CN106423298A - Three-way catalyst and preparation method thereof - Google Patents
Three-way catalyst and preparation method thereof Download PDFInfo
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- CN106423298A CN106423298A CN201611003673.8A CN201611003673A CN106423298A CN 106423298 A CN106423298 A CN 106423298A CN 201611003673 A CN201611003673 A CN 201611003673A CN 106423298 A CN106423298 A CN 106423298A
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- way catalyst
- crosslinking agent
- chloride
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 61
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 37
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims abstract description 19
- 239000000741 silica gel Substances 0.000 claims abstract description 19
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 18
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 23
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 14
- 229920003072 Plasdone™ povidone Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- -1 polyethylene Pyridine pyrrolidone Polymers 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 7
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 6
- 150000002540 isothiocyanates Chemical class 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 235000011187 glycerol Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000001147 anti-toxic effect Effects 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 abstract 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002717 polyvinylpyridine Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003138 coordinated effect Effects 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- VXUYSKXBQCGVSG-UHFFFAOYSA-N pyridine;pyrrolidin-2-one Chemical compound C1=CC=NC=C1.O=C1CCCN1 VXUYSKXBQCGVSG-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 210000003462 vein Anatomy 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, in particular to a three-way catalyst and a preparation method thereof. The three-way catalyst comprises the following raw materials in parts by weight: 1-10 parts of lanthanum chloride, 1-10 parts of scandium chloride, 5-8 parts of polyvinylpyrrolidone, 20-30 parts of titanium dioxide, 15-25 parts of ceramics, 15-25 parts of silica gel, 1-5 parts of sodium sulfate, 4-8 parts of palladium sulfate, 5-7 parts of cerium chloride, 15-25 parts of zirconium dioxide, 15-20 parts of gamma-Al2O3 and 1-5 parts of a cross-linking agent. The three-way catalyst and the preparation method thereof provided by the invention have the benefits that through adding rare earth elements: lanthanum, scandium and cerium, the heat stability of B acid in the catalyst can be improved, so that the active tetragonal zirconium dioxide and titanium dioxide are more stable; the center strength and the density of surface acid are adjusted, the anti-toxic ability is increased, the mechanical strength is improved, and the carbon deposition phenomenon of the surface of the catalyst and the loss of heavy metals are delayed.
Description
Technical field
The present invention designs catalyst field, more particularly, to a kind of three-way catalyst and preparation method thereof.
Background technology
With scientific and technical development, the living standard of people improves constantly, and automobile has become as main flow walking-replacing tool quilt
Widely use, but, with the growth of automobile pollution, vehicle exhaust
Pollution to air is also increasingly serious, and in especially big and big and medium-sized cities, the tail gas of motor vehicle emission has progressively become air pollution
Principal element, the therefore improvement to automobile exhaust pollution become the problem that national governments pay much attention to.
Improvement to automobile exhaust pollution, mainly takes emission controls by improving combustion and two kinds of approach of external purification.External purification is control
The most effective means of automobile exhaust pollution processed.External purification refers to by method physically or chemically, by the pollutant in tail gas
Processed.The method being widely used at present is chemical method, that is, pass through to install Three way catalyst converter by tail gas
Harmful substance CO, HC, NOx conversion become harmless CO2、H2O and N2, thus substantially reducing environmental pollution, improve air quality.
, mostly with precious metal ion as active component, heavy metal is easily from catalyst carrier stream for the three-way catalyst commonly used at present
Lose, cause environmental pollution, the extremely difficult recovery of the noble metal after loss, and noble metal is expensive, this both increases the system of three-way catalyst
Make and use cost.
Content of the invention
In order to solve above-mentioned technical problem, the invention provides a kind of three-way catalyst and its control this method.
The application is realized by following proposal：
A kind of three-way catalyst, including following raw materials：Lanthanum chloride 1-10 part, scandium chloride 1-10 part, plasdone 5-8
Part, titanium dioxide 20-30 part, ceramic 15-25 part, silica gel 15-25 part, sodium sulphate 1-5 part, palladium sulfate 4-8 part, cerium chloride 5-7
Part, zirconium dioxide 15-25 part, γ-Al2O315-20 part, crosslinking agent 1-5 part.
Preferably, a kind of three-way catalyst, including following raw materials：Lanthanum chloride 3-7 part, scandium chloride 3-7 part, polyvinyl pyridine
Pyrrolidone 6-7 part, titanium dioxide 23-27 part, ceramic 18-22 part, silica gel 17-23 part, sodium sulphate 2-4 part, palladium sulfate 5-7 part,
Cerium chloride 6-7 part, zirconium dioxide 18-22 part, γ-Al2O316-19 part, crosslinking agent 2-4 part.
Preferably, a kind of three-way catalyst, including following raw materials：5 parts of lanthanum chloride, 5 parts of scandium chloride, polyvinyl pyridine coughs up alkane
6 parts of ketone, 5 parts of titanium dioxide, 20 parts of pottery, 20 parts of silica gel, 3 parts of sodium sulphate, 6 parts of palladium sulfate, 7 parts of cerium chloride, zirconium dioxide 20
Part, γ-Al2O318 parts, 3 parts of crosslinking agent.
A kind of preparation method of three-way catalyst, by lanthanum chloride, scandium chloride and plasdone are soluble in water, after
Add titanium dioxide, pottery and silica gel, under normal temperature, impregnate 1-2h, add cross-linking agents 0.5-1h, the material after crosslinking is high
Molded instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the sodium hydroxide solution of 0.1mol/L
Soak 10-30min, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality.
Preferably, by sodium sulphate, palladium sulfate, cerium chloride is soluble in water, adds afterwards and impregnates 5-10h under zirconium dioxide normal temperature,
Add cross-linking agents 1-2h, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 100 mesh sieves, described microballoon note
For C.
Preferably, by B, C and γ-Al2O3Mix, add cross-linking agents 10-15min, the material after crosslinking is high
Molded instrument is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, and D is carried out microwave 5-10min, γ-Al2O3100 mesh can be crossed
Sieve.
Preferably, the parameter of high-pressure molding instrument is：Voltage 30～35kv, fltting speed is 90～100mm/h, and pulsewidth is
3ms, frequency is 100Hz.
Preferably, crosslinking agent is dibenzoyl peroxide, isothiocyanates, N hydroxymethyl acrylamide, dimethyl allene
Sour glycol ester and the mixture of glyceraldehyde, described dibenzoyl peroxide, isothiocyanates, N hydroxymethyl acrylamide, two
Methacrylic acid glycol ester and glyceraldehyde mass ratio be 1:1:2:2:3.
Preferably, crosslinking agent is glyceraldehyde；Described crosslinking agent is the mixing of GDMA and glyceraldehyde
Thing, the mass ratio of described GDMA and glyceraldehyde is 1:1.
Preferably, crosslinking agent used in the preparation of A, used in the preparation of crosslinking agent used and described D in the preparation of described C
The mass ratio of crosslinking agent is 2:1:3.
The present invention passes through the heat endurance adding rare-earth elements of lanthanum, scandium, cerium can improve B acid in catalyst, makes activity four
Side's group zirconium dioxide and titanium dioxide are more firm, adjust surface acid center intensity and density, increase antitoxin thing ability, improve machine
Tool intensity, has delayed the carbon deposition phenomenon on the surface of catalyst and the loss of active component.
Specific embodiment
Embodiment 1
A kind of three-way catalyst, including following raw materials：2 parts of lanthanum chloride, 2 parts of scandium chloride, 5 parts of plasdone, dioxy
Change 21 parts of titanium, ceramic 16 parts, 16 parts of silica gel, 2 parts of sodium sulphate, 5 parts of palladium sulfate, 6 parts of cerium chloride, 17 parts of zirconium dioxide, γ-
Al2O317 parts, 2 parts of crosslinking agent, the preparation method of three-way catalyst is：By lanthanum chloride, scandium chloride and plasdone are molten
Yu Shuizhong, adds titanium dioxide, pottery and silica gel afterwards, impregnates 1.1h under normal temperature, adds cross-linking agents 0.6h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the NaOH of 0.1mol/L
Soak 12min in solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality；By sodium sulphate, palladium sulfate,
Cerium chloride is soluble in water, adds afterwards and impregnates 6h under zirconium dioxide normal temperature, adds cross-linking agents 1.2h, and the material after crosslinking is high
Molded instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C；By B, C and γ-Al2O3Mix, add crosslinked
Agent crosslinking 10min, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, D is carried out microwave
Radiation 5min, γ-Al2O3100 mesh sieves can be crossed；The parameter of high-pressure molding instrument is：Voltage 31kv, fltting speed is 92mm/h, pulsewidth
For 3ms, frequency is 100Hz；Crosslinking agent is dibenzoyl peroxide, isothiocyanates, N hydroxymethyl acrylamide, dimethyl propylene
Olefin(e) acid glycol ester and the mixture of glyceraldehyde, described dibenzoyl peroxide, isothiocyanates, N hydroxymethyl acrylamide,
GDMA and glyceraldehyde mass ratio be 1:1:2:2:Crosslinking agent used in 3, A preparation, described C's
In the preparation of crosslinking agent used and described D in preparation, the mass ratio of crosslinking agent used is 2:1:3.
Embodiment 2
A kind of three-way catalyst, including following raw materials：9 parts of lanthanum chloride, 9 parts of scandium chloride, 7 parts of plasdone, dioxy
Change 28 parts of titanium, ceramic 18 parts, 18 parts of silica gel, 4 parts of sodium sulphate, 7 parts of palladium sulfate, 6 parts of cerium chloride, 24 parts of zirconium dioxide, γ-
Al2O318 parts, 4 parts of crosslinking agent, the preparation method of three-way catalyst is：By lanthanum chloride, scandium chloride and plasdone are molten
Yu Shuizhong, adds titanium dioxide, pottery and silica gel afterwards, impregnates 1.8h under normal temperature, adds cross-linking agents 0.9h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the NaOH of 0.1mol/L
Soak 28min in solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality；By sodium sulphate, palladium sulfate,
Cerium chloride is soluble in water, adds afterwards and impregnates 9h under zirconium dioxide normal temperature, adds cross-linking agents 1.8h, and the material after crosslinking is high
Molded instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C；By B, C and γ-Al2O3Mix, add crosslinked
Agent crosslinking 14min, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, D is carried out microwave
Radiation 9min, γ-Al2O3100 mesh sieves can be crossed；The parameter of high-pressure molding instrument is：Voltage 35kv, fltting speed is 99mm/h, pulsewidth
For 3ms, frequency is 100Hz；Crosslinking agent is glyceraldehyde；Crosslinking agent used in the preparation of A, crosslinking agent used in the preparation of described C
In preparation with described D, the mass ratio of crosslinking agent used is 2:1:3.
Embodiment 3
A kind of three-way catalyst, including following raw materials：5 parts of lanthanum chloride, 5 parts of scandium chloride, 6 parts of plasdone, dioxy
Change 25 parts of titanium, ceramic 20 parts, 20 parts of silica gel, 3 parts of sodium sulphate, 6 parts of palladium sulfate, 7 parts of cerium chloride, 20 parts of zirconium dioxide, γ-
Al2O318 parts, 3 parts of crosslinking agent, the preparation method of three-way catalyst is：By lanthanum chloride, scandium chloride and plasdone are molten
Yu Shuizhong, adds titanium dioxide, pottery and silica gel afterwards, impregnates 1.5h under normal temperature, adds cross-linking agents 0.8h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the NaOH of 0.1mol/L
Soak 20min in solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality；By sodium sulphate, palladium sulfate,
Cerium chloride is soluble in water, adds afterwards and impregnates 8h under zirconium dioxide normal temperature, adds cross-linking agents 1.5h, and the material after crosslinking is high
Molded instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C；By B, C and γ-Al2O3Mix, add crosslinked
Agent crosslinking 13min, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, D is carried out microwave
Radiation 8min, γ-Al2O3100 mesh sieves can be crossed；The parameter of high-pressure molding instrument is：Voltage 33kv, fltting speed is 95mm/h, pulsewidth
For 3ms, frequency is 100Hz；Crosslinking agent is the mixture of GDMA and glyceraldehyde, dimethacrylate second
The mass ratio of diol ester and glyceraldehyde is 1:1；Crosslinking agent used in the preparation of A, the preparation of crosslinking agent used and D in the preparation of C
In crosslinking agent used mass ratio be 2:1:3.
Embodiment 4
A kind of three-way catalyst, including following raw materials：0.5 part of lanthanum chloride, 0.8 part of scandium chloride, 2 parts of plasdone,
15 parts of titanium dioxide, 10 parts of pottery, 14 parts of silica gel, sodium sulphate .09 part, 3 parts of palladium sulfate, 4 parts of cerium chloride, 14 parts of zirconium dioxide,
γ-Al2O311 parts, 0.7 part of crosslinking agent, the preparation method of three-way catalyst is：By lanthanum chloride, scandium chloride and polyvinyl pyridine are coughed up
Alkanone is soluble in water, adds titanium dioxide, pottery and silica gel afterwards, impregnates 0.5h under normal temperature, adds cross-linking agents 0.4h, crosslinked
Material high-pressure molding instrument afterwards is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the hydrogen of 0.1mol/L
Soak 8min in sodium hydroxide solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality；By sodium sulphate, sulphur
Sour palladium, cerium chloride is soluble in water, adds afterwards and impregnates 4h under zirconium dioxide normal temperature, adds cross-linking agents 2.5h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C；By B, C and γ-Al2O3Mix, plus
Enter cross-linking agents 3min, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, D is carried out
Microwave 4.5min, γ-Al2O3100 mesh sieves can be crossed；The parameter of high-pressure molding instrument is：Voltage 23kv, fltting speed is 70mm/
H, pulsewidth is 3ms, and frequency is 100Hz；Crosslinking agent is the mixture of GDMA and glyceraldehyde, dimethyl propylene
The mass ratio of olefin(e) acid glycol ester and glyceraldehyde is 1:9；Crosslinking agent used in the preparation of A, crosslinking agent used and D in the preparation of C
Preparation in crosslinking agent used mass ratio be 2:1:3.
Embodiment 5
A kind of three-way catalyst, including following raw materials：12 parts of lanthanum chloride, 15 parts of scandium chloride, 10 parts of plasdone, two
35 parts of titanium oxide, 28 parts of pottery, 20 parts of silica gel, 3 parts of sodium sulphate, 6 parts of palladium sulfate, 7 parts of cerium chloride, 20 parts of zirconium dioxide, γ-
Al2O328 parts, 6 parts of crosslinking agent, the preparation method of three-way catalyst is：By lanthanum chloride, scandium chloride and plasdone are molten
Yu Shuizhong, adds titanium dioxide, pottery and silica gel afterwards, impregnates 2.5h under normal temperature, adds cross-linking agents 1.8h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the NaOH of 0.1mol/L
Soak 40min in solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality；By sodium sulphate, palladium sulfate,
Cerium chloride is soluble in water, adds afterwards and impregnates 18h under zirconium dioxide normal temperature, adds cross-linking agents 2.5h, and the material after crosslinking is used
High-pressure molding instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C；By B, C and γ-Al2O3Mix, add and hand over
Connection agent crosslinking 23min, the material high-pressure molding instrument after crosslinking is prepared into the microballoon that can cross 50 mesh sieves, is designated as D, D is carried out micro-
Wave radiation 18min, γ-Al2O3100 mesh sieves can be crossed；The parameter of high-pressure molding instrument is：Voltage 33kv, fltting speed is 5mm/h, arteries and veins
A width of 3ms, frequency is 110Hz；Crosslinking agent is the mixture of GDMA and glyceraldehyde, dimethacrylate
The mass ratio of glycol ester and glyceraldehyde is 9:1；Crosslinking agent used in the preparation of A, the system of crosslinking agent used and D in the preparation of C
In standby, the mass ratio of crosslinking agent used is 2:1:3.
Comparative example 1
Randomly draw 60 automobiles, the engine of car is spark-ignition engine, fuel oil is gasoline, the highest of car using the age is
6 years, the minimum use age of car was 1 year, and the age that averagely uses of car is 3 years, 60 cars is divided into 6 groups, is designated as one group,
Two groups, three groups, four groups, five groups, six groups it is ensured that the situation of this four groups of cars is consistent, one group uses embodiment 1 gained catalyst, two
Using embodiment 2 gained catalyst, three groups using embodiment 3 gained catalyst, four groups use embodiment 4 gained catalyst to group,
Five groups use embodiment 5 gained catalyst, and six groups use common three-way catalyst, running car 500 Km, record vehicle exhaust
The average emission value of CO, HC, Nox, such as table 1 below：
As can be seen from Table 1, the three-way catalyst that the present invention provides, it is catalyzed CO, and HC, Nox are converted into harmless CO2、
H2O and N2Ability be higher than significantly larger than common three-way catalyst, meet country to tail through the tail gas of this catalyst treatment
The requirement of gas discharge.
Comparative example 2
Randomly draw 70 automobiles, the engine of car is spark-ignition engine, fuel oil is gasoline, the highest of car using the age is
6 years, the minimum use age of car was 1 year, and the age that averagely uses of car is 3 years, 70 cars is divided into 4 groups, is designated as seven groups,
Eight groups, nine groups, ten groups, 11 groups, 11 groups and 12 groups guarantee that the situation of this seven groups of cars is consistent, and the catalyst of seven groups of uses is
Processed the catalyst after travelling 50,000 kilometers of tail gas, catalyst is with the preparation of embodiment 1 methods described；Eight groups use urge
Agent is the catalyst processing after travelling 50,000 kilometers of tail gas, and catalyst is with the preparation of embodiment 2 methods described；Nine groups make
Catalyst is the catalyst processing after travelling 50,000 kilometers of tail gas, and catalyst is with the preparation of embodiment 3 methods described；
The catalyst of ten groups of uses is original conventional typical catalyst；11 groups is to process 50,000 kilometers of tails using catalyst
Typical catalyst after gas；The catalyst of 12 groups of uses is the catalyst processing after travelling 50,000 kilometers of tail gas, and catalyst is
With the preparation of embodiment 4 methods described；The catalyst of 13 groups of uses is the catalyst processing after travelling 50,000 kilometers of tail gas,
Catalyst is with the preparation of embodiment 5 methods described；After running car 500 Km, record five-nine group vehicle exhaust CO, HC, Nox
Average emission value, such as table 2 below：
As shown in Table 2, catalyst long service life described herein, because the active component of catalyst is each group in catalyst
Divide common coordinated effect, from the data in table 2, after processing 50,000 kilometers of tail gas of traveling, it processes tail to catalyst
Gas substantially there is not any change, therefore, it can draw, in the application catalyst, each component synergy decreases catalyst
The loss of middle active component, has delayed the carbon deposition phenomenon of catalyst surface.
In herein described catalyst, main active component derives from lanthanum chloride, scandium chloride, sodium sulphate, palladium sulfate and chlorination
Cerium, main carriers are titanium dioxide, pottery, zirconium dioxide and γ-Al2O3, in embodiment 1, active component is carrier quality
24%；In embodiment 2, active component is the 38% of carrier quality；In embodiment 3, active component is the 31% of carrier quality；By table 1 He
In table 2, the ability of the process tail gas of each catalyst understands, is not that in catalyst, active component is The more the better, for the application
Speech, the proportion increasing active constituent within the specific limits contributes to the raising of catalysis activity, after reaching certain value, increases activity
The proportion of component, catalytic effect can reduce.
Claims (10)
1. a kind of three-way catalyst is it is characterised in that include following raw materials：Lanthanum chloride 1-10 part, scandium chloride 1-10 part, polyethylene
Pyridine pyrrolidone 5-8 part, titanium dioxide 20-30 part, ceramic 15-25 part, silica gel 15-25 part, sodium sulphate 1-5 part, palladium sulfate 4-8
Part, cerium chloride 5-7 part, zirconium dioxide 15-25 part, γ-Al2O315-20 part, crosslinking agent 1-5 part.
2. as claimed in claim 1 a kind of three-way catalyst it is characterised in that include following raw materials：Lanthanum chloride 3-7 part, chlorine
Change scandium 3-7 part, plasdone 6-7 part, titanium dioxide 23-27 part, ceramic 18-22 part, silica gel 17-23 part, sulfuric acid
Sodium 2-4 part, palladium sulfate 5-7 part, cerium chloride 6-7 part, zirconium dioxide 18-22 part, γ-Al2O316-19 part, crosslinking agent 2-4 part.
3. as claimed in claim 1 a kind of three-way catalyst it is characterised in that include following raw materials：5 parts of lanthanum chloride, chlorination
5 parts of scandium, 6 parts of plasdone, 5 parts of titanium dioxide, 20 parts of pottery, 20 parts of silica gel, 3 parts of sodium sulphate, 6 parts of palladium sulfate,
7 parts of cerium chloride, 20 parts of zirconium dioxide, γ-Al2O318 parts, 3 parts of crosslinking agent.
4. a kind of preparation method of three-way catalyst is it is characterised in that by lanthanum chloride, scandium chloride and plasdone are molten
Yu Shuizhong, adds titanium dioxide, pottery and silica gel afterwards, impregnates 1-2h under normal temperature, adds cross-linking agents 0.5-1h, after crosslinking
Material high-pressure molding instrument is prepared into the microballoon that can cross 60 mesh sieves, and described microballoon is designated as A, A is placed in the hydroxide of 0.1mol/L
Soak 10-30min in sodium solution, obtain porous microsphere and be designated as B, deionized water cleans B surface to neutrality.
5. as claimed in claim 4 a kind of preparation method of three-way catalyst it is characterised in that described by sodium sulphate, sulfuric acid
Palladium, cerium chloride is soluble in water, adds afterwards and impregnates 5-10h under zirconium dioxide normal temperature, adds cross-linking agents 1-2h, the thing after crosslinking
Matter high-pressure molding instrument is prepared into the microballoon that can cross 100 mesh sieves, and described microballoon is designated as C.
6. as claimed in claim 5 a kind of preparation method of three-way catalyst it is characterised in that described by B, C and γ-Al2O3
Mix, add cross-linking agents 10-15min, the material high-pressure molding instrument after crosslinking is prepared into can cross the micro- of 50 mesh sieves
Ball, is designated as D, and D is carried out microwave 5-10min, γ-Al2O3100 mesh sieves can be crossed.
7. as claimed in claim 6 a kind of preparation method of three-way catalyst it is characterised in that described high-pressure molding instrument
Parameter is：Voltage 30～35kv, fltting speed is 90～100mm/h, and pulsewidth is 3ms, and frequency is 100Hz.
8. as claimed in claim 1 a kind of preparation method of three-way catalyst it is characterised in that described crosslinking agent be peroxidating
The mixture of dibenzoyl, isothiocyanates, N hydroxymethyl acrylamide, GDMA and glyceraldehyde, institute
State dibenzoyl peroxide, isothiocyanates, N hydroxymethyl acrylamide, GDMA and glyceraldehyde
Mass ratio is 1:1:2:2:3.
9. as claimed in claim 1 a kind of preparation method of three-way catalyst it is characterised in that described crosslinking agent be glycerine
Aldehyde；Described crosslinking agent is the mixture of GDMA and glyceraldehyde, described GDMA
Mass ratio with glyceraldehyde is 1:1.
10. as claimed in claim 6 a kind of preparation method of three-way catalyst it is characterised in that used in the preparation of described A
Crosslinking agent, in the preparation of crosslinking agent used and described D in the preparation of described C, the mass ratio of crosslinking agent used is 2:1:3.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1222127A (en) * | 1996-05-15 | 1999-07-07 | 罗狄亚化学公司 | Cerium oxide and zirconium oxide based compsn., method of prepn.and utilisation in catalysis |
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2016
- 2016-11-15 CN CN201611003673.8A patent/CN106423298A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222127A (en) * | 1996-05-15 | 1999-07-07 | 罗狄亚化学公司 | Cerium oxide and zirconium oxide based compsn., method of prepn.and utilisation in catalysis |
Non-Patent Citations (2)
| Title |
|---|
| 朱洪法等: "《催化剂制备及应用技术》", 30 June 2011, 中国石化出版社 * |
| 王笃政等: "汽车尾气三效催化剂最新研究进展", 《化工中间体》 * |
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