CN109174199B - Method for preparing Fenton-like catalyst and synchronously regenerating active carbon by microwave and application - Google Patents
Method for preparing Fenton-like catalyst and synchronously regenerating active carbon by microwave and application Download PDFInfo
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- CN109174199B CN109174199B CN201811345382.6A CN201811345382A CN109174199B CN 109174199 B CN109174199 B CN 109174199B CN 201811345382 A CN201811345382 A CN 201811345382A CN 109174199 B CN109174199 B CN 109174199B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 title claims description 20
- 229920001661 Chitosan Polymers 0.000 claims abstract description 30
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 8
- 150000002505 iron Chemical class 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 239000004005 microsphere Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 claims description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims 1
- 230000001360 synchronised effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 229910052742 iron Inorganic materials 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- -1 iron ions Chemical class 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000002386 leaching Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 150000004690 nonahydrates Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229960005404 sulfamethoxazole Drugs 0.000 description 3
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 3
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000013313 FeNO test Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/36—Reactivation or regeneration
- C01B32/366—Reactivation or regeneration by physical processes, e.g. by irradiation, by using electric current passing through carbonaceous feedstock or by using recyclable inert heating bodies
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- 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
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Abstract
The invention belongs to the technical field of functional materials and environmental protection, and particularly relates to a method for preparing a Fenton-like catalyst by microwave and synchronously regenerating activated carbon and application thereof, wherein the method uses cheap iron salt, chitosan and the like as raw materials, and quickly carbonizes a chitosan precursor by using heat generated by microwave regeneration of the activated carbon, so that the energy consumption and time for preparing the catalyst are greatly saved; the Fenton-like catalyst obtained by the invention mainly comprises nano ferroferric oxide particles and amorphous carbon, and has stronger magnetism, mechanical strength, chemical stability and better catalytic activity; the method has the advantages of simple process, low energy consumption and high efficiency, and the efficient, stable and cheap Fenton-like catalyst is prepared in an auxiliary manner while the activated carbon is regenerated, so that the method has a wide application prospect in the field of environmental protection.
Description
Technical Field
The invention belongs to the technical field of functional materials and environmental protection, and particularly relates to a method for preparing a Fenton-like catalyst by microwave and synchronously regenerating activated carbon and application thereof.
Background
The advanced oxidation technologies such as an electrocatalytic oxidation method, a photocatalytic method, an ozone oxidation method, a wet oxidation method, a Fenton-like method and the like can decompose and mineralize most of organic matters, and have a good effect of removing refractory organic matters. The heterogeneous Fenton-like method loads the catalyst on a stable matrix, and has the advantages of wide pH application range, small dosage of the medicament, mild application conditions, high degradation efficiency and the like. However, currently, fenton-like catalysts are mainly composed of powdery nanoparticles, and in order to improve catalytic activity, heavy metal elements such as Cu, Ni, and Co are generally doped. Although the catalyst has a large specific surface area and high catalytic activity, the catalyst is difficult to recover in the actual use process, and nano pollution and heavy metal pollution are easily caused after loss. Meanwhile, the traditional catalyst preparation and regeneration methods usually face the problems of long heat treatment time, atmosphere protection, high process energy consumption and the like.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a method for preparing a Fenton-like catalyst by microwave and synchronously regenerating activated carbon and application thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
a method for preparing a Fenton-like catalyst by microwave and synchronously regenerating activated carbon comprises the following steps:
the Fenton-like catalyst precursor and the active carbon which adsorbs the organic matters are mixed and put into a microwave reactor for reaction.
Preferably, the Fenton-like catalyst precursor is chitosan/Fe (OH)3Xerogel microspheres.
Preferably, the microwave reaction power is 600-800W; the time is 2-5 min.
Preferably, after the microwave reaction, the fenton-like catalyst is separated from the activated carbon by a magnet.
Preferably, the preparation method of the fenton-like catalyst precursor comprises the following steps:
step 1, mixing chitosan, ferric salt and an organic acid aqueous solution to prepare sol A;
step 2, dropwise adding the sol A into an alkaline aqueous solution to obtain chitosan/Fe (OH)3Gel microspheres;
step 3, the obtained product isThe chitosan/Fe (OH)3Washing and drying the gel microspheres to obtain chitosan/Fe (OH)3Xerogel microspheres.
Preferably, in the step 1, the mass ratio of the iron element to the chitosan in the sol A is 1 (5-7).
Preferably, in the step 1, the mass fraction of chitosan in the sol A is 0.5-5%.
Preferably, in the step 1, the iron salt is FeCl3、FeNO3、Fe2(SO4)3Any one or more of them.
Preferably, in the step 1, the organic acid may be any one or more of formic acid, acetic acid, citric acid and oxalic acid.
The Fenton-like catalyst can be used for degrading organic matters in wastewater. For example, the method is used for treating wastewater containing dye, sulfamethoxazole, tetracycline hydrochloride, bisphenol A and the like.
Compared with the prior art, the invention has the advantages that,
the invention fully utilizes the heat generated during the microwave regeneration of the active carbon, uses cheap chitosan and iron sources, and synchronously prepares the magnetic biochar-based Fenton catalyst, and the preparation method is simple and environment-friendly, has low process cost, short period and low energy consumption. The prepared Fenton-like catalyst has a developed pore structure, high chemical stability, high mechanical property and high magnetism, and can be quickly separated and recovered from a solution under the action of a magnetic field. The ferroferric oxide nano particles and a small amount of simple substance iron are used as main catalytic sites of the catalyst, are uniformly distributed on the surface of the carbon matrix and are embedded in the carbon matrix, the reusability is good, the leaching amount of iron ions in the using process is small, and the catalyst can be rapidly regenerated after being unstable, so that the stability of the material is recovered.
The catalyst of the invention is characterized in that in the process of contacting with wastewater, solid-phase iron oxide and H2O2Heterogeneous Fenton-like reaction occurs to generate hydroxyl free radical and superoxide free radical with strong oxidizing property. The iron monomer in the catalyst can generate iron-carbon micro-electrolysis effect with the carbon matrix. Both of the above processes can release iron ions into the solutionActing as a homogeneous fenton-like catalyst. And abundant surface oxygen-containing functional groups on the carbon matrix can be complexed with iron ions in the solution, and the formed complex can accelerate Fe2+/Fe3+Thereby further promoting the decomposition of the organic matter.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a scanning electron microscope image of the magnetic biochar microspheres obtained in examples 1, 2 and 3 of the present invention;
FIG. 3 is a transmission electron micrograph of magnetic biochar microspheres obtained in example 1 of the present invention;
FIG. 4 is an XRD spectrum of the magnetic biochar microspheres obtained in examples 1 to 6 of the present invention.
Detailed Description
Example 1:
first), 6g of chitosan is weighed, 2% acetic acid solution is added to 200g, and stirring is carried out until the chitosan is dissolved. Weighing 6.18g of nonahydrate and ferric nitrate (the mass ratio of the iron element to the chitosan is 1:7), slowly adding into the chitosan solution, and continuously stirring until the mixture is uniformly mixed; one end of a peristaltic pump hose is inserted into the mixed solution, the other end of the hose is suspended above a short beaker filled with 300ml of 1mol/LNaOH, the rotating speed of a magnetic rotor in the beaker is set to be 200rmp/min, the rotating speed of the peristaltic pump is set to be 30rmp/min, and the mixed solution is continuously dropped into an alkaline solution in a form of liquid drops to be crosslinked to form gel microspheres. Repeatedly washing the gel microspheres with distilled water until the pH value is not changed any more, and drying the gel microspheres in an oven at 80 ℃ for 2h (drying to constant weight) to prepare xerogel microspheres;
secondly), adding 10g of coal-made active carbon into 200mL of 500mg/L acid orange solution, oscillating for 6h at 120rmp/min on a shaking table at the temperature of 25 ℃, taking out and drying, and calculating the adsorption quantity of the coal-made active carbon;
and thirdly), filtering and drying the granular active carbon saturated with the adsorbed acid orange, weighing 10g of active carbon and 2g of dried gel, uniformly mixing, and putting into a microwave reactor for reaction, wherein the microwave power is set to be 600W, and the microwave reaction time is 2 min. And after the reaction is finished and the biological carbon microspheres are naturally cooled, separating the magnetic biological carbon microspheres by using a magnet, removing surface impurities by using dilute hydrochloric acid, ethanol and deionized water, and finally drying to obtain the magnetic biological carbon Fenton catalyst.
Fourthly), adding the regenerated active carbon into 200mL of acid orange solution with the concentration of 500mg/L, oscillating for 6h on a shaking table with the temperature of 25 ℃ at 120rmp/min, and taking out the active carbon, and calculating the adsorption quantity of the regenerated coal active carbon.
The electron micrograph of the magnetic biochar microspheres obtained in this example is shown in FIG. 2(a), and the cross-sectional view is shown in FIG. 2 (b).
The transmission electron micrograph of the magnetic biochar microspheres obtained in this example is shown in FIG. 3.
In example 1, FeCl for iron nitrate3Or Fe2(SO4)3Instead, the prepared Fenton-like catalyst has the same shape and property.
Example 2:
this embodiment is different from example 1 in that the amount of the nonahydrate and the ferric nitrate added in the first step) was 7.21g (the mass ratio of the iron element to the chitosan was 1:6), and the other steps were the same as example 1.
The electron micrograph of the magnetic biochar microspheres obtained in this example is shown in FIG. 2(c), and the cross-sectional view is shown in FIG. 2 (d).
Example 3:
this embodiment is different from example 1 in that the amount of the nine water and the ferric nitrate added in the step one) is 8.65g (the mass ratio of the iron element to the chitosan is 1:5), and the other steps are the same as example 1.
The electron micrograph of the magnetic biochar microspheres obtained in this example is shown in FIG. 2(e), and the cross-sectional view is shown in FIG. 2 (f).
Example 4:
this embodiment is different from example 2 in that the microwave reaction time in the third step) is 3min, and the rest is the same as example 2.
Example 5:
this embodiment is different from example 2 in that the microwave reaction time in the third step) is 4min, and the rest is the same as example 2.
Example 6:
this embodiment is different from example 2 in that the microwave reaction power in the third step) is 800W, and the other steps are the same as example 2.
Example 7:
the degradation rate of acid orange is taken as an index for investigating the activity of the catalyst, the dissolving-out concentration of iron is taken as an index for investigating the stability of the catalyst, and the influences of different iron elements and the quality of chitosan, the microwave reaction time and the microwave power on the activity and the stability of the catalyst are investigated. 0.1g of the catalyst described in examples 1 to 6 was put into a 100mL conical flask, and 50mL of 25mg/L acid orange solution and 0.1mL of hydrogen peroxide (30 wt%) solution were added in this order, and after reaction for 1 hour in a shaker at a rotation speed of 120rpm and a temperature of 50 ℃, the removal rate of acid orange in the solution and the iron content in the solution were measured without adjusting the pH of the solution.
The method of the invention changes the adsorption quantity of the activated carbon to the acid orange before and after regeneration into an investigation index of the regeneration effect of the activated carbon, and investigates the influence of different microwave reaction time and microwave power on the adsorption quantity of the regenerated granular activated carbon to the acid orange.
The above results are shown in the following table:
as can be seen from the results in the above table, the catalyst of the present invention shows good treatment effect when used for treating dye wastewater, and XRD spectrum results in FIG. 4 show that the material structure is not changed significantly after the reaction is finished, and can still be recovered rapidly by a magnet. Meanwhile, the activated carbon can be well regenerated.
Example 8:
0.1g of the catalyst obtained in example 2 was weighed into a 100mL Erlenmeyer flask, and 50mL of a 25mg/L bisphenol A solution and 0.1mL of a 30 wt% hydrogen peroxide solution were sequentially added to the Erlenmeyer flask, and the initial pH of the solution was an initial value, and after reacting for 1 hour in a shaker at a rotation speed of 120rpm and a temperature of 50 ℃, the removal rate of bisphenol A in the solution was determined to be 99.9%.
Example 9:
0.1g of the catalyst obtained in example 2 was weighed and put into a 100mL Erlenmeyer flask, and 50mL of a 25mg/L sulfamethoxazole solution and 0.1mL of a 30 wt% hydrogen peroxide solution were sequentially added to the Erlenmeyer flask, and the initial pH of the solution was an initial value, and after reaction for 1 hour in a shaker at a rotation speed of 120rpm and a temperature of 50 ℃, the removal rate of sulfamethoxazole in the solution was measured to be 99.2%.
Example 10:
0.1g of the catalyst obtained in example 2 was weighed and put into a 100mL Erlenmeyer flask, and 50mL of a tetracycline hydrochloride solution having a concentration of 25mg/L and 0.1mL of a hydrogen peroxide (30 wt%) solution were sequentially added, and the initial pH of the solution was an initial value, and after reacting for 1 hour in a shaker at a rotation speed of 120rpm and a temperature of 50 ℃, the removal rate of tetracycline hydrochloride in the solution was found to be 95.2%.
Examples 8-10 prove that the catalyst has a good broad spectrum for degrading organic matters.
Example 11:
one), weighing 0.1g of the catalyst obtained in example 2, adding 50mL of 25mg/L acid orange solution and 0.1mL of hydrogen peroxide (30 wt%) solution in sequence, wherein the initial pH of the solution is 6.77, reacting for 1h in a shaker at 120rpm and 50 ℃, and determining the removal rate of acid orange and the concentration of total iron in the solution. The catalyst obtained after the reaction was recovered by a magnet, and the above experiment was repeated after simple washing with pure water for a total of 5 cycles. After the 5 th reaction is finished, recovering the catalyst, cleaning and drying;
secondly), mixing the catalyst with 10g of active carbon, and then putting the mixture into a microwave reactor for reaction, wherein the microwave power is set to be 600W, and the microwave reaction time is 2 min. And after the microwave reaction is finished and the catalyst is naturally cooled, separating the catalyst by using a magnet, removing impurities on the surface of the catalyst by using dilute hydrochloric acid and distilled water, and finally drying to obtain the regenerated catalyst.
And thirdly), repeating the degradation experiment in the step one) by using the regenerated catalyst.
The final results of this example are shown in the following table:
as can be seen from the above results, the catalytic activity of the fenton-like reaction catalyst of the present invention is not reduced after multiple cycles. The leaching amount of iron is kept at a low level all the time, the leaching amount of iron is less than 0.5 percent of the total iron content of the catalyst, the catalyst particles are not broken after 5 times of circulation, and the stability (the leaching amount of iron) can be recovered after simple regeneration.
Comparative example 1:
the difference between this embodiment and example 1 is that no acid orange adsorbing saturated granular activated carbon is added:
first), 6g of chitosan is weighed, 2% acetic acid solution is added to 200g, and stirring is carried out until the chitosan is dissolved. Weighing 6.18g of nonahydrate and ferric nitrate (the mass ratio of the iron element to the chitosan is 1:7), slowly adding into the chitosan solution, and continuously stirring until the mixture is uniformly mixed; one end of a peristaltic pump hose is inserted into the mixed solution, the other end of the hose is suspended above a short beaker filled with 300ml of 1mol/LNaOH, the rotating speed of a magnetic rotor in the beaker is set to be 200rmp/min, the rotating speed of the peristaltic pump is set to be 30rmp/min, and the mixed solution is continuously dropped into an alkaline solution in a form of liquid drops to be crosslinked to form gel microspheres. Repeatedly washing the gel microspheres with distilled water until the pH value is not changed any more, and drying the gel microspheres in an oven at 80 ℃ for 2h (drying to constant weight) to prepare xerogel microspheres;
secondly), 2g of xerogel is put into a microwave reactor for reaction, the microwave power is set to be 600W, and the microwave reaction time is 2 min. And naturally cooling after the reaction is finished.
The experimental results show that: the catalyst with magnetism cannot be prepared.
Comparative example 2:
this embodiment is different from example 1 in that the amount of the nine water and the ferric nitrate added in the first step) is 10.82g (the mass ratio of the iron element to the chitosan is 1:4), and the other steps are the same as example 1.
Comparative example 3:
this embodiment is different from example 1 in that the amount of the nine water and the ferric nitrate added in the first step) is 4.33g (the mass ratio of the iron element to the chitosan is 1:10), and the other steps are the same as example 1.
Comparative example 4
This embodiment is different from example 2 in that the microwave reaction time in the third step) is 2min, and the rest is the same as example 2.
Comparative example 5
This embodiment is different from example 2 in that the microwave reaction time in the third step) is 5min, and the rest is the same as example 2.
Comparative example 6
0.1g of the catalyst described in comparative examples 2 to 5 was charged into a 100mL Erlenmeyer flask, and 50mL of 25mg/L acid orange solution and 0.1mL of hydrogen peroxide (30 wt%) solution were sequentially added to the Erlenmeyer flask, the initial pH of the solution was 6.77, and after reaction for 1 hour in a shaker rotating at 120rpm and at 50 ℃, the removal rate of acid orange in the solution and the content of iron in the solution were measured.
The method of the invention changes the adsorption quantity of the activated carbon to the acid orange before and after regeneration into an investigation index of the regeneration effect of the activated carbon, and investigates the influence of different microwave reaction time and microwave power on the adsorption quantity of the regenerated granular activated carbon to the acid orange.
The above results are shown in the following table:
it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (7)
1. A method for preparing a Fenton-like catalyst by microwave and synchronously regenerating activated carbon is characterized by comprising the following steps of:
mixing a Fenton-like catalyst precursor and coal-made active carbon adsorbed with acid orange, and putting the mixture into a microwave reactor for reaction;
the Fenton-like catalyst precursor is chitosan/Fe (OH)3Xerogel microspheres;
the preparation method of the Fenton-like catalyst precursor comprises the following steps of:
step 1, mixing chitosan, ferric salt and an organic acid aqueous solution to prepare sol A;
step 2, dropwise adding the sol A into an alkaline aqueous solution to obtain chitosan/Fe (OH)3Gel microspheres;
step 3, mixing the chitosan/Fe (OH)3Washing and drying the gel microspheres to obtain chitosan/Fe (OH)3Xerogel microspheres.
2. The method for preparing a Fenton-like catalyst and synchronously regenerating activated carbon by microwaves according to claim 1, wherein the microwave reaction power is 600-800W; the time is 2-5 min.
3. The method for preparing a Fenton-like catalyst and synchronously regenerating activated carbon by microwaves according to claim 1, wherein in the step 1, the mass ratio of the iron element to the chitosan in the sol A is 1 (5-7).
4. The method for preparing a Fenton-like catalyst and synchronously regenerating activated carbon by microwaves according to claim 1, wherein in the step 1, the mass fraction of chitosan in the sol A is 0.5-5%.
5. The microwave Fenton-like catalyst preparation method using microwaves and synchronous activated carbon regeneration according to claim 1, wherein in the step 1, the iron salt is FeCl3、Fe(NO3)3、Fe2(SO4)3Any one or more of them.
6. The method for preparing a Fenton-like catalyst and synchronously regenerating activated carbon by microwaves according to claim 1, wherein in the step 1, the organic acid is any one or more of formic acid, acetic acid, citric acid and oxalic acid.
7. Use of a fenton-like catalyst prepared according to any one of claims 1 to 6 for the degradation of organic material in waste water.
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