CN114849719A - Composite catalyst, preparation method thereof and wastewater treatment method - Google Patents
Composite catalyst, preparation method thereof and wastewater treatment method Download PDFInfo
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- CN114849719A CN114849719A CN202210644636.4A CN202210644636A CN114849719A CN 114849719 A CN114849719 A CN 114849719A CN 202210644636 A CN202210644636 A CN 202210644636A CN 114849719 A CN114849719 A CN 114849719A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 99
- 239000002184 metal Substances 0.000 claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000002351 wastewater Substances 0.000 claims abstract description 41
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 33
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 32
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 29
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 29
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 21
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000006385 ozonation reaction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 15
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 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 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940027987 antiseptic and disinfectant phenol and derivative Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Images
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- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J23/005—Spinels
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/02—Odour removal or prevention of malodour
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention relates to the technical field of wastewater treatment, in particular to a composite catalyst, a preparation method thereof and a wastewater treatment method. The composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and/or an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element and/or an assistant D containing an alkaline earth metal element; based on the mass of the composite catalyst, the mass proportion of the alumina is 5-80%, the mass proportion of the first metal element is 0.05-3%, and the mass proportion of the second metal element is 0.05-3%. The composite catalyst has higher stability, can increase the catalytic ozonation efficiency, prolong the stable service life of the operation in the reaction environment, and can efficiently remove COD in wastewater.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a composite catalyst, a preparation method thereof and a wastewater treatment method.
Background
At present, the waste water contains various refractory impurities and metal salts as well as various refractory organic matters, which pose serious threat to human health. The development of the ozone catalyst with high catalytic performance for removing the organic pollutants difficult to degrade in water can meet the requirements of the safe and efficient water treatment technology at present. The catalytic ozonation technology takes ozone as an oxidant, effectively degrades organic matters and partial inorganic matters (benzene, phenol and derivatives thereof, sulfides, cyanides and the like) in a water body by generating a large number of active hydroxyl free radicals with strong oxidizing property, has the advantages of high reaction rate at low temperature, high pollutant removal efficiency and the like, can effectively degrade the organic matters in water, and is one of the key research and development fields in the water treatment direction.
Catalytic ozonation techniques typically include homogeneous catalysis and heterogeneous catalysis. Compared with a homogeneous catalyst, the heterogeneous ozone catalyst is easier to recover and has wider applicable conditions. However, the existing heterogeneous ozone catalyst still has the problems of low catalytic activity, insufficient stability, metal dissolution and the like, so that a large number of catalysts are stopped at the experimental research stage.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a composite catalyst to solve the problems of low catalytic activity, insufficient stability and easy dissolution of metal of the catalyst in the prior art; the composite catalyst of the invention has stable and high-efficiency catalytic action.
The invention also aims to provide a preparation method of the composite catalyst, which is simple and feasible, mild in condition and environment-friendly.
Another object of the present invention is to provide a method for treating wastewater which is simple and efficient.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier;
the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and/or an auxiliary agent B containing a rare earth metal element;
the second metal element assistant comprises an assistant C containing an alkali metal element and/or an assistant D containing an alkaline earth metal element;
based on the mass of the composite catalyst, the mass proportion of the alumina is 5-80%, the mass proportion of the first metal element in the first metal element auxiliary agent is 0.05-3%, and the mass proportion of the second metal element in the second metal element auxiliary agent is 0.05-3%.
In one embodiment, the transition metal element includes at least one of Mn, Co, Cu, Ni, and Fe.
In one embodiment, the rare earth metal element includes Ce.
In one embodiment, the alkali metal element includes at least one of Na and K.
In one embodiment, the alkaline earth metal element includes at least one of Ca and Mg.
In one embodiment, the additive a includes an oxide corresponding to the transition metal element.
In one embodiment, the additive B comprises an oxide corresponding to the rare earth metal element.
In one embodiment, the auxiliary C comprises an oxide corresponding to the alkali metal element.
In one embodiment, the auxiliary D comprises an oxide corresponding to the alkaline earth metal element.
In one embodiment, the mass ratio of the transition metal element in the auxiliary A to the rare earth metal element in the auxiliary B is (1-3): 1.
in one embodiment, the mass ratio of the alkali metal element in the auxiliary C to the alkaline earth metal element in the auxiliary D is (0.2 to 20): (0.01-1).
In one embodiment, the particle size of the composite catalyst is 3-5 mm, and the specific surface area is 80-500 m 2 /g。
The preparation method of the composite catalyst comprises the following steps:
performing one-step impregnation or step-by-step impregnation on a porous carbon carrier raw material to obtain a mixed system, adjusting the pH of the mixed system to 5-10 by adopting alkali liquor, performing solid-liquid separation, collecting solid matters, and performing drying treatment and roasting treatment;
the one-step impregnation comprises: soaking a porous carbon carrier raw material in a mixed solution formed by soluble aluminum salt, soluble salt of a first metal element auxiliary agent, soluble salt of a second metal element auxiliary agent or alkali and water;
the step-by-step impregnation comprises the following steps: soaking a porous carbon carrier raw material into a soluble aluminum salt solution, and performing primary drying and primary roasting to obtain an aluminum element-loaded porous carbon carrier; and dipping the porous carbon carrier loaded with the aluminum element into a mixed solution formed by soluble salt of a first metal element auxiliary agent, soluble salt of a second metal element auxiliary agent and water.
In one embodiment, the porous carbon support is spherical or columnar.
In one embodiment, the porous carbon carrier has a particle size of 3 to 5mm and a specific surface area of 100 to 1200m 2 The pore volume is 0.5 to 1 mL/g.
In one embodiment, the lye comprises NaOH, KOH, Na 2 CO 3 And K 2 CO 3 At least one of (1).
In one embodiment, the concentration of the alkali liquor is 0.01-1 mol/L.
In one embodiment, the temperature of the drying treatment is 60-200 ℃, and the time of the drying treatment is 2-12 h.
In one embodiment, the temperature of the roasting treatment is 300-1200 ℃, and the time of the roasting treatment is 1-24 h.
In one embodiment, the temperature of the primary drying is 80-150 ℃, and the time of the primary drying is 2-10 h.
In one embodiment, the temperature of the primary roasting is 800-1200 ℃, and the time of the primary roasting is 1-15 h.
In one embodiment, the primary firing and the firing treatment are respectively performed under vacuum conditions or protective gas conditions; the protective gas comprises at least one of hydrogen, nitrogen, or an inert gas.
A method for treating wastewater comprising the steps of:
mixing ozone, waste water and the composite catalyst.
In one embodiment, the wastewater has a COD of 100 to 300mg/L and a pH of 6 to 9.
In one embodiment, the amount of ozone added is 15-300 mg per liter of the wastewater.
In each liter of wastewater, the mass ratio of the ozone to the COD is (1-3): 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the porous activated carbon is used as a carrier, and the alumina, the first metal element assistant and the second metal element assistant in a proper proportion range are loaded, so that the obtained composite catalyst has higher stability, the catalytic ozonation efficiency can be increased, the stable service life of operation in a reaction environment is prolonged, and the COD in wastewater can be efficiently removed.
(2) The composite catalyst is synthesized at room temperature, the environmental condition is mild, and substances harmful to the environment are not used and generated; the synthesis method is simple, porous carbon carriers have rich pore channels, metal ions can be effectively adsorbed, the pH value is adjusted at the later stage, metal component auxiliaries are fixed, and metal loss and loss are effectively avoided.
(3) The wastewater treatment method is suitable for advanced treatment of industrial organic wastewater, especially wastewater (such as printing and dyeing, leather, medicine, papermaking, petrochemical industry and the like) which is high in COD, high in salt and complex in composition and difficult to biochemically treat, and can efficiently remove COD, efficiently remove color and deodorize so as to meet the emission requirement.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a water production cycle evaluation chart of MBR (membrane bioreactor) catalyzed by ozone prepared by the composite catalysts in examples 1 to 4 of the invention;
FIG. 2 is a schematic view of a wastewater treatment system according to the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. 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 commercially available.
According to one aspect of the present invention, the present invention relates to a composite catalyst comprising a porous carbon support, and alumina, a first metal element assistant and a second metal element assistant supported on the porous carbon support;
the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and/or an auxiliary agent B containing a rare earth metal element;
the second metal element assistant comprises an assistant C containing an alkali metal element and/or an assistant D containing an alkaline earth metal element;
based on the mass of the composite catalyst, the mass proportion of the alumina is 5-80%, the mass proportion of the first metal element in the first metal element auxiliary agent is 0.05-3%, and the mass proportion of the second metal element in the second metal element auxiliary agent is 0.05-3%.
The porous activated carbon is used as a carrier, and the composite catalyst obtained by loading the transition metal element and/or the rare earth metal element, the alkali metal element and/or the alkaline earth metal element in a proper proportion range has higher stability, can be used for catalyzing ozone oxidation organic wastewater treatment, and has the advantages of good color and odor removal effects, high-efficiency catalytic degradation of organic matters, good stability, less component loss, no toxicity, no harm, greenness, environmental protection and the like.
In one embodiment, the mass fraction of the alumina based on the mass of the composite catalyst includes, but is not limited to, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%. The first metal element includes a transition metal element and/or a rare earth metal element. The mass ratio of the first metal element in the composite catalyst includes, but is not limited to, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 2.8%, or 3%. The second metal element includes an alkali metal element and/or an alkaline earth metal element, and the mass ratio of the second metal element in the composite catalyst includes, but is not limited to, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 2.8%, or 3%.
In one embodiment, the transition metal element includes at least one of Mn, Co, Cu, Ni, and Fe. In one embodiment, the transition metal element may be any one of Mn, Co, Cu, Ni, and Fe, or a combination of any two, any three, any four, or any five.
In one embodiment, the alkali metal element includes at least one of Na and K.
In one embodiment, the rare earth metal element includes Ce.
In one embodiment, the alkaline earth metal element includes at least one of Ca and Mg.
In one embodiment, the additive a includes an oxide corresponding to the transition metal element.
In one embodiment, the additive B comprises an oxide corresponding to the rare earth metal element.
In one embodiment, the auxiliary C comprises an oxide corresponding to the alkali metal element.
In one embodiment, the additive D includes an oxide corresponding to the alkaline earth metal element.
In one embodiment, the mass ratio of the transition metal element in the auxiliary A to the rare earth metal element in the auxiliary B is (1-3): 1. for example, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.5:1, or 3:1, etc. may be mentioned.
In one embodiment, the mass ratio of the alkali metal element in the auxiliary C to the alkaline earth metal element in the auxiliary D is (0.2 to 20): (0.01-1). For example, it may be 0.2:0.01, 5:0.1, 10:0.6, 15:0.8, 20:1, etc.
In one embodiment, the particle size of the composite catalyst is 3-5 mm, and the specific surface area is 80-500 m 2 /g。
According to another aspect of the present invention, the present invention also relates to a preparation method of the composite catalyst, comprising the following steps:
carrying out one-step impregnation or step-by-step impregnation on a porous carbon carrier raw material to obtain a mixed system, adjusting the pH of the mixed system to 5-10 by adopting alkali liquor, carrying out solid-liquid separation, collecting solid matters, and carrying out drying treatment and roasting treatment;
the one-step impregnation comprises: dipping a porous carbon carrier raw material into a mixed solution formed by soluble aluminum salt, soluble salt of a first metal element auxiliary agent, soluble salt of a second metal element auxiliary agent and water;
the step-by-step impregnation comprises the following steps: soaking a porous carbon carrier raw material into a soluble aluminum salt solution, and performing primary drying and primary roasting to obtain an aluminum element-loaded porous carbon carrier; and dipping the porous carbon carrier loaded with the aluminum element into a mixed solution formed by soluble salt of a first metal element auxiliary agent, soluble salt of a second metal element auxiliary agent and water.
The invention is synthesized at room temperature, has mild environmental condition, and does not use and generate substances harmful to the environment; the synthesis method is simple, porous carbon carriers have rich pore channels and can effectively adsorb metal ions, the pH value is adjusted at the later stage, and metal component auxiliaries are fixed, so that the loss and the loss of metal are effectively avoided.
In one embodiment, the soluble aluminum salt comprises aluminum chloride and/or aluminum sulfate.
In one embodiment, the soluble salt of the first metallic element promoter comprises a soluble salt of a transition metal element and/or a soluble salt of a rare earth metal element. Specifically, the soluble salt of the transition metal element includes a nitrate or a sulfate corresponding to the transition metal element. The soluble salt of the rare earth metal element comprises nitrate or sulfate corresponding to the rare earth element.
In one embodiment, the soluble salt of the second metal element promoter includes a soluble salt of an alkali metal element and/or a soluble salt of an alkaline earth metal element. Specifically, the soluble salt of an alkali metal element includes a nitrate alkali solution corresponding to the alkali metal element. The soluble salt of the alkaline earth metal element comprises nitrate or sulfate corresponding to the alkaline earth metal element.
In one embodiment, the porous carbon support is spherical or columnar. The spherical or columnar composite catalyst can be directly filled into the reactor.
In one embodiment, the porous carbon carrier has a particle size of 3 to 5mm and a specific surface area of 100 to 1200m 2 The pore volume is 0.5 to 1 mL/g.
In one embodiment, the caustic solution comprises NaOH, KOH, or,Na 2 CO 3 And K 2 CO 3 At least one of (1).
In one embodiment, the pH of the mixed system is adjusted to 5, 6, 7, 8, 9, or 10 with a lye.
In one embodiment, the concentration of the alkali liquor is 0.01-1 mol/L. In one embodiment, the concentration of the lye includes, but is not limited to, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.3mol/L, 0.5mol/L, 0.8mol/L or 1 mol/L.
In one embodiment, the temperature of the drying treatment is 60-200 ℃, and the time of the drying treatment is 2-12 h. In one embodiment, the temperature of the drying process includes, but is not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 150 ℃, 180 ℃, or 190 ℃. The time of the drying treatment includes, but is not limited to, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and 12 h. The invention ensures the stability of the composite catalyst by adopting the matching of proper drying temperature and time.
In one embodiment, the temperature of the roasting treatment is 300-1200 ℃, and the time of the roasting treatment is 1-24 h. In one embodiment, the temperature of the firing treatment includes, but is not limited to, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, or 1200 ℃. The time of the roasting treatment includes but is not limited to 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 12h, 15h, 18h, 20h or 22 h. The stability and catalytic activity of the composite catalyst are ensured by adopting proper roasting treatment temperature and roasting treatment time.
In one embodiment, the temperature of the primary drying is 80-150 ℃, and the time of the primary drying is 2-10 h. In one embodiment, the temperature of the primary drying includes, but is not limited to, 90 ℃, 100 ℃, 110 ℃ or 150 ℃. The time for primary drying includes but is not limited to 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h.
In one embodiment, the temperature of the primary roasting is 800-1200 ℃, and the time of the primary roasting is 1-15 h. In one embodiment, the temperature of the primary firing includes, but is not limited to, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, or 1200 ℃. The time of the first roasting includes but is not limited to 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h.
In one embodiment, the primary firing and the firing treatment are respectively performed under vacuum conditions or protective gas conditions; the protective gas comprises at least one of hydrogen, nitrogen, or an inert gas. In one embodiment, the flow rate of the protective gas is 75-85 mL/min, and may be, for example, 72mL/min, 75mL/min, 78mL/min, 80mL/min, or 83 mL/min. In one embodiment, the inert gas comprises argon, helium, or the like.
According to another aspect of the invention, the invention also relates to a wastewater treatment process comprising the steps of: ozone, wastewater and the composite catalyst as described above are mixed.
The wastewater treatment method can efficiently remove COD, efficiently remove color and odor and meet the discharge requirement.
In one embodiment, the wastewater is taken from MBR effluent, the COD value is still as high as 100-300 mg/L, and the biodegradability is poor. In one embodiment, the COD of the wastewater is 100-300 mg/L. For example, including but not limited to 120mg/L, 150mg/L, 170mg/L, 200mg/L, 220mg/L, 250mg/L, 280mg/L, or 300 mg/L. The pH value of the wastewater is 6-9. In one embodiment, the volume space velocity of the wastewater is 2-10 h -1 。
In one embodiment, the amount of ozone added is 15-300 mg per liter of the wastewater; for example, it may be 20mg, 50mg, 70mg, 100mg, 120mg, 150mg, 200mg, 220mg, 250mg, 280mg or 300 mg.
In one embodiment, the mass ratio of the ozone to the COD per liter of the wastewater is (1-3): 1; for example, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.5:1 or 2.8:1 may be used.
According to another aspect of the invention, the invention also relates to a wastewater treatment system, as shown in fig. 2, comprising a reaction bed, an ozone supply device, an ozone generator, a wastewater supply device and a clear water collection device;
the reaction bed is filled with the composite catalyst;
the lower end of the reaction bed is provided with an ozone inlet and a wastewater inlet, and the upper end of the reaction bed is provided with a clear water outlet; the ozone inlet is connected with the ozone supply device through the ozone generator, the waste water inlet is connected with the waste water supply device through the pump body, and the clear water outlet is connected with the clear water collecting device.
The wastewater treatment system can efficiently treat COD in wastewater.
The following will be further described with reference to specific examples.
Example 1
A composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element; based on the mass of the composite catalyst, the mass proportion of the alumina is 5.0%, the mass proportion of the first metal element is about 1.0%, and the mass proportion of the second metal element is about 0.5%;
wherein the mass ratio of the transition metal element to the rare earth metal element is 7: 5;
the transition metal element is selected from Fe
The rare earth metal element is selected from Ce;
the alkali metal element is selected from K;
the preparation method of the composite catalyst comprises the following steps:
(a) dissolving 4.75g of aluminum trichloride hexahydrate, 0.25g of cerium nitrate and 1.05g of ferric nitrate in 100mL of ultrapure water to obtain a yellow clear transparent mixed solution;
(b) using spherical porous active carbon as a carrier, and soaking the mixed solution on 19.06g of porous active carbon carrier;
(c) adjusting the pH value to 8.0 by using 0.1mol/L KOH, filtering, washing by using 2L pure water, and then putting into an oven to dry for 12 hours at the temperature of 80 ℃ to obtain a black catalyst precursor;
(d) and transferring the black precursor to an atmosphere furnace, introducing 80mL/min of nitrogen, and roasting at 550 ℃ for 4h to obtain the composite catalyst (5 AlCF-C).
Example 2
A composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element; based on the mass of the composite catalyst, the mass ratio of the alumina is about 45.5%, the mass ratio of the first metal element is about 0.9%, and the mass ratio of the second metal element auxiliary agent is about 0.3%;
wherein the mass ratio of the transition metal element to the rare earth metal element is 2: 1;
the transition metal element is selected from Fe
The rare earth metal element is selected from Ce;
the alkali metal element is selected from Na;
the preparation method of the composite catalyst comprises the following steps:
(a) 47.50g of aluminum trihydrate, 0.25g of cerium nitrate hexahydrate and 1.05g of ferric nitrate nonahydrate are dissolved in 100mL of ultrapure water to obtain a yellow clear transparent mixed solution;
(b) soaking the solution on 10.05g of porous active carbon carrier by taking spherical porous active carbon as a carrier to obtain suspension;
(c) adjusting the pH value to 8.0 by 0.1mol/L NaOH, filtering, washing by 2L pure water, and drying in an oven at 80 ℃ for 12h to obtain a black catalyst precursor;
(d) the black precursor was transferred to an atmosphere furnace, nitrogen gas at 80mL/min was introduced, and the mixture was calcined at 550 ℃ for 4 hours to obtain a composite catalyst (50 CF-C).
Example 3
A composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element and an assistant D containing an alkaline earth metal element; based on the mass of the composite catalyst, the mass proportion of the alumina is about 45.5%, the mass proportion of the first metal element is about 0.9%, and the mass proportion of the second metal element is about 0.3%;
wherein the mass ratio of the transition metal element to the rare earth metal element is 2: 1;
the mass ratio of the alkali metal element to the alkaline earth metal element is about 20: 1;
the transition metal element is selected from Fe;
the rare earth metal element is selected from Ce;
the alkali metal element is selected from K;
the alkaline earth metal element is selected from Mg;
the preparation method of the composite catalyst comprises the following steps:
(a) taking columnar porous activated carbon as a carrier, and soaking aluminum sulfate solution with the concentration of 1.0mol/L on the 10.19g of porous activated carbon carrier; drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h under nitrogen to obtain activated carbon (50Al-C) loaded with aluminum elements;
(b) dissolving 0.25g of cerous nitrate hexahydrate, 0.02 g of magnesium chloride hexahydrate and 1.05g of ferric nitrate nonahydrate in 100mL of ultrapure water to obtain a yellow clear transparent mixed solution;
(c) soaking the yellow clear transparent solution in 50Al-C, adjusting pH to 8.0 with 0.1mol/L KOH, filtering, washing with 2L pure water, and drying in oven at 80 deg.C for 12 h;
(d) and transferring the dried material to an atmosphere furnace, introducing 80mL/min of nitrogen, and roasting at 550 ℃ for 4h to obtain the catalyst composite catalyst (50 AL-CF-C).
Example 4
A composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element; based on the mass of the composite catalyst, the mass proportion of the alumina is 45%, the mass proportion of the first metal element is about 2.0%, and the mass proportion of the second metal element is about 1.5%;
wherein the mass ratio of the transition metal element to the rare earth metal element is 5: 2;
the transition metal element is selected from Cu and Co;
the rare earth metal element is selected from Ce;
the alkali metal element is selected from K;
the preparation method of the composite catalyst comprises the following steps:
(a) taking columnar porous activated carbon as a carrier, and soaking aluminum sulfate solution with the concentration of 1mol/L on 10.19g of the porous activated carbon carrier; drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 4h in a nitrogen atmosphere to obtain porous carbon (50Al-C) loaded with aluminum elements;
(c) dissolving 0.25g of cerium nitrate hexahydrate, 0.62g of copper nitrate trihydrate and 0.33g of cobalt nitrate hexahydrate in 100mL of ultrapure water to obtain a light blue clear transparent solution;
(c) soaking the light blue transparent solution in 50Al-C obtained in the step (a), adjusting the pH value to be more than 8 by using 0.1mol/L KOH, filtering and washing, and drying at 120 ℃ for 6 hours to obtain a black columnar catalyst;
(d) and transferring the black columnar catalyst to an atmosphere furnace, introducing 80mL/min of nitrogen, and roasting at 550 ℃ for 4h to obtain the composite catalyst (50 Al-CC-C).
Example 5
A composite catalyst comprises a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier; the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and an auxiliary agent B containing a rare earth metal element; the second metal element assistant comprises an assistant C containing an alkali metal element; based on the mass of the composite catalyst, the mass ratio of the alumina is 60%, the mass ratio of the first metal element is 1.5%, and the mass ratio of the second metal element is 2%;
wherein the mass ratio of the transition metal element to the rare earth metal element is 3: 1;
the transition metal element is selected from Fe and Co; wherein the mass ratio of Fe to Co is 1: 4;
the rare earth metal element is selected from Ce;
the alkali metal element is selected from Na.
The preparation method of the composite catalyst comprises the following steps:
soaking a porous carbon carrier raw material in an aluminum sulfate solution, and performing primary drying and primary roasting at the temperature of 120 ℃ for 4 hours at the temperature of 1150 ℃ for 1.5 hours to obtain an aluminum element-loaded porous carbon carrier; the porous carbon carrier loaded with the aluminum element is soaked in a mixed solution formed by nitrate of a first metal element aid, nitrate of a second metal element aid and water to obtain a mixed system, the pH value of the mixed system is adjusted to 8-9 by using 0.5mol/L KOH, then solid-liquid separation is carried out, a solid is collected and washed, and then drying treatment and roasting treatment are carried out, wherein the drying treatment temperature is 150 ℃, the drying treatment time is 5 hours, the roasting treatment temperature is 1100 ℃, and the roasting treatment time is 3 hours.
Example 6
The composite catalyst comprises 5% of aluminum oxide, 0.05% of first metal element and 3% of second metal element; the other conditions were the same as in example 5.
The preparation method of the composite catalyst is the same as that of example 5.
Example 7
The composite catalyst comprises 80% of aluminum oxide, 3% of first metal element and 3% of second metal element by mass; the other conditions were the same as in example 5.
The preparation method of the composite catalyst comprises the following steps:
the method comprises the steps of dipping a porous carbon carrier raw material into a mixed solution formed by aluminum sulfate, nitrate of a first metal element auxiliary agent, nitrate of a second metal element auxiliary agent and water to obtain a mixed system, adjusting the pH value of the mixed system to 7.9-8.2 by using 0.5mol/L KOH, performing solid-liquid separation, collecting and washing solid matters, and performing drying treatment and roasting treatment after washing, wherein the drying treatment temperature is 130 ℃, the drying treatment time is 4 hours, the roasting treatment temperature is 1000 ℃, and the roasting treatment time is 4 hours.
Comparative example 1
The composite catalyst was prepared under the same conditions as in example 5 except that the first metal element promoter was not contained.
The preparation method of the composite catalyst is the same as that of example 5.
Comparative example 2
The composite catalyst was prepared under the same conditions as in example 5 except that the auxiliary agent for the second metal element was not contained.
The preparation method of the composite catalyst is the same as that of example 5.
Examples of the experiments
Firstly, respectively catalyzing ozone oxidation MBR to produce water by using the composite catalysts prepared in the embodiments 1 to 4 by using the catalytic system, wherein the wastewater is taken from MBR effluent, the COD value is 100-300 mg/L, and the pH value is 6-9; the treatment conditions are as follows: under normal temperature and pressure, the adding amount of ozone is 15-300 mg/L, and O 3 (mg/L), wherein COD (mg/L) is 1.0-3.0, and the space velocity of the volume of the wastewater is as follows: 2 to 10 hours -1 。
The specific operation steps are as follows:
MBR produced water raw water of certain membrane enterprises: the water inflow is 400mL/h, the wastewater is directly and continuously added every other day, and the COD is not further treated and fluctuates in the interval of 105-330 mg/L. The processing device and the method as shown in FIG. 2 carry out the following steps: the hydraulic retention time of the wastewater in the heterogeneous ozone catalytic oxidation reactor is 30min, ozone aeration is carried out from the bottom after the catalyst is adsorbed and saturated (24-120h), the ozone adding concentration in the heterogeneous ozone catalytic oxidation reactor is 50-150mg/L, water samples of a water inlet and a water outlet are taken every 24h to test the COD value, the water quantity of the water outlet is 400mL/h, and the COD is 40-100 mg/L.
The treatment result is shown in fig. 1, and as can be seen from fig. 1, the composite catalyst of the present invention has long-acting and high-efficiency catalytic performance, can increase catalytic ozone oxidation efficiency, prolong stable operation service life in a reaction environment, and can efficiently remove COD in wastewater.
Secondly, taking the same amount of composite catalysts in the embodiments 5-7 and the comparative examples 1-2 to mix with ozone respectively, and treating the same wastewater respectively, wherein the specific operation steps are as follows:
diluting MBR produced water raw water of a certain membrane enterprise to a COD value of 200 mg/L: the water inflow of all catalytic reactors is controlled at 400mL/h, the hydraulic retention time of the wastewater in the heterogeneous ozone catalytic oxidation reactor is 30min, and the COD value of the inlet water and the outlet water is consistent when the wastewater is adsorbed to saturation. And then opening an ozone inlet valve at the bottom, aerating the wastewater and ozone at the bottom through an aeration disc, introducing the wastewater and the ozone into a reaction bed, adding the ozone into the heterogeneous ozone catalytic oxidation reactor at a concentration of 100mg/L, taking water samples at a water inlet and a water outlet every 24 hours to test COD (chemical oxygen demand) values, and taking a balance average value of 3-5.
The results of the treatment are shown in Table 1.
TABLE 1 results of wastewater treatment
| Group of | Initial COD of wastewater (mg/L) | COD removal Rate (%) |
| Example 5 | 200 | 70.2％ |
| Example 6 | 200 | 70.5％ |
| Example 7 | 200 | 45.8％ |
| Comparative example 1 | 200 | 23.1％ |
| Comparative example 2 | 200 | 30.0％ |
As can be seen from Table 1, the composite catalyst obtained by using the porous activated carbon as the carrier and loading the alumina, the first metal element assistant and the second metal element assistant in a proper proportion range has high stability, can increase the catalytic ozone oxidation efficiency, prolongs the stable service life of the operation in a reaction environment, and can efficiently remove COD in wastewater.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A composite catalyst is characterized by comprising a porous carbon carrier, and alumina, a first metal element assistant and a second metal element assistant which are loaded on the porous carbon carrier;
the first metal element auxiliary agent comprises an auxiliary agent A containing a transition metal element and/or an auxiliary agent B containing a rare earth metal element;
the second metal element assistant comprises an assistant C containing an alkali metal element and/or an assistant D containing an alkaline earth metal element;
based on the mass of the composite catalyst, the mass proportion of the alumina is 5-80%, the mass proportion of the first metal element in the first metal element auxiliary agent is 0.05-3%, and the mass proportion of the second metal element in the second metal element auxiliary agent is 0.05-3%.
2. The composite catalyst according to claim 1, characterized by comprising at least one of the following features (1) to (8):
(1) the transition metal element comprises at least one of Mn, Co, Cu, Ni and Fe;
(2) the rare earth metal element includes Ce;
(3) the alkali metal element includes at least one of Na and K;
(4) the alkaline earth metal element includes at least one of Ca and Mg;
(5) the auxiliary agent A comprises an oxide corresponding to the transition metal element;
(6) the auxiliary agent B comprises an oxide corresponding to the rare earth metal element;
(7) the auxiliary C comprises an oxide corresponding to the alkali metal element;
(8) the auxiliary agent D comprises an oxide corresponding to the alkaline earth metal element.
3. The composite catalyst according to claim 2, characterized by comprising at least one of the following features (1) to (3):
(1) the mass ratio of the transition metal element of the auxiliary agent A to the rare earth metal element of the auxiliary agent B is (1-3): 1;
(2) the mass ratio of the alkali metal element of the auxiliary C to the alkaline earth metal element of the auxiliary D is (0.2-20): (0.01-1).
4. Composite catalysis according to claim 1The catalyst is characterized in that the particle size of the composite catalyst is 3-5 mm, and the specific surface area is 80-500 m 2 /g。
5. The method for preparing the composite catalyst according to any one of claims 1 to 4, comprising the steps of:
carrying out one-step impregnation or step-by-step impregnation on a porous carbon carrier raw material to obtain a mixed system, adjusting the pH of the mixed system to 5-10 by adopting alkali liquor, carrying out solid-liquid separation, collecting solid matters, and carrying out drying treatment and roasting treatment;
the one-step impregnation comprises: dipping a porous carbon carrier raw material into a mixed solution formed by soluble aluminum salt, soluble salt of a first metal element auxiliary agent, soluble salt of a second metal element auxiliary agent and water;
the step-by-step impregnation comprises the following steps: soaking a porous carbon carrier raw material into a soluble aluminum salt solution, and performing primary drying and primary roasting to obtain an aluminum element-loaded porous carbon carrier; and soaking the porous carbon carrier loaded with the aluminum element in a mixed solution formed by soluble salt of a first metal element assistant, soluble salt of a second metal element assistant and water.
6. The method for producing a composite catalyst according to claim 5, characterized by comprising at least one of the following features (1) to (4):
(1) the porous carbon carrier is spherical or columnar;
(2) the particle size of the porous carbon carrier is 3-5 mm, and the specific surface area is 100-1200 m 2 The pore volume is 0.5-1 mL/g, and the pore diameter is 0.5-5 nm;
(3) the alkali liquor comprises NaOH, KOH and Na 2 CO 3 And K 2 CO 3 At least one of;
(4) the concentration of the alkali liquor is 0.01-1 mol/L.
7. The method for producing a composite catalyst according to claim 5, characterized by comprising at least one of the following features (1) to (5):
(1) the drying temperature is 60-200 ℃, and the drying time is 2-12 h;
(2) the roasting temperature is 300-1200 ℃, and the roasting time is 1-24 h;
(3) the temperature of the primary drying is 80-150 ℃, and the time of the primary drying is 2-10 h;
(4) the temperature of the primary roasting is 800-1200 ℃, and the time of the primary roasting is 1-15 h;
(5) the primary roasting and the roasting treatment are respectively carried out under the vacuum condition or the protective gas condition; the protective gas comprises at least one of hydrogen, nitrogen, or an inert gas.
8. A method for treating wastewater, characterized by comprising the steps of:
mixing ozone, wastewater and the composite catalyst according to any one of claims 1 to 4.
9. The method of treating wastewater according to claim 8, wherein the COD of the wastewater is 100 to 300mg/L and the pH is 6 to 9.
10. The wastewater treatment method according to claim 9, wherein the amount of ozone added is 15 to 300mg per liter of the wastewater;
in each liter of wastewater, the mass ratio of the ozone to the COD is (1-3): 1.
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