CN104525214B - A kind of preparation method and application of alpha-oxidation manganese load iron samarium catalyst - Google Patents
A kind of preparation method and application of alpha-oxidation manganese load iron samarium catalyst Download PDFInfo
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Abstract
The invention discloses the preparation method and application of a kind of alpha-oxidation manganese load iron samarium catalyst.Under the adjustment of citric acid solution, manganese sulfate, potassium permanganate, ferric nitrate, samaric nitrate and dispersant back flow reaction, prepare high-specific surface area (100～130m2/ g) and heat stability high (> 650 DEG C) alpha-oxidation manganese load iron samarium sample F e/Sm-α-MnO2.Catalyst is to high-speed (60,000h-1～100,000h-1) and Low Concentration of Benzene and toluene (500ppm～1000ppm) there is higher elimination efficiency.When 220 DEG C, completely benzene is changed into non-poisonous material CO2And H2O, at this temperature, keeps benzene elimination factor in 100 hours > 90%；When 200 DEG C, it is possible to completely toluene conversion is become non-poisonous material CO2And H2O, at this temperature, keeps toluene elimination factor in 100 hours > 90%.Catalyst has that raw material is cheap, preparation technology is simple, practical, the advantages such as benzene homologues temperature low, efficiency high, non-secondary pollution is completely eliminated.
Description
Technical field
The present invention relates to a kind of alpha-oxidation manganese load iron samarium catalyst Fe/Sm-α-MnO for catalytic combustion elimination benzene homologues2Preparation, and for efficient cryogenic catalytic combustion elimination benzene homologues.
Background technology
Benzene homologues is one of main component of VOCs.It generally includes eight kinds of compounds such as benzene, toluene, ethylbenzene, o-Dimethylbenzene, and the air toxic list that wherein benzene homologues has been formulated by U.S. Environmental Protection Agency (EPA) (USEPA) is classified as priority pollutants.Benzene homologues in air can pass through respiratory tract, digestive tract and skin and enter human body, causes that human body presents all discomforts, thus inducing an illness and then carcinogenic, environmental and human health impacts is caused large effect by it.The treatment technology of benzene homologues mainly burns, the mode of burning disposal has directly burning and catalysis to burn two kinds, the product that directly burning generates easily causes secondary pollution, and catalysis burning is made by catalyst to be made benzene homologues carry out flameless combustion under relatively low initiation temperature to be decomposed into carbon dioxide and steam.Owing to benzene and toluene are for being most difficult to the species of catalytic combustion elimination in benzene homologues, so the present invention represents benzene homologues with benzene and toluene, with prepared catalyst this type of benzene homologues of catalysis burn processing.Both at home and abroad the catalytic combustion elimination of benzene homologues is studied less at present, and the reaction temperature of catalytic removal benzene homologues is higher completely.Such as: " Theeffectofmasstransferonthecatalyticcombustionofbenzene andmethaneoverpalladiumcatalystssupportedonporousmateria the ls " (Catal.Today delivered studies in GonSeoO seminar of Korea S, 83 (2003) 131 139) in paper, it is 60,000h in air speed-1, when the concentration of benzene is 10,000ppm, (air speed is lower than the 100,000h of the present invention-1, benzene concentration is higher than the 1000ppm of the present invention), use FAU zeolite, MCM-41 and KIT-1 Pt-supported catalyst that benzene is carried out catalyst combustion reaction, the temperature of its complete catalytic combustion elimination benzene is mostly more than 300 DEG C.
Manganese oxide (the MnO that this project system is standby2) carrier, belong to α-MnO2, because there being loose structure, there is the manganese ion of mixed valence, the Acidity of Aikalinity on surface is gentle and has excellent ion-exchange performance, becomes another new study hotspot after zeolite type tetrahedron molecular sieve.Its crystal structure is by the octahedron [MnO of common seamed edge6] chain composition, further through octahedra [MnO between chain and chain6] summit oxygen atom with common corner angle be connected, constitute one-dimentional structure.As a kind of novel functional material, have been reported support type α-MnO2Catalytic Thermal Decomposition aminodiphenylamine and liquid phase oxidation alcohols etc. all have ideal catalysis activity, thus there is prospects for commercial application extensively.
This project implementation obtains: project of national nature science fund project (numbering: 21277008；20777005)；Education Commission of Beijing development in science and technology plan general project (KM2013100050010)；Beijing institution of higher education directly under the jurisdiction of a municipal government Construction of Creativity Team promotes the subsidy of planning item (KM2013100050010), is also the research contents of these projects.
Summary of the invention
It is an object of the invention to provide the cheap manganese sulfate of a kind of use is raw material, uses buffer solution and dispersant control method to prepare the alpha-oxidation manganese (α-MnO of high-specific surface area and high thermal stability2), and use it for low-temperature catalytic burning elimination benzene homologues.
The present invention provides a kind of preparation method for catalytic combustion elimination benzene homologues catalyst.
(1) preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.02～1.49 ratios, regulates pH between 3.00～4.75, subsequently by the Sm (NO of 0.01g～0.05g3)3.6H2O and 0.50g～4.50gFe (NO3)3.9H2O is dissolved in above 40ml citric acid solution.By the PVAC polyvinylalcohol (molecular formula (C of 0.0g～2.0g2H4O)n, molecular weight 20000) and to be dissolved in 20ml～60ml concentration be 1.0mol/L～2.0mol/LMnSO4In solution, the buffer solution containing slaine above is joined in this solution, mix homogeneously.It is 0.1mol/L～0.4mol/LKMnO by 120ml～170ml concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4(mol ratio)=0.5～1.0, stir 2～4 hours, seal ageing 12 hours, 80 DEG C～120 DEG C reflux 20～26 hours, rotation steaming 3～4 hours until powdered, with deionized water rinsing to neutral, 100 DEG C～140 DEG C dry 10～12 hours, obtain black presoma, then grind into powder.Take above-mentioned presoma to mix than for 8g:200ml ratio with straight alcohol.Being stirred 24 hours by this mixture, rotation steams to be fallen by solution evaporation for 3 hours～4 hours.The product obtained speed with 1 DEG C/min in pure oxygen atmosphere, it is raised to 300 DEG C～500 DEG C degree roasting 1～4 hour, finally gives Fe/Sm-α-MnO2Product.
(2) present invention also provides for a kind of described catalyst and eliminates the application in benzene homologues at low-temperature catalytic burning.
The catalytic combustion elimination reaction of benzene (or toluene) carries out in fixing bed quartz tube reactor.Crystal reaction tube, external diameter is 10mm, catalyst filling amount 100mg.Passing into the gaseous mixture of benzene homologues and air, wherein Benzene series Concentrations is 500ppm～1000ppm, and air-flow air speed is 60,000h-1～100,000h-1.Gas chromatogram TCD detects reaction end gas CO2With CO, FID detect the content of benzene and other organic species.The effect of the present invention is: under the concentration and air speed of above benzene homologues, and prepared catalyst of the present invention has higher low-temperature catalytic burning elimination activity, and having activities present most is when 200 DEG C～220 DEG C, it is possible to benzene becomes non-poisonous material CO completely with toluene conversion2And H2O, at this temperature, keeps benzene and toluene elimination factor in 100 hours > 90%.Prepare the used raw material sulphuric acid manganese low price of catalyst, and catalyst preparation process is simple, other metal of not load or noble metal.The present invention need not add any fuel, directly utilizes O in air2For oxidant, have that raw material is economical and practical, use procedure energy consumption is low, easy and simple to handle, reaction condition is gentle, secondary pollution can be reduced and can the advantage such as continuous operation.
Accompanying drawing explanation
Fe/Sm-α-the MnO of Fig. 1 embodiment 1,2,3 and 4 preparation2XRD figure
Fig. 2 is the Fe/Sm-α-MnO of the embodiment of the present invention 1,2,3 and 4 preparation2Benzene catalytic combustion activity figure
Fig. 3 is the Fe/Sm-α-MnO of the embodiment of the present invention 1,2,3 and 4 preparation2Toluene catalytic combustion activity figure
Fig. 4 is the Fe/Sm-α-MnO of the embodiment of the present invention 4 preparation2-IV catalyst is to benzene catalysis combustion stability
Fig. 5 is the Fe/Sm-α-MnO of the embodiment of the present invention 4 preparation2-IV catalyst toluene catalytic combustion stability
Detailed description of the invention
Embodiment 1
(1) preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.02 ratios, and regulating pH is 3.00, subsequently by the Sm (NO of 0.01g3)3.6H2O and 0.50gFe (NO3)3.9H2O is dissolved in above 40ml citric acid solution.It is 1.0mol/LMnSO that the buffer solution containing slaine above joins 24ml concentration4In solution, mix homogeneously.It is 0.1mol/LKMnO by 120ml concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4(mol ratio)=0.5, stirs 2 hours, seals ageing 12 hours, 80 DEG C reflux 20 hours, rotation steam 3 hours until powdered, with deionized water rinsing to neutral, 100 DEG C dry 10 hours, obtain black presoma, then grind into powder.Take above-mentioned presoma to mix than for 8g:200ml ratio with straight alcohol.Being stirred 24 hours by this mixture, rotation steams to be fallen by solution evaporation for 3 hours.The product obtained speed with 1 DEG C/min in pure oxygen atmosphere, it is raised to 300 DEG C of roastings 1 hour, finally gives Fe/Sm-α-MnO2-I product.
(2) catalyst activity evaluation.Benzene concentration is 500ppm, and air-flow air speed is 60,000h-1.Gas chromatogram TCD detects reaction end gas CO2With CO, FID detect the content of benzene and other organic species.The temperature of the complete catalytic combustion elimination benzene of catalyst obtained by the embodiment of the present invention 1 (benzene 100% converts) is 290 DEG C, when 200 DEG C, the conversion ratio of benzene reaches 50%, when temperature is in the scope of 150 DEG C～290 DEG C, benzene conversion ratio straight line raises until reaching 100%, in the catalytic combustion elimination of benzene reacts, benzene is fully converted into CO2And H2O；When reaction temperature is 185 DEG C, the conversion ratio of toluene reaches 50%, and when 230 DEG C, the conversion ratio of toluene reaches 100%, and product only has CO2And H2O。
Embodiment 2
(1) preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.15 ratios, regulates pH between 4.00, subsequently by the Sm (NO of 0.03g3)3.6H2O and 1.50gFe (NO3)3.9H2O is dissolved in above 40ml citric acid solution.By the PVAC polyvinylalcohol (molecular formula (C of 0.5g2H4O)n, molecular weight 20000) and to be dissolved in 33.3ml concentration be 1.2mol/LMnSO4In solution, the buffer solution containing slaine above is joined in this solution, mix homogeneously.It is 0.2mol/LKMnO by 140ml concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4(mol ratio)=0.7, stirs 3 hours, seals ageing 12 hours, 90 DEG C reflux 22 hours, rotation steam 3 hours until powdered, with deionized water rinsing to neutral, 120 DEG C dry 10 hours, obtain black presoma, then grind into powder.Take above-mentioned presoma to mix than for 8g:200ml ratio with straight alcohol.Being stirred 24 hours by this mixture, rotation steams to be fallen by solution evaporation for 3 hours.The product obtained speed with 1 DEG C/min in pure oxygen atmosphere, it is raised to 400 DEG C of roastings 2 hours, finally gives Fe/Sm-α-MnO2-II product.
(2) catalyst activity evaluation.Benzene series Concentrations is 500ppm, and air-flow air speed is 60,000h-1.Gas chromatogram TCD detects reaction end gas CO2With CO, FID detect the content of benzene and other organic species.The temperature of the complete catalytic combustion elimination benzene of catalyst obtained by the embodiment of the present invention 2 (benzene 100% converts) is 310 DEG C, when 235 DEG C, the conversion ratio of benzene reaches 50%, when temperature is in the scope of 150 DEG C～310 DEG C, benzene conversion ratio straight line raises until reaching 100%, in the catalytic combustion elimination of benzene reacts, benzene is fully converted into CO2And H2O；When reaction temperature is 200 DEG C, the conversion ratio of toluene reaches 50%, and when 250 DEG C, the conversion ratio of toluene reaches 100%, and product only has CO2And H2O。
Embodiment 3
(1) preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.35 ratios, regulates pH about 4.50, subsequently by the Sm (NO of 0.04g3)3.6H2O and 3.00gFe (NO3)3.9H2O is dissolved in above 40ml citric acid solution.By the PVAC polyvinylalcohol (molecular formula (C of 1.0g2H4O)n, molecular weight 20000) and to be dissolved in 37.5ml concentration be 1.5mol/LMnSO4In solution, the buffer solution containing slaine above is joined in this solution, mix homogeneously.It is 0.30mol/LKMnO by 150ml concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4(mol ratio)=0.8, stirs 4 hours, seals ageing 12 hours, 110 DEG C reflux 24 hours, rotation steam 4 hours until powdered, with deionized water rinsing to neutral, 140 DEG C dry 12 hours, obtain black presoma, then grind into powder.Take above-mentioned presoma to mix than for 8g:200ml ratio with straight alcohol.Being stirred 24 hours by this mixture, rotation steams to be fallen by solution evaporation for 4 hours.The product obtained speed with 1 DEG C/min in pure oxygen atmosphere, it is raised to 450 DEG C of degree roasting 3 hours, finally gives Fe/Sm-α-MnO2-III product.
(2) catalyst activity evaluation.Benzene series Concentrations is 1000ppm, and air-flow air speed is 100,000h-1.Gas chromatogram TCD detects reaction end gas CO2With CO, FID detect the content of benzene and other organic species.The temperature of the complete catalytic combustion elimination benzene of catalyst obtained by the embodiment of the present invention 3 (benzene 100% converts) is 320 DEG C, when 240 DEG C, the conversion ratio of benzene reaches 50%, when temperature is in the scope of 150 DEG C～320 DEG C, benzene conversion ratio straight line raises until reaching 100%, in the catalytic combustion elimination of benzene reacts, benzene is fully converted into CO2And H2O；When reaction temperature is 215 DEG C, the conversion ratio of toluene reaches 50%, and when 250 DEG C, the conversion ratio of toluene reaches 100%, and product only has CO2And H2O。
Embodiment 4
(1) preparation method of above-mentioned catalyst provided by the present invention, comprises the steps:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.49 ratios, and regulating pH is about 4.75, subsequently by the Sm (NO of 0.05g3)3.6H2O and 4.50gFe (NO3)3.9H2O is dissolved in above 40ml citric acid solution.By the PVAC polyvinylalcohol (molecular formula (C of 2.0g2H4O)n, molecular weight 20000) and to be dissolved in 34ml concentration be 2.0mol/LMnSO4In solution, the buffer solution containing slaine above is joined in this solution, mix homogeneously.It is 0.4mol/LKMnO by 170ml concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4(mol ratio)=1.0, stir 4 hours, seal ageing 12 hours, 120 DEG C reflux 26 hours, rotation steam 4 hours until powdered, with deionized water rinsing to neutral, 140 DEG C dry 12 hours, obtain black presoma, then grind into powder.Take above-mentioned presoma to mix than for 8g:200ml ratio with straight alcohol.Being stirred 24 hours by this mixture, rotation steams to be fallen by solution evaporation for 4 hours.The product obtained speed with 1 DEG C/min in pure oxygen atmosphere, it is raised to 500 DEG C of roastings 4 hours, finally gives Fe/Sm-α-MnO2-IV product.
(2) catalyst activity evaluation.Benzene series Concentrations is 1000ppm, and air-flow air speed is 100,000h-1.Gas chromatogram TCD detects reaction end gas CO2With CO, FID detect the content of benzene and other organic species.The temperature of the complete catalytic combustion elimination benzene of catalyst obtained by the embodiment of the present invention 4 (benzene 100% converts) is 220 DEG C, when 190 DEG C, the conversion ratio of benzene reaches 50%, when temperature is in the scope of 150 DEG C～220 DEG C, benzene conversion ratio straight line raises until reaching 100%, in the catalytic combustion elimination of benzene reacts, benzene is fully converted into CO2And H2O；When reaction temperature is 170 DEG C, the conversion ratio of toluene reaches 50%, and when 200 DEG C, the conversion ratio of toluene reaches 100%, and product only has CO2And H2O。
Claims (4)
1. the preparation method of a α manganese oxide load ferrum samarium catalyst, it is characterised in that:
Being mixed with citric acid by a certain amount of NaOH in addition distilled water and be made into buffer solution, wherein NaOH/ citric acid is mixed into buffer solution in molar ratio=1.02～1.49 ratios, regulates pH between 3.00～4.75, subsequently by the Sm (NO of 0.01g～0.05g3)3.6H2O and 0.50g～4.50gFe (NO3)3.9H2O is dissolved in above 40mL citric acid solution；It is 1.0mol/L～2.0mol/LMnSO that the PVAC polyvinylalcohol of 0.0g～2.0g is dissolved in 20mL～60mL concentration4In solution, the buffer solution containing slaine above is joined in this solution, mix homogeneously；It is 0.1mol/L～0.4mol/LKMnO by 120mL～170mL concentration subsequently4Solution instills in above-mentioned mixed solution, wherein KMnO4/MnSO4Mol ratio=0.5～1.0, stir 2～4 hours, seal ageing 12 hours, 80 DEG C～120 DEG C reflux 20～26 hours, rotation steaming 3～4 hours until powdered, with deionized water rinsing to neutral, 100 DEG C～140 DEG C dry 10～12 hours, obtain black presoma, then grind into powder；Take above-mentioned presoma to mix than for 8g:200mL ratio with straight alcohol；Being stirred 24 hours by this mixture, solution evaporation is fallen by rotation steaming for 3～4 hours, then with the speed of 1 DEG C/min in pure oxygen atmosphere, is raised to 300 DEG C～500 DEG C roastings 1～4 hour, finally gives Fe/Sm α MnO2Product.
2. preparation method according to claim 1, it is characterised in that: PVAC polyvinylalcohol molecular formula (C2H4O)n, molecular weight 20000.
3. adopt the application in eliminating benzene homologues of catalyst prepared by preparation method as claimed in claim 1, it is characterised in that: it is placed on above-mentioned catalyst continuously in flowing fixed bed device to pass into benzene or toluene and air Mixture reacts；Reaction pressure is normal pressure～2MPa, and reaction velocity is 60,000h‐1～100,000h‐1, air is with benzene or toluene gaseous mixture, and the concentration of benzene or toluene is 500ppm～1000ppm, reaction temperature 25～300 DEG C.
4. apply according to claim 3, it is characterised in that: above-mentioned reaction mixture gas air is the Standard Gases of preparation, its N2: O2Volume ratio is 79:21.
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| CN111282579B (en) * | 2020-03-20 | 2023-01-20 | 北京工业大学 | Preparation method and application of neodymium-samarium-doped NiO/MgO compound supported platinum catalyst |
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| CN101069849A (en) * | 2006-05-12 | 2007-11-14 | 崔建光 | Carbon oxide and volatile organic compound oxidation decomposing catalyst |
| CN101927179A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application |
| CN101927162A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | Aluminum-manganese-pillared montmorillonite load catalyst for eliminating benzene series at low temperature as well as preparation and application thereof |
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| CN101069849A (en) * | 2006-05-12 | 2007-11-14 | 崔建光 | Carbon oxide and volatile organic compound oxidation decomposing catalyst |
| CN101927179A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application |
| CN101927162A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | Aluminum-manganese-pillared montmorillonite load catalyst for eliminating benzene series at low temperature as well as preparation and application thereof |
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Inventor after: Fu Zhidan Inventor after: Ye Qing Inventor after: Pei Congying Inventor after: Cheng Shuiyuan Inventor after: Kang Tianfang Inventor after: Wang Dao Inventor before: Ye Qing Inventor before: Fu Zhidan Inventor before: Pei Congying Inventor before: Cheng Shuiyuan Inventor before: Kang Tianfang Inventor before: Wang Dao |
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