-Al 2 O 3 : weighing a certain amount of gamma-Al 2 O 3 So that the molar quantity of the silicon of the bottom slag of the household garbage incineration is equal to that of the bottom slag of the household garbage incineration and the gamma-Al 2 O 3 The ratio of the sum of the molar amounts of aluminum in (a) is 2: 1.
Preparing a polyvinyl alcohol solution: adding 5g of 1788 type polyvinyl alcohol particles into 95g of deionized water, and magnetically stirring for 1h at 80 ℃ to obtain a polyvinyl alcohol solution with the mass percent of 5 wt%.
Mixing: the ground household garbage incineration bottom slag and gamma-Al are mixed 2 O 3 Adding into a mortar, adding absolute ethyl alcohol, 5 wt% polyvinyl alcohol solution and calcium carbonate, grinding and mixing uniformly to obtain a mixture. Wherein the added polyvinyl alcohol solution with the weight percent of 5 percent is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 The mass of the calcium carbonate is 10 wt% of the total mass of the slag and the gamma-Al, and the mass of the added calcium carbonate is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 10 wt% of the sum of the masses.
And (3) drying: drying the mixture at 60-70 deg.c.
Pressing: the dried mixture was tabletted in an electric tablet press using a die with a diameter of 22mm under a pressure of 20MPa for 1min to obtain a sheet.
And (3) sintering: and sintering the thin sheet in a muffle furnace at 1050 ℃ for 3h at the heating rate of 5 ℃/min to obtain the ceramic membrane.
As shown in fig. 7, this example also discloses a ceramic film prepared by the above-described ceramic film preparation method.
Comparative example 1
The invention discloses a preparation method of a ceramic membrane, which comprises the following steps:
grinding: crushing the household garbage incineration bottom slag by a crusher and grinding the household garbage incineration bottom slag by a planetary grinder, and screening the household garbage incineration bottom slag by using a 325-mesh filter screen to obtain uniform and fine household garbage incineration bottom slag particles.
And (3) component analysis: carrying out X-ray fluorescence spectrum analysis on the domestic waste incineration bottom slag to obtain the molar weight of silicon and aluminum in the domestic waste incineration bottom slag;
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 650 ℃ for 3h at a sintering rate of 5 ℃/min to obtain gamma-Al 2 O 3 。
Weighing gamma-Al 2 O 3 : weighing a certain amount of gamma-Al 2 O 3 So that the molar quantity of the silicon of the bottom slag of the household garbage incineration is equal to that of the bottom slag of the household garbage incineration and the gamma-Al 2 O 3 The ratio of the sum of the molar amounts of aluminum in (a) is 2: 1.
Preparing a polyvinyl alcohol solution: adding 5g of 1788 type polyvinyl alcohol particles into 95g of deionized water, and magnetically stirring for 1h at 80 ℃ to obtain a polyvinyl alcohol solution with the mass percent of 5 wt%.
Mixing: the ground household garbage incineration bottom slag and gamma-Al are mixed 2 O 3 Adding into a mortar, adding absolute ethyl alcohol, 5 wt% polyvinyl alcohol solution and calcium carbonate, grinding and mixing uniformly to obtain a mixture. Wherein the added polyvinyl alcohol solution with the weight percent of 5 percent is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 The mass of the calcium carbonate is 10 wt% of the total mass of the slag and the gamma-Al, and the mass of the added calcium carbonate is the bottom slag of the incineration of the household garbage and the gamma-Al 2 O 3 10 wt% of the sum of the masses.
And (3) drying: drying the mixture at 60-70 deg.c.
Pressing: the dried mixture was subjected to tableting in an electric tableting machine using a die having a diameter of 22mm under a pressure of 20MPa for 1min to obtain a sheet.
And (3) sintering: and sintering the thin sheet in a muffle furnace at the temperature rise rate of 5 ℃/min at 1100 ℃ for 3h to obtain the ceramic membrane.
As shown in fig. 7, the present comparative example also discloses a ceramic film prepared by the above ceramic film preparation method.
As shown in fig. 1, 2, and 6 to 8, which respectively show scanning electron micrographs of the ceramic films of examples one to four and comparative example 1, the sintering temperature was gradually increased from 900 ℃ to 1050 ℃ in examples one to four, and the pore diameter of the pores on the surface of the ceramic film prepared was gradually increased and the number of pores was gradually increased, that is, the pore diameter of the ceramic film prepared was larger and the number of pores was larger as the sintering temperature was increased. Among them, the pores on the surface of the ceramic film shown in fig. 2 have a uniform pore diameter and a reasonable number of pores, that is, the pores on the surface of the ceramic film formed by sintering at 950 ℃ have a uniform pore diameter and a reasonable number of pores. As can be seen from fig. 6, the ceramic film prepared in the comparative example exhibited fused pores, i.e., the interior of the ceramic film began to melt when the sintering temperature reached 1100 ℃.
The ceramic membranes of the first to fourth examples were used for Cr at an initial concentration of 100mg/L 3+ Solution and Cu of initial concentration of 100mg/L 2+ The solution was filtered to test the ceramic membranes of examples one through four for Cr 3+ And Cu 2+ Separation ratio of (2), Cr 3+ And Cu 2+ The results of the separation ratio test are shown in fig. 9 and 10, respectively. FIG. 9 and FIG. 10 show the pair of ceramic films Cr of the second example 3+ The separation rate of (A) was 84.22%, and the ceramic membrane of example one was used for Cu 2+ The separation rate of (2) reached 98.5%.
The ceramic films of the above examples one to comparative examples one were subjected to mechanical strength tests, and the test results are shown in table 2 below.
Table 2 results of mechanical strength test of ceramic films of examples one to five
Figure BDA0003643119890000151
Figure BDA0003643119890000161
As can be seen from table 2, the ceramic films of examples one to four have better mechanical strength, and particularly, the mechanical strength of the ceramic film obtained by sintering at 950 ℃ in example two can reach 9.9 MPa. Whereas the ceramic membrane of comparative example one is mechanically less strong.
Comparative example No. two
The second comparative example discloses a preparation method of a ceramic membrane, which comprises the following steps:
the method is characterized in that natural phosphate is used as a raw material, grinding and screening are carried out, a 40mm mould is used for pressing to prepare the ceramic membrane, the sintering temperature is controlled to be 1000 ℃, the sintering rate is 5 ℃/min, and the sintering time is 3 h.
Comparative example No. three
The third comparative example discloses a preparation method of a ceramic membrane, which comprises the following steps:
mineral fly ash is used as a raw material, and carboxymethyl cellulose and starch are added into the mineral fly ash to be used as a binding agent and a pore-forming agent respectively. The tubular ceramic membrane is prepared by an extrusion process, the sintering temperature is 1125 ℃, the sintering rate is 5 ℃/min, and the sintering time is 2 h.
Comparative example No. four
The fourth comparative example discloses a preparation method of a ceramic membrane, which comprises the following steps:
the loess and the fly ash are used as raw materials, and carboxymethyl cellulose and methyl methacrylate are added into the raw materials and are respectively used as a binding agent and a pore-forming agent. The ceramic membrane is prepared by roll forming, the sintering temperature is 1130 ℃, the sintering rate is 7 ℃/min, and the sintering time is 2.5 h.
Comparative example five
The fifth comparative example discloses a method for preparing a ceramic membrane, which includes the following steps:
with alpha-Al 2 O 3 As raw materials, carboxymethyl cellulose and glycerol are added as a binder and a plasticizer. The ceramic membrane is prepared by an extrusion molding method, the sintering temperature is 1300 ℃, the sintering speed is 10 ℃/min, and the sintering time is 2 h.
Comparative example six
A sixth comparative example discloses a method for preparing a ceramic membrane, which includes the steps of:
the fly ash is used as a raw material, and a polyvinyl alcohol solution is added into the fly ash to be used as an adhesive. The ceramic membrane is prepared by a grouting method, the sintering temperature is 800 ℃, the sintering rate is 2 ℃/min, and the sintering time is 2 h.
Pure water flux tests were performed at a pressure of 0.3bar for the above examples and comparative ceramic membranes, and the results are shown in table 3 below.
Table 3 pure water flux test results for the above examples and comparative ceramic membranes
Figure BDA0003643119890000171
As is clear from Table 3, the pure water flux of the ceramic membrane prepared in this example was 220kg/m 2 H to 600kg/m 2 H, from the pure water flux range, the ceramic membrane has both a faster filtration efficiency and a better separation rate. The pure water flux of the ceramic membrane of the comparative example I is too large, although the filtering efficiency is high, the separation rate is low, the pure water fluxes of the comparative example II, the comparative example III, the comparative example IV, the comparative example V and the comparative example VI are small, the filtering efficiency is low, and the requirement of the industrial wastewater filtering efficiency is difficult to meet.
Comparative example seven
Comparative example seven discloses a method for preparing a ceramic film, which is different from example two in that calcium carbonate is not used as a pore-forming agent in the preparation of the ceramic film.
The pure water flux was measured for the ceramic membranes of example two and the comparative example seven, and the test structure is shown in fig. 11. As can be seen from fig. 11, the pure water flux of the ceramic membrane of example two was significantly larger than that of the ceramic membrane of comparative example seven. It is known that the addition of calcium carbonate as a pore-forming agent can significantly improve the filtration efficiency of the ceramic membrane because the addition of calcium carbonate can generate a large amount of gas during sintering to increase the amount and pore diameter of pores of the ceramic membrane, thereby improving the filtration efficiency of the ceramic membrane.
The ceramic membrane and the preparation method thereof disclosed in the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the description of the above embodiments is only used to help understanding the ceramic membrane and the preparation method thereof and the core concept thereof; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.

Claims (10)

1. A method for preparing a ceramic membrane, comprising the steps of:
mixing: burning the bottom slag and Al of the domestic garbage 2 O 3 Mixing and milling an organic solvent, a binder, and a pore former to form a mixture;
pressing: pressing the mixture into flakes;
and (3) sintering: and sintering the thin sheet at 900-1050 ℃ to obtain the ceramic membrane.
2. The method for preparing a ceramic membrane according to claim 1, further comprising, before the step of mixing, the steps of:
and (3) component analysis: analyzing the components of the household garbage incineration bottom slag to obtain the molar weight of silicon and aluminum in the household garbage incineration bottom slag;
weighing Al 2 O 3 : weighing Al 2 O 3 So that the molar weight of silicon in the bottom slag of the household garbage incineration and the Al 2 O 3 The ratio of the sum of the molar weight of the medium aluminum is 1: 1-3: 1.
3. The method for preparing a ceramic membrane according to claim 2, further comprising, before the step of mixing, the steps of:
grinding: and grinding the household garbage incineration bottom slag until the particle size of the particles of the household garbage incineration bottom slag is smaller than 325 meshes.
4. Method for producing a ceramic membrane according to claim 1, wherein Al is present in the ceramic membrane 2 O 3 Is gamma-Al 2 O 3 The method also comprises the following steps before the mixing step:
preparation of gamma-Al 2 O 3 : sintering boehmite in a muffle furnace at 600 ℃ to 650 ℃ to form gamma-Al 2 O 3 。
5. The method for preparing a ceramic membrane according to claim 1, wherein the organic solvent comprises at least one of methanol, ethanol, formaldehyde, and acetaldehyde; alternatively, the first and second electrodes may be,
the adhesive comprises at least one of a polyvinyl alcohol solution, a carboxymethyl cellulose solution and a polyethylene glycol solution; alternatively, the first and second liquid crystal display panels may be,
the pore-forming agent is calcium carbonate.
6. The method for producing a ceramic membrane according to claim 5, wherein when the binder comprises a polyvinyl alcohol solution, the step of mixing further comprises:
preparing a polyvinyl alcohol solution: adding deionized water into polyvinyl alcohol particles, and stirring at 80-100 ℃ until the polyvinyl alcohol particles are dissolved to prepare a polyvinyl alcohol solution, wherein the polyvinyl alcohol solution contains 5-10 wt% of polyvinyl alcohol.
7. The ceramic membrane preparation method according to claim 6, wherein the mass of the polyvinyl alcohol solution is larger than that of the bottom slag from incineration of the household garbage and the Al 2 O 3 10 wt% of the sum of the masses.
8. Method for the production of ceramic membranes according to claim 1, wherein prior to the step of pressing, the method comprises the steps of:
and (3) drying: drying the mixture at 60-70 ℃.
9. The method for producing a ceramic membrane according to claim 1, wherein in the step of pressing, the pressing pressure is 20 to 30MPa, and the holding pressure is 1 to 3 min.
10. A ceramic membrane produced by the method according to any one of claims 1 to 9.
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