CN109876668B - Attapulgite-based ceramic microfiltration membrane solution - Google Patents

Attapulgite-based ceramic microfiltration membrane solution Download PDF

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CN109876668B
CN109876668B CN201910236515.4A CN201910236515A CN109876668B CN 109876668 B CN109876668 B CN 109876668B CN 201910236515 A CN201910236515 A CN 201910236515A CN 109876668 B CN109876668 B CN 109876668B
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attapulgite
graphite
ceramic
carbon nitride
membrane
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CN109876668A (en
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薛爱莲
周守勇
赵宜江
魏东阳
李梅生
邢卫红
吴飞跃
张莉莉
褚效中
张艳
黄进
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Huaiyin Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • 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
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
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    • 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
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3856—Carbonitrides, e.g. titanium carbonitride, zirconium carbonitride
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    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins

Abstract

The invention relates to an attapulgite-based ceramic microfiltration membrane casting solution, belonging to the technical field of membrane separation materials. The film-making liquid comprises attapulgite with melamine grafted on the surface, ceramic material particles, a dispersing agent, a thickening agent and water. 2. The unique nanofiber structure of attapulgite is used as a carrier, so that graphite-like phase carbon nitride can be uniformly loaded on the surface of the attapulgite, the defects of agglomeration, difficult separation and the like of the graphite-like phase carbon nitride are overcome, the photocatalytic performance of the graphite-like phase carbon nitride can be better improved, pollution resistance and self-cleaning of the membrane are realized, and the economical efficiency of the membrane separation process is improved.

Description

Attapulgite-based ceramic microfiltration membrane solution
Technical Field
The invention relates to an attapulgite-based ceramic microfiltration membrane casting solution, belonging to the technical field of membrane separation materials.
Background
The ceramic membrane shows unique advantages in a plurality of harsh application systems due to excellent material properties (high temperature resistance, high pressure resistance, corrosion resistance and the like), becomes one of the varieties with the most rapid development and the most development prospect in the membrane field, and is an ideal membrane material applied in the chemical and petrochemical fields. Compared with ceramic membranes prepared from oxide ceramic particles, the ceramic membrane prepared from ceramic fibers (such as titanium oxide fibers and aluminum oxide fibers) on a porous support (X.B. Ke, H.Y. Zhu, X.P. Gao, et al, High-performance ceramic membranes with a separation layer of metal oxide nanoparticles, Advanced Materials, 2007,19: 785-. The separation layer constructed by the ceramic fiber has the following advantages: (1) the mesh structure formed by the ceramic fibers enables high selectivity to be obtained while maintaining high flux, because the ceramic fibers can divide large pores into small pores, and form connected channels so that the total porosity can exceed 70%, compared with the porosity of a traditional ceramic membrane separation layer which is lower than 36%, and inevitably comprises non-connected pores which do not contribute to filtration; (2) in the process of forming the film layer on the porous support body, the ceramic fiber can be rapidly bridged on the surface of the support body due to the shape of the ceramic fiber, and the ceramic fiber is not easy to enter the support body to block a film pore passage so as to influence flux; (3) the ceramic fiber material improves the elastic modulus and the thermal stress resistance of the film layer, so that the film layer has high thermal shock resistance. It follows that the use of fibrous materials to construct the separation layer is an effective approach to the development of high performance ceramic membranes. The porous separation membrane (Zhou Gekko, etc., the preparation method of the ceramic microfiltration membrane using the attapulgite nano-fiber as the separation layer, the national invention patent ZL 201110094814.2) which can be developed by utilizing the natural attapulgite nano-fiber solves the defects of difficult artificial synthesis of nano-fiber materials, high cost, difficult dispersion, low preparation cost, etc., and can effectively reduce the cost of the fiber membrane. Meanwhile, the high porosity of the attapulgite nano-fiber membrane and the surface property of the attapulgite are utilized, and the membrane can be further endowed with the functions of catalysis, self-cleaning and the like through the coupling with other materials.
Graphite-like phase carbon nitride (g-C)3N4) Has a graphite-like layered structure, and is a polymeric non-metal semiconductor. In various semiconductor studies, g-C3N4Has attracted much attention due to its excellent chemical stability and unique electronic band structure. g-C3N4The preparation method is simple, the preparation raw materials are cheap and easy to obtain, and the catalyst can be used as a cheap catalyst to be applied to the fields of hydrogen production and oxygen production by photocatalytic water decomposition, pollutant degradation and organic synthesis. However, the easy recombination of photogenerated electrons and holes makes g-C3N4The catalytic activity of (a) has not yet been satisfactory for large-scale applications. G to C3N4The polymer is firmly loaded on other carriers through chemical bonding, and high-efficiency and stable coupled g-C can be obtained3N4A composite material. But still face the disadvantages of easy agglomeration in the preparation process and difficult dispersion and separation in the use process.
Disclosure of Invention
The invention aims to: the attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane with high efficiency and stability and photocatalytic performance is prepared by uniformly dispersing and immobilizing a melamine and a titanate coupling agent on the surface of attapulgite on the surface of the attapulgite through chemical bonding, and uniformly dispersing and immobilizing a graphite-like carbon nitride polymer generated after roasting on the surface of the attapulgite of a membrane layer through chemical bonding, so that the attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane with high efficiency and stability and photocatalytic performance is obtained, and a low-price and high-performance double-layer porous ceramic microfiltration membrane is provided for coupling a membrane separation technology and a photocatalytic technology.
In order to solve the problems, the following technical means are adopted:
first of the inventionThe method comprises the following steps:
an attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane with photocatalytic performance comprises a support layer and a separation layer, wherein the separation layer is composed of a separation layer matrix and an attapulgite-graphite-like carbon nitride composite material distributed in the separation layer matrix; the attapulgite-graphite-like carbon nitride is prepared by loading graphite-like carbon nitride on the surface of attapulgite serving as a carrier.
The matrix of the separation layer is a ceramic material, preferably one or a mixture of more of silicon carbide, diatomite, mullite, alumina, zirconia or titania.
The graphite-like phase carbon nitride is fixedly carried on the surface of the attapulgite, and the mass of the graphite-like phase carbon nitride is 2-50% of that of the attapulgite.
The length of the fiber of the attapulgite is 500-2000 nm, the diameter of the fiber is 30-70 nm, and the content of the attapulgite is not less than 95 wt%.
The weight of the attapulgite-graphite-like carbon nitride composite material is 35-50% (preferably 40-45%) of the weight of the separation layer matrix.
Second aspect of the invention:
a preparation method of an attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane with photocatalytic performance comprises the following steps:
step 1, carrying out titanate coupling agent modification on attapulgite by adopting a soaking method;
step 2, placing the modified attapulgite obtained in the step 1 in an aqueous solution containing melamine for reaction to obtain an attapulgite suspension liquid with melamine bonded on the surface;
step 3, adding ceramic material particles, a dispersing agent and a thickening agent into the suspension obtained in the step 2, and uniformly mixing to obtain a membrane making solution;
step 4, coating a film on the surface of the support by adopting a film-making solution through a slurry dipping method to prepare an attapulgite-graphite-like graphite phase carbon nitride composite ceramic microfiltration membrane wet film;
and 5, drying the prepared wet film, roasting in a nitrogen atmosphere, and naturally cooling to prepare the attapulgite-graphite-like phase carbon nitride composite ceramic microfiltration membrane.
In the step 1, the attapulgite is soaked in an organic solvent containing 2-10 wt% of titanate coupling agent, the amount of the titanate coupling agent is 1-5% of the mass of the attapulgite, the soaking time is 2-30 h, and the temperature is 10-50 ℃; and after modification, filtering and drying.
In the step 1, the organic solvent is selected from an alcohol solvent, a benzene solvent, an ester solvent or an ether solvent; more preferably a benzene-based solvent or an alcohol-based solvent; toluene or ethanol is more preferred.
The titanate coupling agent is selected from one or a mixture of more of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, isopropyl tri (dioctyl phosphato acyloxy) titanate, propyl dioleate acyloxy (dioctyl phosphato acyloxy) titanate, isopropyl trioleate acyloxy titanate, isopropyl tri (dodecyl benzene sulfonic acid) titanate, isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate or tetraisopropyl di (dioctyl phosphato acyloxy) titanate.
In the step 2, the melamine accounts for 0.8-20 wt% of the aqueous solution containing the melamine, the addition amount of the modified attapulgite accounts for 0.2-5 wt% of the aqueous solution, the reaction time is 1-10 h, and the reaction temperature is 70-100 ℃.
In the step 3, the addition amount of the ceramic material particles is 0.2-6 wt% of the aqueous solution, the addition amount of the dispersing agent is 0.1-1 wt% of the aqueous solution, and the addition amount of the thickening agent is 5-10% of the aqueous solution.
In the step 3, the ceramic material is selected from one or a mixture of more of silicon carbide, diatomite, mullite, alumina, zirconia and titanium oxide; the particle size range of the ceramic material particles is 20-50 μm.
The dispersant is preferably cationic dispersant, such as one or more of polyethyleneimine, polyethylene glycol and ammonium citrate; the thickener is preferably one or more of methylcellulose, polyvinyl alcohol, polyethylene glycol or glycerol.
And in the step 4, the slurry dipping time in the coating by the slurry dipping method is 20-120 s.
In the step 5, the parameters of the roasting process are as follows: heating to 500 ℃ at a speed of 2-10 ℃/min, preserving heat for 2h, heating to 520 ℃ at a speed of 10 ℃/min, and roasting for 2-6 h.
The third aspect of the present invention:
a ceramic membrane preparing liquid comprises attapulgite with melamine grafted on the surface, ceramic material particles, a dispersing agent, a thickening agent and water.
The fourth aspect of the present invention:
the ceramic membrane film-forming liquid is applied to the preparation of ceramic membranes with self-cleaning and photocatalytic functions.
The fifth aspect of the present invention:
the attapulgite is used as a carrier of graphite-like phase carbon nitride and is applied to improving the self-cleaning effect or the photocatalytic effect of the ceramic membrane doped with the graphite-like phase carbon nitride.
The sixth aspect of the present invention:
an attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane with photocatalytic performance is applied to filtering wastewater containing organic matters.
Advantageous effects
1. The separation layer of the ceramic microfiltration membrane is composed of attapulgite fibers, ceramic particles and graphite-like phase carbon nitride, in the pore-forming process, the attapulgite fibers are stacked disorderly, and meanwhile, macropores are divided into small pores to form communicated pore channels, so that the unique nanofiber structure of the attapulgite is fully exerted, the relatively high total porosity (50-80%) and the flow pore channels are provided, and the ceramic membrane with high selectivity and high permeation flux is obtained. The graphite-like carbon nitride uniformly dispersed and immobilized on the surface of the attapulgite film has photocatalytic performance, so that the ceramic membrane prepared not only has high flux and high selectivity, but also has certain photocatalytic performance and self-cleaning performance.
2. The unique nanofiber structure of attapulgite is used as a carrier, so that graphite-like phase carbon nitride can be uniformly loaded on the surface of the attapulgite, the defects of agglomeration, difficult separation and the like of the graphite-like phase carbon nitride are overcome, the photocatalytic performance of the graphite-like phase carbon nitride can be better improved, pollution resistance and self cleaning of a membrane are realized, the economic efficiency of a membrane separation process is improved, and the method has important practical significance on the improvement of the photocatalytic performance of the graphite-like phase carbon nitride.
3. During heating and refluxing, functional groups of melamine and titanate on the surface of the attapulgite are uniformly and firmly dispersed on the surface of the attapulgite through chemical bonding, and the generated graphite-like carbon nitride is promoted to be firmly loaded on the surface of the attapulgite through chemical bonding after roasting.
4. The addition of the graphite-like phase carbon nitride improves the pollution resistance of the ceramic membrane separation layer, and simultaneously, the prepared membrane has photocatalytic performance, so that the coupling of the photocatalytic process and the membrane separation is realized.
5. The purpose of controlling the aperture of the ceramic film can be achieved by adjusting the using amounts of the attapulgite and the graphite-like carbon nitride and the film coating time, and the aperture of the ceramic film can be controlled.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not show the specific techniques or conditions, and the techniques or conditions are described in the literature in the art (for example, refer to inorganic membrane separation techniques and applications, chemical industry publishers, 2003, published by Xunan et al) or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
Attapulgite clay (Attapulgite), called Attapulgite clay (Palygousky) for short, palygorskite and palygorskite are water-containing magnesium-aluminum-rich silicate minerals belonging to the sepiolite family in the mineralogical classification, and the main components of the Attapulgite clay are Attapulgite, and the ideal chemical formula of the Attapulgite clay is as follows: [ Si ]8Mg5O20(OH)2(OH2)4·4H2O]The natural low-cost silicate mineral with a unique fibrous or rod-shaped crystal structure has the diameter of 20-70 nm and the length of about 0.5-5 mu m, and belongs to typical one-dimensional nano fibers. China has huge reserve of attapulgite, and the reserve of the well-proven attapulgite resources in Xuyi county, Huai' an City, Jiangsu province is 1.03 hundred million tons, accounts for 73 percent of the reserve of well-proven attapulgite in China, accounts for 44 percent of the reserve of well-proven attapulgite in the world, and has a prospect reserve of 11.7 hundred million tons. The nano attapulgite has low preparation cost, is suitable for mass production, has low energy consumption in the development and utilization process, has no negative effect on the environment, and is a low-cost and high-performance membrane preparation material.
Graphite-like phase carbon nitride (g-C)3N4) Has a graphite-like layered structure, and is a polymeric non-metal semiconductor. In various semiconductor studies, g-C3N4Has attracted much attention due to its excellent chemical stability and unique electronic band structure. g-C3N4The preparation method is simple, the preparation raw materials are cheap and easy to obtain, and the catalyst can be used as a cheap catalyst to be applied to the fields of hydrogen production and oxygen production by photocatalytic water decomposition, pollutant degradation and organic synthesis. However, the easy recombination of photogenerated electrons and holes makes g-C3N4The catalytic activity of (a) has not yet been satisfactory for large-scale applications. G to C3N4The polymer being bound chemicallyThe coupling type g-C is firmly loaded on other carriers in cooperation, and high-efficiency and stable coupling type g-C can be obtained3N4A composite material. But still face the disadvantages of easy agglomeration in the preparation process and difficult dispersion and separation in the use process.
The method mainly adopts attapulgite and ceramic particles as base materials of a separation layer of a ceramic membrane, and is assisted with melamine to prepare a membrane preparation liquid, functional groups of the melamine and titanate on the surface of the attapulgite are uniformly and firmly dispersed on the surface of the support through chemical bonding, the support is coated with the membrane preparation liquid, and the support is further dried and roasted to prepare the separation layer on the support, so that the microfiltration membrane is obtained. The melamine added in the raw materials in the film making process is converted into graphite-like phase carbon nitride in the roasting process, and the separation layer of the ceramic microfiltration membrane is composed of attapulgite fibers, ceramic particles and graphite-like phase carbon nitride, so that the attapulgite fibers are randomly accumulated in the pore-forming process, and macropores are divided into small pores to form communicated pore channels, thereby fully playing the unique nanofiber structure of the attapulgite, providing larger total porosity (50-80%) and flow pore channels, and obtaining the ceramic membrane with high selectivity and high permeation flux. The graphite-like phase carbon nitride is immobilized on the attapulgite composite ceramic microfiltration membrane, and the graphite-like phase carbon nitride can be dispersed and immobilized on the surface of the attapulgite of the membrane layer, so that the prepared ceramic membrane has high flux and high selectivity, has certain photocatalytic performance, and simultaneously avoids the defects of agglomeration, difficult separation and the like of the graphite-like phase carbon nitride, thereby having important practical significance for the improvement of the photocatalytic performance of the graphite-like phase carbon nitride and the development of membrane separation.
The length of the used attapulgite fiber is 500-2000 nm, the diameter is 30-70 nm, and the content of the attapulgite is not less than 95 wt%. When preparing the membrane preparation solution, firstly, the surface of the attapulgite needs to be modified, so that the surface of the attapulgite is grafted with a coupling agent, and the attapulgite can be treated by adopting a titanate coupling agent soaking method. For example: soaking attapulgite in an organic solvent containing 2-10 wt% of titanate coupling agent, wherein the use amount of the titanate coupling agent is 1-5% of the mass of the attapulgite, the soaking time is 2-30 h, and the temperature is 10-50 ℃; and after modification, filtering and drying. The organic solvent is selected from alcohol solvent, benzene solvent, ester solvent or ether solvent; more preferably a benzene-based solvent or an alcohol-based solvent; toluene or ethanol is more preferred. The titanate coupling agent is selected from one or a mixture of more of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, isopropyl tri (dioctyl phosphato acyloxy) titanate, propyl dioleate acyloxy (dioctyl phosphato acyloxy) titanate, isopropyl trioleate acyloxy titanate, isopropyl tri (dodecyl benzene sulfonic acid) titanate, isopropyl tri (dioctyl pyrophosphato acyloxy) ethylene titanate or tetraisopropyl di (dioctyl phosphato acyloxy) titanate.
Next, grafting melamine on the modified attapulgite, adding the attapulgite into an aqueous solution of the melamine, and heating and refluxing for reaction to obtain an attapulgite suspension with melamine bonded on the surface; the melamine accounts for 4-15 wt% of the aqueous solution containing melamine, the addition amount of the modified attapulgite accounts for 0.2-5 wt% of the aqueous solution, the reaction time is 1-10 h, and the reaction temperature is 70-100 ℃.
Adding other components of the separation layer, including ceramic material particles, a dispersing agent and a thickening agent, into the suspension, and uniformly mixing to obtain a membrane-making solution; for the ceramic material particles, the materials may be selected from the group consisting of: oxide materials such as alumina, zirconia, magnesia, silica, titania, ceria, yttria, and barium titanate; composite oxide materials such as cordierite, mullite, forsterite, steatite, sialon, zircon, ferrite and the like; nitride materials such as silicon nitride and aluminum nitride; carbide-based materials such as silicon carbide; hydroxide materials such as hydroxyapatite; elemental materials such as carbon and silicon; or an inorganic composite material containing two or more of them. Natural minerals (clay, clay minerals, ceramic slag, silica sand, pottery stone, feldspar, white sand) or blast furnace slag, fly ash, etc. can also be used, preferably one or more of silicon carbide, diatomite, mullite, alumina, zirconia or titania. The dispersant is preferably cationic dispersant, such as one or more of polyethyleneimine, polyethylene glycol and ammonium citrate; the thickener is preferably one or more of methylcellulose, polyvinyl alcohol, polyethylene glycol or glycerol.
The material of the support body used for coating can be selected from porous ceramics, porous metal, porous glass or porous intermetallic compounds, the aperture range is 1.5-10 mu m, and the configuration of the porous support body is flat plate, single tube type, multi-channel tube type or honeycomb tube type. The material of the support is preferably 1 or 2 or more selected from among alumina, zirconia, titania, magnesia, and silica, and ceramic powder mainly composed of alumina, zirconia, or titania is more preferable. Here, the term "mainly" means that 50wt% or more (preferably 75wt% or more, more preferably 80wt% to 100 wt%) of the entire ceramic powder is alumina or silica. For example, among porous materials, alumina is inexpensive and excellent in handling properties. Further, since a porous structure having pore diameters suitable for liquid separation can be easily formed, a ceramic separation membrane having excellent liquid permeability can be easily produced. Among the above aluminas, alpha-alumina is particularly preferably used. Alpha-alumina has the characteristics of being chemically stable and having high melting point and mechanical strength. Therefore, by using α -alumina, a ceramic separation membrane that can be utilized in a wide range of applications (e.g., industrial fields) can be manufactured.
Coating the surface of the support body by adopting the membrane-making solution through a slurry dipping method to prepare an attapulgite-graphite-like phase carbon nitride composite ceramic microfiltration membrane wet membrane; and drying the prepared wet film, roasting in a nitrogen atmosphere, and naturally cooling to prepare the attapulgite-graphite-like carbon nitride composite ceramic microfiltration membrane. And the soaking time in the coating by the soaking method is 20-120 s. The parameters of the roasting process are as follows: heating to 500 ℃ at a speed of 2-10 ℃/min, preserving heat for 2h, heating to 520 ℃ at a speed of 10 ℃/min, and roasting for 2-6 h.
In the following examples, membranes were characterized using average pore size, pure water flux. Meanwhile, a 10 mg/L methyl orange solution is adopted for a filtration test, the operating pressure in the filtration process is 1bar, and the feed liquid temperature is 25 ℃. Flux decay rate = (1-stable permeate flux/initial pure water flux) × 100%. Flux recovery rate = (pure water flux of treated membrane/initial pure water flux) × 100%.
Example 1 preparation of titanate coupling agent modified Nano Attapulgite
Soaking 10g of attapulgite in toluene containing 4wt% of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, wherein the use amount of titanate coupling agent is 2.2% of the mass of the attapulgite, the soaking time is 6h, and the temperature is 30 ℃; and after modification, filtering, cleaning and drying.
EXAMPLE 2 preparation of ceramic microfiltration membranes
1. Drying the titanate coupling agent modified nano attapulgite to constant weight at 105 ℃, crushing and sieving by a 200-mesh sieve; putting 100g of pure water into a conical flask, adding 0.8g of melamine, adding 0.5g of modified nano attapulgite, performing ultrasonic treatment for 10min, fully stirring, heating to 81 ℃, stirring and refluxing for 2 hours, adding 0.8g of nano alumina powder, 0.2g of polyethyleneimine and 10g of methyl cellulose, and performing uniform ultrasonic dispersion to obtain the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane preparation solution.
2. Coating a film on the tubular alumina support body for 40s by a slurry dipping method on a self-made film coating device, and coating an outer film to prepare the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film.
3. The attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film is dried for 12h at room temperature, dried for 12h at 110 ℃, then roasted in nitrogen atmosphere, heated to 500 ℃ at the speed of 10 ℃/min, insulated for 2h, heated to 520 ℃ at the speed of 10 ℃/min, roasted for 2h, and naturally cooled to obtain the attapulgite/graphite-like phase carbon nitride composite ceramic microfiltration membrane.
The obtained product has an average pore diameter of 600nm and a pure water flux of 4100 L.m-2·h-1·bar-1. The prepared ceramic microfiltration membrane is used for filtering 10 mg/L methyl orange solution, the membrane flux can be attenuated continuously in the filtering process due to the pollution on the membrane surface, and the permeation flux of the ceramic membrane is 4100 L.m after 4 hours of filtering-2·h-1·bar-1Down to 1140 L.m-2·h-1·bar-1Decrease in fluxThe reduction is 72.2%. The polluted membrane is taken out and put into clear water, and after the clear water is respectively irradiated by a high-pressure mercury lamp for 2.5 hours, the permeation flux is recovered to 95.2 percent
EXAMPLE 3 preparation of microfiltration membranes
1. Drying the titanate coupling agent modified nano attapulgite to constant weight at 105 ℃, crushing and sieving by a 200-mesh sieve; putting 100g of pure water into a conical flask, adding 0.8g of melamine, adding 0.5g of modified nano attapulgite, performing ultrasonic treatment for 10min, fully stirring, heating to 81 ℃, stirring and refluxing for 2 hours, adding 0.8g of nano alumina powder, 0.2g of polyethyleneimine and 10g of methyl cellulose, and performing uniform ultrasonic dispersion to obtain the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane preparation solution.
2. Coating a film on the tubular alumina support body for 60s by a slurry dipping method on a self-made film coating device, and coating an outer film to prepare the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film.
3. The attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film is dried for 12h at room temperature, respectively dried for 12h at 70 ℃ and 110 ℃, then roasted in nitrogen atmosphere, heated to 500 ℃ at the speed of 2 ℃/min, kept warm for 2h, heated to 520 ℃ at the speed of 10 ℃/min, roasted for 6h, and naturally cooled to prepare the attapulgite/graphite-like phase carbon nitride composite ceramic microfiltration membrane.
The obtained product has an average pore diameter of 200nm and a pure water flux of 1600 L.m-2·h-1·bar-1. The prepared ceramic microfiltration membrane is used for filtering 10 mg/L methyl orange solution, the membrane flux can be attenuated continuously in the filtering process due to the pollution on the membrane surface, and the permeation flux of the ceramic membrane is 1600 L.m after 4 hours of filtering-2·h-1·bar-1Down to 230 L.m-2·h-1·bar-1The flux decreased by 85.6%. The polluted membrane is taken out and put into clear water, and after the clear water is respectively irradiated by a high-pressure mercury lamp for 2.5 hours, the permeation flux is recovered to 90.9 percent
EXAMPLE 4 preparation of microfiltration membranes
1. Drying the titanate coupling agent modified nano attapulgite to constant weight at 105 ℃, crushing and sieving by a 200-mesh sieve; putting 110g of pure water into a conical flask, adding 10g of melamine, adding 3g of modified nano attapulgite, performing ultrasonic treatment for 10min, fully stirring, heating to 90 ℃, stirring and refluxing for 4 hours, adding 3.5g of nano alumina powder, 0.3g of polyethyleneimine and 8g of methyl cellulose, and performing uniform ultrasonic dispersion to obtain the attapulgite-graphite-like carbon nitride ceramic microfiltration membrane preparation solution.
2. Coating a film on the tubular alumina support body for 20s by a slurry dipping method on a self-made film coating device, and coating an outer film to prepare the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film.
3. The attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film is dried for 12h at room temperature, dried for 12h at 110 ℃, then roasted in nitrogen atmosphere, heated to 500 ℃ at the speed of 2 ℃/min, insulated for 2h, heated to 520 ℃ at the speed of 10 ℃/min, roasted for 2h, and naturally cooled to obtain the attapulgite/graphite-like phase carbon nitride composite ceramic microfiltration membrane.
The obtained product has an average pore diameter of 400nm and a pure water flux of 3200L m-2·h-1·bar-1. The prepared ceramic microfiltration membrane is used for filtering 10 mg/L methyl orange solution, the membrane flux can be attenuated continuously in the filtering process due to the pollution on the membrane surface, and the permeation flux of the ceramic membrane is 3200 L.m.after 4 hours of filtering-2·h-1·bar-1Reduced to 640 L.m-2·h-1·bar-1The flux decreased by 80%. The polluted membrane is taken out and put into clear water, and after the clear water is respectively irradiated by a high-pressure mercury lamp for 2.5 hours, the permeation flux is recovered to 93.1 percent
Comparative example 1 preparation of microfiltration Membrane
The difference from example 4 is that: and the nano attapulgite bonded with melamine is not added into the film-forming liquid.
1. Putting 110g of pure water into a conical flask, adding 10g of melamine, adding 6.5g of nano-alumina powder, 0.3g of polyethyleneimine and 8g of methylcellulose, and performing ultrasonic dispersion uniformly to obtain the membrane-making solution of the alumina ceramic microfiltration membrane.
2. Coating a film on a tubular alumina support body for 20s by a slurry dipping method on a self-made film coating device, and coating an outer film to prepare the alumina ceramic microfiltration membrane wet film.
3. Drying the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film at room temperature for 12h, drying at 110 ℃ for 12h, then roasting in a nitrogen atmosphere, heating to 500 ℃ at a speed of 2 ℃/min, keeping the temperature for 2h, heating to 520 ℃ at a speed of 10 ℃/min, roasting for 2h, and naturally cooling to obtain the alumina ceramic microfiltration membrane.
The obtained product has an average pore diameter of 200nm and a pure water flux of 1300 L.m-2·h-1·bar-1. The prepared ceramic microfiltration membrane is used for filtering 10 mg/L methyl orange solution, the membrane flux can be attenuated continuously in the filtering process due to the pollution on the membrane surface, and the permeation flux of the ceramic membrane is 1300 L.m after 4 hours of filtering-2·h-1·bar-1Down to 220 L.m-2·h-1·bar-1The flux decreased 84%. And after the polluted membrane is taken out to be placed in clear water and respectively irradiated by a high-pressure mercury lamp for 2.5 hours, the permeation flux is recovered to 7.2 percent. It can be seen that the anti-pollution performance and self-cleaning performance of the material without the attapulgite-like graphite phase carbon nitride are obviously reduced.
Comparative example 2 preparation of microfiltration Membrane
The difference from example 4 is that: the graphite-like carbon nitride is directly added into the membrane-making liquid, and is not loaded by taking attapulgite as a carrier.
1. Drying the titanate coupling agent modified nano attapulgite to constant weight at 105 ℃, crushing and sieving by a 200-mesh sieve; putting 110g of pure water into a conical flask, adding 8.6 g of graphite-like carbon nitride nanoparticles, adding 3g of modified nano-attapulgite, performing ultrasonic treatment for 10min, fully stirring, heating to 90 ℃, stirring and refluxing for 4 hours, adding 3.5g of nano-alumina powder, 0.3g of polyethyleneimine and 8g of methylcellulose, and performing uniform ultrasonic dispersion to obtain the attapulgite-graphite-like carbon nitride ceramic microfiltration membrane preparation solution.
2. Coating a film on the tubular alumina support body for 20s by a slurry dipping method on a self-made film coating device, and coating an outer film to prepare the attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film.
3. The attapulgite-graphite-like phase carbon nitride ceramic microfiltration membrane wet film is dried for 12h at room temperature, dried for 12h at 110 ℃, then roasted in nitrogen atmosphere, heated to 500 ℃ at the speed of 2 ℃/min, insulated for 2h, heated to 520 ℃ at the speed of 10 ℃/min, roasted for 2h, and naturally cooled to obtain the attapulgite/graphite-like phase carbon nitride composite ceramic microfiltration membrane.
The obtained product has an average pore diameter of 410nm and a pure water flux of 3400L · m-2·h-1·bar-1. The prepared ceramic microfiltration membrane is used for filtering 10 mg/L methyl orange solution, the membrane flux can be attenuated continuously in the filtering process due to the pollution on the membrane surface, and the permeation flux of the ceramic membrane is 3400 L.m after 4 hours of filtering-2·h-1·bar-1Down to 610 L.m-2·h-1·bar-1The flux decreased by 82%. And after the polluted membrane is taken out to be placed in clear water and respectively irradiated by a high-pressure mercury lamp for 2.5 hours, the permeation flux is recovered to 51.9 percent. It can be seen from the examples 4 and the comparative example 2 that the microfiltration membrane obtained by crosslinking the attapulgite and the melamine to generate the graphite-like carbon nitride loaded on the surface has the advantages of uniform dispersion of the graphite-like carbon nitride and good self-cleaning effect.

Claims (4)

1. The application of the ceramic membrane film-forming liquid in the preparation of ceramic membranes with self-cleaning and photocatalytic functions is characterized in that the ceramic membrane film-forming liquid comprises attapulgite with melamine grafted on the surface, ceramic material particles, a dispersing agent, a thickening agent and water;
the ceramic membrane comprises a supporting layer and a separation layer, wherein the separation layer is composed of a separation layer matrix and an attapulgite-graphite-like carbon nitride composite material distributed in the separation layer matrix; the attapulgite-graphite-like phase carbon nitride composite material takes attapulgite as a carrier, and graphite-like phase carbon nitride is loaded on the surface of the attapulgite-like graphite-like phase carbon nitride composite material;
the preparation method of the attapulgite with the melamine grafted on the surface comprises the following steps: modifying the attapulgite with a titanate coupling agent by adopting a soaking method; placing the obtained modified attapulgite in an aqueous solution containing melamine for reaction to obtain an attapulgite suspension liquid with melamine bonded on the surface; the step of modifying the titanate coupling agent is as follows: soaking attapulgite in an organic solvent containing 2-10 wt% of titanate coupling agent, wherein the use amount of the titanate coupling agent is 1-5% of the mass of the attapulgite, the soaking time is 2-30 h, and the temperature is 10-50 ℃; after modification, filtering and drying; 0.8-20 wt% of melamine in the aqueous solution containing melamine, 0.2-5 wt% of modified attapulgite in the aqueous solution, 1-10 h of reaction time, 70-100 ℃ of reaction temperature, 0.2-6 wt% of ceramic material particles in the aqueous solution, 0.1-1 wt% of dispersant in the aqueous solution, and 5-10 wt% of thickener in the aqueous solution;
the ceramic material is selected from one or a mixture of more of silicon carbide, diatomite, mullite, alumina, zirconia or titanium oxide; the particle size range of the ceramic material particles is 20-50 μm.
2. The use according to claim 1, wherein the organic solvent is selected from the group consisting of alcohol solvents, benzene solvents, ester solvents, and ether solvents.
3. The use according to claim 1, wherein the titanate coupling agent is selected from one or more of isopropyltris (dioctylphosphato) titanate, propyldioleaato (dioctylphosphato) titanate, isopropyltriolato titanate, isopropyltris (dodecylbenzenesulfonic acid) titanate, isopropyltris (dioctylphosphato) ethylene titanate or tetraisopropylbis (dioctylphosphato) titanate.
4. Use according to claim 1, characterized in that the dispersant is a cationic dispersant; the thickener is one or more of methylcellulose, polyvinyl alcohol, polyethylene glycol or glycerol.
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