CN101982239B - Preparation method of composite metal oxide catalyst for catalytic combustion - Google Patents

Preparation method of composite metal oxide catalyst for catalytic combustion Download PDF

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CN101982239B
CN101982239B CN2010105035066A CN201010503506A CN101982239B CN 101982239 B CN101982239 B CN 101982239B CN 2010105035066 A CN2010105035066 A CN 2010105035066A CN 201010503506 A CN201010503506 A CN 201010503506A CN 101982239 B CN101982239 B CN 101982239B
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catalyst
preparation
mixed solution
solution
catalytic combustion
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CN101982239A (en
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管国锋
万辉
张增建
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Nanjing Tech University
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Abstract

The invention relates to a preparation method of a composite metal oxide catalyst for catalytic combustion; the Cu and Mn salts and organic acid are used as raw materials to prepare a mixed solution according to a certain proportion, then the mixed solution is heated and evaporated at a certain temperature to form gel, and the gel is dried and roasted to prepare the CuMn composite oxide catalyst.

Description

A kind of catalytic combustion is with the preparation method of O composite metallic oxide catalyst
Technical field
The present invention relates to a kind of catalytic combustion and use the O composite metallic oxide catalyst preparation method, relate in particular to a kind of O composite metallic oxide catalyst preparation method who is used for the carboxylic acid esters catalytic combustion, belong to the catalytic combustion environmental protection technical field.
Background technology
Organic exhaust gas is the common pollutant of petroleum chemical industry discharging, often contains hydrocarbon compound, oxygen-containing organic compound, nitrogenous, sulphur, halogen and organic phosphorus compound etc. in the organic exhaust gas.As these waste gas are not added processing, directly enter atmosphere and will cause severe contamination environment, be detrimental to health.
Traditional organic waste-gas purification method comprises absorption method, condensation method and direct firing method etc., these methods often have be prone to produce secondary pollution, energy consumption big, be subject to shortcomings such as organic exhaust gas concentration and temperature restriction.And catalytic combustion technology advantage high with its treatment effeciency, that do not produce secondary pollution and lower energy consumption has received increasing concern.
Catalytic combustion is typical gas-solid-phase catalytic reaction, its essence is the deep oxidation effect that active oxygen is participated in.In catalyticing combustion process, the effect of catalyst is to reduce activation energy, and catalyst surface has suction-operated simultaneously, makes reactant molecule be enriched in the surface and has improved reaction rate, has accelerated the carrying out of reaction.Can make organic exhaust gas under lower initiation temperature condition by catalyst, flameless combustion takes place, and oxidation Decomposition be CO 2And H 2O emits great amount of heat energy simultaneously.
The industrialization catalyst for catalytic combustion mainly concentrates on the noble metal catalyst at present, and noble metal is used for the history that catalytic combustion has had decades, is that the Preparation of catalysts or the research of reaction mechanism have all obtained more deep research.The active order of noble metal in oxidation reaction is generally: Ru<Rh<Pd<Os<Ir<Pt; Consider rare property and high-temperature volatile; Use is confined to Pd, Pt, these three kinds of elements of Rh, and for catalytic combustion, Pd and Pt are research and use maximum catalytically-active materials.The major defect of this type catalyst is resource scarcity, costs an arm and a leg, and anti-toxic is poor, and people strive to find substitute always or reduce its consumption as far as possible.
Because the noble metal resource reduces day by day and costs an arm and a leg, the application of oxide in catalytic combustion of non-precious metal catalyst such as Cu, Mn, Co etc. receives extensive attention.Yet single metal oxide catalyst activity is often not ideal enough, need improve to improve its catalytic activity.O composite metallic oxide catalyst, like Cu-Mn, Cu-Co etc.; Such catalyst under certain conditions; Can reach the catalytic effect of noble metal catalyst, be the focus of catalytic combustion area research, and many high performance composite oxide catalysts are are researched and developed.The supported complex oxide Catalysts Cu Mn/Al that adopted immersion process for preparing such as Huanghai Sea wind (Journal of Chemical Engineering of Chinese Universities 2004 (2), 152~155) 2O 3, prepared the Cu-Mn-O composite oxide catalysts with coprecipitation simultaneously, and investigated catalytic activity toluene.Owing to adopt the composite oxides of traditional infusion process and coprecipitation preparation to be difficult to guarantee multi-component abundant mixing; (Catalysis Today 2004 (93-95) such as Li; 205-209) adopted prepared by reverse microemulsion method and contained Mn catalyst series Mn-Cu, Mn-Zr, Mn-Fe etc., wherein, the Mn-Cu catalyst series is the highest to the catalytic activity of toluene; But this Preparation of catalysts need consume a large amount of organic matters, and the preparation process is complicated, cost is higher.
Summary of the invention
The objective of the invention is to exist that the preparation process is complicated, cost is higher and each component of catalyst is mixed problems such as inhomogeneous to present O composite metallic oxide catalyst; The preparation method of the composite oxide catalysts that a kind of catalytic combustion uses is proposed; It is low that prepared catalyst has a cost of material; Preparation technology is simple, the catalytic activity advantages of higher.
Technical scheme of the present invention is: a kind of catalytic combustion is with the preparation method of O composite metallic oxide catalyst, and concrete steps are following:
A. prepare the copper salt solution of 0.25~1mol/L, the manganese salt solution of 0.25~1mol/L and the organic acid soln of 0.2~0.5mol/L respectively;
B. copper salt solution, manganese salt solution and organic acid soln are processed mixed solution; Wherein the mol ratio of Cu and Mn is 1: 1~7 in the mixed solution, and the mol ratio of organic acid and metal ion is 1~2: 1;
C. with mixed solution heating and be continuously stirring to the generation gel;
D. gel obtains catalyst fines after drying, grinding, roasting;
E. with catalyst fines compressing tablet, fragmentation, screening, obtain catalyst sample.
Above-mentioned mantoquita is preferably a kind of in nitrate, sulfate or the acetate of copper; A kind of in nitrate, sulfate or the acetate that preferred described manganese salt is manganese.Preferred described organic acid is a kind of in citric acid, oxalic acid or the glycolic.
The heating-up temperature of mixed solution is 60~90 ℃ among the preferred steps C.
Drying of gels temperature described in the preferred steps D is 100~120 ℃, and be 8~14h drying time; Sintering temperature is 400~700 ℃, and roasting time is 2~5h.
The average grain diameter of the prepared catalyst sample of the present invention is 0.2~0.6mm.
The prepared catalyst of the present invention can be used for the carboxylic acid esters catalytic combustion and removes; Preferred described carboxylate is one or more in methyl acetate, ethyl acetate or the propyl acetate.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Carboxylate concentration is 1~4g/m in the unstripped gas 3, reaction velocity is 12000~48000L/ (kgh).
Beneficial effect:
(1) catalytic combustion of the present invention's proposition is simple with the O composite metallic oxide catalyst preparation method, and raw material sources are extensive, cheap.
(2) catalytic combustion of the present invention preparation is with O composite metallic oxide catalyst catalytic activity height, and the catalytic combustion that can be widely used in carboxylic acid esters such as methyl acetate removes.
The specific embodiment
Embodiment 1
Cu (NO with the 0.5mol/L of 20mL 3) 2Solution, the Mn (NO of the 0.5mol/L of 20mL 3) 2The citric acid solution of the 0.5mol/L of solution and 40mL is processed mixed solution, n (Cu): n (Mn)=1: 1 wherein, n (citric acid): n (metal ion (Cu+Mn))=1: 1.Mixed solution is transferred in 60 ℃ of water-baths heating and is continuously stirring to the generation gel, and 100 ℃ of dry 8h at 400 ℃ of roasting 2h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.2mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 4g/m in the unstripped gas 3, air speed 48000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 91.94%.
Embodiment 2
CuSO with the 0.25mol/L of 20mL 4Solution, the MnSO of the 0.25mol/L of 60mL 4The oxalic acid solution of the 0.2mol/L of solution and 120mL is processed mixed solution, n (Cu): n (Mn)=1: 3 wherein, n (oxalic acid): n (metal ion)=1.2: 1.Mixed solution is transferred in 80 ℃ of water-baths heating and is continuously stirring to the generation gel, and 100 ℃ of dry 10h at 500 ℃ of roasting 2h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.3mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 2g/m in the unstripped gas 3, air speed 24000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 93.86%.
Embodiment 3
Cu (CH with the 0.25mol/L of 10mL 3COO) 2Solution, the Mn (CH of the 0.25mol/L of 50mL 3COO) 2The glycollic acid solution of the 0.25mol/L of solution and 90mL is processed mixed solution, n (Cu): n (Mn)=1: 5 wherein, n (glycolic): n (metal ion)=1.5: 1.Mixed solution is transferred in 70 ℃ of water-baths heating and is continuously stirring to the generation gel, and 110 ℃ of dry 10h at 500 ℃ of roasting 3h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.4mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 2g/m in the unstripped gas 3, air speed 12000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 95.80%.
Embodiment 4
CuSO with the 0.25mol/L of 10mL 4Solution, the MnSO of the 0.25mol/L of 70mL 4The glycollic acid solution of the 0.25mol/L of solution and 96mL is processed mixed solution, n (Cu): n (Mn)=1: 7 wherein, n (glycolic): n (metal ion)=1.2: 1.Mixed solution is transferred in 80 ℃ of water-baths heating and is continuously stirring to the generation gel, and 110 ℃ of dry 12h at 500 ℃ of roasting 3h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.45mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 2g/m in the unstripped gas 3, air speed 24000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 95.35%.
Embodiment 5
Cu (NO with the 1mol/L of 5mL 3) 2Solution, the Mn (NO of the 1mol/L of 15mL 3) 2The citric acid solution of the 0.5mol/L of solution and 80mL is processed mixed solution, n (Cu): n (Mn)=1: 3 wherein, n (citric acid): n (metal ion)=2: 1.Mixed solution is transferred in 70 ℃ of water-baths heating and is continuously stirring to the generation gel, and 120 ℃ of dry 12h at 600 ℃ of roasting 4h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.45mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 2g/m in the unstripped gas 3, air speed 12000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 94.31%.
Embodiment 6
Cu (NO with the 0.5mol/L of 10mL 3) 2Solution, the Mn (NO of the 0.5mol/L of 50mL 3) 2The oxalic acid solution of the 0.5mol/L of solution and 90mL is processed mixed solution, n (Cu): n (Mn)=1: 5 wherein, n (oxalic acid): n (metal ion)=1.5: 1.Mixed solution is transferred in 80 ℃ of water-baths heating and is continuously stirring to the generation gel, and 120 ℃ of dry 14h at 700 ℃ of roasting 4h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.5mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and methyl acetate concentration is about 2g/m in the unstripped gas 3, air speed 12000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of methyl acetate is 93.46%.
Embodiment 7
Cu (CH with the 0.25mol/L of 10mL 3COO) 2Solution, the Mn (CH of the 0.25mol/L of 70mL 3COO) 2The glycollic acid solution of the 0.5mol/L of solution and 48mL is processed mixed solution, n (Cu): n (Mn)=1: 7 wherein, n (glycolic): n (metal ion)=1.2: 1.Mixed solution is transferred in 90 ℃ of water-baths heating and is continuously stirring to the generation gel, and 110 ℃ of dry 12h at 500 ℃ of roasting 5h, obtain catalyst sample at last.Catalyst is after compressing tablet, fragmentation, screening, and the equal particle diameter of making even is that the catalyst of 0.6mm is subsequent use.
The catalyst activity evaluation is carried out in the continuous-flow fixed-bed quartz reactor.Reactor inside diameter is 14mm, and loaded catalyst is 0.5g, and ethyl acetate concentration is about 1g/m in the unstripped gas 3, air speed 12000L/ (kgh).Reaction temperature is in the time of 500 ℃, and the conversion ratio of ethyl acetate is 96.46%.

Claims (5)

1. a catalytic combustion is with the preparation method of O composite metallic oxide catalyst, and concrete steps are following:
A. prepare the copper salt solution of 0.25~1mol/L, the manganese salt solution of 0.25~1mol/L and the organic acid soln of 0.2~0.5mol/L respectively; Wherein said organic acid is a kind of in citric acid, oxalic acid or the glycolic;
B. copper salt solution, manganese salt solution and organic acid soln are processed mixed solution; Wherein the mol ratio of Cu and Mn is 1: 1~7 in the mixed solution, and the mol ratio of organic acid and metal ion is 1~2: 1;
C. with mixed solution heating and be continuously stirring to the generation gel;
D. gel obtains catalyst fines after drying, grinding, roasting;
E. with catalyst fines compressing tablet, fragmentation, screening, obtain catalyst sample.
2. preparation method according to claim 1 is characterized in that described mantoquita is a kind of in nitrate, sulfate or the acetate of copper; A kind of in nitrate, sulfate or the acetate that described manganese salt is manganese.
3. preparation method according to claim 1, the heating-up temperature that it is characterized in that mixed solution among the step C is 60~90 ℃.
4. preparation method according to claim 1 is characterized in that the Drying of gels temperature is 100~120 ℃ among the step D, and be 8~14h drying time; Sintering temperature is 400~700 ℃, and roasting time is 2~5h.
5. preparation method according to claim 1, the average grain diameter that it is characterized in that catalyst sample in the step e is 0.2~0.6mm.
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CN102319573B (en) * 2011-07-13 2013-02-13 东南大学 Simple and convenient preparation method of copper-manganese compound oxide monolithic catalyst
CN102626636A (en) * 2012-03-22 2012-08-08 杭州中环化工设备有限公司 Nanometer manganese dioxide-copper oxide composite catalyst and its application
CN106540739A (en) * 2015-09-16 2017-03-29 中国石化扬子石油化工有限公司 A kind of preparation method of supported catalyst burning catalyst
CN106362762A (en) * 2016-08-10 2017-02-01 无锡市华星东方电力环保科技有限公司 Synthetic method for Mn-CuOx catalytic material used in field of SCR denitration
CN114602490A (en) * 2022-03-27 2022-06-10 山东亮剑环保新材料有限公司 Preparation method of integral catalytic combustion CO catalyst

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CN1472006A (en) * 2003-07-11 2004-02-04 清华大学 Sundex low-temperature catalytic combustion nanometre composite oxide catalyst and preparing method thereof
CN1660491A (en) * 2004-02-26 2005-08-31 中国科学院大连化学物理研究所 Catalyst of composite oxides of copper and manganese and application
CN101767015A (en) * 2009-01-06 2010-07-07 中国科学院成都有机化学有限公司 Cu-Mn-based catalytic combustion catalyst for treatment of 'triphen' waste gas and preparation method thereof

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KR100648594B1 (en) * 2005-04-01 2006-11-23 희성엥겔하드주식회사 Catalytic compositions for oxidizing particular matters and Catalytic soot filters employing the compositions

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Publication number Priority date Publication date Assignee Title
CN1472006A (en) * 2003-07-11 2004-02-04 清华大学 Sundex low-temperature catalytic combustion nanometre composite oxide catalyst and preparing method thereof
CN1660491A (en) * 2004-02-26 2005-08-31 中国科学院大连化学物理研究所 Catalyst of composite oxides of copper and manganese and application
CN101767015A (en) * 2009-01-06 2010-07-07 中国科学院成都有机化学有限公司 Cu-Mn-based catalytic combustion catalyst for treatment of 'triphen' waste gas and preparation method thereof

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