CN105665027A - Preparation method of high-dispersing supported metal nano catalyst - Google Patents
Preparation method of high-dispersing supported metal nano catalyst Download PDFInfo
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- CN105665027A CN105665027A CN201511020351.XA CN201511020351A CN105665027A CN 105665027 A CN105665027 A CN 105665027A CN 201511020351 A CN201511020351 A CN 201511020351A CN 105665027 A CN105665027 A CN 105665027A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
Abstract
The invention relates to a preparation method of a high-dispersing supported metal nano catalyst and belongs to the technical field of catalyst. The invention provides the preparation method of the supported metal nano catalyst, which includes the steps of: 1) through an excessive impregnation method, adding an activated porous carrier to a polyacrylic acid solution, filtering the solution and drying the solid to obtain a polyacrylic acid-modified carrier; and 2) through an equivalent-volume impregnation method, impregnating the polyacrylic acid-modified carrier in a metal precursor solution, and drying and roasting the impregnated carrier to prepare the supported metal nano catalyst. In the invention, the polyacrylic acid is used for dispersing the active metal to obtain the high-dispersing catalyst, wherein chain-like polyacrylic acid is adsorbed onto the surface and pores of the activated carrier, so that the metal particles are orientedly dispersed since the polyacrylic acid can be complexed with metal ions to prepare the high-dispersing nano catalyst. The method solves the problems of active metal agglomeration, non-uniform dispersion and poor catalytic activity due to impregnation method for industrially preparing the catalyst in the prior art.
Description
Technical field
The present invention relates to the preparation method of high-dispersion loading type metal nano catalyzer, belong to catalyst technical field.
Background technology
Large-scale industrial production, as: hydrogenation reaction, catalytic cracking, petroleum cracking, oxidation of ethylene and synthetic ammonia etc., heterogeneous catalyst is all its integral part. And day by day fierce market competition makes people start to explore the better catalyzer of catalytic performance, metal nanoparticle is loaded to and the oxide compound of bigger serface prepares load type metal catalyst becomes an important research topic.
The preparation method of load type metal catalyst has a lot, such as pickling process, deposition-precipitation method, ion exchange method etc. Pickling process is impregnated on porous support based on active ingredient with salts solution form and penetrates into internal surface, and forms the principle of effective catalyst. Carrier is put into liquid containing active substance usually flood, when after dipping balance, isolate carrier, then be dried the postprocessing working procedures such as calcination activation and obtain catalyzer. Deposition-precipitation method is first immersed in the solution containing active ingredient after for some time by carrier, then adds the highly basic such as sodium hydroxide as precipitation agent, is slowly adding the catalyzer obtaining active particles under precipitation agent and vigorous stirring and being evenly distributed. Ion exchange method utilizes to there is exchangable ion on carrier surface, loads on carrier by active ingredient by ion-exchange, then the obtained catalyzer of the process such as washing, drying and roasting.
Pickling process because of its preparation method simple, cheap, pickling process becomes the method preparing load type metal nanocatalyst of widespread use in industry, but the active metal particles of the obtained catalyzer of this kind of method is easily reunited at carrier surface, crystallization, cause the uneven of its grain size and distribution, active ingredient high dispersing can not be made, thus can not show very high catalytic performance.
Summary of the invention
The technical problem that the present invention solves is to provide the preparation method of load type metal nanocatalyst, and the method polyacrylic acid dispersed active metal, prepares polymolecularity metal nano catalyzer.
The preparation method of load type metal nanocatalyst of the present invention, comprises the steps:
The preparation of a, polyacrylic acid modified carrier: adopting excessive pickling process to be impregnated in polyacrylic acid solution by the porous support after activation, filter, solid drying, obtains polyacrylic acid modified carrier;
The preparation of b, load type metal nanocatalyst: adopt equi-volume impregnating by polyacrylic acid modified carrier impregnation to, in metal precursor solution, dry, roasting, obtains load type metal nanocatalyst.
Wherein, in a step, described porous support is aluminum oxide, silicon oxide or molecular sieve.
In a step, the solvent of described polyacrylic acid solution is at least one in water, ethanol, methyl alcohol.
In a step, the concentration of described polyacrylic acid solution is 1～10mmol/L, and pH value is 5～9, it is preferable that the pH value of polyacrylic acid solution is 5～7.
In a step, the method for described activation is high-temperature roasting, and described high-temperature roasting is preferably 500 DEG C of roasting 3h.
Further, the metal in described load-type nanometer metal catalyst is nickel, palladium, platinum, copper, gold and silver or cobalt.
Wherein, in b step, described metal precursor is at least one in the halogenide of metal, nitrate, acetate; The solvent of described metallic precursor solution is water.
B step adopts repeatedly equi-volume impregnating, described repeatedly be preferably 3 times.
Roasting described in b step is 350～450 DEG C of roasting 5h.
Preferably, described porous support is aluminum oxide, and described metal precursor solution is nickel nitrate aqueous solution, and the charge capacity of metallic nickel is 5～15%.
The present invention's polyacrylic acid dispersed active metal prepares dispersed catalysts, in the surface that the PAA of chain shape is adsorbed onto active carrier and duct, with the directed dispersed metal particle of the effect of its complexation of metal ions, prepare the nanocatalyst of polymolecularity, solve at present industry the active metal caused with preparation catalyst reunite, disperse uneven, to such an extent as to the problem that catalytic activity is not high.
The present invention has the following advantages:
1) method for preparing catalyst of the present invention, can not only improve the dispersion of active metal at carrier surface, simultaneously it can be made to disperse more even in carrier duct, the catalyzer dispersity height for preparing, good stability, catalytic activity height.
2) the present invention is in the preparation of catalyzer, only needs to use active metal or active metal presoma, it is not necessary to the precious metal adding other is as auxiliary agent, reduce the cost of catalyzer, the catalyzer prepared is cheap, and toxin immunity is good, is applicable to suitability for industrialized production.
3) method for preparing catalyst in the present invention is the developing of a kind of methodology, has generality and universality, is applicable to the preparation of all load-type nanometer metal catalysts.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 and 2 load type metal nanocatalyst prepare schematic diagram.
Embodiment
The preparation method of load type metal nanocatalyst of the present invention, comprises the steps:
The preparation of a, polyacrylic acid modified carrier: adopting excessive pickling process to add in polyacrylic acid solution by the porous support after activation, filter, solid drying, obtains polyacrylic acid modified carrier;
The preparation of b, load type metal nanocatalyst: adopt equi-volume impregnating by polyacrylic acid modified carrier impregnation to, in metal precursor solution, dry, roasting, obtains load type metal nanocatalyst.
Wherein, porous support conventional in catalyzer is all applicable to the present invention, such as aluminum oxide, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, cerium oxide, zirconium white, molecular sieve or mixed type metal oxide etc., it is preferable that, described porous support is aluminum oxide, silicon oxide or molecular sieve.
Further, in a step, the solvent of described polyacrylic acid solution should be polar solvent, it is preferable at least one in water, ethanol, methyl alcohol.
The concentration of polyacrylic acid solution will affect dipping effect, and concentration is too low, and impregnation rate is not high, and excessive concentration, soltion viscosity increases, and also will affect dipping effect. Therefore, polyacrylic acid solution concentration is preferably 1～10mmol/L.
In order to make PAA molecular chain better enter into the duct of porous support, it is preferable that the molecular weight of PAA is for being not more than 3000.
In an acidic solution, PAA molecular chain is in rolls up shape, and when the pH value of solution reaches 4.5, PAA starts to ionize out H+Ion, self becomes polyanion, and self repelling of polyanion makes the chain-unfolding of PAA open, and becomes chain-like structure. Therefore, the polyacrylic acid solution pH value in a step is preferably 5～9, it is more preferable to pH value is 5～7. In the pH value of reality regulates, NaOH can be adopted to regulate the pH value of PAA solution.
In the preparation method of load type metal nanocatalyst of the present invention, the porous support after activation is the porous support adopting conventional method to activate such as high-temperature roasting, it is preferable at 500 DEG C of roasting 3h.
Excessive pickling process of the present invention refers to steeps in excessive dipping solution by carrier, and namely dipping solution volume exceedes carrier and can absorb volume. Equi-volume impregnating refers to that the dipping solution by carrier and it can absorb volume mixes, and namely the volume of dipping solution is suitable with the micro pore volume of carrier.
The preparation method of the present invention is applicable to all load-type nanometer metal catalysts, is particularly useful for preparing the catalyzer such as load-type nanometer metal nickel, palladium, platinum, copper, gold and silver, cobalt. The catalyzer of the present invention is made up of active metal and carrier, and PAA, only for the preparation of dispersed active metal during catalyzer, can be burnt in the roasting process of b step, not participate in catalyzed reaction. The active ingredient of catalyzer is active metal, and the metal in described load-type nanometer metal catalyst is preferably nickel, palladium, platinum, copper, gold and silver or cobalt.
Described metal precursor is any one in the halogenide of metal, nitrate, acetate or its two or more arbitrary combination. It is an object of the invention to obtain the metal of catalyzer from these compounds, it is not these compounds, as long as therefore obtaining nano level metal by follow-up calcination steps.
The effect of described metallic precursor solution solvent is dissolution of metals precursor, and metallic precursor is adsorbed onto on carrier better, as long as so the solvent selected can dissolution of metals precursor, it is possible to be single solvent, it is possible to be mixed solvent. For cost-saving, the solvent of metallic precursor solution of the present invention is preferably water.
In order to improve dispersity, b step can adopt repeatedly equi-volume impregnating. Described repeatedly be preferably 3 times. Every time dry after dipping, and then flood, after last impregnation drying, then roasting.
Roasting described in b step is 350～450 DEG C of roasting 5h.
Preferably, described porous support is aluminum oxide, and described metal precursor solution is nickel nitrate aqueous solution, and the charge capacity of metallic nickel is 5～15%. Such as, it is carrier taking aluminum oxide, after polyacrylic acid modified, it be impregnated into and be respectively in the nickel nitrate solution of 5%, 15% by elemental nickel calculated load amount, prepare load type metal nickel catalyzator 5Ni/AP and 15Ni/AP. It is prepared schematic diagram and sees Fig. 1. This catalyzer has good katalysis, particularly 15Ni/AP for carbon dioxide methanation reaction, and reaction can be made to reach thermodynamic(al)equilibrium when 380 DEG C.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, adjust its pH value to 5.5 with the NaOH of 0.1mol/L, taking the activated alumina after 3.015g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 0.779g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 450 DEG C of roasting 5h, obtain catalyzer 5Ni/AP5.5. It is prepared schematic diagram and sees Fig. 1. Not add contrasting as blank of PAA, numbering 5Ni/A.
Embodiment 2
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, adjust its pH value to 7 with the NaOH of 0.1mol/L, taking the activated alumina after 2.998g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 0.771g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 450 DEG C of roasting 5h, obtain catalyzer 5Ni/AP7。
Embodiment 3
Compound concentration is the PAA ethanolic soln 100ml of 10mmol/L, adjust its pH value to 5.5 with the NaOH of 0.1mol/L, taking the activated alumina after 3.008g activation joins in solution, normal temperature (25 DEG C), magnetic stirrer 12h, stops, taking out and filter excessive solution, dried overnight in 110 DEG C of thermostat containers, obtains mixture. Taking the Nickelous nitrate hexahydrate of 2.623g, be mixed with the aqueous solution of 10ml, divide with equi-volume impregnating and be impregnated on complexes carrier 3 times, each dipping time is 30min, and time of drying is 3h. After last dipping, dried overnight in 110 DEG C of thermostat containers. Again at 350 DEG C of roasting 5h, obtain catalyzer 15Ni/AP5.5, it is prepared schematic diagram and sees Fig. 1. Not add contrasting as blank of PAA, numbering 15Ni/A.
Activity rating of catalyst in test example 1 embodiment
Taking 0.2g catalyzer, be placed in the middle of steel pipe that internal diameter is 3.5mm, quartz sand is filled up in both sides. First, reducing 1h in the hydrogen stream of 40ml/min, reduction temperature is 600 DEG C, and temperature rise rate is 10 DEG C/min, then cools to 100 DEG C, under normal pressure, leads to the mixed gas into hydrogen and carbonic acid gas, and ratio is H2: CO2=4:1 (40:10ml), air speed is 15000mlh-1gcat -1, temperature reaction, reacts half an hour respectively at 300,320,340,360,380 DEG C of places, carries out sampling analysis by chromatogram. During reaction, temperature rise rate is 5 DEG C/min. The product rate that embodiment 1 and embodiment 2 product catalysis obtain is in table 1.
Table 1 methanation product rate
A: thermodynamic equilibria, the result obtained by AspenPlus flowsheeting.
It can be seen that with the addition of the sample of PAA from table 1 result, its catalytic activity is significantly improved, particularly in low-temperature zone, this is owing to active metal obtains more even at its Dispersion on surface, has more avtive spot, it is to increase its activity. Sample 15Ni/AP, when 380 DEG C, reaches thermodynamic(al)equilibrium.
Claims (10)
1. the preparation method of load type metal nanocatalyst, it is characterised in that, comprise the steps:
The preparation of a, polyacrylic acid modified carrier: adopting excessive pickling process to be impregnated in polyacrylic acid solution by the porous support after activation, filter, solid drying, obtains polyacrylic acid modified carrier;
The preparation of b, load type metal nanocatalyst: adopt equi-volume impregnating by polyacrylic acid modified carrier impregnation to, in metal precursor solution, dry, roasting, obtains load type metal nanocatalyst.
2. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that: in a step, described porous support is aluminum oxide, silicon oxide or molecular sieve.
3. the preparation method of load type metal nanocatalyst according to claim 1 and 2, it is characterised in that: in a step, the solvent of described polyacrylic acid solution is at least one in water, ethanol, methyl alcohol.
4. the preparation method of load type metal nanocatalyst according to the arbitrary item of claims 1 to 3, it is characterised in that: in a step, the concentration of described polyacrylic acid solution is 1～10mmol/L, and pH value is 5～9, it is preferable that the pH value of polyacrylic acid solution is 5～7.
5. the preparation method of load type metal nanocatalyst according to the arbitrary item of Claims 1 to 4, it is characterised in that: in a step, the method for described activation is high-temperature roasting, and described high-temperature roasting is preferably 500 DEG C of roasting 3h.
6. the preparation method of load type metal nanocatalyst according to the arbitrary item of Claims 1 to 5, it is characterised in that: the metal in described load-type nanometer metal catalyst is nickel, palladium, platinum, copper, gold and silver or cobalt.
7. the preparation method of load type metal nanocatalyst according to the arbitrary item of claim 1～6, it is characterised in that: in b step, described metal precursor is at least one in the halogenide of metal, nitrate, acetate; The solvent of described metallic precursor solution is water.
8. the preparation method of load type metal nanocatalyst according to the arbitrary item of claim 1～7, it is characterised in that: b step adopts repeatedly equi-volume impregnating, described is repeatedly preferably 3 times.
9. the preparation method of load type metal nanocatalyst according to the arbitrary item of claim 1～8, it is characterised in that: the roasting described in b step is 350～450 DEG C of roasting 5h.
10. the preparation method of load type metal nanocatalyst according to the arbitrary item of claim 1～9, it is characterised in that: described porous support is aluminum oxide, and described metal precursor solution is nickel nitrate aqueous solution, and the charge capacity of metallic nickel is 5～15%.
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Cited By (6)
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| CN109112341A (en) * | 2018-07-29 | 2019-01-01 | 浙江大学 | Layer stephanoporate nickel cobalt (alloy)-carbon composite block material preparation method with electromagnetic wave absorption performance |
| CN111097489A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and its preparation |
| CN111097462A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111097488A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111097434A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN116726923A (en) * | 2023-08-09 | 2023-09-12 | 山东久元新材料有限公司 | High-load equal-volume uniform load process and application |
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| CN109112341A (en) * | 2018-07-29 | 2019-01-01 | 浙江大学 | Layer stephanoporate nickel cobalt (alloy)-carbon composite block material preparation method with electromagnetic wave absorption performance |
| CN109112341B (en) * | 2018-07-29 | 2020-02-21 | 浙江大学 | Preparation method of hierarchical porous nickel-cobalt alloy-carbon composite block material with electromagnetic wave absorption performance |
| CN111097489A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and its preparation |
| CN111097462A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111097488A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN111097434A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Paraffin hydrofining catalyst and preparation method thereof |
| CN116726923A (en) * | 2023-08-09 | 2023-09-12 | 山东久元新材料有限公司 | High-load equal-volume uniform load process and application |
| CN116726923B (en) * | 2023-08-09 | 2023-10-27 | 山东久元新材料有限公司 | High-load equal-volume uniform load process and application |
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