CN114225938A - Magnetic nano Fe3O4@ mushroom residue biochar Fenton catalyst and preparation method thereof - Google Patents
Magnetic nano Fe3O4@ mushroom residue biochar Fenton catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229930182555 Penicillin Natural products 0.000 claims abstract description 55
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 claims abstract description 55
- 229940049954 penicillin Drugs 0.000 claims abstract description 55
- 241000233866 Fungi Species 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 20
- 235000001674 Agaricus brunnescens Nutrition 0.000 claims abstract description 16
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 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 abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000005554 pickling Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000000197 pyrolysis Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 230000001580 bacterial effect Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 20
- 238000006731 degradation reaction Methods 0.000 description 20
- 230000003197 catalytic effect Effects 0.000 description 10
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 8
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- 238000001179 sorption measurement Methods 0.000 description 4
- 229910017135 Fe—O Inorganic materials 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 239000010457 zeolite Substances 0.000 description 1
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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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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Abstract
The invention relates to magnetic nano Fe3O4The @ mushroom dreg biochar Fenton catalyst comprises a carrier and an active material, wherein the carrier is penicillin mushroom dreg biochar, and the active material is magnetic nano Fe3O4. The preparation method comprises the following steps: s1, activating the penicillin fungi residues with potassium carbonate/sodium, drying, crushing and sieving; s2, pyrolyzing and carbonizing under the protection of inert atmosphere, pickling, washing with water to neutrality, then washing with absolute ethyl alcohol and drying to obtain penicillin fungi residue biochar; s3, firstly dispersing the penicillin fungi residue biochar in water, adding soluble ferric salt, ferrous salt and a precipitating agent to generate black precipitates, and magnetically separating the products; s4, washing, drying in an oxygen-free environment to obtain magnetic nano Fe3O4@ mushroom dreg biocharA fenton catalyst. The invention mainly utilizes the microcosmic appearance characteristic that penicillin fungi residue contains a large amount of hypha to obtain a cross-linked nanopore structure, and then uses nano Fe3O4The fungus dreg biochar with rich nano-pore structures is loaded to prepare the Fenton catalyst with excellent performance.
Description
Technical Field
The invention relates to the technical field of composite catalysts, in particular to magnetic nano Fe3O4@ mushroom residue biochar Fenton catalyst and preparation method thereof.
Background
The Fenton process is used as an efficient and economic wastewater advanced oxidation process and is widely used for treating various pollutants difficult to degrade. The Fenton reaction is divided into homogeneous phase reaction and heterogeneous phase reaction, and compared with the heterogeneous phase Fenton reaction, the traditional homogeneous phase Fenton process has the problems of large sludge production, secondary pollution, narrow pH range, high subsequent treatment cost and the like. Therefore, the heterogeneous Fenton process is more widely applied, but the problem that the catalyst is easy to lose still exists. Therefore, there is a need for an improved preparation of new catalysts to improve the fenton process. In recent years, a heterogeneous fenton-like process based on a metal oxide, a metal-supported solid catalyst, and a metal ion-doped solid catalyst has attracted attention of researchers. The most widely studied solid Fenton catalyst is a supported nano catalyst, the supported matter mainly comprises transition metal and oxides thereof, the carrier mainly comprises carbon-based materials, zeolite, clay, metal organic framework and the like, and the catalyst activates H2O2OH is generated to degrade organic pollutants. On the other hand, the load box catalyst is beneficial to realizing solid-liquid separation, the catalyst is recycled, and the iron mud production can be greatly reduced.
Magnetic nano Fe3O4Is a heterogeneous Fenton-like catalyst which can effectively decompose H2O2OH is generated, and further organic pollutants are degraded. The Biochar (Biochar, BC) has the characteristics of adjustable morphological structure and electronic structure, large specific surface area, strong adsorption capacity, easy functionalization, strong acid and alkali resistance and the like, and is considered to be a catalytic carrier material with great application prospect. Therefore, thisThe invention aims to provide a magnetic nano Fe-based material3O4The carbon-based supported nano-catalyst.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages, the present invention provides a magnetic nano-Fe3O4@ bacterial residue biochar Fenton catalyst and preparation method thereof, penicillin bacterial residue is used as raw material to prepare bacterial residue biochar through carbonization treatment, and the bacterial residue biochar is used for loading magnetic nano Fe3O4The cross-linked nanopore structure can be obtained by utilizing the microscopic morphology characteristics of a large amount of hyphae contained in the penicillin fungi residue, and then the nanometer Fe3O4 is loaded on the fungi residue biochar with the abundant nanopore structure to prepare the novel Fenton catalyst which shows excellent Fenton catalytic performance.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a magnetic nano-Fe3O4The @ mushroom dreg biochar Fenton catalyst comprises a carrier and an active material, wherein the carrier is penicillin mushroom dreg biochar, and the active material is magnetic nano Fe3O4。
In a second aspect, the present invention provides a magnetic nano-Fe3O4The preparation method of the @ mushroom dreg biochar Fenton catalyst comprises the following steps:
s1, mixing the penicillin fungi residues with potassium carbonate/sodium, adding water, stirring, activating, drying, crushing and sieving to obtain activated dried penicillin fungi residues;
s2, pyrolyzing and carbonizing the activated dried penicillin fungi residues under the protection of inert atmosphere, pickling, washing with water to be neutral, then washing with absolute ethyl alcohol, and drying to obtain penicillin fungi residue biochar (ARBC);
s3, firstly dispersing the penicillin fungi residue biochar in water, then adding soluble ferric salt, soluble ferrous salt and a precipitator to generate black precipitate, and magnetically separating the black precipitate;
s4, washing the black precipitate, and drying the black precipitate in an oxygen-free environment to obtain magnetic nano Fe3O4@ bacterial residue biochar Fenton catalyst.
According to the preferred embodiment of the invention, in S1, the mass ratio of the penicillin fungi residue to the potassium carbonate/sodium is 1:1-1.2, the activation temperature is 30 +/-2 ℃, and the activation time is 2-3 h. The activation treatment has the effects of fully mixing the mushroom dregs with the activating agent, enabling the fine gap structure of the biochar generated by later-stage pyrolysis to be more developed and distributed more densely and have higher porosity, increasing the specific surface area of the biochar, and being beneficial to loading active substances.
According to the preferred embodiment of the present invention, in S1, the drying temperature is 80 ℃, and the drying is carried out to a constant weight; pulverizing and sieving with 60 mesh sieve.
According to the preferred embodiment of the present invention, in S2, the inert gas is nitrogen/argon, and the activated dried penicillin fungi residue is pyrolyzed and carbonized under the protection of nitrogen/argon, wherein the pyrolysis temperature is 690-710 ℃ (preferably 700 ℃); the pyrolysis time is 2-4h (preferably 2 h); the heating rate is 8-12 deg.C/min (preferably 10 deg.C/min). If the pyrolysis temperature is too low, the specific surface area of the prepared biochar is too small, the temperature is too high, pores collapse, and the formation of cross-linked pores is not facilitated, and preferably 700 ℃, so that the high specific surface area can be ensured, and the collapse of an internal cross-linked structure of the biochar can be avoided.
According to the preferred embodiment of the present invention, in S2, the acid washing is performed with diluted hydrochloric acid; the drying is carried out under the protection of vacuum or nitrogen/argon, so as to avoid the oxidation, the breakage and the damage and the collapse of a cross-linked nanopore structure of the penicillin fungi residue biochar (ARBC). After pyrolysis and carbonization and before acid washing, cooling the pyrolysis and carbonization product, crushing the product in a crusher, and sieving the crushed product with a 60-mesh sieve to obtain powdery penicillin fungi residue biochar. And the pyrolysis carbonization product is crushed and sieved again, so that the bacterial residue biochar can be washed to be neutral quickly during subsequent acid washing and water washing, and the influence of acid residue on the performance of the catalyst is avoided.
According to a preferred embodiment of the present invention, in S2, the drying is vacuum drying, the drying temperature is 50-65 ℃, preferably 60 ℃, and the drying time is 20-30h, preferably 24 h.
According to a preferred embodiment of the present invention, in S3, the soluble ferric salt and the soluble ferrous salt are added in a ratio satisfying: fe3+：Fe2+The molar ratio was 2: 1. Preferably, the soluble ferric iron is any one of ferric chloride and a hydrate thereof, ferric sulfate and a hydrate thereof; the soluble ferrous salt is any one of ferrous chloride and hydrate thereof, ferrous sulfate and hydrate thereof.
According to a preferred embodiment of the present invention, in S3, the precipitant is sodium hydroxide solution.
According to the preferred embodiment of the invention, in S3, penicillin fungi residue biochar is subjected to ultrasonic dispersion in water, soluble ferric salt and soluble ferrous salt are added, stirring is started, NaOH solution is added, stirring reaction is carried out at a constant temperature of 55-65 ℃, the whole reaction process is ensured to be carried out under the protection of oxygen-free gas or nitrogen/argon gas, stirring and cooling are continued after the reaction is finished, and a magnet is used for separating products.
According to the preferred embodiment of the present invention, in S3, penicillin fungi residue biochar and Fe are used3O4Weighing penicillin fungi residue biochar (ARBC), soluble ferric salt and soluble ferrous salt according to the mass ratio of 1:1-2, and enabling magnetic nano Fe in the product3O4The loading is close to 50-66.6 wt%.
According to the preferred embodiment of the present invention, in S3, the molar amount of NaOH in NaOH solution and Fe3O4The molar weight ratio of (A) to (B) is 8-10: 1.
According to the preferred embodiment of the present invention, the specific operations of S3 are: adding water into a reaction vessel, introducing nitrogen/argon gas at normal temperature while stirring to exhaust air in the reaction vessel and the water, adding weighed penicillin fungi residue biochar (ARBC) into the reaction vessel, and performing ultrasonic dispersion; then adding the weighed soluble ferric salt and ferrous salt, putting the mixture into a constant-temperature water bath reaction area at the temperature of 55-60 ℃ under stirring, and stirring until the mixture is completely and uniformly mixed; adding 2-4mol/L hydroxide solution at constant speed at constant temperature of 55-60 deg.C, generating black precipitate, reacting under stirring for 2-2.5h to ensure the whole reaction is carried out under nitrogen/argon protection, stirring and cooling after the reaction is finished, and separating the product with magnet.
According to the preferred embodiment of the invention, in S4, the product is washed 3-5 times with ultrapure water to be neutral, then washed 2-4 times with absolute ethyl alcohol to remove water and ash in the product, filtered, and the filtered cake is dried in vacuum or nitrogen/argon for 20-30h (preferably 24h) to obtain the magnetic nano Fe3O4@ bacterial residue biochar Fenton catalyst.
(III) advantageous effects
At present, penicillin is mainly produced by a strain culture method. Due to the fact that annual output of penicillin is extremely high, if fungi residues are not properly treated and accumulated in a large amount, fungi residues penicillin easily flows into underground soil or water, penicillin in surrounding environment is overflowed, a large amount of penicillin-tolerant bacteria is induced, and the like, and ecological balance is affected. The invention provides a new use way for realizing the reduction and harmlessness of the penicillin fungi residues and changing waste into valuable.
The mushroom dreg biochar prepared by the invention loads magnetic nano Fe3O4The cross-linked nanopore structure can be obtained by utilizing the microscopic morphology characteristics of a large amount of hyphae contained in the penicillin fungi residue, and then the nanometer Fe3O4 is loaded on the fungi residue biochar with the abundant nanopore structure to prepare the novel Fenton catalyst which shows excellent Fenton catalytic performance.
Compared with the prior art, the magnetic nano Fe of the invention3O4The @ mushroom dreg biochar Fenton catalyst has the following technical effects:
(1) the stability is strong: the ARBC (bacterial dreg biochar) and the catalyst can be firmly combined through Fe-O, and the catalyst can be tightly locked in a carrier pore channel by crosslinking the three-dimensional reticular micropores, so that the method is very favorable for solving the problem of metal loss of the catalyst;
(2) in-situ cocatalyst effect: the ARBC is rich in acid-containing groups and oxygen-containing groups, can improve the Fe (II) electron transfer rate between Fe (III) and Fe (III), and promotes the generation of OH;
(3) the nano confinement activity is high: in the ARBC-rich cross-linked network micropores, the mass transfer distance between OH and a target pollutant is short, and the micropore confinement structure is very likely to generate reaction activity, path and active species which are obviously different from a macroscopic body;
(4) strong adsorption capacity: the specific surface area of the ARBC is large, the ARBC has extremely strong adsorption performance, the transmission and permeation of pollutants among materials are accelerated, a micro-interface limited-area catalytic Fenton-like reaction system with virtuous cycle of adsorption-oxidation can be formed, and the integral oxidation efficiency of the Fenton-like system can be greatly enhanced;
(5) the recycling and circulating performance is good: nano Fe3O4The magnetism has stronger magnetism, the catalyst can be magnetically recycled, and the cycle number can reach more than 5 times.
Drawings
FIG. 1 is a SME chart of the penicillin mushroom residue biochar prepared in the example 1 after acid washing.
FIG. 2 shows Nano-Fe prepared in example 23O4@ ARBC cyan700℃Surface SEM image of fenton catalyst.
FIG. 3 shows Nano-Fe prepared in example 23O4@ ARBC cyan700℃Infrared spectrum of fenton catalyst.
FIG. 4 shows Nano-Fe prepared in example 23O4@ ARBC cyan700℃XRD pattern of fenton catalyst.
FIG. 5 shows the use of Nano-Fe in example 33O4@ ARBC cyan700℃A degradation rate curve graph of rhodamine B treated by a Fenton catalyst; adding equal amount of hydrogen peroxide and equal amount of Nano-Fe3O4@ ARBC cyan700℃A sample of fenton catalyst is a control.
FIG. 6 is a graph comparing the degradation rate of rhodamine B in water treated by different Fenton catalysts for 2h in example 3 and comparative examples 3-5.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
Example 1
The embodiment is a preparation example of penicillin fungi residue biochar, and the preparation process is as follows:
(1) activation of mushroom dregs: taking penicillin fungi residue of a certain pharmaceutical factory for drying, sieving with a 60-mesh sieve, and then activating the dry penicillin residues: and (3) mixing the dry mushroom residue and potassium carbonate according to a mass ratio of 1:1, adding a certain amount of distilled water, and stirring in a magnetic stirrer, wherein the reaction temperature is controlled at 30 ℃ and the reaction time is 2 hours. And after the reaction is finished, centrifuging by using a centrifuge, controlling the rotating speed at 5000r/min, and controlling the centrifuging time to be 5 min. And drying the centrifuged mushroom dregs at 80 ℃ to constant weight, crushing, and sieving by a 60-mesh sieve to obtain activated mushroom dregs.
(2) Pyrolysis and carbonization: dividing the activated mushroom dregs into two parts, respectively putting the two parts into a tubular furnace, and pyrolyzing the two parts under the protection of nitrogen, wherein the pyrolysis temperature is respectively set to be 700 ℃ and 600 ℃, the pyrolysis speed is 10 ℃/min, and the pyrolysis time is 2 h. Cooling, pulverizing in a pulverizer, and sieving with 60 mesh sieve to obtain the fungus residue charcoal powder.
(3) Acid washing the mushroom dreg charcoal powder: hydrochloric acid is adopted as acid for acid washing, the concentration is 3mol/L, and the acid washing time is 2 hours. Washing with deionized water for 3 times after acid washing, washing with anhydrous ethanol for 3 times, drying in drying oven at 60 deg.C for 24 hr to obtain penicillin fungi residue biochar ARBC green700℃And ARBC cyan600℃。
As shown in figure 1, is the biochar ARBC cyan of penicillin fungi residues600℃(left panel) and ARBC cyan700℃(right panel) SEM image. Under the same multiplying power, the left picture shows that a plurality of holes are distributed on the penicillin fungi residue biochar, but the holes are more sparsely distributed, the right picture distributes a large number of communicated three-dimensional holes on the biochar surface, the sizes of the holes are uniform, the aperture of most of the holes is about 1 mu m or slightly smaller than 1 mu m, the aperture of a small number of the holes is larger than 1 mu m, the hole distribution is very dense, and the number of the holes is 3-4 times that of the left picture.
Comparative example 1
In this example, the raw material for preparing penicillin fungi residue biochar was replaced by streptomycin fungi residue collected from a pharmaceutical factory based on example 1. The method of example 1 was followed, with the pyrolysis temperature controlled at 700 ℃ to produce the charcoal ARBC chain of streptomycin mushroom dregs700℃。
Comparative example 2
In this example, the raw material for producing biochar was replaced with "coffee grounds" in addition to example 1. The coffee grounds used in the coffee shop are washed by deionized water for several times, then dried and sieved by a 60-mesh sieve. Coffee grounds biochar HCBC was prepared according to the method of example 1, with the pyrolysis temperature controlled at 700 deg.C700℃。
Example 2
This example is for the preparation of Nano-Fe3O4The preparation example of the @ charcoal fenton catalyst is as follows:
(1) according to the mol ratio of Fe3+：Fe2+5.4058g FeCl were weighed out in a ratio of 2:13·6H2O (0.02mol) and 2.7820g FeSO4·7H2O (0.01mol), biochar in mass ratio: fe3O4Is 1: 2 weighing 4.640g of biochar.
The biochar is four, and is the penicillin fungi residue biochar ARBC cyan of example 1700℃And penicillin fungi residue biochar ARBC cyan600℃Comparative example 1. streptomycin residue biochar ARBC chain700℃And the coffee grounds biochar HCBC of comparative example 2.
(2) 300ml of ultrapure water was taken in a 500ml three-necked flask, and nitrogen gas was introduced thereto at room temperature for 30min while stirring to exhaust the air in the flask. Putting the biochar into the flask, performing ultrasonic dispersion, and adding FeCl3·6H2O and FeSO4·7H2And O, transferring the mixture into a constant-temperature water bath kettle with the stirring temperature of 60 ℃ for stirring until the mixture is completely mixed.
(3) At the constant temperature of 60 ℃, 30mL of NaOH solution with the volume fraction of 3mol/L is dripped into the mixed solution by a constant flow pump, then the vignetting black precipitate is generated, and the reaction is continued to be stirred for 2h, so that the whole reaction is ensured to be carried out under the protection of nitrogen. After the reaction was completed, the mixture was stirred, cooled and separated with a magnet.
(4) Washing the product with ultrapure water for 5 times, washing the product with absolute ethyl alcohol for 3 times, performing suction filtration, and drying the filter cake in a vacuum drying oven for 24 hours to respectively obtain four Fenton catalysts, Nano-Fe3O4@ ARBC cyan700℃，Nano-Fe3O4@ ARBC cyan600℃，Nano-Fe3O4@ ARBC chain700℃，Nano-Fe3O4@ coffee grounds charcoal HCBC700℃。
As shown in FIG. 2, it is a Fenton catalyst Nano-Fe3O4@ ARBC cyan700℃Surface SEM image of (a); the graph shows that compared with simple biochar, the surface of the biochar is loaded with curled nano-scale particles which are magnetic nano Fe3O4Indicating that the active substance has been successfully loaded.
As shown in FIG. 3, it is a Fenton catalyst Nano-Fe3O4@ ARBC cyan700℃An infrared spectrum of (1); it can be seen from the graph that the catalyst contains OH (3418.5 cm)-1)、C＝C(1561.7cm-1)、COC(1193.2cm-1)、Fe-O(492.5cm-1) The ARBC and the catalyst can be firmly combined through Fe-O through the functional groups, the catalyst can be tightly locked in a carrier pore channel through the cross-linked three-dimensional reticular micropores, the problem of metal loss of the catalyst is solved, and the acid-containing groups and the oxygen-containing groups can improve the electron transfer rate between Fe (III) and Fe (II), promote the generation of OH and facilitate the rapid reaction of the catalytic reaction.
As shown in FIG. 4, it is a Fenton catalyst Nano-Fe3O4@ ARBC cyan700℃XRD pattern of (a); fe can be seen from the figure3O4The existence of active substances further proves that the catalyst is successfully loaded.
Example 3
This example is carried out using the Fenton catalyst Nano-Fe prepared in example 23O4@ ARBC cyan700℃The experimental method of the example of catalytic degradation of organic matter in water is as follows:
putting 100ml (the concentration is 150mg/L) of rhodamine B (RhB) simulated wastewater into a 250ml conical flask, and adding 0.1g of Fenton catalyst Nano-Fe3O4@ ARBC cyan700℃3ml of H2O2(30%), sealing with a sealing film, placing in a shaking table for reaction at 25 ℃ for 2h, taking samples every 10min, measuring the concentration change of RhB by using a spectrophotometer, and analyzing the degradation effect. ResultsShows that the degradation rate reaches 66.40% in 60min and 99.88% in 2 h.
In the experiment, the same amount of hydrogen peroxide and the same amount of Nano-Fe are added in a single dropping way3O4@ ARBC cyan700℃A sample of fenton catalyst is a control.
As shown in FIG. 5, hydrogen peroxide and Fenton catalyst Nano-Fe were added3O4@ ARBC cyan700℃In the conical flask, the degradation speed of rhodamine B is very high, and the degradation rate reaches 66.40% in 60 min. While only an equal amount of Nano-Fe was added alone3O4@ ARBC cyan700℃In the conical flask of the Fenton catalyst, the degradation speed of rhodamine B is higher, and the degradation rate reaches about 50% in 60 min. This shows that the Fenton catalyst prepared by the invention is Nano-Fe3O4@ ARBC cyan700℃When used alone, the catalyst also has good catalytic degradation effect of organic matters, and the catalytic degradation effect is far higher than that of single hydrogen peroxide.
Comparative example 3
This example is carried out using the Fenton catalyst Nano-Fe prepared in example 23O4@ ARBC cyan600℃Examples of catalytic degradation of organic matter in water were carried out, and the experimental methods were the same as those described above.
The result shows that the degradation rate reaches 55.70% at 60min, and 88.60% at 2 h. Thus, the Fenton catalyst prepared at the carbonization temperature of 700 ℃ has better performance than 600 ℃ during pyrolysis and carbonization.
Comparative example 4
This example is carried out using the Fenton catalyst Nano-Fe prepared in example 23O4@ ARBC chain700℃Examples of catalytic degradation of organic matter in water were carried out, and the experimental methods were the same as those described above.
The result shows that the degradation rate reaches 45.4% in 60min and 64.5% in 2 h. Therefore, the performance of the Fenton catalyst prepared by taking the penicillin fungi residues as the raw materials is better than that of the streptomycin fungi residues under the same pyrolysis carbonization condition.
Comparative example 5
This example is carried out using the Fenton catalyst Nano-Fe prepared in example 23O4@ coffee grounds charcoal HCBC700℃Examples of catalytic degradation of organic matter in water were carried out, and the experimental methods were the same as those described above.
The result shows that the degradation rate reaches 75.6% in 60min and 89.5% in 2 h. Therefore, the Fenton catalyst prepared by using the penicillin fungi residues as the raw materials has better performance than the coffee residues under the same pyrolysis carbonization condition.
As shown in FIG. 6, a graph comparing the degradation rate of rhodamine B in water treated by Fenton catalyst for 2h in example 3 and comparative examples 3-5 is shown.
In conclusion, the penicillin fungi residue is used as the raw material to prepare the penicillin fungi residue biochar, and the magnetic Nano-Fe is loaded through adsorption3O4Then, the Fenton catalyst Nano-Fe is obtained3O4The @ mushroom residue biochar has excellent organic matter degradation performance, and the degradation capability of the @ mushroom residue biochar is obviously superior to that of the streptomycin mushroom residue and coffee residue biochar-loaded Nano-Fe3O4A fenton catalyst. Meanwhile, in the pyrolysis carbonization process, the prepared biochar loaded Nano-Fe is at the temperature of 700 DEG C3O4The Fenton catalyst is superior to the 600 ℃ catalyst, so when preparing the penicillin fungi residue biochar, the pyrolysis temperature is preferably controlled to be 690-710 ℃ and the preparation is carried out under the protection of vacuum or nitrogen/argon.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. Magnetic nano Fe3O4The @ mushroom dreg biochar Fenton catalyst is characterized by comprising a carrier and an active material, wherein the carrier is penicillin mushroom dreg biochar, and the active material is magnetic nano Fe3O4。
2. Magnetic nano Fe3O4The preparation method of the @ mushroom dreg biochar Fenton catalyst is characterized by comprising the following steps of:
s1, mixing the penicillin fungi residues with potassium carbonate/sodium, adding water, stirring, activating, drying, crushing and sieving to obtain activated dried penicillin fungi residues;
s2, pyrolyzing and carbonizing the activated dried penicillin fungi residues under the protection of inert atmosphere, pickling, washing with water to be neutral, then washing with absolute ethyl alcohol, and drying to obtain penicillin fungi residue biochar;
s3, firstly dispersing the penicillin fungi residue biochar in water, then adding soluble ferric salt, soluble ferrous salt and a precipitator to generate black precipitate, and magnetically separating the black precipitate;
s4, washing the black precipitate, and drying the black precipitate in an oxygen-free environment to obtain magnetic nano Fe3O4@ bacterial residue biochar Fenton catalyst.
3. The preparation method of claim 2, wherein in S1, the mass ratio of the penicillin mushroom dregs to the potassium carbonate/sodium is 1: 1-1.2; the activation temperature was 30. + -. 2 ℃.
4. The preparation method according to claim 2, wherein in S2, the inert gas is nitrogen/argon, and the activated dried penicillin fungi residues are pyrolyzed and carbonized under the protection of nitrogen/argon, and the pyrolysis temperature is 690-710 ℃; the pyrolysis time is 2-4 h; the heating rate is 8-12 ℃/min.
5. The method according to claim 2, wherein in S2, the acid washing is performed with dilute hydrochloric acid; the drying is carried out under vacuum or under the protection of nitrogen/argon; after pyrolysis and carbonization and before acid washing, cooling the pyrolysis and carbonization product, crushing the product in a crusher, and sieving the crushed product with a 60-mesh sieve to obtain powdery penicillin fungi residue biochar.
6. The preparation method according to claim 2, wherein in S3, the soluble ferric salt and the soluble ferrous salt are added in a ratio satisfying: fe3+：Fe2+The molar ratio is 2: 1; the soluble ferric iron is any one of ferric chloride and hydrate thereof, ferric sulfate and hydrate thereof; the soluble ferrous salt is any one of ferrous chloride and hydrate thereof, ferrous sulfate and hydrate thereof.
7. The preparation method of claim 2, wherein in S3, the penicillin fungi residue biochar is ultrasonically dispersed in water, soluble ferric salt and soluble ferrous salt are added, stirring is started, NaOH solution is added, stirring reaction is carried out at a constant temperature of 55-65 ℃, the whole reaction process is ensured to be carried out under the protection of oxygen-free gas or nitrogen/argon gas, stirring and cooling are continued after the reaction is finished, and a magnet is used for separating the product.
8. The method according to claim 7, wherein in S3, the penicillin mushroom residue biochar is mixed with Fe3O4Weighing penicillin fungi residue biochar, soluble ferric salt and soluble ferrous salt according to the mass ratio of 1:1-2 to obtain magnetic nano Fe in the product3O4The loading of (B) is 50-66.6 wt%.
9. The preparation method according to claim 2, wherein the specific operation of S3 is: adding water into a reaction vessel, introducing nitrogen/argon gas at normal temperature while stirring to exhaust air in the reaction vessel and the water, adding the weighed penicillin fungi residue biochar into the reaction vessel, and performing ultrasonic dispersion; then adding the weighed soluble ferric salt and ferrous salt, putting the mixture into a constant-temperature water bath reaction area at the temperature of 55-60 ℃ under stirring, and stirring until the mixture is completely and uniformly mixed; adding hydroxide solution at constant speed at constant temperature of 55-60 deg.C, generating black precipitate, maintaining stirring for 2-2.5 hr to ensure the whole reaction is carried out under nitrogen/argon protection, stirring and cooling after the reaction is finished, and separating the product with magnet.
10. The preparation method according to claim 2, wherein in S4, the product is washed with ultrapure water for 3-5 times to neutral, then washed with absolute ethanol for 2-4 times to remove water and ash in the product, filtered, and dried in vacuum or nitrogen/argon for 20-30h to obtain the magnetic nano Fe3O4@ bacterial residue biochar Fenton catalyst.
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