CN107362791B - 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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- CN107362791B CN107362791B CN201710640990.9A CN201710640990A CN107362791B CN 107362791 B CN107362791 B CN 107362791B CN 201710640990 A CN201710640990 A CN 201710640990A CN 107362791 B CN107362791 B CN 107362791B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 150000002471 indium Chemical class 0.000 claims abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 23
- 238000010792 warming Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000009938 salting Methods 0.000 claims description 11
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000003756 stirring Methods 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 8
- 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
- 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 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
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 2
- 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 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
- 238000005660 chlorination reaction Methods 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
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 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
- 230000002950 deficient Effects 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
- 230000000694 effects Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000008236 heating water Substances 0.000 description 7
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 238000002242 deionisation method 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
- 239000013078 crystal 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
- 238000000034 method Methods 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
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 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 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002328 LaMnO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 229910017604 nitric acid 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
- 238000006467 substitution reaction Methods 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
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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
- B01J23/10—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 present invention by control glycine fuel, sample obtained have large specific surface area and high high-temp stability；It is adulterated additionally by the non-stoichiometric at A or B to increase the defective bit of material, improves active oxygen transfer ability and activation capacity.Its preparation process is simple, and cost is lower than noble metal catalyst, is a kind of novel catalyst, has apparent 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+δThe preparation method and applications of (- 0.2 < x, y < 0.2).
Background technique
Natural gas is one of the energy being commonly used.Since the greenhouse effects of methane are CO225 times.Natural gas
Imperfect combustion and direct emission containing methane waste product can bring atmosphere pollution.Currently, being to improve methane using Production by Catalytic Combustion Process
Efficiency of combustion reduces the effective means of air pollution.The heat release of methane completely burned oxidation reaction process is strong and generates 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.Currently, methane catalytic combustion catalyst can be divided mainly into noble metal catalyst and
Non-precious metal catalyst.Noble metal catalyst has preferable activity and stronger stability, becomes most commonly used research pair
As.But because the cost is relatively high and limits the popularity application of this kind of catalyst.And non-precious metal catalyst is mainly
Perovskite type metal oxide catalyst and hexa-aluminate catalyst series, these two types of catalyst are urged because showing good high temperature
Change activity and thermal stability, it is considered to be the catalysis material of most probable substitution noble metal catalyst.But poor low temperature is living
It is impatient wait improve, so as to its industrial application.
Hexa-aluminate generates temperature excessively high (> 1200 because of its crystal orientationoC), serious aggregation and burning often occur for material particles
Knot, leads to the lower specific surface area of last phase hexa-aluminate and big crystallite dimension, so that catalytic performance is limited；And Ca-Ti ore type is urged
Agent is due to its good catalytic activity and high high-temp stability and relatively low cost the advantages that by more and more
Concern.
The space structure that the good catalytic activity of perovskite allows largely to adulterate from it, 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, including LaMnO at present3
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, and Hend Najjar et al. (Applied Catalysis B Environmental, 2011,106
(1): 149-159 LaMnO) is synthesized using solution combustion one-step synthesis3, T90 = 690 oC；2013, Jean-Marc
Giraudon et al. (Catalysis Science & Technology, 2013,3 (4): 1002-1016) by
LaMnO3The position B mix Al, realize LaMn0.9Al0.1O3T90 = 650 oC, the 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 novel 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.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome perovskite type methyl hydride catalyst for catalytic combustion in the prior art
Specific surface area is low, and the lower defect of activity is urged to provide the methane catalytic combustion that a kind of high-temperature stability is good, catalytic activity is high
Agent, and then preparation method is provided.
The purpose of the present invention is to provide a kind of new perovskite type catalysts applied to methane catalytic combustion field
Y1-xIn1-yO3+δ, mode is adulterated using cationic non-stoichiometric, does not introduce new element, cation vacancy while keeps calcium
Perovskite like structure, and then more Lacking oxygens are brought, the locomotivity of active oxygen is enhanced, it is anti-to be conducive to catalytic oxidation-reduction
It answers.It is synthesized using glycine sol-gel auto-combustion, improves and optimize relatively low (≤10 m of the universal specific surface area of perovskite2
g-1) status, realize perovskite specific surface area reach 24 m2 g-1Or more.Preparation process of the present invention is simple, and catalyst is to first
The activity and stability of alkane significantly improve, and have apparent industrial application value.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of perovskite type catalyst for methane catalytic combustion, the catalyst are Ca-Ti ore type ABO3Structure, A
It is In element for Y element and B；And pass through the adjusting of Y and In molar ratio, regulate and control deficiency Y1-xIn1-yO3+δPerovskite material
Lacking oxygen, and then realize the regulation of catalyst activity.
The Y1-xIn1-yO3+δCatalyst, it is characterised in that: -0.2 < x < 0.2, -0.2 < y < 0.2, and x and y etc.
The non-stoichiometry vacancy of O is indicated in 0, δ.
This catalyst is prepared using self-propagating combustion, including the following steps:
1, a certain amount of glycine solid is weighed, is dissolved in 100-1000 parts of deionized water, bottom liquid A is made into；It weighs again
A certain amount of inorganic yttrium salts and indium salts, which are dissolved in 20-30 parts of deionized water, is made into salting liquid B；
2, step 1 indsole liquid A is uniformly mixed in being stirred continuously with salting liquid B and obtains mixed liquor C；
3, the mixed liquor C in step 2 is put into 60-80 in water-bathoC water bath with thermostatic control heating, while carrying out high-speed stirring
It mixes (revolving speed is in 1000-10000 r/min), stops stirring and heating after constant temperature 10-20 h, obtain solution D；
4, the solution D in step 3 is put into baking oven with temperature programming at a slow speed to 180o1 ~ 3 day is kept the temperature after C, obtains sample
Product E；
5, it is put into Muffle furnace after smashing into the sample E in step 4 to pieces powder with 5oThe speed of C/min is warming up to 600oC
After roast 4-8h, then again with 10oC/min is warming up to 800 DEG C of roasting 2h, obtains the catalyst.
The molar ratio of glycine dosage and the total dosage of metal inorganic salt in the step 1 is 0.2 ~ 3:1；
Yttrium source in the step 1 is one of yttrium nitrate, yttrium sulfate and yttrium chloride or a variety of；Indium source is nitric acid
One of indium, indium sulfate and inidum chloride are a variety of.
Yttrium source and indium source in the step 1 carry out non-stoichiometric processing, Y/ to Y and In respectively at A, B
In molar ratio is 0.5 ~ 2:1, the regulation of Lai Shixian perovskite defect.
Temperature programming program at a slow speed in the step 4: in drying temperature 0-100oHeating rate is 5-20 within the scope of CoC/min；In drying temperature 100-180oHeating rate is 10-40 within the scope of CoC/day。
Remarkable advantage of the invention is:
1) a kind of new perovskite type catalyst Y for being applied to catalysis combustion field has been synthesized1-xIn1-yO3+δ(-0.2<x,
Y < 0.2) material；
2) have found it in the excellent activity in methane catalytic combustion field；
3) a kind of doping way (omission doping, currently predominantly metallic element doping) of more simple economy is used to make
It makes Lacking oxygen and improves activity, provide new approach while saving raw material to improve activity.
4) a kind of easier synthetic method-self-propagating combustion is provided, the calcium of high specific surface area has been synthesized
Titanium ore.
Detailed description of the invention
Fig. 1 is the XRD diagram of catalyst obtained in embodiment 1-7, (a- embodiment 1；B- embodiment 2；C- embodiment 3；
D- embodiment 4；E- embodiment 5；F- embodiment 6；G- embodiment 7).
Specific embodiment
Below by specific example to a kind of new Ca-Ti ore type catalysis for methane catalytic combustion of the present invention
Agent Y1-xIn1-yO3+δThe preparation method of (- 0.2 < x, y < 0.2) material is described further.
Embodiment 1:
At room temperature, 1.5164 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；Weigh 3.9070 g yttrium nitrate hexahydrate solids again and 3.8192 g, tetra- points five water indium nitrate solid be dissolved in 150 ml go from
Salting liquid B is made into sub- water；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；
It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted 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, 1.5089 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；3.8687 g yttrium nitrate hexahydrate solids are weighed again and tetra- points five water indium nitrate solid of 3.8192g is dissolved in the deionization of 150 ml
Salting liquid B is made into water；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；
It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/
Min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y1.01InO3。
Embodiment 3:
At room temperature, 1.5014g glycine solid is weighed, is dissolved in the beaker of the deionized water of 100 ml, bottom liquid A is made into；
3.8304g yttrium nitrate hexahydrate solid is weighed again and tetra- points five water indium nitrate solid of 3.8192g is dissolved in the deionized water of 150 ml
It is made into salting liquid B；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred (2000
R/min), stop stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min program
100 DEG C are warming up to, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；By sample
Product E is put into Muffle furnace after smashing into powder to pieces with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/min
800 DEG C of roasting 2h are warming up to, catalyst YInO is obtained3。
Embodiment 4:
At room temperature, 1.4939 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；3.7921 g yttrium nitrate hexahydrate solids are weighed again and tetra- points five water indium nitrate solid of 3.8192g is dissolved in the deionization of 150 ml
Salting liquid B is made into water；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；
It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/
Min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y0.99InO3。
Embodiment 5:
At room temperature, 1.4864 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；3.7538 g yttrium nitrate hexahydrate solids are weighed again and tetra- points five water indium nitrate solid of 3.8192g is dissolved in the deionization of 150 ml
Salting liquid B is made into water；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/
Min temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day, which is kept the temperature, after C obtains the faint yellow sponge of sample E(
Shape)；It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y0.98InO3。
Embodiment 6:
At room temperature, 1.4564 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；3.6006g yttrium nitrate hexahydrate solid is weighed again and tetra- points five water indium nitrate solid of 3.8192g is dissolved in the deionized water of 150 ml
In be made into salting liquid B；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；
It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/
Min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y0.94InO3。
Embodiment 7:
At room temperature, 1.4263 g glycine solids are weighed, is dissolved in the beaker of the deionized water of 100 ml, is made into bottom liquid
A；3.4474 g yttrium nitrate hexahydrate solids are weighed again and 3.8192 g, tetra- points five water indium nitrate solid is dissolved in the deionization of 150 ml
Salting liquid B is made into water；A, B liquid are uniformly mixed after obtaining C liquid and carry out 80oC water bath with thermostatic control, while quickly being stirred
(2000 r/min) stops stirring after 10h and heating water bath obtains colloidal sol D；Colloidal sol D is put into 80oWith 5 in C baking ovenoC/min
Temperature programming is to 100 DEG C, then with 15oC/day temperature programming is to 180o1 day is kept the temperature after C obtain sample E(and is faint yellow spongy)；
It is put into Muffle furnace after smashing into sample E to pieces powder with 5oThe speed of C/min is warming up to 600o4h is roasted after C, then with 10oC/
Min is warming up to 800 DEG C of roasting 2h, obtains catalyst Y0.9InO3。
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Fig. 1 is the XRD diagram of catalyst obtained in embodiment 1-7, and as shown in Figure 1, all embodiments have been respectively formed mesh
Cubic perovskite crystal phase is marked, crystal phase separation does not occur.
Using fixed bed quartz tube reactor, CH is utilized4+O2→CO2+H2O reaction carries out catalyst activity test, tool
Gymnastics conduct: taking catalyst sample 0.2g, is placed in U-shaped quartz ampoule, and carrying out temperature programming, (temperature in catalyst bed is by heat
Galvanic couple is controlled).Gas composition for evaluating catalyst activity is: 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
Are as follows: R=(C0-C1)/C0× 100%, wherein R indicates the conversion ratio of reaction gas, C0For the concentration of inlet reaction gas, C1For outlet
The concentration for locating reaction gas, uses CH4Temperature (T when conversion 50% and 90%50And T90) catalytic activity of catalyst is evaluated, knot
Fruit sees attached list 1.Catalyst of the invention perovskite catalyst more existing for methyl hydride combustion has bright it can be seen from subordinate list 1
Show higher specific surface area and better catalytic activity.
Subordinate list 1: methane catalytic combustion activity and document contrast table in embodiment 1-7
Claims (4)
1. a kind of application of perovskite type catalyst, it is characterised in that: the catalyst is Ca-Ti ore type ABO3Structure, A are Y
Element and B are In element；Deficiency Y is synthesized with the adjusting of In non-stoichiometric by Y1-xIn1-yO3+δPerovskite material；
Y1-xIn1-yO3+δ- 0.2 in catalyst < and x < 0.2, -0.2 < y < 0.2, and x and y indicates that the non-stoichiometry of O is empty not equal to 0, δ
Position；Application of the catalyst in methane catalytic combustion.
2. application according to claim 1, which is characterized in that perovskite type catalyst Y1-xIn1-yO3+δThe preparation of material is adopted
With self-propagating combustion, comprising the following steps:
(1) a certain amount of glycine solid is weighed, is dissolved in 100-1000 parts of deionized water, bottom liquid A is made into；It weighs again certain
The inorganic yttrium salts and indium salts of amount, which are dissolved in 20-30 parts of deionized water, is made into salting liquid B；
(2) step (1) indsole liquid A is uniformly mixed in being stirred continuously with salting liquid B and obtains mixed liquor C；
(3) the mixed liquor C in step (2) is put into 60-80 in water-bathoC water bath with thermostatic control heating, while high-speed stirred is carried out,
Revolving speed is 1000-10000 r/min, stops stirring and heating after constant temperature 10-20 h, obtains solution D；
(4) solution D in step (3) is put into baking oven with temperature programming at a slow speed to 180o1 ~ 3 day is kept the temperature after C, obtains sample
E；
(5) it is put into Muffle furnace after smashing into the sample E in step (4) to pieces powder with 5oThe speed of C/min is warming up to 600oC
After roast 4-8h, then with 10oC/min is warming up to 800 DEG C of roasting 2h, obtains the catalyst；
Temperature programming program at a slow speed in step (4): in drying temperature 0-100oHeating rate is 5-20 within the scope of CoC/min；
In drying temperature 100-180oHeating rate is 10-40 within the scope of CoC/day。
3. application according to claim 2, it is characterised in that: the glycine dosage and metal inorganic salt in step (1) are total
The molar ratio of dosage is 0.2 ~ 3:1；Yttrium salt and the corresponding Y/In molar ratio of indium salts are 0.5 ~ 2:1.
4. application according to claim 2, it is characterised in that: the yttrium salt in step (1) is yttrium nitrate, yttrium sulfate and chlorination
One of yttrium is a variety of；Indium salts are one of indium nitrate, indium sulfate and inidum chloride or a variety of.
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| JP2003321225A (en) * | 2002-04-26 | 2003-11-11 | National Institute For Materials Science | Method for producing lanthanum ruthenate |
| CN1970142A (en) * | 2006-11-08 | 2007-05-30 | 中国科学技术大学 | Visible light responsive photocatalyst and its preparing process |
| CN101502794A (en) * | 2006-11-08 | 2009-08-12 | 中国科学技术大学 | Photocatalytic application of compound YMO3(M=in, al) |
| CN103374429A (en) * | 2012-04-12 | 2013-10-30 | 中国石油化工股份有限公司 | Composite oxide oxygen carrier, preparation method and applications |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
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| JP2003321225A (en) * | 2002-04-26 | 2003-11-11 | National Institute For Materials Science | Method for producing lanthanum ruthenate |
| CN1970142A (en) * | 2006-11-08 | 2007-05-30 | 中国科学技术大学 | Visible light responsive photocatalyst and its preparing process |
| CN101502794A (en) * | 2006-11-08 | 2009-08-12 | 中国科学技术大学 | Photocatalytic application of compound YMO3(M=in, al) |
| CN103374429A (en) * | 2012-04-12 | 2013-10-30 | 中国石油化工股份有限公司 | Composite oxide oxygen carrier, preparation method and applications |
| CN104923225A (en) * | 2014-03-18 | 2015-09-23 | 中国科学院大连化学物理研究所 | Supported noble metal catalyst and preparation and application thereof |
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