CN105665027B - The preparation method of high-dispersion loading type metal nano catalyst - Google Patents
The preparation method of high-dispersion loading type metal nano catalyst Download PDFInfo
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- CN105665027B CN105665027B CN201511020351.XA CN201511020351A CN105665027B CN 105665027 B CN105665027 B CN 105665027B CN 201511020351 A CN201511020351 A CN 201511020351A CN 105665027 B CN105665027 B CN 105665027B
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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
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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
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Abstract
The present invention relates to the preparation methods of high-dispersion loading type metal nano catalyst, belong to catalyst technical field.The technical problem to be solved by the present invention is to provide the preparation methods of load type metal nanocatalyst.This method is first added in the porous carrier after activation in polyacrylic acid solution using excessive infusion process, filtering, and solid drying obtains polyacrylic acid modified carrier；Again using equi-volume impregnating by polyacrylic acid modified carrier impregnation to metal front liquid solution, drying is roasted to get load type metal nanocatalyst.The present invention prepares dispersed catalysts with polyacrylic acid dispersed active metal, the polyacrylic acid of chain is adsorbed onto in the surface and duct of active carrier, dispersed metal particle is oriented with the effect of its complexation of metal ions, the nanocatalyst of polymolecularity is prepared, solve at present industry in caused by preparation catalyst active metal reunite, disperse it is uneven so that the problem of catalytic activity is not high.
Description
Technical field
The present invention relates to the preparation methods of high-dispersion loading type metal nano catalyst, belong to catalyst technical field.
Background technology
Large-scale industrial production, such as：Hydrogenation reaction, catalytic cracking, petroleum cracking, ethylene and synthesis ammonia etc. are non-equal
Phase catalyst is all its pith.And increasingly fierce market competition makes people start to explore catalytic performance and be preferably catalyzed
Metal nanoparticle is loaded on the oxide of bigger serface and load type metal catalyst is prepared as a weight by agent
The research topic wanted.
The preparation method of load type metal catalyst has very much, such as infusion process, deposition-precipitation method, ion-exchange.Leaching
Stain method is to be impregnated into the form of salting liquid on porous carrier based on active component and penetrate into inner surface, and forms effective catalyst
Principle.Usually carrier is put into the liquid containing active material and is impregnated, after balance is impregnated, isolates carrier, then carry out
The postprocessing working procedures such as drying and roasting activation obtain catalyst.Deposition-precipitation method is that carrier is first immersed in containing the molten of active component
In liquid after a period of time, the highly basic such as sodium hydroxide are added as precipitating reagent, are obtained in the case where being slowly added to precipitating reagent and being vigorously stirred
Obtain the catalyst that active particles are evenly distributed.Ion-exchange be using on carrier surface there are exchangeable ion, by activearm
It point is loaded on carrier, is washed out, catalyst is made in the processing such as drying and roasting by ion exchange.
Infusion process is cheap because preparation method is simple, and infusion process becomes industry-wide and prepares support type
The method of metal nano catalyst, however the active metal particles of catalyst made from this method are easily rolled into a ball in carrier surface
Poly-, crystallization leads to the uneven of its grain size and distribution, it is impossible to make active component high degree of dispersion, thus cannot show non-
Often high catalytic performance.
Invention content
The technical problem to be solved by the present invention is to provide the preparation method of load type metal nanocatalyst, this method is with poly- third
Polymolecularity metal nano catalyst is prepared in olefin(e) acid dispersed active metal.
The preparation method of load type metal nanocatalyst of the present invention, includes the following steps：
A, the preparation of polyacrylic acid modified carrier：Porous carrier after activation is impregnated by polypropylene using excessive infusion process
In acid solution, filtering, solid drying obtains polyacrylic acid modified carrier；
B, the preparation of load type metal nanocatalyst：Polyacrylic acid modified carrier impregnation is arrived using equi-volume impregnating
It is dry in metal front liquid solution, it roasts to get load type metal nanocatalyst.
Wherein, in a steps, the porous carrier is aluminium oxide, silica or molecular sieve.
In a steps, the solvent of the polyacrylic acid solution is at least one of water, ethyl alcohol, methanol.
In a steps, a concentration of 1~10mmol/L of the polyacrylic acid solution, pH value is 5~9, and preferably polyacrylic acid is molten
The pH value of liquid is 5~7.
In a steps, the method for the activation is high-temperature roasting, and the high-temperature roasting is preferably 500 DEG C of roasting 3h.
Further, the metal in the load-type nanometer metal catalyst is nickel, palladium, platinum, copper, gold, silver or cobalt.
Wherein, in b step, at least one of the halide, nitrate, acetate of the metal precursor for metal；
The solvent of the metallic precursor solution is water.
Using multiple equi-volume impregnating in b step, described is preferably repeatedly 3 times.
350~450 DEG C of roasting 5h are roasted to described in b step.
Preferably, the porous carrier is aluminium oxide, and the metal front liquid solution is nickel nitrate aqueous solution, golden
The load capacity for belonging to nickel is 5~15%.
The present invention prepares dispersed catalysts with polyacrylic acid dispersed active metal, and the PAA of chain is adsorbed onto active load
In the surface and duct of body, dispersed metal particle is oriented with the effect of its complexation of metal ions, receiving for polymolecularity is prepared
Rice catalyst, solve at present industry in caused by preparation catalyst active metal reunite, disperse it is uneven so that
In catalytic activity is not high the problem of.
The present invention has the following advantages：
1) method for preparing catalyst of the invention, can not only improve dispersibility of the active metal in carrier surface, while energy
It is made to disperse in carrier duct more uniform, the catalyst dispersion degree being prepared is high, stability is good, and catalytic activity is high.
2) present invention is in the preparation of catalyst, it is only necessary to active metal or active metal presoma is used, without adding it
His noble metal reduces the cost of catalyst, the catalyst being prepared is cheap, and mithridatism is good, is suitble to as auxiliary agent
Industrialized production.
3) method for preparing catalyst in the present invention is a kind of developing of methodology, has general and universality, is applicable in
In the preparation of all load-type nanometer metal catalysts.
Description of the drawings
Fig. 1 prepares schematic diagram for 1 and 2 load type metal nanocatalyst of the embodiment of the present invention.
Specific embodiment
The preparation method of load type metal nanocatalyst of the present invention, includes the following steps：
A, the preparation of polyacrylic acid modified carrier：Porous carrier after activation is added in by polyacrylic acid using excessive infusion process
In solution, filtering, solid drying obtains polyacrylic acid modified carrier；
B, the preparation of load type metal nanocatalyst：Polyacrylic acid modified carrier impregnation is arrived using equi-volume impregnating
It is dry in metal front liquid solution, it roasts to get load type metal nanocatalyst.
Wherein, common porous carrier is suitable for the present invention in catalyst, such as aluminium oxide, silica, titanium oxide, oxidation
Zinc, magnesia, cerium oxide, zirconium oxide, molecular sieve or mixed type metal oxide etc., it is preferred that the porous carrier is oxidation
Aluminium, silica or molecular sieve.
Further, in a steps, the solvent of the polyacrylic acid solution should be polar solvent, preferably water, ethyl alcohol, first
At least one of alcohol.
The concentration of polyacrylic acid solution will influence dipping effect, and concentration is too low, and impregnation rate is not high, and excessive concentration, molten
Fluid viscosity increases, and will also influence dipping effect.Therefore, polyacrylic acid solution concentration is preferably 1~10mmol/L.
In order to which PAA strands is made preferably to enter in the duct of porous carrier, preferably the molecular weight of PAA be no more than
3000。
In an acidic solution, PAA strands, which are in, rolls up shape, and when the pH value of solution reaches 4.5, PAA starts to ionize out H+Ion, itself becomes polyanion, itself repelling for polyanion opens the chain-unfolding of PAA, become chain structure.Therefore, a
Polyacrylic acid solution pH value in step is preferably 5~9, and more preferable pH value is 5~7.In practical pH value is adjusted, it can be used
NaOH adjusts the pH value of PAA solution.
In the preparation method of load type metal nanocatalyst of the present invention, the porous carrier after activation is using conventional side
The porous carrier of method such as high-temperature roasting activation, preferably roasts 3h at 500 DEG C.
Excess infusion process of the present invention refers to steep carrier in excessive dipping solution, i.e. dipping solution volume surpasses
It crosses carrier and can absorb volume.Equi-volume impregnating refers to mix carrier with the dipping solution of its absorbable volume, that is, impregnates molten
The volume of liquid is suitable with the micro pore volume of carrier.
The preparation method of the present invention is suitable for all load-type nanometer metal catalysts, is particularly suitable for preparing support type
The catalyst such as nano metal nickel, palladium, platinum, copper, gold, silver, cobalt.The catalyst of the present invention is made of active metal and carrier, and PAA is only
Dispersed active metal when being used to prepare catalyst can be burned off in the roasting process of b step, be not involved in catalysis reaction.Catalysis
The active component of agent is active metal, the metal in the load-type nanometer metal catalyst be preferably nickel, palladium, platinum, copper, gold,
Silver or cobalt.
The metal precursor is any one of halide, nitrate, acetate of metal or its is two or more
Arbitrary combination.It is not these compounds, therefore only the purpose of the present invention is obtaining the metal of catalyst from these compounds
Nano level metal is obtained by subsequent calcination steps.
The effect of the metallic precursor solution solvent is dissolving metallic precursor, and metallic precursor is made preferably to be adsorbed onto
On carrier, as long as so select solvent can dissolve metallic precursor, can be single solvent, can be mixed solvent.
To be cost-effective, the solvent of metallic precursor solution of the present invention is preferably water.
In order to improve dispersion degree, multiple equi-volume impregnating can be used in b step.Described repeatedly preferably 3 times.Dipping every time
After dry, then impregnate, after last time impregnation drying, then roast again.
350~450 DEG C of roasting 5h are roasted to described in b step.
Preferably, the porous carrier is aluminium oxide, and the metal front liquid solution is nickel nitrate aqueous solution, golden
The load capacity for belonging to nickel is 5~15%.For example, using aluminium oxide as carrier, after polyacrylic acid modified, it be impregnated into and calculated by elemental nickel
Load capacity is respectively in 5%, 15% nickel nitrate solution, and load type metal Raney nickel 5Ni/AP and 15Ni/AP is prepared.
It prepares schematic diagram and sees Fig. 1.The catalyst has good catalytic action, particularly 15Ni/ for carbon dioxide methanation reaction
AP can make reaction reach thermodynamical equilibrium at 380 DEG C.
The specific embodiment of the present invention is further described with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, with the NaOH tune of 0.1mol/L its pH value to 5.5, is weighed
Activated alumina after 3.015g activation is added in solution, room temperature (25 DEG C), and magnetic stirrer 12h stops, leaching out
Excessive solution, is dried overnight in 110 DEG C of insulating boxs, obtains compound.The Nickelous nitrate hexahydrate of 0.779g is weighed, is configured to
The aqueous solution of 10ml is divided 3 times with equi-volume impregnating and is impregnated on complexes carrier, and each dip time is 30min, when dry
Between be 3h.After last time impregnates, it is dried overnight in 110 DEG C of insulating boxs.5h is roasted at 450 DEG C again, obtains catalyst 5Ni/
AP5.5.It prepares schematic diagram and sees Fig. 1.Using do not add PAA as blank, number 5Ni/A.
Embodiment 2
Compound concentration is the PAA aqueous solution 100ml of 1mmol/L, with the NaOH tune of 0.1mol/L its pH value to 7, is weighed
Activated alumina after 2.998g activation is added in solution, room temperature (25 DEG C), and magnetic stirrer 12h stops, leaching out
Excessive solution, is dried overnight in 110 DEG C of insulating boxs, obtains compound.The Nickelous nitrate hexahydrate of 0.771g is weighed, is configured to
The aqueous solution of 10ml is divided 3 times with equi-volume impregnating and is impregnated on complexes carrier, and each dip time is 30min, when dry
Between be 3h.After last time impregnates, it is dried overnight in 110 DEG C of insulating boxs.5h is roasted at 450 DEG C again, obtains catalyst 5Ni/
AP7。
Embodiment 3
Compound concentration is the PAA ethanol solution 100ml of 10mmol/L, with its pH value of the NaOH tune of 0.1mol/L to 5.5, is claimed
The activated alumina after 3.008g activation is taken to be added in solution, room temperature (25 DEG C), magnetic stirrer 12h stops, and filters
Fall excessive solution, be dried overnight in 110 DEG C of insulating boxs, obtain compound.The Nickelous nitrate hexahydrate of 2.623g is weighed, is prepared
Into the aqueous solution of 10ml, divided 3 times with equi-volume impregnating and be impregnated on complexes carrier, each dip time is 30min, dry
Time is 3h.After last time impregnates, it is dried overnight in 110 DEG C of insulating boxs.5h is roasted at 350 DEG C again, obtains catalyst
15Ni/AP5.5, prepare schematic diagram and see Fig. 1.Using do not add PAA as blank, number 15Ni/A.
The activity rating of catalyst in 1 embodiment of test example
0.2g catalyst is weighed, is placed among the steel pipe that internal diameter is 3.5mm, quartz sand is filled up in both sides.First, in 40ml/
1h is restored in the hydrogen stream of min, reduction temperature is 600 DEG C, and heating rate is 10 DEG C/min, then cools to 100 DEG C, normal pressure
Under, the mixed gas of hydrogen and carbon dioxide is passed through, ratio is H2：CO2=4:1(40:10ml), air speed is 15000ml h- 1gcat -1, temperature reaction reacts half an hour at 300,320,340,360,380 DEG C, sampling analysis carried out with chromatography respectively.Instead
Seasonable heating rate is 5 DEG C/min.The yield that embodiment 1 and 2 product of embodiment are catalyzed is shown in Table 1.
1 methanation yield of table
a：Thermodynamic equilibria, the result obtained by Aspen Plus flowsheetings.
It can see from 1 result of table, be added to the sample of PAA, catalytic activity is significantly improved, particularly exists
Low-temperature zone this is because active metal obtains more uniform in its Dispersion on surface, has more active sites, improves its work
Property.Sample 15Ni/AP reaches thermodynamical equilibrium at 380 DEG C.
Claims (12)
1. the preparation method of load type metal nanocatalyst, which is characterized in that include the following steps：
A, the preparation of polyacrylic acid modified carrier：It is molten that porous carrier after activation is impregnated by polyacrylic acid using excessive infusion process
In liquid, filtering, solid drying obtains polyacrylic acid modified carrier；A concentration of 1~10mmol/L of the polyacrylic acid solution,
PH value is 5~9；
B, the preparation of load type metal nanocatalyst：Using equi-volume impregnating by polyacrylic acid modified carrier impregnation to metal
It is dry in precursor solution, it roasts to get load type metal nanocatalyst.
2. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that：In a steps, institute
Porous carrier is stated as aluminium oxide, silica or molecular sieve.
3. the preparation method of load type metal nanocatalyst according to claim 1 or 2, it is characterised in that：A steps
In, the solvent of the polyacrylic acid solution is at least one of water, ethyl alcohol, methanol.
4. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that：In a steps, gather
The pH value of acrylic acid solution is 5~7.
5. the preparation method of load type metal nanocatalyst according to claim 1 or 2, it is characterised in that：A steps
In, the method for the activation is high-temperature roasting.
6. the preparation method of load type metal nanocatalyst according to claim 5, it is characterised in that：The high temperature roasting
It burns for 500 DEG C of roasting 3h.
7. the preparation method of load type metal nanocatalyst according to claim 1 or 2, it is characterised in that：It is described negative
Metal in load type metallic catalyst is nickel, palladium, platinum, copper, gold, silver or cobalt.
8. the preparation method of load type metal nanocatalyst according to claim 1 or 2, it is characterised in that：B step
In, at least one of the halide, nitrate, acetate of the metal precursor for metal；The metallic precursor solution
Solvent be water.
9. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that：Using more in b step
Secondary equi-volume impregnating.
10. the preparation method of load type metal nanocatalyst according to claim 9, it is characterised in that：Described is repeatedly 3
It is secondary.
11. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that：Described in b step
Be roasted to 350~450 DEG C roasting 5h.
12. the preparation method of load type metal nanocatalyst according to claim 1, it is characterised in that：It is described porous
Carrier is aluminium oxide, and the metal front liquid solution is nickel nitrate aqueous solution, and the load capacity of metallic nickel is 5~15%.
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| 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 |
| 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 |
| 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 |
| 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 |
| CN116060087B (en) * | 2021-10-29 | 2024-05-07 | 中国石油化工股份有限公司 | Grading method of hydrogenation catalyst and application of grading method in refining microcrystalline wax |
| 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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