CN112973693B - Microfiber composite nano metal catalyst and preparation method and application thereof - Google Patents
Microfiber composite nano metal catalyst and preparation method and application thereof Download PDFInfo
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- 229920001410 Microfiber Polymers 0.000 title claims abstract description 77
- 239000003658 microfiber Substances 0.000 title claims abstract description 77
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011122 softwood Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
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- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229920005594 polymer fiber Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 108700005457 microfibrillar Proteins 0.000 claims 1
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- 238000010525 oxidative degradation reaction Methods 0.000 claims 1
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- 239000002923 metal particle Substances 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 9
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- 238000006555 catalytic reaction Methods 0.000 abstract description 4
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- 238000006731 degradation reaction Methods 0.000 description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000005067 remediation Methods 0.000 description 2
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229930003779 Vitamin B12 Natural products 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
- 235000019163 vitamin B12 Nutrition 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Images
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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
- 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
- B01J23/755—Nickel
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a microfiber composite nano metal catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) preparing a precursor of the microfiber composite material from the microfiber and the lignocellulose by a wet papermaking method, and drying the precursor; (2) sintering the dried precursor of the micro-fiber composite material in protective gas to obtain a carrier of the micro-fiber composite material; (3) and uniformly immersing the carrier in a solution containing metal elements, loading the metal elements on the carrier, uniformly dropwise adding a reducing agent into the solution, continuously stirring, and drying to obtain the microfiber composite nano metal catalyst. The catalyst can simultaneously exert the advantages of the nano metal particles and the microfiber composite material, overcomes the defects of easy oxidation, easy agglomeration and difficult recovery of the nano metal particles, and is favorable for the catalyst to show more excellent characteristics in the aspect of catalysis.
Description
Technical Field
The invention relates to the technical field of papermaking, in particular to a microfiber composite nano metal catalyst and a preparation method and application thereof.
Background
With the explosive development of modern industry, the environmental pollution problem is receiving more and more attention. Industrial wastewater is one of the important sources of water environment pollution, and effective treatment and restoration of polluted environment are important components of ecological civilization construction in China. At present, nanotechnology is widely applied to the degradation of water pollutants and in-situ environmental remediation. Many researches show that the nano metal particles are excellent catalysts, can effectively treat polluted industrial wastewater and have great application potential in the field of environmental remediation (Liu H., et al. Chem Eng J. 2013, 215: 90-95; O Carroll D., et al. Adv Water resource 2013, 51: 104-. There are many kinds of nano metals, and taking nano zero-valent iron (NZVI) as an example, the advantage of high surface reactivity due to its large specific surface area (O Carroll d., et al. Adv Water resource 2013, 51: 104-. Despite the many advantages of nano-metal particles, the drawbacks are also highlighted. The characteristics of high manufacturing cost, easy surface oxidation, easy particle agglomeration and difficult recycling limit the application of the material in industry (Amir A., et al. Chem Eng J.2011, 170(2-3): 492 497; Jievarangankul P., et al. Chem Eng J.2011, 170(2-3): 482. 491.). Researchers have attempted to improve the stability and dispersibility of the nano-metal particles using different modification methods, including the use of two-component systems (Fang z., et al, J Hazard mater 2011, 185(2): 958-. Among them, the introduction of a carrier to prepare a nano metal-carrier composite catalyst is proved to be effective in improving the performance of the catalyst, and therefore, the selection of the carrier is also a key factor.
As a novel carrier, the microfiber composite materials were first proposed by the professor Tatarchuk of the university of Olympic, USA (Tatarchuk B.J., et al, Mixed fiber composite structures high surface area-high conductivity polymers [ P ]), and applied to the preparation of gas masks and the treatment of volatile organic compounds. The microfiber composite material has many advantages, including adjustable raw materials, high void ratio, high loading capacity, high mechanical strength, wide application range, etc. (Chang B., et al. Chem Eng J. 2006, 115(3): 195-202.). The unique three-dimensional reticular structure can effectively reduce the bed resistance in the fixed bed reaction and enhance the mass and heat transfer (Yang H., et al. Chem Eng Sci. 2008, 63(10): 2707-. Meanwhile, the catalyst can also reduce the internal diffusion resistance of the catalyst and improve the contact efficiency of the catalyst (Kalluri R.R., et al Sep purify technol. 2008, 62(2): 304-316.). The microfiber composite material is mainly prepared by a wet papermaking technology, and the method is low in cost and easy for large-scale production.
Nano-metal particles have been used in the degradation of a variety of contaminants. Taking NZVI as an example, when Amir et al (Amir A., et al, Chem Eng J.2011, 170(2-3): 492 497) apply NZVI to the degradation process of tetrachloroethylene, it is found that the addition of vitamin B12 can effectively increase the degradation rate of pollutants, and at the same time, can prolong the service life of the catalyst and reduce the loss of iron in the use process. Carroll et al (O Carroll D., et al. Adv Water resource, 2013, 51: 104-122.) summarize the application of NZVI in chloride degradation, and it is believed that the current NZVI has low catalytic efficiency in practical application due to agglomeration, surface passivation and other problems, thereby increasing the usage amount of the catalyst in the degradation process and increasing the cost. The extensive research on the chemical reaction mechanism is beneficial to increase the possibility of industrialization of NZVI. They also found that NZVI has the effect of reducing and fixing heavy metal wastewater. In recent years, with the continuous development of organic industry, people focus on the application of NZVI to the treatment of organic wastewater, especially the organic wastewater which cannot be effectively treated by the traditional method. Fang et al (Fang Z., et al J Hazard Mater. 2011, 185(2): 958-969.) use Ni as an auxiliary agent to prepare Ni/Fe bi-component nano-metal particles and apply the Ni/Fe bi-component nano-metal particles to the degradation of polybrominated diphenyl ethers (PBDEs). The result shows that the catalyst can effectively degrade PBDEs (the conversion rate reaches 100%) at normal temperature and normal pressure. Qiu et al (Qiu x., et al, J Hazard mater 2011, 193: 70-81.) supported NZVI on mesoporous silica, also showed good PBDEs degradation efficiency and recyclability. In addition, compounds such as antibiotics, bisphenol A, etc. have also been shown to be removable by NZVI.
As mentioned above, the nano metal particles can be loaded on a proper carrier to obtain better catalytic effect, and the microfiber composite material as a novel carrier can be applied to the preparation of novel catalysts. The Tatarchuk professor of Orben university firstly proposes the concept of microfiber composite material and develops the application research in gas masks, VOC purification, fuel cells, etc. (Zhu W.H., et al. J Power sources 2002, 111(2): 221-. Yuranov et al (Yuranov i., et al, Appl cat a-gen, 2005, 281(1): 55-60.) synthesized Fe/ZSM-5 molecular sieve membrane catalyst on microfiber composite material carrier and applied to hydroxylation reaction of benzene to prepare phenol, found that the microfiber composite material can effectively combine catalytic reaction, heat exchange process and separation steps, so that the operation is simpler and more convenient. Yan et al (Yan Y., et al. Sep purify technol. 2014, 133: 365-. In conclusion, the microfiber composite material is used as a carrier and combined with a catalyst to effectively improve the activity of the catalyst, so that the novel microfiber composite nano metal catalyst is prepared by combining the microfiber composite material with nano metal particles, and the innovation points mainly comprise the following points:
(1) the novel microfiber composite nano metal catalyst is provided, and combines nano metal particles with a microfiber composite material, so that the advantages of developed three-dimensional network structure, large porosity, flexible geometric configuration and the like of the microfiber composite material and the catalytic performance of the nano metal particles can be simultaneously exerted.
(2) The bed resistance of the structured fixed bed can be effectively reduced, the mass transfer and heat transfer are enhanced, the contact efficiency of the catalyst is increased, and the reaction efficiency of the catalytic reaction is improved.
Aiming at the problems of the existing catalyst, the invention aims to apply the catalyst to the restoration of a water environment system on the basis of the combination of theory and practice.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the defects in the prior art, the invention provides a microfiber composite nano metal catalyst and a preparation method and application thereof, wherein the catalyst can simultaneously exert the advantages of nano metal particles and microfiber composite materials, overcomes the defects of easy oxidation, easy agglomeration and difficult recovery of the nano metal particles, and is beneficial to the catalyst to show more excellent characteristics in the aspect of catalysis.
The technical scheme is as follows: a preparation method of a microfiber composite nano metal catalyst comprises the following steps:
(1) preparing microfiber composite material precursor from microfiber and lignocellulose through a wet papermaking method, and drying, wherein the mass ratio of the microfiber to the lignocellulose is (1/9-9): 1;
(2) sintering the dried precursor of the micro-fiber composite material in protective gas to obtain a carrier of the micro-fiber composite material;
(3) uniformly immersing a carrier in a solution containing metal elements, loading the metal elements on the carrier, then uniformly dropwise adding a reducing agent into the solution, continuously stirring to completely reduce the metal elements in the solution, and drying to obtain the micro-fiber composite nano metal catalyst, wherein the concentration of the solution containing the metal elements is 0.1-10 mol/L.
Preferably, the microfibers in the step (1) are one or more of ceramic fibers, carbon fibers, metal fibers, glass fibers and polymer fibers; the lignocellulose is one or two of softwood fiber and hardwood fiber.
Preferably, the metal element in the step (3) is one or more of iron, copper, cobalt and manganese, the solution corresponding to the metal element is sulfate, chloride or nitrate, and the concentration of the solution is 0.1-10 mol/L.
Preferably, the reducing agent in step (3) is sodium borohydride or potassium borohydride.
Preferably, the loading method in step (3) is one or two of ultrasound, heating, impregnation and ion exchange.
Preferably, the drying in the step (1) is carried out for 30-120 min at the temperature of 100-; the specific process of the sintering in the step (2) is to heat the mixture from room temperature to 480 ℃ at a speed of 3-7 ℃/min, keep the temperature constant at 480 ℃ for 10-30min, then heat the mixture to 950-.
Preferably, the protective gas in step (2) is nitrogen, helium or argon.
The microfiber composite nano metal catalyst prepared by the preparation method is provided.
The microfiber composite nano metal catalyst is applied to catalytic oxidation degradation of organic matters.
Preferably, the organic substance is phenol or a phenol derivative.
Has the advantages that: the microfiber composite nano metal catalyst and the preparation method and the application thereof provided by the invention have the following beneficial effects:
1. the catalyst carrier has low manufacturing cost, simple manufacturing method, stable product quality, good effect and easy industrial production;
2. the nano metal particles in the catalyst are uniformly loaded, the particle size of the particles is small, the particles are not easy to agglomerate and oxidize, and the contact efficiency is high;
3. the microfiber is adopted as a carrier, so that the advantages of the microfiber composite material and the nano metal particles can be exerted at the same time, and the catalytic efficiency is effectively improved;
4. the catalyst is easy to recover, the catalyst is saved, and the cost is reduced; the catalyst loss is reduced, and the risk of secondary pollution is reduced;
5. the catalyst can well and uniformly and dispersedly load the nano metal particles on the carrier of the micro-fiber composite material, and improves the application range and contact efficiency of the catalyst and the application efficiency of the catalyst by utilizing the advantages of high load capacity, adjustable porosity, high mechanical strength and wide application range of the micro-fiber composite material.
Drawings
Fig. 1 is a reaction flow chart of the fixed bed catalytic degradation reaction of m-methyl phenol using the microfiber composite nanometal catalyst prepared by the present invention in example 1 and example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
The following examples illustrate the preparation of a micro-fiber composite nano-copper catalyst and a micro-fiber composite nano-iron catalyst.
Example 1
The preparation method of the microfiber composite nano copper catalyst comprises the following steps: weighing 6 g of nickel fiber with the length of 2-3 mm and the diameter of 6.5 mu m and 10g of softwood fiber, adding the nickel fiber and the softwood fiber into 2L of water, dissociating in a fiber standard dissociator for 10 min, filtering and molding on a manual sheet-making machine to obtain a precursor of the micro-fiber composite material, and drying by using a drying and pressing machine at 110 ℃; placing the dried precursor of the microfiber composite material in a high-temperature tube array type sintering furnace under the protection of nitrogen for temperature programmed sintering; before sintering, a sintering furnace is firstly vacuumized, then nitrogen is introduced, the operation is repeated for three times, and then the temperature is raised according to the following procedures: heating from room temperature to 480 ℃ at the speed of 4 ℃/min, keeping the temperature constant at 480 ℃ for 20min, heating to 950 ℃ at the speed of 4.7 ℃/min, sintering at 950 ℃ for 20min, and naturally cooling to room temperature to obtain a microfiber composite material carrier; weighing 1.5 g of microfiber composite material carrier, and immersing in 1.0 mol/L CuSO4Heating and soaking the solution for 24 hours, and then uniformly dropwise adding 1.6 mol/L NaBH into the solution4And continuously stirring the solution until the solution is black, taking out the micro-fiber composite material, washing the micro-fiber composite material by using deionized water, and drying the micro-fiber composite nano-copper catalyst to obtain the micro-fiber composite nano-copper catalyst.
The microfiber composite nano copper catalyst prepared in example 1 is used for the fixed bed catalytic degradation reaction of m-methylphenol, and an experimental flow chart is shown in fig. 1, wherein the height of a bed layer is 2 cm, the reaction temperature is 60 ℃, and the feeding flow rate is 2 m/min. The oxidant is H2O2The concentration of m-methyl phenol is 500 mg/L, and the ratio of the feeding concentration of the oxidant to the feed concentration of the degradation product is the stoichiometric ratio: c7H8O + 17H2O2→ 7CO2 + 21H2The conversion rate of O, m-methyl phenol reaches 99%, and the reaction activity is not obviously reduced after 24 hours.
Example 2
The preparation method of the microfiber composite nano iron catalyst comprises the following steps: weighing 7 g of 2-3 mm long and 6.5 μm diameterAdding stainless steel fiber of m and needle wood fiber of 10g into 2L of water, dissociating in a fiber standard dissociator for 10 min, filtering and molding on a manual sheet-making machine to obtain a precursor of the microfiber composite material, and drying by a drying and pressing machine at 110 ℃; placing the dried precursor of the microfiber composite material in a high-temperature tube array type sintering furnace under the protection of nitrogen for temperature programmed sintering; before sintering, a sintering furnace is firstly vacuumized, then nitrogen is introduced, the operation is repeated for three times, and then the temperature is raised according to the following procedures: heating from room temperature to 480 ℃ at the speed of 5 ℃/min, keeping the temperature constant at 480 ℃ for 20min, heating to 1050 ℃ at the speed of 4.7 ℃/min, sintering at 1050 ℃ for 20min, and naturally cooling to room temperature to obtain a microfiber composite material carrier; weighing 1.5 g of microfiber composite material carrier, and immersing in 0.1 mol/L FeCl3And 0.1 mol/L polyvinylpyrrolidone, soaking for 24h, and then uniformly dropwise adding 0.3 mol/L NaBH into the solution4And continuously stirring the solution for 5min, taking out the micro-fiber composite material, washing the micro-fiber composite material by using deionized water, and drying to obtain the micro-fiber composite nano iron catalyst.
The microfiber composite nano iron catalyst prepared in example 2 is used for fixed bed catalytic degradation reaction of phenol, and an experimental flow chart is shown in fig. 1, wherein the height of a bed layer is 3 cm, the reaction temperature is 80 ℃, and the feeding flow rate is 2 ml/min. The oxidant is H2O2The phenol concentration is 1000 mg/L, and the ratio of the feeding concentration of the oxidant to the feed concentration of the degradation product is the stoichiometric ratio: c6H6O + 14H2O2→ 6CO2 + 17H2The conversion rate of O and phenol reaches 99 percent, and the reaction activity is not obviously reduced after 24 hours.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a microfiber composite nano metal catalyst is characterized by comprising the following steps:
(1) preparing microfiber composite material precursor from microfiber and lignocellulose through a wet papermaking method, and drying, wherein the mass ratio of the microfiber to the lignocellulose is (1/9-9): 1;
(2) sintering the dried precursor of the micro-fiber composite material in protective gas to obtain a carrier of the micro-fiber composite material;
(3) uniformly immersing a carrier in a solution containing metal elements, loading the metal elements on the carrier, then uniformly dropwise adding a reducing agent into the solution, continuously stirring to completely reduce the metal elements in the solution, and drying to obtain the microfiber composite nano metal catalyst, wherein the metal elements are one or more of iron, copper, cobalt and manganese, and the concentration of the solution containing the metal elements is 0.1-10 mol/L.
2. The method for preparing a microfiber composite nanometal catalyst according to claim 1, wherein the method comprises the following steps: the microfibers in the step (1) are one or more of ceramic fibers, carbon fibers, metal fibers, glass fibers and polymer fibers; the lignocellulose is one or two of softwood fiber and hardwood fiber.
3. The method for preparing a microfiber composite nanometal catalyst according to claim 1, wherein the method comprises the following steps: and (4) the reducing agent in the step (3) is sodium borohydride or potassium borohydride solution.
4. The method for preparing a microfiber composite nanometal catalyst according to claim 1, wherein the method comprises the following steps: the loading method in the step (3) is one or two of ultrasonic treatment, heating, impregnation and ion exchange.
5. The method for preparing a microfiber composite nanometal catalyst according to claim 1, wherein the method comprises the following steps: the drying in the step (1) is carried out for 30-120 min at the temperature of 100-; the specific process of the sintering in the step (2) is to heat the mixture from room temperature to 480 ℃ at a speed of 3-7 ℃/min, keep the temperature constant at 480 ℃ for 10-30min, then heat the mixture to 950-.
6. The method for preparing a microfiber composite nanometal catalyst according to claim 1, wherein the method comprises the following steps: and (3) the protective gas in the step (2) is nitrogen, helium or argon.
7. A microfibrillar composite nanometal catalyst prepared by the preparation method according to any one of claims 1 to 6.
8. The application of the microfiber composite nano metal catalyst of claim 7 in catalytic oxidative degradation of organic matters.
9. Use of the microfibre composite nanometal catalyst according to claim 8 characterised in that: the organic matter is phenol or phenol derivatives.
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