CN107500296A - A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation - Google Patents
A kind of bar-shaped β Mo2C controlledly synthesis and its application in inverse water gas shift reation Download PDFInfo
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Abstract
The invention discloses a kind of one-dimensional rod-like β Mo2C controlledly synthesis and its application in inverse water gas shift reation, belong to catalysis transform of carbon dioxide and utilize field, product is the CO of high added value.The present invention by ammonium paramolybdate by being dissolved in deionized water and HNO3Mixed solution in hydro-thermal obtain the molybdenum trioxide with uniform Rod-like shape, and in 100~160ml/min 20vt%CH4/H2It is carbonized in gaseous mixture in 590~800 DEG C of temperature programmings, obtains a kind of molybdenum carbide of one-dimensional rod-like pattern.Compared with the molybdenum carbide of nano particle accumulation, it has higher specific surface area and the number in more activated centres, all has excellent CO in the inverse water gas shift reation under simple catalytic action and under cold plasma and molybdenum carbide synergy2Conversion ratio and CO selectivity.
Description
Technical field
The invention belongs to catalysis transform of carbon dioxide to utilize field, and in particular to one-dimensional rod-like β type molybdenum carbides are catalyzed merely,
One-dimensional rod-like β types molybdenum carbide produces carbon monoxide with the inverse water gas shift reation of cooperation of cold plasma catalysis.
Background technology
With the growth of population in the world and the quickening of process of industrialization, since the last century, the row of global carbon dioxide
High-volume steeply rise, only whole year in 2016, global CO2Discharge capacity just be up to 32,100,000,000 tons.A large amount of discharges of carbon dioxide cause
Seawater acidifying, the environmental problem getting worse such as climate warming, turn into one of social concern urgently to be resolved hurrily.At the same time, two
Carbonoxide is also the C1 resources that content is most abundant in the world.Therefore, the methods of carbon dioxide being passed through into catalyzed conversion is converted into height
The synthesis gas of added value, methanol, low-carbon alkene, aldehyde, acid, ether, ester etc., have great importance.
CO2Catalytic hydrogenation generates CO and H2O(CO2+H2=CO+H2O, Δ H298K=41.2kJ/mol) reaction be considered as
CO2Convert one of most important, most promising reaction.Pass through this reaction, CO2CO is converted into, to pass through non-fossil sources route
Producing synthesis gas provides possibility, turns into following structure green chemical industry system, reduces CO2The basis of discharge.
The catalyst for being presently used for above-mentioned reaction system is broadly divided into noble metal catalyst and non-precious metal catalyst.It is expensive
Metallic catalyst is mainly Pt/TiO2,Rh/Al2O3,Pd-La2O3/ MWCNT etc., it shows excellent in above-mentioned reaction system
Activity (Applied Catalysis A-General, 2012,423:100-107.), but catalyst cost it is higher, no
Beneficial to heavy industrialization application.Non-precious metal catalyst mainly includes Cu bases catalyst and Ni base catalyst, wherein Cu bases are urged
The universal less stable of agent, and Ni bases catalyst is then poor to CO selectivity.
We show in the previous work in laboratory：α-MoC with face-centred cubic structure1-xThere is preferably inverse water-gas shift
Catalytic activity, by the load of noble metal, activity can be lifted further；But β-the Mo with hexagonal closs packing structure2C
Activity it is very low, see Fig. 2.We have found that synthesizing bar-shaped molybdenum oxide precursor by hydro-thermal method, carbonisation is controlled, can be prepared
High-specific surface area, the β-Mo with one-dimensional rod-like pattern2C.Above-mentioned one-dimensional rod-like β-Mo2C catalyst is anti-in inverse water-gas shift
Answering performance, there is not been reported.
Plasma shows the advantage of uniqueness with catalyzed combination in thermodynamically stable small molecule reaction is activated.Methane
Oxygen-free aromatization reaction by thermodynamical equilibrium due to being limited, CH at 700 DEG C4Equilibrium conversion be less than 10%.Using pulse
Two segmented modes that spark-discharge plasma is combined with Ni/HZSM-5,400 DEG C, than input energy be 68.6kJ/L and nH2/
nCH4When=1, methane conversion 72%, aromatics yield is up to 32.7% (300min) (Green Chemistry 2007,9
(6),647-653).The reaction of synthesizing gas by reforming methane with co 2 is a strong endothermic reaction, and low temperature is by thermodynamics and power
It is very low to learn limited reactions thing conversion ratio.But in dielectric barrier discharge (DBD) cold plasma and Cu-Ni/ γ-Al2O3Catalyst
Under synergy, 450 DEG C, nCH4/nCO2=1, under the conditions of WHSV=36000ml/g/h, CH4And CO2Conversion ratio be respectively
69% and 74%, far above thermodynamical equilibrium conversion ratio (Journal of Molecular Catalysis, 2011,25 (01):11-16).Tu etc. by the cold grades of DBD from
Daughter and Cu/ γ-Al2O3, Mn/ γ-Al2O3And Cu-Mn/ γ-Al2O3Catalyst, which combines, is used for low temperature CO2Hydrogenation reaction, with
It is plasma-activated merely to compare, under plasma and catalyzing cooperation effect, CO2Conversion ratio improve 6~36%, Mn/ γ-
Al2O3With highest CO selectivity (IEEE Transactions on Plasma Science 2016,44 (4), 405-
411).But up to the present, there is not yet molybdenum carbide catalyst and Athermal plasma are conjointly employed in into inverse water-gas shift
The relevant report of reaction.
The content of the invention
It is an object of the invention to provide a kind of β-Mo of one-dimensional rod-like2C preparation method, the type catalyst is applied to
In inverse water gas shift reation, there is the characteristics of catalytic activity is high, heat endurance is good and CO is selectively high, make up existing catalyst
Or cost is high, or heat endurance is poor, or the selectively low deficiencies of CO.
In order to achieve this, the technical scheme is that：A kind of one-dimensional rod-like β-Mo2C controllable preparation and its in list
Application in pure catalysis, cold plasma and catalyzing cooperation effect subinverse water gas shift reation.
A kind of one-dimensional rod-like β-Mo2The preparation method of C catalyst, the preparation method comprise the following steps：
(1) ammonium paramolybdate is dissolved in deionized water and HNO3Mixed solution in, wherein, ammonium paramolybdate and mixed solution are used
It is 8.4g to measure ratio：240ml；Deionized water and 65%HNO in mixed solution3Volume ratio be 5:1；Will be above-mentioned molten after stirring
Liquid is transferred in reactor, 200 DEG C of hydro-thermal 22h, Temperature fall；Centrifuging to precipitate, and is washed with water several times, and it is in faintly acid to make it,
Thereafter 24h is stood in 60 DEG C of air dry oven, obtains the molybdenum trioxide with uniform Rod-like shape.
(2) presoma obtained by step (1) is carbonized in methane and hydrogen mixed gas in 590~800 DEG C；
One-dimensional rod-like β-the Mo2C is to carry out temperature programming by the bar-shaped molybdenum trioxide to Hydrothermal Synthesiss for presoma
Be carbonized controlledly synthesis：Carburizing atmosphere is 100~160ml/min CH4/H2Gaseous mixture, CH in gaseous mixture4Volume fraction be
20%；Temperature programming carbonisation is that 5 DEG C/min is warming up to 300 DEG C, then rises to 700 DEG C through 1 DEG C/min, in 700 DEG C of insulations
2h, it is slowly dropped to after room temperature in 1%O212h is passivated in/Ar.
The present invention provides the one-dimensional rod-like β-Mo that above-mentioned preparation method obtains2C catalyst, the β-Mo2C catalyst is straight
200~400nm of footpath, long 1.5~3 μm is bar-shaped, and its specific surface area reaches 182m2/g。
The present invention provides above-mentioned one-dimensional rod-like β-Mo2Application of the C catalyst in inverse water gas shift reation.
Further, in the above-mentioned technical solutions, the reaction atmosphere of the inverse water gas shift reation is CO2And H2Gaseous mixture,
Reaction pressure is normal pressure.
Further, in the above-mentioned technical solutions, the CO2Gas and H2The volume ratio of gas is 1:1~1:4.
Further, in the above-mentioned technical solutions, the reaction hotbed of described simple catalysis is 300 DEG C~600 DEG C.
Further, in the above-mentioned technical solutions, the Athermal plasma incorporation way is that dielectric impedance (DBD) is put
Electricity, centre frequency are 10~30kHz, and applied voltage is 20~40V.
Further, in the above-mentioned technical solutions, mass space velocity 300,000~1 of the reaction in simple catalysis,
500,000 mL/g/h。
Further, in the above-mentioned technical solutions, the reaction is in one-dimensional rod-like β-Mo2C and cooperation of cold plasma are made
300,000~1,500,000mL/g/h of mass space velocity of used time.
Beneficial effect of the present invention：
(1) one-dimensional rod-like β-Mo prepared by the present invention2C, which has, is higher than block β-Mo2C specific surface area, it is 182m2/ g, after
Person is 10m2/g。
(2) prior art is used for catalyst presence or the cost height of hydrogenation of carbon dioxide reaction of carbon monoxide, or low temperature
Activity is low, or the deficiencies of CO poor selectivities, is shown in Table 3.One-dimensional rod-like β-Mo provided by the invention2C preparation methods are simple, against the current
There is higher low temperature active and CO selectivity in vapour transformationreation；In addition, it shows under the conditions of inverse water gas shift reation
Good stability, the conditions such as high temperature, the strongly reducing atmosphere of this reaction are applicable to, in CO2Catalyzed conversion field has wide
Utilization prospects.
(3) molybdenum carbide provided by the invention and the inverse water gas shift reation of cooperation of cold plasma catalysis, can break through tradition
Thermodynamical equilibrium present in thermocatalytic limits, so as to obtain higher CO2Conversion rate, it is the recycling of carbon dioxide
Provide new approach.
Brief description of the drawings
The width of accompanying drawing 5 of the present invention, subordinate list 3 are opened：
Fig. 1 is block β-Mo prepared by comparative example 1.12One-dimensional rod-like pattern β-Mo prepared by C (a), embodiment 12C(b)、
The bar-shaped MoO that comparative example 1.2 is prepared using other method3Bar-shaped β-the Mo obtained through identical temperature programming carbonization method2C (notes
For β-Mo2C-rod-2, d) and comparative example 1.3 prepare bar-shaped MoO3β-the Mo obtained through common carbonization method2C (be designated as β-
Mo2C-rod (w/o TPC), c) SEM comparison diagrams；
Fig. 2 is block β-Mo prepared by comparative example 1.12C, the bar-shaped MoO that comparative example 1.2 is prepared using other method3Through phase
β-the Mo that same temperature programming carbonization method obtains2C-2, comparative example 1.3 β-Mo2C-rod (w/o TPC), comparative example 1.4
Commercial Cu/ZnO/Al2O3The one-dimensional rod-like pattern β-Mo that catalyst is prepared with embodiment 12C is catalyzed against the current at 300 DEG C~600 DEG C
The CO of vapour transformationreation2Conversion ratio comparison diagram；
Fig. 3 is the block β-Mo of comparative example 2.12C, the bar-shaped MoO that comparative example 2.2 is prepared using other method3Through identical
β-the Mo that temperature programming carbonization method obtains2C-2, comparative example 2.3 β-Mo2C-rod (w/o TPC), the commercialization of comparative example 2.4
Cu/ZnO/Al2O3Catalyst and the hollow tube of comparative example 2.5 (referring to no catalyst filling, only fill quartz sand, similarly hereinafter) and embodiment 2
One-dimensional rod-like pattern β-Mo2C is in cold plasma and the CO of the inverse water gas shift reation of catalyzing cooperation effect2Conversion ratio comparison diagram；
Fig. 4 is the block β-Mo of comparative example 2.12C and the one-dimensional rod-like pattern molybdenum carbide of embodiment 2 respectively with cold plasma
Under body concerted catalysis effect, the CO of vapour transformationreation against the current during input power difference2Conversion ratio comparison diagram；
Fig. 5 is the one-dimensional rod-like pattern β-Mo prepared to embodiment 22When C acts on cooperation of cold plasma, 8h stability
The CO of the inverse water gas shift reation of test catalysis2Conversion ratio figure.
Embodiment
Following nonlimiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
One-dimensional rod-like β-the Mo of embodiment 12C preparation and simple catalytically active assessment
(1) prepare
8.4g ammonium paramolybdates are dissolved in 200ml deionized waters and 40ml 65%HNO3Mixed solution in, after stirring
Above-mentioned solution is transferred in reactor, 200 DEG C of hydro-thermal 22h, Temperature fall；Centrifuging to precipitate, and is washed with water several times, make it be in
Neutrality, 24h is stood in 60 DEG C of air dry oven thereafter, obtain the molybdenum trioxide with uniform Rod-like shape.
Take bar-shaped MoO prepared by 0.2g3(40-60 mesh) sample is placed in quartz reactor, is passed through 20%CH4/H2(150
ML/min) gaseous mixture, 300 DEG C are risen to 5 DEG C/min heating rate, then final 700 DEG C of carburizing temperature are risen to 1 DEG C/min,
And it is incubated 2h.Then after being down to room temperature, in 1%O212h is passivated in/Ar atmosphere and obtains one-dimensional rod-like molybdenum carbide catalyst sample.
SEM figures are shown in Fig. 1 b.
(2) active evaluation test
Inverse water gas shift reation is carried out in internal diameter 4mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.30mg one-dimensional rod-like molybdenum carbide (40- is weighed respectively
60 mesh) catalyst and 0.12g quartz sands (40-60 mesh) is uniformly placed in quartz ampoule after mixing, with 15%CH4/H2Gaseous mixture pair
Catalyst carries out pretreatment 2h in 590 DEG C, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:
2, gas space velocity 300,000mL/g/h, reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under the conditions of this, 300 DEG C
When CO2Conversion ratio is 7.7%, as shown in Figure 2.
Block β-the Mo of comparative example 1.12C preparation and simple catalytically active assessment
(1) prepare
Take 1.2g MoO3(40-60 mesh) sample is placed in fixed bed reactors, is passed through 20%CH4/H2Gaseous mixture enters stroke
Sequence heating carbonization, after rising to 300 DEG C by room temperature with 5 DEG C/min heating rates, then is risen to 1 DEG C/min heating rates by 300 DEG C
700 DEG C, the constant temperature 2h at 700 DEG C.Room temperature is subsequently cooled to, in 1%O2After being passivated 12h in/Ar atmosphere, the bulk of bulk is obtained
Molybdenum carbide catalyst, as a comparison.SEM figures are shown in Fig. 1 a.
(2) active evaluation test
Inverse water gas shift reation is carried out in internal diameter 4mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.30mg block β-Mo are weighed respectively2C (40-60 mesh)
Catalyst and 0.12g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 15%CH4/H2Gaseous mixture is to catalyst
Pretreatment 2h is carried out in 590 DEG C, activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas
Air speed is 300,000mL/g/h, and reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under the conditions of this, CO at 300 DEG C2Turn
Rate is 0.1%, as shown in Figure 2.
The other method of comparative example 1.2 prepares bar-shaped β-Mo2C preparation and simple catalytically active assessment
(1) prepare
2g molybdenum powders are added in 10ml deionized waters and form uniform mixture, then by 20ml 30wt%H2O2It is slow
Slowly it is added in said mixture, solution is changed into light yellow, stirs 30min to react complete；Above-mentioned solution is transferred to hydro-thermal
In kettle, 180 DEG C of hydro-thermal 48h, slow cooling；Gained is precipitated and filters and is washed three times with water and ethanol respectively, 80 DEG C are dried overnight
It is dry, obtain and uniformly grow bar-shaped MoO3。
Take the above-mentioned MoO of 0.2g3(40-60 mesh) sample is placed in fixed bed reactors, is passed through 20%CH4/H2Gaseous mixture is carried out
Temperature programming is carbonized, and after rising to 300 DEG C by room temperature with 5 DEG C/min heating rates, then is risen by 300 DEG C with 1 DEG C/min heating rates
To 700 DEG C, the constant temperature 2h at 700 DEG C.Room temperature is subsequently cooled to, in 1%O2In/Ar atmosphere be passivated 12h after, obtain bar-shaped β-
Mo2C catalyst (is designated as bar-shaped β-Mo2C-2), as a comparison.SEM figures are shown in Fig. 1 d.
(2) active evaluation test
Inverse water gas shift reation is carried out in internal diameter 4mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.30mg above-mentioned shape β-Mo are weighed respectively2C(40-60
Mesh) catalyst and 0.12g quartz sands (40-60 mesh) is uniformly placed in quartz ampoule after mixing, with 15%CH4/H2Gaseous mixture is to urging
Agent carries out pretreatment 2h in 590 DEG C, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2,
Gas space velocity is 300,000mL/g/h, and reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under the conditions of this, at 300 DEG C
CO2Conversion ratio is 4.1%, as shown in Figure 2.
1.3 bar-shaped MoO of comparative example3β-the Mo being commonly carbonized2C is prepared and simple catalytically active assessment
(1) prepare
8.4g ammonium paramolybdates are dissolved in 200ml deionized waters and 40ml 65%HNO3Mixed solution in, after stirring
Above-mentioned solution is transferred in reactor, 200 DEG C of hydro-thermal 22h, Temperature fall；Centrifuging to precipitate, and is washed with water several times, make it be in
Neutrality, 24h is stood in 60 DEG C of air dry oven thereafter, obtain the molybdenum trioxide with uniform Rod-like shape.
Take bar-shaped MoO prepared by 0.2g3(40-60 mesh) sample is placed in quartz reactor, is passed through 20%CH4/H2(150
ML/min) gaseous mixture, 700 DEG C are risen to 10 DEG C/min heating rate, and is incubated 2h.Then after being down to room temperature, in 1% O2/
Passivation 12h obtains bar-shaped molybdenum carbide catalyst sample and (is designated as β-Mo in Ar atmosphere2C-rod(w/o TPC).SEM figures are shown in Fig. 1 c.
(2) test
Inverse water gas shift reation is carried out in internal diameter 4mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.30mg bar-shaped molybdenum carbide (40-60 mesh) is weighed respectively
Catalyst and 0.12g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 15%CH4/H2Gaseous mixture is to catalyst
Pretreatment 2h is carried out in 590 DEG C, activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas
Air speed is 300,000mL/g/h, and reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under the conditions of this, CO at 300 DEG C2Turn
Rate is 4.7%, as shown in Figure 2.
1.4 commercial Cu/ZnO/Al of comparative example2O3Simple catalytically active assessment
Commercial Cu/ZnO/Al2O3(HiFUEL W220) catalyst is directly purchased from Alfa Aesar.
Inverse water gas shift reation is carried out in internal diameter 4mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.30mg commercial Cu/ZnO/Al is weighed respectively2O3Catalysis
Agent and 0.12g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 5%H2/ Ar gaseous mixtures are to catalyst in 250
DEG C pretreatment 2h is carried out, activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas space velocity is
300,000mL/g/h, reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under the conditions of this, CO at 300 DEG C2Conversion ratio is
1.2%, as shown in Figure 2.
One-dimensional rod-like β-the Mo of embodiment 22C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.10mg one-dimensional rod-like molybdenum carbide (40- is weighed respectively
60 mesh) catalyst and 0.19g quartz sands (40-60 mesh) is uniformly placed in quartz ampoule after mixing, with 15%CH4/H2Gaseous mixture pair
Catalyst carries out pretreatment 2h in 590 DEG C, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:
2, gas space velocity 1,500,000mL/g/h, dielectric impedance (DBD) discharge centers frequency is 30kHz, applied voltage 40V.This
Under the conditions of, CO2Conversion ratio is 33.4%, CO selectivity>99% (the real reaction temperature as caused by electric discharge is 290~330 DEG C,
Thermocatalytic equilibrium conversion is 19.3% at 300 DEG C, and 25.5%) thermocatalytic equilibrium conversion is at 350 DEG C, as shown in Figure 3.
Block β-the Mo of comparative example 2.12C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.10mg block molybdenum carbide (40-60 mesh) is weighed respectively
Catalyst and 0.19g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 15%CH4/H2Gaseous mixture is to catalyst
Pretreatment 2h is carried out in 590 DEG C, activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas
Air speed is 1,500,000mL/g/h, and dielectric impedance (DBD) discharge centers frequency is 30kHz, applied voltage 40V.This condition
Under, CO2Conversion ratio is 13.8%, CO selectivity>99% (the real reaction temperature as caused by electric discharge be 290~330 DEG C, 300 DEG C
Lower thermocatalytic equilibrium conversion is 19.3%, and 25.5%) thermocatalytic equilibrium conversion is at 350 DEG C, as shown in Figure 3.
Bar-shaped MoO prepared by the other method of comparative example 2.23β-the Mo obtained through identical temperature programming carbonization method2C-2
With cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.10mg β-Mo are weighed respectively2C-2 (40-60 mesh) is urged
Agent and 0.19g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 15%CH4/H2Gaseous mixture to catalyst in
590 DEG C carry out pretreatment 2h, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas space
Speed is 1,500,000mL/g/h, and dielectric impedance (DBD) discharge centers frequency is 30kHz, applied voltage 40V.Under the conditions of this,
CO2Conversion ratio is 26.6%, CO selectivity>99% (the real reaction temperature as caused by electric discharge be 290~330 DEG C, 300 DEG C at
Thermocatalytic equilibrium conversion is 19.3%, and 25.5%) thermocatalytic equilibrium conversion is at 350 DEG C, as shown in Figure 3.
2.3 bar-shaped MoO of comparative example3β-the Mo being commonly carbonized2C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.10mg bar-shaped MoO is weighed respectively3Commonly it is carbonized
β-Mo2C (40-60 mesh) catalyst and 0.19g quartz sands (40-60 mesh) are placed in quartz ampoule after uniformly mixing, with 15%CH4/
H2Gaseous mixture carries out pretreatment 2h to catalyst in 590 DEG C, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses
CO2： H2=1:2, gas space velocity 1,500,000mL/g/h, dielectric impedance (DBD) discharge centers frequency is 30kHz, outer power-up
Press as 40V.Under the conditions of this, CO2Conversion ratio is 27.3%, CO selectivity>99% (real reaction temperature is as caused by electric discharge
Thermocatalytic equilibrium conversion is 19.3% at 290~330 DEG C, 300 DEG C, at 350 DEG C thermocatalytic equilibrium conversion for 25.5%),
As shown in Figure 3.
2.4 commercial Cu/ZnO/Al of comparative example2O3Activity rating
Commercial Cu/ZnO/Al2O3(HiFUEL W220) catalyst is directly purchased from Alfa Aesar.
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.10mg Cu/ZnO/Al is weighed respectively2O3(40-60
Mesh) catalyst and 0.19g quartz sands (40-60 mesh) is uniformly placed in quartz ampoule after mixing, with 5%H2/ Ar gaseous mixtures are to catalysis
Agent carries out pretreatment 2h in 250 DEG C, and activity rating is then carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas
Body air speed is 1,500,000mL/g/h, and dielectric impedance (DBD) discharge centers frequency is 30kHz, applied voltage 40V.This condition
Under, CO2Conversion ratio is 17.2%, CO selectivity>99% (the real reaction temperature as caused by electric discharge be 290~330 DEG C, 300
Thermocatalytic equilibrium conversion is 19.3% at DEG C, and 25.5%) thermocatalytic equilibrium conversion is at 350 DEG C, as shown in Figure 3.
Activity rating of the blank pipe of comparative example 2.5 under cold plasma effect
Inverse water gas shift reation is carried out in internal diameter 8mm quartz ampoule fixed bed reactors.Each road gas stream needed for experiment
Amount has mass flowmenter to adjust and control, and reactor is flowed into after mixing.0.20g quartz sands (40-60 mesh) are weighed uniformly to mix
After be placed in quartz ampoule, activity rating is carried out under the conditions of following：Reaction atmosphere uses CO2：H2=1:2, gas flow is
250mL/min (as hereinbefore), dielectric impedance (DBD) discharge centers frequency are 30kHz, applied voltage 40V.This condition
Under, CO2Conversion ratio is about 5%, CO selectivity>99% (the real reaction temperature as caused by electric discharge be 290~330 DEG C, 300 DEG C
Lower thermocatalytic equilibrium conversion is 19.3%, and 25.5%) thermocatalytic equilibrium conversion is at 350 DEG C, as shown in Figure 3.
One-dimensional rod-like β-the Mo of embodiment 32C and the inverse water-gas shift stability test of cooperation of cold plasma catalysis
The present embodiment is the 8h stability tests of one-dimensional rod-like molybdenum carbide catalyst, during catalyst preparation and activity
Evaluation test condition is same as Example 2.As can be seen that in 8h, the reactivity of catalyst is not decreased obviously, such as Fig. 5 institutes
Show.
Table 1 is the one-dimensional rod-like β-Mo that block molybdenum carbide (a) prepared by comparative example 1.1 prepares with embodiment 12C (b) ratio
Surface area contrasts；
Table 1
Table 2 is the one-dimensional rod-like pattern β-Mo that block molybdenum carbide prepared by ratio 1.1 is prepared with embodiment 12C respectively with it is cold
Under plasma body cooperative catalytic action, the CO of inverse water gas shift reation is catalyzed in input power difference2Conversion ratio, CO selectivity
And CH4Selectivity contrast；
Table 2
Table 3 is Rod-like shape β-Mo prepared by embodiment 12Block β-Mo prepared by C and comparative example 1.12C and document report
Comparative result.
Table 3
In table 3,aThe test temperature of reaction rate；bThe test pressure of all catalyst reaction speed is normal pressure；cReaction gas
Composition:CO2:H2=1:2；dReaction gas forms:CO2:H2=1:1；eReaction gas forms:21%CO2/ 30%H2/N2Balance Air；fInstead
Should gas composition:25%CO2/ 25% H2/ 50%Ar2Balance Air.
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Claims (7)
- A kind of 1. one-dimensional rod-like β-Mo2The preparation method of C catalyst, the preparation method comprise the following steps：(1) ammonium paramolybdate is dissolved in deionized water and HNO3Mixed solution in, wherein, ammonium paramolybdate and mixed solution amount ratio For 8.4g：240ml；Deionized water and 65%HNO in mixed solution3Volume ratio be 5:1；Above-mentioned solution is turned after stirring Move on in reactor, 200 DEG C of hydro-thermal 22h, Temperature fall；Centrifuging to precipitate, and is washed with water several times, and it is in faintly acid to make it, thereafter 24h is stood in 60 DEG C of air dry oven, obtains the molybdenum trioxide with uniform Rod-like shape；(2) presoma obtained by step (1) is carbonized in methane and hydrogen mixed gas in 590~800 DEG C；Carburizing atmosphere is 100~160ml/min CH4/H2Gaseous mixture, CH in gaseous mixture4Volume fraction be 20%；Program liter Warm carbonisation is that 5 DEG C/min is warming up to 300 DEG C, then rises to 700 DEG C through 1 DEG C/min, 2h is incubated at 700 DEG C, after being down to room temperature In 1%O212h is passivated in/Ar.
- 2. the one-dimensional rod-like β-Mo that preparation method obtains according to claim 12C catalyst, it is characterised in that the β- Mo2C catalyst is 200~400nm of diameter, and long 1.5~3 μm is bar-shaped, and its specific surface area reaches 182m2/g。
- 3. bar-shaped β-Mo as claimed in claim 22Application of the C catalyst in inverse water gas shift reation.
- 4. application according to claim 3, it is characterised in that the inverse water gas shift reation is in cold plasma and bar-shaped β-Mo2C catalyst synergy is lower to be carried out.
- 5. the application according to claim 3 or 4, it is characterised in that the inverse water gas shift reation atmosphere is CO2And H2It is mixed Close gas, CO2And H2Atmosphere ratio be 1:1~1:4, reaction pressure is normal pressure.
- 6. application according to claim 4, it is characterised in that bar-shaped β-Mo2The reaction temperature that C is catalyzed merely be 300 DEG C~ 600℃；Bar-shaped β-Mo2When C acts on cooperation of cold plasma, the mode for introducing cold plasma is discharged for dielectric impedance DBD, Using dc source, centre frequency 30kHz, input power is 25~45W, and discharge temp is room temperature.
- 7. the application according to claim 3 or 4, it is characterised in that the mass space velocity in the reaction condition is 300,000 ~1,500,000mL/g/h.
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