CN103551166A - Nano alloy modified cerium oxide powder applied to soot combustion reaction, and preparation method thereof - Google Patents
Nano alloy modified cerium oxide powder applied to soot combustion reaction, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano alloy modified cerium oxide powder applied to soot combustion reaction, and a preparation method thereof, and relates to cerium oxide powder. The powder is prepared from a platinum nano alloy phase and a cerium oxide or cerium-zirconium mixed oxide carrier. The method comprises the following steps: mixing organic salt of each metal component, and then preparing into a mixed metal ion octyl ether solution or a mixed metal ion dibenzyl ether solution; adding a mixed surfactant to the mixed metal ion octyl ether solution or the mixed metal ion dibenzyl ether solution, so as to obtain a reduction-type mixed metal particle dispersed solution; heating and refluxing the reduction-type mixed metal particle dispersed solution, and then adding a high-polarity alcohol solvent to separate out nano particles in a gathering manner; dispersing into a low-boiling point organic solvent after removing the alcohol solvent in a volatilizing manner, so as to prepare nano alloy disperse precursor solution; putting the carrier into a container, and wetting by using an organic solvent, so as to obtain a wetting vector; injecting the nano alloy disperse precursor solution to the wetting carrier, lastingly stirring until a mobile phase volatilizes, so as to obtain wetting powder; drying and burning, so as to obtain the product.
Description
Technical field
The present invention relates to cerium oxide powder, especially relate to and adopt the Nanoalloy material with efficient oxygen reducing ability to carry out finishing to cerium oxide powder, to improve the material preparation technology of carbon granule catalytic oxidation activity and modified oxidized cerium powder of a kind of Nanoalloy reacting for carbon-smoke combustion of method and preparation method thereof.
Background technology
Adopt particulate matter trap (DPF) to carry out filtering to the particle in tail gas, that in diesel engine vent gas treatment technology, the most effective particle is removed means, and minimum to the dynamic property of motor vehicle and economic influence, and by introduce completely oxidizing catalyst in grain catcher, the heat decomposition temperature of carbon soot particles can be down to 150～400 ℃, effectively to prevent that carbon granule from excessively accumulation occurring on filter, and cause plugged filter, thereby improve diesel engine performance.The platinum family noble metal of take has the advantage of catalytic oxidation efficiency (comprising that Emission control is active) and low temperature ignition as sponsoring the soot combustion catalyst of agent, therefore be often used in the design of practical soot combustion catalyst system, as Chinese patent CN102240544A and the disclosed noble metal type catalyst of CN102794175A, yet, because noble metal is expensive and scarcity of resources, so this type catalyst is subject to the serious restriction of cost of material in commercialization process.Practical catalyst system and catalyzing by the assistance of active carrier, amass, but owing to being subject to the restriction of noble metal intrinsic hydrogen reduction characteristic, under this improved procedure, single reaction site inversion frequency is not still improved to increase the reaction accessible surface of noble metal composition conventionally.
Summary of the invention
The object of this invention is to provide a kind of modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction that can reduce combustion temperature of soot and preparation method thereof.
The described modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction is comprised of platinum base Nanoalloy phase and cerium oxide or cerium zirconium compound oxide carrier; Described platinum base Nanoalloy is that metallic element forms by platinum and First Transition; The content of described Nanoalloy phase is 0.2%～10% of carrier quality by mass percentage; The composition general formula of platinum base Nanoalloy is Pt
x(M1M2)
1-x, wherein M1, M2 are that First Transition is any two compatibility in metallic iron, cobalt, nickel, x is 0.1～0.6.
The preparation method of the described modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction, comprises the following steps:
1) after the organic salt of each metal component is weighed in proportion and mixing, be mixed with hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution;
2) under agitation, in hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution, add mixed surfactant, obtain reduced form hybrid metal particle dispersing solution, described mixed surfactant adopts the mixture of dihydroxylic alcohols, aliphatic acid and fatty amine;
3) by step 2) the reduced form hybrid metal particle dispersing solution that obtains adds after hot reflux, adds high polarity alcoholic solvent to make nano particle segregation;
4) volatilization is removed after alcoholic solvent, is dispersed in low boiling point organic solvent, makes Nanoalloy decentralized precursor solution;
5) carrier is placed in to container, and makes it wetting with organic solvent, obtain wetting carrier;
6) to implantation step 4 in the wetting carrier of step 5) gained) gained Nanoalloy decentralized precursor solution, continue stirring until mobile phase volatilization, obtain moistening powder, dry, after calcining, obtain the modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction.
In step 1), described organic salt can adopt Nanoalloy to form acetylacetonate and the naphthenate of metal; Total metal ion molar concentration of described hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution can be each concentration of metal ions ratio of 0.01～0.08mol/L(and adjusts according to the metal proportioning of target alloy system); It is platinum, iron, cobalt, nickel that described Nanoalloy forms metal.
In step 2) in, described dihydroxylic alcohols can adopt and face a high-carbon glycol, a kind of as in 1,2 ethohexadiol, 1,2 decanediol, 1,2 hexadecane glycol etc., and the consumption of dihydroxylic alcohols can be 0.5～10 times of metal ion molal quantity; It is 12～18 higher fatty acids that aliphatic acid can adopt carbon number, as laurate, and myristic acid, oleic acid, consumption is 0.5～5 times of metal ion total mole number; It is 12～18 higher fatty acids that fatty amine can adopt carbon number, as lauryl amine, and palmitamide, oleyl amine, consumption is 0.5～5 times of metal ion total mole number.
In step 3), described in add hot reflux temperature can be 270 ℃, the time that adds hot reflux can be 20～180min; Described high polarity alcoholic solvent can be selected from a kind of in methyl alcohol, ethanol, isopropyl alcohol etc., and the addition of high polarity alcoholic solvent by volume percentage can be 20%～50% of hybrid metal particle dispersing solution volume.
In step 4), described low boiling point organic solvent can be selected from toluene or n-hexane etc.
In step 5), described carrier can be selected from cerium oxide powder or cerium zirconium compound oxide powder; Described organic solvent can adopt toluene or n-hexane etc.
In step 6), in described Nanoalloy decentralized precursor solution, alloy mass is 0.2%～10% of carrier quality by mass percentage; The temperature of described calcining can be 260～700 ℃.
The present invention adopts Nanoalloy material to carry out modification to cerium oxide and cerium Zirconium oxide powder, provides and with transition metal such as iron-cobalt-nickels, noble metal platinum has been carried out the method for alloying modification, and producing general formula is Pt
x(M1M2)
1-xnanoalloy phase, wherein M1, M2 are that First Transition is any two compatibility in metallic iron, cobalt, nickel, x changes between 0.1～0.6.By dip loading, Nanoalloy particle is introduced on cerium oxide or cerium Zirconium oxide powder, wherein alloy phase load capacity is 0.2～10% of carrier quality.The prepared modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction of the present invention has good catalytic oxidation activity at carbon-smoke combustion: can be by soot T
50temperature is reduced to 400 ℃ of left and right from 642 ℃, within the scope of the Applicable temperature while falling into diesel engine operation.Under identical appreciation condition, meet and exceed the various carbon soot particles combustion catalyst of having reported.
The present invention is metal (iron, cobalt, nickel) by introducing First Transition, noble metal active is carried out to Nanoalloy modulation mutually, increase the noble metal specific activity of complete oxidation catalytic center, improve reaction conversions frequency, and carry out compatibility with cerium base or cerium zirconium base active carrier, maintain its reaction accessible surface long-pending with Surface Oxygen efficiency of transmission, to reduce noble metal dosage and to promote the soot particulate oxidation activity of integer catalyzer.Measured data shows, through the modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction of optimization of the present invention, can reduce approximately 30～180 ℃ of the maximum weightless temperatures of soot.Meanwhile, preparation method of the present invention is simple, and easy operating, applicable to industrial production.
Accompanying drawing explanation
Fig. 1 is reference example 1(catalyst-free), the unmodified cerium oxide of reference example 2() and the particle modified cerium oxide of embodiment 1(Nanoalloy) the conversion ratio-temperature curve of carbon soot particles.In Fig. 1, abscissa be ignition temperature (℃), ordinate is soot conversion ratio (%); Curve a is modified oxidized cerium, and curve b is cerium oxide, and curve c is that soot is blank.
Fig. 2 is that the present invention is for 500000 times of TEM pictures of the modified oxidized cerium powder of Nanoalloy of carbon-smoke combustion reaction.
The specific embodiment
In order to illustrate content of the present invention, enumerate some embodiment and adopt following testing standard to evaluate.
Catalyst activity is evaluated flow process: carbon-smoke combustion forms gas-phase product, its flame mechanism correspondence reducing in proportion of quality, by thermogravimetric analyzer, be recorded in the mass change situation of specifying catalyst and soot reactant in reaction atmosphere and temperature-rise period, the soot complete oxidation that can evaluate catalysis material to be measured is active, catalytic oxidation ability can adopt the feature ignition temperature of carbon soot particles to represent, under catalyst action, it is larger that the ignition temperature of carbon soot particles reduces amplitude, and the complete oxidation activity of corresponding catalyst is better.The present invention selects the initiation temperature (T of carbon soot particles
10), burn rate corresponding temperature (T when maximum
50) and after-flame temperature (T
90) as catalyst activity evaluation criterion, they represent that respectively carbon-smoke combustion completes the temperature spot of 10%, 50% and 90% correspondence.
Reference example 1
In the situation that not adding catalyst, directly 50mg carbon soot particles is put into TG-209 thermogravimetric analyzer, under air atmosphere, with the heating rate of 10 ℃/min, be warming up to 800 ℃ from 30 ℃, the weight-loss curve of gained is converted into conversion rate curve as shown in Figure 1, its T
10, T
50and T
90temperature be respectively 583 ℃, 642 ℃ and 681 ℃.
Reference example 2
By commercially available nano ceric oxide powder, according to mass ratio, be to mix at 5: 1 with carbon soot particles, with spoon, stir, put it in TG-209 thermogravimetric analyzer test crucible, under air atmosphere, (air velocity is 20ml/min) is raised to 800 ℃ with the heating rate of 10 ℃/min from 30 ℃.The weight-loss curve of gained is converted into conversion rate curve (referring to Fig. 1), T
10, T
50and T
90temperature be respectively 553 ℃, 616 ℃ and 640 ℃.
Reference example 3
Taking the cerous nitrate of 0.1M and the mixed solution 100ml(cerium of zirconyl nitrate and zirconium mol ratio is 9: 1), add 1.30g surfactant PVP, after stirring, the sal volatile of 0.4M of usining is converted into subcarbonate precipitation as precipitating reagent by metal ion, continue to stir after 0.5h, put it in water heating kettle in 160 ℃ of heating 16h, be cooled to after room temperature, cerium zirconium compound oxide presoma is washed to obtain in centrifugation.Presoma is dried to nights at 110 ℃, and in 600 ℃ of roasting 8h, obtains support C e
0.9zr
0.1o
ycomposite oxides.
By the above-mentioned Ce that makes
0.9zr
0.1o
ycomposite oxide power is to mix at 5: 1 with carbon soot particles according to mass ratio, with spoon, stir, put it in TG-209 thermogravimetric analyzer test crucible, under air atmosphere, (air velocity is 20ml/min) is raised to 800 ℃ with the heating rate of 10 ℃/min from 30 ℃.The weight-loss curve of gained is converted into the similar conversion rate curve with Fig. 1, T
10, T
50and T
90temperature be respectively 422 ℃, 528 ℃ and 602 ℃.
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in benzyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of benzyl ether solvent dilution metal component total mol concentration, making hybrid metal ion benzyl ether solution; Under agitation, in hybrid metal benzyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use toluene wetting ceria supports powder 10g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, obtain the modified oxidized cerium powder product of Nanoalloy for carbon-smoke combustion reaction.
By the above-mentioned modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction making, according to mass ratio, be to mix at 5: 1 with carbon soot particles, with spoon, stir, put it in TG-209 thermogravimetric analyzer test crucible, under air atmosphere, (air velocity is 20ml/min) is raised to 800 ℃ with the heating rate of 10 ℃/min from 30 ℃.The weight-loss curve of gained is converted into conversion rate curve (referring to Fig. 1), T
10, T
50and T
90temperature be respectively 342 ℃, 406 ℃ and 480 ℃.
Embodiment 2
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add methyl alcohol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in n-hexane, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use n-hexane wetting cerium Zirconium oxide support powder 50g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, obtain the modified oxidized cerium powder of the Nanoalloy catalyst prod for carbon-smoke combustion reaction.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 367 ℃, 466 ℃ and 549 ℃.
Embodiment 3
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.7g ferric acetyl acetonade (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.02mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add propyl alcohol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
38ni
27fe
35nanoalloy decentralized precursor solution.
As in container, and use toluene wetting cerium Zirconium oxide support powder 50g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 700 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 315 ℃, 436 ℃ and 519 ℃.
Embodiment 4
According to alloy metering ratio, require, by 1.23g acetylacetone,2,4-pentanedione platinum (3.14mmol), 0.3g nickel acetylacetonate (1.13mmol), 0.33g acetylacetone cobalt (0.9mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
61ni
22co
17nanoalloy decentralized precursor solution.
As in container, and use toluene wetting cerium Zirconium oxide support powder 50g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 700 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 342 ℃, 443 ℃ and 485 ℃.
Embodiment 5
According to alloy metering ratio, require, by 0.18g acetylacetone,2,4-pentanedione platinum (0.46mmol), 0.7g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 180min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
9ni
52co
39nanoalloy decentralized precursor solution.
As in container, and use toluene wetting ceria supports powder 50g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 359 ℃, 443 ℃ and 511 ℃.
Embodiment 6
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 decanediol 2.5mmol, myristic acid 3mmol and oleyl amine 2mmol add hot reflux 60min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use toluene wetting cerium Zirconium oxide support powder 20g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 387 ℃, 427 ℃ and 489 ℃.
Embodiment 7
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.54g nickel naphthenate (1.39mmol), 0.73g cobalt naphthenate (1.93mmol) is dissolved in benzyl ether and makes concentrated solution, concentrated solution mixed and use most 0.01mol/L of benzyl ether solvent dilution metal component total mol concentration, making hybrid metal ion benzyl ether solution; Under agitation, in hybrid metal benzyl ether solution, add 1,2 ethohexadiol 20mmol, oleic acid 5mmol and palmitamide 6.5mmol add hot reflux 30min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in n-hexane, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use n-hexane wetting cerium oxide powder 20g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 700 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 397 ℃, 462 ℃ and 495 ℃.
Embodiment 8
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 6mmol, laurate 10mmol and oleyl amine 2mmol add hot reflux 20min at 270 ℃ of temperature; After cooling, add isopropyl alcohol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use toluene wetting ceria supports powder 20g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 353 ℃, 412 ℃ and 507 ℃.
Embodiment 9
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.08mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, oleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in n-hexane, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use n-hexane wetting cerium Zirconium oxide support powder 0.5g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 600 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst sample soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 312 ℃, 366 ℃ and 466 ℃.
Embodiment 10
According to alloy metering ratio, require, by 0.77g acetylacetone,2,4-pentanedione platinum (1.97mmol), 0.36g nickel acetylacetonate (1.39mmol), 0.69g acetylacetone cobalt (1.93mmol) is dissolved in octyl ether and makes concentrated solution, concentrated solution mixed and use most 0.04mol/L of octyl ether solvent dilution metal component total mol concentration, making hybrid metal ion octyl ether solution; Under agitation, in hybrid metal octyl ether solution, add 1,2 hexadecane glycol 2.5mmol, linoleic acid 3mmol and oleyl amine 2mmol add hot reflux 40min at 270 ℃ of temperature; After cooling, add ethanol to separate out alloying pellet accumulation type precipitation, after fully dry, be dispersed in toluene, make and consist of Pt
38ni
27co
35nanoalloy decentralized precursor solution.
As in container, and use toluene wetting ceria supports powder 50g; Under agitation, inject Nanoalloy decentralized precursor solution (Nanoalloy content is 0.1g), continue stirring until mobile phase and substantially volatilize, product is moistening powder; Rising temperature to powder moves to powder in high temperature furnace after being dried completely; Under air atmosphere, in 260 ℃ of calcinings, obtain the modified oxidized cerium powder of Nanoalloy catalyst prod.
Catalyst prod soot complete oxidation active testing flow process, with embodiment 1, records T
10, T
50and T
90temperature be respectively 409 ℃, 486 ℃ and 569 ℃.
Claims (10)
1. for the modified oxidized cerium powder of Nanoalloy of carbon-smoke combustion reaction, it is characterized in that being formed by platinum base Nanoalloy phase and cerium oxide or cerium zirconium compound oxide carrier; Described platinum base Nanoalloy is that metallic element forms by platinum and First Transition; The content of described Nanoalloy phase is 0.2%～10% of carrier quality by mass percentage; The composition general formula of platinum base Nanoalloy is:
Pt
x（M1M2）
1-x
Wherein M1, M2 are that First Transition is any two compatibility in metallic iron, cobalt, nickel, and x is 0.1～0.6.
2. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 1, is characterized in that comprising the following steps:
1) after the organic salt of each metal component is weighed in proportion and mixing, be mixed with hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution;
2) under agitation, in hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution, add mixed surfactant, obtain reduced form hybrid metal particle dispersing solution, described mixed surfactant adopts the mixture of dihydroxylic alcohols, aliphatic acid and fatty amine;
3) by step 2) the reduced form hybrid metal particle dispersing solution that obtains adds after hot reflux, adds high polarity alcoholic solvent to make nano particle segregation;
4) volatilization is removed after alcoholic solvent, is dispersed in low boiling point organic solvent, makes Nanoalloy decentralized precursor solution;
5) carrier is placed in to container, and makes it wetting with organic solvent, obtain wetting carrier;
6) to implantation step 4 in the wetting carrier of step 5) gained) gained Nanoalloy decentralized precursor solution, continue stirring until mobile phase volatilization, obtain moistening powder, dry, after calcining, obtain the modified oxidized cerium powder of Nanoalloy for carbon-smoke combustion reaction.
3. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, is characterized in that in step 1), and described organic salt adopts Nanoalloy to form acetylacetonate and the naphthenate of metal; Total metal ion molar concentration of described hybrid metal ion octyl ether solution or hybrid metal ion benzyl ether solution is 0.01～0.08mol/L; It is platinum, iron, cobalt, nickel that described Nanoalloy forms metal.
4. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, is characterized in that in step 2) in, described dihydroxylic alcohols adopts and faces a high-carbon glycol, and the consumption of dihydroxylic alcohols is 0.5～10 times of metal ion molal quantity; Aliphatic acid adopts the higher fatty acids that carbon number is 12～18, and the consumption of aliphatic acid is 0.5～5 times of metal ion total mole number; Fatty amine adopts the higher fatty acids that carbon number is 12～18, and fatty amine consumption is 0.5～5 times of metal ion total mole number.
5. as claimed in claim 4 for the preparation method of the modified oxidized cerium powder of Nanoalloy of carbon-smoke combustion reaction, it is characterized in that, described in face a high-carbon glycol and be selected from a kind of in 1,2 ethohexadiol, 1,2 decanediol, 1,2 hexadecane glycol; Described carbon number is that 12～18 higher fatty acids is selected from a kind of in laurate, myristic acid, oleic acid; Described carbon number is that 12～18 higher fatty acids is selected from a kind of in lauryl amine, palmitamide, oleyl amine.
6. as claimed in claim 2 for the preparation method of the modified oxidized cerium powder of Nanoalloy of carbon-smoke combustion reaction, it is characterized in that in step 3), described in add hot reflux temperature be 270 ℃, the time that adds hot reflux is 20～180min.
7. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, it is characterized in that in step 3), described high polarity alcoholic solvent is selected from a kind of in methyl alcohol, ethanol, isopropyl alcohol, and the addition of high polarity alcoholic solvent by volume percentage is 20%～50% of hybrid metal particle dispersing solution volume.
8. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, is characterized in that in step 4), described low boiling point organic solvent is selected from toluene or n-hexane.
9. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, is characterized in that in step 5), described carrier is selected from cerium oxide powder or cerium zirconium compound oxide powder; Described organic solvent can adopt toluene or n-hexane.
10. the preparation method of the modified oxidized cerium powder of Nanoalloy reacting for carbon-smoke combustion as claimed in claim 2, it is characterized in that in step 6), in described Nanoalloy decentralized precursor solution, alloy mass is 0.2%～10% of carrier quality by mass percentage; The temperature of described calcining can be 260～700 ℃.
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| CN115770503A (en) * | 2022-12-09 | 2023-03-10 | 玉溪师范学院 | Carbon smoke catalyst preparation device and method facilitating addition of lauric acid |
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| CN115770503A (en) * | 2022-12-09 | 2023-03-10 | 玉溪师范学院 | Carbon smoke catalyst preparation device and method facilitating addition of lauric acid |
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