CN106807396B - A kind of spherical soot combustion catalyst of monodisperse micron and its preparation method and application - Google Patents
A kind of spherical soot combustion catalyst of monodisperse micron and its preparation method and application Download PDFInfo
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- CN106807396B CN106807396B CN201611227939.7A CN201611227939A CN106807396B CN 106807396 B CN106807396 B CN 106807396B CN 201611227939 A CN201611227939 A CN 201611227939A CN 106807396 B CN106807396 B CN 106807396B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 239000004071 soot Substances 0.000 title claims abstract description 39
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012798 spherical particle Substances 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical group OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- -1 transition metal salt Chemical class 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 39
- 239000002131 composite material Substances 0.000 description 18
- 238000001354 calcination Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J23/70—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
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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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
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
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- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a kind of spherical soot combustion catalysts of monodisperse micron and its preparation method and application, the catalyst is monodisperse micron spherical particle transition metal oxide type catalyst, the spherical particle size distribution of monodisperse micron is 200~1000 nm, and the catalyst contains transition metal element Mn.The catalyst of the method for the invention preparation is free of any noble metal, and low in cost, yield is efficient, is not necessarily to professional equipment, has great industrialization production value.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of single point for purifying soot in exhaust gas from diesel vehicle
Dissipate spherical soot combustion catalyst of micron 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 contact of the active site with carbon particle in default of porous structure and then lead to catalyst activity
It is too low, or because the preparation cost of porous structure is excessively high, or high cost and easy Poisoning because of noble metal, thus
It is unfavorable for the sizable application of carbon soot particles oxidation catalyst.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of that present invention to provide a kind of spherical soot combustion catalysts of monodisperse micron
And its preparation method and application.
On the one hand, the present invention provides a kind of soot combustion catalysts, which is characterized in that the catalyst is that monodisperse is micro-
Rice spherical particle transition metal oxide type catalyst, the spherical particle size distribution of monodisperse micron are 200~1000nm,
The catalyst contains transition metal element Mn.
Material of the present invention has crystallization structure, and monodispersed micron spherical morphology, uniform particle diameter, in solid dirt is presented
There is potential application foreground in terms of the combustion degradation for contaminating object.
Preferably, further include transition metal element Cu in the catalyst, wherein the molar ratio of Cu/Mn be no more than 1,
Preferably no more than 0.7.After mixing Cu in Mn oxide, (the comparison soot conversion of catalytic activity, especially high-temperature catalytic activity
Rate reaches characteristic temperature T when 90%90) significantly improve；And Cu/Mn ratio influences significantly catalytic activity, and optimal is Cu/Mn
=1:1.
Preferably, the specific surface area of the catalyst is 2~50m2/ g, preferably 5~10m2/g；Pore size be 5~
150nm, preferably 10~132nm；0.01~0.50cm of Kong Rongwei3/ g, preferably 0.02~0.10cm3/g。
On the other hand, the present invention also provides the preparation methods of the spherical soot combustion catalyst of monodisperse micron, by transition
Metal salt solution A and alkaline solution B stirs certain time after quickly mixing, then at 400~600 DEG C after centrifugation washing, dry
Lower calcining 1~5 hour, obtains the spherical soot combustion catalyst of monodisperse micron.
The present invention uses a kind of improved coprecipitation of preparation method-of cheap and simple, specifically, by alkaline solution
(precipitant solution) and transition metal salt solution quickly mix so that the two fast reaction and homogeneous nucleation, then in stirring later
It mixes each nucleus in ageing process and synchronizes and grow up, the product of uniform particle diameter has been finally obtained after calcining, that is, a kind of and carbon is prepared
The base metal base high activated catalyst (the spherical soot combustion catalyst of monodisperse micron) of high efficiency particulate contact.Institute in the present invention
Method is stated convenient for operation and amplification production, raw material is cheap and easy to get, is not necessarily to professional equipment, has great industrial application prospect.
Preferably, the transition metal salt is the nitrate of Cu or manganese, acetate, at least one in sulfate, chloride
Kind, the molar concentration of the middle transition metal ions of the transition metal salt solution A is 0.01~0.50mol/L.
Preferably, solute is bicarbonate or/and carbonate, preferably bicarbonate in the alkaline solution B.The carbon
Hydrochlorate is ammonium carbonate or/and sodium carbonate, and the bicarbonate is sodium bicarbonate or/and ammonium hydrogen carbonate, in order to precipitated
A large amount of CO are formed in the process2Gas.The concentration of the alkaline solution B is 0.5~5.0mol/L.
Preferably, the volume ratio of the transition metal salt solution A and alkaline solution B is (0.1~10): 1, preferably (0.5
~5): 1.
Preferably, the stirring for stirred under 0~100 DEG C (preferably 0~40 DEG C, more preferably room temperature) 5 minutes~
24 hours.
Preferably, the heating rate of the calcining is 0.5~10 DEG C, preferably 1 DEG C/min.
Preferably, the transition metal salt solution A and alkaline solution B hybrid mode are that alkaline solution B is quickly poured into transition
In metal salt solution A, transition metal salt solution A is quickly poured into alkaline solution B or transition metal salt solution A and alkaline solution B
Parallel-flow precipitation, preferably alkaline solution B are quickly poured into transition metal salt solution A.Wherein transition metal salt solution A and alkalinity are molten
The rate of liquid B quickly mixed is > 50mL/min.
In another aspect, the present invention also provides a kind of above-mentioned spherical soot combustion catalysts of monodisperse micron of stating in motor vehicle
Application in vent gas treatment.The spherical soot combustion catalyst of monodisperse micron prepared by the present invention can be by carbon soot particles 360
DEG C or less burning it is complete.
The present invention provides a kind of spherical soot combustion catalyst of monodisperse micron and preparation method thereof, the material is with altogether
The precipitation method are made, and generate under low temperature (0~40 DEG C), do not add any organic matter, and crystallization is good after calcining, and it is micro- that monodisperse is presented
Rice spherical morphology, and uniform particle diameter, can be complete in 360 DEG C or less burnings by carbon soot particles.The catalyst of this method preparation is not
Low in cost containing any noble metal, yield is efficient, is not necessarily to professional equipment, has great industrialization production value.
Detailed description of the invention
Fig. 1 is the transmission electron microscope figure of CuMn composite oxide catalysts obtained by the embodiment of the present invention 1；
Fig. 2 is the element surface scan figure picture of CuMn composite oxide catalysts obtained by the embodiment of the present invention 1；
Fig. 3 is the X ray diffracting spectrum of CuMn composite oxide catalysts obtained by the embodiment of the present invention 1；
Fig. 4 is MnO obtained by the embodiment of the present invention 2δThe scanning electron microscope diagram of oxide catalyst；
Fig. 5 is MnO obtained by the embodiment of the present invention 2δThe X ray diffracting spectrum of oxide catalyst；
Fig. 6 is the CuMn composite oxide catalysts of 1-4 of embodiment of the present invention preparation in NOx/O2To carbon soot particles in atmosphere
Catalyzed conversion effect picture；
Fig. 7 is that the present invention uses CuMn composite oxide catalysts obtained by different hybrid modes in NOx/O2In atmosphere
To the catalyzed conversion effect picture of carbon soot particles, wherein 4 just fall, 1 instead, 3 positive drops, 2 anti-drops；
Fig. 8 is SEM image of the present invention using CuMn composite oxide catalysts obtained by different hybrid modes, wherein
A just falls, b instead, c just drips, d is counter drips.
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 heretofore described spherical soot combustion catalyst of monodisperse micron is the transition metal oxide type of well-crystallized
Catalyst includes transition metal element Mn or Cu+Mn.The pattern of the spherical soot combustion catalyst of monodisperse micron is
Well dispersed micron ball particle, diameter can be 200~1000nm.
The heretofore described spherical soot combustion catalyst of monodisperse micron is made using improved coprecipitation.With
Under illustratively illustrate the preparation method of the spherical soot combustion catalyst of monodisperse micron provided by the invention.
A certain amount of, a certain proportion of raw material is dissolved into a certain amount of solvent (such as water, alcohol solution etc.) and is obtained
To transition metal salt solution A (hereinafter referred to as solution A).Raw material can be the nitrate of Cu or Mn, acetate, sulfate
Or one or more of chloride.In solution A the concentration of metal ion can be 0.01~0.50mol/L, preferably 0.10~
0.30mol/L.When selecting mantoquita and manganese salt simultaneously, the ratio of Cu/Mn can be 0~1, preferably 0~0.7 in solution A.
Precipitating reagent is dissolved into a certain amount of solvent (such as water, alcohol solution etc.) and obtains alkaline solution B.Alkaline solution
Precipitating reagent used in B can be bicarbonate, the alkaline matters, preferably carbonic acid such as carbonate (such as ammonium carbonate or/and sodium carbonate)
Hydrogen salt (such as ammonium hydrogen carbonate, sodium bicarbonate etc.).The concentration of precipitating reagent can be 0.5~5.0mol/L in gained alkaline solution B, excellent
It is selected as 0.5~1.0mol/L.
Under stirring condition, solution A, alkaline solution B are mixed, certain time is stirred under certain temperature, generates precipitating.Wherein
Solution A, alkaline solution B hybrid mode can be that alkaline solution B is quickly poured into solution A and (just falls) or solution A is quickly poured into alkali
Property solution B in (instead), alkaline solution B instill (positive drop) or solution A in solution A instill in alkaline solution B it is (anti-drop) or molten
Liquid A, alkaline solution B parallel-flow precipitation, preferably alkaline solution B are quickly poured into solution A and (just fall).Positive and negative difference is: heavy
It is positive and adds in shallow lake agent solution addition transition metal salt solution, otherwise add to be anti-.It drips and is with the difference fallen: by the way of being added dropwise
When, it can be 1-50mL/min that speed, which is added,.When being quickly poured by the way of (plus), speed is added and is generally more than
50mL/min, preferably greater than 600mL/ minute, more preferably above 1200mL/min.Solution A, alkaline solution B mixing can be can be 0
It carries out at~100 DEG C, preferably 0~40 DEG C, is more preferably carried out at 25 DEG C of room temperature, it is more energy saving.Solution A, alkaline solution B are mixed
Closing the time is 5 minutes to 24 hours, preferably 10 minutes to 1 hour, can complete in the short time to react.The solution A and alkali
The volume ratio of property solution B can be (0.1~10): 1, preferably (0.5~5): 1.
Deposit is calcined after centrifugation washing and being dried under certain condition after centrifugation washing, dry
Obtain oxide.Calcination atmosphere can be static or moving air, preferably still air.The temperature of calcining can be 400~600
DEG C, preferably 450~550 DEG C, more preferably 500 DEG C can cause crystallization degree moderate in preference temperature section calcining, while single
Dispersion micron ball pattern can be kept.Calcination time can be 1~5 hour, preferably 2 hours.When calcining with 0.5~10 DEG C/
The speed of minute (preferably 1 DEG C/min) is warming up to calcination temperature, after keeping the temperature a period of time, furnace cooling.
Soot combustion catalyst prepared by the present invention is monodisperse micron spherical particle transition metal oxide type catalyst,
Particle diameter distribution is 200~1000nm between particle.The obtained Mn oxide of the present invention or CuMn composite oxides are because of its tool
There is special monodisperse micron spherical morphology and be conducive to contact with being sufficiently mixed for the carbon particle of torispherical, and then increases carbon
The contact site of grain-catalyst, finally increases its catalytic activity.In fields such as motor vehicle (especially diesel vehicle) vent gas treatments
There is potential application foreground.
The present invention obtains the soot combustion catalyst of high activity using the method for very cheap and simple.
It can be 2~50m by the specific surface area that BET method or/instrument can obtain catalyst prepared by the present invention2/g。
It can be 5~150nm that catalyst pore size prepared by the present invention, which can be obtained, by BJH method or/instrument, and Kong Rongke is
0.01~0.50cm3/g。
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 manganese nitrate solution of the copper nitrate of 3.75mmol and 3.75mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, B is quickly poured into A that (the added-time adds
Enter speed 1800mL/min), it reacts 30 minutes at room temperature.After centrifugation washing and being dried, in static atmosphere of air
Final product is obtained in 500 DEG C of calcining 2h.The specific surface area of CuMn composite oxide catalysts (Cu1Mn1) manufactured in the present embodiment
For 8m2/ g, pore size 10-132nm, Kong Rongwei 0.04cm3/g。
Fig. 1 is transmission electron microscope (TEM) figure of CuMn composite oxide catalysts obtained by the embodiment of the present invention.
Visible products therefrom is monodispersed micron spherical particle in figure, particle diameter distribution narrow (particle size is about 200~1000nm),
High dispersive, and rough surface.These shape characteristics are conducive to contact of the carbon particle with catalyst granules, and then promote catalytic
The raising of energy.
Fig. 2 is the element surface scan figure picture of CuMn composite oxide catalysts obtained by the embodiment of the present invention.It can in figure
See, tri- element of Cu, Mn, O is uniformly distributed on micron ball, has no apparent component segregation.
Fig. 3 is the X ray diffracting spectrum of CuMn composite oxide catalysts obtained by the embodiment of the present invention.It can in figure
See, products therefrom crystallization is good.
Embodiment 2
The manganese nitrate solution of 7.5mmol is dissolved in 30 milliliters of water and obtains solution A, by 0.03mol NaHCO3It is dissolved into 30
Alkaline solution B is obtained in milliliter water.Under stirring condition, B is quickly poured into A (addition of falling added-time speed 1800mL/min), room temperature
Lower reaction 30 minutes.After centrifugation washing and being dried, whole production is obtained in 500 DEG C of calcining 2h in static atmosphere of air
Object.MnO manufactured in the present embodimentδThe specific surface area of oxide catalyst is 21m2/ g, pore size 33nm, Kong Rongwei
0.22cm3/g。
Fig. 4 is MnO obtained by the embodiment of the present inventionδScanning electron microscope (SEM) figure of oxide catalyst.In figure
It can be seen that products therefrom is monodispersed micron spherical particle, particle diameter distribution narrow (about 200~600nm), high dispersive.These shapes
Looks feature is conducive to coming into full contact with for carbon particle and catalyst granules, and then promotes the raising of catalytic performance.
Fig. 5 is MnO obtained by the embodiment of the present inventionδThe X ray diffracting spectrum of oxide catalyst.As it can be seen that institute in figure
It is higher to obtain product crystallization degree.
Embodiment 3
The manganese nitrate solution of the copper nitrate of 5.0mmol and 2.5mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, B is quickly poured into A that (the added-time adds
Enter speed 1800mL/min), it reacts 30 minutes at room temperature.After centrifugation washing and being dried, in static atmosphere of air
Final product is obtained in 500 DEG C of calcining 2h.The specific surface area of CuMn composite oxide catalysts (Cu2Mn1) manufactured in the present embodiment
For 22m2/ g, pore size 10-143nm, Kong Rongwei 0.16cm3/g。
Embodiment 4
The manganese nitrate solution of the copper nitrate of 2.5mmol and 5.0mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, B is quickly poured into A that (the added-time adds
Enter speed 1800mL/min), it reacts 30 minutes at room temperature.After centrifugation washing and being dried, in static atmosphere of air
Final product is obtained in 500 DEG C of calcining 2h.The specific surface area of CuMn composite oxide catalysts (Cu1Mn2) manufactured in the present embodiment
For 22m2/ g, pore size 28nm, Kong Rongwei 0.18cm3/g。
Effect example
The spherical soot combustion catalyst of monodisperse micron to verify of the invention urges carbon soot particles in exhaust gas from diesel vehicle
Change removal effect, spy's simulation exhaust gas from diesel vehicle condition designs and carry out in laboratory conditions following experiment.
Embodiment 5
CuMn composite oxide catalysts, the 0.01g by the embodiment 1-4 0.1g prepared are packed into fixed bed reactors
Carbon soot particles, 1g quartz sand particle composition mixture, be passed through following gaseous mixture at room temperature: the concentration of NO is 500ppm, O2
Concentration be 10 (V) %, N2For Balance Air, total flow 0.2L/min.As a comparison, by 0.1g's in another test
The removal of CuMn composite oxide catalysts, other conditions are constant.Catalyst is to soot in 100~700 DEG C of temperature ranges of test
The changing effect of grain, is as a result listed in Fig. 6, it is known that the CuMn composite oxide catalysts of the 0.1g prepared using embodiment 1 can
It is carbon soot particles are complete in 360 DEG C or less burnings, it is known that the CuMn composite oxides of the 0.1g prepared using embodiment 2,3,4 are urged
Agent can be complete by burning at 441 DEG C, 399 DEG C, 435 DEG C respectively for carbon soot particles.It can also learn that manganese is aoxidized from Fig. 6
After mixing Cu in object, (comparison soot conversion ratio reaches characteristic temperature when 90% for catalytic activity, especially high-temperature catalytic activity
T90) significantly improve；And Cu/Mn ratio influences significantly catalytic activity, and optimal is Cu/Mn=1:1.
Comparative experiments group
The manganese nitrate solution of the copper nitrate of 3.75mmol and 3.75mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, following 4 kinds of mixing sides are respectively adopted
Formula: alkaline solution B is quickly poured into solution A and (just falls, the addition of falling added-time speed 1800mL/min) or solution A is quickly poured into alkali
Property solution B in (instead the addition of falling added-time speed 1800mL/min), alkaline solution B instill in solution A that (positive drop, when dropwise addition are added
Speed is 7.5mL/min) or solution A instill in alkaline solution B (anti-drop, it is 7.5mL/min that speed, which is added, in when dropwise addition).Then
It reacts 30 minutes at room temperature.After centrifugation washing and being dried, obtained in static atmosphere of air in 500 DEG C of calcining 2h
Final product.
Fig. 8 is SEM image of the present invention using CuMn composite oxide catalysts obtained by different hybrid modes, wherein
A just falls, b instead, c just drips, d is counter drips, as can be known from Fig. 8 in the case where same materials, using fall plus method height can be obtained
The uniform micron ball of dispersion particle diameter, and the product that method obtains is added dropwise and sticks to each other.
The CuMn combined oxidation by comparative example 1 using the 0.1g of different hybrid modes preparation is packed into fixed bed reactors
The mixture that object catalyst, the carbon soot particles of 0.01g, 1g quartz sand particle form, be passed through following gaseous mixture at room temperature: NO's is dense
Degree is 500ppm, O2Concentration be 10 (V) %, N2For Balance Air, total flow 0.2L/min.Test 100~700 DEG C of humidity provinces
As a result interior catalyst is listed in Fig. 7 to the changing effect of carbon soot particles, it is known that the activity sequence of gained sample are as follows: instead just fall >
> anti-drop > is just dripped.
Embodiment 6
The manganese nitrate solution of the copper nitrate of 5.0mmol and 2.5mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, B is quickly poured into A that (the added-time adds
Enter speed 1200mL/min), it reacts 30 minutes at room temperature.After centrifugation washing and being dried, in static atmosphere of air
Final product is obtained in 500 DEG C of calcining 2h.
Embodiment 7
The manganese nitrate solution of the copper nitrate of 5.0mmol and 2.5mmol is dissolved in 30 milliliters of water and obtains solution A, it will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains alkaline solution B.Under stirring condition, B is quickly poured into A that (the added-time adds
Enter speed 600mL/min), it reacts 30 minutes at room temperature.By centrifugation washing and be dried after, in static atmosphere of air in
500 DEG C of calcining 2h obtain final product.
In summary as it can be seen that catalyst provided by the invention, has monodisperse micron spherical morphology, uniform particle sizes, crystallization
Well.Coprecipitation simple economy provided by the present invention, raw material is cheap, versatility with higher.This catalyst is solid
There is potential application foreground in terms of the combustion degradation of body pollution object.
Be it is necessary to described herein finally: above embodiments are served only for making technical solution of the present invention further detailed
Ground explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention
The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.
Claims (3)
1. a kind of application of soot combustion catalyst in exhaust gas from diesel vehicle in the catalytic eliminating of carbon soot particles, feature exist
In the catalyst is monodisperse micron spherical particle transition metal oxide type catalyst, spherical of the monodisperse micron
Grain particle diameter distribution is 200~1000 nm, and the transition metal element in the catalyst is Mn and Cu, wherein the molar ratio of Cu/Mn
Example is 1:1 or 2:1；
The soot combustion catalyst is prepared by following methods: after transition metal salt solution A and alkaline solution B are quickly mixed
Certain time is stirred, then is calcined 1~5 hour at 400~600 DEG C after centrifugation washing, dry, the monodisperse micron is obtained
Spherical soot combustion catalyst；
The transition metal salt solution A and alkaline solution B hybrid mode are that alkaline solution B is quickly poured into transition metal salt solution A
In or transition metal salt solution A be quickly poured into alkaline solution B；
The transition metal salt is the nitrate of Cu or manganese, acetate, at least one of sulfate, chloride, the transition
The molar concentration of the middle transition metal ions of metal salt solution A is 0.01~0.50mol/L；
Solute is bicarbonate or/and carbonate in the alkaline solution B, and the concentration of the alkaline solution B is 0.5~5.0
mol/L；The volume ratio of the transition metal salt solution A and alkaline solution B is (0.1~10): 1.
2. application according to claim 1, which is characterized in that the specific surface area of the catalyst is 2~50m2/ g, aperture
Size is 5~150nm, 0.01~0.50 cm of Kong Rongwei3/g。
3. application according to claim 1, which is characterized in that the stirring is the stirring 5 minutes~24 at 0~100 DEG C
Hour.
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| CN101811052A (en) * | 2010-04-16 | 2010-08-25 | 济南大学 | Diesel vehicle soot combustion catalyst prepared by taking hydrotalcite-like compound as precursor and preparation method thereof |
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| CN101811052A (en) * | 2010-04-16 | 2010-08-25 | 济南大学 | Diesel vehicle soot combustion catalyst prepared by taking hydrotalcite-like compound as precursor and preparation method thereof |
| CN103691481A (en) * | 2013-12-23 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Supported hierarchical pore Beta molecular sieve based catalyst and preparation method and application thereof |
| CN104383962A (en) * | 2014-12-01 | 2015-03-04 | 中国科学院上海硅酸盐研究所 | Base metal load type multistage pore zeolite molecular sieve catalyst of efficient catalytic combustion soot particles and preparation and application of catalyst |
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