CN106807385B - A kind of soot combustion catalyst of nest like and its preparation method and application - Google Patents
A kind of soot combustion catalyst of nest like and its preparation method and application Download PDFInfo
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- CN106807385B CN106807385B CN201611226589.2A CN201611226589A CN106807385B CN 106807385 B CN106807385 B CN 106807385B CN 201611226589 A CN201611226589 A CN 201611226589A CN 106807385 B CN106807385 B CN 106807385B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 239000004071 soot Substances 0.000 title claims abstract description 52
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002070 nanowire Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 238000009825 accumulation Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000975 co-precipitation Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- B01J35/56—
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/647—
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
Abstract
The present invention relates to soot combustion catalysts of a kind of nest like and its preparation method and application, the soot combustion catalyst of the nest like is the compound oxide type catalyst with nest like structure and morphology made of nano wire accumulation, and the compound oxide type catalyst contains transition metal element Cu+Ce+Zr.The present invention prepares soot combustion catalyst using homogeneous co-precipitation process, and calcined product crystallization is good, carbon soot particles can be made to reach maximum combustion rate at 400 DEG C or so, and have extraordinary water-fast sulfur tolerance.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to the one kind purified for carbon soot particles in exhaust gas from diesel vehicle
Soot combustion catalyst of nest like and its preparation method and application.
Background technique
Diesel vehicle is widely used in real life due to advantages such as its economy, thermal effect height and voyage length.
However, the particulate matter (PM, predominantly carbon black granules) and nitrogen oxides of diesel emission have seriously endangered environment and the mankind, because
This, efficient post-processing purification process is imperative.In general, a particulate filter (DPF) is used to collect exhaust gas from diesel vehicle
In carbon black granules, the carbon black granules of collection can be in a quite high temperature (> 600 DEG C) by O2Oxidation.However, diesel engine
Delivery temperature generally at 150 to 400 DEG C, lower temperature makes it difficult for the carbon black granules in tail gas to be burnt, and makes for a long time
DPF is caused to inactivate after.Therefore, a kind of efficient catalyst is developed, making carbon black granules, complete oxidation is at a lower temperature
One extremely urgent work.
It is commonly used in the catalyst of carbon soot particles oxidation, such as: CeO2Based compound, perovskite oxide, noble metal base
Catalyst etc., or be unfavorable for active site and carbon particle come into full contact with and then cause catalyst in default of porous structure
Activity is too low, or because the preparation cost of porous structure is excessively high, or high cost and easy Poisoning because of noble metal,
To limit its sizable application.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide it is a kind of it is with porous structure, catalytic activity is high, and have
There are the non-noble metal-based catalysts of preferable resistant to sulfur water resistance.
On the one hand, the present invention provides a kind of soot combustion catalyst of nest like, the carbon-smoke combustion of the nest like is urged
Agent is the compound oxide type catalyst with nest like structure and morphology made of nano wire accumulation, the compound oxide type
Catalyst contains transition metal element Cu+Ce+Zr.
Crystallization is good after firing for the soot combustion catalyst of nest like of the present invention, but also has by nano wire heap
Nest like structure and morphology made of product can make carbon soot particles reach most fast burn rate at 400 DEG C or so, and have good
Water-fast sulfur tolerance has potential application foreground in terms of the combustion degradation of solid pollutant.
Preferably, the molar ratio of Cu:Ce:Zr is x:(100-x-y in the soot combustion catalyst of the nest like): y,
Wherein x+y < 50, and x and y are not 0.Cu, being uniformly distributed for tri- element of Ce, Zr are also beneficial to concerted catalysis between three simultaneously
The realization of effect.Wherein CeO2 can large supply active oxygen, Zr can adulterate into CeO2Lattice simultaneously improves its thermal stability and increases
Add activity, CuO stimulating activity oxygen and then can be reacted with carbon soot particles.
Preferably, in the soot combustion catalyst of the nest like nano wire diameter be 1~10nm, length be 50~
500nm。
Preferably, the specific surface area of the catalyst is 100~200m2/ g, pore size are 20~50nm, Kong Rongwei
0.50-1.00cm3/g。
On the other hand, the present invention also provides a kind of preparation methods of the soot combustion catalyst of nest like, comprising:
Precipitating reagent is added in the solution A containing the source Cu, the source Ce and the source Zr and arrives solution B；
Acquired solution B is handled 4~10 hours at 70~95 DEG C, obtains product C；
Products therefrom C is handled 5~20 hours at 90~100 DEG C, then after centrifugation washing, drying and calcination, is obtained
The soot combustion catalyst of the nest like.
The present invention prepares the soot combustion catalyst of the nest like using homogeneous co-precipitation process.Specifically, it will first sink
Shallow lake agent is added in the solution A containing the source Cu, the source Ce and the source Zr, and it is anti-that precipitating occurs after handling 4~10 hours at 70~95 DEG C
It answers, obtains product C.Products therefrom C will be handled 5~20 hours at 90~100 DEG C, so that product cures, stablizes.Then again
Be centrifuged, dry after obtain desciccate.By gained desciccate after calcining, the bird that crystallization is good, catalytic activity is high is obtained
The soot combustion catalyst of nido.This method is low in cost, and yield is efficient, is not necessarily to professional equipment, has great industry metaplasia
Produce value.
Preferably, the source Cu is at least one of the nitrate of Cu, acetate, sulfate, chloride, the source Ce
For at least one of the nitrate of Ce, acetate, sulfate, chloride, the source Zr is nitrate, acetate, the sulphur of Zr
At least one of hydrochlorate, chloride, the molar concentration of the middle metal ion of the solution A are 0.01~0.50mol/L.
Preferably, the precipitating reagent is the substance that hydrolysis or decomposition can generate ammonia, preferably urea, ammonium carbonate, grass
At least one of sour ammonium.
Preferably, the concentration of precipitating reagent is 1~5mol/L in the solution B.
Preferably, the temperature of the calcining is 350~600 DEG C, the time is 1~5 hour.
Preferably, the heating rate of the calcining is 0.5-10 DEG C/min, preferably 1 DEG C/min.
In another aspect, the present invention also provides a kind of soot combustion catalysts of nest like in motor-driven vehicle gas disposal
Using.
Soot combustion catalyst of the present invention is a kind of composite oxide catalysts without precious metal, be can be used to effectively
The burning of carbon soot particles in ground catalytic diesel oil tail gas.
The present invention is prepared with homogeneous co-precipitation process, and calcined product crystallization is good, and carbon soot particles can be made to reach at 400 DEG C or so
To maximum combustion rate, and there is extraordinary water-fast sulfur tolerance.This method is low in cost, and yield is efficient, sets without profession
It is standby, there is great industrialization production value.The homogeneous co-precipitation process is inexpensively easy convenient for operation and amplification production, raw material
, it is not necessarily to professional equipment, there is great industrial application prospect.
Detailed description of the invention
Fig. 1 is CuCeZrO obtained in embodiment 1xThe transmission electron microscope photo and element of composite oxides point
Butut；
Fig. 2 is CuCeZrO obtained in embodiment 1xThe X ray diffracting spectrum of composite oxides；
Fig. 3 is CuCeZrO obtained in embodiment 1xThe nitrogen adsorption desorption curve and graph of pore diameter distribution of composite oxides；
Fig. 4 is CuCeZrO in embodiment 2xComposite oxides are in NOx+O2And NOx+O2+SO2+H2Under two kinds of different atmospheres of O
To the catalyzed conversion effect picture of carbon soot particles；
Fig. 5 is CuCeZrO in embodiment 3xComposite oxides are to carbon monoxide, the total catalytic effect of propylene and propane.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The soot combustion catalyst of heretofore described nest like is compound oxide type catalyst, and the catalyst is free of
Any noble metal and well-crystallized.And the soot combustion catalyst of nest like of the present invention is to accumulate with nano wire
Nest like structure and morphology.Wherein the diameter of the nano wire is 1~10nm, and length is 50~500nm.The catalyst contains
Transition metal element Cu+Ce+Zr.
In the present invention, the molar ratio of Cu:Ce:Zr is x:(100-x-y in the soot combustion catalyst of the nest like):
Y, wherein x+y < 50, and x and y are not 0.
The present invention using unusual cheap and simple method (improved homogeneous co-precipitation process), obtain high activity, it is high
The soot combustion catalyst of resistant to sulfur, high water resistance characteristic.Illustrate to following exemplary the carbon-smoke combustion of nest like provided by the invention
The preparation method of catalyst.
A certain amount of, a certain proportion of raw material (source Cu, the source Ce and the source Zr) is dissolved into a certain amount of water obtain it is molten
Liquid A.Raw material can be one or more of nitrate, acetate, sulfate or chloride of Cu, Ce or Zr.Wherein
The source Cu, the source Ce or the source Zr are preferably nitrate.The concentration of metal ion (Cu ion, Ce ion and Zr ion) in solution A can
For 0.01~0.50mol/L, preferably 0.10-0.30mol/L.The molar ratio of Cu:Ce:Zr is x:(100-x- in solution A
Y): y, wherein x+y < 50, and x and y are not 0, preferably 23:54:23.
A certain amount of precipitating reagent is dissolved into A and obtains solution B.Heretofore described precipitating reagent can be pyrohydrolysis generation
The substance of ammonia, preferably urea, ammonium carbonate, ammonium oxalate etc., more preferably urea.Precipitating reagent used can be 1 in the solution B
~5mol/L, preferably 1.5-3.0mol/L.
Under certain temperature, solution B is made to be stirred to react certain time, obtains solution C.The treatment temperature of solution B can be 70-95
DEG C, preferably 75-85 DEG C, conducive to homogeneous precipitation is obtained.Handling the time can be 4-10h, preferably 5-8h.As a kind of preferred side
Case, the treatment temperature of solution B are 75-85 DEG C, and the processing time is 5-8h.
Under certain temperature, certain time is handled to solution C, so that product cures, stablizes.The treatment temperature of solution C can be
90-100 DEG C, preferably 95 DEG C, conducive to the mutually stable sediment of structure, object is obtained.Handling the time can be 5-20h, preferably 8-
15h.As a preferred embodiment, the treatment temperature of solution C is 95 DEG C, and the processing time is 8-15h.
After solution C processing, desciccate is obtained by centrifugation washing and after being dried.By gained desciccate one
Calcining obtains oxide, last furnace cooling under fixed condition.The calcination condition of desciccate be still air or moving air, it is excellent
It is selected as still air.Calcination temperature can be 350-600 DEG C, preferably 350-500 DEG C.Calcination time can be 1-5h, preferably 2h.
The heating rate of calcining can be 0.5-10 DEG C/min, preferably 1 DEG C/min.As a preferred embodiment, the calcination condition
Be: in still air, 1 degree is warming up to 350-500 DEG C per minute, calcines 2h, furnace cooling.
The specific surface area for the catalyst that the present invention can must be prepared by BET method or/instrument can be 100~200m2/g。
The present invention can be 20~50nm by the catalyst pore size that BJH method or/instrument can must be prepared.
0.50~the 1.00cm of Kong Rongwei for the catalyst that the present invention can must be prepared by BJH method or/instrument3/g。
The soot combustion catalyst of nest like prepared by the present invention, in motor vehicle (especially diesel vehicle) vent gas treatment etc.
There is potential application foreground in field.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
The Cu of 52.35mmol will be amounted to, the nitrate of Ce, Zr are dissolved in 225mL water, and Cu/Ce/Zr molar ratio is 23:54:
23, the urea of 451.85mmol is added after dissolving completely, is stirred to react 6.5h in 80 DEG C of water-baths after stirring and dissolving；Sealing
Afterwards, continue to handle 11h in 95 DEG C of drying boxes；It is calcined after cleaning-drying: 350 DEG C of calcining 2h in still air, 1 degree every deciliter
Temperature, furnace cooling.The specific surface area that the present embodiment prepares catalyst is 186m2/ g, aperture 33nm, Kong Rongwei 0.90cm3/g。
Fig. 1 is the resulting CuCeZrO of the embodiment of the present inventionxThe transmission electron microscope photo and element of composite oxides
Distribution map, it is seen that in micro-meter scale, product is accumulated in a jumble by nano wire, forms the appearance structure of nest like, wherein institute
The diameter for stating nano wire in the soot combustion catalyst of nest like is 1~10nm, and length is 50~500nm.The soot of nest like
The combustion catalyst structure is conducive to the carbon particle in catalyst capture air-flow, and then realizes the abundant of active site and reactant
Contact.Cu, tri- element of Ce, Zr are uniformly distributed the realization for being also beneficial to synergic catalytic effect between three simultaneously；
Fig. 2 is the resulting CuCeZrO of the embodiment of the present inventionxThe X ray diffracting spectrum of composite oxides, visible gained in figure
Product crystallization is good；
Fig. 3 is the resulting CuCeZrO of the embodiment of the present inventionxThe nitrogen adsorption desorption curve and pore-size distribution of composite oxides
Figure.Visible product pore-size distribution is narrow, is 20-50nm.
Effect example
To verify CuCeZrO of the inventionxComposite oxide catalysts are de- to the catalysis of carbon soot particles in exhaust gas from diesel vehicle
Except effect, spy's simulation exhaust gas from diesel vehicle condition designs and carries out in laboratory conditions following experiment.
Embodiment 2
The CuCeZrO of the 0.1g prepared by 1 method of embodiment is packed into fixed bed reactorsxComposite oxide catalysts
With the carbon soot particles mixture of 0.01g, be passed through following gaseous mixture at room temperature: the concentration of NO is 500ppm, O2Concentration be 10
(V) %, total flow 0.2L/min.
As a comparison, another group of test is carried out, above-mentioned atmosphere is changed to: NO 500ppm, O210 (V) %, SO2
100ppm, vapor 10 (V) %, total flow 0.2L/min, other test parameters are constant.
It tests catalyst in 100-700 DEG C of temperature range and as a result Fig. 4 is listed in the changing effect of carbon soot particles.It can be seen that should
Catalyst may make carbon particle in 400-450 DEG C of quickly oxidation elimination, and the SO of high concentration is introduced in reaction atmosphere2, H2O is simultaneously
Have no significant effect catalytic activity.
Embodiment 3
The CuCeZrO of the 0.1g prepared by 1 method of embodiment is packed into fixed bed reactorsxComposite oxide catalytic
Agent is passed through following gaseous mixture: CO (0.5%), C at room temperature3H6(400ppm), C3H8(200ppm), O2(5%), nitrogen is balance
Gas, total flow 0.2L/min.
It tests catalyst in 50-430 DEG C of temperature range and as a result Fig. 5 is listed in the changing effect of carbon soot particles.It can be seen that this is urged
Agent can be by carbon monoxide, propylene, and common pollutant is eliminated in 400 DEG C or less complete oxidations in the exhaust gas from diesel vehicle such as propane,
Demonstrate the certain practical potentiality of this catalyst.
To sum up, CuCeZrO of the inventionxComposite oxide catalysts can realize diesel vehicle in lower temperature section
The quick catalysis removing of carbon soot particles in tail gas.The catalyst has excellent resistance to SO_2 and water vapor poisoning capability, applicability
By force, and make and use it is simple and easy, for carbon soot particles in economically and efficiently catalytic eliminating exhaust gas from diesel vehicle have important meaning
Justice and practical value.
Finally it is necessary to explanations: above embodiments are served only for saying technical solution of the present invention in further detail
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention is made
Some nonessential modifications and adaptations all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of soot combustion catalyst of nest like, which is characterized in that the soot combustion catalyst of the nest like be with
The compound oxide type catalyst of nest like structure and morphology made of nano wire accumulation, the compound oxide type catalyst contain
Transition metal element Cu+Ce+Zr；The preparation method of the soot combustion catalyst of the nest like includes:
Precipitating reagent is added in the solution A containing the source Cu, the source Ce and the source Zr and obtains solution B；
Acquired solution B is handled 4~10 hours at 70~95 DEG C, obtains product C；
Products therefrom C is handled 5~20 hours at 90~100 DEG C, then after centrifugation washing, drying and calcination, is obtained described
The soot combustion catalyst of nest like；
Wherein, the temperature of the calcining is 350~600 DEG C, and the time is 1~5 hour.
2. the soot combustion catalyst of nest like according to claim 1, which is characterized in that the soot of the nest like fires
Burning the molar ratio of Cu:Ce:Zr in catalyst is x:(100-x-y): y, wherein x+y < 50, and x and y are not 0.
3. the soot combustion catalyst of nest like according to claim 1, which is characterized in that the soot of the nest like fires
The diameter for burning nano wire in catalyst is 1~10 nm, and length is 50~500 nm.
4. the soot combustion catalyst of nest like according to claim 1, which is characterized in that the soot of the nest like fires
The specific surface area for burning catalyst is 100~200 m2/ g, pore size are 20~50 nm, 0.50~1.00 cm of Kong Rongwei3/g。
5. the soot combustion catalyst of nest like according to claim 1, which is characterized in that the source Cu is the nitric acid of Cu
At least one of salt, acetate, sulfate, chloride, the source Ce are nitrate, acetate, sulfate, the chloride of Ce
At least one of, the source Zr is at least one of the nitrate of Zr, acetate, sulfate, chloride, the solution A
Middle metal ion molar concentration be 0.01~0.50mol/L.
6. the soot combustion catalyst of nest like according to claim 1, which is characterized in that the precipitating reagent be hydrolysis or
Decompose the substance that can generate ammonia.
7. the soot combustion catalyst of nest like according to claim 6, which is characterized in that the precipitating reagent be urea,
At least one of ammonium carbonate, ammonium oxalate.
8. the soot combustion catalyst of nest like according to claim 1, which is characterized in that precipitating reagent in the solution B
Concentration be 1~5 mol/L.
9. a kind of soot combustion catalyst of the nest like as described in any one of claim 1-8 is in motor-driven vehicle gas disposal
Using.
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| CN101024182A (en) * | 2007-01-11 | 2007-08-29 | 清华大学 | Catalyst for eliminating carbon smoke from copper and cerium and preparing method |
| CN101767012A (en) * | 2009-12-25 | 2010-07-07 | 昆明理工大学 | Low-temperature combustion catalyst for eliminating diesel engine carbon black |
| CN102527403A (en) * | 2011-12-27 | 2012-07-04 | 浙江工业大学 | Cerium-based solid solution catalyst and preparation method |
| WO2014197771A1 (en) * | 2013-06-06 | 2014-12-11 | Clean Diesel Technologies, Inc. | Diesel exhaust treatment systems and methods |
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|---|---|---|---|---|
| CN101024182A (en) * | 2007-01-11 | 2007-08-29 | 清华大学 | Catalyst for eliminating carbon smoke from copper and cerium and preparing method |
| CN101767012A (en) * | 2009-12-25 | 2010-07-07 | 昆明理工大学 | Low-temperature combustion catalyst for eliminating diesel engine carbon black |
| CN102527403A (en) * | 2011-12-27 | 2012-07-04 | 浙江工业大学 | Cerium-based solid solution catalyst and preparation method |
| WO2014197771A1 (en) * | 2013-06-06 | 2014-12-11 | Clean Diesel Technologies, Inc. | Diesel exhaust treatment systems and methods |
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