CN107362791A - A kind of methane catalytic combustion catalyst and preparation method thereof - Google Patents
A kind of methane catalytic combustion catalyst and preparation method thereof Download PDFInfo
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- CN107362791A CN107362791A CN201710640990.9A CN201710640990A CN107362791A CN 107362791 A CN107362791 A CN 107362791A CN 201710640990 A CN201710640990 A CN 201710640990A CN 107362791 A CN107362791 A CN 107362791A
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- catalytic combustion
- yttrium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004471 Glycine Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 9
- 150000002471 indium Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 14
- 238000009938 salting Methods 0.000 claims description 11
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 9
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 150000003746 yttrium Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 230000007812 deficiency Effects 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims description 2
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 claims description 2
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000001902 propagating effect Effects 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000008236 heating water Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910002328 LaMnO3 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a kind of non-stoichiometric perovskite type methyl hydride catalyst for catalytic combustion Y1‑xIn1‑yO3+δAnd preparation method thereof.Using self- propagating micro-gel flooding, using glycine as fuel and complexing agent, inorganic yttrium, indium salts are raw material, carry out the preparation of catalyst.Burning and evaporation rate of the invention by controlling glycine fuel, obtained sample have large specific surface area and high high-temp stability；Additionally by A or B positions non-stoichiometric adulterate to increase material the defects of position, improve active oxygen transfer ability and activation capacity.Its preparation technology is simple, and cost is less than noble metal catalyst, is a kind of new catalyst, has obvious industrial application value.
Description
Technical field
The invention belongs to technical field of material and catalytic applications, and in particular to perovskite type catalyst Y1- xIn1-yO3+δ(-0.2<x, y<0.2) preparation method and applications.
Background technology
Natural gas is one of energy being commonly used.Because the greenhouse effects of methane are CO225 times.Natural gas
Imperfect combustion and direct discharge containing methane waste product can bring atmosphere pollution.At present, it is to improve methane using Production by Catalytic Combustion Process
Efficiency of combustion, reduce the effective means of air pollution.The heat release of methane completely burned oxidation reaction process is strong and produces a large amount of water
Steam easily makes sintering of catalyst or structure collapses, thus the main target of methane catalytic combustion catalyst research and development is to improve catalyst
Low-temperature catalytic activity and high high-temp stability.At present, methane catalytic combustion catalyst can be divided mainly into noble metal catalyst and
Non-precious metal catalyst.Noble metal catalyst has preferably active and stronger stability, turns into most commonly used research pair
As.But limit the popularity application of this kind of catalyst because cost is of a relatively high.And non-precious metal catalyst is mainly
Perovskite type metal oxide catalyst and hexa-aluminate catalyst series, this two classes catalyst are urged because showing good high temperature
Change activity and heat endurance, it is considered to be most probable substitutes the catalysis material of noble metal catalyst.But its poor low temperature is lived
It is impatient to wait to improve, so as to its commercial Application.
Hexa-aluminate is too high because of its crystal orientation generation temperature（>1200oC）, serious aggregation and burning often occur for material particles
Knot, causes the relatively low specific surface area of last phase hexa-aluminate and big crystallite dimension, so as to which catalytic performance is limited；And Ca-Ti ore type is urged
The advantages that agent is because of its good catalytic activity and high high-temp stability and relatively low cost and by increasing
Concern.
The good catalytic activity of perovskite comes from the space structure that it allows largely to adulterate, so as to bring a large amount of Lacking oxygens
And improve the locomotivity of active oxygen.The perovskite type catalyst of most study is lanthanum Mn-based perofskite at present, including LaMnO3
And its doping type perovskite La1-xAxMn1-yByO3(0≤x, y≤1), wherein A, B Cr, Fe, Co, Ni, Mg, Al, Ca, Sr,
Ba, Ce etc..2011, Hend Najjar et al.（Applied Catalysis B Environmental, 2011, 106
(1):149-159）LaMnO is synthesized using solution combustion one-step synthesis3, its T90 = 690 oC；2013, Jean-Marc
Giraudon et al.（Catalysis Science & Technology, 2013, 3(4):1002-1016）By
LaMnO3B positions mix Al, realize LaMn0.9Al0.1O3T90 = 650 oC, its LaMnO to undope3：T90 = 680 oC.So
And above-mentioned perovskite type catalyst is still higher to the complete conversion temperature of methane, main cause is that specific surface area is not still high
（≤10 m2 g-1）.Therefore new perovskite and new synthetic method are found, researchs and develops that specific surface area is higher, and methane is urged
It is particularly important to change the lower catalyst of burning conversion temperature.
The content of the invention
The technical problems to be solved by the invention are to overcome perovskite type methyl hydride catalyst for catalytic combustion in the prior art
The defects of specific surface area is low, and activity is relatively low, urges so as to provide the methane catalytic combustion that a kind of high-temperature stability is good, catalytic activity is high
Agent, and then its preparation method is provided.
It is an object of the invention to provide a kind of new perovskite type catalyst applied to methane catalytic combustion field
Y1-xIn1-yO3+δ, pattern is adulterated using cation non-stoichiometric, does not introduce new element, keeps calcium while cation vacancy
Perovskite like structure, and then more Lacking oxygens are brought, the locomotivity of active oxygen is enhanced, it is anti-to be advantageous to catalytic oxidation-reduction
Should.Synthesized using glycine sol-gel auto-combustion, improve and to optimize the universal specific surface area of perovskite relatively low（≤10 m2
g-1）Present situation, realize that perovskite specific surface area reaches 24 m2 g-1More than and.Preparation technology of the present invention is simple, and catalyst is to first
The activity and stability of alkane significantly improve, and have obvious industrial application value.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of perovskite type catalyst for methane catalytic combustion, the catalyst are Ca-Ti ore type ABO3Structure, its A position are Y
Element and B positions are In elements；And pass through the regulation of Y and In mol ratios, regulation and control deficiency Y1-xIn1-yO3+δThe oxygen of perovskite material
Room, and then realize the regulation and control of catalyst activity.
Described Y1-xIn1-yO3+δCatalyst, it is characterised in that： -0.2<x<0.2, -0.2<y<0.2, δ represents that O's is non-
Stoichiometry room.
This catalyst, including following steps are prepared using self-propagating combustion：
1st, a certain amount of glycine solid is weighed, is dissolved in the deionized water of 100-1000 parts, is made into bottom liquid A；Weigh again certain
The inorganic yttrium salts and indium salts of amount, which are dissolved in the deionized water of 20-30 parts, is made into salting liquid B；
2nd, step 1 midsole liquid A is well mixed with salting liquid B in being stirred continuously and obtains mixed liquor C；
3rd, the mixed liquor C in step 2 is put into 60-80 in water-bathoC waters bath with thermostatic control are heated, while carry out high-speed stirred（Turn
Speed is in 1000-10000 r/min）, stop stirring and heating after constant temperature 10-20 h, obtain solution D；
4th, the solution D in step 3 is put into baking oven with temperature programming at a slow speed to 180o1 ~ 3 day is incubated after C, obtains sample E；
5th, it is put into after smashing into the sample E in step 4 to pieces powder in Muffle furnace with 5oC/min speed is warming up to 600oAfter C
4-8h is calcined, then again with 10oC/min is warming up to 800 DEG C of roasting 2h, obtains the catalyst.
The mol ratio of glycine dosage and the total dosage of metal inorganic salt in described step 1 is 0.2 ~ 3：1；
Yttrium source in described step 1 is the one or more in yttrium nitrate, yttrium sulfate and yttrium chloride；Indium source is indium nitrate, sulphur
One or more in sour indium and inidum chloride.
Yttrium source and indium source in described step 1, non-stoichiometric processing, Y/ are carried out to Y and In respectively in A, B position
In mol ratios are 0.5 ~ 2：1, to realize the regulation and control of perovskite defect.
Temperature programming program at a slow speed in the step 4：In drying temperature 0-100oHeating rate is 5-20 in the range of CoC/min；In drying temperature 100-180oHeating rate is 10-40 in the range of CoC/day。
The remarkable advantage of the present invention is：
1）A kind of new perovskite type catalyst Y for being applied to catalysis combustion field is synthesized1-xIn1-yO3+δ(-0.2<x, y<
0.2) material；
2）It is found that its excellent activity in methane catalytic combustion field；
3）Employ a kind of doping way of more simple economy（Omission doping, currently predominantly metallic element doping）To manufacture oxygen
Room and raising activity, new approach is provided while saving raw material to improve activity.
4）A kind of easier synthetic method-self-propagating combustion is provided, has synthesized the calcium of high specific surface area
Titanium ore.
Brief description of the drawings
Fig. 1 is the XRD of catalyst obtained in embodiment 1-7,（A- embodiments 1；B- embodiments 2；C- embodiments 3；
D- embodiments 4；E- embodiments 5；F- embodiments 6；G- embodiments 7）.
Embodiment
A kind of new Ca-Ti ore type for methane catalytic combustion of the present invention is catalyzed below by instantiation
Agent Y1-xIn1-yO3+δ(-0.2<x, y<0.2) preparation method of material is described further.
Embodiment 1：
At room temperature, weigh 1.5164g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Again
Weigh the water yttrium nitrate solids of 3.9070 g six and the water indium nitrate solids of 3.8192 g tetra- points five are dissolved in 150 ml deionized water
In be made into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred
（2000 r/min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；
It is put into after smashing into sample E to pieces powder in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/
Min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y1.02InO3。
Embodiment 2：
At room temperature, weigh 1.5089 g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Again
Weigh the water yttrium nitrate solids of 3.8687 g six and the water indium nitrate solids of 3.8192g tetra- points five are dissolved in 150 ml deionized water
It is made into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000
r/min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min program liters
Temperature is to 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；By sample E
It is put into after smashing into powder to pieces in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min heats up
To 800 DEG C of roasting 2h, catalyst Y is obtained1.01InO3。
Embodiment 3：
At room temperature, weigh 1.5014g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Claim again
The water yttrium nitrate solids of 3.8304g six and the water indium nitrate solids of 3.8192g tetra- points five is taken to be dissolved in 150 ml deionized water and being made into
Salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000 r/
min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min program liters
Temperature is to 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；By sample E
It is put into after smashing into powder to pieces in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min heats up
To 800 DEG C of roasting 2h, catalyst YInO is obtained3。
Embodiment 4：
At room temperature, weigh 1.4939g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Claim again
The water yttrium nitrate solids of 3.7921 g six and the water indium nitrate solids of 3.8192g tetra- points five is taken to be dissolved in 150 ml deionized water and matching somebody with somebody
Into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000 r/
min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min temperature programmings
To 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；Sample E is smash
It is put into after being broken into powder in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min is warming up to
800 DEG C of roasting 2h, obtain catalyst Y0.99InO3。
Embodiment 5：
At room temperature, weigh 1.4864 g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Again
Weigh the water yttrium nitrate solids of 3.7538 g six and the water indium nitrate solids of 3.8192g tetra- points five are dissolved in 150 ml deionized water
It is made into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000
r/min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min program liters
Temperature is to 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；By sample E
It is put into after smashing into powder to pieces in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min heats up
To 800 DEG C of roasting 2h, catalyst Y is obtained0.98InO3。
Embodiment 6：
At room temperature, weigh 1.4564 g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Again
Weigh the water yttrium nitrate solids of 3.6006g six and the water indium nitrate solids of 3.8192g tetra- points five are dissolved in 150 ml deionized water and matched somebody with somebody
Into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000 r/
min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min temperature programmings
To 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；Sample E is smash
It is put into after being broken into powder in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min is warming up to
800 DEG C of roasting 2h, obtain catalyst Y0.94InO3。
Embodiment 7：
At room temperature, weigh 1.4263 g glycine solids, in the beaker for the deionized water for being dissolved in 100 ml, be made into bottom liquid A；Again
Weigh the water yttrium nitrate solids of 3.4474 g six and the water indium nitrate solids of 3.8192 g tetra- points five are dissolved in 150 ml deionized water
It is made into salting liquid B；A, B liquid are well mixed after obtaining C liquid and carry out 80oC waters bath with thermostatic control, while quickly stirred（2000
r/min）, stop stirring after 10h and heating water bath obtain colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovensoC/min program liters
Temperature is to 100 DEG C, then with 15oC/day temperature programmings are to 180o1 day, which is incubated, after C obtains sample E（It is faint yellow spongy）；By sample E
It is put into after smashing into powder to pieces in Muffle furnace with 5oC/min speed is warming up to 600o4h is calcined after C, then with 10oC/min heats up
To 800 DEG C of roasting 2h, catalyst Y is obtained0.9InO3。
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Fig. 1 is the XRD of catalyst obtained in embodiment 1-7, and as shown in Figure 1, all embodiments have been respectively formed mesh
Cubic perovskite crystalline phase is marked, crystalline phase separation does not occur.
Using fixed bed quartz tube reactor, CH is utilized4+O2→CO2+H2O reactions carry out catalyst activity test, and it has
Gymnastics conduct：Catalyst sample 0.2g is taken, is placed in U-shaped quartz ampoule, carries out temperature programming（Temperature in beds is by heat
Galvanic couple is controlled）.Gas for evaluating catalyst activity forms：1%CH4/N2, 6%O2/ air, N2Balance, gas
Body total flow is about 150mL/min (i.e. air speed ≈ 45000ml g-1 h-1), 5 DEG C of min of heating rate-1, each temperature spot perseverance
The warm time is 10 min.Tail gas measuring is detected using five component analysis instrument, and catalyst is to CH4Transformation efficiency calculation formula
For：R=(C0-C1)/C0× 100%, wherein, R represents the conversion ratio of reaction gas, C0For the concentration of porch reaction gas, C1For outlet
Locate the concentration of reaction gas, use CH4Temperature during conversion 50% and 90%（That is T50And T90）To evaluate the catalytic activity of catalyst, knot
Fruit sees attached list 1.The catalyst of the present invention has bright for the more existing perovskite catalyst of methyl hydride combustion it can be seen from subordinate list 1
Show higher specific surface area and more preferable catalytic activity.
Subordinate list 1：Methane catalytic combustion activity and document contrast table in embodiment 1-7
Claims (6)
- A kind of 1. methane catalytic combustion catalyst, it is characterised in that：The catalyst is Ca-Ti ore type ABO3Structure, its A position are Y members Element and B positions are In elements；Deficiency Y is synthesized with the regulation of In non-stoichiometrics by Y1-xIn1-yO3+δPerovskite material.
- 2. methane catalytic combustion catalyst according to claim 1, it is characterised in that：Y1-xIn1-yO3+δIn catalyst- 0.2<x<0.2, -0.2<y<0.2.
- A kind of 3. preparation method of methane catalytic combustion catalyst as claimed in claim 1 or 2, it is characterised in that perovskite Type catalyst Y1-xIn1-yO3+δThe preparation of material uses self-propagating combustion, comprises the following steps：（1）A certain amount of glycine solid is weighed, is dissolved in the deionized water of 100-1000 parts, is made into bottom liquid A；Weigh again certain The inorganic yttrium salts and indium salts of amount, which are dissolved in the deionized water of 20-30 parts, is made into salting liquid B；（2）By step in being stirred continuously（1）Midsole liquid A is well mixed with salting liquid B obtains mixed liquor C；（3）By step（2）In mixed liquor C be put into 60-80 in water-bathoC waters bath with thermostatic control are heated, while carry out high-speed stirred, Rotating speed is 1000-10000 r/min, stops stirring and heating after constant temperature 10-20 h, obtains solution D；（4）By step（3）In solution D be put into baking oven with temperature programming at a slow speed to 180o1 ~ 3 day is incubated after C, obtains sample E；（5）By step（4）In sample E smash into powder to pieces after be put into Muffle furnace with 5oC/min speed is warming up to 600oC After be calcined 4-8h, then with 10oC/min is warming up to 800 DEG C of roasting 2h, obtains the catalyst.
- 4. the preparation method of methane catalytic combustion catalyst according to claim 3, it is characterised in that：Step（1）In The mol ratio of glycine dosage and the total dosage of metal inorganic salt is 0.2 ~ 3：1；Y/In mol ratios corresponding to yttrium salt and indium salts are 0.5 ~ 2：1.
- 5. the preparation method of methane catalytic combustion catalyst according to claim 3, it is characterised in that：Step（1）In Yttrium salt is the one or more in yttrium nitrate, yttrium sulfate and yttrium chloride；Indium salts are one kind in indium nitrate, indium sulfate and inidum chloride It is or a variety of.
- 6. the preparation method of methane catalytic combustion catalyst according to claim 3, it is characterised in that：Step（4）In Temperature programming program at a slow speed：In drying temperature 0-100oHeating rate is 5-20 in the range of CoC/min；In drying temperature 100- 180 oHeating rate is 10-40 in the range of CoC/day。
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