CN110773166A - Preparation method and application of biomass carbon-based bimetallic catalyst for water treatment - Google Patents
Preparation method and application of biomass carbon-based bimetallic catalyst for water treatment Download PDFInfo
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- CN110773166A CN110773166A CN201911022690.XA CN201911022690A CN110773166A CN 110773166 A CN110773166 A CN 110773166A CN 201911022690 A CN201911022690 A CN 201911022690A CN 110773166 A CN110773166 A CN 110773166A
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- sodium alginate
- aerogel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002028 Biomass Substances 0.000 title claims abstract description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 25
- 239000000661 sodium alginate Substances 0.000 claims abstract description 25
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 25
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000004964 aerogel Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011324 bead Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 7
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002509 fulvic acid Substances 0.000 claims description 7
- 229940095100 fulvic acid Drugs 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- HJPBEXZMTWFZHY-UHFFFAOYSA-N [Ti].[Ru].[Ir] Chemical compound [Ti].[Ru].[Ir] HJPBEXZMTWFZHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000004021 humic acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 abstract description 2
- 229940072056 alginate Drugs 0.000 abstract description 2
- 235000010443 alginic acid Nutrition 0.000 abstract description 2
- 229920000615 alginic acid Polymers 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 9
- 238000001728 nano-filtration Methods 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 7
- 239000000149 chemical water pollutant Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 241000512259 Ascophyllum nodosum Species 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
Abstract
A preparation method and application of a biomass carbon-based bimetallic catalyst for water treatment belong to the crossed fields of materials science, chemistry and environmental engineering. The invention utilizes the principle that alginate can generate stable crosslinking effect and form insoluble gel, and drops sodium alginate gel with certain concentration to Cu
2+，Fe
2+Gelling in the solution, fixing, freeze-drying and roasting to form the bimetallic carbon aerogel catalyst. Wherein, carbon gasThe gel provides a larger specific surface area and a plurality of loading sites, and Cu and Fe ions are reduced into a nano-state zero-valent metal by C and loaded in the aerogel to be used as a catalytic active center. The catalyst prepared by the method is nontoxic and harmless, is simple to operate, has low cost, is easy to realize industrialization, is applied to a heterogeneous electricity-Fenton method for treating refractory wastewater, and has a good catalytic effect in a wide pH range.
Description
Technical Field
The invention provides a preparation and application method of a biomass carbon aerogel supported Cu and Fe bimetallic catalyst based on alginate. The method belongs to the crossed field of materials science, chemistry and environmental engineering.
Background
The Fenton oxidation method is one of advanced oxidation technologies, has the characteristics of high efficiency, no selectivity, quick reaction and the like, is a hotspot studied by researchers all the time, and is widely applied to the field of treatment of various kinds of wastewater difficult to degrade. However, the traditional Fenton reaction is only effective in a very narrow pH range, namely 2.8-4, while the actual industrial wastewater has a wide pH range, and Fe is adopted in the reaction
2+As catalyst, H
2O
2As precursors of oxidizing agents OH, Fe
2+The participated reaction is a homogeneous catalytic reaction, and Fe is generated after Fenton chain reaction is stopped
2+The catalyst is difficult to recover and exists in the form of iron mud, so that secondary pollution is easily caused. H
2O
2Reagents are expensive and are prone to risk and loss of concentration during transport and storage. Heterogeneous electro-Fenton technology can utilize cathode to generate H in situ
2O
2And the heterogeneous catalyst has obvious wastewater treatment effect in a wide pH range, is easy to recover and is beneficial to industrial application. However, the development of heterogeneous electro-Fenton still lacks a highly efficient and low-cost heterogeneous catalyst, which is also a key and difficult point limiting the application of this technology.
The sodium alginate is a by-product after iodine and mannitol are extracted from brown algae kelp or gulfweed, and the kelp and the gulfweed have a large number of artificial cultivation bases in coastal areas of China, are low in cost, easy to obtain a large number of raw materials, have the characteristics of no toxicity, no harm, good biocompatibility and the like, and are widely applied to the fields of food industry, biomedical engineering and the like.
Sodium alginate forms a gel with a viscosity when dissolved in water, and the gel encounters Ca
2+、Ba
2+Etc. of most divalent cations (Mg)
2+Except for Fe required for Fenton reaction), a crosslinking reaction can occur to generate gel with an irreversible eggshell structure, divalent ions crosslinked with the gel can be uniformly loaded on the gel, and Fe required for Fenton reaction
2+Or Cu
2+The cross-linking reaction can be carried out for divalent cations, which provides a theoretical basis for the application in the heterogeneous electro-Fenton technology. Sodium alginate is a natural polysaccharide, which contains abundant carbon elements, and can obtain an excellent carbon carrier after carbonization, and simultaneously metal ions can be reduced into nanoscale zero-valent metal by carbon, so that the sodium alginate is not easy to precipitate and provides an excellent catalytic site.
At present, researches on the development of heterogeneous advanced oxidation catalysts based on the characteristics of sodium alginate are only reported, but researches and patents on the application of sodium alginate-based carbon aerogel microsphere bimetallic catalysts in advanced oxidation technologies for water treatment, particularly electric Fenton technologies, are not reported.
Disclosure of Invention
The heterogeneous electro-Fenton catalyst based on sodium alginate, which is applied to the field of water treatment, provided by the invention, has the advantages of no toxicity and harm of raw materials, simple preparation steps, low cost, good catalytic effect under a wide pH environment, and easiness in realization of industrial application.
The preparation process of the catalyst comprises the following steps:
(1) preparing sodium alginate sol: adding sodium alginate into deionized water, wherein the mass volume ratio of the sodium alginate to the deionized water is 2 g-4 g/100mL, stirring and heating in a water bath to form gel, wherein the water bath temperature is 60 ℃, and the water bath time is 0.5-1 h;
(2) preparing sodium alginate-Cu/Fe gel: dropwise adding the sodium alginate gel in (1) into Cu (NO) at a rate of 1 drop/s by using a syringe pump
3)
2With FeCl
2In the mixed solution of (1), Cu (NO)
3)
2With FeCl
2Cu (NO) in the mixed solution of (2)
3)
2With FeCl
2The mass concentration of the substances is 0.05-0.5 mol/L and 0.01-0.05 mol/L respectively, the mixture is placed for 4-12 hours, the solution is filtered, gel beads are taken out and washed for 3-5 times by using dilute hydrochloric acid with the mass fraction of 3%, and then the gel beads are washed by deionized water until the pH value is not changed;
(3) placing the gel beads obtained after washing in a refrigerator at the temperature of-18 ℃ for freezing for 3-6 h, and then placing in a vacuum freeze drying oven for drying for 1-5 d to form alginic acid-Fe/Cu aerogel beads;
(4) and (3) placing the aerogel beads obtained in the step (3) into a tubular atmosphere furnace for roasting and carbonizing, wherein the conditions are as follows: roasting temperature is 600-1200 ℃, heating rate is 3-6 ℃/min, heating to the roasting temperature and keeping for 1-3 h, N
2And introducing the carbon aerogel bimetallic catalyst into an atmosphere furnace heating pipe at the speed of 150-250 mL/min, naturally cooling, and taking out to obtain the carbon aerogel bimetallic catalyst.
The catalyst prepared by the method is applied as a heterogeneous catalyst in heterogeneous electro-Fenton to treat organic wastewater, and the conditions are as follows: the anode adopts a ruthenium iridium titanium electrode, the cathode adopts a carbon fiber electrode, the pH value is 3-9, the voltage is 1.5-4.5V, the reaction time is 90-150 min, the electrode spacing is 5-10 mm, the mass-volume ratio of the catalyst to the organic wastewater is 1-6 g/L, air aeration is adopted, and the aeration rate is 100-500 mL/min.
The organic wastewater refers to wastewater which contains a macromolecule conjugated system and humic acid, fulvic acid and the like with an aromatic structure and is difficult to biodegrade.
According to the invention, the sodium alginate-based carbon aerogel microspheres provide larger specific surface area and more loading sites, Cu and Fe ions can be reduced to nano-state zero-valent metal by C and loaded in aerogel to be used as a catalytic active center, the carbon aerogel microsphere carrier adsorbs pollutants on the surface of the carbon aerogel microsphere carrier, and the catalytic active sites loaded on the surface catalyze H reduced by a cathode
2O
2Produce OH, thereby degrading pollutants into small molecular organic matters or directly mineralizing the pollutants into CO
2And H
2And O. The whole system is easy to operate, low in current density and high in current efficiency, has good catalytic degradation effect on various pollutants difficult to degrade under wide pH value, and is an excellent catalyst with industrial application prospect.
Drawings
FIG. 1 is a SEM representation of the catalysts used in examples 1 and 2.
Figure 2 is an EDS characterization of the catalysts used in examples 1 and 2.
Figure 3 is a XRD characterization pattern of the catalysts used in examples 1 and 2.
FIG. 4 is a graph showing the time-dependent change of the concentration of fulvic acid simulated wastewater treated by the catalyst in example 1.
FIG. 5 is a graph showing the change of COD of the nanofiltration concentrate of the actual landfill leachate treated by the catalyst-catalyzed electro-Fenton in example 2 with time.
FIG. 6 is a graph showing the effect of stability of the catalyst of example 2 after 6 repeated uses.
Detailed Description
In order to better explain the spirit and content of the invention and to further illustrate the use of the invention, several non-limiting examples of the invention are given below, i.e. the content of the invention includes but is not limited to the following several examples.
Example 1
Adding sodium alginate into deionized water, wherein the mass volume ratio of the sodium alginate to the deionized water is 2g/100mL, stirring and heating in a water bath to form gel, wherein the water bath temperature is 60 ℃, and the water bath time is 1 h. The sodium alginate gel was dropped into 500mL of Cu (NO) at a rate of 1 drop/s using a syringe pump
3)
2With FeCl
2In the mixed solution of (1), wherein Cu (NO)
3)
2With FeCl
2The amount concentration of the substances is 0.1mol/L and 0.025mol/L respectively, the solution is placed for 8 hours, the solution is filtered, gel beads are taken out and washed for 5 times by dilute hydrochloric acid with the mass fraction of 3 percent, and then the gel beads are washed by deionized water until the pH value is not changed. And (3) freezing the gel beads obtained in the previous step in a refrigerator at the temperature of 18 ℃ below zero for 3h, and then drying the gel beads in a vacuum freeze drying oven for 3d to form alginic acid-Fe/Cu aerogel beads. And (2) placing the obtained aerogel beads in a tubular atmosphere furnace for roasting and carbonization, wherein the conditions are as follows: roasting at 800 deg.C, heating at 3 deg.C/min to set temperature, and maintaining for 2 hr, N
2And (3) introducing the carbon aerogel bimetallic catalyst into an atmosphere furnace heating pipe with the pipe diameter of 100mm and the length of 900mm at the speed of 150mL/min in the carbonization process, naturally cooling, and taking out to obtain the carbon aerogel bimetallic catalyst.
As can be seen from figure 1, the catalyst has an obvious honeycomb macroporous structure inside, so that a rich carrier space is provided for the loading of active components, a large amount of catalyst active components are loaded on an internal carbon skeleton, the active components are uniformly distributed on an aerogel carrier in a cubic particle shape, and the particle size is 0.5-10 mu m. As shown in fig. 2, the EDS results indicate that Cu and Fe account for 15% and 4% of the active ingredient, respectively, indicating that Cu and Fe were successfully supported on the framework of the carbon aerogel.
In order to further determine the components and the existing forms of the active components, the catalyst is subjected to XRD characterization, and FIG. 3 is an XRD diffraction pattern of the catalyst, and diffraction peaks of Cu and an alloy formed by Cu and Fe are determined by comparing JCPDS standard diffraction patterns, so that the active components actually contain Cu and Fe and exist in a simple substance state.
The catalyst is used for treating 300mg/L fulvic acid simulation wastewater by using a heterogeneous electro-Fenton technology, and the specific operation is as follows: adding 25mL of the fulvic acid simulation wastewater into an electrolytic cell with the volume of 30mL, wherein the anode adopts a commercial ruthenium iridium electrode, the cathode adopts a carbon fiber electrode, the cathode and the anode are connected with a 2.5V direct current power supply, the electrode spacing is 8mm, a catalyst is arranged in the middle, the mass-volume ratio of the catalyst to the fulvic acid simulation wastewater is 4g/L, and the amount of the added substance is 0.05mol/L of Na
2SO
4Air is blown in from the bottom of the electrolytic cell at a rate of 300mL/min to provide oxygen required by cathode reaction, and the fulvic acid degradation rate reaches 81% after the reaction is carried out for 150 min.
Example 2
Adding sodium alginate into deionized water, wherein the mass volume ratio of the sodium alginate to the deionized water is 4g/100mL, stirring and heating in a water bath to form gel, wherein the water bath temperature is 60 ℃, and the water bath time is 1 h. The sodium alginate gel was dropped into 500mL of Cu (NO) at a rate of 1 drop/s using a syringe pump
3)
2With FeCl
2In the mixed solution of (1), wherein Cu (NO)
3)
2With FeCl
2The amount concentration of the substance(s) is 0.1mol/L and 0.05mol/L respectively, the solution is placed for 12 hours, the solution is filtered, the gel beads are taken out and washed for 5 times by using dilute hydrochloric acid with the mass fraction of 3 percent, and then the gel beads are washed by deionized water until the pH value is not changed. Freezing the gel beads in a refrigerator at-18 deg.C for 3 hr, and drying in a vacuum freeze drying oven for 5 days to obtain alginic acid-Fe/Cu aerogel beads. And (2) placing the obtained aerogel beads in a tubular atmosphere furnace for roasting and carbonization, wherein the conditions are as follows: roasting at 900 deg.C, heating at a rate of 5 deg.C/min to a set temperature, and maintaining for 3 hr, N
2Introducing the carbon aerogel bimetallic catalyst into an atmosphere furnace heating pipe with the pipe diameter of 100mm and the length of 900mm at the speed of 250mL/min in the carbonization process, naturally cooling, and taking out to obtain the carbon aerogel bimetallic catalyst.
The prepared catalyst is used for treating the landfill leachate nanofiltration concentrated solution after coagulation pretreatment by using a heterogeneous electro-Fenton technology, a water sample is taken from a landfill leachate nanofiltration treatment working section of a certain landfill, and the water quality is as follows: the COD is 1800mg/L, the pH value is 7.4, 25mL of the nanofiltration concentrated solution is added into an electrolytic cell with the volume of 30mL, a commercial ruthenium iridium electrode is adopted as an anode, a carbon fiber electrode is adopted as a cathode, a 3.5V direct current power supply is connected to the anode and the cathode, the electrode spacing is 6mm, a catalyst is placed in the middle, the mass-volume ratio of the catalyst to organic wastewater is 6g/L, air is blown in from the bottom of the electrolytic cell at 500mL/min to provide oxygen required by cathode reaction, after the reaction is carried out for 120min, the COD of the nanofiltration concentrated solution is reduced to 391.6mg/L, and the removal rate is 78.24%.
Example 3
Adding sodium alginate into deionized water, wherein the mass volume ratio of the sodium alginate to the deionized water is 3.5g/100mL, stirring and heating in a water bath to form gel, wherein the water bath temperature is 60 ℃, and the water bath time is 1 h. The sodium alginate gel was dropped into 500mL of Cu (NO) at a rate of 1 drop/s using a syringe pump
3)
2With FeCl
2In the mixed solution of (1), wherein Cu (NO)
3)
2With FeCl
2The amount concentration of the substance(s) is 0.3mol/L and 0.05mol/L respectively, the solution is placed for 12 hours, the solution is filtered, the gel beads are taken out and washed for 5 times by using dilute hydrochloric acid with the mass fraction of 3 percent, and then the gel beads are washed by deionized water until the pH value is not changed. And (3) freezing the gel beads obtained in the previous step in a refrigerator at the temperature of 18 ℃ below zero for 3h, and then drying the gel beads in a vacuum freeze drying oven for 4d to form alginic acid-Fe/Cu aerogel beads. And (2) placing the obtained aerogel beads in a tubular atmosphere furnace for roasting and carbonization, wherein the conditions are as follows: roasting at 850 deg.C, heating at 4 deg.C/min to set temperature, and maintaining for 3 hr, N
2And (3) introducing the carbon aerogel bimetallic catalyst into an atmosphere furnace heating pipe with the pipe diameter of 100mm and the length of 900mm at the speed of 200mL/min in the carbonization process, naturally cooling, and taking out to obtain the carbon aerogel bimetallic catalyst.
The prepared catalyst is used for treating the landfill leachate nanofiltration concentrated solution after coagulation pretreatment by using a heterogeneous electro-Fenton technology, a water sample is taken from a landfill leachate nanofiltration treatment working section of a certain landfill, and the water quality is as follows: the COD is 1800mg/L, the pH value is 7.4, 25mL of the nanofiltration concentrated solution is added into an electrolytic cell with the volume of 30mL, a commercial ruthenium iridium electrode is adopted as an anode, a carbon fiber electrode is adopted as a cathode, a 2.5V direct current power supply is connected to a cathode and an anode, the electrode spacing is 5mm, a catalyst is placed in the middle, the mass-to-volume ratio of the catalyst to organic wastewater is 5g/L, air is blown in from the bottom of the electrolytic cell at 500mL/min to provide oxygen required by cathode reaction, after the reaction is carried out for 120min, the COD of the nanofiltration concentrated solution is reduced to 439.7mg/L, and the removal rate reaches 75.57%.
Claims (3)
1. A preparation method of a biomass carbon-based bimetallic catalyst for water treatment is characterized by comprising the following steps:
(1) preparing sodium alginate sol: adding sodium alginate into deionized water, wherein the mass volume ratio of the sodium alginate to the deionized water is 2 g-4 g/100mL, stirring and heating in a water bath to form gel, wherein the water bath temperature is 60 ℃, and the water bath time is 0.5-1 h;
(2) preparing sodium alginate-Cu/Fe gel: dropwise adding the sodium alginate gel in (1) into Cu (NO) at a rate of 1 drop/s by using a syringe pump
3)
2With FeCl
2In the mixed solution of (1), Cu (NO)
3)
2With FeCl
2Cu (NO) in the mixed solution of (2)
3)
2With FeCl
2The mass concentration of the substances is 0.05-0.5 mol/L and 0.01-0.05 mol/L respectively, the mixture is placed for 4-12 hours, the solution is filtered, gel beads are taken out and washed for 3-5 times by using dilute hydrochloric acid with the mass fraction of 3%, and then the gel beads are washed by deionized water until the pH value is not changed;
(3) placing the gel beads obtained after washing in a refrigerator at the temperature of-18 ℃ for freezing for 3-6 h, and then placing in a vacuum freeze drying oven for drying for 1-5 d to form alginic acid-Fe/Cu aerogel beads;
(4) and (3) placing the aerogel beads obtained in the step (3) into a tubular atmosphere furnace for roasting and carbonizing, wherein the conditions are as follows: roasting temperature is 600-1200 ℃, heating rate is 3-6 ℃/min, heating to the roasting temperature and keeping for 1-3 h, N
2And introducing the carbon aerogel bimetallic catalyst into an atmosphere furnace heating pipe at the speed of 150-250 mL/min, naturally cooling, and taking out to obtain the carbon aerogel bimetallic catalyst.
2. Use of the catalyst prepared by the method of claim 1 as a heterogeneous catalyst in a heterogeneous electro-Fenton, wherein:
treating organic wastewater under the conditions of: the anode adopts a ruthenium iridium titanium electrode, the cathode adopts a carbon fiber electrode, the pH value is 3-9, the voltage is 1.5-4.5V, the reaction time is 90-150 min, the electrode spacing is 5-10 mm, the mass-volume ratio of the catalyst addition amount to the organic wastewater is 1-6 g/L, air aeration is adopted, and the air flow is 100-500 mL/min.
3. The use as claimed in claim 2, wherein: the organic wastewater refers to humic acid or fulvic acid containing a macromolecular conjugated system or an aromatic structure.
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