CN104084210A - Preparation method of double-doping composite oxide catalyst for methane combustion - Google Patents
Preparation method of double-doping composite oxide catalyst for methane combustion Download PDFInfo
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- CN104084210A CN104084210A CN201410346085.9A CN201410346085A CN104084210A CN 104084210 A CN104084210 A CN 104084210A CN 201410346085 A CN201410346085 A CN 201410346085A CN 104084210 A CN104084210 A CN 104084210A
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Abstract
The invention discloses a preparation method of a double-doping composite oxide catalyst for methane combustion. The catalyst is applied to a catalytic combustion reaction of low-concentration methane and is prepared by virtue of a coexistence method. The preparation method comprises the following steps of with citric acid as a complexing agent, simultaneously reacting and complexing raw solutions containing La, Mg, Sn and Co, and roasting at 900 DEG C for 3 hours so as to generate the double-doping composite oxide catalyst, wherein the molar ratio of doped Mg atoms to La atoms is (0-0.2) to (2-1.8), the molar ratio of doped Co atoms to Sn atoms is (0-0.3) to (2-1.7), and the optimal molar ratio of La atoms to Mg atoms to Sn atoms to Co atoms is 1.8 to 0.2 to 1.7 to 0.3. The preparation method of the catalyst is simple, low in cost and free of pollution, and the catalyst is high in catalytic activity and good in structural stability when being applied to catalytic combustion of low-concentration methane.
Description
Technical field
The present invention relates to a kind of preparation method of double-doped composite oxide catalysts, refer to especially the preparation method of a kind of double-doped composite oxides for the catalyst of low-concentration methane catalyst combustion reaction.
Background technology
China's coal bed gas resource is very abundant, but at present the exploitation utilization of coal bed gas is existed to very large deficiency, and total extraction rate is less than 50%, and after extraction, still has a greater part of coal bed gas to be directly discharged in atmosphere by mine ventilation, is called wind gas-removing.In wind gas-removing, contain methane gas, according to according to a preliminary estimate, the methane of annual China's coal-mine wind gas-removing loss is 16,100,000,000 m
3～200 hundred million m
3chasing after its reason, is mainly because methane content in wind gas-removing is not generally higher than 3%, because methane concentration is too low, utilize technical difficulty large, at present, wind gas-removing is mainly discharged in atmosphere, is not almost also fully utilized in countries in the world, although the concentration of methane is low in wind gas-removing, but total amount is huge especially, is equivalent to like this have every year 2160 ten thousand t～2,700 ten thousand t standard coals to be wasted, and has produced serious environmental pollution (CH
4the greenhouse effects that form are CO
226 times).If can wind gas-removing effectively be utilized, huge economic benefit, social benefit and environmental benefit will be produced.In recent years, the method that scientists has proposed low-concentration methane burning realizes the effective utilization to wind gas-removing, and realizing one of key of this technology is the research and development of low-concentration methane combustion catalyst.
At present, in methane catalytic combustion reaction, applying more catalyst is noble metal catalyst, and it can effectively reduce methyl hydride combustion temperature, just burning is complete between 200～400 DEG C to make methane, but because noble metal is expensive, heat endurance is poor, therefore and be not suitable for large-scale application.Old friends have launched cheap and easy to get, the research of the catalyst of transition metal oxide that oxygen storage capacity is stronger, as the oxide of Ce, Mn, Fe, Cu, but these oxides are as methyl hydride combustion catalyst, heat resistance is poor, in the time of high temperature, between component, easily react to each other, reduce the catalytic activity of catalyst.For example, so people turn one's attention to again stable in properties and the not non-noble metal composite oxide catalyst of easy-sintering of low temperature, hexa-aluminate oxide, double-perovskite type oxide, spinel oxide etc.These composite oxide of metal all comprise A, two kinds of metallic elements of B, wherein A bit element is generally alkaline-earth metal, thulium, B position is generally transition metal, can improve its catalytic activity therefore select suitable preparation method to prepare some specific composite oxide of metal as methyl hydride combustion catalyst.
In existing research, someone adopts infusion process that active constituent loading is prepared to methyl hydride combustion catalyst to the larger carrier of specific area; Also there is people to prepare methyl hydride combustion catalyst by coprecipitation, still, adopt at present same raw coexistence method to prepare the pyrochlore-type composite metal oxide simultaneously adulterating with B position A position relative less as the research of methyl hydride combustion catalyst.Therefore this patent provides a kind of preparation method of double-doped O composite metallic oxide catalyst, react for the methyl hydride combustion of low concentration, and can significantly improve the catalytic activity of methyl hydride combustion catalyst.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of double-doped composite oxide catalysts, this catalyst utilization is with raw concurrent laws preparation, make complexing agent with citric acid, to contain the original solution simultaneous reactions complexing of A, A ', B and B ' atom, form double-doped composite oxide catalysts, this catalyst is applied to the methane catalytic combustion reaction of low concentration, can makes low-concentration methane completing combustion at lower temperature.
The preparation method of catalyst of the present invention is with glass putty, lanthanum nitrate, and magnesium nitrate, cobalt nitrate is reactant, citric acid is complexing agent.Specific features is: the mol ratio of citric acid and each metallic atom is 1: 1, takes glass putty, the La (NO of certain metering ratio
3)
36H
2o, Mg (NO
3)
26H
2o, Co (NO
3)
26H
2o and citric acid are placed in there-necked flask, measuring appropriate 32.5wt% nitric acid adds wherein again, be made into the metal original solution containing nitric acid, under with the raw condition coexisting, several metal original solutions reflux 6～8 hours in 80～90 DEG C of constant temperature, then solution is moved into beaker, again 70 DEG C of water bath with thermostatic control reactions 6～8 hours, put into the oven dry of spending the night of 100 DEG C of IR bakes, 500 DEG C of roastings of Muffle furnace make Nitrates decompose for 3 hours, then 900 DEG C of roastings 3 hours, make containing lanthanum, magnesium, tin, the codope pyrochlore type multiple oxide catalyst of cobalt element.And utilize chemical analysis to determine the mol ratio of each metallic atom in the catalyst generating, consistent with the initial rate of charge of various metal nitrates.
Catalyst of the present invention is obtained good catalytic effect in methyl hydride combustion process.Specific experiment operation adopts and contains the hybrid reaction gas that percent by volume is 2% methane, 18% oxygen and 80% nitrogen, passing into catalyst granules is housed is 0.25～0.42mm, consumption is in the fixed-bed quartz reactor (diameter 10mm) of 200mg, with mass flowmenter control gas flow rate, air speed is 48000h
-1, temperature programming speed is 5 DEG C/min, adopts FQ-W type CH
4infrared spectrum analyser analysis, calculate this reaction and be issued to the CH after stable in different temperatures
4conversion ratio.In addition, adopt the thing phase composition of the D8ADVANCE type powder x-ray diffraction instrument detecting catalyst that German Bruker company produces, the running parameter of this instrument is as follows: radiation source is CuK
α(λ=0.15406nm), operating voltage is 36kV, electric current is 20mA, 10 °～80 ° of sweep limits, 2 °/min of sweep speed.
In double-doped O composite metallic oxide catalyst of the present invention, A, A ', B, B ' element specifically refer to La, Mg, Sn, Co element.Adopted and only contrasted containing the metal oxide of A, two kinds of elements of B, in its methane catalytic combustion active testing, catalytic activity is well below the composite oxide of metal of codope.
The codope metal oxide that the present invention also adopts A, A ', B, B ' element to be respectively La, Fe, Sn, Co element contrasts, result shows that the catalytic activity of the codope catalyst that contains La, Mg, Sn, Co in methyl hydride combustion active testing is best, and the material showing in XRD test is single-phase pyrochlore type multiple oxide structure, without assorted peak.
A ' the position foreign atom that the present invention is selected and the mol ratio of A position atom are 0～0.2: the mol ratio of 2～1.8, B ' position foreign atom and B position atom is 0～0.3: 2～1.7.
Advantage of the present invention is: the double-doped composite oxide catalysts of preparing, has good catalytic activity as methyl hydride combustion catalyst, heat endurance and structural stability.And method for preparing catalyst is simple, with low cost, the intermediate product loss of preparation process is little, and reactant reaction is complete.
Essential characteristics of the present invention is:
1. adopting the catalyst of preparing with raw concurrent laws is double-doped composite oxide catalysts, this catalyst is for methane catalytic combustion reaction, initiation temperature and completely conversion temperature are respectively 417.4 DEG C and 670.1 DEG C, and methyl hydride combustion catalytic activity is far superior to unadulterated O composite metallic oxide catalyst.
2. adopting the double-doped O composite metallic oxide catalyst of preparing with raw concurrent laws, is single-phase pyrochlore-type O composite metallic oxide catalyst, produces without dephasign, and this catalyst contains La, Mg, Sn, Co metallic element.This catalyst activity is better than the codope pyrochlore type multiple oxide catalyst that contains La, Fe, Sn, Co metallic element.
3. adopt the double-doped metal composite oxide catalyst of preparing with raw concurrent laws, the Mg element of selecting is neither also non-thulium of alkali metal, widen the range of choice of metallic element, in addition, Co element is variable valency metal element, is doped to redox reaction more easily occurs in Sn ion.And Mg and Co are mutually collaborative has good resistance to elevated temperatures, so the double-doped catalyst being made up of La, Mg, Sn, Co can improve the catalytic efficiency of methane catalytic combustion, can under higher temperature, keep again the stability of catalyst.
Brief description of the drawings
Fig. 1 is (1) La-Mg-Sn-Co-O double-doped O composite metallic oxide catalyst; (2) La-Fe-Sn-Co-O double-doped O composite metallic oxide catalyst; (3) the methyl hydride combustion catalytic activity resolution chart of La-Sn-O O composite metallic oxide catalyst.
Fig. 2 is (1) La-Mg-Sn-Co-O double-doped O composite metallic oxide catalyst; (2) La-Fe-Sn-Co-O double-doped O composite metallic oxide catalyst; (3) X ray diffracting spectrum of La-Sn-O O composite metallic oxide catalyst.
Corresponding reaction temperature T when table 1 is respectively 10%, 50%, 90% for the methane conversion under different catalysts catalytic condition
10, T
50and T
90.
Detailed description of the invention
Embodiment 1: take 2.0178g glass putty, 7.7944gLa (NO
3)
36H
2o, 0.5128gMg (NO
3)
26H
2o, 0.8731gCo (NO
3)
26H
2o, 8.4056g citric acid is placed in there-necked flask, the nitric acid that measures again 80mL32.5wt% adds wherein, be made into the metal original solution containing nitric acid, under with the raw condition coexisting, several metal original solutions reflux 6～8 hours in 80～90 DEG C of constant temperature, then solution is moved into beaker, again 70 DEG C of water bath with thermostatic control reactions 6～8 hours, putting into 100 DEG C of IR bakes spends the night and is dried into half xerogel, 500 DEG C of roastings of Muffle furnace 3 hours, then 900 DEG C of roastings 3 hours, obtain 0.01molLa-Mg-Sn-Co-O double-doped O composite metallic oxide catalyst.
Comparative example 1: take 2.3742g glass putty, 8.6604gLa (NO
3)
36H
2o, 8.4056g citric acid is placed in there-necked flask, the red fuming nitric acid (RFNA) that measures 80mL32.5wt% adds wherein, be made into the metal original solution containing nitric acid, under with the raw condition coexisting, several metal original solutions reflux 6～8 hours in 80～90 DEG C of constant temperature, then solution is moved into beaker, again 70 DEG C of water bath with thermostatic control reactions 6～8 hours, putting into 100 DEG C of IR bakes spends the night and is dried into half xerogel, 500 DEG C of roastings of Muffle furnace 3 hours, then 900 DEG C of roastings 3 hours, obtain 0.01molLa-Sn-O O composite metallic oxide catalyst.
Comparative example 2: take 2.0178g glass putty, 7.7944gLa (NO
3)
36H
2o, 0.8080gFe (NO
3)
29H
2o, 0.8731gCo (NO
3)
26H
2o, 8.4056g citric acid is placed in there-necked flask, the nitric acid that measures 80mL32.5wt% adds wherein, be made into the metal original solution containing nitric acid, under with the raw condition coexisting, several metal original solutions reflux 6～8 hours in 80～90 DEG C of constant temperature, then solution is moved into beaker, again 70 DEG C of water bath with thermostatic control reactions 6～8 hours, putting into 100 DEG C of IR bakes spends the night and is dried into half xerogel, 500 DEG C of roastings of Muffle furnace 3 hours, then 900 DEG C of roastings 3 hours, obtain 0.01molLa-Fe-Sn-Co-O double-doped O composite metallic oxide catalyst.
The catalyst making carries out the test of catalytic activity according to the methods below:
Get embodiment 1, the catalyst 200mg that comparative example 1 and 2 makes, particle is that 0.25～0.42mm is placed in fixed-bed quartz reactor (diameter 10mm), first logical nitrogen 10～15min, the air that is used in emptying reactor, mass flowmenter control gas flow rate is 30L/h, until infrared spectrum analyser pointer nulling and after stablizing, pass into that to contain percent by volume be 2% methane, the hybrid reaction gas of 18% oxygen and 80% nitrogen, controlling mass flowmenter gas flow rate is 20L/h, when infrared spectrum analyser pointed 100 and after stablizing, start to heat up, temperature programming speed is 5 DEG C/min.Record and calculate reaction and be issued to the CH after stablizing in different temperatures
4conversion ratio.
Claims (2)
1. the preparation method of a double-doped O composite metallic oxide catalyst, this catalyst adopts with raw concurrent laws preparation, it is characterized in that, make complexing agent with citric acid, there are four kinds of metallic atoms to participate in reacting and coexisting an individual system simultaneously simultaneously, the mol ratio of citric acid and each metallic atom is 1: 1, takes glass putty, the La (NO of certain metering ratio
3)
36H
2o, Mg (NO
3)
26H
2o, Co (NO
3)
26H
2o and citric acid are placed in there-necked flask, measuring appropriate 32.5wt% nitric acid adds wherein again, be made into the metal original solution containing nitric acid, under with the raw condition coexisting, several metal original solutions reflux 6～8 hours in 80～90 DEG C of constant temperature, then solution is moved into beaker, again 70 DEG C of water bath with thermostatic control reactions 6～8 hours, put into the oven dry of spending the night of 100 DEG C of IR bakes, 500 DEG C of roastings of Muffle furnace make Nitrates decompose for 3 hours, 900 DEG C of roastings 3 hours again, obtain the codope pyrochlore-type O composite metallic oxide catalyst of a kind of La-Mg-Sn-Co-O, and this catalyst is applied to the methane catalytic combustion reaction of low concentration.
2. the preparation method of a kind of double-doped O composite metallic oxide catalyst according to claim 1, be applied to low-concentration methane catalyst combustion reaction, it is characterized in that, the mol ratio of Mg foreign atom and La atom is 0～0.2: 2～1.8, the mol ratio of Co foreign atom and Sn atom is 0～0.3: 2～1.7, the optimum doped metallic elements of selecting is Mg and Co, and the molar ratio of its optimal catalyst is La: Mg: Sn: Co=1.8: 0.2: 1.7: 0.3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368327A (en) * | 2014-10-23 | 2015-02-25 | 江西宝安新材料科技有限公司 | Catalyst for catalytic methane oxidation and preparation method thereof |
| CN107282052A (en) * | 2017-06-20 | 2017-10-24 | 内蒙古大学 | A kind of preparation of nickel Zr catalyst and the technique reacted for methane catalytic combustion |
| CN113275017A (en) * | 2021-05-28 | 2021-08-20 | 内蒙古大学 | Preparation method and application of composite pyrochlore catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293201A (en) * | 2008-05-30 | 2008-10-29 | 内蒙古大学 | Method for preparing methyl hydride combustion catalyst |
| CN101879445A (en) * | 2010-07-15 | 2010-11-10 | 济南大学 | Composite rear earth pyrochlore-type oxide catalyst for catalyzing burning for removing soot of diesel vehicle and preparation method thereof |
-
2014
- 2014-07-21 CN CN201410346085.9A patent/CN104084210B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293201A (en) * | 2008-05-30 | 2008-10-29 | 内蒙古大学 | Method for preparing methyl hydride combustion catalyst |
| CN101879445A (en) * | 2010-07-15 | 2010-11-10 | 济南大学 | Composite rear earth pyrochlore-type oxide catalyst for catalyzing burning for removing soot of diesel vehicle and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIE CHENG ET AL: "Catalytic combustion of methane over cobalt doped lanthanum stannate pyrochlore oxide", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104368327A (en) * | 2014-10-23 | 2015-02-25 | 江西宝安新材料科技有限公司 | Catalyst for catalytic methane oxidation and preparation method thereof |
| CN104368327B (en) * | 2014-10-23 | 2016-09-07 | 江西宝安新材料科技有限公司 | A kind of catalyst for Catalytic methane oxidation and preparation method thereof |
| CN107282052A (en) * | 2017-06-20 | 2017-10-24 | 内蒙古大学 | A kind of preparation of nickel Zr catalyst and the technique reacted for methane catalytic combustion |
| CN113275017A (en) * | 2021-05-28 | 2021-08-20 | 内蒙古大学 | Preparation method and application of composite pyrochlore catalyst |
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| CN104084210B (en) | 2016-04-27 |
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