CN103447039A - Cobalt-base catalyst taking carbon nano tubes as carriers and applications thereof - Google Patents
Cobalt-base catalyst taking carbon nano tubes as carriers and applications thereof Download PDFInfo
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- CN103447039A CN103447039A CN 201210172460 CN201210172460A CN103447039A CN 103447039 A CN103447039 A CN 103447039A CN 201210172460 CN201210172460 CN 201210172460 CN 201210172460 A CN201210172460 A CN 201210172460A CN 103447039 A CN103447039 A CN 103447039A
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Abstract
The invention provides a cobalt-base catalyst taking carbon nano tubes as the carriers. Manganese element can be added as the auxiliary agent, the active metal components can be mainly distributed inside or outside of the tube channel of the carrier carbon nano tubes, wherein the content of Co is 10% to 30%, and the content of Mn is 0% to 15%.The cobalt-base catalyst is applied to catalyzing Fischer-Tropsch reactions, which take synthesis gas (CO and H2) as the raw material, the catalyst, whose active metal components are mainly distributed in the tubes, has a higher conversion rate, and the catalyst, whose active metal components are mainly distributed out of the tubes, has a higher yield of alkene with a carbon number of 2 to 4.
Description
One, technical field:
The present invention relates to the loaded catalyst of a kind of reactive metal cobalt directional profile inside and outside CNT and the application in Fischer-Tropsch synthesis thereof.
Two, background technology:
CNT (carbon nanotube, CNT) is that Japanese scientist Ijima found first in 1991, by single carbon atom, is assembled under certain condition and is formed the special material with metal or semiconductor property that a kind of electron delocalization is very large.CNT also can be regarded curling into by graphite-structure as, there is large specific area, good electric conductivity, excellent mechanical mechanics property and very high chemical stability, CNT is except at nano electron device, absorbing material, the aspects such as biological medicine carrier have outside potential important use, also may be used for heterogeneous catalytic reaction as the carrier of catalyst.Especially, while forming due to CNT, graphite linings curling causes the inside and outside cloud density difference of CNT, and pipe is outer with to compare cloud density in pipe higher, is the electron rich state.Therefore, select CNT as carrier, not only can utilize its pipeline configuration confinement effect, also may utilize the difference of its inside and outside electronic property to carry out the character of regulating catalyst, thereby optimize its catalytic performance.
Patent CN200580046303 has developed the method that a class prepares carbon nanotube loaded metal component catalyst, and for catalytic reaction.Patent CN200910082376 has developed a kind of carbon nanotube loaded Raney nickel, for steam living beings reformation hydrogen production.Patent CN200610054880 has developed a kind of carbon nanotube loaded Ru catalyst for the synthesis of ammonia react.Patent CN200910241875 has developed the electrocatalytic reaction of a kind of high capacity amount Pt/CNT catalyst for hydrogen reduction.But these methods all fail to recognize that difference and the CNT duct confinement effect of the inside and outside electronic property of CNT can change the performance of catalyst to the impact of loaded catalyst active component character, also fail to prepare the catalyst of active component directed dispersion inside and outside CNT for catalytic reaction.
Synthesis gas (CO+H
2) be converted into C under catalyst action
2above hydro carbons and alcohols are called as Fischer-Tropsch synthesis.Be nineteen twenty-three by German Kaiser Wilhelm coal research F.Fischer and H.Tropsch find first.Because synthesis gas can be obtained by coal, natural gas and biomass conversion, therefore Fischer-Tropsch synthesis also provides the route that is generated fuels and chemicals by coal, natural gas and living beings petroleum replacing, the problem of can partial rcsponse petroleum resources anxiety bringing.Fischer-Tropsch synthesis is produced C
2above hydro carbons and alcohols are the carbon chain growth processes of a polymerization, usually are subject to the restriction of the Anderson-Shultz-Flory regularity of distribution, and gains can be that carbon number is from the mixture more than 1-30.Therefore the synthetic maximum difficult point of Fischer-Tropsch is how to use catalyst to acquire the narrow product of carbon number distribution to distribute.In addition, at Fischer-Tropsch, in synthetic hydrocarbon product, alkene is more valuable than alkane, particularly the alkene of low carbon number wherein.
Chinese patent CN201010160486, CN201010160490, CN200510130076, CN200680022459 etc. have all invented load type cobalt-base catalyst and have been applied to Fischer-Tropsch synthesis, and the carrier that adopts is silica, aluminium oxide, or other complex carriers, and added lanthanum, cerium, zirconiums etc. are as auxiliary agent, improve the selective of specific product in Fischer-Tropsch synthesis.But all fail to utilize the confinement effect of CNT uniqueness and the Fischer-Tropsch synthesis performance that electronic effect is improved catalyst.
Three, summary of the invention
The present invention prepares a kind of reactive metal cobalt directed loaded catalyst disperseed inside and outside CNT, and is applied to Fischer-Tropsch synthesis.
CNT, by nitric acid purifying, open pipe, is then joined in cobalt nitrate, manganese nitrate solution and floods, and slow solvent evaporated, through roasting reduction, make the catalyst that active metal component mainly disperses in CNT; Or be pre-charged with the organic solvent paraxylene in the CNT of purifying open pipe, and be extracted in water, adding cobalt nitrate, manganese nitrate, solvent evaporated, through roasting reduction, make the catalyst that active metal component mainly disperses outside CNT.Be applied to Fischer-Tropsch synthesis by these two kinds, changed carbon number distribution in the Fischer-Tropsch synthesis product and the ratio of alkene and alkane.
Four, the specific embodiment:
Further illustrate the present invention by following examples, but should be appreciated that protection scope of the present invention is not limited in following examples.
Embodiment 1:
In the 100mL three-neck flask, add 1.5g CNT (the organic institute in Chengdu), the red fuming nitric acid (RFNA) of 60mL14M, 120 ℃ of lower stirring and refluxing 14h.With No. 4 sand core funnel suction filtrations of 60 purpose, to neutral, dry 6h under 120 ℃, obtain the CNT that the open pipe purifying is crossed.
Embodiment 2:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.274g Co (NO
3)
26H
2o, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co/CNTs (in)-Co10.
Embodiment 3:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.436g Co (NO
3)
26H
2o, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe under 350 ℃, be designated as Co/CNTs (in)-Co15, its TEM image is shown in accompanying drawing 1, and visible active metal component mainly is distributed in the CNT pipe.
Embodiment 4:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.617g Co (NO
3)
26H
2o, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co/CNTs (in)-Co20.
Embodiment 5:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.838g Co (NO
3)
26H
2o, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co/CNTs (in)-Co25.
Embodiment 6:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 1.058g Co (NO
3)
26H
2o, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co/CNTs (in)-Co30.
Embodiment 7:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.441g Co (NO
3)
26H
2o, the Mn (NO of 0.038g 50%
3)
2solution, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co-Mn/CNTs (in)-Co15Mn1.
Embodiment 8:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.463g Co (NO
3)
26H
2o, the Mn (NO of 0.202g 50%
3)
2solution, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co-Mn/CNTs (in)-Co15Mn5.
Embodiment 9:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.487g Co (NO
3)
26H
2o, the Mn (NO of 0.384g 50%
3)
2, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co-Mn/CNTs (in)-Co15Mn9.
Embodiment 10:
Add 25mL water in the beaker of 50mL, the CNT that 0.5g open pipe purifying is crossed, magnetic agitation 30min, more ultrasonic 15min make it to disperse as far as possible.Add 0.529g Co (NO
3)
26H
2o, the Mn (NO of 0.694g 50%
3)
2, magnetic agitation 20min, more ultrasonic 15min, three times so repeatedly.In 35 ℃ of water-baths, under magnetic agitation, slow evaporate to dryness spends the night.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed in pipe, be designated as Co-Mn/CNTs (in)-Co15Mn15.
Embodiment 11:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.436g Co (NO
3)
26H
2o, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe, be designated as Co-Mn/CNTs (out)-Co 15.
Embodiment 12:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.441g Co (NO
3)
26H
2o, the Mn (NO of 0.038g 50%
3)
2solution, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe, be designated as Co-Mn/CNTs (out)-Co15Mn1.
Embodiment 13:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.463g Co (NO
3)
26H
2o, the Mn (NO of 0.202g 50%
3)
2, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe, be designated as Co-Mn/CNTs (out)-Co 15Mn5.
Embodiment 14:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.487g Co (NO
3)
26H
2o, the Mn (NO of 0.384g 50%
3)
2solution, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe under 350 ℃, be designated as Co-Mn/CNTs (out)-Co15Mn9, its TEM image is shown in accompanying drawing 2, and visible active metal component mainly is distributed in outside the CNT pipe.
Embodiment 14:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.487g Co (NO
3)
26H
2o, the Mn (NO of 0.384g 50%
3)
2solution, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe, be designated as Co-Mn/CNTs (out)-Co15Mn9.
Embodiment 15:
Add the 20mL paraxylene in the 50mL beaker, the CNT that 0.5g open pipe purifying is crossed, ultrasonic 30min, magnetic agitation 15min, 2 times so repeatedly.The ammoniacal liquor 1.5mL that adds 25wt%, extraction, the CNT of water intaking Xiangli,, be transferred in beaker to micro-wet with No. 4 sand core funnel suction filtrations, adds 25mL water, adds 0.529g Co (NO
3)
26H
2o, the Mn (nO of 0.694g 50%
3)
2solution, 35 ℃ of lower magnetic forces stir, evaporate to dryness.Be placed in 120 ℃ of dry 6h of baking oven.Take out sample 0.3g and put into quartz ampoule, under 350 ℃, through hydrogen reducing 10h, obtain the catalyst that active component is mainly disperseed outside pipe, be designated as Co-Mn/CNTs (out)-Co15Mn15.
Embodiment 16
Get the 0.3g catalyst, be placed in long 40cm, in the fat tripe quartz ampoule of internal diameter 6mm, at 230 ℃, pressure 0.1MPa, H
2/ CO=1.0, react under GHSV=3000mL/ (hg) condition, and the time is 9.5h.Adopt on-line chromatographic analysis product content, calculate reaction conversion ratio and each selectivity of product.Each catalyst Fischer-Tropsch synthesis performance of embodiment 2-15 is as shown in table 1, table 2 and table 3.As can be seen from the table, the Catalyst Conversion that reactive metal disperses outside pipe is lower slightly, and olefin(e) centent is higher, and adding of Mn auxiliary agent contributes to reduce methane selectively within the specific limits, improves C
5above hydrocarbon selective and C
2-C
4olefine selective.
The Fischer-Tropsch synthesis performance of table 1 different loads amount Co/CNT (in) catalyst
The Fischer-Tropsch synthesis performance of the different Mn load capacity of table 2 Co-Mn/CNT (in) catalyst
The Fischer-Tropsch synthesis performance of the different Mn load capacity of table 3 Co-Mn/CNT (out) catalyst
The accompanying drawing explanation:
Fig. 1 is the TEM image of Co/CNTs (in)-Co15 sample; Fig. 2 is the TEM image of Co-Mn/CNTs (out)-Co15Mn9 sample.
Claims (5)
1. the cobalt-base catalyst that CNT is carrier, it is characterized in that: in catalyst weight, in described catalyst, the content of Co is 5～30wt%, and Mn content is 0～15wt%, and all the other are CNT.
2. according to catalyst claimed in claim 1, it is characterized in that active metal component Co mainly is distributed in the pipe interior of described carrier carbon nanotube.
3. according to catalyst claimed in claim 1, it is characterized in that active metal component Co mainly is distributed in the pipeline external of described carrier carbon nanotube.
4. according to claim 1,2 or 3 application of described catalyst in Fischer-Tropsch synthesis.
5. Fischer-Tropsch synthesis is at 230 ℃ of temperature, pressure 0.1MPa, H according to claim 4
2/ CO=1.0, carry out under GHSV=3000mL/ (hg) condition.
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| CN104403682A (en) * | 2014-12-09 | 2015-03-11 | 中国科学院山西煤炭化学研究所 | Photocatalysis Fischer-Tropsch synthesis method and used catalyst |
| CN105195147A (en) * | 2015-10-21 | 2015-12-30 | 扬州大学 | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst |
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| CN110898833A (en) * | 2019-12-11 | 2020-03-24 | 福州大学 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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| CN104403682A (en) * | 2014-12-09 | 2015-03-11 | 中国科学院山西煤炭化学研究所 | Photocatalysis Fischer-Tropsch synthesis method and used catalyst |
| CN104403682B (en) * | 2014-12-09 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | The catalyzer of a kind of photochemical catalysis Fischer-Tropsch synthesis method and use |
| CN105195147A (en) * | 2015-10-21 | 2015-12-30 | 扬州大学 | Dehydrogenation catalyst with copper nanoparticles loaded inside carbon nano tube and preparation method of dehydrogenation catalyst |
| CN105251488A (en) * | 2015-10-21 | 2016-01-20 | 扬州大学 | Dehydrogenation catalyst capable of loading copper nanoparticles on surface of CNT (carbon nanotube) with high dispersion and preparation method of dehydrogenation catalyst |
| CN107134579A (en) * | 2017-04-17 | 2017-09-05 | 中山市卡耐特塑料有限公司 | A kind of preparation method of carbon material for positive conductive agent |
| CN111001413A (en) * | 2019-09-20 | 2020-04-14 | 中山大学 | Catalyst for oxidizing and degrading ibuprofen by sulfate radical and preparation method thereof |
| CN111001413B (en) * | 2019-09-20 | 2021-05-11 | 中山大学 | Catalyst for oxidizing and degrading ibuprofen by sulfate radical and preparation method thereof |
| CN110898833A (en) * | 2019-12-11 | 2020-03-24 | 福州大学 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN111632622A (en) * | 2020-07-10 | 2020-09-08 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of carbon nano tube metal symbiotic material |
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Application publication date: 20131218 |