CN104888776A - Perovskite type catalyst for chloroethylene catalytic elimination and preparation method of perovskite type catalyst - Google Patents
Perovskite type catalyst for chloroethylene catalytic elimination and preparation method of perovskite type catalyst Download PDFInfo
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- CN104888776A CN104888776A CN201510274856.2A CN201510274856A CN104888776A CN 104888776 A CN104888776 A CN 104888776A CN 201510274856 A CN201510274856 A CN 201510274856A CN 104888776 A CN104888776 A CN 104888776A
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Abstract
The invention relate to a catalyst for chloroethylene catalytic elimination and a preparation method of the perovskite type catalyst. The catalyst has the composition of LaMnNxO<3+delta>, wherein N refers to precious metal Pt, Pd and Ru and the precious metal enters a perovskite structure so as to form the AB1B2O<3+delta> non-stoichiometric perovskite type catalyst, wherein A refers to La, B1 refers to Mn, and B2 refers to Pt, Pd, Ru and the like. The catalyst is simple in preparation method, is high in catalytic activity, and can completely convert low-concentration chloroethylene into carbon dioxide, hydrogen chloride and water in an air atmosphere.
Description
Technical field
The invention belongs to catalytic combustion environmental technology field, refer more particularly to a kind of precious metal doping perovskite type catalyst for the reaction of vinyl chloride catalytic removal and preparation method used.
Background technology
Vinyl chloride is one of common chlorohydrocarbon, and it is the important monomer raw material of various polymeric materials that matrix was produced and be to PVC industryization with polyvinyl chloride, is also commonly used for the intermediate of synthetic chemistry medicine or organic solvent etc.This and national economy are closely bound up and demand large, but are inevitable in escape to air in process of production.The more important thing is, vinyl chloride stable chemical nature, not only contaminated environment, and to animals and humans, there is teratogenesis, carcinogenic, mutagenic effect.Therefore, China also formulates strict standard to limit the discharge of vinyl chloride, specifies that its maximum permissible concentration is 2ppm.Therefore, eliminate vinyl chloride pollution and have important meaning.
Catalytic combustion is a kind of desirable technique eliminating low concentration chloro-hydrocarbons, and common catalyst generally has noble metal carrier catalyst, molecular sieve type catalyst, transition metal composite oxide catalytic agent.US. Patent NO.4059676 adopts Pt/Al
2o
3noble metal carrier catalyst is used for vinyl chloride catalytic removal, although it accelerates low-temperature catalytic activity, because product HCl makes catalyst occur deactivation phenomenom at 275 DEG C in catalyst surface accumulation.Though molecular sieve type catalyst has the characteristics such as larger specific area, adjustable surface acidity and ion-exchange, these characteristics also limit its scope of application, and CN 102133541 adopts Cr
2o
3-CeO
2modification is carried out to H-USY and H-ZSM-5 molecular sieve, but 298 DEG C and 265 DEG C are respectively to the temperature that trichloro-ethylene transforms completely.Transition metal composite oxide catalytic agent is cheap, has good anti-fluorine poisoning ability and catalytic activity, enjoys researcher to pay close attention to, CeO prepared by document (Chin. J. Catal., 2012,33:557 – 562)
2-MnOx catalyst can realize vinyl chloride at 220 DEG C and transform completely.Perovskite is the one of composite oxides, and its general formula is ABO
3, A position and/or B position all can be replaced by other ionic metal moiety that radius is close and keep its structure substantially not change.People as required by regulating kind and/or the stoichiometric proportion of A position and/or B position ion, can change Lacking oxygen, cation price defect concentration and changing the catalytic capability of catalyst.Perofskite type oxide has composite nalysis stability and flexibly can " chemical tailoring " characteristic and enjoy the favor of researcher.
This patent is with ABO
3type perovskite is main, and precious metals pt, Pd, Ru are doped to its crystal structure inside, to improving vinyl chloride low-temperature oxidation activity.
Summary of the invention
The object of the invention is to be that openly a kind of noble metal (Pt, Pd, Ru) for the reaction of vinyl chloride catalytic removal enters and has in perovskite structure, define AB
1b
2o
3+ δthe perovskite type catalyst of non-metering ratio.This method for preparing catalyst is simple, and catalytic activity is high, and no coupling product does not cause secondary pollution, is applicable to the low-temperature catalyzed elimination of vinyl chloride.
Catalyst its preparation method of the present invention is as follows.
(1) be that the solubility lanthanum nitrate of 1:1 and manganese nitrate are dissolved in organic solvent and H by soluble precious-metal presoma, La/Mn mol ratio
2the mixed solution of O, wherein: the presoma of noble metal Ru is nitric acid ruthenium, ruthenic chloride, the one in acetic acid ruthenium; The presoma of Pd is palladium nitrate, the acid of chlorine palladium, the one in palladium acetylacetonate, palladium; The presoma of Pt is the one in platinum nitrate, chloroplatinic acid, platinum acetate, acetylacetone,2,4-pentanedione platinum; Organic solvent is ethanol, ethylene glycol, acetone one or more, organic solvent is 10% ~ 50% with water consumption ratio.
(2) in above-mentioned mixed solution, add complexing agent and surfactant, stir, the consumption of its complexing agent is the weight content in catalyst is 0.01% ~ 70%, and the consumption of surfactant is the weight content in catalyst is 0.05 ~ 20%.
(3) above-mentioned solution fully stirs and obtains colloid by after water and organic solvent evaporation, and 110-150 DEG C of drying, 400-800 DEG C of roasting 2-12h obtains.
Auxiliary agent and organic solvent is introduced in solution preparation process.Auxiliary agent is one or more in neopelex, lauryl sodium sulfate, polyvinylpyrrolidone, TBAB, softex kw, polyethylene glycol, organic solvent is ethanol, ethylene glycol, acetone one or more.
Perovskite type catalyst provided by the invention, has preparation method simple, the advantages such as catalytic activity is high, no coupling product generation.The catalyst adopting the inventive method to prepare, in air atmosphere, can be converted into carbon dioxide, hydrogen chloride and water by the vinyl chloride in waste gas.
Detailed description of the invention
The present invention is that a kind of noble metal for the reaction of vinyl chloride catalytic removal enters and has in perovskite structure, defines AB
1b
2o
3+ δthe perovskite type catalyst of non-metering ratio, specific embodiment is as follows.
6.498g lanthanum nitrate and 7.158g 50% manganese nitrate are dissolved in 30ml water by embodiment 1, then add 8.406g citric acid.Mixed solution is added thermal agitation and obtains colloid, at 120 DEG C after drying, put into Muffle furnace roasting 3h at 750 DEG C, obtain LaMnO
3black powder catalyst.
6.498g lanthanum nitrate and 7.158g 50% manganese nitrate are dissolved in 30ml solvent (ethanol: water=2:1) by embodiment 2, then add 8.406g citric acid and 0.217g neopelex.Mixed solution is added thermal agitation and obtains colloid, at 120 DEG C after drying, put into Muffle furnace roasting 3h at 750 DEG C, obtain the LaMnO adding auxiliary agent and organic solvent
3black powder catalyst.
Embodiment 3 is by 6.498g lanthanum nitrate, 7.158g 50% manganese nitrate and 9.934g 1.0wt% RuCl
3solution is dissolved in 30ml water.Under constant agitation, then add 8.406g citric acid, mixed solution is added thermal agitation and obtains colloid, at 120 DEG C after drying, put into Muffle furnace roasting 3h at 750 DEG C, obtain LaMnRu
0.02o
3+ δdoping type catalyst.
6.498g lanthanum nitrate and 7.158g 50% manganese nitrate are dissolved in 30ml water by embodiment 4.Under constant agitation, then add 8.406g citric acid, mixed solution is added thermal agitation and obtains colloid, at 120 DEG C after drying, put into Muffle furnace roasting 3h at 750 DEG C, obtain black powder sample.Take 4.107g 1.0wt% RuCl
3solution incipient impregnation, in the black sample of 2.0g porphyrize, at room temperature leaves standstill 12h, dry at 100 DEG C, finally puts into Muffle furnace roasting 3h at 500 DEG C, obtains 1%Ru/LaMnO
3+ δloaded catalyst.
Embodiment 5 is by 6.498g lanthanum nitrate, 7.158g50% manganese nitrate and 9.934g 1.0wt% RuCl
3solution is dissolved in 30ml solvent (ethanol: water=2:1), then adds 8.406g citric acid and 0.217g neopelex.Mixed solution fully added thermal agitation and obtains colloid by after water and organic solvent evaporation, at 120 DEG C after drying, putting into Muffle furnace roasting 3h at 750 DEG C, obtaining the LaMnRu adding auxiliary agent organic solvent
0.02o
3+ δdoping type catalyst.
All catalyst activity evaluations for vinyl chloride catalytic combustion are carried out in fixed-bed micro-reactor (internal diameter is 6mm quartz), and the consumption of catalyst is 0.20-0.48ml, and temperature adopts K type thermocouple automatically to control.C
2h
3cl and air are mixed into reactor and burn, and its flow adopts mass flowmenter to control.At ambient pressure, T
10%, T
50%, T
90%the reaction temperature when conversion ratio representing vinyl chloride is respectively 10%, 50% and 90%, primary product is carbon dioxide, water and hydrogen chloride.
Table 1 is the catalytic combustion activity of vinyl chloride in embodiment different catalysts.
Claims (6)
1., for a perovskite type catalyst for vinyl chloride low-temperature catalytic oxidation reaction, what it is characterized in that catalyst consists of LaMnN
xo
3+ δ, wherein N is one or more in precious metals pt, Pd, Ru etc.
2. as described in right 1, a kind of perovskite type catalyst for the reaction of vinyl chloride low-temperature catalytic oxidation is characterized in that noble metal enters and has in perovskite structure, defines and has AB
1b
2o
3+ δthe perovskite structure of non-metering ratio, wherein A is La, B
1for Mn, B
2for one or more in Pt, Pd, Ru etc.
3. a kind of perovskite type catalyst for the reaction of vinyl chloride low-temperature catalytic oxidation as described in right 1, noble metal weight content is in the catalyst 0.1 ~ 5%.
4. a kind of preparation of perovskite type catalyst for the reaction of vinyl chloride low-temperature catalytic oxidation as described in right 1, it is characterized in that adopting the mixed solution of organic solvent and water to be solvent in preparation process, and add complexing agent and surfactant, its complexing agent is one or more in glycine, citric acid, urea, oxalic acid, and surfactant is one or more in neopelex, lauryl sodium sulfate, polyvinylpyrrolidone, TBAB, softex kw, polyethylene glycol.
5. as claimed in claim 1 a kind of for vinyl chloride low-temperature catalytic oxidation reaction perovskite type catalyst, it is characterized in that preparation process is as follows:
(1) be that the solubility lanthanum nitrate of 1:1 and manganese nitrate are dissolved in organic solvent and H by soluble precious-metal presoma, La/Mn mol ratio
2the mixed solution of O, wherein: the presoma of noble metal Ru is nitric acid ruthenium, ruthenic chloride, the one in acetic acid ruthenium; The presoma of Pd is palladium nitrate, the acid of chlorine palladium, the one in palladium acetylacetonate, palladium; The presoma of Pt is the one in platinum nitrate, chloroplatinic acid, platinum acetate, acetylacetone,2,4-pentanedione platinum; Organic solvent be ethanol, ethylene glycol, acetone one or more, organic solvent is 10% ~ 50% with water consumption ratio;
(2) in above-mentioned mixed solution, add complexing agent and surfactant, stir, the consumption of its complexing agent is the weight content in catalyst is 0.01% ~ 70%, and the consumption of surfactant is the weight content in catalyst is 0.05 ~ 20%;
(3) above-mentioned solution fully stirs and obtains colloid by after water and organic solvent evaporation, and 110-150 DEG C of drying, 400-800 DEG C of roasting 2-12h obtains.
6. method as claimed in claim 3, at oxygen enrichment (oxygen content 5-21(v) %) under condition by vinyl chloride (concentration is 100ppm-1(v) %), change into carbon dioxide, hydrogen chloride and water completely in the temperature range of 150-350 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233882A (en) * | 2017-06-14 | 2017-10-10 | 华东理工大学 | The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application |
| CN109317143A (en) * | 2018-10-25 | 2019-02-12 | 华东理工大学 | It is a kind of for being catalyzed the noble metal perovskite type catalyst and preparation method thereof of burning |
| CN110743545A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Ethylene oxide double-active-site combustion catalyst and preparation and application thereof |
| CN111085200A (en) * | 2019-12-11 | 2020-05-01 | 山东科技大学 | Catalyst for purifying fuel oil tail gas particles and harmful gas and preparation method thereof |
| CN111151264A (en) * | 2018-11-07 | 2020-05-15 | 中国科学院大连化学物理研究所 | Catalyst for treating salt-containing wastewater through catalytic wet oxidation, and preparation method and application thereof |
| CN112604700A (en) * | 2020-12-16 | 2021-04-06 | 浙江大学 | Phosphorylated perovskite catalyst and preparation method and application thereof |
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| US5622680A (en) * | 1990-07-25 | 1997-04-22 | Specialites Et Techniques En Traitement De Surfaces-Stts | Post-combustion catalysts |
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2015
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| US5622680A (en) * | 1990-07-25 | 1997-04-22 | Specialites Et Techniques En Traitement De Surfaces-Stts | Post-combustion catalysts |
| CN1665590A (en) * | 2002-07-09 | 2005-09-07 | 大发工业株式会社 | Catalyst for exhaust gas purification |
Non-Patent Citations (3)
| Title |
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| CHUANHUI ZHANG，ET AL: ""Catalytic oxidation of vinyl chloride emission over LaMnO3 and LaB0.2Mn0.8O3 (B=Co, Ni, Fe) catalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233882A (en) * | 2017-06-14 | 2017-10-10 | 华东理工大学 | The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application |
| CN109317143A (en) * | 2018-10-25 | 2019-02-12 | 华东理工大学 | It is a kind of for being catalyzed the noble metal perovskite type catalyst and preparation method thereof of burning |
| CN111151264A (en) * | 2018-11-07 | 2020-05-15 | 中国科学院大连化学物理研究所 | Catalyst for treating salt-containing wastewater through catalytic wet oxidation, and preparation method and application thereof |
| CN110743545A (en) * | 2019-09-29 | 2020-02-04 | 浙江工业大学 | Ethylene oxide double-active-site combustion catalyst and preparation and application thereof |
| CN111085200A (en) * | 2019-12-11 | 2020-05-01 | 山东科技大学 | Catalyst for purifying fuel oil tail gas particles and harmful gas and preparation method thereof |
| CN112604700A (en) * | 2020-12-16 | 2021-04-06 | 浙江大学 | Phosphorylated perovskite catalyst and preparation method and application thereof |
| CN112604700B (en) * | 2020-12-16 | 2022-07-01 | 浙江大学 | Phosphorylated perovskite type catalyst and preparation method and application thereof |
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