CN107282051A - A kind of preparation of cobalt cerium catalyst and the technique reacted for methane catalytic combustion - Google Patents
A kind of preparation of cobalt cerium catalyst and the technique reacted for methane catalytic combustion Download PDFInfo
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- CN107282051A CN107282051A CN201710468959.1A CN201710468959A CN107282051A CN 107282051 A CN107282051 A CN 107282051A CN 201710468959 A CN201710468959 A CN 201710468959A CN 107282051 A CN107282051 A CN 107282051A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/04—Catalyst added to fuel stream to improve a reaction
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Abstract
A kind of preparation of cobalt cerium catalyst and the technique present invention reacted for methane catalytic combustion provide a kind of experimental method for utilizing Ce, Co doping pyrochlore-type catalyst to be reacted for methane catalytic combustion, and its catalyst composition is La2‑XCexCo0.3Sn1.7O7(X=0、0.1、0.2、0.3、0.4、0.5).Catalyst is with SnCl4·5H2O, La（NO3）3·6H2O and Co（NO3）2·6H2O and Ce（NO3）3·6H2O solids and deionized water, absolute ethyl alcohol are that raw material is prepared by hydro-thermal reaction, supercritical drying drying method.The catalyst is by temperature programming catalytic methane combustion reaction under the high temperature conditions under oxygen atmosphere, and product is water and carbon dioxide.The characteristics of catalyst has high stability, methane high conversion.
Description
Technical field
The present invention relates to a kind of preparation of methane catalytic combustion catalysts, belonging to derived energy chemical field, there is provided catalysis
The preparation method and catalytic reaction condition of agent.
Background technology
Traditional combustion of natural gas mode capacity usage ratio is less high, and discharges substantial amounts of pernicious gas, such as CO, NOx,
HC etc., NOx can cause acid rain and photochemical fog, and the gas such as CO, HC also causes harm to environment.［ Zheng Jiandong, adulterate six aluminic acids
The preparation of salt high temperature catalyst and in methane catalytic combustion performance research ［ D ］ Beijing：Beijing University of Chemical Technology, 2008 ］.
Catalyst combustion reaction is a kind of reaction that combustion reaction is carried out using the catalytic oxidation effect of solid catalyst.Catalysis
Combustion reaction is carried out and independent of high temperature radical reaction at low temperature, therefore can significantly suppress to depend on thermal response
Oxynitrides NOx generation.［ SCHWIEDERLE R, TISCHER S.Experimental and numerical
investigation of the ignition of methane combustion in a platinum coated
Honeycomb monolith ［ J ］ .Submitted to the 29th Symposium (Inter-national) on
Combustion,2002,26(2):78-80 ］.
Methane catalytic combustion catalyst mainly has noble metal catalyst, Engineering of Supported Metal Oxide Catalysts and compound gold
Belong on oxide catalyst three major types.Wherein, precious metals pt, Rh, Pd etc. have good low-temperature catalytic activity, but because of high temperature
The factor such as easy-sintering inactivation, poor heat resistance, expensive, using by a definite limitation.Engineering of Supported Metal Oxide Catalysts is past
There is obvious active component during toward due to high temperature and carrier reacts phenomenon, and cause the reduction of its catalytic activity.
Transition-metal oxide catalyst has preferable heat resistance, by being ground to transition-metal oxide catalyst
Study carefully, it is found that it has higher activity in methyl hydride combustion reaction.Wherein the transition metal oxide such as Mn, Fe, Co, Ni, Cu is made
It is more active for the research of non-noble metal combustion catalyst.E.Garbowski, M.C.Marion, M C.Marion,
M.Priment.Catalytic properties and surface states of cobalt-containing
Oxidation catalysts ［ J ］ .Applied Catalysis.1990,64:209~224 ］.
Pyrochlore type multiple oxide is another kind of high-temperature catalytic material, and structure is face-centred cubic structure, and its formula is
A2B2O7, wherein A, B is+3 and+4 valencys or+2 and+5 valency metal cations respectively.Jie Cheng, Hailin Wang in 2008 etc.
The pyrochlore La of Co doping is investigated2Sn2O7Catalytic activity test has been carried out to methane catalytic combustion reaction, has as a result shown and does not mix
Miscellaneous unidirectional La2Sn2O7Activity is relatively low, and mixes after Co ions, and activity is greatly improved, and methane conversion has reached at 580 DEG C
90%.［ J.Cheng, H.L.Z.P. Hao, S.B. Wang.Catalytic combustion of methane over
cobalt doped lanthanum stannate pyrochlore oxide[J].Catalysis Communications.
2008, 9:690-695..
The content of the invention
The purpose of the present invention is mainly to provide a kind of preparation of Ce, Co doping type pyrochlore catalyst and its urged for methane
Change the chemical technology and reaction condition of combustion reaction.
Two kinds of metals of Ce, Co are doped into i.e. La in pyrochlore catalyst by the present invention simultaneously first2-XCexCo0.3Sn1.7O7
(X=0,0.1,0.2,0.3,0.4,0.5), and for methane catalytic combustion reaction.Test result indicates that, catalyst is in low temperature bar
Methane conversion is significantly improved under part, catalytic activity is improved.In an experiment, 450 DEG C in conversion ratio up to 100%.
The catalyst of the present invention is made up of five kinds of elements of La, Ce, Co, Sn, O.
The preparation method of catalyst of the present invention is prepared using hydro-thermal method.
Preparation method is as follows.
（1）Take a certain amount of SnCl4·5H2O, La（NO3）3·6H2O and Co（NO3）2·6H2O and Ce
（NO3）3·6H2O solids, are dissolved in deionized water and are made into salting liquid.
（2）25% ammoniacal liquor is slowly added dropwise in above-mentioned solution under agitation, to pH value of solution=11, continues to stir 1h.
（3）Reactant is placed in hydro-thermal autoclave, baking oven heating, 150 DEG C of reaction 24h.
（4）Centrifugation, takes precipitation, distilled water, absolute ethyl alcohol are respectively washed twice.
（5）Obtained gel is mixed with a certain amount of absolute ethyl alcohol, is placed in autoclave, 270 DEG C, surpass under 10MPa and face
Dry 1h in boundary.
（6））2h is calcined at 1000 DEG C.
This experiment agents useful for same is all use for laboratory AR.
The reaction method that the catalyst of the present invention is applied to methane catalytic combustion is as follows：
Catalyst tabletting, grinding are filtered out to the catalyst of 40-60 mesh, take catalyst 0.5g to load into 6mm reaction tube, instead
It is 300-800 DEG C, gaseous mixture N to answer temperature2:O2:CH4=80:18:2, nitrogen is Balance Air, and reaction velocity is 4800 l ﹒ g-1﹒ h-1。
Compared with the prior art the present invention has following innovation and feature.
Two kinds of metals of Ce, Co are doped into pyrochlore catalyst simultaneously by a certain percentage first, and for methyl hydride catalyzed
In combustion reaction.
Catalytic reaction significantly improves methane reaction conversion ratio at relatively low temperature.
Brief description of the drawings
Fig. 1 is the La prepared1.7Ce0.3Co0.3Sn1.7O7The X-ray diffraction of photochemical catalyst（XRD）Collection of illustrative plates.
Fig. 2 is the La prepared1.7Ce0.3Co0.3Sn1.7O7The H of photochemical catalyst2- temperature programmed reduction（TPR）Collection of illustrative plates.
Embodiment
With reference to embodiment, the present invention is further illustrated, and the present invention includes but is not limited to the following examples.
Solid 4.8870g SnCl are weighed respectively4·5H2O, 6.0362g La（NO3）3·6H2O and 0.7159g Co
（NO3）2·6H2O and 1.068g Ce（NO3）3·6H2O, is dissolved in 100ml deionized waters, under agitation slow drop
The ammoniacal liquor for plus 25%, until pH=11, continue to stir 1h.Reactant is placed in stainless steel water thermal high kettle, 150 DEG C add in baking oven
Heat, reacts 24h.The precipitation that above-mentioned reactant is centrifuged, distilled water, absolute ethyl alcohol are respectively washed twice.Mixed afterwards with absolute ethyl alcohol
It is placed in autoclave, 270 DEG C, 1h is dried under the conditions of 10MPa.Be calcined 2h at 1000 DEG C in Muffle furnace afterwards, catalyst
La1.7Ce0.3Co0.3Sn1.7O7。Similar method can prepare the catalyst of different proportion.
La prepared by the above method1.7Ce0.3Co0.3Sn1.7O740-60 purposes are filtered out after catalyst tabletting, grinding to urge
Agent is filled into a diameter of 6mm reaction tube.Catalyst amount 0.5g, 300-800 DEG C of reaction temperature, unstripped gas composition methane
2%, oxygen 18%, nitrogen 80%, raw gas flow 0.040L/min, air speed is 4800h-1。
Above catalyst carries out catalyst combustion reaction Evaluation results and shown, before the activity relatively doping of the catalyst significantly
Improve, methane conversion only has 5% or so close to 100% undoped with catalyst at 450 DEG C.It can be matched somebody with somebody by changing metal
Than regulation catalytic activity, and reaction stability is good, is excellent methane catalytic combustion catalysts.
Claims (1)
1. a kind of experimental method of methane catalytic combustion, it is characterised in that the composition of catalyst, preparation method；Catalyst be Ce,
The La of Co doping2-XCexCo0.3Sn1.7O7(X=0,0.1,0.2,0.3,0.4,0.5) metal oxide, metal oxide is activity
Component；Catalyst utilizes hydro-thermal reaction, and SnCl is added in deionized water4·5H2O, La（NO3）3·6H2O and Co（NO3）2·
6H2O and Ce（NO3）3·6H2O solids formation solution, the hydrosol of a certain amount of 25% ammoniacal liquor is added afterwards, after will mixing
Thing is placed in autoclave reacts 24h at 150 DEG C, centrifuges, is washed with distilled water, absolute ethyl alcohol, mixed in absolute ethyl alcohol
Close and 1h is dried 270 DEG C in autoclave, under 10MPa, by 1000 DEG C of calcining 2h of Muffle furnace, obtain catalyst；It is methyl hydride catalyzed
Combustion reaction temperature is 300-800 DEG C, unstripped gas composition N2:O2:CH4=80:18:2, raw gas flow is 0.040L/min, empty
Speed is 4800h-1。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113830836A (en) * | 2021-09-11 | 2021-12-24 | 浙江大学 | Preparation method of pyrochlore type nitrogen-doped multi-element metal oxide |
| CN115337933A (en) * | 2022-07-11 | 2022-11-15 | 华东理工大学 | Efficient photocatalytic reduction of CO 2 Preparation method and application of tin-doped cobaltosic oxide material with oxygen vacancies |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623657A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Sosoloid catalyst of methyl alkyl catalyzing burned and its preparation process |
| CN1623658A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Sosoloid catalyst of methyl alkyl catalyzing burned and its preparation process |
-
2017
- 2017-06-20 CN CN201710468959.1A patent/CN107282051A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623657A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Sosoloid catalyst of methyl alkyl catalyzing burned and its preparation process |
| CN1623658A (en) * | 2003-12-04 | 2005-06-08 | 中国科学院兰州化学物理研究所 | Sosoloid catalyst of methyl alkyl catalyzing burned and its preparation process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113830836A (en) * | 2021-09-11 | 2021-12-24 | 浙江大学 | Preparation method of pyrochlore type nitrogen-doped multi-element metal oxide |
| CN113830836B (en) * | 2021-09-11 | 2023-02-14 | 浙江大学 | Preparation method of pyrochlore type nitrogen-doped multi-element metal oxide |
| CN115337933A (en) * | 2022-07-11 | 2022-11-15 | 华东理工大学 | Efficient photocatalytic reduction of CO 2 Preparation method and application of tin-doped cobaltosic oxide material with oxygen vacancies |
| CN115337933B (en) * | 2022-07-11 | 2024-03-22 | 华东理工大学 | Efficient photocatalytic reduction of CO 2 Preparation method and application of tin-doped cobaltosic oxide material with oxygen vacancies |
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Application publication date: 20171024 |