CN106799225A - A kind of potassium support type soot combustion catalyst and its preparation method and application - Google Patents
A kind of potassium support type soot combustion catalyst and its preparation method and application Download PDFInfo
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- CN106799225A CN106799225A CN201611226613.2A CN201611226613A CN106799225A CN 106799225 A CN106799225 A CN 106799225A CN 201611226613 A CN201611226613 A CN 201611226613A CN 106799225 A CN106799225 A CN 106799225A
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- catalyst
- solution
- potassium
- soot combustion
- support type
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 239000004071 soot Substances 0.000 title claims abstract description 50
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 41
- 239000011591 potassium Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 230000001788 irregular Effects 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 42
- 239000012670 alkaline solution Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 239000011812 mixed powder Substances 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical group OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000000779 smoke Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000000975 co-precipitation Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000001052 transient effect Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- 239000010949 copper Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 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
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 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
- B01J23/16—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
- 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
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of potassium support type soot combustion catalyst and its preparation method and application, the catalyst is potassium carrying transition metal oxide type catalyst, the catalyst is nano particle pattern in irregular shape, particle diameter distribution is 20~1000 nm, the content of K is no more than 20 wt% in the potassium support type soot combustion catalyst, and the potassium support type soot combustion catalyst contains transient metal Mn.The present invention obtains the soot combustion catalyst of high activity using the method for very cheap and simple.Described coprecipitation is easy to operate and amplify production, and raw material is cheap and easy to get, without professional equipment, with great commercial application prospect.
Description
Technical field
The invention belongs to catalysis material technical field, and in particular to for a kind of potassium load type carbon of diesel car tail gas refining
Cigarette combustion catalyst and its preparation method and application.
Background technology
Diesel vehicle is widely used due to the advantage such as its economy, thermal effect are high and voyage is long in real life.
However, the particulate matter (PM, predominantly carbon black granules) of diesel emission and nitrogen oxides serious harm environment and the mankind, because
This, efficient post processing purification technique is imperative.Generally, a particulate filter (DPF) is used to collect exhaust gas from diesel vehicle
In carbon black granules, the carbon black granules of collection can an at a relatively high temperature (>600 DEG C) by O2Oxidation.However, diesel engine
Delivery temperature it is general at 150 to 400 DEG C, its relatively low 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, complete oxidation is at a lower temperature to make carbon black granules
One extremely urgent work.
The catalyst of carbon soot particles oxidation is commonly used in, such as：CeO2Based compound, perovskite oxide, noble metal base
Catalyst etc., or be unfavorable for contact of the avtive spot with carbon particle in default of loose structure and then cause catalyst activity
It is too low, or because the preparation cost of loose structure is excessively high, or because the high cost and easy Poisoning of noble metal, so that
It is unfavorable for the sizable application of carbon soot particles oxidation catalyst.Therefore it is badly in need of a kind of preparation method of cheap and simple to obtain non-noble gold
Category base high activated catalyst.
The content of the invention
In view of the shortcomings of the prior art, present invention aim at a kind of potassium support type soot combustion catalyst of offer and its system
Preparation Method and application.
On the one hand, the invention provides a kind of potassium support type soot combustion catalyst, the catalyst is potassium load transitions
Metal-oxide catalyst, the catalyst is nano particle pattern in irregular shape, and particle diameter distribution is 20~1000nm,
The content of K is no more than 20wt% in the potassium support type soot combustion catalyst, and the potassium support type soot combustion catalyst contains
There is transient metal Mn.
Material crystallization of the present invention is good, superior activity, and has preferably recycling performance, in solid pollutant
Combustion degradation aspect have potential application foreground.
It is preferred that the potassium support type soot combustion catalyst also contains transition metal Cu, the transition metal Cu and Mn
Molar ratio be no more than 0.7.
It is preferred that the specific surface area of the catalyst is 5~20m2/ g, pore size is 20~120nm, and pore volume is 0.02
~0.20cm3/g。
On the other hand, present invention also offers a kind of preparation method of potassium support type soot combustion catalyst, including：
Certain hour is stirred after solution A containing manganese salt and mantoquita and alkaline solution B are mixed, then after centrifugation washing, drying
Obtain desciccate；
Desciccate is added in potassium salt soln, mixed powder is obtained after being evaporated at 50~90 DEG C；
Gained mixed powder is calcined 1~5 hour at 400~600 DEG C, the potassium support type soot combustion catalyst is obtained.
The present invention combines coprecipitation and infusion process prepares the potassium support type soot combustion catalyst.Specifically, first
Solution A and alkaline solution B mixing just containing manganese salt and mantoquita, react generation deposit, then after centrifugation, drying
Obtain desciccate.Gained desciccate is uniformly mixed with potassium salt soln, reaction obtains product under low temperature (50~90 DEG C)
(mixed powder), sylvite has been loaded on powder (so-called desciccate) during being somebody's turn to do, and does not use any organic matter during this,
The potassium support type soot combustion catalyst that crystallization is good after calcining, catalysis activity is high.The method is with low cost, and yield is efficient,
Without professional equipment, with great industrialization production value.
It is preferred that the manganese salt is at least one in nitrate, acetate, sulfate, the chloride of Mn, the mantoquita
It is at least one in nitrate, acetate, sulfate, the chloride of Cu, the molar concentration of the middle metal ion of the solution A
It is 0.01~0.50mol/L, preferably 0.10~0.30mol/L.
It is preferred that solute is bicarbonate or/and carbonate, preferably bicarbonate, the alkali in the alkaline solution B
Property solution B concentration be 0.5~5.0mol/L, preferably 0.5~1.0mol/L.
It is preferred that the volume ratio of the solution A and alkaline solution B is (0.1~10)：1.
It is preferred that the stirring is to be stirred 5 minutes~24 hours at 0~100 DEG C, 10 points are stirred preferably at 25 DEG C
Clock~1 hour.
It is preferred that the heating rate of the calcining is 0.5~10 DEG C/min, preferably 1 DEG C/min.
It is preferred that calcination atmosphere can be moving air or still air, preferably still air.
It is preferred that calcining heat is preferably 500 DEG C, calcination time is preferably 2 hours.
It is preferred that the solution A and alkaline solution B hybrid modes be quickly poured into solution A for alkaline solution B in, solution A drop
Enter in alkaline solution B or solution A and alkaline solution B parallel-flow precipitations, preferably alkaline solution B is quickly poured into solution A.
It is preferred that the sylvite is at least one in nitrate, acetate, sulfate, the chloride of K, the sylvite
Mass content be 5~20wt%.
Another further aspect, present invention also offers a kind of potassium support type soot combustion catalyst in motor-driven vehicle gas disposal
Using.
The present invention combines coprecipitation and infusion process, and reaction at low temperature obtains product, any organic matter is not used, through forging
Crystallization is good after burning, and catalysis activity is high, can make carbon soot particles 340 DEG C low-temperature burning completely, and with following well
Ring performance.The present invention obtains the soot combustion catalyst of high activity using the method for very cheap and simple.Described is total to
The precipitation method are easy to operate and amplify production, and raw material is cheap and easy to get, without professional equipment, with great commercial application prospect.
Brief description of the drawings
Fig. 1 is the scanning electron microscope diagram of the potassium support type soot combustion catalyst obtained by the embodiment of the present invention 1；
Fig. 2 is the X ray diffracting spectrum of the potassium support type soot combustion catalyst obtained by the embodiment of the present invention 1；
Fig. 3 is catalytic effect of the potassium support type soot combustion catalyst to soot in the embodiment of the present invention 1；
Fig. 4 is circulation catalytic effect of the potassium support type soot combustion catalyst to soot in the embodiment of the present invention 2.
Specific embodiment
The present invention is further illustrated below by way of following implementation methods, it should be appreciated that following implementation methods are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention combines coprecipitation and infusion process prepares potassium support type soot combustion catalyst, and the catalyst is
Potassium carrying transition metal oxide type catalyst, the catalyst is nano particle pattern in irregular shape, and particle diameter distribution is
20~1000nm, the content of K is no more than 20wt% in the potassium support type soot combustion catalyst.Potassium salts content is too low, is catalyzed
Performance is not good, too high, and volatile loss simultaneously causes high cost.The potassium support type soot combustion catalyst contains transition gold
Category Mn.
Above-mentioned potassium support type soot combustion catalyst also contains transition metal Cu, the mol ratio of the transition metal Cu and Mn
Example is no more than 0.7.
The inventive method is with low cost, and yield efficiently, without professional equipment, is worth with great industrialization production.With
Under exemplarily illustrate the present invention provide potassium support type soot combustion catalyst preparation method.
A certain amount of raw material (manganese source, Cu sources) is dissolved into a certain amount of solvent (such as water, alcohol water mixed solvent
Deng) in obtain the solution A (below can abbreviation solution A) containing manganese salt and mantoquita.Raw material can be the nitrate of Mn, acetic acid
One or more in salt, sulfate or chloride.Mn sources are preferably nitrate.The nitrate of Cu, acetate, sulfate or chlorine
One or more in compound.Cu sources are preferably nitrate.The concentration of metal ion (manganese ion or/and copper ion) in solution A
Can be 0.01~0.50 mol/L, preferably 0.10~0.30 mol/L.The molar ratio of Cu/Mn is 0-0.7 in solution A.
Precipitating reagent is dissolved into a certain amount of solvent (such as water, alcohol water mixed solvent etc.) and obtains alkaline solution B (below
Can abbreviation solution B).Precipitating reagent used by solution B can be bicarbonate (such as sodium acid carbonate, ammonium hydrogen carbonate etc.), carbonate (example
Such as sodium carbonate, ammonium carbonate) etc. alkaline matter, preferably bicarbonate.The concentration of solution B can be 0.5~5.0mol/L, preferably
It is 0.5~1.0mol/L.
Under stirring condition, solution A, solution B mixing stir certain hour under uniform temperature, obtain containing deposit
Mixed solution.The volume ratio of wherein described solution A and alkaline solution B can be (0.1~10)：1.The solution A and solution B it is mixed
Conjunction mode can be that solution B is quickly poured into solution A, or in solution A instillation solution B, or solution A, solution B parallel-flow precipitation, it is excellent
Solution B is elected as to be quickly poured into solution A, quick mixing cause in precipitation process simultaneously homogeneous nucleation, it is synchronous grow up, ultimately result in
The product of uniform particle diameter.When by the way of being quickly poured into, it adds speed to be generally more than 50mL/min, preferably greater than 600ml/
Minute, more preferably above 1200mL/min.When by the way of being added dropwise, it can be 1-50mL/min that it adds speed.It is solution A, molten
Liquid B stirrings can be carried out at 0~100 DEG C, preferably be carried out at 25 DEG C, without being heated or cooled, with energy-saving effect.Stirring
Time can be 5 minutes to 24 hours, preferably be 10 minutes to 1 hour, and reaction is quick, required time is short, saving of work and time).
By mixed solution of the gained containing deposit by after centrifugation washing and dried process, obtaining desciccate.Its
Middle drying temperature can be 60~120 DEG C, and drying time can be 1~24 hour.
By a certain amount of sylvite and desciccate common distribution in solvent (such as water, alcohol water mixed solvent etc.), 50~
90 DEG C of stirrings are evaporated, and obtain mixed powder.Wherein sylvite can be the nitrate of K, acetate, in sulfate or chloride one
Plant or several.The mass content of the sylvite is 5~20wt%.
Gained mixed powder is calcined under certain condition and obtains furnace cooling after oxidation product.Be can obtain by calcining steady
Fixed oxide catalyst.The calcination condition for mixing vermicelli can be static or moving air, preferably still air.Calcining heat
It can be 400~600 DEG C, preferably 500 DEG C.Calcination time can be 1~5h, preferably 2 hours.Heating rate during calcining can be
0.5~10 DEG C/min, preferably 1 DEG C/min.
The specific surface area of the catalyst that the present invention can obtain preparation of the present invention by BET methods can be 5~20m2/g。
The present invention can be 20~120nm by the catalyst pore size that BJH methods can obtain preparation of the present invention.
The pore volume that the present invention can obtain the catalyst of preparation of the present invention by BJH methods is 0.02~0.20cm3/g。
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that 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 the concrete numerical value of hereafter example.
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, will
0.03mol NaHCO3It is dissolved into 30 milliliters of water and obtains solution B.Under stirring condition, B (adds speed in being quickly poured into A
1800mL/min), react 30 minutes at room temperature.By after centrifugation washing and dried process, by desciccate and 1mmol KNO3
Ultrasonic disperse is evaporated in 50ml water in 80 DEG C of water-baths.The powder obtained after being evaporated is in static atmosphere of air in 500 DEG C
Calcining 2h obtains end-product.Tested through BET methods, the specific surface area that the present embodiment prepares catalyst is 18m2/ g, pore size
It is 22-78nm, pore volume is 0.15cm3/g。
Fig. 1 is the SEM (SEM) of the potassium support type soot combustion catalyst obtained by the embodiment of the present invention
Figure.Visible products therefrom is nano particle in irregular shape in figure, and particle size is about 20-1000nm, these shape characteristics
It is close with carbon particle particle size, be conducive to being fully contacted for carbon particle and catalyst granules, and then promote carrying for catalytic performance
It is high.
Fig. 2 is the X ray diffracting spectrum of the potassium support type soot combustion catalyst obtained by the embodiment of the present invention, can in figure
See product well-crystallized.Fig. 3 be in the embodiment of the present invention 1 potassium support type soot combustion catalyst to the catalytic effect of soot, from
Understand that support type soot combustion catalyst can make carbon soot particles complete in 343 DEG C of low-temperature burning in Fig. 3.
Effect example
To verify catalytic eliminating of transition metal (compound) oxide catalyst of the invention to carbon soot particles in exhaust gas from diesel vehicle
Effect, spy's simulation exhaust gas from diesel vehicle condition, designs and carries out following experiment in laboratory conditions.
Embodiment 2
Load potassium support type soot combustion catalyst, the 0.01g of the 0.1g prepared by the method for embodiment 1 in fixed bed reactors
Carbon soot particles, 1g quartz sand particles composition mixture, following gaseous mixture is passed through at room temperature：The concentration of NO is 500ppm, O2
Concentration be 10 (V) %, N2It is Balance Air, total flow is 0.2L/min.450 DEG C are raised to from room temperature with 5 degree of speed per minute,
Catalyst is taken out after completion of the reaction add the carbon soot particles of 0.01g and be sufficiently mixed, reload fixed bed reactors, be passed through
Reaction gas is stated, 450 DEG C are warmed up to 5 degree of speed per minute from room temperature.So test repeatedly, 4 times (corresponding diagram 4 is got the bid altogether
Note " 1st”、“2nd”、“3rd”、“4th”).Catalyst is tied to the changing effect of carbon soot particles in 250-425 DEG C of temperature range of test
Fruit is listed in Fig. 4.It can be seen that sample not only has catalysis activity very high, and when being catalyzed for the 4th time, its activity can be with fresh sample
Analogy, it was demonstrated that the catalyst excellent durability.
Visible in sum, the catalyst that the present invention is provided, crystallization is good, and excellent performance, endurance quality is good.Institute of the present invention
The preparation method simple economy of offer, raw material is cheap, with versatility higher.Burning of this catalyst in solid pollutant
Degraded aspect has potential application foreground.
Finally be necessary described herein be：Above example is served only for making further in detail technical scheme
Ground explanation, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's the above of the invention
Some the nonessential modifications and adaptations made belong to protection scope of the present invention.
Claims (10)
1. a kind of potassium support type soot combustion catalyst, it is characterised in that the catalyst is potassium carrying transition metal oxide
Type catalyst, the catalyst is nano particle pattern in irregular shape, and particle diameter distribution is 20~1000 nm, and the potassium is born
The content of K is no more than 20 wt% in load type soot combustion catalyst, and the potassium support type soot combustion catalyst contains transition gold
Category Mn.
2. potassium support type soot combustion catalyst according to claim 1, it is characterised in that the potassium support type carbon-smoke combustion
The catalyst also molar ratio containing transition metal Cu, the transition metal Cu and Mn is no more than 0.7.
3. high porosity soot combustion catalyst according to claim 1 and 2, it is characterised in that the ratio of the catalyst
Surface area is 5~20 m2/ g, pore size is 20~120 nm, and pore volume is 0.02~0.20 cm3/g。
4. a kind of preparation method of the potassium support type soot combustion catalyst as any one of claim 1-3, its feature exists
In, including：
Certain hour is stirred after solution A containing manganese salt and mantoquita and alkaline solution B are mixed, then after centrifugation washing, drying
Obtain desciccate；
Desciccate is added in potassium salt soln, mixed powder is obtained after being evaporated at 50~90 DEG C；
Gained mixed powder is calcined 1~5 hour at 400~600 DEG C, the potassium support type soot combustion catalyst is obtained.
5. preparation method according to claim 4, it is characterised in that the manganese salt is nitrate, acetate, the sulfuric acid of Mn
At least one in salt, chloride, the mantoquita is at least one in nitrate, acetate, sulfate, the chloride of Cu,
The molar concentration of the middle metal ion of the solution A is 0.01~0.50mol/L, preferably 0.10~0.30 mol/L.
6. the preparation method according to claim 4 or 5, it is characterised in that solute is bicarbonate in the alkaline solution B
Or/and carbonate, preferably bicarbonate, the concentration of the alkaline solution B is 0.5~5.0 mol/L, preferably 0.5~
1.0 mol/L。
7. the preparation method according to any one of claim 4-6, it is characterised in that the solution A and alkaline solution B's
Volume ratio is（0.1~10）：1.
8. the preparation method according to any one of claim 4-7, it is characterised in that the solution A and alkaline solution B are mixed
During conjunction mode is quickly poured into solution A for alkaline solution B, solution A instilled in alkaline solution B or solution A and alkaline solution B cocurrents
Precipitation, preferably alkaline solution B is quickly poured into solution A.
9. the preparation method according to any one of claim 4-8, it is characterised in that the sylvite is nitrate, the vinegar of K
At least one in hydrochlorate, sulfate, chloride, the mass content of the sylvite is 5~20wt%.
10. a kind of potassium support type soot combustion catalyst as any one of claim 1-3 is in motor-driven vehicle gas disposal
Application.
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| CN111804294A (en) * | 2020-04-24 | 2020-10-23 | 济南大学 | Preparation method of stable potassium-based carbon smoke combustion catalyst and obtained product |
| CN112218718A (en) * | 2018-08-09 | 2021-01-12 | N.E.化学株式会社 | Exhaust gas purifying catalyst |
| CN112218719A (en) * | 2018-08-09 | 2021-01-12 | N.E.化学株式会社 | Exhaust gas purifying catalyst |
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