CN109569584A - One kind having the active NO of good low temperaturexStorage reduction catalyst - Google Patents
One kind having the active NO of good low temperaturexStorage reduction catalyst Download PDFInfo
- Publication number
- CN109569584A CN109569584A CN201811561198.5A CN201811561198A CN109569584A CN 109569584 A CN109569584 A CN 109569584A CN 201811561198 A CN201811561198 A CN 201811561198A CN 109569584 A CN109569584 A CN 109569584A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- houghite
- deionized water
- predecessor
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 230000009467 reduction Effects 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000003860 storage Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 15
- 238000000975 co-precipitation Methods 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000003915 air pollution Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 43
- 239000011572 manganese Substances 0.000 description 14
- 235000019391 nitrogen oxide Nutrition 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002927 oxygen compounds Chemical class 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229960003753 nitric oxide Drugs 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000003643 water by type Substances 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite 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
- B01J35/615—100-500 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
The present invention provides one kind to have the active NO of good low temperaturexStorage reduction catalyst and preparation method thereof belongs to the technical field of Air Pollution Control.The present invention uses cationic surfactant aid coprecipitation method, is prepared for the Mn substituted type houghite mixed oxide catalyst of active component high degree of dispersion, which has good NOxStorage reduction removal ability.Preparation method are as follows: the soluble salt solutions containing Mn, Mg, Al are dissolved in deionized water and obtain solution a, by NaOH and Na2CO3It is dissolved in deionized water and obtains solution b, solution a and b is added dropwise simultaneously into deionized water, it controls rate of addition and maintains pH in a certain range, cetab (CTAB) is added after precipitating, gained mixed solution obtains houghite predecessor after stirring in water bath, cooling, suction filtration, washing, drying, then after houghite predecessor being roasted under the high temperature conditions, composite oxide catalysts are made.This method simple process, easy to operate easily controllable, low in cost, oxide catalyst specific surface area obtained is larger, and crystal grain is small and is evenly distributed, and has good stability.(150oC~350oC) catalytic activity with higher, active component utilization rate height are environmental-friendly at low temperature for the low temperature catalyst.
Description
Technical field
There is the active NO of good low temperature the present invention relates to a kind ofxStorage reduction catalyst belongs to atmosphere pollution control
Technical field processed.
Background technique
According to statistics, Chinese automobile volume of production and marketing in 2017 is more than 29,000,000.With the continuous development of economic level, vapour
Vehicle volume of production and marketing will keep the impetus of sustainable growth.The high speed development of automobile industry also brings energy shortage and environmental pollution
Problem.Nitrogen oxides (NOx) be automotive emission major pollutants, it can cause acid rain, photochemical fog, soil
A series of problem of environmental pollutions such as eutrophication, or even can also endanger the health of the mankind.Under this overall background, lean burn technology
It comes into being.Lean Burning Technique is the effective measures for reducing motor vehicle exhaust emission and reducing fuel consumption.Lean-combustion engine is steady
Surely the air-fuel ratio 23~27 to work, oxygen concentration is generally greater than 5 % in tail gas, has and saves fuel, reduce greenhouse gases, CO and
The advantages that granular material discharged；But the presence of excess of oxygen has inevitably resulted in high concentration nitrogen oxide (NOx) generation with
Discharge.
1996, Toyota Company's proposition restored (NO with nitrogen oxides storagexStorage Reduction, NSR) skill
Art solves the NO of lean-combustion enginex Pollution problem.The working principle of nitrogen oxides storage reduction technique are as follows: in the lean-burn stage,
NOxThrough processes such as absorption, oxidation and diffusions, finally it is stored in material in the form of NO3-N and NO2-N.In fuel-rich rank
Section, NO3-N and NO2-N decompose, and release NOx, in HC, CO and H2It is reduced in the presence of equal reducing agents environmental-friendly
N2.Nitrogen oxides storage reduction technique is because having denitration efficiency height, not additional reducing agent and preferably solving low temperature especially
It is cold start-up and idling NO when drivingxThe advantages that with the emission problem of unburned HC, and become and be suitable for removing lean-combustion engine nitrogen
A kind of effective means of oxide；Wherein, high-performance nitrogen oxides storage reducing catalyst design and develop be the technology core
The heart.
Nitrogen oxides storage reducing catalyst is mainly made of carrier, storage component and active component.Toyota Company's exploitation
Typical nitrogen oxides storage reducing catalyst be Pt/BaO/Al2O3, the Japanese market of no sulphur or ultra low sulfur fuels at
Function, which is launched, to be used.Typical Pt/BaO/Al2O3Catalyst is in 300 oC or so storage activity with higher.However for diesel oil
Tail gas temperature is usually lower, and when automobile is run at a low speed, exhaust temperature is down to 150 oC, therefore for traditional Pt/Ba/
Al2O3Catalyst NO at a lower temperaturexAmount of storage is less, and NO oxidability is weak under low temperature, so as to cause catalytic activity compared with
It is low, therefore, wide active temperature windows are developed, the nitrogen oxides storage reducing catalyst with good low temperature catalytic activity is the neck
The emphasis in domain.
Summary of the invention
For the not low temperature resistant problem of current NSR catalyst, the object of the present invention is to provide one kind with good low
The active NO of temperaturexStorage reduction catalyst.
The present invention is realized by following measures:
Catalyst of the present invention is a kind of composite oxide catalysts, including four kinds of manganese, magnesium, aluminium, oxygen elemental compositions, manganese,
The ratio between amount of substance of magnesium, three metal ion species of aluminium is (5-20): (55-70): 25, the invention also discloses a kind of above-mentioned catalysis
The preparation method of agent, comprising the following steps:
(1) soluble salt solutions are prepared according to the composition of catalyst and its mass ratio of the material；
(2) with NaOH and Na2CO3Mixed ammonium/alkali solutions be precipitating reagent, NaOH and Na2CO3Concentration molar ratio is 2；
(3) a certain amount of cationicsurfactants are weighed to be dissolved in the water-bath for being placed on first-class temperature in deionized water sufficiently
It stirs to dissolve；
(4) at room temperature, above-mentioned mixing salt solution and mixed ammonium/alkali solutions are instilled simultaneously in the container for filling deionized water, is acutely stirred
It mixes, and keeps pH value in 8-12, CTAB is added after dripping off, gained slurries are placed in aging 2-24 h in 50-80 oC water-bath, it is cold
But to room temperature, then filtering is washed with deionized to neutrality, gained filter cake after 1-12 h drying, is made in 60-100 oC
Houghite predecessor；
(5) gained houghite predecessor is placed in Muffle furnace, in 500-800 oC roasting temperature 5-10 h up to compound
Oxide catalyst.
The preparation method of aforementioned present invention, soluble salt solutions are manganese nitrate, magnesium nitrate and aluminum nitrate.
In step described in aforementioned present invention (2), the molar concentration of NaOH is preferably 0.5-2 mol/L.The step (3)
In, the molar ratio of cationic surfactant and metal ion is 0.1:1.
The present invention uses cationic surfactant aid coprecipitation method, and the Mn for being prepared for active component high degree of dispersion replaces
Type houghite mixed oxide catalyst, preparation method simple process of the present invention is easily controllable, pollution-free, at low cost, low
Temperature is lower to have good NOxStorage reduction removal ability, to NOxPurification efficiency it is high, be suitable for lean-combustion engine tail gas
NOxImprovement.
Detailed description of the invention
Fig. 1 is the XRD spectra of embodiment 1,2,3,4 and comparative example 5.
Fig. 2 is the NO of embodiment 3 at different temperaturesxAdsorb spectrogram.
Fig. 3 is NO of the embodiment 3 under different adsorption tempsxSpectrogram is desorbed.
Fig. 4 is embodiment 1,2,3,4 and comparative example 5 15 NO in 150 oCxPoor-rich combustion circulation NOx's
Removal rate.
Specific embodiment
In order to illustrate more clearly of the present invention, following embodiment is enumerated, but it is without any restrictions to the scope of the present invention.
Embodiment 1
Being prepared using coprecipitation has the active NO of good low temperature containing transient metal MnxStorage reduction composite oxides are urged
Agent.The following steps are included:
(1) a certain amount of Mn (NO is weighed respectively according to stoichiometric ratio Mn:Mg:Al=5:70:253)2 ·4H2O、Mg(NO3)2
·6H2O and Al (NO3)3 ·9H2O nitrate is dissolved in deionized water, is configured to mixing salt solution a；
(2) claim a certain amount of NaOH and Na2CO3It is configured to the mixed ammonium/alkali solutions b that molar concentration rate is 2；
(3) a certain amount of cationicsurfactants are weighed to be dissolved in deionized water, is placed in the water-bath of certain temperature and fills
Divide and stirs to dissolve；
(4) mixing salt solution and mixed ammonium/alkali solutions is added dropwise simultaneously into deionized water, while being vigorously stirred is uniformly mixed it, control
Rate of addition processed maintains pH that the cationicsurfactants of step (3) preparation are added after 8-12, precipitating, by institute
Mixed solution is placed in 50-80 oC stirred in water bath 2-24 h, then cool to room temperature, filter, wash to filtrate and become
Property, filter cake is put into 60-100 oC in baking oven and dries 1-12 h, obtains houghite predecessor；
(5) houghite predecessor is placed in Muffle furnace, is warming up to 500-800 oC constant temperature calcining 5-10 h up to composite oxygen
Compound catalyst.By test, specific surface area is larger, is 144 m2/ g, average grain diameter is smaller, is 14.3 nm, and pattern is
The vermicular structure of class reunited together, agglomeration may be related with high-temperature calcination.
Embodiment 2
Being prepared using coprecipitation has the active NO of good low temperature containing transient metal MnxStorage reduction composite oxides are urged
Agent.The following steps are included:
(1) a certain amount of Mn (NO is weighed respectively according to stoichiometric ratio Mn:Mg:Al=10:60:253)2 ·4H2O、Mg(NO3)2
·6H2O and Al (NO3)3 ·9H2O nitrate is dissolved in deionized water, is configured to mixing salt solution a；
(2) claim a certain amount of NaOH and Na2CO3It is configured to the mixed ammonium/alkali solutions b that molar concentration is respectively 2；
(3) it weighs a certain amount of cationic surfactant to be dissolved in deionized water, is placed in the water-bath of certain temperature and sufficiently stirs
It mixes and makes it dissolve；
(4) mixing salt solution and mixed ammonium/alkali solutions is added dropwise simultaneously into deionized water, while being vigorously stirred is uniformly mixed it, control
Rate of addition processed maintains pH that cationicsurfactants are added after 8-12, precipitating, gained mixed solution is placed in
50-80 oC stirred in water bath 2-24 h, then cools to room temperature, and filters, washs to filtrate and become neutral, filter cake is put into baking
60-100 oC dries 1-12 h in case, obtains houghite predecessor；
(5) houghite predecessor is placed in Muffle furnace, is warming up to 500-800 oC constant temperature calcining 5-10 h up to composite oxygen
Compound catalyst.By test, composite oxide catalysts specific surface area made from this method is 136 m2/ g, average grain diameter are
15.9 nm。
Embodiment 3
Being prepared using coprecipitation has the active NO of good low temperature containing transient metal MnxStorage reduction composite oxides are urged
Agent.The following steps are included:
(1) a certain amount of Mn (NO is weighed respectively according to stoichiometric ratio Mn:Mg:Al=15:60:253)2 ·4H2O、Mg(NO3)2
·6H2O and Al (NO3)3 ·9H2O nitrate is dissolved in deionized water, is configured to mixing salt solution a；
(2) claim a certain amount of NaOH and Na2CO3It is configured to the mixed ammonium/alkali solutions b that molar concentration is respectively 2；
(3) a certain amount of cationicsurfactants are weighed to be dissolved in deionized water, is placed in the water-bath of certain temperature and fills
Divide and stirs to dissolve；
(4) mixing salt solution and mixed ammonium/alkali solutions is added dropwise simultaneously into deionized water, while being vigorously stirred is uniformly mixed it, control
Rate of addition processed maintains pH that cationicsurfactants are added after 8-12, precipitating, gained mixed solution is placed in
50-80 oC stirred in water bath 2-24 h, then cools to room temperature, and filters, washs to filtrate and become neutral, filter cake is put into baking
60-100 oC dries 1-12 h in case, obtains houghite predecessor；
(5) houghite predecessor is placed in Muffle furnace, is warming up to 500-800 oC constant temperature calcining 5-10 h up to composite oxygen
Compound catalyst.By test, composite oxide catalysts specific surface area made from this method is 133 m2/ g, average grain diameter are
22.6 nm, pattern are the nanometer spherical being evenly distributed.
Embodiment 4
Being prepared using coprecipitation has the active NO of good low temperature containing transient metal MnxStorage reduction composite oxides are urged
Agent.The following steps are included:
(1) a certain amount of Mn (NO is weighed respectively according to stoichiometric ratio Mn:Mg:Al=20:55:253)2 ·4H2O、Mg(NO3)2
·6H2O and Al (NO3)3 ·9H2O nitrate is dissolved in deionized water, is configured to mixing salt solution a；
(2) claim a certain amount of NaOH and Na2CO3It is configured to the mixed ammonium/alkali solutions b that molar concentration is respectively 2；
(3) a certain amount of cationicsurfactants are weighed to be dissolved in deionized water, is placed in the water-bath of certain temperature and fills
Divide and stirs to dissolve；
(4) mixing salt solution and mixed ammonium/alkali solutions is added dropwise simultaneously into deionized water, while being vigorously stirred is uniformly mixed it, control
Rate of addition processed maintains pH that cationicsurfactants are added after 8-12, precipitating, gained mixed solution is placed in
50-80 oC stirred in water bath 2-24 h, then cools to room temperature, and filters, washs to filtrate and become neutral, filter cake is put into baking
60-100 oC dries 1-12 h in case, obtains houghite predecessor；
(5) houghite predecessor is placed in Muffle furnace, is warming up to 500-800 oC constant temperature calcining 5-10 h up to composite oxygen
Compound catalyst.By test, composite oxide catalysts specific surface area made from this method is 139 m2/ g, average grain diameter are
19.6 nm。
Comparative example 5
NO is prepared using coprecipitationxStorage reduction composite oxide catalysts.The following steps are included:
(1) a certain amount of Mg (NO is weighed respectively according to stoichiometric ratio Mg:Al=3:13)2 ·6H2O and Al (NO3)3 ·9H2O
Nitrate is dissolved in 100 mL deionized waters, is configured to mixing salt solution a；
(2) claim a certain amount of NaOH and Na2CO3It is configured to the mixed ammonium/alkali solutions b that molar concentration is respectively 2；
(3) a certain amount of cationicsurfactants are weighed and are dissolved in deionized water (cationic surfactant and metal
The molar ratio of ion is 0.1:1), it is placed on to be sufficiently stirred in the water-bath of certain temperature and makes it dissolve；
(4) mixing salt solution and mixed ammonium/alkali solutions is added dropwise simultaneously into deionized water, while being vigorously stirred is uniformly mixed it, control
Rate of addition processed maintains pH that cationicsurfactants are added after 8-12, precipitating, gained mixed solution is placed in
50-80 oC stirred in water bath 2-24 h, then cools to room temperature, and filters, washs to filtrate and become neutral, filter cake is put into baking
60-100 oC dries 1-12 h in case, obtains houghite predecessor；
(5) houghite predecessor is placed in Muffle furnace, is warming up to 500-800 oC constant temperature calcining 5-10 h up to composite oxygen
Compound catalyst.
Test case 1
The catalyst prepared in Example 3, simulated exhaust gas discharge atmosphere, carry out in catalyst sample evaluation system static
NOxStore reduction experiment test.Constant temperature static state active testing temperature is 150 oC, 200 oC, 250 oC, 300 oC, 350 o
C.Exit NO, NO are continuously recorded using nitrogen-oxide analyzer, during experiment2、NOxConcentration, evaluating catalyst result see Fig. 2 and
3, catalyst n O is calculated separately using formulaxAdsorption capacity (NAC) and NOxStorage capacity (NSC).It is computed, catalyst n OxIt inhales
Attached ability (NAC) and NOxStorage capacity (NSC) is shown in Table 1, and the catalyst of embodiment 3 is when adsorption temp is 150 oC, when penetrating
Between (TB) longest, NOxAdsorbance (NAC) is also up to 1229 μm of olg-1, illustrate the catalyst at low temperature and have and is good
NOxStorage performance.
The NO of 1 embodiment of table, 3 catalystxStorage capacity
TBTime of break-through；NAC- Catalyst Adsorption NOxAmount；NSC-is via NOxThe NO obtained is desorbedxStorage capacity.
Test case 2
The catalyst prepared in Example 1,2,3,4 and comparative example 5 carries out NOxPoor-rich combustion recycle dynamic experiment.
Dynamic activity test temperature is 150 oC, lean combustion atmosphere are as follows: 120 s, 500 ppm NO+7.5 vol.% O2 He air-flow, mix
Conjunction gas flow is 100 mL/min, and fuel-rich atmosphere is 60 s, 5 vol.% H2N2Air-flow, mixed gas flow are 100 mL/
Min is recycled 15 times.Exit NO is continuously recorded using nitrogen-oxide analyzer, in experimentationxConcentration.Test result is shown in figure
4, it is computed and obtains each catalyst n OxAverage removal rate, from Table 2, it can be seen that with it is no doping Mn comparative example 5
It compares, embodiment 1,2,3,4 all has good NO at 150 oCxRemoval rate, average removal rate is all in 70 % or more.
The NO of 2 embodiment catalyst of tablexAverage removal rate
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 5 |
| NOxAverage removal rate (%) | 72.5 | 71.5 | 72.3 | 70.0 | 54.7 |
Claims (5)
1. one kind has the active NO of good low temperaturexStorage reduction catalyst, it is characterized in that: the catalyst is a kind of compound
Oxide catalyst, including four kinds of manganese, magnesium, aluminium, oxygen elemental compositions, the ratio between manganese, magnesium, amount of substance of three metal ion species of aluminium be
(5-20): (55-70): 25.
2. the preparation method of the catalyst according to claim 1, it is characterised in that the following steps are included:
(1) soluble salt solutions are prepared according to the composition of catalyst and its mass ratio of the material；
(2) with NaOH and Na2CO3Mixed ammonium/alkali solutions be precipitating reagent, NaOH and Na2CO3Concentration molar ratio is 2；
(3) a certain amount of cationicsurfactants are weighed to be dissolved in the water-bath for being placed on certain temperature in deionized water sufficiently
It stirs to dissolve；
(4) at room temperature, above-mentioned mixing salt solution and mixed ammonium/alkali solutions are instilled simultaneously in the container for filling deionized water, acutely
Stirring, and keep pH value in 8-12, surfactant is added after dripping off, gained slurries are placed in aging 2- in 50-80oC water-bath
24 h, are cooled to room temperature, then filtering is washed with deionized to neutrality, and gained filter cake is dried in 60-100oC by 1-12 h
Afterwards, houghite predecessor is made；
(5) gained houghite predecessor is placed in Muffle furnace, in 500-800 oC roasting temperature 5-10 h up to compound
Oxide catalyst.
3. method according to claim 2, it is characterised in that the soluble salt solutions are manganese nitrate, magnesium nitrate and nitric acid
Aluminium.
4. preparation method according to claim 2, it is characterised in that in the step (2), the molar concentration of NaOH is
0.5-2.0 mol/L。
5. preparation method according to claim 2 or 3, it is characterised in that the cation surface activating in the step (3)
The molar ratio of agent CTAB and metal ion is 0.1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811561198.5A CN109569584A (en) | 2018-12-20 | 2018-12-20 | One kind having the active NO of good low temperaturexStorage reduction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811561198.5A CN109569584A (en) | 2018-12-20 | 2018-12-20 | One kind having the active NO of good low temperaturexStorage reduction catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109569584A true CN109569584A (en) | 2019-04-05 |
Family
ID=65930182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811561198.5A Pending CN109569584A (en) | 2018-12-20 | 2018-12-20 | One kind having the active NO of good low temperaturexStorage reduction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109569584A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570383A (en) * | 2022-03-30 | 2022-06-03 | 西安交通大学 | Copper-manganese composite catalyst, preparation method and application |
| CN114700082A (en) * | 2022-04-28 | 2022-07-05 | 江苏蓝溪环境科技有限公司 | Preparation method of catalyst for ozone tail gas destruction |
| CN114887618A (en) * | 2022-05-10 | 2022-08-12 | 济南大学 | MnO with magnesium-aluminum composite oxide as carrier x High-efficiency ultralow-temperature denitration catalyst |
| CN115228456A (en) * | 2021-12-17 | 2022-10-25 | 中国石油天然气股份有限公司 | High-efficiency catalyst for catalytic decomposition of nitrous oxide |
| CN115253666A (en) * | 2022-07-04 | 2022-11-01 | 江苏理工学院 | Method for removing VOCs (volatile organic compounds) by coupling hydrotalcite-like compound with low-temperature plasma and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785996A (en) * | 2010-03-10 | 2010-07-28 | 天津大学 | Catalyst for eliminating carbon soot particles and nitrogen oxides simultaneously, preparation and application thereof |
| CN105413695A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 1,3-butadiene through ethanol condensation, preparation method of catalyst and application of catalyst |
| CN106179228A (en) * | 2016-09-01 | 2016-12-07 | 桂林理工大学 | A kind of preparation method of bagasse charcoal/magnesium aluminum-hydrotalcite compound adsorbent |
-
2018
- 2018-12-20 CN CN201811561198.5A patent/CN109569584A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101785996A (en) * | 2010-03-10 | 2010-07-28 | 天津大学 | Catalyst for eliminating carbon soot particles and nitrogen oxides simultaneously, preparation and application thereof |
| CN105413695A (en) * | 2015-12-22 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing 1,3-butadiene through ethanol condensation, preparation method of catalyst and application of catalyst |
| CN106179228A (en) * | 2016-09-01 | 2016-12-07 | 桂林理工大学 | A kind of preparation method of bagasse charcoal/magnesium aluminum-hydrotalcite compound adsorbent |
Non-Patent Citations (4)
| Title |
|---|
| HONGJIAN ZHU，ET AL: ""Catalytic oxidation of soot on mesoporous ceria-based mixed oxides with cetyltrimethyl ammonium bromide (CTAB)-assisted synthesis"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| PENGJIA TAN，ET AL: ""Ni-Mg-Al solid basic layered double oxide catalysts prepared using surfactant-assisted coprecipitation method for CO2 reforming of CH4"", 《CHINESE JOURNAL OF CATALYSIS》 * |
| SHIGUO WU，ET AL: ""Synthesis, characterization and catalytic performance of FeMnTiOxmixed oxides catalyst prepared by a CTAB-assisted process formid-low temperature NH3-SCR"", 《APPLIED CATALYSIS A: GENERAL》 * |
| 李倩: ""Co、Mn 水滑石基复合氧化物催化剂上碳烟和NOx的催化消除"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115228456A (en) * | 2021-12-17 | 2022-10-25 | 中国石油天然气股份有限公司 | High-efficiency catalyst for catalytic decomposition of nitrous oxide |
| CN115228456B (en) * | 2021-12-17 | 2023-07-28 | 中国石油天然气股份有限公司 | High-efficiency catalyst for catalytic decomposition of nitrous oxide |
| CN114570383A (en) * | 2022-03-30 | 2022-06-03 | 西安交通大学 | Copper-manganese composite catalyst, preparation method and application |
| CN114700082A (en) * | 2022-04-28 | 2022-07-05 | 江苏蓝溪环境科技有限公司 | Preparation method of catalyst for ozone tail gas destruction |
| CN114700082B (en) * | 2022-04-28 | 2024-05-17 | 江苏蓝溪环境科技有限公司 | Preparation method of catalyst for ozone tail gas destruction |
| CN114887618A (en) * | 2022-05-10 | 2022-08-12 | 济南大学 | MnO with magnesium-aluminum composite oxide as carrier x High-efficiency ultralow-temperature denitration catalyst |
| CN115253666A (en) * | 2022-07-04 | 2022-11-01 | 江苏理工学院 | Method for removing VOCs (volatile organic compounds) by coupling hydrotalcite-like compound with low-temperature plasma and application |
| CN115253666B (en) * | 2022-07-04 | 2023-05-30 | 江苏理工学院 | Method for removing VOCs by hydrotalcite-like coupling low-temperature plasma and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109569584A (en) | One kind having the active NO of good low temperaturexStorage reduction catalyst | |
| CN105314648B (en) | CHA type Si-Al molecular sieves and its preparation method and application | |
| JP4090547B2 (en) | Exhaust gas purification catalyst | |
| CN106268787A (en) | A kind of samarium doping MnOxlow-temperature SCR catalyst and its preparation method and application | |
| CN105289641A (en) | Cobalt-load cerium manganese oxide catalyst and preparation method thereof | |
| CN100371072C (en) | Preparation process of selective reduction catalyst for lean-burn gasoline motor car exhausted gas nitrogen oxide | |
| CN110354799A (en) | A kind of cerium dioxide nano material possessing good low temperature NOx storage capacity | |
| CN107282101A (en) | A kind of loaded modified method in situ of the molecular sieve catalysts of SAPO 34 for diesel car tail gas refining | |
| CN101722010B (en) | Novel nitrogen oxide storage and reduction catalyst for exhaust gas purification of lean burn gasoline engine or diesel engine | |
| CN101239313A (en) | Copper cerium aluminium catalyst capable of simultaneously removing carbon smoke granule and nitrogen oxide and preparation | |
| CN109433254A (en) | A kind of confinement molecular sieve denitrating catalyst and preparation method thereof | |
| CN106582874A (en) | High temperature resistant phosphotungstic acid adsorbed iron-based oxide catalyst and preparation method thereof | |
| CN112275314A (en) | Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof | |
| CN102728383A (en) | Preparation method of high temperature stable monolithic catalyst for purifying tail gas of automobile | |
| CN106582665A (en) | Macroporous Ce-Zr based composite metal oxide catalyst, preparation method, and application thereof | |
| CN105771967A (en) | Metal oxide-vanadate/attapulgite catalyst | |
| CN100398198C (en) | Diesel vehicle exhaust carbon-smoke combustion and Nox storage-reduction dual-functional catalyst and its preparing method | |
| CN105233814A (en) | Cerium oxide catalyst for catalyzing and purifying nitric oxides, preparation method and application | |
| CN104383962A (en) | Base metal load type multistage pore zeolite molecular sieve catalyst of efficient catalytic combustion soot particles and preparation and application of catalyst | |
| CN111330633A (en) | Diesel vehicle oxidation type catalyst with low-temperature adsorption capacity and preparation method thereof | |
| CN105964252A (en) | Diesel engine exhaust pollutant control catalyst matched with DPF/CDPF (diesel particulate filter/catalyzed diesel particulate filter) for use, as well as preparation and application | |
| CN1132687C (en) | Automobile tail gas cleaning catalyst and its preparation method | |
| CN103464142B (en) | Catalyst for removing nitrogen oxide through ammonia selective catalytic reduction and preparation method of catalyst | |
| CN109289906B (en) | Ammonia gas purification catalyst and preparation method and application thereof | |
| CN109590016B (en) | Catalyst for diesel engine based on modified hydrotalcite derived oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190405 |