CN106861718A - A kind of cleaning catalyst for tail gases of automobiles and preparation method thereof - Google Patents
A kind of cleaning catalyst for tail gases of automobiles and preparation method thereof Download PDFInfo
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- CN106861718A CN106861718A CN201710156174.0A CN201710156174A CN106861718A CN 106861718 A CN106861718 A CN 106861718A CN 201710156174 A CN201710156174 A CN 201710156174A CN 106861718 A CN106861718 A CN 106861718A
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- tail gases
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000007789 gas Substances 0.000 title claims abstract description 30
- 238000004140 cleaning Methods 0.000 title claims abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 18
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 20
- 238000005406 washing Methods 0.000 abstract description 14
- 238000001556 precipitation Methods 0.000 abstract description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000003643 water by type Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000004088 simulation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000420 cerium oxide Inorganic materials 0.000 description 6
- 150000002823 nitrates Chemical class 0.000 description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000000505 pernicious effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
-
- 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
- B01J37/033—Using Hydrolysis
-
- 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
- B01J37/035—Precipitation on carriers
-
- 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof, the catalyst includes following component, based on catalyst weight percent：The oxide of cerium accounts for 45~99.5wt%, and the oxide of zirconium accounts for 0~55wt%；Catalytic active component is the oxide of palladium or/and the oxide of nickel, accounts for 0.5~10wt%.The present invention, through precipitation, washing, dry, roasting, grinding, is obtained auto-exhaust catalyst with cerous nitrate, zirconium nitrate, ammoniacal liquor, palladium bichloride, nickel chloride as raw material.Prepared catalyst is 60 DEG C to the initiation temperature of CO, and the initiation temperature to NO is 105 DEG C, with good low temperature ignition performance, and can keep good carbon monoxide and nitric oxide production conversion ratio at 280 DEG C or so.Catalyst preparation process is simple, and repeatability is good, and the active component of load is the oxide of palladium or/and the oxide of nickel, and is carried out at normal temperatures, low cost, can be further with good application prospect in automotive exhaust catalysis field.
Description
Technical field
The present invention relates to a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof, belong to vehicle maintenance service field.
Background technology
With the fast development of automobile industry, the problem of environmental pollution that vehicle exhaust brings is urgently to be resolved hurrily.In motor vehicle emission
Tail gas in, its main pernicious gas has carbon monoxide (CO), nitrogen oxides (NOX) and hydrocarbon (HC) etc..Solve tail
One of effective ways of gas exhaust emission are the installation catalytic cleaners at automobile exhaust pipe, and catalytic cleaner it is critical only that
Catalyst.
The composition of auto-exhaust catalyst generally used in actual production for：Carried in ceramic honeycomb or metal alloy
The coating of bigger serface is coated on body, then the precious metal catalyst active component such as supporting Pt, Rh, Pd.Existing vehicle exhaust is urged
There is its limitation in agent.On the one hand, it is expensive because Precious Metals Resources are limited, therefore reduce consumption and the guarantor of noble metal
Card noble metal is combined into study hotspot with coating.On the other hand, catalyst starting catalytic temperature drift, and in high temperature ageing
Catalytic performance declines to a great extent afterwards, therefore reduces the light-off temperature of catalyst, and it is again a problem to prevent high temperature sintering.
Chinese patent literature CN105688963A discloses a kind of vehicle maintenance service catalyst and preparation method thereof and answers
With.Rare earth element, neutral salt are mixed and obtained by auto-exhaust catalyst prepared by the invention with carborundum as carrier with noble metal platinum
Obtain catalyst colloid and be adsorbed on carrier.The catalyst can realize the catalyzed conversion to NO in vehicle exhaust.But catalyst
Temperature needed for catalysis NO is high, and conversion is incomplete, does not also provide the catalyzed conversion effect to other two kinds of pernicious gases HC and CO
Really.
Chinese patent literature CN1436592A discloses a kind of preparation method of cleaning catalyst for tail gases of automobiles, and the method is led to
Wet chemistry method is crossed with aluminum oxide as matrix, addition lanthanum, zirconium, cerium, yttrium and praseodymium element composition obtain composite alumina, then load expensive
Metal active constituent is constituted.The catalyst can realize the catalyzed conversion to vehicle exhaust, while rationally make use of rare earth element.
But catalyst noble metal consumption is big, and infusion process carried noble metal is used, noble metal utilisation is low and aluminum oxide and noble metal
Combination degree is poor.
Thus, research and development auto-exhaust catalyst is significant.Catalyst low temperature activating characteristic how is improved, is dropped
The cold start emission of low automobile；The utilization rate of noble metal is improved, cost is reduced；Improve the resistance to elevated temperatures of catalyst and use the longevity
Life, as problem demanding prompt solution.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof.This hair
Bright auto-exhaust catalyst preparation process is simple, with low cost, has excellent purifying property to vehicle exhaust, and CO is risen
Combustion temperature is 60 DEG C, and the initiation temperature to NO is 105 DEG C, with good low temperature ignition performance, it is possible to achieve a good oxygen
Change the removing of nitrogen and carbon monoxide.
Technical scheme is as follows：
A kind of cleaning catalyst for tail gases of automobiles, including following component, based on catalyst weight percent：The oxide of cerium is accounted for
45~99.5wt%, the oxide of zirconium accounts for 0~55wt%；Catalytic active component is the oxide of palladium or/and the oxide of nickel, is accounted for
0.5~10wt%.
According to currently preferred, described cleaning catalyst for tail gases of automobiles, including following component, by catalyst weight hundred
Divide than meter：The oxide of cerium accounts for 50~80wt%, and the oxide of zirconium accounts for 15~45wt%；Catalytic active component is the oxide of palladium
Or/and the oxide of nickel, account for 0.5~5wt%.
According to currently preferred, when the hopcalite that catalytic active component is palladium and nickel, the oxide of nickel
Account for the 0.5-3.5% of catalyst quality.
A kind of preparation method of cleaning catalyst for tail gases of automobiles, including step is as follows：
(1) soluble-salt of the soluble-salt of cerium, zirconium is dissolved in deionized water, stirs to obtain metal salt solution；
(2) ammoniacal liquor is added dropwise in the metal salt solution in step (1), to metal salt solution in alkalescence, in 70~100
Stirred at DEG C, obtain product A；
(3) the product A that will be obtained in step (2) is scrubbed, dry, roasting, grinding, obtain catalyst support powder；
(4) catalyst support powder obtained in step (3) is scattered in deionized water, nickel is added dropwise under stirring
Or/and the soluble salt solutions of palladium, obtain mixed solution；
(5) sodium carbonate liquor is added dropwise in the mixed solution in step (4), to mixed solution in alkalescence, in normal temperature
Lower stirring, obtains product B；
(6) the product B that will be obtained in step (5) is scrubbed, dry, roasting, grinding, obtain final product purifying vehicle exhaust and urge
Agent.
Preparation in accordance with the present invention, it is preferred that the soluble-salt of cerium and zirconium in step (1) metal salt solution
The mol ratio of soluble-salt is 0.1-4：1.
Preparation in accordance with the present invention, it is preferred that in the step (1) soluble-salt of cerium be cerous nitrate, zirconium can
Soluble is zirconium nitrate.
Preparation in accordance with the present invention, it is preferred that the mass fraction of ammoniacal liquor is 10%-30% in the step (2).
Preparation in accordance with the present invention, it is preferred that the pH of step (2) the neutral and alkali scope is 8.5-11.
Preparation in accordance with the present invention, it is preferred that mixing time is 6-16h in the step (2).
Preparation in accordance with the present invention, it is preferred that drying condition is in the step (3)：10- is dried at 60~75 DEG C
18h。
Preparation in accordance with the present invention, it is preferred that roasting condition is in the step (3)：It is calcined at 300~600 DEG C
2-6h。
Preparation in accordance with the present invention, it is preferred that step (4) catalyst support powder is scattered in deionized water
Afterwards, concentration is 1-2g/L.
Preparation in accordance with the present invention, it is preferred that when while the soluble-salt of nickel and palladium is added dropwise in the step (4)
When, the soluble-salt of nickel is 0.5-5 with the molar ratio of the soluble-salt of palladium：1.
Preparation in accordance with the present invention, it is preferred that the molar concentration of sodium carbonate liquor is 0.05- in the step (5)
0.5mol/L。
Preparation in accordance with the present invention, it is preferred that the pH of step (5) the neutral and alkali scope is 8-12.
Preparation in accordance with the present invention, it is preferred that mixing time is 0.5-3h in the step (5).
Preparation in accordance with the present invention, it is preferred that drying condition is in the step (6)：6- is dried at 65~75 DEG C
12h。
Preparation in accordance with the present invention, it is preferred that roasting condition is in the step (6)：It is calcined at 200~500 DEG C
2-6h。
The invention has the advantages that：
1. in the preparation process of catalyst of the present invention, using the precipitation method, using ammoniacal liquor as precipitating reagent, the cerium zirconium of synthesis is made
Solid solution is more uniform, and specific surface area is bigger, it is more uniform that catalytic active component is distributed in the carrier so that catalyst is urged
Change performance more superior.
2. the catalyst low-temperature activity that prepared by the present invention is good, and the initiation temperature to CO is 60 DEG C, and the initiation temperature to NO is
105 DEG C, with good low temperature ignition performance, and high catalytic efficiency, removal efficiency of the CO and NO up to 100%.
3. in the preparation process of catalyst of the present invention, the oxide of cerium zirconium sosoloid supported palladium or/and the oxide of nickel are adopted
With the precipitation method, compare for infusion process, can more preferably realize the utilization rate of palladium and nickel, and carry out at normal temperatures, reaction is simple, section
Resource-saving.
4. the oxide of present invention palladium or/and the oxide of nickel compare noble metal systems, low cost as active component
It is honest and clean, can be further with good application prospect in automotive exhaust catalysis field.
Brief description of the drawings
Fig. 1 is the catalytic effect figure that catalyst obtained in the embodiment of the present invention 2 is removed to NO and CO.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but not as a limitation of the invention.
Experimental technique described in following embodiments, unless otherwise specified, is conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
The evaluation method of catalyst activity：
Vehicle exhaust to simulating carries out catalysis test, and test condition is：Air speed 60,000h-1, CO contents 1000ppm, NO
Content 1000ppm, Ar are Balance Air.
Embodiment 1
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 55.97wt%, and the oxide of zirconium accounts for 39.88wt%；Catalytic active component is the oxide of palladium and the oxide of nickel
The mixture of composition, accounts for 4.15wt% (wherein altogether：The oxide of nickel accounts for the 3.05wt% of catalyst quality, and the oxide of palladium is accounted for
The 1.1wt% of catalyst quality).
Preparation process is as follows：
(1) 5.2321g cerous nitrates, 5.1490g zirconium nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 25% is added dropwise in metal salt solution, the pH to metal salt solution is 9, is put
The strong stirring 6h in 90 DEG C of oil bath pan, obtains product A；
(3) 12h by product A washings, after alcohol washes, is dried at 60 DEG C, 2h is calcined at 400 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 1.667ml, 10g/L is added dropwise under stirring
Palladium chloride solution and 5.06ml, 20g/L nickel chloride solution, obtain mixed solution；
(5) sodium carbonate liquor of 0.1mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 11, in 1h is stirred under normal temperature, obtains product B；
(6) 12h by product B washings, after alcohol washes, is dried at 65 DEG C, 2h is calcined at 500 DEG C, be ground to it is powdered,
Obtain cleaning catalyst for tail gases of automobiles.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 110 DEG C, and removal efficiency reaches 100% at 250 DEG C；
CO initiation temperatures are 70 DEG C, and removal efficiency reaches 98% at 350 DEG C.
Embodiment 2
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 57.3wt%, and the oxide of zirconium accounts for 41wt%；Catalytic active component is the oxide of palladium, accounts for 1.7wt%.
Preparation process is as follows：
(1) 5.2120g cerous nitrates, 5.1523g zirconium nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 25% is added dropwise in metal salt solution, the pH to metal salt solution is 9, is put
The strong stirring 12h in 90 DEG C of oil bath pan, obtains product A；
(3) 12h by product A washings, after alcohol washes, is dried at 65 DEG C, 3h is calcined at 500 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 2.5ml, 10g/L is added dropwise under stirring
Palladium chloride solution, obtains mixed solution；
(5) sodium carbonate liquor of 0.1mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 9.5, in 2h is stirred under normal temperature, obtains product B；
(6) 12h by product B washings, after alcohol washes, is dried at 65 DEG C, 2h is calcined at 300 DEG C, be ground to it is powdered,
Obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 105 DEG C, and removal efficiency reaches 100% at 210 DEG C；
CO initiation temperatures are 60 DEG C, and removal efficiency reaches 100% at 325 DEG C.
Embodiment 3
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 98.3wt%, and the oxide of zirconium accounts for 0wt%；Catalytic active component is the oxide of palladium, accounts for 1.7wt%.
Preparation process is as follows：
(1) 10.4241g cerous nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 30% is added dropwise in metal salt solution, the pH to metal salt solution is 10, is put
The strong stirring 10h in 90 DEG C of oil bath pan, obtains product A；
(3) 18h by product A washings, after alcohol washes, is dried at 65 DEG C, 3h is calcined at 550 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 1.667ml, 10g/L is added dropwise under stirring
Palladium chloride solution, obtain mixed solution；
(5) sodium carbonate liquor of 0.5mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 11, in 0.5h is stirred under normal temperature, obtains product B；
(6) 8h by product B washings, after alcohol washes, is dried at 75 DEG C, 6h is calcined at 300 DEG C, be ground to it is powdered,
Obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 126 DEG C, and removal efficiency reaches 82% at 350 DEG C；CO
Initiation temperature is 90 DEG C, and removal efficiency reaches 85% at 350 DEG C.
Embodiment 4
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 56.88wt%, and the oxide of zirconium accounts for 40.64wt%；Catalytic active component is the oxide of nickel, accounts for 2.48wt%.
Preparation process is as follows：
(1) 5.2191g cerous nitrates, 5.1499g zirconium nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 25% is added dropwise in metal salt solution, the pH to metal salt solution is 9.5,
Strong stirring 12h in 90 DEG C of oil bath pan is put in, product A is obtained；
(3) 12h by product A washings, after alcohol washes, is dried at 65 DEG C, 4h is calcined at 500 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 4.05ml, 20g/L is added dropwise under stirring
Nickel chloride solution, obtains mixed solution；
(5) sodium carbonate liquor of 0.1mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 10, in 2h is stirred under normal temperature, obtains product B；
(6) 10h by product B washings, after alcohol washes, is dried at 65 DEG C, 2h is calcined at 300 DEG C, be ground to it is powdered,
Obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 130 DEG C, and removal efficiency reaches 65% at 330 DEG C；CO
Initiation temperature is 100 DEG C, and removal efficiency reaches 100% at 380 DEG C.
Embodiment 5
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 79.54wt%, and the oxide of zirconium accounts for 18.75wt%；Catalytic active component is the oxide of palladium, accounts for 1.71wt%.
Preparation process is as follows：
(1) 7.8186g cerous nitrates, 2.5471g zirconium nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 20% is added dropwise in metal salt solution, the pH to metal salt solution is 9, is put
The strong stirring 14h in 90 DEG C of oil bath pan, obtains product A；
(3) 12h by product A washings, after alcohol washes, is dried at 75 DEG C, 3h is calcined at 450 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 2.5ml, 10g/L is added dropwise under stirring
Palladium chloride solution, obtains mixed solution；
(5) sodium carbonate liquor of 0.2mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 9.5, in 1h is stirred under normal temperature, obtains product B；
(6) 6h by product B washings, after alcohol washes, is dried at 65 DEG C, 4h is calcined at 450 DEG C, be ground to it is powdered,
Obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 100 DEG C, and removal efficiency reaches 98% at 250 DEG C；CO
Initiation temperature is 75 DEG C, and removal efficiency reaches 90% at 400 DEG C.
Embodiment 6
Cleaning catalyst for tail gases of automobiles prepared by the precipitation method, including following component, based on catalyst weight percent：Cerium
Oxide accounts for 57.18%, and the oxide of zirconium accounts for 40.46%；Catalytic active component is the oxide of palladium and the oxide composition of nickel
Mixture, 2.36wt% is accounted for altogether (wherein：The oxide of nickel accounts for the 1.24% of catalyst quality, the oxide of palladium accounts for catalyst
Quality 1.12%).
Preparation process is as follows：
(1) 5.2702g cerous nitrates, 5.1513g zirconium nitrates are dissolved in 150ml deionized waters, stir to obtain metal salt solution；
(2) ammoniacal liquor that mass fraction is 30% is added dropwise in metal salt solution, the pH to metal salt solution is 9, is put
The strong stirring 8h in 90 DEG C of oil bath pan, obtains product A；
(3) 12h by product A washings, after alcohol washes, is dried at 65 DEG C, 6h is calcined at 500 DEG C, be ground to it is powdered,
Obtain catalyst carrier；
(4) catalyst carrier of 1g is scattered in 100ml deionized waters, 1.667ml, 10g/L is added dropwise under stirring
Palladium chloride solution and 2.03ml, 20g/L nickel chloride solution, obtain mixed solution；
(5) sodium carbonate liquor of 0.5mol/L is added dropwise in the mixed solution in step (4), to the pH of mixed solution
It is 10, in 0.5h is stirred under normal temperature, obtains product B；
(6) 12h by product B washings, after alcohol washes, is dried at 65 DEG C, 2h is calcined at 400 DEG C, be ground to it is powdered,
Obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 105 DEG C, and removal efficiency reaches 100% at 265 DEG C；
CO initiation temperatures are 65 DEG C, and removal efficiency reaches 95% at 350 DEG C.
Comparative example 1
As described in Example 2, preparation catalyst is used unlike.
Catalyst carrier obtained in the step of by 1g (3) is impregnated into the palladium chloride solution of 10g/L, and then washing, alcohol are washed
Afterwards, 12h is dried at 65 DEG C, 2h is calcined at 300 DEG C, be ground to powdered, obtain auto-exhaust catalyst.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 120 DEG C, and removal efficiency reaches 65% at 300 DEG C；CO
Initiation temperature is 120 DEG C, and removal efficiency reaches 82% at 320 DEG C.
Comparative example 2
As described in Example 2, unlike：
Step is calcined 4h in (6) at 800 DEG C.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 105 DEG C, and removal efficiency reaches 90% at 300 DEG C；CO
Initiation temperature is 70 DEG C, and removal efficiency reaches 85% at 355 DEG C.
Comparative example 3
As described in Example 2, unlike：
Step is calcined 4h in (6) at 900 DEG C.
Tested using the vehicle exhaust of simulation, NO initiation temperatures are 140 DEG C, and removal efficiency reaches 88% at 320 DEG C；CO
Initiation temperature is 100 DEG C, and removal efficiency reaches 80% at 380 DEG C.
By comparative example 2 and comparative example 1, infusion process is not easy to make active component load completely, causes to obtain
Catalyst have to the removal efficiency of NO and CO and significantly reduce.
Comparative example 2 and comparative example 2,3 understand that the sintering temperature of catalyst is too high, can have a strong impact on urging for catalyst
Change efficiency.
Claims (10)
1. a kind of cleaning catalyst for tail gases of automobiles, it is characterised in that the catalyst includes following component, by catalyst weight percentage
Than meter：The oxide of cerium accounts for 45~99.5wt%, and the oxide of zirconium accounts for 0~55wt%；Catalytic active component is the oxide of palladium
Or/and the oxide of nickel, account for 0.5~10wt%.
2. the cleaning catalyst for tail gases of automobiles according to claim, it is characterised in that the catalyst includes following component, presses
Catalyst weight percent meter：The oxide of cerium accounts for 50~80wt%, and the oxide of zirconium accounts for 15~45wt%；Catalytic active component
It is the oxide or/and the oxide of nickel of palladium, accounts for 0.5~5wt%.
3. a kind of preparation method of cleaning catalyst for tail gases of automobiles, including step is as follows：
(1) soluble-salt of the soluble-salt of cerium, zirconium is dissolved in deionized water, stirs to obtain metal salt solution；
(2) ammoniacal liquor is added dropwise in the metal salt solution in step (1), to metal salt solution in alkalescence, at 70~100 DEG C
Stirring, obtains product A；
(3) the product A that will be obtained in step (2) is scrubbed, dry, roasting, grinding, obtain catalyst carrier；
(4) catalyst carrier obtained in step (3) is scattered in deionized water, nickel or/and palladium is added dropwise under stirring
Soluble salt solutions, obtain mixed solution；
(5) sodium carbonate liquor is added dropwise in the mixed solution in step (4), to mixed solution in alkalescence, is stirred under normal temperature
Mix, obtain product B；
(6) the product B that will be obtained in step (5) is scrubbed, dry, roasting, grinding, obtain final product purifying vehicle exhaust catalysis
Agent.
4. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (1)
The soluble-salt of cerium and the mol ratio of the soluble-salt of zirconium are 0.1-4 in metal salt solution：1；
Preferably, the soluble-salt of cerium is cerous nitrate in the step (1), and the soluble-salt of zirconium is zirconium nitrate.
5. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (2)
The mass fraction of middle ammoniacal liquor is 10%-30%.
6. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (2)
The pH of neutral and alkali scope is 8.5-11.
7. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (3)
Middle roasting condition is：2-6h is calcined at 300~600 DEG C.
8. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (4)
In when the soluble-salt of nickel and palladium is simultaneously added dropwise, the soluble-salt of nickel is 0.5-5 with the molar ratio of the soluble-salt of palladium：1.
9. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (5)
The pH of neutral and alkali scope is 8-12.
10. the preparation method of cleaning catalyst for tail gases of automobiles according to claim 3, it is characterised in that the step (6)
Middle roasting condition is：2-6h is calcined at 200~500 DEG C.
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