CN107500296B - A kind of rodlike β-Mo2The controlledly synthesis of C and its application in inverse water gas shift reation - Google Patents
A kind of rodlike β-Mo2The controlledly synthesis of C 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-Mo2The controlledly synthesis of C and its application in inverse water gas shift reation belong to catalysis transform of carbon dioxide using field, and product is the CO of high added value.The present invention is by being dissolved in deionized water and HNO for ammonium paramolybdate3Mixed solution in hydro-thermal obtain the molybdenum trioxide with uniform Rod-like shape, and in the 20vt%CH of 100~160ml/min4/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, the number with higher specific surface area and more activated centres, no matter in the inverse water gas shift reation under simple catalytic action and under cold plasma and molybdenum carbide synergistic effect all with excellent CO2Conversion 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 carbide is catalyzed merely,
One-dimensional rod-like β type molybdenum carbide and cooperation of cold plasma are catalyzed inverse water gas shift reation and produce carbon monoxide.
Background technique
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
It high-volume steeply rises, only whole year in 2016, global CO2Discharge amount be as high as 32,100,000,000 tons.A large amount of discharges of carbon dioxide cause
Seawater acidification, the environmental problems such as climate warming get worse, become one of social concern urgently to be resolved.At the same time, two
Carbonoxide is also the most abundant C1 resource of content in the world.Therefore, height is converted by the methods of catalyzed conversion by carbon dioxide
Synthesis gas, methanol, low-carbon alkene, aldehyde, acid, ether, ester of added value 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.It is reacted by this, CO2It is converted into CO, to pass through non-fossil sources route
Producing synthesis gas provides possibility, becomes the following building green chemical industry system, reduces CO2The basis of discharge.
Currently, the catalyst 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. is shown excellent in above-mentioned reaction system
Activity (Applied Catalysis A-General, 2012,423:100-107.), but the higher cost of catalyst, no
Conducive to heavy industrialization application.Non-precious metal catalyst mainly includes Cu base catalyst and Ni base catalyst, and wherein Cu base is urged
The universal stability of agent is poor, and Ni base catalyst is then poor to the selectivity of CO.
We show in the previous work in laboratory: the α-MoC with face-centred cubic structure1-xThere is preferable inverse water-gas shift
Catalytic activity, by the load of noble metal, activity can be promoted further；But β-the Mo with hexagonal closs packing structure2C
Activity it is very low, see Fig. 2.We have found that synthesizing rodlike molybdenum oxide presoma 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 and catalyzed combination show unique advantage in activating thermodynamically stable small molecule reaction.Methane
Oxygen-free aromatization reaction by thermodynamical equilibrium due to being limited, CH at 700 DEG C4Equilibrium conversion 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 object conversion ratio.But in dielectric barrier discharge (DBD) cold plasma and Cu-Ni/ γ-Al2O3Catalyst
Under synergistic effect, 450 DEG C, nCH4/nCO2=1, under the conditions of WHSV=36000ml/g/h, CH4And CO2Conversion ratio be respectively
69% and 74%, it is much higher than thermodynamical equilibrium conversion ratio (Journal of Molecular Catalysis, 2011,25 (01): 11-16).Tu etc. by DBD it is cold it is equal 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 improves 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 inverse water-gas shift
The relevant report of reaction.
Summary of the invention
The object of the present invention is to provide a kind of β-Mo of one-dimensional rod-like2The type catalyst is applied to by the preparation method of C
In inverse water gas shift reation, has the characteristics that catalytic activity is high, thermal stability is good and CO is selectively high, make up existing catalyst
Or at high cost or thermal stability is poor or the selectively low deficiency of CO.
In order to achieve this, the technical scheme is that a kind of one-dimensional rod-like β-Mo2The controllable preparation of C 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 include the following steps:
(1) ammonium paramolybdate is dissolved in deionized water and HNO3Mixed solution in, wherein ammonium paramolybdate and mixed solution are used
Amount is than being 8.4g:240ml；Deionized water and 65%HNO in mixed solution3Volume ratio be 5:1；It after mixing evenly will be above-mentioned molten
Liquid is transferred in reaction kettle, 200 DEG C of hydro-thermal 22h, Temperature fall；It is centrifuged to obtain precipitating, and is washed with water several times, keeps its weakly acidic,
Thereafter the molybdenum trioxide for obtaining that there is uniform Rod-like shape for 24 hours is stood in 60 DEG C of air dry oven.
(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 Mo2It is that presoma carries out temperature programming that C, which is by the rodlike molybdenum trioxide to hydrothermal synthesis,
Be carbonized controlledly synthesis: carburizing atmosphere is the CH of 100~160ml/min4/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, is kept the temperature at 700 DEG C
2h 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 diameter, long 1.5~3 μm rodlike, 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 breeding ground being catalyzed merely 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.
The invention has the advantages that:
(1) one-dimensional rod-like β-Mo prepared by the present invention2C, which has, is higher than bulk β-Mo2The specific surface area of C is 182m2/ g, after
Person is 10m2/g。
(2) catalyst presence or at high cost or low temperature of the prior art for hydrogenation of carbon dioxide reaction of carbon monoxide
The deficiencies of active low or CO poor selectivity, it is shown in Table 3.One-dimensional rod-like β-Mo provided by the invention2C preparation method is simple, against the current
Low temperature active and CO selectivity with higher in vapour conversion reaction；In addition, it shows under the conditions of inverse water gas shift reation
Good stability is applicable to the conditions such as high temperature, the strongly reducing atmosphere of this reaction, in CO2Catalyzed conversion field has wide
Utilization prospects.
(3) molybdenum carbide provided by the invention and cooperation of cold plasma are catalyzed inverse water gas shift reation, can break through tradition
The limitation of thermodynamical equilibrium present in thermocatalytic, to obtain higher CO2Conversion rate is the resource utilization of carbon dioxide
Provide new approach.
Detailed description of the invention
5 width of attached drawing of the present invention, subordinate list 3 are opened:
Fig. 1 is blocky β-Mo prepared by comparative example 1.12One-dimensional rod-like pattern β-Mo prepared by C (a), embodiment 12C(b)、
The rodlike MoO that comparative example 1.2 is prepared using other methods3Rodlike β-the Mo obtained through identical temperature programming carbonization method2C (note
For β-Mo2C-rod-2, d) and comparative example 1.3 prepare rodlike MoO3β-the Mo obtained through common carbonization method2C (is denoted as β-
Mo2C-rod (w/o TPC), c) SEM comparison diagram；
Fig. 2 is blocky β-Mo prepared by comparative example 1.12C, the rodlike MoO that comparative example 1.2 is prepared using other methods3Through phase
β-the Mo that same temperature programming carbonization method obtains2β-the Mo of C-2, comparative example 1.32C-rod (w/o TPC), comparative example 1.4
Commercial Cu/ZnO/Al2O3One-dimensional rod-like pattern β-Mo prepared by catalyst and embodiment 12C is catalyzed against the current at 300 DEG C~600 DEG C
The CO of vapour conversion reaction2Conversion ratio comparison diagram；
Fig. 3 is the blocky β-Mo of comparative example 2.12C, the rodlike MoO that comparative example 2.2 is prepared using other methods3Through identical
β-the Mo that temperature programming carbonization method obtains2β-the Mo of C-2, comparative example 2.32The commercialization of C-rod (w/o TPC), comparative example 2.4
Cu/ZnO/Al2O32.5 hollow tube of catalyst and comparative example (referring to no catalyst filling, only fill quartz sand, similarly hereinafter) and embodiment 2
One-dimensional rod-like pattern β-Mo2C acts on the CO of inverse water gas shift reation in cold plasma and catalyzing cooperation2Conversion ratio comparison diagram；
Fig. 4 is the blocky 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 conversion reaction against the current when input power difference2Conversion ratio comparison diagram；
Fig. 5 is the one-dimensional rod-like pattern β-Mo prepared to embodiment 22When C and cooperation of cold plasma act on, 8h stability
Test is catalyzed the CO of inverse water gas shift reation2Conversion ratio figure.
Specific embodiment
Following nonlimiting examples can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
1 one-dimensional rod-like β-Mo of embodiment2The preparation of C and simple catalytically active assessment
(1) it prepares
8.4g ammonium paramolybdate is dissolved in 200ml deionized water and 40ml 65%HNO3Mixed solution in, after mixing evenly
Above-mentioned solution is transferred in reaction kettle, 200 DEG C of hydro-thermal 22h, Temperature fall；It is centrifuged to obtain precipitating, and be washed with water several times, make it be in
Neutrality stands thereafter the molybdenum trioxide for obtaining having uniform Rod-like shape for 24 hours in 60 DEG C of air dry oven.
Take rodlike 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 rises to 300 DEG C with the heating rate of 5 DEG C/min, then rises to 700 DEG C of final carburizing temperature with 1 DEG C/min,
And keep the temperature 2h.Then it is cooled to room temperature, in 1%O2It is passivated 12h in/Ar atmosphere and obtains one-dimensional rod-like molybdenum carbide catalyst sample.
SEM figure is shown in Fig. 1 b.
(2) active evaluation test
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 4mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.One-dimensional rod-like molybdenum carbide (the 40- of 30mg is weighed respectively
60 mesh) catalyst and 0.12g quartz sand (40-60 mesh) is placed in quartz ampoule after evenly 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 this condition, 300 DEG C
When CO2Conversion ratio is 7.7%, as shown in Figure 2.
1.1 bulk β-Mo of comparative example2The preparation of C and simple catalytically active assessment
(1) it prepares
Take 1.2g MoO3(40-60 mesh) sample is placed in fixed bed reactors, is passed through 20%CH4/H2Gaseous mixture carries out journey
Sequence heating carbonization, after rising to 300 DEG C by room temperature with 5 DEG C/min heating rate, then is risen to by 300 DEG C with 1 DEG C/min heating rate
700 DEG C, the constant temperature 2h at 700 DEG C.It then cools to room temperature, in 1%O2After being passivated 12h in/Ar atmosphere, block-like bulk is obtained
Molybdenum carbide catalyst, as a comparison.SEM figure is shown in Fig. 1 a.
(2) active evaluation test
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 4mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.Blocky β-the Mo of 30mg is weighed respectively2C (40-60 mesh)
Catalyst and 0.12g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly 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 this condition, 300 DEG C when CO2Turn
Rate is 0.1%, as shown in Figure 2.
1.2 other methods of comparative example prepare rodlike β-Mo2The preparation of C and simple catalytically active assessment
(1) it prepares
2g molybdenum powder is added in 10ml deionized water and forms uniform mixture, then by the 30wt%H of 20ml2O2It is slow
Slowly it is added in said mixture, solution becomes light yellow, stirs 30min with fully reacting；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 uses water and ethanol washing three times respectively, 80 DEG C are dried overnight
It is dry, it obtains and uniformly grows rodlike 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 carries out
Temperature programming carbonization, after rising to 300 DEG C by room temperature with 5 DEG C/min heating rate, then is risen by 300 DEG C with 1 DEG C/min heating rate
To 700 DEG C, the constant temperature 2h at 700 DEG C.It then cools to room temperature, in 1%O2After being passivated 12h in/Ar atmosphere, rodlike β-is obtained
Mo2C catalyst (is denoted as rodlike β-Mo2C-2), as a comparison.SEM figure is shown in Fig. 1 d.
(2) active evaluation test
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 4mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The above-mentioned shape β-Mo of 30mg is weighed respectively2C(40-60
Mesh) catalyst and 0.12g quartz sand (40-60 mesh) is placed in quartz ampoule after evenly 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 this condition, 300 DEG C when
CO2Conversion ratio is 4.1%, as shown in Figure 2.
The rodlike MoO of comparative example 1.33β-the Mo being commonly carbonized2C preparation and simple catalytically active assessment
(1) it prepares
8.4g ammonium paramolybdate is dissolved in 200ml deionized water and 40ml 65%HNO3Mixed solution in, after mixing evenly
Above-mentioned solution is transferred in reaction kettle, 200 DEG C of hydro-thermal 22h, Temperature fall；It is centrifuged to obtain precipitating, and be washed with water several times, make it be in
Neutrality stands thereafter the molybdenum trioxide for obtaining having uniform Rod-like shape for 24 hours in 60 DEG C of air dry oven.
Take rodlike 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 rises to 700 DEG C with the heating rate of 10 DEG C/min, and keeps the temperature 2h.Then it is cooled to room temperature, in 1% O2/
Passivation 12h obtains rodlike molybdenum carbide catalyst sample and (is denoted as β-Mo in Ar atmosphere2C-rod(w/o TPC).SEM figure is shown in Fig. 1 c.
(2) it tests
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 4mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The rodlike molybdenum carbide (40-60 mesh) of 30mg is weighed respectively
Catalyst and 0.12g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly 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 this condition, 300 DEG C when CO2Turn
Rate is 4.7%, as shown in Figure 2.
1.4 commercialization 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 carries out in the quartz ampoule fixed bed reactors of internal diameter 4mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The commercial Cu/ZnO/Al of 30mg is weighed respectively2O3Catalysis
Agent and 0.12g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly mixing, with 5%H2/ Ar gaseous mixture is 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 are
300,000mL/g/h, reaction temperature is 300 DEG C~600 DEG C, every 50 DEG C of points.Under this condition, 300 DEG C when CO2Conversion ratio is
1.2%, as shown in Figure 2.
2 one-dimensional rod-like β-Mo of embodiment2C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.One-dimensional rod-like molybdenum carbide (the 40- of 10mg is weighed respectively
60 mesh) catalyst and 0.19g quartz sand (40-60 mesh) is placed in quartz ampoule after evenly 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 be 33.4%, CO selectivity > 99% (by discharge caused by real reaction temperature be 290~330 DEG C,
Thermocatalytic equilibrium conversion is 19.3% at 300 DEG C, and thermocatalytic equilibrium conversion is 25.5%), as shown in Figure 3 at 350 DEG C.
2.1 bulk β-Mo of comparative example2C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The blocky molybdenum carbide (40-60 mesh) of 10mg is weighed respectively
Catalyst and 0.19g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly 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 that (the real reaction temperature caused by discharging is 290~330 DEG C, 300 DEG C to 13.8%, CO selectivity > 99%
Lower thermocatalytic equilibrium conversion is 19.3%, and thermocatalytic equilibrium conversion is 25.5%), as shown in Figure 3 at 350 DEG C.
The rodlike MoO of 2.2 other methods of comparative example preparation3β-the Mo obtained through identical temperature programming carbonization method2C-2
With cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.β-the Mo of 10mg is weighed respectively2C-2 (40-60 mesh) is urged
Agent and 0.19g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly 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 this condition,
CO2Conversion ratio is that (the real reaction temperature caused by discharging is at 290~330 DEG C, 300 DEG C to 26.6%, CO selectivity > 99%
Thermocatalytic equilibrium conversion is 19.3%, and thermocatalytic equilibrium conversion is 25.5%), as shown in Figure 3 at 350 DEG C.
The rodlike MoO of comparative example 2.33β-the Mo being commonly carbonized2C and cooperation of cold plasma catalytically active assessment
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The rodlike MoO of 10mg is weighed respectively3Commonly it is carbonized
β-Mo2C (40-60 mesh) catalyst and 0.19g quartz sand (40-60 mesh) are placed in quartz ampoule after evenly mixing, with 15%CH4/
H2Gaseous mixture carries out pretreatment 2h in 590 DEG C to catalyst, 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 are 30kHz, outer power-up
Pressure is 40V.Under this condition, CO2Conversion ratio is that (by discharging, caused real reaction temperature is 27.3%, CO selectivity > 99%
Thermocatalytic equilibrium conversion is 19.3% at 290~330 DEG C, 300 DEG C, at 350 DEG C thermocatalytic equilibrium conversion be 25.5%),
As shown in Figure 3.
2.4 commercialization 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 carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.The Cu/ZnO/Al of 10mg is weighed respectively2O3(40-60
Mesh) catalyst and 0.19g quartz sand (40-60 mesh) is placed in quartz ampoule after evenly mixing, with 5%H2/ Ar gaseous mixture is 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 be 17.2%, CO selectivity > 99% (by discharge caused by real reaction temperature be 290~330 DEG C, 300
Thermocatalytic equilibrium conversion is 19.3% at DEG C, and thermocatalytic equilibrium conversion is 25.5%), as shown in Figure 3 at 350 DEG C.
Activity rating of 2.5 blank pipe of comparative example under cold plasma effect
Inverse water gas shift reation carries out in the quartz ampoule fixed bed reactors of internal diameter 8mm.Each road gas stream needed for testing
Amount has mass flowmenter regulation and control, flows into reactor after mixing.0.20g quartz sand (40-60 mesh) is weighed uniformly to mix
It is placed in quartz ampoule, activity rating is carried out under the conditions of following: reaction atmosphere uses CO2: H2=1:2, gas flow are
250mL/min (as hereinbefore), dielectric impedance (DBD) discharge centers frequency are 30kHz, applied voltage 40V.This condition
Under, CO2Conversion ratio is about that (the real reaction temperature caused by discharging is 290~330 DEG C, 300 DEG C to 5%, CO selectivity > 99%
Lower thermocatalytic equilibrium conversion is 19.3%, and thermocatalytic equilibrium conversion is 25.5%), as shown in Figure 3 at 350 DEG C.
3 one-dimensional rod-like β-Mo of embodiment2C and cooperation of cold plasma are catalyzed inverse water-gas shift stability test
The present embodiment is the 8h stability test of one-dimensional rod-like molybdenum carbide catalyst, in the process the preparation and activity of catalyst
Evaluation test condition is same as Example 2.As can be seen that the reactivity of catalyst is not decreased obviously, such as Fig. 5 institute in 8h
Show.
Table 1 is blocky molybdenum carbide (a) prepared by comparative example 1.1 and one-dimensional rod-like β-Mo prepared by embodiment 12The ratio of C (b)
Surface area comparison；
Table 1
Table 2 is blocky molybdenum carbide prepared by ratio 1.1 and one-dimensional rod-like pattern β-Mo prepared by embodiment 12C respectively with it is cold
Under plasma body cooperative catalytic action, it is not catalyzed the CO of inverse water gas shift reation simultaneously in input power2Conversion ratio, CO selectivity
And CH4Selectivity comparison；
Table 2
Table 3 is Rod-like shape β-Mo prepared by embodiment 12Blocky 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 rates is normal pressure；cReaction gas
Composition: CO2:H2=1:2；dReaction gas composition: CO2:H2=1:1；eReaction gas composition: 21%CO2/ 30%H2/N2Balance Air；fInstead
Should gas composition: 25%CO2/ 25% H2/ 50%Ar2Balance Air.
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Claims (7)
1. a kind of one-dimensional rod-like β-Mo2The preparation method of C catalyst, the preparation method include 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；After mixing evenly by above-mentioned solution
It is transferred in reaction kettle, 200 DEG C of hydro-thermal 22h, Temperature fall；It is centrifuged to obtain precipitating, and is washed with water several times, keeps its weakly acidic,
The molybdenum trioxide for obtaining that there is uniform Rod-like shape for 24 hours is stood in 60 DEG C of air dry oven afterwards；
(2) presoma obtained by step (1) is carbonized in methane and hydrogen mixed gas in 590~800 DEG C；
Carburizing atmosphere is the CH of 100~160mL/min4/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, in 700 DEG C of heat preservation 2h, is cooled 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, which is characterized in that the β-
Mo2C catalyst is 200~400nm of diameter, long 1.5~3 μm rodlike, and specific surface area reaches 182m2/g。
3. rodlike β-Mo as claimed in claim 22Application of the C catalyst in inverse water gas shift reation.
4. application according to claim 3, which is characterized in that the inverse water gas shift reation is in cold plasma and rodlike
β-Mo2C catalyst synergistic effect is lower to be carried out.
5. application according to claim 3 or 4, which is characterized 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, which is characterized in that rodlike β-Mo2The reaction temperature that C is catalyzed merely be 300 DEG C~
600℃；Rodlike β-Mo2When C and cooperation of cold plasma act on, introduces the mode of cold plasma and discharges for dielectric impedance DBD,
Using DC power supply, centre frequency 30kHz, input power is 25~45W, and discharge temp is room temperature.
7. application according to claim 3 or 4, which is characterized in that the mass space velocity in the reaction condition is 300,000
~1,500,000mL/g/h.
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