CN111215071B - Porous catalyst with Fe/Cu bimetal and preparation method and application thereof - Google Patents
Porous catalyst with Fe/Cu bimetal and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003245 coal Substances 0.000 claims abstract description 70
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 68
- 239000010949 copper Substances 0.000 claims description 57
- 238000000034 method Methods 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002351 wastewater Substances 0.000 claims description 16
- 150000003254 radicals Chemical class 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229940124350 antibacterial drug Drugs 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229940124530 sulfonamide Drugs 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 150000003456 sulfonamides Chemical class 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 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 21
- 229960005404 sulfamethoxazole Drugs 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- -1 comprises adsorption Chemical compound 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
-
- 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
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a porous catalyst with Fe/Cu bimetal, a preparation method and application thereof. The porous catalyst comprises a coal gangue framework and Fe/Cu bimetal generated on the coal gangue framework in situ. Researches show that the main component of the coal gangue comprises SiO2、Al2O3、Fe2O3CaO, MgO, etc., wherein SiO2And Al2O3Form the main skeleton of the coal gangue, and Fe2O3The content of (A) can be as high as more than 10%. The applicant of the application takes the coal gangue as an iron source, and generates Fe/Cu bimetal on a coal gangue framework in situ, and has the following advantages: (1) reasonably utilizing the coal gangue and realizing waste utilization; (2) the skeleton of the coal gangue has a higher specific surface area, and can provide more active sites for the Fe/Cu bimetal, so that the Fe/Cu bimetal is fully contacted with substances reacted with the Fe/Cu bimetal, and the reaction efficiency is improved.
Description
Technical Field
The invention relates to the technical field of water treatment by catalytically activating peroxyacetic acid, in particular to a porous catalyst with Fe/Cu bimetal, and a preparation method and application thereof.
Background
Sulfamethoxazole is a commonly used sulfanilamide antibacterial drug and is widely applied to industries such as medical treatment, breeding and the like. In recent years, the concentration of sulfamethoxazole detected in part of surface water and underground water in China exceeds ng/L level. Sulfamethoxazole has three-effect, can induce the diffusion of resistance genes, influence the microbial population structure, and threaten aquatic organisms and human health, and is necessary to be purified by adopting a green and efficient technology. At present, the removal technology of sulfamethoxazole mainly comprises adsorption, biodegradation, advanced oxidation and the like. The advanced oxidation technology has the advantages of high treatment efficiency, small secondary pollution, convenient management and operation, high mineralization rate of pollutants and remarkable advantages.
The coal gangue is used as coal associated solid waste and is produced in a large amount in the coal mining, washing, processing and producing processes. The annual output of coal gangue accounts for about 10-25% of the coal mining amount, but due to low utilization rate, the current stockpiling amount reaches more than 50 hundred million tons, not only occupies a large amount of land resources, but also poses serious threat to the environment. At present, no coal gangue is applied in the field of removing sulfonamide antibacterial drugs in water, so that the application of the coal gangue to the removal of the sulfonamide antibacterial drugs in water is a new idea for realizing the 'treatment of waste by waste' and recycling the coal gangue.
Disclosure of Invention
The invention aims to solve the technical problem of providing a porous catalyst with Fe/Cu bimetal, which reasonably utilizes coal gangue, and a preparation method and application thereof.
In order to achieve the above object, the present invention firstly provides a porous catalyst having an Fe/Cu bimetal, the porous catalyst comprising a coal gangue skeleton and an Fe/Cu bimetal in-situ generated on the coal gangue skeleton.
Researches show that the main component of the coal gangue comprises SiO2、Al2O3、Fe2O3CaO, MgO, etc., wherein SiO2And Al2O3Form the main skeleton of the coal gangue, and Fe2O3The content of (A) can be as high as more than 10%. The applicant of the application takes the coal gangue as an iron source, and generates Fe/Cu bimetal on a coal gangue framework in situ, and has the following advantages: (1) reasonably utilizing the coal gangue and realizing waste utilization; (2) the skeleton of the coal gangue has a higher specific surface area, and can provide more active sites for the Fe/Cu bimetal, so that the Fe/Cu bimetal is fully contacted with substances reacted with the Fe/Cu bimetal, and the reaction efficiency is improved.
Further, the porous catalyst is used to catalytically activate peroxyacetic acid. The porous catalyst can be used for catalytically activating peroxyacetic acid to HO·、CH3C(＝O)OO·、CH3C(＝O)O·And the like, active species (also referred to as radicals) having strong oxidizing properties. For Fe/Cu bimetallic, Fe0、Cu0Can directly catalyze and activate the peroxyacetic acid, which is caused by Fe/Cu dual goldThe method belongs to the characteristics of a primary battery, peroxyacetic acid can be catalytically activated through electrode reaction, namely the peroxyacetic acid obtains electrons on positive electrode Cu and generates free radicals, and meanwhile, Fe dissolved out from negative electrode Fe2+Can also participate in the catalytic activation of the peroxyacetic acid. Proved by verification, because Fe/Cu double metals in the porous catalyst are distributed more uniformly, a small amount of porous catalyst can be used for sufficiently catalyzing and activating peracetic acid, rich free radicals with strong oxidizing property are generated, and the water treatment efficiency is obviously improved. In the prior art, hydrogen peroxide is catalytically activated into an active substance for water treatment, but hydrogen peroxide can be catalytically activated only under acidic conditions; through the verification of the applicant of the application, compared with hydrogen peroxide, peracetic acid can be catalytically activated in a wider pH range, and active species generated by catalytic activation also have strong oxidizing property, so that the peracetic acid used as a free radical precursor has better application prospect than hydrogen peroxide. By "catalytically activated" is meant accelerating the process of converting peroxyacetic acid to more oxidizing radicals.
Further, in the reaction of catalytically activating peroxyacetic acid, the mass ratio of the porous catalyst to the peroxyacetic acid is (65.7-131.5): 1.
in order to achieve the above object, the present invention secondly provides a method for preparing a porous catalyst having an Fe/Cu bimetal, which uses coal gangue as both an iron source and an attachment skeleton of the Fe/Cu bimetal.
In the invention, the coal gangue not only provides an iron source, but also makes full use of the skeleton of the coal gangue, so that the Fe/Cu bimetal can fully play a role in catalytic activation while the coal gangue is maximally utilized.
Further, the method comprises the following steps:
(1) obtaining coal gangue and a copper source;
(2) reducing the iron source and the copper source by adopting a reducing agent to generate Fe/Cu bimetal.
Cu production by reduction with a reducing agent0And generating Fe in situ on the coal gangue skeleton0Simultaneously, the in-situ generation on the coal gangue skeletonFe (b) of0And Cu2+And carrying out a replacement reaction to generate Fe/Cu bimetal on the coal gangue framework in situ.
Further, the copper source is a salt containing copper ions; the reducing agent is borohydride. Thus, the time required for the reduction reaction is short. Among them, sodium borohydride and potassium borohydride are preferably used as the borohydride.
Further, the method also comprises the step of pretreating the coal gangue, wherein the pretreatment is acid impregnation. Through acid dipping, on one hand, iron ions can be dissolved, and on the other hand, the framework can be etched, so that the specific surface area is increased.
Further, the method also comprises the step of pretreating the coal gangue, wherein the pretreatment is grinding and screening so as to obtain coal gangue powder with the particle size of less than or equal to 48 mu m. Thereby, the specific surface area of the final porous catalyst is further increased.
Further, Fe in the coal gangue2O3The content is more than or equal to 10 percent. This ensures that the final porous catalyst skeleton contains a large amount of Fe/Cu bimetallic.
After verification, when Fe is contained in the coal gangue2O3When the content is more than or equal to 10 percent, 10g to 30g of coal gangue with the grain diameter of less than or equal to 48 mu m is put into every 100mL of sulfuric acid solution with the concentration of 4mol/L to 4.5mol/L and is soaked in acid for 10 hours to 15 hours, so that higher iron ion elution amount and reasonable specific surface area can be obtained, and a more complete framework is reserved. And when the molar ratio of Fe/Cu is 3.0-4.0 and the mass ratio of borohydride to coal gangue is 0.3-0.4, less porous catalysts can be used for catalytically activating the peroxyacetic acid.
In order to achieve the purpose, the invention also provides a method for removing the sulfonamide antibacterial drugs in the wastewater, which comprises the step of putting the porous catalyst with the Fe/Cu bimetal or the porous catalyst with the Fe/Cu bimetal prepared by the method and a free radical precursor into the wastewater containing the sulfonamide antibacterial drugs, wherein the free radical precursor is preferably peroxyacetic acid.
Proved by verification, the peracetic acid catalyzed and activated by the porous catalyst with Fe/Cu bimetal can quickly remove sulfanilamide antibacterial drugs, especially sulfamethoxazole, in water under mild conditions, and has high efficiency.
As can be seen from the above, the present invention has the following advantageous effects:
1. the preparation method of the porous catalyst with Fe/Cu bimetal has simple process, reasonably utilizes the active components and the frame structure of the coal gangue, realizes waste utilization, and has low application cost.
2. The porous catalyst with Fe/Cu bimetal can efficiently catalyze and activate peracetic acid so as to remove pollutants such as sulfamethoxazole in water in a short time, and has small secondary pollution.
3. The porous catalyst with Fe/Cu bimetal has wide suitable pH range and can be applied to the direct treatment of acid and alkaline wastewater.
4. The porous catalyst with Fe/Cu bimetal has wide suitable temperature range and can be applied to the direct treatment of multi-region wastewater.
5. The invention provides a method for preparing a free radical by using peroxyacetic acid as a free radical precursor, which can be catalytically activated under the acidic pH condition, even under the neutral or alkalescent pH condition, can generate various free radicals, and has a sterilization function in the wastewater treatment process.
The present invention will be further described with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The present invention will now be described more fully hereinafter. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is explained, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
The coal gangue adopted in the embodiment is from an ancient coal field Luban mountain coal mine, the main components and the mass fraction wt% of the coal gangue are shown in Table 1, and the content of the unshown components is less than 0.3 wt%.
TABLE 1
| Compound (I) | wt％ |
| SiO2 | 43.97 |
| Al2O3 | 18.43 |
| Fe2O3 | 14.75 |
| CaO | 12.11 |
| TiO2 | 4.4 |
| MgO | 2.18 |
| Na2O | 1.63 |
| K2O | 1.34 |
The porous catalyst with Fe/Cu bimetal prepared by utilizing the coal gangue comprises a coal gangue framework and Fe/Cu bimetal generated on the coal gangue framework in situ.
The preparation method of the porous catalyst with Fe/Cu bimetal comprises the following steps:
(1) the coal gangue is ground and sieved by a 500-mesh sieve, and the obtained coal gangue powder is less than or equal to 25 mu m.
(2) Acid soaking: adding 10-30 g of coal gangue powder into every 100mL of sulfuric acid solution with the concentration of 4-4.5 mol/L, and then soaking for 14 hours.
(3) Reduction reaction
A. Adding copper sulfate according to the Fe/Cu molar ratio of 3 and uniformly mixing;
B. adding potassium borohydride according to the mass ratio of the potassium borohydride to the coal gangue of 0.4, and uniformly mixing;
C. after the reaction is carried out for 12 hours, the solid is centrifugally separated and cleaned, and the porous catalyst with Fe/Cu bimetal is obtained after drying.
The main reaction equation is as follows:
4Fe3++3BH4 -+9H2O→4Fe0+3H2BO3 -+12H++6H2
Fe(H2O)6 3++3BH4 -+3H2O→Fe0+3B(OH)3+10.5H2
Fe0+2H+→H2+Fe2+
Fe(H2O)6 2++2BH4 -→Fe0+2B(OH)3+7H2
4Cu2++BH4 -+8OH-→4Cu0+BO2 -+6H2O
Fe0+Cu2+→Cu0+Fe2+
BH4 -+H++3H2O＝4H2+H3BO3
the use of a porous catalyst with an Fe/Cu bimetallic comprises the following steps:
(1) adding peroxyacetic acid into the wastewater to be treated containing sulfamethoxazole;
(2) then adding the porous catalyst with Fe/Cu bimetal, and reacting for a period of time to remove sulfamethoxazole in the wastewater.
The advantageous effects of the present invention are illustrated below by specific examples.
The process parameters for preparing the porous catalyst having Fe/Cu bimetallic in examples 1-8 are shown in table 2. The performance of the obtained porous catalyst with Fe/Cu bimetal is tested, and the test process is as follows: 7.605mg of peracetic acid was added to 1L of wastewater having a sulfamethoxazole content of 1. mu. mol, the pH was controlled to 7, and then 700mg of a porous catalyst was added, and the reaction was carried out at room temperature with stirring while sampling every two minutes and determining the sulfamethoxazole content of the sampled products, the test results being shown in Table 2. In Table 2, the highest removal rate refers to the removal rate at which the sulfamethoxazole content does not change any more as the number of sampling times increases.
TABLE 2
| Example numbering | Concentration of sulfuric acid | Usage amount of coal gangue | Maximum removal rate | Time required to reach maximum removal rate |
| Example 1 | 4mol/L | 8g | 100％ | 10 minutes |
| Example 2 | 4mol/L | 10g | 100％ | 8 minutes |
| Example 3 | 4mol/L | 30g | 100％ | 10 minutes |
| Example 4 | 4mol/L | 35g | 100％ | 12 minutes |
| Example 5 | 4.5mol/L | 8g | 100％ | 12 minutes |
| Example 6 | 4.5mol/L | 10g | 100％ | 10 minutes |
| Example 7 | 4.5mol/L | 30g | 100％ | 8 minutes |
| Example 8 | 4.5mol/L | 35g | 100％ | 10 minutes |
In Table 2, it can be seen from comparative examples 1 to 4 or examples 5 to 8 that as the amount of coal gangue used increases, the time required to achieve the highest removal rate decreases because the content of sulfuric acid is less than that sufficient iron ions are extracted; however, when the amount of the coal gangue is too small, that is, when the content of the sulfuric acid is too large, the time for reaching the highest removal rate is rather prolonged, which may be that the sulfuric acid destroys the skeleton stability of the coal gangue, resulting in a decrease in the specific surface area of the final porous catalyst.
Also, 7.605mg of peracetic acid was added to 1L of wastewater containing 1. mu. mol of sulfamethoxazole, and when performance tests were performed using the porous catalyst of example 2 but at different amounts of use, the maximum removal rate was 97% if the amount added was less than 600mg, it was difficult to completely remove sulfamethoxazole; if the addition amount is more than 800mg, the time for achieving 100% removal rate is not shortened.
Also, 7.605mg of peracetic acid was added to 1L of wastewater containing 1. mu. mol of sulfamethoxazole, the initial pH of the wastewater was further adjusted to 6, 8 and 9 with sulfuric acid and sodium hydroxide solution, and then complete removal of sulfamethoxazole was achieved within 10 minutes when performance tests were carried out using the porous catalyst of example 2 each at a use amount of 700 mg. Therefore, the porous catalyst and the peroxyacetic acid have wide suitable pH range, and can be applied to the direct treatment of acid and alkaline wastewater.
Also, 7.605mg of peracetic acid was added to 1L of wastewater containing 1. mu. mol of sulfamethoxazole, and the temperature was further controlled at 5 ℃, 10 ℃ and 30 ℃, and then when the performance test was conducted using the porous catalyst of example 2 in each amount of 700mg, sulfamethoxazole was completely removed within 10 minutes. Therefore, the porous catalyst and the peroxyacetic acid have wide suitable temperature range, and can be applied to the direct treatment of the wastewater in multiple regions.
5.32mg, 6.08mg, 9.13mg and 9.89mg of peracetic acid were added to 1L of wastewater containing 1. mu. mol of four sulfamethoxazole compounds, respectively, the temperature was controlled at room temperature and the pH was 7, and then the performance test was carried out using the porous catalyst of example 2 each at a use amount of 700 mg. Proved that when the peroxyacetic acid is 6.08mg and 9.13mg, the time for completely removing the sulfamethoxazole is 10 minutes and 6 minutes respectively; when the amount of the peroxyacetic acid is 5.32mg, the highest removal rate is 97 percent, and sulfamethoxazole is difficult to completely remove; when the amount of peracetic acid was 9.89mg, the time required to completely remove sulfamethoxazole was also 6 minutes, indicating that part of peracetic acid was wasted.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (6)
1. A porous catalyst having a Fe/Cu bi-metal, characterized by: the porous catalyst comprises a coal gangue framework and Fe/Cu bimetal generated on the coal gangue framework in situ; the preparation method of the catalyst comprises the following steps:
(1) obtaining coal gangue and copper source, wherein the coal gangue provides iron source and Fe in the coal gangue2O3The content is more than or equal to 10 percent;
(2) firstly, grinding and screening coal gangue to obtain coal gangue powder with the particle size of less than or equal to 48 mu m; then 10g to 30g of coal gangue with the grain diameter less than or equal to 48 mu m is put into every 100mL of sulfuric acid solution with the concentration of 4mol/L to 4.5mol/L for acid dipping for 10 hours to 15 hours;
(3) reducing an iron source and a copper source by adopting a reducing agent to generate the Fe/Cu bimetallic porous catalyst, wherein the Fe/Cu molar ratio is 3.0-4.0.
2. The porous catalyst with Fe/Cu bi-metal of claim 1, wherein: the porous catalyst is used for catalytically activating peroxyacetic acid to generate active species.
3. The porous catalyst with Fe/Cu bi-metal of claim 2, wherein: in the reaction of catalytically activating peroxyacetic acid, the mass ratio of the porous catalyst to the peroxyacetic acid is (65.7-131.5): 1.
4. the preparation method of the porous catalyst with Fe/Cu bimetal is characterized in that: the method comprises the following steps:
(1) obtaining coal gangue and copper source, wherein the coal gangue provides iron source and Fe in the coal gangue2O3The content is more than or equal to 10 percent;
(2) firstly, grinding and screening coal gangue to obtain coal gangue powder with the particle size of less than or equal to 48 mu m; then 10g to 30g of coal gangue with the grain diameter less than or equal to 48 mu m is put into every 100mL of sulfuric acid solution with the concentration of 4mol/L to 4.5mol/L for acid dipping for 10 hours to 15 hours;
(3) reducing an iron source and a copper source by adopting a reducing agent to generate the Fe/Cu bimetallic porous catalyst, wherein the Fe/Cu molar ratio is 3.0-4.0.
5. The method of preparing a porous catalyst having an Fe/Cu bimetal according to claim 4, wherein: the copper source is a salt containing copper ions; the reducing agent is borohydride.
6. The method for removing the sulfanilamide antibacterial drugs in the wastewater is characterized by comprising the following steps: the method comprises the step of putting the porous catalyst with Fe/Cu bimetal of any one of claims 1 to 3 or the porous catalyst with Fe/Cu bimetal prepared by the method of any one of claims 4 to 5 and a free radical precursor into wastewater containing sulfonamide antibacterial drugs, wherein the free radical precursor is peroxyacetic acid.
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