CN111215067B - Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst - Google Patents

Preparation method and application of lutecium gadolinium modified delta-manganese oxide compound supported platinum catalyst Download PDF

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CN111215067B
CN111215067B CN202010202674.5A CN202010202674A CN111215067B CN 111215067 B CN111215067 B CN 111215067B CN 202010202674 A CN202010202674 A CN 202010202674A CN 111215067 B CN111215067 B CN 111215067B
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傅之丹
叶青
董宁
陈梦月
陈永宝
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Beijing University of Technology
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Abstract

The invention discloses a preparation method and application of a platinum catalyst loaded by a lutetium-gadolinium exchange delta-manganese oxide compound. The preparation of the catalyst is that under the strong acid environment regulated by concentrated nitric acid, dispersant is added, manganese sulfate and potassium permanganate carry out reflux reaction to prepare delta-manganese oxide, then lutetium nitrate and gadolinium nitrate are used for dipping the delta-manganese oxide, and surfactant is added simultaneously to obtain Lu-Gd/delta-MnO exchanged with lutetium and gadolinium 2 Compounding, and mixing Pt (en) 2 Cl 2 The ligand is loaded on the catalyst and is prepared into a high specific surface area (100-130 m) after high-temperature and hydrogen reduction treatment 2 (g) and high thermal stability: (>650 ℃ Pt/Lu-Gd-delta-MnO 2 A catalyst. The catalyst prepared by the invention has high space velocity (60,000h) ‑1 ～100,000h ‑1 ) And low concentration toluene and ethyl acetate (500 ppm-1000 ppm) have higher elimination efficiency. The catalyst prepared by the invention has the advantages of cheap raw materials, simple preparation process, strong practicability, low temperature for completely eliminating Volatile Organic Compounds (VOCs), high efficiency, no secondary pollution and the like.

Description

Preparation method and application of platinum-supported catalyst of lutecium gadolinium modified delta-manganese oxide compound
Technical Field
The invention relates to a platinum Pt/Lu-Gd-delta-MnO loaded lutetium-gadolinium exchange delta-manganese oxide for catalytic combustion and elimination of Volatile Organic Compounds (VOCs) 2 The preparation of the catalyst and the application of the catalyst in low-temperature high-efficiency catalytic combustion for eliminating VOCs.
Background
Benzene series is one of the main components of Volatile Organic Compounds (VOCs). It typically includes eight compounds, benzene, toluene, ethylbenzene, o-xylene, among which the benzene series has been listed as a priority pollutant by the United States Environmental Protection Agency (USEPA) for the list of toxic pollutants in the atmosphere. Benzene series in the air can enter human bodies through respiratory tracts, digestive tracts and skins, so that the human bodies are discomforted, diseases are induced, further cancer is generated, and the benzene series has great influence on the environment and the health of the human bodies. Ethyl acetate (C) 4 H 8 O 2 ) Is a typical waveOrganic volatile compounds (VOCs) have excellent solubility and quick drying, and are organic chemical raw materials and industrial solvents with wide application. Is widely used in the production process of acetate fiber, ethyl fiber, chlorinated rubber, vinyl resin, acetate fiber resin, synthetic rubber, paint and the like. The VOCs treatment technology mainly comprises incineration, wherein two modes of direct combustion and catalytic combustion are adopted for incineration treatment, products generated by direct combustion easily cause secondary pollution, and the catalytic combustion is to decompose benzene series into carbon dioxide and water vapor by means of flameless combustion at a lower ignition temperature by means of a catalyst. As toluene is the most difficult species to be eliminated by catalytic combustion in benzene series, the toluene is used for representing the benzene series, and the toluene and ethyl acetate are used for representing VOCs gas. At present, the research on the catalytic combustion elimination of the benzene series is less at home and abroad, and the reaction temperature for completely catalyzing and eliminating the benzene series is higher. For example: in The paper "The effect of The thermal comfort of benzene and methane over palladium catalysts supported on porous materials" (Total. Today,83 (2003) 131-139) published by The research of The Korean Gon SeoO subject group, the space velocity was 60,000h -1 Benzene concentration of 10,000ppm (space velocity lower than 100,000h of the invention) -1 Benzene concentration is higher than 1000ppm of the invention), benzene is catalyzed and combusted by FAU zeolite, MCM-41 and KIT-1 loaded Pd catalyst, and the temperature for completely catalyzing, combusting and eliminating benzene is mostly above 300 ℃.
Manganese oxide (MnO) prepared by the method 2 ) Support of delta-MnO 2 Due to the porous structure, the manganese ions with mixed valence states, mild acid-base property of the surface and excellent ion exchange performance, the method becomes a new research hotspot after zeolite-type tetrahedral molecular sieves. Its crystal structure is composed of octahedron [ MnO ] with common edges 6 ]Chain formation, with octahedra [ MnO ] passing between chains 6 ]The oxygen atoms at the top points are connected by common edges to form a one-dimensional structure. As a novel functional material, supported MnO has been reported 2 Has ideal catalytic activity in catalytic thermal decomposition and catalytic oxidation of organic matters, thereby having wide industrial application prospect.
The implementation of this project resulted in: national science foundation project (accession number: 21277008; the subsidization of the national emphasis research and development plan (2I 005011201702) is also the research content of the projects.
Disclosure of Invention
The invention aims to provide a method for preparing a lutetium gadolinium exchange modified compound delta-manganese oxide (delta-MnO) with high specific surface area and high thermal stability by using cheap potassium permanganate and manganese sulfate as raw materials and using concentrated nitric acid and a dispersing agent to regulate and reflux in a strong acid environment 2 ) Load platinum Pt/Lu-Gd-delta-MnO 2 And the catalyst is used for eliminating Volatile Organic Compounds (VOCs) by low-temperature catalytic combustion.
The invention provides a preparation method of a catalyst for eliminating Volatile Organic Compounds (VOCs) by catalytic combustion.
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, formula (C) 2 H 4 O) n ) Adding 50-100mL of distilled water to form a solution (0.5-1 wt%), adding the solution into a three-neck flask, uniformly stirring at 65-75 ℃, and then adding K 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.15 mol/L-0.50 mol/L, wherein n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA = (0.015 to 0.05) mol:1g of the total weight of the composition. Then adding MnSO 4 Adding the solution (0.10 mol/L-0.75 mol/L) into the mixed solution, stirring for 6-10 h, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]= (0.5 to 1.0) mol:1mol, simultaneously dripping 15-20mL of concentrated nitric acid (5.0-6.0 mol/L), maintaining a strong acid environment with pH =2-3, and keeping the concentration at 5-10W/cm 2 Performing ultrasonic treatment for 1-2 h, stirring for 1-2 h, refluxing at 100-110 deg.C for 24-48h, vacuum filtering, washing with deionized water to neutrality, drying at 80-120 deg.C to obtain brown solid, and treating with pure oxygen (O) 2 ) Roasting at 300-400 deg.c for 1-4 hr to obtain one-dimensional delta-MnO 2 。
20-50mL of lutetium nitrate Lu (NO) 3 ) 3 ·6H 2 O solution (0.001-0.005 mol/L) and gadolinium nitrate Gd (NO) 3 ) 3 ·6H 2 O solution (0.001-0.005 mol/L) is stirred and mixed evenly to form mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at a rate of 5-10W/cm 2 Carrying out intensity ultrasonic treatment for 1-2 h, then continuously stirring for 2-6 h, and standing for later use. In addition, F127 (Pluronic, polyoxyethylene, HO (C) is added at 120-140 deg.C 2 H 4 O) m (C 3 H 6 O) n H, molecular weight = 1000-7000) powder was dissolved in 20-50mL of distilled water and 20-50mL of ethanol to form a 0.5-2wt% F127 solution, stirred until F127 was completely dissolved, then 1.0-1.5mL of HCl solution (36-38 wt%) was added, stirring was continued for 1-5H, and delta-MnO prepared above was added 2 To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO 2 In the slurry, and at a rate of 5-10W/cm 2 The ultrasonic treatment is carried out for 1 to 2 hours, the mixture is continuously stirred for 2 to 6 hours, the mixture is refluxed for 24 hours, and the solution is evaporated after rotary evaporation for 3 to 4 hours. The obtained product is heated to 300 to 400 ℃ at the speed of 1 to 2 ℃/min in pure oxygen atmosphere and is roasted for 2 to 4 hours, and Lu-Gd/delta-MnO is finally obtained 2 And (3) a compound.
Adding ethylenediamine (en) to 50-100mL of H 2 PtCl 6 Solution (5-10 mmol L) -1 ) In which n [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:2-3mol, and uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 And (3) precursor solution. In addition, lu-Gd/delta-MnO was added 2 Adding 50-100mL Polyacrylic acid PAA (Polyacrylic acid, molecular formula (C) 3 H 4 O 2 ) n ) In solution (1-15 mg/L), wherein Lu-Gd/delta-MnO is added 2 : polyacrylic acid PAA =1g:10mL, mixed well and stirred to form a suspension, and the concentration is 5-10W/cm 2 The intensity of the ultrasonic wave is kept for 1 to 2 hours, and then the ultrasonic wave is continuously stirred for 2 to 6 hours. Mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In suspension, wherein n [ Pt (en) 2 Cl 2 ]：Lu-Gd-δ-MnO 2 = (0.005-0.01) mol:1-2g, stirring for 4 hours, then carrying out rotary evaporation for 3-4 hours to evaporate the solution to obtain a solid, filtering, washing with distilled water, and finally drying at 60-80 ℃ for 12-24 hours to obtain a black solid.The solid obtained is reacted in H 2 (5-10％H 2 Ar) atmosphere in a tube furnace porcelain boat at 400-500 ℃ for 1-3h, and the heating rate is 5-10 ℃/min. After natural cooling to room temperature, the heat treated sample was washed in hydrochloric acid for 10-12h. Finally, the sample is centrifugally separated, washed to be neutral by deionized water, washed by ethanol and dried at 80-100 ℃ to obtain the Pt/Lu-Gd-delta-MnO product 2 。
(2) The invention also provides application of the catalyst in eliminating VOCs gas through low-temperature catalytic combustion.
The catalytic combustion elimination reaction of VOCs gas represented by toluene and ethyl acetate is carried out in a fixed bed quartz tube reactor. A miniature quartz reaction tube. Introducing a mixed gas of toluene or ethyl acetate and air, wherein the concentration of the toluene and the ethyl acetate is 500ppm to 1000ppm, and the air flow space velocity is 60,000h -1 ～100,000h -1 . Gas chromatography TCD detection reaction tail gas CO 2 And CO, FID detects the content of other organic species such as toluene or ethyl acetate. The invention has the following effects: under the concentration and space velocity of the toluene or ethyl acetate, the catalyst prepared by the invention has higher low-temperature catalytic combustion elimination activity, and can completely convert the toluene into nontoxic CO at the temperature of 220-240 DEG C 2 And H 2 O, at the temperature, the elimination rate of the toluene is kept for 100 hours>90 percent, can completely convert the ethyl acetate into non-toxic CO at the temperature of 180 to 220 DEG C 2 And H 2 O, at the temperature, the elimination rate of ethyl acetate is kept within 100 hours>90 percent. The price of the potassium permanganate used as the raw material for preparing the catalyst is low, and the catalyst has simple preparation process and is not loaded with other metals or noble metals. The invention does not need to add any fuel and directly utilizes O in the air 2 Is an oxidant, and has the advantages of economical and practical raw materials, low energy consumption in the using process, simple and convenient operation, mild reaction conditions, capability of reducing secondary pollution, continuous work and the like.
Drawings
FIG. 1 is a diagram of Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 XRD pattern of (1)
FIG. 2 shows examples 1 and 2 of the present invention,3 and 4 prepared Pt/Lu-Gd-delta-MnO 2 N of (A) 2 Adsorption/desorption curve diagram
FIG. 3 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 Catalytic combustion activity of toluene
FIG. 4 is a Pt/Lu-Gd-delta-MnO prepared in examples 1, 2, 3 and 4 of the present invention 2 Catalytic combustion activity of ethyl acetate
FIG. 5 is a Pt/Lu-Gd-delta-MnO prepared in example 4 of the present invention 2 Catalyst p-toluene catalytic Combustion stability
FIG. 6 is a Pt/Lu-Gd-delta-MnO prepared in example 4 of the present invention 2 -I catalyst stability to catalytic combustion of ethyl acetate
Detailed Description
Example 1
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C) 2 H 4 O) n ) Adding 50mL of distilled water to form a solution (0.5 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 65 ℃, and then adding K 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.15mol/L, where n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA =0.015mol:1g. Then adding MnSO 4 Adding solution (0.10 mol/L) into the above mixed solution, and stirring for 6 hr, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]=0.5mol:1mol, and simultaneously dropwise adding 15mL of concentrated nitric acid (5.0 mol/L), maintaining a strong acid environment with pH =2 and keeping the concentration at 5W/cm 2 Performing ultrasonic treatment for 1h, stirring for 1h, refluxing at 100 deg.C for 24h, vacuum filtering, washing with deionized water to neutrality, oven drying at 80 deg.C to obtain brown solid, and purifying with pure oxygen (O) 2 ) Roasting at the medium temperature of 300 ℃ for 1h to obtain one-dimensional delta-MnO 2 。
20mL of lutetium nitrate Lu (NO) 3 ) 3 ·6H 2 O solution (0.001 mol/L) and gadolinium nitrate Gd (NO) 3 ) 3 ·6H 2 Stirring and mixing the O solution (0.001 mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at 5W/cm 2 Carrying out intensity ultrasonic treatment for 1h, continuously stirring for 2h, and standing for later use. In addition, F127 (Pluronic, polyoxyethylene, HO (C) was reacted at 120 ℃ C 2 H 4 O) m (C 3 H 6 O) n H) The powder was dissolved in 20mL of distilled water and 20mL of ethanol to form a 0.5wt% F127 solution, stirred until F127 was completely dissolved, then 1.0mL of HCl solution (36 wt%) was added, stirring was continued for 1h, and the delta-MnO prepared above was added 2 To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO 2 In the slurry, and at 5W/cm 2 After 1h of sonication and 2h of continued stirring, the mixture was refluxed for 24h and the solution was evaporated by rotary evaporation for 3h. Heating the obtained product to 300 ℃ at the speed of 1 ℃/min in pure oxygen atmosphere and roasting for 2 hours to finally obtain Lu-Gd/delta-MnO 2 And (c) a complex.
Ethylenediamine (en) was added to 50mL H of chloroplatinic acid 2 PtCl 6 Solution (5 mmol L) -1 ) In which n [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:2mol, uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 And (3) precursor solution. In addition, lu-Gd/delta-MnO was added 2 To 50mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C)) 3 H 4 O 2 ) n ) In solution (1 mg/L), wherein Lu-Gd/delta-MnO 2 : polyacrylic acid PAA =1g:10mL, mixed well and stirred to homogeneity to form a suspension, and the concentration is 5W/cm 2 The intensity of (1) was sonicated for 1h and stirring was continued for 2h. Mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In suspension, wherein n [ Pt (en) 2 Cl 2 ]：Lu-Gd-δ-MnO 2 =0.005mol:1g, stirred for 4 hours, then rotary evaporated for 3 hours to evaporate the solution to obtain a solid, filtered, washed with distilled water and finally dried at 60 ℃ for 12 hours to obtain a black solid. The solid obtained is reacted in H 2 (5％H 2 Ar) atmosphere in a tube furnace porcelain boat at 400 ℃ for 1h, and the heating rate is 5 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 10h. Finally, the samples were centrifuged and washed to neutrality with deionized waterThen washing with ethanol, and drying at 80 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO 2 -I。
(2) And (4) evaluating the activity of the catalyst. The concentration of toluene or ethyl acetate is 500ppm, the air flow space velocity is 60,000h -1 . Gas chromatography TCD detection reaction tail gas CO 2 And CO, FID detects the content of toluene or ethyl acetate and other organic species. The temperature for eliminating the toluene (100 percent conversion of the toluene) by the catalyst prepared in the embodiment 1 of the invention through complete catalytic combustion is 220 ℃, the conversion rate of the toluene reaches 50 percent at 210 ℃, when the temperature is in the range of 190-220 ℃, the conversion rate of the toluene is linearly increased until reaching 100 percent, and the toluene is completely converted into CO in the catalytic combustion elimination reaction of the toluene 2 And H 2 O; the conversion rate of ethyl acetate reaches 50% when the reaction temperature is 150 ℃, the conversion rate of ethyl acetate reaches 100% when the reaction temperature is 180 ℃, and the reaction product only contains CO 2 And H 2 O。
Example 2
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C) 2 H 4 O) n ) 70mL of distilled water was added to form a solution (0.7 wt%) which was added to a three-necked flask, stirred at 69 ℃ and then K was added thereto 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.30mol/L, where n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA =0.03mol:1g of the total weight of the composition. Then adding MnSO 4 Adding solution (0.5 mol/L) into the above mixed solution, and stirring for 7h, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]= (0.7mol 2 Performing ultrasonic treatment for 1h, stirring for 1h, refluxing at 100 deg.C for 30h, vacuum filtering, washing with deionized water to neutrality, oven drying at 90 deg.C to obtain brown solid, and introducing into pure oxygen (O) 2 ) Roasting at 350 ℃ for 2h to obtain one-dimensional delta-MnO 2 。
30mL of lutetium nitrate Lu (NO) 3 ) 3 ·6H 2 O solution (0.003 mol/L) and gadolinium nitrate Gd (NO) 3 ) 3 ·6H 2 Stirring and mixing the O solution (0.003 mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at 7W/cm 2 Carrying out intensity ultrasonic treatment for 1h, continuously stirring for 4h, and standing for later use. In addition, F127 (Pluronic, polyoxyethylene, HO (C)) was reacted at 130 deg.C 2 H 4 O) m (C 3 H 6 O) n H) Dissolving the powder in 30mL of distilled water and 30mL of ethanol to form a solution with a concentration of 1wt% of F127, stirring until F127 is completely dissolved, adding 1.0mL of HCl solution (36 wt%) of hydrochloric acid, stirring for 3h, and adding the delta-MnO prepared above 2 To form a mixed slurry. Adding the above mixed solution of rare earth into delta-MnO 2 In the slurry, and at 7W/cm 2 The mixture was refluxed for 24 hours and the solution was evaporated off by rotary evaporation for 3 hours. Heating the obtained product to 300 ℃ at the speed of 1 ℃/min in pure oxygen atmosphere and roasting for 3 hours to finally obtain Lu-Gd/delta-MnO 2 And (c) a complex.
Ethylenediamine (en) was added to chloroplatinic acid 70mL H 2 PtCl 6 Solution (7 mmol L) -1 ) In which n [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:2mol, uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 And (3) precursor solution. In addition, lu-Gd/delta-MnO was added 2 To 70mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C)) 3 H 4 O 2 ) n ) In solution (7 mg/L) with Lu-Gd/delta-MnO 2 : polyacrylic acid PAA =1g:10mL, mixed well and stirred to homogeneity to form a suspension, and the concentration is 7W/cm 2 The intensity of (1) was sonicated for 1h and stirring was continued for another 3h. Mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In suspension, wherein n [ Pt (en) 2 Cl 2 ]：Lu-Gd-δ-MnO 2 =0.007mol:1g, stirred for 4 hours, then rotary evaporated for 3 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 70 ℃ for 12 hours to give a black solid. The solid obtained is reacted in H 2 (7％H 2 Treating in a tube furnace porcelain boat with Ar) atmosphere at 400 ℃ for 1h at a heating rateAt a temperature of 7 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 10h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 90 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO 2 -II。
(2) And (4) evaluating the activity of the catalyst. The concentration of toluene or ethyl acetate is 500ppm, the air flow space velocity is 60,000h -1 . Gas chromatography TCD detection reaction tail gas CO 2 And CO, FID detects the content of toluene and other organic species. The temperature of the catalyst for completely catalyzing, burning and eliminating the toluene (toluene is 100 percent converted) prepared in the embodiment 2 of the invention is 260 ℃, the conversion rate of the toluene reaches 50 percent at 235 ℃, when the temperature is in the range of 220-260 ℃, the conversion rate of the toluene is linearly increased to 100 percent, and the toluene is completely converted into CO in the catalytic burning elimination reaction of the toluene 2 And H 2 O; the conversion rate of ethyl acetate reaches 50% when the reaction temperature is 180 ℃, the conversion rate of ethyl acetate reaches 100% when the reaction temperature is 220 ℃, and the reaction product only contains CO 2 And H 2 O。
Example 3
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, formula (C) 2 H 4 O) n ) Adding 90mL of distilled water to form a solution (1 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 70 ℃, and then adding K 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.40mol/L, where n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA =0.04mol:1g of the total weight of the composition. Then adding MnSO 4 Adding solution (0.5 mol/L) into the above mixed solution, stirring for 9h, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]=0.9mol:1mol, and simultaneously dripping 20mL of concentrated nitric acid (6.0 mol/L), maintaining a strong acid environment with pH =3 and keeping the pH at 9W/cm 2 Performing ultrasonic treatment for 2h, stirring for 2h, refluxing at 110 deg.C for 48h, vacuum filtering, washing with deionized water to neutrality, oven drying at 120 deg.C to obtain brown solid, and purifying with pure oxygen (O) 2 ) Roasting at the medium temperature of 400 ℃ for 4h to obtain one-dimensional delta-MnO 2 。
50mL of lutetium nitrate Lu (NO) 3 ) 3 ·6H 2 O solution (0.004 mol/L) and gadolinium nitrate Gd (NO) 3 ) 3 ·6H 2 Stirring and mixing the O solution (0.004 mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at 5W/cm 2 Carrying out intensity ultrasonic treatment for 2h, continuously stirring for 5h, and standing for later use. In addition, F127 (Pluronic, polyoxyethylene, HO (C)) was reacted at 140 deg.C 2 H 4 O) m (C 3 H 6 O) n H) The powder was dissolved in 40mL of distilled water and 40mL of ethanol to form a 1.5wt% F127 solution, stirred until F127 was completely dissolved, then 1.3mL of HCl solution (38 wt%) was added, stirring was continued for 4h, and the delta-MnO prepared above was added 2 To form a mixed slurry. Adding the above mixed solution of rare earth into delta-MnO 2 In the slurry, and at 9W/cm 2 The mixture was refluxed for 24 hours and the solution was evaporated by rotary evaporation for 4 hours. Heating the obtained product to 400 ℃ at the speed of 2 ℃/min in pure oxygen atmosphere, and roasting for 4 hours to finally obtain Lu-Gd/delta-MnO 2 And (c) a complex.
Ethylenediamine (en) was added to chloroplatinic acid 90mL H 2 PtCl 6 Solution (9 mmol L) -1 ) In which n is [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:3mol, uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 And (3) precursor solution. In addition, lu-Gd/delta-MnO was added 2 To 90mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C)) 3 H 4 O 2 ) n ) In solution (13 mg/L) with Lu-Gd/delta-MnO 2 : polyacrylic acid PAA =1g:10mL, mixed well and stirred to form a suspension, and the concentration is 9W/cm 2 The intensity of (2) was sonicated for 2h and stirring was continued for another 6h. Mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In which n [ Pt (en) ] 2 Cl 2 ]：Lu-Gd-δ-MnO 2 =0.009mol:2g, stirred for 4 hours, then rotary evaporated for 4 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 80 ℃Drying for 24h gave a black solid. The solid obtained is reacted in H 2 (9％H 2 Ar) atmosphere in a tube furnace porcelain boat at 500 ℃ for 3h, and the heating rate is 9 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 12h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 90 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO 2 -III。
(2) And (4) evaluating the activity of the catalyst. The concentration of benzene or ethyl acetate is 1000ppm, the air flow space velocity is 100,000h -1 . Gas chromatography TCD detection of reaction tail gas CO 2 And CO, FID detects the content of toluene and other organic species. The temperature of the catalyst for completely catalyzing, burning and eliminating the toluene (100 percent conversion of the toluene) prepared in the embodiment 3 of the invention is 240 ℃, the conversion rate of the toluene reaches 50 percent at 210 ℃, when the temperature is in the range of 200-240 ℃, the conversion rate of the toluene is linearly increased to 100 percent, and the toluene is completely converted into CO in the catalytic burning elimination reaction of the toluene 2 And H 2 O; the conversion rate of ethyl acetate reaches 50% at the reaction temperature of 160 ℃, 100% at the reaction temperature of 200 ℃, and only CO is contained in the reaction product 2 And H 2 O。
Example 4
(1) The preparation method of the catalyst provided by the invention comprises the following steps:
mixing polyvinyl alcohol PVA (polyvinyl alcohol-vinyl polymer, molecular formula (C) 2 H 4 O) n ) Adding 100mL of distilled water to form a solution (1 wt%) and adding the solution into a three-neck flask, stirring the solution uniformly at 75 ℃, and then adding K 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.50mol/L, where n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA =0.05mol:1g. Then mixing MnSO 4 Adding the solution 0.75mol/L into the above mixed solution, and stirring for 10 hr, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]=1.0mol:1mol, simultaneously dripping 20mL of concentrated nitric acid 6.0mol/L, maintaining a strong acid environment with pH =3, and keeping the concentration at 10W/cm 2 Ultrasonic treating for 2 hr, stirring for 2 hr, refluxing at 110 deg.C for 48 hr, and pumpingFiltering, washing with deionized water to neutral, oven drying at 120 deg.C to obtain brown solid, and purifying with pure oxygen (O) 2 ) Roasting at the temperature of 400 ℃ for 4h to obtain one-dimensional delta-MnO 2 。
50mL of lutetium nitrate Lu (NO) 3 ) 3 ·6H 2 O solution (0.005 mol/L) and gadolinium nitrate Gd (NO) 3 ) 3 ·6H 2 Stirring and mixing the O solution (0.005mol/L) uniformly to form a mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at 10W/cm 2 Carrying out intensity ultrasonic treatment for 2h, continuously stirring for 6h, and standing for later use. In addition, F127 (Pluronic, polyoxyethylene, HO (C)) was reacted at 140 deg.C 2 H 4 O) m (C 3 H 6 O) n H) Dissolving the powder in 50mL of distilled water and 50mL of ethanol to form a 2wt% F127 solution, stirring until the F127 is completely dissolved, adding 1.5mL of HCl solution (38 wt%), stirring for 5h, and adding the delta-MnO prepared above 2 To form a mixed slurry. Adding the rare earth mixed solution into delta-MnO 2 In a slurry, and at 10W/cm 2 After 2h of sonication and continued stirring for 6h, the mixture was refluxed for 24h and the solution was evaporated by rotary evaporation for 4 h. Heating the obtained product to 400 ℃ at the speed of 2 ℃/min in pure oxygen atmosphere, and roasting for 4 hours to finally obtain Lu-Gd/delta-MnO 2 And (3) a compound.
Ethylenediamine (en) was added to chloroplatinic acid 100mL H 2 PtCl 6 Solution (10 mmol L) -1 ) In which n [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:3mol, and uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 And (3) precursor solution. In addition, lu-Gd/delta-MnO was added 2 Added to 100mL of Polyacrylic acid PAA (Polyacrylic acid, formula (C) 3 H 4 O 2 ) n ) In solution (15 mg/L), wherein Lu-Gd/delta-MnO 2 : polyacrylic acid PAA =1g:10mL, thoroughly mixed and stirred to form a suspension, and the concentration is 10W/cm 2 The intensity of (2) was sonicated for 2h and stirring was continued for another 6h. Mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In which n [ Pt (en) ] 2 Cl 2 ]：Lu-Gd-δ-MnO 2 =0.01mol:2g, stirred for 4 hours, then rotary evaporated for 4 hours to evaporate the solution to give a solid, filtered, washed with distilled water and finally dried at 80 ℃ for 24 hours to give a black solid. The solid obtained is reacted in H 2 (10％H 2 Ar) atmosphere in a tube furnace porcelain boat at 500 ℃ for 3h, and the heating rate is 10 ℃/min. After natural cooling to room temperature, the heat-treated sample was washed in HCl (37 wt%) for 12h. Finally, centrifugally separating the sample, washing the sample to be neutral by using deionized water, then washing the sample by using ethanol, and drying the sample at 100 ℃ to obtain the obtained product Pt/Lu-Gd-delta-MnO 2 -IV。
(2) And (4) evaluating the activity of the catalyst. The concentration of benzene or ethyl acetate is 1000ppm, the air flow space velocity is 100,000h -1 . Gas chromatography TCD detection reaction tail gas CO 2 And CO, FID detects the content of toluene and other organic species. The temperature for eliminating the toluene (100 percent conversion of the toluene) by the catalyst prepared in the embodiment 4 of the invention through complete catalytic combustion is 250 ℃, the conversion rate of the toluene reaches 50 percent at 230 ℃, when the temperature is in the range of 150-230 ℃, the conversion rate of the toluene is linearly increased until reaching 100 percent, and the toluene is completely converted into CO in the catalytic combustion elimination reaction of the toluene 2 And H 2 O; the conversion rate of ethyl acetate reaches 50% at the reaction temperature of 170 ℃, the conversion rate of ethyl acetate reaches 100% at the reaction temperature of 210 ℃, and the reaction product only contains CO 2 And H 2 O。

Claims (3)

1. A preparation method of a platinum catalyst loaded by a lutetium-gadolinium modified delta-manganese oxide compound is characterized by comprising the following steps:
adding polyvinyl alcohol PVA into 50-100mL of distilled water to form 0.5wt% -1wt% solution, adding the solution into a three-neck flask, uniformly stirring at 65-75 ℃, and then adding K 2 MnO 4 Adding to the above solution, K 2 MnO 4 The final concentration is 0.15 mol/L-0.50 mol/L, wherein n [ K ] 2 MnO 4 ]: polyvinyl alcohol PVA = (0.015-0.05) mol:1g of a compound; then MnSO with the concentration of 0.10 mol/L-0.75 mol/L is added 4 Adding the solution into the mixed solution, stirring for 6-10 h, wherein n [ KMnO ] 4 ]：n[MnSO 4 ]＝(0.5～1.0)mol:1mol, simultaneously dripping 15-20mL of concentrated nitric acid with the concentration of 5.0-6.0mol/L, maintaining the strong acid environment with the pH =2-3, and keeping the concentration at 5-10W/cm 2 Performing ultrasonic treatment at the intensity of 1-2 h, continuously stirring for 1-2 h, refluxing for 24-48h at 100-110 ℃, performing suction filtration, washing to be neutral by deionized water, drying at 80-120 ℃ to obtain brown solid, and roasting the brown solid for 1-4 h at 300-400 ℃ in pure oxygen to obtain one-dimensional delta-MnO 2 ；
20 to 50mL of lutetium nitrate Lu (NO) with the concentration of 0.001 to 0.005mol/L 3 ) 3 ·6H 2 O solution and gadolinium nitrate Gd (NO) with the concentration of 0.001 to 0.005mol/L 3 ) 3 ·6H 2 Stirring and mixing the O solution uniformly to form a mixed solution, wherein n [ Lu (NO) 3 ) 3 ]：n[Gd(NO 3 ) 3 ]=1mol:1mol, and at a rate of 5-10W/cm 2 Carrying out intensity ultrasonic treatment for 1-2 h, then continuously stirring for 2-6 h, and standing for later use; further, dissolving polyoxyethylene F127 powder in 20-50mL of distilled water and 20-50mL of ethanol at 120-140 ℃ to form a 0.5-2wt% F127 solution, stirring until F127 is completely dissolved, adding 1.0-1.5mL of 36-38wt% hydrochloric acid solution, stirring for 1-5h, and adding the delta-MnO prepared above 2 Forming a mixed slurry; adding the rare earth mixed solution into delta-MnO 2 In the slurry, and at a rate of 5-10W/cm 2 Carrying out ultrasonic treatment for 1-2 h, continuously stirring for 2-6 h, refluxing the mixture for 24h, and carrying out rotary evaporation for 3-4 h to evaporate the solution; the obtained product is heated to 300 to 400 ℃ at the speed of 1 to 2 ℃/min in pure oxygen atmosphere and is roasted for 2 to 4 hours, and Lu-Gd-delta-MnO is finally obtained 2 A complex;
adding ethylenediamine (en) to 50-100mL of H 2 PtCl 6 Solution of H 2 PtCl 6 The solution concentration is 5-10mmol L -1 In which n [ H ] 2 PtCl 6 ]: n [ Ethylenediamine (en)]=1mol:2-3mol, and uniformly mixing and stirring to obtain Pt (en) 2 Cl 2 Precursor solution; in addition, lu-Gd-delta-MnO is added 2 Adding the mixture into 50 to 100mL polyacrylic acid PAA solution with the concentration of 1 to 15mg/L, wherein Lu-Gd-delta-MnO 2 : polyacrylic acid PAA =1g:10mL, mixed well and stirred to form a suspension, and the suspension is added with 5-10 percentW/cm 2 The intensity ultrasound is carried out for 1 to 2 hours, and then the mixture is continuously stirred for 2 to 6 hours; mixing Pt (en) 2 Cl 2 Adding the precursor solution into Lu-Gd-delta-MnO 2 In which n [ Pt (en) ] 2 Cl 2 ]：Lu-Gd-δ-MnO 2 = (0.005-0.01) mol:1-2g, stirring for 4 hours, then carrying out rotary evaporation for 3-4 hours to evaporate the solution to obtain a solid, filtering, washing with distilled water, and finally drying at 60-80 ℃ for 12-24 hours to obtain a black solid; the solid obtained is reacted in H 2 Treating in a tube furnace porcelain boat in an Ar mixed atmosphere at 400-500 ℃ for 1-3h 2 H in mixed Ar atmosphere 2 5-10% of volume percentage; the heating rate is 5-10 ℃/min; naturally cooling to room temperature, and washing the heat-treated sample in a hydrochloric acid solution for 10-12h; finally, the sample is centrifuged, washed to neutrality with deionized water, then washed with ethanol and dried at 80-100 ℃ to obtain the product.
2. The application of the catalyst prepared by the preparation method according to claim 1 in the elimination of volatile organic compounds is characterized in that: putting the catalyst in a continuous flow fixed bed device, and introducing mixed gas of toluene or ethyl acetate and air to react; the reaction pressure is normal pressure-2 MPa, the reaction space velocity is 60,000h -1 ～100,000h -1 In the mixed gas of air and toluene or the mixed gas of air and ethyl acetate, the concentration of toluene or ethyl acetate is 500 ppm-1000 ppm, and the reaction temperature is 25-300 ℃.
3. Use according to claim 2, characterized in that: the air in the air mixture is prepared standard air, N 2 ：O 2 The volume ratio is 79:21.
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