CN114797760A - Filtering membrane with dual functions of catalytic oxidation and adsorption and preparation method thereof - Google Patents
Filtering membrane with dual functions of catalytic oxidation and adsorption and preparation method thereof Download PDFInfo
- Publication number
- CN114797760A CN114797760A CN202210367131.8A CN202210367131A CN114797760A CN 114797760 A CN114797760 A CN 114797760A CN 202210367131 A CN202210367131 A CN 202210367131A CN 114797760 A CN114797760 A CN 114797760A
- Authority
- CN
- China
- Prior art keywords
- membrane
- ceramic membrane
- adsorption
- catalytic oxidation
- channel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012528 membrane Substances 0.000 title claims abstract description 190
- 238000001914 filtration Methods 0.000 title claims abstract description 44
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 38
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 230000009977 dual effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 130
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000011049 filling Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- 239000010865 sewage Substances 0.000 abstract description 19
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 4
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 108091006146 Channels Proteins 0.000 description 28
- 108090000862 Ion Channels Proteins 0.000 description 13
- 102000004310 Ion Channels Human genes 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 229910000314 transition metal oxide Inorganic materials 0.000 description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- -1 suspended matters Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01D67/0039—Inorganic membrane manufacture
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F2101/00—Nature of the contaminant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to the technical field of drinking water purification and sewage and wastewater treatment, in particular to a filtering membrane with dual functions of catalytic oxidation and adsorption and a preparation method thereof. The filtering membrane comprises a ceramic membrane with a metal oxide loaded on the surface and an adsorbing material filled in a channel of the ceramic membrane. The preparation method comprises the steps of preparing a metal salt solution, soaking the ceramic membrane in the metal salt solution, drying and calcining; and filling the adsorbing material into the channel of the calcined ceramic membrane, and packaging. The ceramic membrane is used as a base membrane of the filter membrane, metal oxide is loaded on the surface of the ceramic membrane, the adsorbing material is filled in the channel of the ceramic membrane, and the persulfate and the adsorbing material act together to activate the persulfate and play a role in adsorption, so that the water treatment efficiency can be improved, and the advanced treatment of a water body is facilitated.
Description
Technical Field
The invention relates to the field of drinking water treatment and sewage and wastewater treatment, in particular to a filtering membrane with dual functions of catalytic oxidation and adsorption and a preparation method thereof.
Background
The concentration of organic micro-pollutants in water is low, but the removal difficulty is high, the organic micro-pollutants are easy to exist in the water for a long time, and are easy to accumulate in animals, plants and human bodies, so that certain damage is caused to the human bodies.
Advanced oxidation and membrane treatment are two common means in water treatment, and the advanced oxidation and the membrane treatment are combined for use, so that the removal efficiency of pollutants can be improved. The advanced oxidation technology is used for treating organic pollutants, active substances such as sulfate radicals or hydroxyl radicals with strong oxidation capacity are generated, and the active substances can oxidize organic matters into low-toxicity or non-toxic micromolecular substances, so that the purposes of degrading pollutants and purifying water bodies are achieved. The membrane separation technology is mainly used for filtering particulate matters, colloids, microorganisms, macromolecular organic matters and the like in the water body so as to achieve the aim of purifying the water body.
At present, advanced oxidation and membrane separation are generally used as two treatment units to cooperatively treat the water body. Advanced oxidation is taken as pretreatment, which is easy to cause powder catalyst leakage to enter a membrane filtration system to block membrane pores, so that the membrane flux is reduced, and the membrane pollution speed is accelerated; and the advanced oxidation is used as post-treatment, so that the difficulty of separating and recovering the catalyst is high, and the cost is increased.
Disclosure of Invention
The invention aims to provide a filtering membrane with dual functions of catalytic oxidation and adsorption, which takes a ceramic membrane as a base membrane, loads metal oxide on the surface of the ceramic membrane, fills an adsorption material in a channel of the ceramic membrane, and has the combined action of activating persulfate to realize catalytic oxidation, playing a role of adsorption, improving the sewage treatment efficiency and performing advanced treatment on a water body.
The invention also aims to provide a preparation method of the filtering membrane with double functions of catalytic oxidation and adsorption, which comprises the steps of immersing the ceramic membrane in a metal salt solution, calcining to obtain the ceramic membrane of the metal oxide, and improving the loading strength of the metal oxide on the surface of the ceramic membrane by adopting an immersion-calcination mode.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
In one aspect, an embodiment of the present invention provides a filtration membrane with dual functions of catalytic oxidation and adsorption, including a ceramic membrane with a metal oxide loaded on a surface thereof, and an adsorption material filled in a channel of the ceramic membrane.
On the other hand, the embodiment of the invention provides a preparation method of a filtering membrane with dual functions of catalytic oxidation and adsorption, which comprises the following steps: preparing a metal salt solution, soaking the ceramic membrane in the metal salt solution, drying and calcining; screening an adsorbing material, filling the adsorbing material into the channel of the calcined ceramic membrane, and packaging.
Compared with the prior art, the embodiment of the invention has at least the following advantages or beneficial effects:
according to the invention, the ceramic membrane is taken as a base membrane, metal oxide is loaded on the base membrane, the metal oxide can activate persulfate, and macromolecular organic matters in water are decomposed into small molecules, so that the concentration of the organic matters outside the ceramic membrane can be reduced, the aggregation of the organic matters outside the ceramic membrane is further reduced, the pollution speed of the ceramic membrane is slowed down, and the service life of the ceramic membrane is prolonged; moreover, after the organic matters in the sewage are firstly degraded outside the ceramic membrane, the organic matters entering the ceramic membrane channel are further reduced, meanwhile, the metal oxide loaded in the ceramic membrane channel can further catalyze, oxidize and decompose the organic matters, and the decomposed organic matters are adsorbed by combining with the porous material packaged in the channel, so that the advanced treatment of the water body is realized, and the removal efficiency of the organic matters is improved.
In the invention, the ceramic membrane is immersed in the metal salt solution and then calcined, and the metal oxide grows in situ on the surface of the ceramic membrane, so that the load strength of the metal oxide on the ceramic membrane can be improved, and the metal oxide is prevented from falling off in the use process. The adsorbing material is filled in the channel of the ceramic membrane, and the preparation method is simple and convenient to operate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to specific examples.
In one aspect, an embodiment of the present invention provides a filtration membrane with dual functions of catalytic oxidation and adsorption, including a ceramic membrane with a metal oxide loaded on a surface thereof, and an adsorption material filled in a channel of the ceramic membrane.
The ceramic membrane is an asymmetric membrane formed by preparing an inorganic ceramic material through a special process. The ceramic membrane is classified into a tubular ceramic membrane and a flat ceramic membrane. In the embodiment of the present invention, the tubular ceramic membrane or the flat ceramic membrane may be selected according to the actual use environment.
The tube wall of the tubular ceramic membrane is densely distributed with micropores, under the action of pressure, raw material liquid flows in the membrane tube or outside the membrane, small molecular substances or liquid permeate the membrane, and large molecular substances or solid are intercepted by the membrane, so that the purposes of separation, concentration, purification and the like are achieved.
Micropores are densely distributed on the surface of the flat ceramic membrane, the permeation rate is different when the diameters of permeated substance molecules are different within a certain membrane aperture range, the pressure difference between two sides of the membrane is used as a driving force, the membrane is used as a filtering medium, and under the action of a certain pressure, when raw material liquid flows through the surface of the membrane, only water, inorganic salt and small molecular substances are allowed to permeate through the membrane, and macromolecular substances such as suspended matters, colloids and microorganisms in the water are prevented from passing through the membrane.
The ceramic membrane has the advantages of high separation efficiency, stable effect, good chemical stability, acid and alkali resistance, organic solvent resistance, bacteria resistance, high temperature resistance, pollution resistance, high mechanical strength, good regeneration performance, simple separation process, low energy consumption, simple operation, convenient maintenance, long service life and the like, is applied to various fields of deep processing of foods, beverages, plants (medicines), biological medicines, fermentation, fine chemical engineering and the like, and is mainly used for separation, clarification, purification, concentration, sterilization, desalting and the like in the technical process.
In the sewage treatment process, the colloid, suspended matters and part of macromolecular organic matters in the sewage are isolated outside the ceramic membrane through the ceramic membrane, primary filtration is realized, but because the ceramic membrane cannot completely filter the organic matters and the like, the catalyst loaded on the ceramic membrane can activate persulfate in the sewage, active substances (sulfate radicals, hydroxyl radicals and the like) are generated, advanced oxidation is carried out, further, the ceramic membrane is separated, the organic matters entering a ceramic membrane channel through the ceramic membrane are degraded, the sewage is subjected to deep treatment, and the degradation rate of organic pollutants is improved.
The metal oxide can activate persulfate, so that the persulfate can generate active substances with strong oxidizing property to react with organic matters in the water body to degrade the organic matters. In the invention, the metal oxide is loaded on the surface (including the inner surface of the channel) of the ceramic membrane, and the adsorption material in the channel is combined, so that the dual functions of catalytic oxidation and adsorption can be simultaneously generated in the water body, and the sewage treatment efficiency and the organic matter removal rate can be greatly improved in the ceramic membrane filtration process.
Wherein the loading amount of the metal oxide is 5-10g/m 2 . The loading amount of the metal oxide is controlled within the range, the sewage treatment effect is good, and the synergistic effect of the metal oxide and the ceramic membrane is best. When the loading amount of the metal oxide is less than 5g/m 2 During the process, the loading is low, so that the metal oxide is unevenly distributed on the ceramic membrane, the activation of the metal oxide on persulfate is influenced, and the treatment effect of the filtering membrane on sewage is further influenced. When the amount of the supported metal oxide is more than 10g/m 2 During the process, excessive metal oxide is accumulated on the ceramic membrane, so that the filtering effect of the ceramic membrane is influenced, namely the effective flux of the ceramic filtering membrane is reduced, the speed of water passing through the ceramic membrane is reduced, and the corresponding speed of sewage treatment is also reduced.
In some embodiments of the present invention, the metal oxide is a transition metal oxide, and the transition metal oxide is one or more of iron oxide, copper oxide, manganese oxide, cobalt oxide, and a composite metal oxide thereof. The transition metal oxide and the persulfate form a heterogeneous catalysis system, the application cost is low, the activation efficiency is high, no additional energy input is needed, and the transition metal oxide catalyst is easy to recover. The transition metal oxide is matched with the ceramic membrane for use, so that the efficiency of sewage treatment can be improved, the energy consumption of sewage treatment is reduced, and the sewage treatment system is convenient to manage.
In some embodiments of the invention, the adsorbent material is one or more of granular activated carbon, zeolite, coke, diatomaceous earth, and ceramsite. The porous material is selected as the adsorbent, so that impurities in water and degraded organic matters can be effectively adsorbed, the adsorption effect is good, and the pollutant removal rate is high. When the activated carbon is used as an adsorption material, the activated carbon not only has an adsorption function, but also has an effect of activating persulfate, and is matched with the transition metal oxide on the ceramic membrane, so that the activation efficiency is further improved.
In some embodiments of the present invention, the particle size of the adsorbing material is 1-5mm, and the specific surface area is 400-1200m 2 (ii)/g, the average pore diameter is 2-50 nm.
The grain diameter of the adsorbing material is 1-5 mm. The particle size of the adsorbing material is controlled to be 1-5mm, the granular adsorbing material is convenient to fill in the membrane channel, and is convenient to discharge from the membrane channel, and moreover, after the adsorbing material with the particle size larger than 1mm is filled in the membrane channel, the ceramic membrane cannot be blocked, and the membrane flux cannot be influenced. And when the particle size of the adsorbing material is larger than 5mm, the adsorbing material is inconvenient to fill in a membrane channel because of overlarge particle size, and the activating performance and the adsorbing performance of the adsorbing material on persulfate are reduced to some extent when the particle size of the adsorbing material is larger than 5 mm. Therefore, in the invention, the grain diameter of the adsorbing material is controlled to be 1-5mm, so that the adsorbing material is convenient to fill in a membrane channel and has excellent activation performance and adsorption performance.
When the activated carbon is used as the adsorbing material, the specific surface area of the activated carbon is 400-1200m 2 (ii) in terms of/g. When the specific surface area of the activated carbon is less than 400m 2 When the specific surface area of the activated carbon is more than 1200m, the adsorption property is poor, the sewage treatment capacity is weak, the degraded organic matters are not favorably adsorbed, and the aim of deeply treating the sewage cannot be achieved 2 After the volume fraction is increased, the price of the activated carbon is high, the preparation cost is high, and moreover, the specific surface area of the activated carbon is more than 1200m 2 After the concentration of the active carbon is over, the organic matters in the active carbon are not easy to be desorbed, namely the active carbon is not easy to be recycled.
In another aspect, in some embodiments of the present invention, a method for preparing a catalytic oxidation and adsorption dual-function filtration membrane is provided, including: preparing a metal salt solution, soaking the ceramic membrane in the metal salt solution, drying and calcining; screening an adsorbing material, filling the adsorbing material into the channel of the calcined ceramic membrane, and packaging.
In some embodiments of the present invention, the metal salt solution is one or more of cobalt nitrate, iron nitrate, copper nitrate, and manganese chloride.
In some embodiments of the invention, the metal salt solution has a concentration of 5 to 10mg/L and a soaking time of 24 to 48 hours.
In some embodiments of the present invention, the calcination process is performed by heating to 300-500 ℃ at 2-5 ℃/min in air atmosphere, and maintaining the temperature for 3-5 h. The metal salt on the surface of the ceramic membrane can be oxidized into metal oxide by calcining at the calcining temperature (300-500 ℃), the metal salt can enter the micropores of the ceramic membrane in the dipping process, and the metal oxide is loaded in situ in the calcining process, so that the loading strength of the metal oxide and the ceramic membrane is high.
In some embodiments of the present invention, the drying process is performed by heat treatment in an oven at 60-80 ℃ for 4-6 h. After the ceramic membrane is soaked, the ceramic membrane is firstly dried, in the drying process, the solution on the ceramic membrane is evaporated, so that the metal salt can be fixed on the ceramic membrane, and then the ceramic membrane is calcined, so that the metal salt is prevented from flowing on the ceramic membrane, and the metal oxide is prevented from being unevenly distributed due to the flowing of the metal salt in the calcining process of the ceramic membrane.
In some embodiments of the present invention, before impregnating the ceramic membrane, the method further comprises: and (3) placing the ceramic membrane in an ethanol water solution, and ultrasonically cleaning for 20-30 min. Before loading the metal salt, the ceramic membrane is cleaned to remove impurities on the surface and in the pores of the ceramic membrane, so that the metal salt loading rate can be improved, and the influence of the impurities on the ceramic membrane on water body purification can be avoided.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
With Al 2 O 3 Using flat ceramic membrane as base membrane, and mixing Al 2 O 3 And (3) placing the flat ceramic membrane in an ultrasonic cleaning instrument, adding ethanol water, and cleaning for 30 min. After cleaning, Al is added 2 O 3 The flat ceramic membrane is drained and then dried in an oven at 60 ℃ for later use.
The specific surface area is 400-500m 2 The granular activated carbon per gram was sieved through a 60 mesh sieve, and the average pore diameter of the oversize fraction was found to be 4.1 nm. Ultrasonically cleaning the activated carbon sieved by a 60-mesh sieve in an ethanol solution for 30min, draining, and drying at 80 ℃ for 12h for later use.
Preparing 5g/L cobalt nitrate solution, soaking the ceramic membrane in the cobalt nitrate solution for 12 hours, draining, placing in an oven, performing heat treatment at 60 ℃ for 4 hours, and drying; and then placing the ceramic membrane in a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min, preserving the temperature for 4h, taking out, and naturally cooling to room temperature.
Filling the dried activated carbon into a channel of the ceramic membrane after calcination, controlling the filling rate of the activated carbon to be 95%, and then filling Al 2 O 3 And packaging the channel of the flat ceramic membrane, and communicating the channel with the water outlet pipe to obtain the filtering membrane of the embodiment.
Example 2
With Al 2 O 3 Using flat ceramic membrane as base membrane, and mixing Al 2 O 3 And (3) placing the flat ceramic membrane in an ultrasonic cleaning instrument, adding ethanol water, and cleaning for 30 min. After cleaning, Al is added 2 O 3 Draining the flat ceramic membrane, and drying in an oven at 60 ℃ for later use.
The specific surface area is 500-600m 2 The granular activated carbon per gram was sieved through a 50 mesh sieve, and the average pore diameter of the oversize fraction was found to be 4.2 nm. Ultrasonically cleaning the activated carbon sieved by a 50-mesh sieve in an ethanol water solution for 20min, draining, and drying at 50 ℃ for 18h for later use.
Preparing 10g/L copper nitrate solution, soaking the ceramic membrane in the copper nitrate solution for 12 hours, draining, placing in a drying oven, carrying out heat treatment at 60 ℃ for 6 hours, and drying; and then placing the ceramic membrane in a muffle furnace, heating to 500 ℃ at the speed of 4 ℃/min, preserving the heat for 3 hours, taking out, and naturally cooling to room temperature.
Filling the dried activated carbon into a channel of a calcined ceramic membrane, controlling the filling rate of a catalyst to be 80%, and then filling Al 2 O 3 And packaging the channel of the flat ceramic membrane, and communicating the channel with the water outlet pipe to obtain the filtering membrane of the embodiment.
Example 3
The ceramic membrane and activated carbon treated in example 1 were used.
Preparing 8g/L ferric nitrate solution, soaking the ceramic membrane in the ferric nitrate solution for 18 hours, draining, placing in a drying oven, performing heat treatment at 60 ℃ for 6 hours, and drying; and then placing the ceramic membrane in a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, preserving the temperature for 5 hours, taking out, and naturally cooling to room temperature.
Filling the dried activated carbon into a channel of a calcined ceramic membrane, controlling the filling rate of a catalyst to be 90%, and then filling Al 2 O 3 And packaging the channel of the flat ceramic membrane, and communicating the channel with the water outlet pipe to obtain the filtering membrane of the embodiment.
Example 4
Ceramic membranes and activated carbon were used after treatment as in example 1.
Preparing 5g/L manganese chloride solution, soaking the ceramic membrane in the manganese chloride solution for 24 hours, draining, placing in an oven, performing heat treatment at 60 ℃ for 6 hours, and drying; and then placing the ceramic membrane in a muffle furnace, heating to 350 ℃ at the speed of 4 ℃/min, preserving the heat for 4 hours, taking out, and naturally cooling to room temperature.
Filling the dried activated carbon into a channel of a calcined ceramic membrane, controlling the filling rate of a catalyst to be 95%, and then filling Al 2 O 3 And packaging the channel of the flat ceramic membrane, and communicating the channel with the water outlet pipe to obtain the filtering membrane of the embodiment.
Example 5
The ceramic membrane and activated carbon treated in example 1 were used.
Filling the dried activated carbon into a channel of the calcined ceramic membrane, controlling the filling rate of the catalyst to be 95%, and then filling Al into the channel 2 O 3 And packaging the channel of the flat ceramic membrane, and communicating the channel with the water outlet pipe to obtain the filtering membrane of the embodiment.
Examples of the experiments
1. Metal oxide loading test
The filtration membranes prepared in examples 1 to 4 were used as test objects, the mass of the ceramic membrane was measured before loading the metal oxide, after loading the metal salt, drying and calcining, the mass of the ceramic membrane was measured again, and the difference in mass between the two times was divided by the effective area of the ceramic membrane to obtain the loading amount of the metal oxide, and the results are shown in table 1.
TABLE 1 Supports for metal oxides in ceramic membranes of examples 1-4
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Load amount (g/m) 2 ) | 6.3 | 7.1 | 6.5 | 7.6 |
2. Metal oxide load Strength test
The filtration membranes of examples 1 to 4 were used repeatedly 10 times in sewage treatment, and the metal ion concentration in each aqueous solution was measured by ICP-OES, and the mass sum of the metal oxide in the aqueous solution was calculated to obtain the amount of the lost metal oxide, and the amount of the lost metal oxide was divided by the effective area of the ceramic membrane to obtain the amount of the lost metal oxide, and the results are shown in table 2.
TABLE 2 amount of metal oxide lost from filtration membranes of examples 1-4
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Loss (g/m) 2 ) | 0.00015 | 0.00016 | 0.00021 | 0.00022 |
From the above table 2, it can be seen that the filtration membranes prepared in examples 1 to 4 have high strength of supporting the metal oxide on the ceramic membrane, and after 10 times of repeated use, the amount of the metal oxide lost was small, and the stability of the filtration membranes was good.
2. Testing of organic matter degradation
(1) Preparing 10mg/L bisphenol A as polluted water. Separately, 5 beakers were charged with bisphenol A solution (concentration C) 0 ) Then, 0.2mmol/L of oxone (the concentration of oxone in the system) was added. Then, the filtration membranes of the above embodiments 1 to 4 were immersed in the corresponding beakers, the water outlet pipes of the filtration membranes were connected to a circulation pump, the circulation pump was started, and the purified water was collected, the concentration (C) of bisphenol A in the water treated with the filtration membranes was measured every 10min, and the C/C was calculated 0 The results are shown in Table 1.
TABLE 1 EXAMPLES 1-4 Performance of bisphenol A degradation by filtration Membrane
From table 1 above, it can be derived: through comparison experiments, the catalyst is loaded on the surface of the membrane and the activated carbon is filled in the channels of the membrane, so that the dual effects of degradation and adsorption can be realized, the removal rate of the bisphenol A in the water can be effectively improved, and the effect of the Co oxide loaded catalyst is the best.
(2) Preparing a methyl orange solution with the concentration of 10mg/L as a polluted water body. Methyl orange solution (concentration C) was added to each of 5 beakers 0 ) Then, 0.2mmol/L potassium hydrogen persulfate was added. Then, the filtration membranes of the above embodiments 1 to 4 were immersed in the corresponding beakers, the water outlet pipes of the filtration membranes were connected to the circulation pump, the circulation pump was started, and the purified water was collected, the concentration (C) of methyl orange in the water treated with the filtration membrane was measured every 10min, and the C/C was calculated 0 The results are shown in Table 2.
Table 2 examples 1-4 filter membrane degradation performance of methyl orange
From table 2 above, it can be derived:
through comparison experiments, the catalyst is loaded on the surface of the membrane and the activated carbon is filled in the membrane channel, so that the dual effects of degradation and adsorption can be realized, and the removal rate of the dye in water can be effectively improved.
In summary, in the embodiments 1 to 4 provided by the present invention, the ceramic film is used as the base film, and the transition metal oxide is loaded on the ceramic film, and the transition metal oxide can activate the persulfate. The transition metal oxide loaded on the surface of the ceramic membrane enables the surface of the ceramic membrane to generate advanced oxidation, and macromolecular organic matters in water are decomposed into small molecules, so that the concentration of the organic matters outside the ceramic membrane can be reduced, the aggregation of the organic matters outside the ceramic membrane is reduced, the pollution speed of the ceramic membrane is slowed down, and the service life of the ceramic membrane is prolonged; and moreover, after the organic matters in the sewage are partially degraded in the ceramic membrane, the organic matters entering the ceramic membrane channel are further reduced, the metal oxide is also loaded in the ceramic membrane channel, the channel is filled with the adsorption material, advanced oxidation is carried out in the ceramic membrane channel, the organic matters can be further decomposed, the adsorption effect of the porous material in the membrane channel is combined, the decomposed organic matters are adsorbed, the advanced treatment of the water body is realized, and the removal efficiency of the organic matters is improved.
In the invention, the ceramic membrane is immersed in the metal salt solution and then calcined, and the metal oxide is loaded on the surface of the ceramic membrane in situ, so that the loading strength of the metal oxide and the ceramic membrane can be improved, and the metal oxide is prevented from falling off in the use process. The adsorbing material is filled in the channel of the ceramic membrane, and the preparation method is simple and convenient to operate.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A filtering membrane with dual functions of catalytic oxidation and adsorption is characterized by comprising a ceramic membrane with a metal oxide loaded on the surface and an adsorbing material filled in a channel of the ceramic membrane.
2. The dual-function filtration membrane of catalytic oxidation and adsorption of claim 1, wherein the adsorption material is one or more of granular activated carbon, zeolite, coke, diatomaceous earth, and ceramsite.
3. The dual function filtration membrane of catalytic oxidation and adsorption of claim 1, wherein the metal oxide is one or more of iron oxide, copper oxide, manganese oxide, cobalt oxide and composite metal oxides thereof.
4. The filtration membrane with dual functions of catalytic oxidation and adsorption as claimed in claim 1, wherein the particle size of the adsorption material is 1-5mm, and the specific surface area is 400-1200m 2 (ii)/g, the average pore diameter is 2-50 nm.
5. A method for preparing a catalytic oxidation and adsorption dual function filtration membrane according to any one of claims 1 to 4, comprising: preparing a metal salt solution, soaking the ceramic membrane in the metal salt solution, drying and calcining; and filling the adsorbing material into the channel of the calcined ceramic membrane, and packaging.
6. The method for preparing a catalytic oxidation and adsorption dual function filtration membrane according to claim 5, wherein the metal salt solution is one or more of nitrate, sulfate or chloride solution of Co, Fe, Mn, Cu.
7. The preparation method of the catalytic oxidation and adsorption dual-function filtration membrane according to claim 5, wherein the concentration of the metal salt solution is 5-10mg/L, and the immersion time is 24-48 h.
8. The method for preparing a filtering membrane with dual functions of catalytic oxidation and adsorption as claimed in claim 5, wherein the calcination process comprises raising the temperature to 300-600 ℃ at a rate of 2-5 ℃/min in an air atmosphere, and maintaining the temperature for 3-5 h.
9. The preparation method of the catalytic oxidation and adsorption dual-function filtering membrane according to claim 5, wherein the drying process is a heat treatment in an oven at 60-80 ℃ for 4-6 h.
10. The method for preparing a catalytic oxidation and adsorption dual function filtration membrane according to claim 5, further comprising, before impregnating said ceramic membrane: and (3) placing the ceramic membrane in an ethanol water solution, and ultrasonically cleaning for 20-30 min.
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