CN110292935A - A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof - Google Patents
A kind of doped meso-porous LaCoO of Mn3Perovskite type catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011572 manganese Substances 0.000 claims abstract description 27
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011240 wet gel Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 13
- 229910002254 LaCoO3 Inorganic materials 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910017487 LaCo0.2Mn0.8O3 Inorganic materials 0.000 description 3
- 235000003283 Pachira macrocarpa Nutrition 0.000 description 3
- 241001083492 Trapa Species 0.000 description 3
- 235000014364 Trapa natans Nutrition 0.000 description 3
- 235000009165 saligot Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000012956 testing procedure Methods 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention belongs to purifying vehicle exhaust catalysis technical fields, and in particular to a kind of doped meso-porous LaCoO of Mn of template preparation3Perovskite type catalyst and its preparation method and application.The present invention is using SBA-15 as template, using citric acid as metal ion network mixture, citric acid, lanthanum nitrate, cobalt nitrate, manganese nitrate are uniformly dissolved in ethanol water, SBA-15 is added after being sufficiently complexed to metal ion and citric acid, it is stirred for being evaporated to wet gel state, obtains mesoporous perovskite type catalyst after grinding calcining, washing and drying after re-dry to xerogel.LaCoO prepared by the present invention3There is perovskite type catalyst big specific surface area, good low temperature CO catalytic activity, raw material to be easy to get, is at low cost, and preparation flow is simple to operation.
Description
Technical field
The invention belongs to purifying vehicle exhaust catalysis technical fields, and in particular to a kind of Mn of template preparation is doped meso-porous
LaCoO3Perovskite type catalyst and its preparation method and application.
Background technique
Important sources one of of the vehicle exhaust as atmosphere pollution, have been subjected to more and more extensive concern.Vehicle exhaust
In CO, NOxEqual polluted gas have caused threat to the health of the mankind, so, the control gesture of vehicle exhaust is must
Row.
Currently, noble metal catalyst is most catalyst that comes into operation, but because its price height, scarcity of resources, high temperature are easy
The disadvantages of sintering, Yi Yinqi S, P are poisoned and lead to its inactivation, so being difficult to noble metal catalyst large-area applications in automobile number
It measures on huge national market.And ABO3Type perovskite oxide because its it is resourceful it is cheap, high-temperature stability is good, structure
Defect is abundant, while also having the catalytic capability to compare favourably with noble metal catalyst, so being expected to replace noble metal catalyst.
LaCoO3Type perovskite catalyst shows higher catalytic activity to CO catalytic oxidation, but uses conventional method system
Standby perovskite catalyst specific surface area is lower, in practical applications, since activity is poor, is urged with it directly as vehicle exhaust
Agent is using the discharge standard that cannot reach vehicle exhaust, so the application of perovskite catalyst receives very big limitation.Therefore,
In order to improve the specific surface area of catalyst, improves catalytic activity, be to improve its ratio with the mesoporous perovskite catalyst of Template synthesis
A kind of feasible method of surface area.
Summary of the invention
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of doped meso-porous LaCoO of Mn of template preparation3
Perovskite type catalyst and its preparation method and application.
For achieving the above object, the technical scheme adopted by the invention is as follows:
A kind of doped meso-porous LaCoO of Mn3The preparation method of perovskite type catalyst, includes the following steps:
(1) sol-gal process is used, using SBA-15 molecular sieve as template, using citric acid as metal ion network mixture, by lemon
Lemon acid, lanthanum nitrate, cobalt nitrate, manganese nitrate are uniformly dissolved in ethanol water, and SBA-15 molecular sieve is added, and stirring is evaporated to wet solidifying
Gluey state, then wet gel is dry to xerogel, finally xerogel grinding is placed in Muffle furnace and is calcined；
(2) it is cooled to room temperature after calcining, disperses calcined product in NaOH solution, after stirring, washing, drying,
Obtain the doped meso-porous LaCoO of Mn3Perovskite type catalyst.
In above scheme, the lanthanum nitrate, cobalt nitrate, manganese nitrate molar ratio be 1:0.5~0.9:0.1~0.5.
In above scheme, the amount of the SBA-15 molecular sieve material and the lanthanum nitrate, cobalt nitrate, manganese nitrate total material
The ratio of amount is 1.5~2.5.
In above scheme, the citric acid and the lanthanum nitrate, cobalt nitrate, manganese nitrate total material amount ratio be 1~
2。
In above scheme, the SBA-15 molecular sieve is mesopore molecular sieve, and the specific surface area of the SBA-15 molecular sieve is
560~720m2/g。
In above scheme, the temperature of step (1) described calcining is 600 DEG C~800 DEG C, and heating rate is 3 DEG C/min~5
DEG C/min, soaking time is 2h~4h.
In above scheme, the temperature of step (2) described stirring is 60 DEG C~80 DEG C, and the time is 6h~8h.
In above scheme, the temperature of step (2) described drying is 60 DEG C~70 DEG C, and the time is 8h~10h.
In above scheme, the SBA-15 molecular sieve is prepared via a method which to obtain: by P123 (EO20PO70EO20) and
F127(EO106PO70EO106) be dissolved in suitable deionized water and hydrochloric acid solution, the magnetic agitation 4h in 35 DEG C~50 DEG C water-baths
~6h is slowly instilled in above-mentioned solution after the two is completely dissolved, then by tetraethyl orthosilicate (TEOS), 35 DEG C~50 DEG C water-baths
Under continue to stir 16h~for 24 hours, obtained milky mixed liquor is transferred in the reaction kettle of polytetrafluoroethyllining lining, drying is placed in
In case, 36h~48h is purified at 80 DEG C~110 DEG C.
Beneficial effects of the present invention: the present invention is using SBA-15 as template, using the LaCo of sol-gal process preparation1-xMnxO3
There is (x=0.1,0.3,0.5) perovskite catalyst big specific surface area, good low temperature CO catalytic activity, raw material to be easy to get, at
This is low, and preparation flow is simple to operation；In the present invention, the position B of perovskite catalyst is doped with the manganese ion of optimal proportion, increases
The lattice defect and active site of catalyst, make 90% (T of CO conversion ratio90) and conversion ratio be 50% (T50) temperature it is aobvious
Writing reduces.
Detailed description of the invention
Fig. 1 is the XRD spectrum of SBA-15 prepared by the present invention.
Fig. 2 is the FE-FEM map of SBA-15 prepared by the present invention.
Fig. 3 is the mesoporous LaCoO of Examples 1 to 3 preparation3The XRD spectrum of perovskite type catalyst.
Fig. 4 is mesoporous LaCoO prepared by embodiment 13The FE-TEM map of perovskite type catalyst.
Fig. 5 is the mesoporous LaCoO of Examples 1 to 3 preparation3Catalyzed conversion activity curve of the perovskite type catalyst to CO.
Fig. 6 is mesoporous LaCo prepared by embodiment 4~61-xMnxO3The XRD spectrum of perovskite type catalyst.
Fig. 7 is mesoporous LaCo prepared by embodiment 41-xMnxO3The FE-TEM map of perovskite type catalyst.
Fig. 8 is mesoporous LaCo prepared by embodiment 4~61-xMnxO3Perovskite type catalyst is bent to the catalyzed conversion activity of CO
Line.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, the SBA-15 is made as follows: by P123 (EO20PO70EO20) and F127
(EO106PO70EO106) be dissolved in suitable deionized water and hydrochloric acid solution, magnetic agitation 4h, complete to the two in 35 DEG C of water-baths
After dissolution, then tetraethyl orthosilicate (TEOS) slowly instilled in above-mentioned solution, continues stirring under 35 DEG C of water-baths for 24 hours, will obtain
Milky mixed liquor be transferred in the reaction kettle of polytetrafluoroethyllining lining, be placed in drying box, purify 36h at 110 DEG C, will be brilliant
Product after change takes out, and is cooled to room temperature, is centrifuged, filters, washing to neutrality, being put into baking oven and remove moisture removal；It will finally dry
Product afterwards is placed in Muffle furnace, is removed template agent removing after rising to 350 DEG C of calcining 6h with the heating rate of 2 DEG C/min, is obtained white
Mesoporous powder SBA-15.
The XRD spectrum of preparation gained SBA-15 in (100), (110) and (200) crystal face as shown in Figure 1, occur significantly
SiO2Characteristic diffraction peak has obtained the SBA-15 of preferable structure.The FE-TEM map of the SBA-15 is as shown in Fig. 2, prepared
Mesoporous SBA-15 there is obvious orderly duct striped, specific surface area 603m2/g。
Embodiment 1
Mesoporous LaCoO3Perovskite type catalyst is prepared by method: weighing 0.02mol citric acid, 0.01mol nitre
Sour lanthanum, 0.01mol cobalt nitrate, 0.02mol citric acid, 10ml deionized water, 30ml ethyl alcohol and 0.02mol SBA-15, by nitric acid
Lanthanum, cobalt nitrate, citric acid are uniformly dissolved in ethanol water, and 10h is stirred at room temperature, and SBA-15 are added in mixed liquor, 40 DEG C are stirred
6h is mixed to wet gel state, then wet gel is placed in drying box, 80 DEG C of dry 12h to xerogel, then after xerogel is ground
It is placed in Muffle furnace and calcines, be raised to 600 DEG C from room temperature with the rate of 4 DEG C/min, keep the temperature 2h at this temperature, then furnace cooling is to room
The product of temperature, calcining is scattered in the NaOH solution of 2mol/L, 60 DEG C of washing 6h, then after being washed repeatedly with deionized water, is placed in
70 DEG C of drying 10h, obtain mesoporous LaCoO3Perovskite type catalyst.
Mesoporous LaCoO manufactured in the present embodiment3The XRD spectrum of perovskite type catalyst as shown in figure 3, from the figure 3, it may be seen that with
SBA-15 is template, the LaCoO prepared using sol-gal process3Perovskite type catalyst belongs to rhombohedral system LaCoO3
(JCPDS#48-0123, R-3c) Perovskite Phase.Mesoporous LaCoO described in the present embodiment3The FE-TEM of perovskite type catalyst
Map is as shown in figure 4, as shown in Figure 4, mesoporous LaCoO described in the present embodiment3The microstructure of perovskite type catalyst is certain
For meso-hole structure.
To mesoporous LaCoO obtained in the present embodiment3Perovskite type catalyst carries out CO catalyzed conversion active testing, step
It is as follows: to use 93vol%Ar, 5vol%O2, 2vol%CO composition mixed gas carry out simulated automotive exhaust gas component.CO catalysis oxidation
Active testing carries out in miniature quartz reactor, in gas-solid reaction device, reacts quartz ampoule pipe range 120mm, outer diameter 12mm, interior
Diameter 8mm tests the temperature difference < 3 DEG C.0.1g catalyst sample powder is coated uniformly on 0.5g silica wool, stone is then put it into
In English glass tube, then the quartz glass tube for installing sample is placed in tube furnace and is heated.Gas flow rate is 200ml/min, air speed
For 20000h-1, for the gas after reaction through six-way valve sample introduction, reaction end gas (is furnished with FID using GC-7890II type gas chromatograph
With TCD dual detector) analyze remaining CO content in product.Test Range of measuring temp be 75 DEG C~250 DEG C, test temperature every
Point is 25 DEG C, and the single testing time is 13min.Test results are shown in figure 5, as shown in Figure 5, mesoporous described in the embodiment
LaCoO3Perovskite type catalyst reaches 50% (T to CO conversion ratio at 154 DEG C50=154 DEG C), CO conversion ratio is reached at 175 DEG C
To 90% (T90=175 DEG C).
Embodiment 2
The present embodiment prepares mesoporous LaCoO3The step of perovskite type catalyst, is roughly the same with embodiment 1, difference
Be: calcination temperature is 700 DEG C.
Mesoporous LaCoO manufactured in the present embodiment3The XRD spectrum of perovskite type catalyst as shown in figure 3, from the figure 3, it may be seen that with
SBA-15 is template, the LaCoO prepared using sol-gal process3Perovskite type catalyst belongs to rhombohedral system LaCoO3
(JCPDS#48-0123, R-3c) Perovskite Phase.Mesoporous LaCoO manufactured in the present embodiment3Perovskite type catalyst urges CO
It is same as Example 1 to change activity of conversion testing procedure.As shown in Figure 5, mesoporous LaCoO manufactured in the present embodiment3Ca-Ti ore type is urged
Agent reaches 50% (T to CO conversion ratio at 130 DEG C50=130 DEG C), 90% (T is reached to CO conversion ratio at 148 DEG C90=148
℃).Thus illustrate, mesoporous LaCoO prepared by the embodiment3Perovskite type catalyst low temperature CO catalytic activity is compared with embodiment 1
It is good.
Embodiment 3
The present embodiment prepares mesoporous LaCoO3The step of perovskite type catalyst, is roughly the same with embodiment 1, difference
Be: calcination temperature is 800 DEG C.
Mesoporous LaCoO manufactured in the present embodiment3The XRD spectrum of perovskite type catalyst as shown in figure 3, from the figure 3, it may be seen that with
SBA-15 is template, the LaCoO prepared using sol-gal process3Perovskite type catalyst belongs to rhombohedral system LaCoO3
(JCPDS#48-0123, R-3c) Perovskite Phase.Mesoporous LaCoO manufactured in the present embodiment3Perovskite type catalyst urges CO
It is same as Example 1 to change activity of conversion testing procedure.As shown in Figure 5, mesoporous LaCoO manufactured in the present embodiment3Ca-Ti ore type is urged
Agent reaches 50% (T to CO conversion ratio at 147 DEG C50=147 DEG C), 90% (T is reached to CO conversion ratio at 170 DEG C90=170
℃).Thus illustrate, mesoporous LaCoO prepared by the embodiment3Perovskite type catalyst low temperature CO catalytic activity is compared with embodiment 1
It is good.
Embodiment 4
The doped meso-porous LaCo of Mn1-xMnxO3(X=0.1) perovskite type catalyst is prepared by method: being weighed
0.02mol citric acid, 0.01mol lanthanum nitrate, 0.009mol cobalt nitrate, 0.001mol manganese nitrate, 0.02mol citric acid, 10ml
Deionized water, 30ml ethyl alcohol and 0.02mol SBA-15, citric acid, lanthanum nitrate, cobalt nitrate, manganese nitrate, citric acid is uniformly molten
In ethanol water, 10h is stirred at room temperature, SBA-15 is added in metal ion mixed liquor, 40 DEG C of stirring 6h to wet gel shape
State, then wet gel is placed in drying box, 80 DEG C of dry 12h to xerogel, then xerogel grinding is placed in Muffle furnace and is forged
It burns, is raised to 700 DEG C from room temperature with the rate of 4 DEG C/min, keep the temperature 2h at this temperature, then furnace cooling is to room temperature, the product of calcining
It is scattered in the NaOH solution of 2mol/L, 60 DEG C of washing 6h, then after being washed repeatedly with deionized water, is placed in 70 DEG C of drying 10h,
Obtain the doped meso-porous LaCo of Mn0.9Mn0.1O3(LCM-0.1) perovskite type catalyst.
The XRD spectrum of mesoporous LCM-0.1 perovskite type catalyst manufactured in the present embodiment as shown in fig. 6, it will be appreciated from fig. 6 that
Using SBA-15 as template, water chestnut side is belonged to using the doped meso-porous LCM-0.1 perovskite type catalyst of Mn prepared by sol-gal process
Crystallographic system LaCo0.2Mn0.8O3Perovskite Phase.The FE-TEM map of mesoporous LCM-0.1 perovskite type catalyst described in the present embodiment
As shown in fig. 7, as shown in Figure 7, mesoporous LCM-0.1 perovskite type catalyst sample regional area described in the present embodiment may have
Some holes road is destroyed, but it is 57m that population of samples, which has had already appeared obvious orderly cellular structure sample specific surface area,2/g。
Catalyzed conversion active testing step and reality of the mesoporous LCM-0.1 perovskite type catalyst manufactured in the present embodiment to CO
It is identical to apply example 1.Test results are shown in figure 8.As seen from the figure, mesoporous LCM-0.1 perovskite type catalyst manufactured in the present embodiment
50% (T is reached to CO conversion ratio at 133 DEG C50=133 DEG C), 90% (T is reached to CO conversion ratio at 145 DEG C90=145 DEG C).
Embodiment 5
The present embodiment prepares the doped meso-porous LaCo of Mn1-xMnxO3The step of perovskite type catalyst and the substantially phase of embodiment 4
Together, the difference is that: Mn doping is 0.3 (X=0.3), i.e. 0.007mol cobalt nitrate, 0.003mol manganese nitrate
The XRD spectrum of mesoporous LCM-0.3 perovskite type catalyst manufactured in the present embodiment as shown in fig. 6, it will be appreciated from fig. 6 that
Using SBA-15 as template, water chestnut side is belonged to using the doped meso-porous LCM-0.3 perovskite type catalyst of Mn prepared by sol-gal process
Crystallographic system LaCo0.2Mn0.8O3Perovskite Phase.Mesoporous LCM-0.3 perovskite type catalyst specific surface area manufactured in the present embodiment is
69m2/g.Catalyzed conversion active testing step and reality of the mesoporous LCM-0.3 perovskite type catalyst manufactured in the present embodiment to CO
It is identical to apply example 1.Test results are shown in figure 8.As seen from the figure, mesoporous LCM-0.1 perovskite type catalyst manufactured in the present embodiment
50% (T is reached to CO conversion ratio at 127 DEG C50=127 DEG C), 90% (T is reached to CO conversion ratio at 143 DEG C90=143 DEG C).
Embodiment 6
The present embodiment prepares the doped meso-porous LaCo of mesoporous Mn1-xMnxO3The step of perovskite type catalyst and embodiment 4 are substantially
It is identical, the difference is that: Mn doping is 0.5 (X=0.5), i.e. 0.005mol cobalt nitrate, 0.005mol manganese nitrate.
The XRD spectrum of mesoporous LCM-0.5 perovskite type catalyst manufactured in the present embodiment as shown in fig. 6, it will be appreciated from fig. 6 that
Using SBA-15 as template, water chestnut side is belonged to using the doped meso-porous LCM-0.5 perovskite type catalyst of Mn prepared by sol-gal process
Crystallographic system LaCo0.2Mn0.8O3Perovskite Phase.The mesoporous LCM-0.3 perovskite type catalyst specific surface area of embodiment preparation is 77m2/
g.Catalyzed conversion active testing step and embodiment 1 of the mesoporous LCM-0.5 perovskite type catalyst manufactured in the present embodiment to CO
It is identical.Test results are shown in figure 8.As seen from the figure, mesoporous LCM-0.1 perovskite type catalyst manufactured in the present embodiment is 111
DEG C 50% (T is reached to CO conversion ratio50=122 DEG C), 90% (T is reached to CO conversion ratio at 143 DEG C90=143 DEG C).Thus it says
Bright, mesoporous LCM-0.5 perovskite type catalyst prepared by the present embodiment shows excellent low temperature CO catalytic activity.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (10)
1. a kind of doped meso-porous LaCoO of Mn3The preparation method of perovskite type catalyst, which comprises the steps of:
(1) use sol-gal process, using SBA-15 molecular sieve as template, using citric acid as metal ion network mixture, by citric acid,
Lanthanum nitrate, cobalt nitrate, manganese nitrate are uniformly dissolved in ethanol water, and SBA-15 molecular sieve is added, and stirring is evaporated to wet gel shape
State, then wet gel is dry to xerogel, finally xerogel grinding is placed in Muffle furnace and is calcined；
(2) it is cooled to room temperature after calcining, disperses calcined product in NaOH solution, after stirring, washing, drying, obtained
The doped meso-porous LaCoO of Mn3Perovskite type catalyst.
2. preparation method according to claim 1, which is characterized in that the molar ratio of the lanthanum nitrate, cobalt nitrate, manganese nitrate
For 1:0.5 ~ 0.9:0.1 ~ 0.5.
3. preparation method according to claim 1, which is characterized in that the amount of the SBA-15 molecular sieve material and the nitre
Sour lanthanum, cobalt nitrate, manganese nitrate total material amount ratio be 1.5 ~ 2.5.
4. preparation method according to claim 1, which is characterized in that the citric acid and the lanthanum nitrate, cobalt nitrate, nitre
The ratio of the amount of sour manganese total material is 1 ~ 2.
5. preparation method according to claim 1, which is characterized in that the temperature of step (1) described calcining is 600 DEG C ~ 800
DEG C, heating rate is 3 DEG C/min ~ 5 DEG C/min, and soaking time is 2h ~ 4h.
6. preparation method according to claim 1, which is characterized in that the SBA-15 molecular sieve is mesopore molecular sieve, than
Surface area is 560 ~ 720 m2/g。
7. preparation method according to claim 1, which is characterized in that the temperature of step (2) described stirring is 60 DEG C ~ 80
DEG C, the time is 6h ~ 8h；The temperature of the drying is 60 DEG C ~ 70 DEG C, and the time is 8h ~ 10h.
8. preparation method according to claim 1, which is characterized in that the SBA-15 molecular sieve is prepared via a method which
It obtains: by P123(EO20PO70EO20) and F127(EO106PO70EO106) be dissolved in suitable deionized water and hydrochloric acid solution, 35
DEG C ~ 50 DEG C of water-baths in magnetic agitation 4h ~ 6h, after the two is completely dissolved, then tetraethyl orthosilicate is slowly instilled to above-mentioned solution
In, continue to stir 16h ~ for 24 hours under 35 DEG C ~ 50 DEG C water-baths, obtained milky mixed liquor is transferred to the anti-of polytetrafluoroethyllining lining
It answers in kettle, is placed in drying box, crystallization 36h ~ 48h at 80 DEG C ~ 110 DEG C.
9. the doped meso-porous LaCoO of any preparation method preparation gained Mn of claim 1 ~ 83Perovskite type catalyst.
10. the doped meso-porous LaCoO of Mn described in claim 93Perovskite type catalyst is in purifying vehicle exhaust catalysis technical field
Using.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229238A (en) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | Ordered porous perovskite catalyst for synergistically catalyzing and oxidizing NO and toluene and preparation method and application thereof |
| CN114425395A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Porous perovskite type sulfur-tolerant shift catalyst and preparation method and application thereof |
| CN115779937A (en) * | 2022-11-25 | 2023-03-14 | 南昌航空大学 | Method for activating surface lattice oxygen of perovskite type oxide and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017504A (en) * | 1998-07-16 | 2000-01-25 | Universite Laval | Process for synthesizing perovskites using high energy milling |
| US20110082030A1 (en) * | 2009-10-01 | 2011-04-07 | Gm Global Technology Operations, Inc. | Washcoating technique for perovskite catalysts |
| CN102600855A (en) * | 2012-01-10 | 2012-07-25 | 北京工业大学 | Three-dimensional order large-hole-structure La0.6Sr0.4Fe0.8Bi0.2O3, synthetic method and application thereof |
| CN104607201A (en) * | 2014-12-18 | 2015-05-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof |
| CN108714426A (en) * | 2018-06-15 | 2018-10-30 | 武汉理工大学 | A kind of nanocube perovskite type catalyst and its preparation method and application |
-
2019
- 2019-04-24 CN CN201910335622.2A patent/CN110292935A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017504A (en) * | 1998-07-16 | 2000-01-25 | Universite Laval | Process for synthesizing perovskites using high energy milling |
| US20110082030A1 (en) * | 2009-10-01 | 2011-04-07 | Gm Global Technology Operations, Inc. | Washcoating technique for perovskite catalysts |
| CN102600855A (en) * | 2012-01-10 | 2012-07-25 | 北京工业大学 | Three-dimensional order large-hole-structure La0.6Sr0.4Fe0.8Bi0.2O3, synthetic method and application thereof |
| CN104607201A (en) * | 2014-12-18 | 2015-05-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Ordered mesoporous LaCoO3 and LaMnO3 supported nano Ag catalyst and preparation and application thereof |
| CN108714426A (en) * | 2018-06-15 | 2018-10-30 | 武汉理工大学 | A kind of nanocube perovskite type catalyst and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| HONG LIANG ET AL: "Influence of partial Mn-substitution on surface oxygen species of LaCoO3 catalysts", 《CATALYSIS TODAY》 * |
| YAOHUI WU ET AL: "Catalytic reduction of NO by CO over B-site partially substituted LaM0.25Co0.75O3 (M = Cu, Mn, Fe) perovskite oxide catalysts: The correlation between physicochemical properties and catalytic performance", 《APPLIED CATALYSIS A, GENERAL》 * |
| 商晓辉: "SBA-15的表面改性及介孔La0.8Sr0.2CoO3型催化剂的制备", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111229238A (en) * | 2020-02-27 | 2020-06-05 | 湘潭大学 | Ordered porous perovskite catalyst for synergistically catalyzing and oxidizing NO and toluene and preparation method and application thereof |
| CN111229238B (en) * | 2020-02-27 | 2023-03-14 | 湘潭大学 | Ordered porous perovskite catalyst for synergistically catalyzing and oxidizing NO and toluene and preparation method and application thereof |
| CN114425395A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Porous perovskite type sulfur-tolerant shift catalyst and preparation method and application thereof |
| CN114425395B (en) * | 2020-10-10 | 2024-02-20 | 中国石油化工股份有限公司 | Porous perovskite sulfur-resistant shift catalyst and preparation method and application thereof |
| CN115779937A (en) * | 2022-11-25 | 2023-03-14 | 南昌航空大学 | Method for activating surface lattice oxygen of perovskite type oxide and application |
| CN115779937B (en) * | 2022-11-25 | 2023-09-15 | 南昌航空大学 | Method for activating lattice oxygen on surface of perovskite oxide and application of method |
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