CN105214653A - 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, its step is, metal precursor, reducing agent and CNT is joined in the aqueous solution and fully mixes, carry out heating using microwave under elevated pressure conditions, obtain product.The preparation technology of catalyst provided by the invention is simple, preparation condition is gentle, raw material all adopts green reagent, adopt microwave reduction, whole process has the feature of environmental protection, efficient energy-saving, and catalyst stability is good, without the need to oxygen barrier operation, prepared catalyst achieves catalytic hydrogenation reaction at room temperature for the first time, and catalytic activity is high, catalyst is easily separated, and is beneficial to industrial applications.
Description
Technical field
The present invention relates to the catalyst of catalytic hydrogenation reaction, be specifically related to a kind of carbon nanotube loaded nanoparticle catalyst.
Background technology
The catalyst being applied to catalytic hydrogenation reaction can be divided into homogeneous catalyst and heterogeneous catalysis usually.Homogeneous catalyst catalytic activity is high, reaction condition is gentle, but is difficult to the separation realizing catalyst, thus improves cost and residual catalyst can cause the degraded of product.Heterogeneous catalysis (loaded catalyst) efficiently solves the separation problem of catalyst, thus industrially obtain and apply more widely, but loaded catalyst due in course of reaction with reactant office two-phase, often need higher reaction temperature, especially in hydrogenation of polymer field, loaded catalyst is adopted all to need at high temperature to carry out.This just increases the cost in actual industrial production.
CNT is as a kind of new carbon, and advantages such as having high length-diameter ratio, high-specific surface area, resistance to acids and bases is strong, high temperature resistant, intensity is high, heat-conductive characteristic is good is the ideal chose as catalyst carrier.But because CNT is nanoscale, therefore very easily reunite, the preparation method of traditional carbon nanotube loaded catalyst normally carries out surface-functionalized by strong acid (red fuming nitric acid (RFNA), the concentrated sulfuric acid etc.) to CNT, make hydroxyl on carbon nano tube surface band, carboxyl, epoxy radicals isopolarity group, improve the dispersiveness of CNT on the one hand, carry out complexing by these polar groups and metal cation and the load of metal cation will be realized on the other hand, then by obtaining carbon nanotube loaded catalyst after reduction.Traditional carbon nanotube loaded method for preparing catalyst needs to use a large amount of corrosive strong acid and CNT to carry out the back flow reaction modification of (usually at more than 10h) for a long time in the preparation process of catalyst, complex process, experiment condition is harsh, operating difficulties, and pollute large, dangerous high, and the modification of strong acid can cause the structural damage of carbon nano tube surface bond valence simultaneously, modified CNT is lost, and the heat-conductive characteristic itself had is good, intensity advantages of higher.
Summary of the invention
(1) technical problem that will solve
The complex process utilizing strong acid to prepare to exist in the process of carbon nanotube loaded nanoparticle catalyst for conventional art, operating difficulties, dangerous high, simultaneously also can the heat conductivity of destroying carbon nanometer tube self and the defect of intensity, the invention provides the method for the carbon nanotube loaded nanoparticle catalyst of a kind of easy to operate, that reaction condition is gentle preparation.
(2) technical scheme
Method of the present invention, comprises the steps:
Metal precursor, reducing agent and CNT are joined in the aqueous solution and fully mixes, carry out heating using microwave under elevated pressure conditions, obtain carbon nanotube loaded nanoparticle catalyst.
In the present invention, the preferred multi-walled carbon nano-tubes of described CNT, the average caliber of described multi-walled carbon nano-tubes is 30nm ~ 100nm, length is 1-2 μm, purity is 95% ~ 100%.
In the present invention, the condition of described high-pressure microwave heating is: temperature 50 ~ 180 DEG C, pressure 400 ~ 800psi, power 400 ~ 1000W, heat time 0.5 ~ 5h.Heat conducting mode of heating is passed through compared to traditional, Microwave-assisted firing has the feature of homogeneous heating, green high-efficient, energy-conserving and environment-protective, and due to selective to polar solvent of microwave, therefore heating has selective, significantly reduces the possibility that side reaction occurs.
In the present invention, described reducing agent is ascorbic acid, ethylene glycol, citric acid, natrium citricum etc., adopt reducing agent to be green reagent, environmentally safe, and cost is low.
In the present invention, described metal precursor is RhCl
3, PdCl
2or RuCl
3.Pt system noble metal has high activity and selective in catalytic hydrogenation reaction, and especially Rh, Pd, Ru tri-kinds of noble metals show the high-performance not available for other metals in large molecule hydrogenation reaction.
In the present invention, in the described aqueous solution, metal precursor, reducing agent and CNT are according to mass volume ratio 50 ~ 300g/L, 20 ~ 200g/L, the 1 ~ 20g/L with water
Method of the present invention, its operating procedure is preferably:
(1) CNT is dissolved in deionized water solution by mass concentration 5mg/ml ~ 30mg/ml, magnetic agitation 0.5 ~ 5h, water bath sonicator 0.5 ~ 5h, obtains carbon nano-tube aqueous solutions;
(2) be dissolved in deionized water by metal precursor by mass concentration 1mg/ml ~ 20mg/ml, magnetic agitation, to being uniformly dispersed, obtains metal front liquid;
(3) be dissolved in deionized water by reducing agent by mass concentration 5mg/ml ~ 40mg/ml, magnetic agitation, to being uniformly dispersed, obtains aqueous ascorbic acid;
(4) step (1) gained carbon nano-tube aqueous solutions, step (2) gained metal front liquid and step (3) gained aqueous ascorbic acid are mixed in proportion, magnetic agitation 0.5 ~ 5h, temperature be 50 ~ 180 DEG C, pressure is 400 ~ 800psi, power be 400 ~ 1000W under heating using microwave 0.5 ~ 5h, obtain carbon nanotube loaded nanoparticle catalyst.
Another object of the present invention is the carbon nanotube loaded nanoparticle catalyst that Sustainable use method of the present invention obtains.
Last object of the present invention is the application of carbon nanotube loaded nanoparticle catalyst in the reaction of insatiable hunger conjunction hydrogenation of polymer that Sustainable use the present invention obtains.
Utilize the described nanoparticle catalyst of invention in the process of carrying out catalytic hydrogenation reaction, nanoparticle catalyst mixes with mol ratio 0.5 ~ 1.5:2000 with carbon-carbon double bond content in unsaturated polymer according to active metal component in catalyst with unsaturated polymer glue, reacts under the condition of 30 ~ 100 DEG C.
The application of carbon nanotube loaded nanoparticle catalyst of the present invention in hydrogenation reaction, specifically comprises the steps:
1) described carbon nanotube loaded nanoparticle catalyst is mixed with unsaturated polymer glue, nanoparticle catalyst mixes with mol ratio 0.5 ~ 1.5:2000 with carbon-carbon double bond content in unsaturated polymer according to active metal component in catalyst with unsaturated polymer glue, join in autoclave, priority nitrogen and hydrogen matter change the air in mixed glue solution and described reactor, obtain question response glue;
2) in described question response glue, pass into hydrogen, under temperature 30 ~ 100 DEG C, Hydrogen Vapor Pressure 1 ~ 5MPa, speed of agitator 100 ~ 1500rpm condition, react 1 ~ 10h, obtain catalytic hydrogenation product.
The application of method of the present invention in catalysis chemigum hydrogenation, comprises the steps:
1) acrylonitrile-butadiene rubber being 2% ~ 50% by carbon nanotube loaded nanoparticle catalyst of the present invention and concentration mixes, join in autoclave, in nanoparticle catalyst, active metal and carbon-carbon double bond content in acrylonitrile-butadiene rubber are than being 1:2000, nitrogen and hydrogen is passed into respectively in described reactor, matter changes the air in described glue and reactor, obtains question response glue;
2) in described question response glue, pass into hydrogen, under temperature 30 ~ 80 DEG C, Hydrogen Vapor Pressure 1 ~ 5MPa, speed of agitator are 100 ~ 1000rpm condition, react 6 ~ 10h, obtain catalytic hydrogenation product.
(3) beneficial effect
1) in the present invention, relate to a kind of preparation method of carbon nanotube loaded catalyst newly, abandon the method that traditional strong acid functionalization realizes the load of active component, then adopt the mode of microwave reduction parcel improve the dispersion of CNT and realize the load of active component, the preparation process of whole catalyst is at room temperature carried out, without the need to using poisonous and harmful reagent, simple to operation, be aided with microwave reduction method, there is the feature of environmental protection, efficient energy-saving, meet the aim of Green Chemistry completely.
2) preparation method of catalyst of the present invention, reaction condition is gentle, can not the excellent heat conductivity of destroying carbon nanometer tube self, therefore obtained carbon nanotube loaded beaded catalyst realizes the hydrogenation reaction that polymer is closed in catalysis insatiable hunger at normal temperatures first, has broad application prospects in suitability for industrialized production.
3) the present invention prepare carbon nanotube loaded beaded catalyst good stability, without the need to oxygen barrier operation, hydrogenation conditions is gentle, catalytic activity is high.
Accompanying drawing explanation
Figure 1 shows that the high resolution transmission electron microscopy photo of the carbon nanotube loaded nanoparticle catalyst of embodiment 1 gained.
Figure 2 shows that the proton nmr spectra spectrogram of acrylonitrile-butadiene rubber before and after catalytic hydrogenation reaction (NBR) and hydrogenated nitrile-butadiene rubber (HNBR).
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The present embodiment relates to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, comprises the steps:
1) by metal precursor PdCl
2, reducing agent natrium citricum and CNT according to soluble in water with mass volume ratio 50 ~ 300g/L, the 20 ~ 200g/L of water, 1 ~ 20g/L, to described mixed solution magnetic agitation 4h, make three kinds of material Homogeneous phase mixing;
2) by the solution after described mixing temperature 120 DEG C, pressure 500psi, heating using microwave 0.5 ~ 5h under the condition of power 600W, wash 5 times with deionized water and ethanol respectively, and vacuum drying 24h at 80 DEG C, obtains carbon nanotube loaded nanoparticle catalyst.
Embodiment 2
The present embodiment relates to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, comprises the steps:
1) CNT is dissolved in deionized water by mass concentration 10mg/mL, magnetic agitation 3h, water bath sonicator 3h, obtains carbon nano-tube aqueous solutions;
2) by metal precursor RhCl
3be dissolved in deionized water by 5mg/mL, magnetic agitation, to being uniformly dispersed, obtains metal front liquid;
3) be dissolved in deionized water by ascorbic acid with mass volume ratio 20mg/mL, magnetic agitation, to being uniformly dispersed, obtains aqueous ascorbic acid;
4) step (1) gained carbon nano-tube aqueous solutions, step (2) gained metal front liquid and step (3) gained aqueous ascorbic acid are mixed in proportion, magnetic agitation 3h, temperature be 80 DEG C, pressure is 400psi, power be 800W under heating using microwave 2h, 5 times are washed respectively with deionized water and ethanol, vacuum drying 24h at 80 DEG C, obtains carbon nanotube loaded nanoparticle catalyst.
The high resolution transmission electron microscopy photo of the carbon nano-tube catalyst of described area load Rh nano particle as shown in Figure 1.
As seen from the figure, catalyst prepared by the present embodiment, metallic particles is uniformly distributed in carbon nano tube surface, and the noble metal nano particles particle diameter obtained is at about 4nm and even particle size distribution.
Embodiment 3
The present embodiment relates to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, comprises the steps:
(1) CNT is dissolved in deionized water solution by mass concentration 10ml/ml, magnetic agitation 0.5h, water bath sonicator 5h, obtains carbon nano-tube aqueous solutions;
(2) by metal precursor RhCl
3be dissolved in deionized water by mass concentration 5mg/ml, magnetic agitation, to being uniformly dispersed, obtains metal front liquid;
(3) be dissolved in deionized water by reducing agent ascorbic acid by mass concentration 20mg/ml, magnetic agitation, to being uniformly dispersed, obtains aqueous ascorbic acid;
(4) step (1) gained carbon nano-tube aqueous solutions, step (2) gained metal front liquid and step (3) gained aqueous ascorbic acid are mixed in proportion, magnetic agitation 5h, temperature be 50 DEG C, pressure is 800psi, power be 1000W under heating using microwave 5h, obtain carbon nanotube loaded nanoparticle catalyst.
Embodiment 4
The present embodiment relates to a kind of preparation method of carbon nanotube loaded nanoparticle catalyst, comprises the steps:
(1) CNT is dissolved in deionized water solution by mass concentration 10mg/ml, magnetic agitation 5h, water bath sonicator 0.5h, obtains carbon nano-tube aqueous solutions; (2) by metal precursor RhCl
3be dissolved in deionized water by mass concentration 5mg/ml, magnetic agitation, to being uniformly dispersed, obtains metal front liquid;
(3) be dissolved in deionized water by reducing agent ascorbic acid by mass concentration 20ml/ml, magnetic agitation, to being uniformly dispersed, obtains aqueous ascorbic acid;
4) step (1) gained carbon nano-tube aqueous solutions, step (2) gained metal front liquid and step (3) gained aqueous ascorbic acid are mixed in proportion, magnetic agitation 0.5h, temperature be 180 DEG C, pressure is 500psi, power be 400W under heating using microwave 5h, 5 times are washed respectively with deionized water and ethanol, vacuum drying 24h at 80 DEG C, obtains carbon nanotube loaded nanoparticle catalyst.
Embodiment 5
The present embodiment relates to and utilizes carbon nanotube loaded nanoparticle catalyst catalysis dimethylbenzene acrylonitrile-butadiene rubber (dimethylbenzene NBR) of the present invention to carry out the reaction of hydrogenation, and concrete steps are as follows:
1) by embodiment 2 gained catalyst 285.09mg (containing Rh12.3729mg, i.e. 0.1201mmol) with mass concentration be that the dimethylbenzene NBR glue 37.5g of 40% is (containing NBR15g, carbon-carbon double bond 0.2402mol) mixing, join in autoclave, nitrogen and each 3 times of hydrogen is passed into respectively in described reactor, matter changes the air in described glue and reactor, obtains question response glue;
2) in described question response glue, pass into hydrogen, react 8h at temperature 50 C, Hydrogen Vapor Pressure 4MPa, speed of agitator under being 800rpm condition, obtain catalytic hydrogenation product.After exhaust, cooling, by centrifugation catalyst, adopt the structure of proton nmr spectra assay products and the conversion ratio calculating hydrogenation reaction is 96.20%.
Embodiment 6
The present embodiment relates to utilize carbon nanotube loaded nanoparticle catalyst catalysis insatiable hunger of the present invention to close reaction that polymer natural rubber carries out hydrogenation, and concrete steps are as follows:
1) by embodiment 3 gained catalyst 285.09mg (containing Rh12.3729mg, i.e. 0.1201mmol) with mass concentration be that the dimethylbenzene NR glue 32g of 30% is (containing NR17.85g, carbon-carbon double bond 0.2402mol) mixing, join in autoclave, nitrogen and each 3 times of hydrogen is passed into respectively in described reactor, matter changes the air in described glue and reactor, obtains question response glue;
2) in described question response glue, pass into hydrogen, react 10h at temperature 50 C, Hydrogen Vapor Pressure 4MPa, speed of agitator under being 1000rpm condition, obtain catalytic hydrogenation product.After exhaust, cooling, by centrifugation catalyst, adopt the structure of proton nmr spectra assay products and the conversion ratio calculating hydrogenation reaction is 94.85%.
Embodiment 7
The present embodiment relates to utilize carbon nanotube loaded nanoparticle catalyst catalysis insatiable hunger of the present invention to close reaction that polymer poly butadiene carries out hydrogenation, and concrete steps are as follows:
1) by embodiment 4 gained catalyst 285.09mg (containing Rh12.3729mg, i.e. 0.1201mmol) with mass concentration be 40% dimethylbenzene according to butadiene glue 31.875g (containing polybutadiene 17.85g, carbon-carbon double bond 0.2402mol) mixing, join in autoclave, nitrogen and each 3 times of hydrogen is passed into respectively in described reactor, matter changes the air in described glue and reactor, obtains question response glue;
2) in described question response glue, pass into hydrogen, react 10h at temperature 30 DEG C, Hydrogen Vapor Pressure 3MPa, speed of agitator under being 1000rpm condition, obtain catalytic hydrogenation product.After exhaust, cooling, by centrifugation catalyst, adopt the structure of proton nmr spectra assay products and the conversion ratio calculating hydrogenation reaction is 97.56%.
Comparative example 1
Compare with embodiment 1, its difference is, the catalyst adopted is the homogeneous phase Wilkinson catalyst RhCl [PPh of equivalent Rh content
3]
3catalyst is carried out the catalytic hydrogenation reaction that same embodiment 5 condition is identical, the conversion ratio calculating hydrogenation reaction is 45.6%, this illustrates that traditional catalyst is difficult to obtain high degree of hydrogenation to large molecule hydrogenation at low temperature 50 DEG C, and Rh catalyst prepared in the present invention achieves under the reaction condition of gentleness first to macromolecular complete hydrogenation.
Comparative example 2
Compare with embodiment 1, its difference is, in described high-pressure microwave heating process, its heating condition is 230 DEG C, and catalyst the method obtained carries out the identical catalytic hydrogenation reaction of same embodiment 5 condition, and the conversion ratio calculating hydrogenation reaction 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 basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. the preparation method of a carbon nanotube loaded nanoparticle catalyst, it is characterized in that, be added to the water metal precursor, reducing agent and CNT fully mixing, carries out heating using microwave under elevated pressure conditions, obtain carbon nanotube loaded nanoparticle catalyst.
2. method according to claim 1, is characterized in that, the condition of described high-pressure microwave heating is: temperature 50 ~ 180 DEG C, pressure 400 ~ 800psi, power 400 ~ 1000W, heat time 0.5 ~ 5h.
3. method according to claim 1 and 2, is characterized in that, described reducing agent is ascorbic acid, ethylene glycol, citric acid or natrium citricum.
4. method according to claim 1 and 2, is characterized in that, described metal precursor is RhCl
3, PdCl
2or RuCl
3.
5. method according to claim 1 and 2, is characterized in that, in the described aqueous solution, metal precursor, reducing agent and CNT are according to mass volume ratio 50 ~ 300g/L, 20 ~ 200g/L, the 1 ~ 20g/L with water.
6. the method according to any one of Claims 1 to 5, is characterized in that, comprises the steps:
(1) CNT is dissolved in deionized water solution by mass concentration 5mg/ml ~ 30mg/ml, magnetic agitation 0.5 ~ 5h, water bath sonicator 0.5 ~ 5h, obtains carbon nano-tube aqueous solutions;
(2) be dissolved in deionized water by metal precursor by mass concentration 1mg/ml ~ 20mg/ml, magnetic agitation, to being uniformly dispersed, obtains metal front liquid;
(3) be dissolved in deionized water by reducing agent by mass concentration 5mg/ml ~ 40mg/ml, magnetic agitation, to being uniformly dispersed, obtains aqueous ascorbic acid;
(4) step (1) gained carbon nano-tube aqueous solutions, step (2) gained metal front liquid and step (3) the gained reducing agent aqueous solution are mixed in proportion, magnetic agitation 0.5 ~ 5h, temperature be 50 ~ 180 DEG C, pressure is 400 ~ 800psi, power be 400 ~ 1000W under heating using microwave 0.5 ~ 5h, obtain carbon nanotube loaded nanoparticle catalyst.
7. the carbon nanotube loaded nanoparticle catalyst that method described in any one of claim 1 ~ 6 is obtained.
8. the application of carbon nanotube loaded nanoparticle catalyst according to claim 7 in insatiable hunger conjunction polymer thing catalytic hydrogenation reaction.
9. application according to claim 8, it is characterized in that, described carbon nanotube loaded nanoparticle catalyst mixes with the mol ratio 0.5 ~ 1.5:2000 of carbon-carbon double bond content in unsaturated polymer according to active metal component in catalyst with unsaturated polymer glue, reacts under the condition of temperature 30 ~ 100 DEG C.
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| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
| CN107051552A (en) * | 2017-05-22 | 2017-08-18 | 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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| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
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| CN107051552A (en) * | 2017-05-22 | 2017-08-18 | 安徽大学 | Preparation of magnetic carbon nanotube-loaded rhodium catalyst and application of catalyst in selective hydrogenation of nitrile rubber |
| 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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