CN110589950A - Cu/Fe-HT-CM hydrotalcite catalytic membrane, preparation method and application - Google Patents
Cu/Fe-HT-CM hydrotalcite catalytic membrane, preparation method and application Download PDFInfo
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- CN110589950A CN110589950A CN201910800236.6A CN201910800236A CN110589950A CN 110589950 A CN110589950 A CN 110589950A CN 201910800236 A CN201910800236 A CN 201910800236A CN 110589950 A CN110589950 A CN 110589950A
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- 239000012528 membrane Substances 0.000 title claims abstract description 134
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 86
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 27
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 26
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000010949 copper Substances 0.000 claims abstract description 60
- 239000000919 ceramic Substances 0.000 claims abstract description 42
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 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 claims abstract description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 14
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000010865 sewage Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000009285 membrane fouling Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006385 ozonation reaction Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010180 surface X-ray diffraction Methods 0.000 description 2
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- -1 made of Al)2O3 Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention provides a Cu/Fe-HT-CM hydrotalcite catalytic membrane, which comprises: the ceramic membrane is used as a carrier, cheap materials such as copper nitrate, ferric nitrate, magnesium nitrate, aluminum nitrate and the like are used as precursors to synthesize hydrotalcite-like compounds with high catalytic activity, and the hydrotalcite-like compounds are modified on the surface of the ceramic membrane to form the hydrotalcite-like membrane catalyst. The surface of the Cu/Fe-HT-CM hydrotalcite catalytic membrane provided by the invention can not only realize the generation of hydroxyl radicals with high oxidation capacity by catalyzing ozone, but also realize the high-efficiency removal of refractory organic pollutants by directly reacting organic matters with ozone molecules or reacting with OH generated by ozone decomposition; meanwhile, the interception function of the catalytic membrane can also assist in strengthening the ozone oxidation of the refractory organic matters. Furthermore, the catalytic ozonation reaction on the membrane surface can also effectively inhibit the formation of membrane fouling.
Description
Technical Field
The invention belongs to the technical field of advanced sewage treatment, and particularly relates to a Cu/Fe-HT-CM hydrotalcite catalytic membrane, a preparation method and application thereof.
Background
With the rapid development of industry and agriculture and the acceleration of urbanization, the current situation of more and more shortage of water resources in China is caused, and the total discharge amount of sewage and the complexity of pollutants in the sewage are increasingly serious. Not only limits the development of the industry, but also severely restricts the pursuit of people for healthy water sources. Therefore, in order to reach a certain reuse water standard, the sewage is reused as a water resource for further water treatment process of production or life. An advanced treatment process is adopted according to the requirements of raw water quality of sewage (wastewater), treated COD (chemical oxygen demand), refractory organic matters, endocrine disruptors and the like. The deep treatment method comprises the following steps: a coagulating sedimentation method, a micro electrolysis method, an activated carbon method, a wet oxidation method, a catalytic oxidation method, a membrane separation method and other physical and chemical methods. The catalytic ozone oxidation technology utilizes the high oxidation property of ozone, converts the ozone into hydroxyl free radicals with stronger oxidation property and low selectivity through a catalyst, and can oxidize organic matters which are difficult to be independently oxidized or degraded by the ozone. In view of the high-efficiency removal effect of the catalytic ozonation method on refractory organic matters and the advantages of no secondary pollution and the like, the technology is widely applied to the advanced treatment of sewage at present. But at the same time, it has certain limitations, firstly, in the advanced treatment stage, the concentration of the refractory organic matter is low, the reaction rate between ozone and pollutants is not high, and the cost of ozone generation is high, which results in high cost of ozone treatment; and secondly, small suspended matters are generated in the process of catalyzing the ozone to oxidize the organic matters, so that the treatment efficiency of the subsequent process is influenced.
Ceramic membranes are inorganic ceramic materials (mainly made of Al)2O3，ZrO2，TiO2And SiO2Etc.) are prepared by a special process. The method has the advantages of high separation efficiency, stable chemical properties, low energy consumption and the like, and is widely applied to water treatment processes. However, there is a membrane fouling phenomenon during the membrane filtration process. The particles, colloidal particles or solute macromolecules in the water deposit on the membrane surface or block the membrane pores, thereby causing the membrane flux and the produced water quality to be reduced. The membrane pollution is an important factor for inhibiting the expansion of the membrane application, and the formation of the pollution not only influences the stable operation of the membrane, but also greatly shortens the service life of the membrane compared with the design value. Therefore, appropriate measures must be taken to mitigate the adverse effects of membrane fouling.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a Cu/Fe-HT-CM hydrotalcite catalytic membrane, a preparation method, an application device and an application method.
The technical scheme provided by the invention is as follows: a Cu/Fe-HT-CM hydrotalcite-like catalytic membrane takes a ceramic membrane as a carrier, Cu and Fe metal ions with ozone catalytic active components are mixed to serve as a Cu/Fe-HT type hydrotalcite-like catalyst precursor with a double-layer structure, and then Cu/Fe-HT type hydrotalcite-like is loaded on the surface of the ceramic membrane by a hydrothermal synthesis method; the Cu/Fe-HT-CM hydrotalcite catalytic membrane is mainly prepared by reacting and roasting a mixed salt solution A of copper nitrate, ferric nitrate, magnesium nitrate and aluminum nitrate, a urea alkali solution B and a ceramic membrane.
The other technical scheme provided by the invention is as follows: a preparation method of a Cu/Fe-HT-CM hydrotalcite catalytic membrane comprises the following steps:
(1) copper nitrate, ferric nitrate, magnesium nitrate and aluminum nitrate are selected as precursors of a catalyst and dissolved in an aqueous solution according to a certain proportion to form a mixed salt solution A, and urea is used as an alkaline solution B;
(2) the ceramic membrane is a commercial tubular ceramic membrane, and the separation aperture of the ceramic membrane is 0.2-0.1 um; soaking a ceramic membrane in dilute nitric acid, washing the ceramic membrane to be neutral by using deionized water, soaking the ceramic membrane in an alumina colloidal solution, and roasting the ceramic membrane in a reducing atmosphere to obtain a catalytic membrane base membrane;
(3) putting a ceramic membrane into a reactor with stirring, sequentially injecting a mixed salt solution A and an alkali solution B into the reactor, stirring, gradually heating to 100-105 ℃, and keeping for 2-4 hours to obtain a pre-catalytic membrane;
(4) and (3) roasting the pre-catalytic membrane in a tubular furnace, and naturally cooling to room temperature to finally obtain the Cu/Fe-HT-CM hydrotalcite catalytic membrane.
Further, Cu in the mixed salt solution A2+:Mg2+The molar concentration of (A) is 2:1-1: 2.
Further, Fe in the mixed salt solution A3+:Al3+The molar concentration ratio of (A) to (B) is 2:1 to 1: 2.
Further, in the step (2): the mass fraction of the dilute nitric acid is 5%, and the soaking time of the ceramic membrane in the dilute nitric acid is 24-48 h.
Further, in the step (2), the ceramic membrane is immersed in the alumina colloidal solution for 30-60 min, and the temperature rise rate is increased to 500 ℃ at 10 ℃/min.
Further, in the step (2), roasting for 2-4 hours at 450-600 ℃ in a reducing atmosphere to obtain the catalytic membrane base membrane.
Further, the reducing atmosphere is H2Or CH4At least one of (1).
Further, the step (4) specifically includes: the stirring speed is controlled to be 400-600 rpm/min, the mixture is continuously stirred for 1-3 h, and the mixture is gradually heated to 100 ℃ and kept for 3-4 h.
Further, the roasting conditions in the step (4) are as follows: roasting at 550-650 ℃ for 2-4 h.
The other technical scheme provided by the invention is as follows: an application of a Cu/Fe-HT-CM hydrotalcite catalytic membrane in treatment of refractory coal chemical industry sewage.
The beneficial effects of the invention are embodied in that:
(1) the hydrotalcite-like (Cu/Fe-HT) catalytic membrane used in the invention has simple preparation method and wide material source, and ceramic base membranes with different separation apertures can be selected according to actual requirements;
(2) the catalytic ozone oxidizer with the hydrotalcite-like (Cu/Fe-HT) catalytic membrane as the core combines a catalyst with a traditional ceramic membrane, and improves the ozone oxidation reaction rate by concentrating the pollutant concentration in sewage through the membrane, thereby improving the ozone use efficiency;
(3) the catalytic ozone oxidizer with the hydrotalcite-like (Cu/Fe-HT) catalytic membrane as the core combines the mode of the catalyst and the traditional ceramic membrane, and solves the problem that the subsequent process is influenced by particles formed by mechanical abrasion in the use process of the existing catalyst;
(4) the hydrotalcite-like compound (Cu/Fe-HT) catalyzes the oxidation reaction on the surface of the membrane, can effectively improve the problem of membrane pollution, prolongs the membrane cleaning period and reduces the operation cost.
Drawings
FIG. 1 is a surface X-ray diffraction spectrum of a Cu/Fe-HT hydrotalcite-like catalytic membrane prepared by the method of the invention;
FIG. 2 is a schematic structural diagram of the Cu/Fe-HT hydrotalcite-like catalytic membrane reactor of the present invention.
In the figure: 1-a reactor; 2-eye sight; 3-an ozone inlet; 4-a lower end inlet; 5-a sewage emptying port; 6-an ozone distributor; 7-an ozone aeration disc; an 8-Cu/Fe-HT hydrotalcite-like catalytic membrane; 9-a sewage outlet; 10-hydrophobic, breathable film; 11-pressure safety valve; 12-a vent; 13-manhole.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted, and the technical effects achieved by the present invention clearer, the technical solutions of the embodiments of the present invention will be further described in detail with reference to the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
A Cu/Fe-HT-CM hydrotalcite catalytic membrane takes a ceramic membrane as a carrier, Cu and Fe metal ions with ozone catalytic active components are mixed to serve as a Cu/Fe-HT type hydrotalcite catalytic precursor with a double-layer structure, and then Cu/Fe-HT type hydrotalcite is loaded on the surface of the ceramic membrane through a hydrothermal synthesis method; the Cu/Fe-HT-CM hydrotalcite catalytic membrane is mainly prepared by reacting and roasting a mixed salt solution A of copper nitrate, ferric nitrate, magnesium nitrate and aluminum nitrate, a urea alkali solution B and a ceramic membrane.
The preparation method of the Cu/Fe-HT-CM hydrotalcite catalytic membrane comprises the following steps:
1) the ceramic membrane is a commercial tubular ceramic membrane, and the separation aperture of the ceramic membrane is 0.2-0.1 um; soaking the ceramic membrane in dilute nitric acid (mass fraction of 5%) for 24-48H, washing with deionized water to neutrality, immersing the ceramic membrane in aluminide colloid solution for 30-60 min, heating to 500 deg.C at a heating rate of 10 deg.C/min, and reducing in reducing atmosphere (H)2Or CH4) Roasting for 2-4 h to obtain a catalytic membrane base membrane;
2) copper nitrate (AR), ferric nitrate (AR), magnesium nitrate (AR) and aluminum nitrate (AR) are selected as catalytic precursors and dissolved in an aqueous solution according to a certain proportion to form a mixed salt solution A, wherein Cu2+:Mg2+The molar concentration ratio of (A) to (B) is controlled to be 2:1-1:2, Fe3+:Al3+The molar concentration ratio of (A) is controlled within the range of 2:1 to 1: 2. In addition, the concentration molar ratio of the divalent cation to the trivalent cation is 3: 1. as a specific example, the divalent cation molar concentration is 1.2mol/L and the trivalent cation molar concentration is controlled to be 0.4 mol/L.
3) Selecting a urea solution as the alkali solution B;
4) putting the catalytic membrane substrate film into a reactor with stirring, sequentially injecting a mixed salt solution A and an alkali solution B, continuously stirring for 1-3 h at a stirring speed of 400-600 rpm/min, gradually heating to 100 ℃ and keeping for 3-4 h to obtain a pre-catalytic membrane;
5) and (3) putting the pre-catalytic membrane into a tubular furnace, roasting at 550-650 ℃ for 2-4 h, and naturally cooling to room temperature to finally obtain the Cu/Fe-HT-CM hydrotalcite catalytic membrane. Referring to fig. 1, the surface X-ray diffraction spectrum is shown in fig. 1. From FIG. 1, it can be seen that the prepared Cu/Fe-HT-CM hydrotalcite-like catalytic membrane has typical hydrotalcite characteristic diffraction peaks, which indicates that the material has a hydrotalcite structure with a lamellar structure.
The Cu/Fe-HT-CM hydrotalcite-like compound is different from the prior art, the oxidation reaction on the surface of the membrane is catalyzed by the Cu/Fe-HT-CM hydrotalcite-like compound, the problem of membrane pollution can be effectively improved, the membrane cleaning period is prolonged, and the operation cost is reduced. The preparation method of the Cu/Fe-HT-CM hydrotalcite catalytic membrane is simple, the material source is wide, and ceramic base membranes with different separation apertures can be selected according to actual requirements.
The Cu/Fe-HT-CM hydrotalcite catalytic membrane provided by the invention can be applied to treatment of refractory coal chemical industry sewage. Referring to fig. 2, fig. 2 is a schematic structural diagram of the Cu/Fe-HT hydrotalcite-like catalytic membrane reactor according to the present invention.
The catalytic reactor comprises a catalytic reactor tank body 1, wherein a pressure safety valve 11, a gas discharge port 12 and a manhole 13 are arranged at the top end of the reactor tank body 1; the ozone inlet 3 is connected with an internal ozone distributor 6 and an ozone aeration disc 7 at the lower end of the reactor 1; a catalytic membrane supporting device is arranged in the reactor 1, a Cu/Fe-HT hydrotalcite-like catalytic membrane 8 is embedded in the catalytic membrane, and the top of the Cu/Fe-HT hydrotalcite-like catalytic membrane 8 is connected with a hydrophobic breathable membrane component 10; the bottom of the reactor 1 is provided with a water inlet 4 and a water outlet 5, and a water outlet 10 after reaction is designed at the upper part of the reactor 1.
The invention provides a method for treating refractory organic matters by using a Cu/Fe-HT hydrotalcite-like catalytic membrane reactor with a Cu/Fe-HT hydrotalcite-like catalytic membrane as a core, wherein the method comprises the following steps:
1) sewage and ozone enter the reactor from the lower end of the reactor, catalytic ozone oxidation reaction is carried out on the surface of the Cu/Fe-HT-CM catalytic membrane, and then the effluent quality is further improved after separation action of the catalytic membrane;
2) CO produced by catalytic oxidation during operation2And the remaining of O3The gas enters the top of the reactor through the hydrophobic breathable film at the top end of the catalytic film and is finally discharged through the vent hole at the top end of the reactor;
3) the application method of the catalytic membrane reactor in water treatment mainly comprises the following operating parameters: the pH range of the inlet water is 6.5-8.5, the ratio of inlet air to inlet water is 0.5: 1-2: 1, and the operating pressure is 0.1-0.3 MPa.
In a specific embodiment, a suitable amount of the Cu/Fe-HT-hydrotalcite-like catalytic membrane 8 is selected and filled in the reactor 1 according to the amount of water to be treated. Sewage enters the reactor through a sewage inlet 4, and then ozone enters the reactor through an ozone distributor 6 and an ozone aeration disc 7 after passing through an ozone inlet 3. Catalytic ozone oxidation reaction is carried out on the surface of the inner side membrane of the catalytic membrane 8, and organic matters which are difficult to degrade in sewage are degraded. The treated sewage is controlled to be 0.1-0.3 MPa under the action of internal pressure, and is discharged from an outlet 9 at the upper part of the reactor after penetrating through the catalytic membrane. The tail gas generated by the reaction passes through a hydrophobic breathable film 10 at the top of the catalytic film and is finally discharged out of the system through a tail gas outlet 12 at the top of the reactor.
Compared with the prior art, the application of the Cu/Fe-HT-CM hydrotalcite catalytic membrane provided by the invention combines the catalyst with the traditional ceramic membrane, so that the concentration of pollutants in sewage can be concentrated through the membrane, the ozone oxidation reaction rate is improved, the ozone use efficiency is improved, and the influence of particles formed by mechanical abrasion in the use process of the existing catalyst on the subsequent process can be reduced.
It should be understood by those skilled in the art that the Cu/Fe-HT-CM based hydrotalcite catalytic membrane, the preparation method and the application of the present invention are not limited to the examples described in the embodiment, and the above detailed description is only for the purpose of explaining the present invention and is not intended to limit the present invention. Other embodiments will be apparent to those skilled in the art from the following detailed description, which is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1. The Cu/Fe-HT-CM hydrotalcite-like catalytic membrane is characterized in that a ceramic membrane is used as a carrier, Cu and Fe metal ions with ozone catalytic active components are mixed to be used as a Cu/Fe-HT hydrotalcite-like catalyst precursor with a double-layer structure, and then Cu/Fe-HT hydrotalcite-like is loaded on the surface of the ceramic membrane by a hydrothermal synthesis method; the Cu/Fe-HT-CM hydrotalcite catalytic membrane is mainly prepared by reacting and roasting a mixed salt solution A of copper nitrate, ferric nitrate, magnesium nitrate and aluminum nitrate, a urea alkali solution B and a ceramic membrane.
2. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 1, wherein the method comprises the following steps:
(1) copper nitrate, ferric nitrate, magnesium nitrate and aluminum nitrate are selected as precursors of a catalyst and dissolved in an aqueous solution according to a certain proportion to form a mixed salt solution A, and urea is used as an alkaline solution B;
(2) the ceramic membrane is a commercial tubular ceramic membrane, and the separation aperture of the ceramic membrane is 0.2-0.1 um; soaking a ceramic membrane in dilute nitric acid, washing the ceramic membrane to be neutral by using deionized water, soaking the ceramic membrane in an alumina colloidal solution, and roasting the ceramic membrane in a reducing atmosphere to obtain a catalytic membrane base membrane;
(3) putting a ceramic membrane into a reactor with stirring, sequentially injecting a mixed salt solution A and an alkali solution B into the reactor, stirring, gradually heating to 100-105 ℃, and keeping for 2-4 hours to obtain a pre-catalytic membrane;
(4) and (3) roasting the pre-catalytic membrane in a tubular furnace, and naturally cooling to room temperature to finally obtain the Cu/Fe-HT-CM hydrotalcite catalytic membrane.
3. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein the mixed salt solution A contains Cu2+:Mg2+Mole ofThe concentration is 2:1-1: 2.
4. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein Fe in the mixed salt solution A3+:Al3+The molar concentration ratio of (A) to (B) is 2:1 to 1: 2.
5. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein in the step (2): the mass fraction of the dilute nitric acid is 5%, and the soaking time of the ceramic membrane in the dilute nitric acid is 24-48 h.
6. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein the ceramic membrane in step (2) is immersed in the alumina colloidal solution for 30-60 min, and the temperature rise rate is increased from 10 ℃/min to 500 ℃.
7. The preparation method of the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein in the step (2), the catalytic membrane-based membrane is obtained by roasting at 450-600 ℃ in a reducing atmosphere for 2-4 h.
8. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 7, wherein the reducing atmosphere is H2Or CH4At least one of (1).
9. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein the step (4) specifically comprises: the stirring speed is controlled to be 400-600 rpm/min, the mixture is continuously stirred for 1-3 h, and the mixture is gradually heated to 100 ℃ and kept for 3-4 h.
10. The method for preparing the Cu/Fe-HT-CM hydrotalcite-like catalytic membrane according to claim 2, wherein the calcination conditions in step (4) are as follows: roasting at 550-650 ℃ for 2-4 h.
11. The Cu/Fe-HT-CM hydrotalcite catalytic membrane according to claim 1 or the Cu/Fe-HT-CM hydrotalcite catalytic membrane prepared by the method according to claims 2 to 10, wherein the Cu/Fe-HT-CM hydrotalcite catalytic membrane is applied to treatment of refractory coal chemical industry sewage.
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