CN105214653B - A kind of preparation method of carbon nanotube loaded nanoparticle catalyst - Google Patents
A kind of preparation method of carbon nanotube loaded nanoparticle catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, step is to be added in aqueous solution metal precursor, reducing agent and carbon nanotube and mix well, and carries out microwave heating under high pressure to get product.The preparation process of catalyst provided by the invention is simple, preparation condition is mild, raw material is all made of green reagent, using microwave reduction, whole process has the characteristics that environmentally protective, energy-efficient, and catalyst stability is good, is not necessarily to oxygen barrier operation, prepared catalyst realizes catalytic hydrogenation reaction at room temperature for the first time, and catalytic activity is high, catalyst can be easily separated, and be conducive to industrial applications.
Description
Technical field
The present invention relates to the catalyst of catalytic hydrogenation reaction, and in particular to a kind of carbon nanotube loaded nano particle catalysis
Agent.
Background technology
Catalyst applied to catalytic hydrogenation reaction can be generally divided into homogeneous catalyst and heterogeneous catalysis.Homogeneously urge
Agent catalytic activity is high, reaction condition is mild, but is difficult to realize the separation of catalyst, to improve cost and remaining urge
Agent can cause the degradation of product.Heterogeneous catalysis (loaded catalyst) efficiently solves the separation problem of catalyst,
It thus has industrially obtained more being widely applied, but loaded catalyst is due to during the reaction with reactant respectively two
Phase generally requires higher reaction temperature, especially in hydrogenation of polymer field, is required at high temperature using loaded catalyst
It carries out.This just increases the cost in actual industrial production.
Carbon nanotube as a kind of new carbon, have strong high length-diameter ratio, high-specific surface area, resistance to acid and alkali, high temperature resistant,
The advantages that intensity is high, heat-conductive characteristic is good, is the ideal chose as catalyst carrier.But since carbon nanotube is nanometer ruler
Degree, therefore easily reunite, the preparation method of traditional carbon nanotube loaded catalyst is typically to pass through strong acid (concentrated nitric acid, dense sulphur
Acid etc.) carbon nanotube is carried out surface-functionalized, make hydroxyl on carbon nano tube surface band, carboxyl, epoxy group isopolarity group, one
Aspect improves the dispersibility of carbon nanotube, is on the other hand complexed and will realized by these polar groups and metal cation
The load of metal cation, then by obtaining carbon nanotube loaded catalyst after reduction.Traditional carbon nanotube loaded catalysis
Agent preparation method needs to carry out for a long time with carbon nanotube using a large amount of corrosive strong acid in the preparation process of catalyst
The back flow reaction of (usually in 10h or more) is modified, complex process, and experiment condition is harsh, operating difficulties, and is polluted big, dangerous
Height, and the modification of strong acid can lead to carbon nano tube surface bond valence structural damage simultaneously so that modified carbon nanotube loses
The advantages that heat-conductive characteristic is good, intensity is high possessed by itself.
Invention content
(1) technical problems to be solved
For traditional technology existing technique during carbon nanotube loaded nanoparticle catalyst is prepared using strong acid
It is complexity, operating difficulties, dangerous high, at the same can also the heat conductivity of destroying carbon nanometer tube itself and the defect of intensity, the present invention
A kind of method for preparing carbon nanotube loaded nanoparticle catalyst easy to operate, reaction condition is mild is provided.
(2) technical solution
Method of the present invention, includes the following steps：
Metal precursor, reducing agent and carbon nanotube are added in aqueous solution and mixed well, is carried out under high pressure
Microwave heating is to get carbon nanotube loaded nanoparticle catalyst.
In the present invention, the preferred multi-walled carbon nanotube of carbon nanotube, the average caliber of the multi-walled carbon nanotube is
30nm~100nm, length are 1-2 μm, purity is 95%~100%.
In the present invention, the condition of the high-pressure microwave heating is：50~180 DEG C, 400~800psi of pressure of temperature, power
400~1000W, 0.5~5h of heating time.Compared to traditional mode of heating by heat transfer, Microwave-assisted firing has
The characteristics of homogeneous heating, green high-efficient, energy conservation and environmental protection, and since microwave is to the selectivity of polar solvent, heating has choosing
Selecting property significantly reduces the possibility of side reaction generation.
In the present invention, the reducing agent is ascorbic acid, ethylene glycol, citric acid, sodium citrate etc., is using reducing agent
It is green reagent, environmentally safe and at low cost.
In the present invention, the metal precursor is RhCl3、PdCl2Or RuCl3.Pt systems noble metal is in catalytic hydrogenation reaction
Other metal institutes are shown in macromolecular hydrogenation reaction with high activity and selectivity, especially tri- kinds of noble metals of Rh, Pd, Ru
The high-performance not having.
In the present invention, metal precursor, reducing agent and carbon nanotube are according to the mass volume ratio with water in the aqueous solution
50~300g/L, 20~200g/L, 1~20g/L
Method of the present invention, operating procedure are preferably：
(1) carbon nanotube is dissolved in deionized water solution by mass concentration 5mg/ml~30mg/ml, magnetic agitation 0.5~
5h, 0.5~5h of water bath sonicator is to get carbon nano-tube aqueous solutions；
(2) metal precursor is dissolved in by mass concentration 1mg/ml~20mg/ml in deionized water, magnetic agitation is extremely divided
It dissipates uniformly to get metal front liquid；
(3) reducing agent is dissolved in by mass concentration 5mg/ml~40mg/ml in deionized water, magnetic agitation is equal to disperseing
It is even, obtain aqueous ascorbic acid；
It (4) will be anti-bad obtained by metal front liquid obtained by carbon nano-tube aqueous solutions, step (2) obtained by step (1) and step (3)
Hematic acid aqueous solution mixes in proportion, 0.5~5h of magnetic agitation, temperature is 50~180 DEG C, pressure is 400~800psi, power
For 0.5~5h of microwave heating under 400~1000W, carbon nanotube loaded nanoparticle catalyst is obtained.
Another object of the present invention is carbon nanotube loaded nanometer made from Sustainable use method of the present invention
Grain catalyst.
Final object of the present invention is Sustainable use carbon nanotube loaded nanoparticle catalyst produced by the present invention
Application in terms of unsaturated hydrogenation of polymer reaction.
Using inventing the nanoparticle catalyst during carrying out catalytic hydrogenation reaction, nanoparticle catalyst and
Unsaturated polymer glue is according to carbon-carbon double bond content in active metal component in catalyst and unsaturated polymer with molar ratio
0.5~1.5：2000 mixing, are reacted under conditions of 30~100 DEG C.
Application of the carbon nanotube loaded nanoparticle catalyst of the present invention in terms of hydrogenation reaction, specifically includes as follows
Step：
1) the carbon nanotube loaded nanoparticle catalyst is mixed with unsaturated polymer glue, nano particle catalysis
Agent with unsaturated polymer glue according to active metal component in catalyst with carbon-carbon double bond content in unsaturated polymer to rub
That ratio 0.5~1.5：2000 mixing, are added in autoclave, successively change mixed glue solution and described with nitrogen and hydrogen matter
Air in reaction kettle obtains glue to be reacted；
2) it is passed through hydrogen into the glue to be reacted, in 30~100 DEG C of temperature, 1~5MPa of Hydrogen Vapor Pressure, speed of agitator
1~10h is reacted under the conditions of 100~1500rpm, obtains catalytic hydrogenation product.
Application of the method for the present invention in terms of being catalyzed chemigum hydrogenation, includes the following steps：
1) by carbon nanotube loaded nanoparticle catalyst of the present invention and a concentration of 2%~50% nitrile rubber
Mixing, is added in autoclave, active metal is with carbon-carbon double bond content ratio in nitrile rubber in nanoparticle catalyst
1：2000, nitrogen and hydrogen are each led into the reaction kettle, matter changes the air in the glue and reaction kettle, must wait for anti-
Answer glue；
2) it is passed through hydrogen into the glue to be reacted, in 30~80 DEG C of temperature, 1~5MPa of Hydrogen Vapor Pressure, speed of agitator
To react 6~10h under the conditions of 100~1000rpm to get catalytic hydrogenation product.
(3) advantageous effect
1) in the present invention, it is related to a kind of preparation method of new carbon nanotube loaded catalyst, has abandoned traditional
The method that strong acid functionalization realizes the load of active component, then improve carbon nanotube by the way of microwave reduction package
Dispersion and realize the load of active component, the preparation process of entire catalyst carries out, at room temperature without using poisonous and harmful
Reagent, it is simple to operate, it is aided with microwave reduction method, has the characteristics that environmentally protective, energy-efficient, complies fully with green
The objective of chemistry.
2) preparation method of catalyst of the present invention, reaction condition is mild, will not destroying carbon nanometer tube itself it is excellent
Heat conductivity, therefore carbon nanotube loaded beaded catalyst obtained is realized be catalyzed unsaturated polymer at normal temperatures for the first time
Hydrogenation reaction has broad application prospects in industrialized production.
3) the carbon nanotube loaded beaded catalyst stability of the invention prepared is good, is not necessarily to oxygen barrier operation, hydrogenation reaction item
Part is mild, catalytic activity is high.
Description of the drawings
Fig. 1 show the high resolution transmission electron microscopy of the 1 carbon nanotube loaded nanoparticle catalyst of gained of embodiment
Photo.
Fig. 2 show the nuclear magnetic resonance of nitrile rubber (NBR) and hydrogenated nitrile-butadiene rubber (HNBR) before and after catalytic hydrogenation reaction
Hydrogen composes spectrogram.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment is related to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, includes the following steps：
1) by metal precursor PdCl2, reducing agent sodium citrate and carbon nanotube according to the mass volume ratio 50 with water~
300g/L, 20~200g/L, 1~20g/L are soluble in water, to the mixed solution magnetic agitation 4h, three kinds of substances are made uniformly to mix
It closes；
2) by the microwave heating under conditions of 120 DEG C of temperature, pressure 500psi, power 600W of the solution after the mixing
0.5~5h is washed 5 times with deionized water and ethyl alcohol respectively, is dried in vacuo at 80 DEG C for 24 hours to get carbon nanotube loaded nanometer
Grain catalyst.
Embodiment 2
The present embodiment is related to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, includes the following steps：
1) carbon nanotube is dissolved in deionized water, magnetic agitation 3h by mass concentration 10mg/mL, water bath sonicator 3h obtains carbon
Nanotube aqueous solution；
2) by metal precursor R hCl3It is dissolved in deionized water by 5mg/mL, magnetic agitation obtains golden to being uniformly dispersed
Belong to precursor liquid；
3) ascorbic acid is dissolved in mass volume ratio 20mg/mL in deionized water, magnetic agitation is obtained to being uniformly dispersed
Aqueous ascorbic acid；
It 4) will be anti-bad obtained by metal front liquid obtained by carbon nano-tube aqueous solutions, step (2) obtained by step (1) and step (3)
Hematic acid aqueous solution mixes in proportion, magnetic agitation 3h, temperature is 80 DEG C, pressure 400psi, microwave adds under power is 800W
Hot 2h is washed 5 times with deionized water and ethyl alcohol, is dried in vacuo at 80 DEG C and is urged for 24 hours to get carbon nanotube loaded nano particle respectively
Agent.
High resolution transmission electron microscopy photo such as Fig. 1 of the carbon nano-tube catalyst of the area load Rh nano particles
It is shown.
As seen from the figure, catalyst manufactured in the present embodiment, metallic particles are uniformly distributed in carbon nano tube surface, and what is obtained is expensive
Metal nanoparticle grain size 4nm or so and particle diameter distribution it is uniform.
Embodiment 3
The present embodiment is related to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, includes the following steps：
(1) carbon nanotube is dissolved in deionized water solution, magnetic agitation 0.5h, water bath sonicator by mass concentration 10ml/ml
5h is to get carbon nano-tube aqueous solutions；
(2) by metal precursor RhCl3It is dissolved in deionized water by mass concentration 5mg/ml, magnetic agitation is equal to disperseing
It is even to get metal front liquid；
(3) reducing agent ascorbic acid is dissolved in by mass concentration 20mg/ml in deionized water, magnetic agitation is equal to disperseing
It is even, obtain aqueous ascorbic acid；
It (4) will be anti-bad obtained by metal front liquid obtained by carbon nano-tube aqueous solutions, step (2) obtained by step (1) and step (3)
Hematic acid aqueous solution mixes in proportion, magnetic agitation 5h, temperature is 50 DEG C, pressure 800psi, microwave adds under power is 1000W
Hot 5h obtains carbon nanotube loaded nanoparticle catalyst.
Embodiment 4
The present embodiment is related to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, includes the following steps：
(1) carbon nanotube is dissolved in deionized water solution, magnetic agitation 5h, water bath sonicator by mass concentration 10mg/ml
0.5h is to get carbon nano-tube aqueous solutions；(2) by metal precursor RhCl3It is dissolved in deionized water by mass concentration 5mg/ml,
Magnetic agitation is to being uniformly dispersed to get metal front liquid；
(3) reducing agent ascorbic acid is dissolved in by mass concentration 20ml/ml in deionized water, magnetic agitation is equal to disperseing
It is even, obtain aqueous ascorbic acid；
It 4) will be anti-bad obtained by metal front liquid obtained by carbon nano-tube aqueous solutions, step (2) obtained by step (1) and step (3)
Hematic acid aqueous solution mixes in proportion, magnetic agitation 0.5h, the microwave in the case where temperature is 180 DEG C, pressure 500psi, power are 400W
5h is heated, is washed 5 times, is dried in vacuo at 80 DEG C for 24 hours to get carbon nanotube loaded nano particle with deionized water and ethyl alcohol respectively
Catalyst.
Embodiment 5
The present embodiment relates to the use of carbon nanotube loaded nanoparticle catalyst catalysis dimethylbenzene butyronitrile of the present invention
Rubber (dimethylbenzene NBR) carries out plus the reaction of hydrogen, is as follows：
1) by 2 gained catalyst 285.09mg (12.3729mg containing Rh, i.e. 0.1201mmol) of embodiment and mass concentration
For 40% dimethylbenzene NBR glues 37.5g (containing NBR15g, carbon-carbon double bond 0.2402mol) mixing, it is added to autoclave
In, nitrogen and each 3 times of hydrogen are each led into the reaction kettle, matter changes the air in the glue and reaction kettle, must wait for
React glue；
2) it is passed through hydrogen into the glue to be reacted, in temperature 50 C, Hydrogen Vapor Pressure 4MPa, speed of agitator 800rpm
Under the conditions of reaction 8h to get catalytic hydrogenation product.After exhaust, cooling, by centrifuging catalyst, using nuclear magnetic resonance spectroscopy
It analyzes the structure of product and the conversion ratio for calculating hydrogenation reaction is 96.20%.
Embodiment 6
The present embodiment relates to the use of carbon nanotube loaded nanoparticle catalyst of the present invention and is catalyzed unsaturated polymerization
Object natural rubber carries out plus the reaction of hydrogen, is as follows：
1) by 3 gained catalyst 285.09mg (12.3729mg containing Rh, i.e. 0.1201mmol) of embodiment and mass concentration
For 30% dimethylbenzene NR glues 32g (containing NR17.85g, carbon-carbon double bond 0.2402mol) mixing, it is added in autoclave,
Nitrogen and each 3 times of hydrogen are each led into the reaction kettle, matter changes the air in the glue and reaction kettle, must wait reacting
Glue；
2) it is passed through hydrogen into the glue to be reacted, is in temperature 50 C, Hydrogen Vapor Pressure 4MPa, speed of agitator
10h is reacted under the conditions of 1000rpm to get catalytic hydrogenation product.After exhaust, cooling, by centrifuging catalyst, using nuclear-magnetism
The structure of resonance hydrogen spectrum analysis product and the conversion ratio for calculating hydrogenation reaction are 94.85%.
Embodiment 7
The present embodiment relates to the use of carbon nanotube loaded nanoparticle catalyst of the present invention and is catalyzed unsaturated polymerization
Object polybutadiene carries out plus the reaction of hydrogen, is as follows：
1) by 4 gained catalyst 285.09mg (12.3729mg containing Rh, i.e. 0.1201mmol) of embodiment and mass concentration
It mixes, adds according to butadiene glue 31.875g (17.85g containing polybutadiene, carbon-carbon double bond 0.2402mol) for 40% dimethylbenzene
Enter into autoclave, nitrogen and each 3 times of hydrogen is each led into the reaction kettle, matter changes the glue and reaction kettle
In air, obtain glue to be reacted；
2) it is passed through hydrogen into the glue to be reacted, is in 30 DEG C of temperature, Hydrogen Vapor Pressure 3MPa, speed of agitator
10h is reacted under the conditions of 1000rpm to get catalytic hydrogenation product.After exhaust, cooling, by centrifuging catalyst, using nuclear-magnetism
The structure of resonance hydrogen spectrum analysis product and the conversion ratio for calculating hydrogenation reaction are 97.56%.
Comparative example 1
Compared with embodiment 1, difference lies in used catalyst is that the homogeneous Wilkinson of equivalent Rh contents is catalyzed
Agent RhCl [PPh3]3, catalyst is subjected to 5 condition of embodiment identical catalytic hydrogenation reaction, calculates the conversion ratio of hydrogenation reaction
It is 45.6%, this illustrates that traditional catalyst adds hydrogen to be difficult to obtain high degree of hydrogenation macromolecular at 50 DEG C of low temperature, and in the present invention
In prepared Rh catalyst realize the complete hydrogenation to macromolecular under mild reaction conditions for the first time.
Comparative example 2
Compared with embodiment 1, difference lies in, in the high-pressure microwave heating process, heating condition is 230 DEG C,
Catalyst made from the method is subjected to 5 condition of embodiment identical catalytic hydrogenation reaction, calculates the conversion ratio of hydrogenation reaction
It is 29.2%.This illustrates that the temperature of microwave reduction has significant impact for the catalytic activity of prepared catalyst.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (7)
1. a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, which is characterized in that include the following steps：
(1) carbon nanotube is dissolved in deionized water solution, 0.5~5h of magnetic agitation, water by mass concentration 5mg/ml~30mg/ml
0.5~5h of ultrasound is bathed to get carbon nano-tube aqueous solutions；
(2) metal precursor is dissolved in by mass concentration 1mg/ml~20mg/ml in deionized water, magnetic agitation is equal to disperseing
It is even to get metal front liquid；
(3) reducing agent is dissolved in by mass concentration 5mg/ml~40mg/ml in deionized water, magnetic agitation to being uniformly dispersed,
Obtain the aqueous solution of reducing agent；
(4) by reducing agent water obtained by metal front liquid obtained by carbon nano-tube aqueous solutions, step (2) obtained by step (1) and step (3)
Solution mixes in proportion, 0.5~5h of magnetic agitation, temperature is 50~180 DEG C, pressure is 400~800psi, power 400
0.5~5h of microwave heating under~1000W, obtains carbon nanotube loaded nanoparticle catalyst.
2. according to the method described in claim 1, it is characterized in that, the reducing agent be ascorbic acid, ethylene glycol, citric acid or
Sodium citrate.
3. according to the method described in claim 1, it is characterized in that, the metal precursor is RhCl3、PdCl2Or RuCl3。
4. according to the method described in claim 1, it is characterized in that, metal precursor, reducing agent and carbon nanotube in aqueous solution
According to 50~300g/L of mass volume ratio, 20~200g/L, the 1~20g/L with water.
5. carbon nanotube loaded nanoparticle catalyst made from any one of Claims 1 to 4 the method.
6. the carbon nanotube loaded nanoparticle catalyst described in claim 5 is in terms of unsaturated polymer catalyzing hydrogenation reaction
Application.
7. application according to claim 6, which is characterized in that the carbon nanotube loaded nanoparticle catalyst and insatiable hunger
With polymer glue according to carbon-carbon double bond content in active metal component in catalyst and unsaturated polymer molar ratio 0.5~
1.5：2000 mixing, react under conditions of 30~50 DEG C of temperature.
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| CN106345522A (en) * | 2016-08-25 | 2017-01-25 | 北京化工大学 | Carbon dot/rhodium composite nano catalyst, and preparation and application thereof |
| CN106512993B (en) * | 2016-08-30 | 2018-11-16 | 北京化工大学 | Palladium-ruthenium bimetal nano catalyst preparation and plus hydrogen application |
| CN107051552B (en) * | 2017-05-22 | 2019-09-27 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
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