CN102553579B - Preparation method of high-dispersity supported nano metal catalyst - Google Patents
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Abstract
The invention discloses a preparation method of a high-dispersity supported nano metal catalyst, particularly a preparation method of a supported nano noble metal catalyst, belonging to the technical field of catalyst preparation. The preparation method comprises the following steps: 1) impregnating a support into a metal precursor solution, and uniformly stirring; 2) carrying out ultrasonic dispersion under heating conditions; 3) drying, and roasting; 4) carrying out alkali-free liquid-phase controllable reduction; and 5) carrying out vacuum drying. By utilizing the actions of stirring and ultrasonic dispersion, the metal precursor is evenly adsorbed to the surface of the support, thereby implementing high dispersity of the active component; the roasting is utilized to enhance the interactions between the metal and the support; and the alkali-free liquid-phase controllable reduction is utilized to synthesize the nano metal catalyst of which the dimension is 2-10nm, the shape is spherical, cubic or polyhedral and the bare crystal face is (111), (100) or (110), thereby implementing the controllable preparation of the high-dispersity supported nano metal catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of high-dispersity supported nano metal catalyst, particularly the preparation method of high-dispersion loading type nano-noble metal catalyst.
Technical background
Load type metal catalyst, particularly loaded noble metal catalyst, due to its catalytic activity can not be substituted and selective, occupy extremely important status in the fields such as oil, chemical industry, medicine, agricultural chemicals, food, environmental protection, the energy, electronics.Hydro-reduction in oil and chemical industry, oxidative dehydrogenation, catalytic reforming, hydrocrack, hydrodesulfurization, reduction amination, telomerize, in the reaction such as coupling, disproportionation, ring expansion, cyclisation, carbonylation, formylated, dechlorination and asymmetric syntheses, noble metal is all good catalyst.At field of Environment Protection noble metal catalyst, be widely used in purifying vehicle exhaust, catalytic organism burning, CO, NO oxidation etc.Aspect new forms of energy, noble metal catalyst is the part of most critical in new fuel cell exploitation.According to statistics, the rhodium in the world 70%, 40% platinum and 50% palladium are all applied to the preparation of catalyst.But Precious Metals Resources lacks and is expensive, causes catalyst cost greatly to increase.So people are finding the method for preparing catalyst that reduces noble metal dosage always.In the situation that keeping catalytic activity constant, the decentralization that improves metal is the effective way that reduces noble metal dosage.
The conventional preparation method of load type metal catalyst has infusion process, the precipitation method, deposition-precipitation method etc.Tradition infusion process is subject to the impact of the solvation effect of immersion solvent and the cluster effect of active component, is difficult for making active group high degree of dispersion, and in follow-up roasting and high temperature reduction process, active component may crystallite coalescence, causes catalytic activity to reduce.The precipitation method need the digestion time that adds order, form, temperature, pH value, mother liquor of precipitation of ammonium of finely regulating component, and the step details such as filtration, washing, active material and carrier ion are precipitated out simultaneously, just likely make active particles be evenly distributed on carrier.Though this method is simple to operate, be difficult to guarantee that active component is uniformly distributed.Deposition-precipitation method is used the highly basic such as NaOH, KOH instead as precipitating reagent on the basis of the precipitation method, could obtain active particles and is uniformly distributed slowly adding under precipitating reagent and vigorous stirring.But, be stirred in so efficiently in extensive preparation, may not necessarily be successful.In addition, conventional method all adopts hydrogen or carbon monoxide high temperature reduction, may cause the sintering of metal particle, causes being difficult to obtain dispersed catalysts.
The nano metal infusion process that development in recent years is got up, obtain in advance the method that nano-metal particle loads to carrier surface again, although can obtain the catalyst that metal dispersity is higher, but a little less than the interaction in catalyst between metal and carrier, in use metal Nano structure fades away, and particle size also increases gradually, and activity declines gradually, last inactivation, temporarily more difficult be applied to industrial.
Some patent reports high-dispersion loading type metallic catalyst preparation method's progress.Patent (CN200310106720.8) has been reported the method for preparing polymolecularity metal catalyst in load type from plasma.The catalyst that the method using plasma is processed before roasting has certain novelty, but does not explain the essence of action of plasma, and preparation condition is complicated, is unfavorable for large-scale production.Patent (CN02131246.X) has been reported a kind of high dispersive palladium catalyst of preparing through lamellar precursor and preparation method thereof.The method adopts lamellar precursor method really can improve metal dispersity, but its preparation process is more complicated, and finally adopts high-temperature hydrogen reduction, causes metal particle sintering to a certain degree.Patent (CN201010034506.6) has been reported the ultrasonic method of preparing metal carbon nanotube compound.Utilize the method can make metal evenly spread to carbon nano tube surface, but the method does not have roasting metal carbon nanotube compound, a little less than interaction between metal and CNT, in use metal Nano structure will fade away, and particle size also can increase gradually; The method adopts high price borohydride salts as reducing agent, and the size of metallic particles and pattern are difficult to regulation and control, and cost is higher, is unfavorable for industrial amplification; Meanwhile, the carrier of the method is only CNT, and range of application is narrower.Patent (CN02108585.4) has reported that a kind of liquid-phase reduction prepares the method for high dispersive carrier metal catalyst.But the method does not have ultrasonic dispersion and calcination steps, metal is only difficult to be distributed to equably carrier surface under stirring action, and the catalyst of roasting does not cause less stable a little less than because of its Support-metal strong interaction; The liquid-phase reduction of this patent report must carry out under organic base exists, and metallic precursor is only halide, and range of application is narrower; This liquid phase reduction only can obtain prill, cannot regulate and control the size of metal particle and pattern.Patent (CN200810236524.5) has been reported the carbon-supported metal hydrogenation Catalysts and its preparation method of a kind of nanometer ruthenium.This patent also adopts liquid-phase reduction, but need to add alkali before reduction, regulates pH value, does not add structure directing reagent and protective agent in reduction process, can not regulate and control size and the pattern of metal particle, only obtains the prill of Size Distribution very wide (40 – 80nm); This patent does not still have ultrasonic dispersion and calcination steps, is more difficult to get high dispersive and long-life catalyst.Therefore, develop a kind of high-dispersity supported nano metal catalyst, particularly the preparation method of high-dispersion loading type nano-noble metal catalyst is significant.
Summary of the invention
The object of this invention is to provide a kind of high-dispersity supported nano metal catalyst, the preparation method of high-dispersion loading type nano-noble metal catalyst particularly, the method can improve metal dispersity, reduce the load capacity of noble metal, strengthen the stability of catalyst, can regulate and control size, pattern and the crystal face of metal particle simultaneously.
The object of the invention is to be realized by following technical scheme, the preparation method of high-dispersity supported nano metal catalyst provided by the invention, comprises the following steps:
(1) by carrier impregnation in metallic precursor solution, stir:
Specifically, take the metallic precursor wiring solution-forming of certain mass, make its concentration remain on 0.001 – 0.1mol/L, carrier is placed in to metallic precursor solution, stirring at room 1 – 20 hours, is distributed in metallic precursor solution carrier equably;
(2) ultrasonic dispersion under heating condition:
The mixed liquor of metallic precursor in step (1) and carrier ultrasonic solvent evaporates to solution under heating condition is dry, make metallic precursor be adsorbed onto equably carrier surface;
(3) dry, roasting:
The adsorption sample that step (2) is obtained dry 1 – 20 hours at 200 ℃ of 100 – in baking oven, then 600 ℃ of roastings of 200 –, 1 – is 20 hours;
(4) the controlled reduction of alkali-free liquid phase:
The sample that step (3) is obtained adds reducing agent, structure directing reagent and protective agent to carry out the controlled reduction of liquid phase under the condition without alkalinity additive, prepare to have and be of a size of 2 – 10nm, pattern is that spherical, cube or polyhedron and exposed crystal face are the metallic catalyst of (111), (100) or (110);
(5) vacuum drying:
The sample that step (4) is obtained after filtration, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain high-dispersity supported nano metal catalyst of the present invention.
Preparation method of the present invention is applicable to all load-type nanometer metal catalysts, is particularly useful for preparing loaded nano precious metals pt, Pd, Rh, Au, Ag, Ru catalyst.
Any or its any combination in halide, nitrate, acetate, oxalates, phosphate and acetylacetonate complex that the described metallic precursor of step (1) is metal, because the object of the invention is to obtain the metal that catalyst is used from these compounds, not these compounds, as long as obtain nano level metal by following step.
The effect of the described metallic precursor solution solvent of step (1) is dissolution of metals precursor, make metallic precursor be adsorbed onto better on carrier, so as long as the solvent of selecting is energy dissolution of metals precursor, it can be single solvent, can be mixed solvent, also can adopt not at following listed solvent; The solvent of metallic precursor solution of the present invention one of is preferably as follows or combination of two or two or more arbitrary proportion combinations, and listed solvent comprises water, methyl alcohol, ethanol, acetone, chloroform, toluene, acetonitrile, benzene, cyclohexane, pyridine, ethylene glycol, ethyl acetate, ether.
The described carrier of step (1) is any in aluminium oxide, silica, titanium dioxide, active carbon or zinc oxide, preferential oxidation aluminium.When carrier is Alpha-alumina, its surface area is 1 – 10m preferably
2/ g, can adopt in advance and process 2 – acquisition in 4 hours through 800 ℃ of 400 –.
The described ultrasonic temperature of step (2) is 100 ℃ of 20 –, and preferably 30 – is 60 ℃; The ultrasonic energy dispersive of every gram of catalyst is 10 – 500W, preferably 150 – 350W.
The reducing agent of the controlled reduction of step (4) alkali-free liquid phase adopts at least one in strong reductant, middle strong reductant or weak reductant, described strong reductant is selected from sodium borohydride or hydrazine hydrate, described middle strong reductant is selected from least one in ascorbic acid, formic acid, sodium formate, sodium acetate, and described weak reductant is selected from least one in citric acid, glucose, ethylene glycol; Described structure directing reagent has a kind of sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide, KI, citric acid, natrium citricum, potassium citrate, ammonium citrate of being selected from least; Described protective agent has a kind of polyvinylpyrrolidone (PVP), softex kw (CTAB), hexadecyltrimethylammonium chloride (CTAC), polyethylene oxygen-polypropylene oxygen-polyethylene oxygen (P123) of being selected from least; Above-mentioned reducing agent and the mol ratio of metallic precursor are (2 – 5): 1; The mol ratio of structure directing reagent and protective agent and metallic precursor is (5 – 20): 1, and ratio between structure directing reagent and protective agent can be 1:(1 – 5), be preferably 1:2; Reduction temperature is 150 ℃ of 40 –, and preferably 80 – is 120 ℃, compares with conventional high-temperature hydrogen reducing, has greatly reduced reduction temperature, has avoided sintering and the reunion of metallic particles.
Feature of the present invention is, this preparation method has utilized and stirred and ultrasonic peptizaiton makes metallic precursor be adsorbed onto equably carrier surface, thereby has realized the high dispersive of active component; Utilize high-temperature roasting to strengthen the interaction between metal and carrier; By adding the reducing agent of varying strength to regulate nanocrystalline nucleation rate in alkali-free Liquid reduction reaction process; add different structure guiding reagent to regulate the speed of growth of different crystal faces; add different protective agents to suppress nanocrystalline reunion; synthesized and be of a size of 2 – 10nm; pattern is that spherical, cube or polyhedron and exposed crystal face are the metallic catalyst of (111), (100) or (110), thereby has realized the controlled preparation of high-dispersity supported nano metal catalyst.When the metal in catalyst is selected precious metals pd, can be under lower temperature and low noble metal load capacity (only for carrier quality 0.5%) efficiently catalysis CO gas phase carbonylation become oxalate, CO conversion per pass reaches 48%, and oxalate is selectively greater than 99%, oxalate space-time yield 1063 g L
-1h
-1(air speed is 3000h
-1).When adopting other precious metals pt, Rh, Au, Ag, Ru, same experiment draw active component still can high degree of dispersion at carrier surface, under low noble metal load capacity, still there is good catalytic activity, thereby reduce the use amount of noble metal.In addition, catalyst preparation process is simple, and cost is low, is conducive to realize industrialization.
Accompanying drawing explanation
Fig. 1 is 2% Pd/Al of embodiment 1 preparation
2o
3the transmission electron microscope photo of nanocatalyst.
Fig. 2 is 2% Pd/Al of embodiment 1 preparation
2o
3the high-resolution-ration transmission electric-lens photo of nanocatalyst.
Fig. 3 is 1% Pd/Al of embodiment 2 preparations
2o
3the transmission electron microscope photo of nanocatalyst.
Fig. 4 is 1% Pd/Al of embodiment 2 preparations
2o
3the high-resolution-ration transmission electric-lens photo of nanocatalyst.
Fig. 5 is 0.5% Pd/Al of embodiment 3 preparations
2o
3the transmission electron microscope photo of nanocatalyst.
Fig. 6 is 0.5% Pt/Al of embodiment 4 preparations
2o
3the transmission electron microscope photo of nanocatalyst.
Fig. 7 is 0.5% Au/Al of embodiment 5 preparations
2o
3the transmission electron microscope photo of nanocatalyst.
Fig. 8 is 0.5% Ru/Al of embodiment 6 preparations
2o
3the transmission electron microscope photo of nanocatalyst.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1: prepare 2% Pd/Al
2o
3nanocatalyst
Take the Pd (NO that 1g aluminium oxide is impregnated into 5mL 37.6mmol/L
3)
2-in the aqueous solution, stir 3 hours, in 40 ℃ of water-baths with the ultrasonic dispersion of energy of 250W 4 hours, 110 ℃ dry 4 hours, 350 ℃ of roastings 4 hours, add 0.070g ascorbic acid, 0.353g KBr, 0.444g PVP, 100 ℃ are reduced 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 1, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 4 – 5nm.Fig. 2 is shown in by high-resolution-ration transmission electric-lens photo, and the main exposed crystal face of Pd is (111) face as seen from the figure.
Embodiment 2: prepare 1% Pd/Al
2o
3nanocatalyst
Take the Pd (NO that 1g aluminium oxide is impregnated into 2.5mL 37.6mmol/L
3)
2-in the aqueous solution, then add 2.5mL ethanol, stir 3 hours, in 40 ℃ of water-baths with the ultrasonic dispersion of energy of 250W 4 hours, 110 ℃ dry 4 hours, 350 ℃ of roastings 4 hours, add 0.105g citric acid, 0.353g KBr, 0.523g P123,90 ℃ are reduced 15 hours, and then add 0.018g ascorbic acid to continue 90 ℃ of reduction 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 3, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 4 – 6nm.Fig. 4 is shown in by high-resolution-ration transmission electric-lens photo, and the main exposed crystal face of Pd is (111) face as seen from the figure.
Embodiment 3: prepare 0.5% Pd/Al
2o
3nanocatalyst
Take the Pd (OAc) that 1g aluminium oxide is impregnated into 1.25mL 37.6mmol/L
2-in acetone soln, add 4mL acetone, stir 3 hours, in 35 ℃ of water-baths with the ultrasonic dispersion of energy of 200W 4 hours, 110 ℃ are dried 4 hours, 400 ℃ of roastings 2 hours, add 1mL 0.4mol/L solution of potassium borohydride, 0.353g KBr, 0.444g PVP, 100 ℃ of reduction 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 5, and Pd is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 3 – 5nm.
Embodiment 4: prepare 0.5% Pt/Al
2o
3nanocatalyst
Take the K that 1g aluminium oxide is impregnated into 1mL 25mmol/L
2ptCl
4in the aqueous solution, add 4mL acetone, stir 2 hours, in 35 ℃ of water-baths with the ultrasonic dispersion of energy of 200W 4 hours, 110 ℃ are dried 4 hours, 400 ℃ of roastings 2 hours, add 0.070g ascorbic acid, 0.353g KBr, 0.444g PVP, 100 ℃ of reduction 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 6, and Pt is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 2 – 3nm.
Embodiment 5: prepare 0.5% Au/Al
2o
3nanocatalyst
Take the HAuCl that 1g aluminium oxide is impregnated into 1mL 25mmol/L
4in the aqueous solution, add 4mL acetone, stir 2 hours, in 35 ℃ of water-baths with the ultrasonic dispersion of energy of 200W 4 hours, 110 ℃ are dried 4 hours, 400 ℃ of roastings 2 hours, add 0.070g ascorbic acid, 0.353g KBr, 0.444g PVP, 100 ℃ of reduction 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 7, and Au is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 4 – 6nm.
Embodiment 6: prepare 0.5% Ru/Al
2o
3nanocatalyst
Take the RuCl that 1g aluminium oxide is impregnated into 2mL 25mmol/L
3in acetone soln, add again 3mL acetone, stir 2 hours, in 35 ℃ of water-baths with the ultrasonic dispersion of energy of 200W 4 hours, 110 ℃ are dried 4 hours, 400 ℃ of roastings 2 hours, add 0.070g ascorbic acid, 0.353g KBr, 0.444g PVP, 100 ℃ of reduction 30 minutes, water and ethanol washing three times, dry 10 hours of 60 ℃, vacuum.Transmission electron microscope photo is shown in Fig. 8, and Ru is dispersed in carrier surface as seen from the figure, and particle is mainly spherical, has a small amount of irregular polyhedrons, and average-size is 4 – 6nm.
Claims (8)
1. a preparation method for high-dispersity supported nano metal catalyst, is characterized in that preparation process is as follows:
(1) by carrier impregnation in metal precursor solution, stir, carrier is distributed in metal precursor solution equably;
(2) ultrasonic dispersion under heating condition:
The metal precursor that step (1) is obtained and the mixed liquor of the carrier ultrasonic solvent evaporates to solution under heating condition is dry, makes metal precursor be adsorbed onto equably carrier surface;
(3) dry, roasting:
The adsorption sample that step (2) is obtained dry 1 – 20 hours at 200 ℃ of 100 –, then 600 ℃ of roastings of 200 –, 1 – is 20 hours;
(4) the controlled reduction of alkali-free liquid phase:
The sample that step (3) is obtained adds reducing agent, structure directing reagent and protective agent to carry out the controlled reduction reaction of alkali-free liquid phase, prepare and be of a size of 2 – 10nm, pattern is that spherical, cube or polyhedron and exposed crystal face are the metallic catalyst of (111), (100) or (110); Described reducing agent adopts at least one in strong reductant, middle strong reductant or weak reductant, described strong reductant is selected from sodium borohydride or hydrazine hydrate, described middle strong reductant is selected from least one in ascorbic acid, formic acid, sodium formate, sodium acetate, and described weak reductant is selected from least one in citric acid, glucose, ethylene glycol; Described structure directing reagent has a kind of sodium chloride, potassium chloride, sodium bromide, KBr, sodium iodide, KI, citric acid, natrium citricum, potassium citrate, ammonium citrate of being selected from least; Described protective agent has a kind of polyvinylpyrrolidone, softex kw, hexadecyltrimethylammonium chloride, polyethylene oxygen-polypropylene oxygen-polyethylene oxygen of being selected from least; Above-mentioned reducing agent and the mol ratio of metal precursor are 2 – 5:1; The mol ratio of structure directing reagent and protective agent and metal precursor is 5 – 20:1, and ratio between structure directing reagent and protective agent is 1:1 – 5; Reduction temperature is 150 ℃ of 40 –;
(5) vacuum drying:
The sample that step (4) is obtained after filtration, washing, put into dry 1 – of vacuum drying chamber 20 hours, just obtain high-dispersity supported nano metal catalyst.
2. preparation method according to claim 1, is characterized in that: the metal in described load-type nanometer metal catalyst is precious metals pt, Pd, Rh, Au, Ag or Ru.
3. preparation method according to claim 1 and 2, is characterized in that: the metal precursor of step (1) adopts any or its two or more any combination in halide, nitrate, acetate, oxalates, phosphate and the acetylacetonate complex of metal.
4. preparation method according to claim 1 and 2, it is characterized in that: in the metal precursor solution of described step (1), the used solvent that can form solution with metal precursor adopts any or its two or more any combination of the following stated solvent, and described solvent comprises water, methyl alcohol, ethanol, propyl alcohol, butanols, acetone, chloroform, toluene, acetonitrile, benzene, cyclohexane, pyridine, ethylene glycol, ethyl acetate, ether.
5. preparation method according to claim 1 and 2, is characterized in that: the carrier of described step (1) is any in aluminium oxide, silica, titanium dioxide, active carbon or zinc oxide.
6. preparation method according to claim 1 and 2, is characterized in that: the heating-up temperature of described step (2) is 100 ℃ of 20 –; The ultrasonic energy dispersive of every gram of catalyst is 10 – 500W.
7. preparation method according to claim 6, is characterized in that: the heating-up temperature of described step (2) is 60 ℃ of 30 –; The ultrasonic energy dispersive of every gram of catalyst is 150 – 350W.
8. preparation method according to claim 1, is characterized in that: structure directing reagent and the ratio between protective agent of described step (4) are 1:2; Reduction temperature is 120 ℃ of 80 –.
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