CN114130401B - Copper-lanthanum co-modified aluminum-based catalyst and preparation method thereof - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- -1 Copper-lanthanum co-modified aluminum Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 238000004043 dyeing Methods 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 8
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 8
- 229940012189 methyl orange Drugs 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a copper-lanthanum co-modified aluminum-based catalyst, which solves the problems of narrow applicable pH condition, large amount of iron mud generation and lower catalytic efficiency of a Fenton catalyst. The invention comprises the following steps: 1) Mixing a Cu source and a La source, and adding the mixture into the pseudo-boehmite dispersion to obtain a blue precursor; 2) Dropwise adding an alkali solution into the blue precursor solution, maintaining the pH value to be 8.5-10.5, and continuously stirring for reaction to obtain a mixed solution; filtering, cleaning, drying, grinding and roasting the precipitate obtained after the mixed solution is aged; 4) Grinding and shaping the roasted product to obtain a granular catalyst CL-Al 2 O 3 . The invention also provides a catalyst prepared by the method. The copper-lanthanum co-modified aluminum-based catalyst has the advantages of high catalytic efficiency, good stability, wide pH application range and small iron mud yield, and is particularly suitable for treating printing and dyeing wastewater.
Description
Technical Field
The invention relates to the technical field of environmental functional materials, in particular to a copper-lanthanum co-modified aluminum-based catalyst and a preparation method thereof.
Background
Fenton reaction mainly depends on Fe 2+ Catalytic H 2 O 2 To oxidatively cleave organic matter, under ideal conditions Fe 2+ The strongly oxidizing species OH and O can be produced by free radical chain reaction 2 - (equations 1-2). The Fenton reaction has the advantages of higher speed, easy operation, lower cost and H 2 O 2 Has environmental friendliness, so that the method is often used as an advanced oxidation means to pretreat industrial wastewater difficult to biochemically treat so as to improve biochemistry. However, the Fenton technology has limited operating conditions. Only under strongly acidic conditions (pH<3)，Fe 2+ Has stronger activity, and once the alkalinity of the solution is enhanced, fe 2+ Extremely easy to precipitate and finally convert into Fe (OH) 3 The reaction is deactivated. The pH conditions applicable to the Fenton technique are therefore relatively stringent. Meanwhile, a large amount of iron mud is easy to generate in the reaction process, and extra cost is added for subsequent treatment. These drawbacks limit the effectiveness of the homogeneous Fenton reaction in practical industrial wastewater treatment applications.
Fe 2+ +H 2 O 2 →Fe 3+ +·OH+OH - (1)
Fenton-like technology takes nonferrous transition metal as an active site for catalyzing hydrogen peroxide, and aims to replace Fe 2+ Role in Fenton reaction, but the final purpose is to promote H under catalysis 2 O 2 The O-O bond of (C) is broken to generate oxygen active species, and the target substance is further oxidized and decomposed.
The heterogeneous Fenton-like catalyst can provide a sufficient solid-liquid phase interface, greatly reduce precipitation of an active phase, effectively improve the utilization efficiency of hydrogen peroxide, reduce the generation of iron mud and reduce the operation cost. Therefore, heterogeneous Fenton has better application prospect than homogeneous Fenton-like reaction.
The existing heterogeneous Fenton-like catalyst is usually prepared by taking transition metals such as Fe, cu, mn and the like as active components, mutually matching and mixing, and preparing by a coprecipitation method or an impregnation method, and the heterogeneous Fenton-like catalyst can alleviate the problem of large production of homogeneous Fenton iron mud to a certain extent, but has the problems that the metal activity is not fully exerted, and the hydrogen peroxide utilization rate is low, so that the catalytic efficiency is not ideal.
Disclosure of Invention
The invention aims to solve the technical problems and provide a preparation method of the copper-lanthanum co-modified aluminum-based catalyst, which is simple in process, easy to prepare and low in production cost.
The copper-lanthanum co-modified aluminum-based catalyst prepared by the preparation method provided by the invention has the advantages of high catalytic efficiency, good stability, wide pH application range and small iron mud yield, and is particularly suitable for treating printing and dyeing wastewater.
The preparation method of the copper-lanthanum co-modified aluminum-based catalyst comprises the following steps:
1) Mixing a Cu source and a La source, and adding the mixture into the pseudo-boehmite dispersion to obtain a blue precursor;
2) Dropwise adding an alkali solution into the blue precursor solution, maintaining the pH value to be 8.5-10.5, and continuously stirring for reaction to obtain a mixed solution;
3) Filtering, cleaning, drying, grinding and roasting the precipitate obtained after the mixed solution is aged;
4) Grinding and shaping the roasted product to obtain a granular catalyst CL-Al 2 O 3 。
In the step 1), the Cu source is selected from Cu (NO) 3 ) 2 、CuSO 4 、CuCl 2 At least one of (a) and (b); the La source is selected from La 2 (SO 4 ) 3 、La(NO 3 ) 3 、LaCl 3 At least one of them.
In the step 1), the addition amount of the Cu source is 10-20 mol percent of that of the pseudo-boehmite Al source, and the addition amount of the La source is 5-50 mol percent of that of the Cu source.
In the step 1), the concentration of the pseudo-boehmite dispersion is 0.2-2mol/L.
In the step 2), the reaction temperature is 40-80 ℃.
In the step 2), the alkali solution added dropwise is NaOH, KOH or NH 3 ·H 2 At least one of O, controlling OH in alkaline solution - The concentration is 0.5-1mol/L, and the stirring time is 2-4 h.
In the step 3), the aging temperature is 50-80 ℃, the aging time is 12-24h, and the drying temperature is 50-80 ℃.
In the step 3), the roasting temperature is 400-800 ℃ and the roasting time is 2-4 h.
The copper-lanthanum co-modified aluminum-based catalyst is prepared by the method.
Aiming at the problems existing in the background technology, the invention constructs a La, cu co-modified aluminum-based catalyst, introduces La (III) transition metal which can be used as Lewis acid to be added with H in a Lewis acid-base addition mode 2 O 2 Coupling is carried out, and oxygen vacancies can be introduced at the same time, thereby improving H 2 O 2 Contact with the catalyst accelerates the electron transport efficiency, thereby improving H 2 O 2 The degradation efficiency of the organic matters is further improved. Catalytic hydrogen peroxide generation by Cu (I) in Fenton-like process and La as Lewis acid coupling hydrogen peroxide generation by O 2 - And promote the degradation of organic matters together. La (III) enters a CuO crystal phase in a doping mode, lattice defects can be introduced, so that the activation energy of the surface of a catalyst is improved, the transfer and transfer of electrons in the oxidation-reduction process are facilitated, the oxidation capacity of hydrogen peroxide can be promoted, the degradation efficiency of pollutants Cu (II)/Cu (I) is improved, the oxidation-reduction potential is lower, and hydrogen peroxide decomposition is easier to catalyze than Fe (III)/Fe (II). The Cu-based compound can lead H to be in a wide range of pH3-7 2 O 2 Effectively decompose and generate oxygen active species, thereby greatly widening the application range of pH; by the synergistic effect of Cu and La, as Al 2 O 3 As the carrier, the high-efficiency heterogeneous Fenton reaction catalyst is constructed, the problem of mass production of iron mud in the homogeneous Fenton reaction can be effectively reduced, the hazardous waste disposal cost is reduced,and under the condition of pH5-7, the Fenton system has the advantages that the COD degradation efficiency of organic matters in printing and dyeing wastewater is more than 50%, the ion dissolution is less than 5%, the degradation efficiency of Fenton reaction on the organic matters is improved in a wider pH range, and the method has significance of practical industrial application.
On the basis, the addition amount of the Cu source is preferably 10 to 20 mol percent of that of the pseudo-boehmite Al source so as to ensure that the Cu oxide can be uniformly dispersed in the Al 2 O 3 The surface is too much to cause active material agglomeration, reduce the exposure of active sites, influence the catalytic efficiency, and too little to cause insufficient contact between the active sites and organic matters; the addition amount of the La source is 5-50 mol percent of that of the Cu source, so that lattice defects are introduced by small amount doping, the La source is covered on the Cu active site due to excessive doping, the generation of vacancies is inhibited, and the active components and H are influenced due to the excessive doping 2 O 2 And the electron transport efficiency is reduced.
Adding an alkali solution dropwise into the blue precursor solution for coprecipitation reaction, preferably controlling the pH of the reaction to be 8.5-10.5, wherein too high can lead to precipitate agglomeration, too low can lead to incomplete precipitation of a metal source, and the reaction temperature is 40-80 ℃, and too high or too low can influence the precipitation efficiency and the generation of crystal lattice vacancies.
The beneficial effects are as follows:
(1) The preparation method of the catalyst is simple, easy to operate, high in yield, convenient for industrial mass production, and convenient for subsequent granulation and molding.
(2) CL-Al prepared by the method of the invention 2 O 3 The catalyst has stable property, the removal efficiency of methyl orange can still be more than 70 percent after the catalyst is subjected to catalytic reaction for a plurality of times, and the dissolution rate of metal ions is less than 5 percent, so that the generation of iron mud is effectively avoided.
(3) CL-Al prepared by the invention 2 O 3 The catalyst has wider application range, compared with the traditional Fenton reaction, the severe pH condition limit is broken through. Under the condition of pH3-7, the Fenton-like system coupled with hydrogen peroxide can carry out high-efficiency treatment on methyl orange solution and actual printing and dyeing wastewater, and COD degradation efficiency>50％。
Drawings
FIG. 1 is a graph comparing the COD removal results of the methyl orange solutions of examples 1-5 according to the present invention.
Fig. 2 is a graph showing the effect of reuse according to embodiment 2 of the present invention.
Detailed Description
Example 1: the preparation method of the copper-lanthanum co-modified aluminum-based catalyst comprises the following steps:
preparing pseudo-boehmite dispersion with the concentration of 2 mol/L: 22.864g of pseudo-boehmite is weighed and dispersed in 200mL of deionized water, fully sonicated and stirred. 9.644g of Cu (NO) were then weighed out separately 3 ) 2 ·3H 2 O，8.66g La(NO 3 ) 3 ·6H 2 O is added to the dispersion, and La source: the molar ratio of the Cu source is 0.5:1. stirring was carried out at room temperature for 2h. Then the mixed solution is placed in a water bath kettle, the temperature of the solution is maintained at 60 ℃, and 1mol/L NaOH solution is dropwise added into the solution under the condition of stirring speed of 200r/min, so that the pH of the solution is maintained to 10.5. After 2h, stirring was stopped and aged at 60℃for 12h. The resulting precipitate was centrifuged and washed three times with deionized water and dried overnight in an oven at 80 ℃. Taking out, grinding, calcining in muffle furnace for 4 hr at 600deg.C, cooling to room temperature, taking out the sample, grinding uniformly, and marking as CL-Al 2 O 3 -0.5。
Example 2:
a process for preparing Cu-La co-modified Al-base catalyst includes such steps as preparing the pseudo-boehmite dispersion liquid with concentration of 1mol/L, ultrasonic stirring. And then respectively weighing4.572gCuCl 2 ·H 2 O，1.06g LaCl 3 6H2O was added to the dispersion, at which time the La source: the molar ratio of the Cu source is 0.1:1. stirring for 3h at room temperature. Then the mixed solution is placed in a water bath kettle, the temperature of the solution is maintained at 80 ℃, and 1mol/L NaOH solution is dropwise added into the solution under the condition of stirring speed of 200r/min, so that the pH of the solution is maintained to 8.5. After 2h, stirring was stopped and aged at 50℃for 20h. The resulting precipitate was centrifuged and washed three times with deionized water and dried overnight in an oven at 50 ℃. Taking out, grinding, calcining in muffle furnace for 3 hr at high tempAfter the temperature is 500 ℃ and the room temperature is reduced, taking out the sample, grinding the sample uniformly, and marking the prepared catalyst as CL-Al 2 O 3 -0.1。
Example 3: a preparation method of a copper-lanthanum co-modified aluminum-based catalyst comprises the steps of preparing a pseudo-boehmite dispersion liquid with the concentration of 0.2mol/L, fully carrying out ultrasonic treatment and stirring. Then, 0.998g of CuSO was weighed out separately 4 ·5H 2 O，0.011g La 2 (SO 4 ) 3 Adding into the dispersion liquid, wherein La source: the molar ratio of the Cu source is 0.05:1. stirring is carried out at room temperature for 4h. Then the mixed solution is placed in a water bath kettle, the temperature of the solution is maintained at 40 ℃, and 1mol/L NaOH solution is dropwise added into the solution under the condition of stirring speed of 200r/min, so that the pH of the solution is maintained to 9. After 2h, stirring was stopped and aged at 80℃for 24h. The resulting precipitate was centrifuged and washed three times with deionized water and dried overnight in an oven at 70 ℃. Taking out, grinding, calcining in a muffle furnace for 2h at 800 ℃, cooling to room temperature, taking out the sample, grinding uniformly, and marking the prepared catalyst as CL-Al 2 O 3 -0.05。
Comparative example 1: a method for preparing copper-lanthanum co-modified aluminum-based catalyst is different from example 2 in that La salt is not added in the preparation process of the precursor. The catalyst prepared is Cu-Al 2 O 3 。
Comparative example 2: a method for preparing a copper-lanthanum co-modified aluminum-based catalyst is different from example 2 in that Cu salt is not added in the preparation process of a precursor. The catalyst prepared is named La-Al 2 O 3 。
Comparative example 3: preparation of aluminium-based catalyst (control)
Preparing pseudo-boehmite dispersion with the concentration of 0.4 mol/L: 35.22g of pseudo-boehmite is weighed and dispersed in 200mL of deionized water, fully sonicated and stirred. Then the solution is placed in a water bath kettle, the temperature of the solution is maintained at 60 ℃, and 1mol/L NaOH solution is dropwise added into the solution under the condition of stirring speed of 200r/min, so that the pH of the solution is maintained to 9. After 2h, stirring was stopped and aged at 60℃for 12h. The resulting precipitate was centrifuged and washed three times with deionized water and dried overnight in an oven at 80 ℃. Taking outGrinding, calcining in muffle furnace for 4 hr at 600deg.C, cooling to room temperature, taking sample, grinding uniformly, and marking as gamma-Al 2 O 3 。
Comparison experiment:
experiment 1: and constructing a Fenton-like system by combining the catalyst and hydrogen peroxide, taking methyl orange as a target pollutant, and evaluating the degradation efficiency of the methyl orange under the Fenton-like system. The specific operation is as follows: 200mg/L of methyl orange solution (200 mL) was prepared, 1g/L of the catalyst (examples 1-4) was added to the solution, the pH of the solution was adjusted to 5, and the solution was stirred at 200r/min for 2 hours to saturate the catalyst with adsorption. Subsequently, 30mmol/L H was added 2 O 2 To start the reaction, the reaction temperature is 35+/-2 ℃ and the reaction time is 2 hours. The rotational speed is maintained constant during the reaction. Samples were taken at intervals, filtered through 0.22 μm acetate membranes, the filtered water samples were tested for CODcr, and the removal efficiency of CODcr from the methyl orange solution was calculated.
As shown in fig. 1, the adsorption efficiency of all catalysts to methyl orange was less than 10%. In all examples, the catalyst prepared in example 2 had the highest activity and the CODcr removal after 2 hours could reach 86%. The catalyst activity shown in example 1 was about 30% lower than that in example 2. The catalyst prepared in example 3 had a catalytic efficiency about 15% lower than that of example 2, but the overall removal efficiency of COD in examples 1 and 3 was still greater than 50%. Comparative examples 1 and 3 show little catalytic activity. The low activity of comparative example 1 indicates that a single La component cannot catalyze the decomposition of hydrogen peroxide. The catalyst shown in comparative example 2 has low catalytic activity due to the modification without La, and has only 30% of COD degradation efficiency on methyl orange solution. Thus, the Cu-La co-modified aluminum-based catalyst shows good Fenton-like catalytic activity, can effectively degrade methyl orange, and has much higher degradation efficiency than the gamma-Al modified by Cu alone, and La modified and unmodified 2 O 3 . Among them, example 2 had the highest catalytic activity, and the subsequent evaluation was carried out using example 2 as a main reference.
Experiment 2: example 2 was combined with hydrogen peroxide and examined for catalytic activity and COD removal in methyl orange solution at different pH conditionsAnd (5) removing rate. The specific operation mode is as follows: 200mL of a methyl orange solution (200 mg/L) was prepared, 1g/L of the catalyst prepared in example 2 was added to the solution, and the mixture was stirred sufficiently at a rate of 200r/min for 2 hours to reach adsorption saturation. The pH of the solution was then adjusted to 3,5,7, respectively. Adding 30% H to the solution 2 O 2 The concentration of hydrogen peroxide in the mixed solution reaches 30mmol/L. The reaction temperature is 35+/-2 ℃ and the reaction time is 2 hours. The rotational speed is maintained constant during the reaction. Sampling at intervals, filtering with 0.22 μm acetate fiber membrane, and detecting CODcr and metal Cu in the filtered water sample 2+ ,La 3+ And Al 3+ 。
As can be seen from table 1, the COD degradation efficiency of the Fenton-like reaction system on methyl orange gradually decreases with the increase of the reaction pH. At ph=3, the catalytic effect is best, and the COD degradation rate can reach 91%. At ph=7, the COD degradation efficiency was 74%. Overall, example 2 satisfies COD removal efficiency at pH3-7>70%, and has wide application range. Cu was measured at pH5-7 2+ ，La 3+ Al and 3+ the dissolution rates of the water-soluble polymer are all less than 5%, and good stability is shown.
TABLE 1
| pH | 3 | 5 | 7 |
| COD removal Rate (%) | 91 | 86 | 74 |
| Cu 2+ Dissolution Rate (%) | 6.9 | 3.8 | 2.1 |
| La 3+ Dissolution Rate (%) | 4.9 | 2.3 | 1.1 |
| Al 3+ Dissolution Rate (%) | 7.7 | 4.9 | 2.3 |
Experiment 3: example 2 was combined with hydrogen peroxide and the cyclic stability of example 2 was examined at ph=5. The specific operation mode is as follows: 200mL of a methyl orange solution (200 mg/L) was prepared, 1g/L of the catalyst prepared in example 2 was added to the solution, and the mixture was stirred sufficiently at a rate of 200r/min for 2 hours to reach adsorption saturation. The pH of the solution was then adjusted to 5. Adding 30% H to the solution 2 O 2 The concentration of hydrogen peroxide in the mixed solution reaches 30mmol/L. The reaction temperature is 35+/-2 ℃ and the reaction time is 2 hours. After the reaction is finished, the catalyst is centrifugally separated, washed three times by deionized water and put into a muffle furnace for calcination and regeneration. Calcination temperature is 600 ℃ and time is 4 hours. The regenerated catalyst is subjected to the next round of catalytic experiments, and the steps are repeated for three times, so that the COD of the solution after each round of catalytic reaction is measured.
As shown in FIG. 2, after three catalytic-regeneration reactions, the degradation efficiency of the catalyst prepared in example 2 to methyl orange COD in the Fenton-like system can still reach more than 75%, so that the catalyst has better cycle stability.
Experiment 4: the catalyst prepared in example 2 was combined with hydrogen peroxide to construct Fenton-like system, and the removal effect of the Fenton-like system on COD of the actual printing and dyeing wastewater was evaluated. The specific operation is as follows: 200mL of actual printing and dyeing wastewater is taken. 3g/L of the catalyst prepared in example 2 was added to the solution, and the mixture was stirred sufficiently at a rate of 200r/min for 2 hours to reach adsorption saturation. The pH of the solution was then adjusted to 3. Adding 30% H to the solution 2 O 2 The concentration of hydrogen peroxide in the mixed solution reaches 50mmol/L. The reaction temperature is 35+/-2 ℃ and the reaction time is 2 hours. The rotational speed is maintained constant during the reaction. Samples were taken at intervals, filtered through 0.22 μm acetate membranes, and the filtered water samples were tested for CODcr and compared to the results of the homogeneous Fenton reaction. The homogeneous Fenton reaction is operated as follows: 200mL of actual printing and dyeing wastewater is taken, and the pH is adjusted to 3. 0.681g FeSO was added to the mixed solution 4 ·7H 2 O and 100mmol/LH 2 O 2 The reaction was started. The reaction temperature is 35+/-2 ℃, the reaction time is 2 hours, and the rotating speed is 200r/min. Samples were taken at intervals, filtered through 0.22 μm acetate membranes and the filtered water samples were tested for CODcr.
As shown in table 2, the Fenton-like reaction system formed by example 2 and hydrogen peroxide has the removal efficiency of 56% on actual printing and dyeing wastewater, the Fenton-like system has the removal efficiency of only 27%, the Fenton-like removal effect is 2 times that of Fenton, and further shows that the Fenton-like catalyst prepared by the invention also has good catalytic activity in the process of catalyzing hydrogen peroxide to degrade actual printing and dyeing wastewater, is far greater than that of a homogeneous Fenton reagent, has no iron sludge generation, and has good application prospect.
TABLE 2
Claims (6)
1. The application of a catalyst in degrading methyl orange solution or actual printing and dyeing wastewater in a Fenton-like system coupled with hydrogen peroxide is characterized in that the catalyst is a copper-lanthanum co-modified aluminum-based catalyst, the reaction condition is pH3-7, and the preparation method of the catalyst comprises the following steps:
1) Mixing a Cu source and a La source, and adding the mixture into the pseudo-boehmite dispersion to obtain a blue precursor; the addition amount of the Cu source is 10-20 mol percent of the pseudo-boehmite Al source, and the addition amount of the La source is 5-50 mol percent of the Cu source;
2) Dropwise adding an alkali solution into the blue precursor solution, maintaining the pH value to be 8.5-10.5, and continuously stirring for reaction to obtain a mixed solution;
3) Filtering, cleaning, drying, grinding and roasting the precipitate obtained after the mixed solution is aged; the aging temperature is 50-80 ℃, the aging time is 12-24 hours, and the drying temperature is 50-80 ℃;
4) Grinding and shaping the roasted product to obtain a granular catalyst CL-Al 2 O 3 。
2. The use according to claim 1, wherein in step 1) the Cu source is selected from Cu (NO 3 ) 2 、CuSO 4 、CuCl 2 At least one of (a) and (b); the La source is selected from La 2 (SO 4 ) 3 、La(NO 3 ) 3 、LaCl 3 At least one of them.
3. The use according to claim 2, wherein in step 1) the concentration of pseudo-boehmite dispersion is between 0.2 and 2mol/L.
4. The use according to claim 2, wherein in step 2) the reaction temperature is 40-80 ℃.
5. The use according to claim 1, wherein in step 2) the base is NaOH, KOH or NH 3 ·H 2 At least one of O, controlling OH in alkaline solution - The concentration is 0.5-1mol/L, and the stirring time is 2-4 h.
6. The use according to claim 1, wherein in step 3) the calcination temperature is 400-800 ℃ and the calcination time is 2-4 hours.
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