CN105251488A - Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst - Google Patents
Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst Download PDFInfo
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- CN105251488A CN105251488A CN201510682360.9A CN201510682360A CN105251488A CN 105251488 A CN105251488 A CN 105251488A CN 201510682360 A CN201510682360 A CN 201510682360A CN 105251488 A CN105251488 A CN 105251488A
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Abstract
The invention relates to a catalyst for preparation of o-phenyl phenol and a preparation method of the catalyst, in particular to a dehydrogenation catalyst capable of loading copper nanoparticles on the surface of a CNT (carbon nanotube) with high dispersion and a preparation method of the dehydrogenation catalyst. According to the dehydrogenation catalyst, the copper nanoparticles are uniformly loaded outside the CNT, wherein the mass percentage of copper is 5%-60%. The dehydrogenation catalyst is prepared through steps as follows: the multi-wall CNT is pretreated with concentrated nitric acid, silver nitrate is loaded on the outer surface of the CNT, the CNT is cut off at the high temperature, residual silver on the surface of the CNT is washed off with nitric acid, a certain amount of copper nitrate is dissolved with water and ultrasonically loaded outside the CNT, finally, copper ions are reduced into metallic copper under high-temperature H2 atmosphere, so that the outer surface of the CNT is in a spinous state, and the copper nanoparticles can be uniformly loaded on the outer surface of the CNT. According to the dehydrogenation catalyst, the conversion rate of cyclohexanone dimer for catalytic dehydrogenation preparation of o-phenyl phenol can be up to 100%, and the selectivity of the o-phenyl phenol can be up to 96%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for the preparation of o-phenyl phenol, particularly relate to a kind of carbon nano tube surface high-dispersion load copper nano-particle dehydrogenation and preparation method thereof.
Background technology
O-phenyl phenol (OPP) is a kind of purposes organic chemical intermediates very widely, can be used for the aspects such as vegetable and fruit is fresh-keeping, cosmetics are anticorrosion, the preservation of timber against decay, it or strong bactericide, disinfectant, microbial inhibitor, Antisepticize and mildew preventive in addition, in recent years, also developed both at home and abroad multiple with o-phenyl phenol be raw material produce oil-soluble o-phenyl phenol formaldehyde resin, emulsifying agent, synthetic dyestuffs, in the middle of flame-retardant high-molecular dyestuff.Current main employing cyclohexanone is both at home and abroad raw material, obtains cyclohexanone dimer, then through catalytic dehydrogenation, refine and obtain o-phenyl phenol through condensation dehydration.
Prepared by o-phenyl phenol for catalytic dehydrogenation, manyly patent discloses precious metal catalyst preparation technology.Chinese invention patent CN101555196 discloses the Pt/C catalyst with alkali metal or alkaline earth metal carbonate modification, catalyst and cyclohexanone dimer to be added in reactor agitating heating in a nitrogen atmosphere, obtaining o-phenyl phenol content is 91.3%, cyclohexanone dimer conversion ratio 100%.Japan Patent JP56-053632 adopts the Pt/ γ-A1 of K or Na of 1-10%, the Pt of 0.1-3%
2o
3or Pt/SiO
2-A1
2o
3make catalyst, dimer is synthesized OPP at 250-550 DEG C with gas phase and catalyst exposure, in use after 3000 hours, dimer conversion ratio 95%, OPP selective 92.1%.But this catalyst using noble metal as active component, cost is higher, and catalyst price per ton, up to more than 1,500,000 yuan, is unfavorable for promoting the use of, and therefore, in order to reduce costs, the non-precious metal catalyst of research and development low cost, tool is of great significance.
In non-precious metal catalyst preparing, Chinese invention patent CN1911508 adopts primary catalyst metal Ni, Cu, and co-catalyst is Cr, K etc., adopts infusion process load at active γ-Al
2o
3on, the selective of its o-phenyl phenol is up to 90%, and the conversion ratio of cyclohexenyl hexamethylene ketone is up to 98%, and this catalyst is not very desirable on catalytic efficiency and catalytic selectivity; Chinese invention patent CN1947838 adopts coprecipitation to prepare copper/magnesia catalyst, show that cyclohexenyl hexamethylene ketone conversion ratio reaches 100%, the yield of o-phenyl phenol is up to 95%, but, the preparation process of this catalyst is more, and complicated operation is higher to equipment requirement, therefore, in practicality is promoted, there is larger limitation.
Summary of the invention
For above-mentioned prior art, the technical problem to be solved in the present invention is to provide that a kind of cost is low, catalytic efficiency is high, selective good, the dehydrogenation for the preparation of o-phenyl phenol that preparation manipulation is easy.
In order to solve the problem, the invention provides a kind of carbon nano tube surface supported copper nano particle dehydrogenation, wherein the mass fraction of copper nano-particle is 5% ~ 60%.
The preparation process of above-mentioned catalyst is as follows:
(1) pretreatment of CNT: take a certain amount of multi-walled carbon nano-tubes, adds the nitric acid of 3 ~ 5mol/L, and 80 ~ 150 DEG C of hydro-thermals stir 2 ~ 6 hours, suction filtration, is washed to neutrality, puts into baking oven dry for standby subsequently;
(2) CNT cuts off:
A. be that the CNT obtained in step (1) joins in the liquor argenti nitratis ophthalmicus of 0.002 ~ 0.008mol/L by 5:1 ~ 40:1 according to the mass ratio of CNT and silver nitrate, 1 ~ 4h is stirred at 30 ~ 50 DEG C of temperature, raised temperature to 60 ~ 70 DEG C subsequently, until solvent all volatilizees, put into baking oven subsequently and dry;
B. by obtain in step (2) a CNT at N
2be warming up to 100 ~ 500 DEG C in atmosphere and keep 1 ~ 4h, then switching to O
2in atmosphere after 100 ~ 500 DEG C of maintenance 1 ~ 4h, be cooled to room temperature;
C. soaked and ultrasonic wave stir process by the CNT 2 ~ 3mol/L dust technology obtained in step (2) b, suction filtration, is washed to neutrality, puts into baking oven and dries, and obtains the CNT after cutting off;
(3) copper nano-particle external loading:
A. be that the CNT that step (2) c obtains joins in the aqueous solution of the copper nitrate of 0.05mol/L ~ 0.5mol/L by 1:0.2 ~ 1:5 according to the mass ratio of CNT and copper nitrate, after 40 ~ 50 DEG C of ultrasonic agitation 4 ~ 6h, continue to be stirred to solvent to volatilize completely, put into baking oven and dry;
B. the CNT obtained in step (3) a is put into H
2in atmosphere at 220 ~ 260 DEG C reduction treatment 2 ~ 4h.
In the above-mentioned methods, step (1) have employed hydro-thermal reaction, reacts more more violent than traditional back flow reaction mode, and carbon nano tube surface can be made to be oxidized by nitric acid more fully; Adopt step (2) cut off CNT, can increase CNT in follow-up test with the contact area of salting liquid, make metallic attachment on the carbon nanotubes more even, raising catalytic efficiency; In step (3), utilize the aqueous solution as the carrier of salt, be make use of the larger surface tension that water has, thus metal salt solution can be made to be difficult to enter into CNT inside, ensure that the load of metallic at CNT outer surface.
The carbon nano tube surface supported copper nano particle dehydrogenation prepared according to said method, copper nano-particle can be made to be evenly dispersed in the outer surface of CNT, thus substantially increase the catalytic activity of non-precious metal, experiment proves, use the conversion ratio of catalyst rings hexanone dimer of the present invention to reach 100%, the selective of o-phenyl phenol reaches 96%.And the preparation method of carbon nano tube surface supported copper nano particle dehydrogenation of the present invention, easy and simple to handle, require low for production equipment, be suitable for promoting the use of in large-scale production.
Accompanying drawing explanation
Fig. 1 to be Copper mass fraction be 10% carbon nano tube surface supported copper nano particle dehydrogenation (scale is 100nm);
Fig. 2 to be Copper mass fraction be 20% carbon nano tube surface supported copper nano particle dehydrogenation (scale is 100nm);
Fig. 3 to be Copper mass fraction be 30% carbon nano tube surface supported copper nano particle dehydrogenation (scale is 100nm);
Fig. 4 to be Copper mass fraction be 40% carbon nano tube surface supported copper nano particle dehydrogenation (scale is 100nm);
Fig. 5 to be Copper mass fraction be 50% carbon nano tube surface supported copper nano particle dehydrogenation (scale is 100nm).
Detailed description of the invention
The present invention can be more clearly described from following embodiment, but the present invention is not limited in following embodiment.
Embodiment 1: the preparation 1 of carbon nano tube surface supported copper nano particle dehydrogenation
1. take 1g multi-walled carbon nano-tubes, add the nitric acid of 5mol/L, 120 DEG C of hydro-thermal stir process 4 hours, suction filtration, be washed to neutrality, put into baking oven dry for standby subsequently;
2. by the CNT after above-mentioned acid treatment, join in the liquor argenti nitratis ophthalmicus of 100mL0.004mol/L, stir 2 hours at 50 DEG C of temperature, rear raised temperature to 70 DEG C, until solvent all volatilizees, puts into baking oven subsequently and dries.By the CNT after oven dry at N
2be warming up to 300 DEG C in atmosphere and keep 1 hour, after switch to O
2atmosphere, 300 DEG C keep 1 hour.The HNO of 2mol/L is used after being cooled to room temperature
3solution soaks and ultrasonic agitation process, suction filtration, is washed to neutrality, puts into baking oven subsequently and dries, and obtains the CNT after cutting off;
3. get the Cu(NO of 0.38 gram
3)
23H
2o is dissolved in the water of 15mL, add wherein 1 gram cut off after CNT, 40 DEG C of ultrasonic agitation 4 hours, continue subsequently to stir until water volatilizees completely, put into baking oven and dry.Again by the CNT after load at H
2in atmosphere, 260 DEG C of reduction treatments 4 hours, obtain the outer surface load type carbon nanotube copper-based catalysts that Copper mass fraction is 10%, as shown in Figure 1.
Embodiment 2: the preparation 2 of carbon nano tube surface supported copper nano particle dehydrogenation
Operating process as embodiment 1, unlike the Cu(NO added in step 3
3)
23H
2the quality of O is 0.76g, obtains the outer surface load type carbon nanotube copper-based catalysts that Copper mass fraction is 20%, as shown in Figure 2.
Embodiment 3: the preparation 3 of carbon nano tube surface supported copper nano particle dehydrogenation
Operating process as embodiment 1, unlike the Cu(NO added in step 3
3)
23H
2the quality of O is 1.14g, obtains the outer surface load type carbon nanotube copper-based catalysts that Copper mass fraction is 30%, as shown in Figure 3.
Embodiment 4: the preparation 4 of carbon nano tube surface supported copper nano particle dehydrogenation
Operating process as embodiment 1, unlike the Cu(NO added in step 3
3)
23H
2the quality of O is 1.52g, obtains the outer surface load type carbon nanotube copper-based catalysts that Copper mass fraction is 40%, as shown in Figure 4.
Embodiment 5: the preparation 5 of carbon nano tube surface supported copper nano particle dehydrogenation
Operating process as embodiment 1, unlike the Cu(NO added in step 3
3)
23H
2the quality of O is 1.90g, obtains the outer surface load type carbon nanotube copper-based catalysts that Copper mass fraction is 50%, as shown in Figure 5.
Embodiment 6: catalyst performance is assessed
It is 3mm bead that reactor bottom loads the high diameter of about 10cm, middle part constant temperature zone load 1 gram of embodiment 1 obtained catalyst, top preheating section 15 ~ 20cm, filler is the bead of diameter 3mm, and reactor lower part cooling system adopts 60 DEG C of thermostatical circulating waters.After catalyst activation, temperature is adjusted to reaction temperature 330 DEG C, adjustment hydrogen flow rate is 5mL/min, after stable, in reaction tube, add reaction raw materials cyclohexenyl hexamethylene ketone by micro-injection pump, got a sample every one hour, with composition and the content of gas chromatographic analysis product.Obtaining the conversion ratio of cyclohexenyl hexamethylene ketone after 10 hours is 99.82%, and the selective of o-phenyl phenol is 92.21%.
Embodiment 7: the catalyst Contrast on effect of different Cu mass fraction
The copper nano-particle catalyst of the different loads amount prepared according to enforcement 1 ~ embodiment 5, when other conditions are identical, catalytic effect is as shown in the table:
Active contrast table after the reaction in 10 hours of different Copper mass fraction catalyst
| Embodiment | Copper mass fraction | Conversion ratio/% | Selective/% |
| Embodiment 1 | 10% | 99.82 | 92.21 |
| Embodiment 2 | 20% | 99.94 | 95.91 |
| Embodiment 3 | 30% | 99.27 | 94.58 |
| Embodiment 4 | 40% | 98.99 | 89.59 |
| Embodiment 5 | 50% | 98.59 | 87.81 |
As can be seen from the above table, when Copper mass fraction is 20%, catalytic effect is best.When Copper mass fraction continues to increase, the conversion ratio of catalyst and selectively all present downward trend.The conversion ratio and selective minimum when Copper mass fraction is 50%.1-5 can learn by reference to the accompanying drawings, and the dispersiveness of the copper of accompanying drawing 2 is best, and carbon nano tube surface presents needle prick shape simultaneously, and this can make copper nano-particle more be dispersed in CNT outer surface.In Fig. 5, the dispersiveness of copper is the poorest, and copper nano-particle compares Fig. 2 more greatly, and these make embodiment 5 catalytic activity minimum.
Claims (8)
1., for the preparation of a catalyst for o-phenyl phenol, be major catalyst with copper, it is characterized in that: metallic copper nano particle is evenly dispersed in CNT outer surface.
2. catalyst according to claim 1, is characterized in that: the mass fraction of described metallic copper nano particle is 5% ~ 60%.
3. a preparation method for catalyst as claimed in claim 1, is characterized in that preparation process is as follows:
The pretreatment of CNT: add nitric acid in multi-walled carbon nano-tubes, hydro-thermal fully stirs rear suction filtration, after filter residue is washed to neutrality, puts into drying box and dries;
CNT cuts off:
Join in liquor argenti nitratis ophthalmicus by the CNT obtained in step (1), solvent evaporated after fully stirring, dries again;
By obtain in step a CNT at N
2be warming up to 100 ~ 500 DEG C in atmosphere and keep 1 ~ 4h, then switching to O
2in atmosphere after 100 ~ 500 DEG C of maintenance 1 ~ 4h, be cooled to room temperature;
Soaked and ultrasonic wave stir process by the CNT dust technology obtained in step b, suction filtration, is washed to neutrality, dries;
Copper nano-particle external loading: join in the aqueous solution of copper nitrate by the CNT obtained in step (2), solvent evaporated after ultrasonic agitation is also dried, then put into H
2reduction treatment in atmosphere.
4. preparation method according to claim 3, is characterized in that: in step (1), the concentration of nitric acid used is 3 ~ 5mol/L, and hydrothermal temperature is 80 ~ 150 DEG C, and hydro-thermal mixing time is 2 ~ 6h.
5. preparation method according to claim 3, is characterized in that: in step (2) a, liquor argenti nitratis ophthalmicus concentration used is 0.002 ~ 0.008mol/L; The mass ratio of CNT used and silver nitrate is 5:1 ~ 40:1; Whipping temp is 30 ~ 50 DEG C, and mixing time is 1 ~ 4h, and the temperature of evaporating solvent is 60 ~ 70 DEG C.
6. the preparation method according to claim 3 or 5, is characterized in that: in step (2) c, the concentration of dust technology used is 2 ~ 3mol/L; Ultrasonic agitation temperature is 40 ~ 50 DEG C; The ultrasonic agitation time is 4 ~ 6h.
7. preparation method according to claim 3, is characterized in that: in step (3), the concentration of copper nitrate solution used is 0.05mol/L ~ 0.5mol/L; The mass ratio of CNT used and copper nitrate is 1:0.2 ~ 1:5.
8. the preparation method according to claim 3 or 7, is characterized in that: in step (3), reduction treatment temperature is 220 ~ 260 DEG C; Recovery time is 2 ~ 4h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510682360.9A CN105251488A (en) | 2015-10-21 | 2015-10-21 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
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|---|---|---|---|
| CN201510682360.9A CN105251488A (en) | 2015-10-21 | 2015-10-21 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
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Cited By (4)
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| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
| CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
| CN109248684A (en) * | 2018-08-15 | 2019-01-22 | 肇庆市华师大光电产业研究院 | A kind of MWCNT@Cu composite catalyst and its preparation method and application |
| CN112275319A (en) * | 2020-11-03 | 2021-01-29 | 扬州工业职业技术学院 | Organic selenium catalyst loaded with carbon nano tube and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970919A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Modified carbon nano tube material |
| CN108335916A (en) * | 2017-12-20 | 2018-07-27 | 肇庆市华师大光电产业研究院 | A kind of multi-walled carbon nanotube@X combination electrodes and its preparation method and application |
| CN109248684A (en) * | 2018-08-15 | 2019-01-22 | 肇庆市华师大光电产业研究院 | A kind of MWCNT@Cu composite catalyst and its preparation method and application |
| CN112275319A (en) * | 2020-11-03 | 2021-01-29 | 扬州工业职业技术学院 | Organic selenium catalyst loaded with carbon nano tube and preparation method and application thereof |
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Application publication date: 20160120 |