CN109261157A - A kind of Ni@LaCO3OH composite material and preparation method and application - Google Patents
A kind of Ni@LaCO3OH composite material and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of Ni@LaCO3OH composite material and preparation method and application.The Ni@LaCO3The preparation method of OH composite material is that metal hydride is being contained CO2Atmosphere under heat reaction, be cooled to room temperature and obtain the Ni@LaCO3OH composite material.The Ni@LaCO3For OH composite material as methanation catalyst in use, when temperature reaches 200 DEG C, the gaseous product other than methane is not detected in chromatography of gases and mass spectrum up to 90% or more in carbon dioxide conversion.In 20 circulations, more than having no the decline of apparent performance, long catalytic life in the reaction of 400h.Compared with previous catalyst, present invention significantly reduces methanation reaction temperatures, and substantially increase catalyst life, have many advantages, such as that simple process, mild condition, yield are high, pollution-free, can be used for industrialization production.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of Ni@LaCO3OH composite material and preparation method
And application.
Background technique
Currently, the supply of global energy still relies primarily on the burning of fossil fuel.From Rio the United Nations ring in 1992
Border has so far with the United Nations Framework Convention on Climate Change for developing conference formulation to be added to from 196, whole world contracting party
In the discussion of problem, i.e. Global climate change and conflict of interests.And what is stood in the breach is exactly greenhouse effects problem.
Carbon dioxide is the exhaust gas of burning, is the arch-criminal of greenhouse effects, but is also a kind of nontoxic, cheap carbon source, a kind of
Thermodynamically stable molecule.The reduction of carbon dioxide and cycling and reutilization are not only to solve the panacea good recipe of greenhouse effects, and
The effective means of compound probability raw material.
Carbon dioxide methanation reaction is also known as Sabatier reaction, and reaction equation is as follows:
CO2+4H2→CH4+2H2O, Δ H=-252.9kJmol-1
The exothermic heat of reaction, and be favorable thermodynamics (Δ G298K=-130.8kJmol-1).However, this is one by dynamic
The process of mechanics limitation, needs suitable catalyst to guarantee the speed and selectivity of this reaction.
Traditional catalyst is by taking Ni base catalyst as an example, Ni/Al2O3Catalyst is the carbon dioxide catalyst to attract most attention, with
Other catalyst are compared, and Ni's is cheap, and all very high to the catalytic and selectivity of carbon dioxide methanation reaction.But Ni
Base catalyst also has disadvantage, since carbon distribution often occurs in its catalytic temperature relatively high (250~450 DEG C), leads to catalyst inactivation.This
Outside, loaded catalyst active component under high temperature reformation reaction condition is easy to be sintered and be agglomerated into crystalline substance, in turn result in hole collapse,
Specific surface area decline, active component agglomeration make catalyst activity reduction.In addition, with the progress of reaction process, catalysis
Agent surface is also easy to that carbon distribution occurs, so that Adsorption, the blocking of catalyst duct, eventually lead to catalyst inactivation.
It can be seen that although carbon dioxide methanation catalysts have obtained original progress, also apart from industrialization
There is comparable road to walk.The target of researcher is to find highly selective and high stability catalyst.
Hydrogen storage material introducing methanation reaction system there may be into enlightenment to this.For hydrogen storage material
How speech safely and effectively stores Hydrogen Energy and is their ability to a large amount of widely applied maximum bottlenecks.Therefore, solid-state hydrogen storage material is with it
Safety receives a lot of attention better than gaseous state or liquid hydrogen storage mode.However, these materials are also not enough to meet safety simultaneously at present
Property the big, economical and effective of high, small in size, energy density etc. require.The raw material for finally having the market competitiveness will be great comprehensive
Strength is closed, has price, environmental-friendly while high user's acceptance advantage concurrently.And methane just has this potential quality, because of its tool
Have efficiently, it is abundance, nontoxic, and natural gas flies into huge numbers of families already, there is very high acceptance.Moreover, methane/hydrogen
Gas gaseous mixture is also important one of industrial chemicals gas, this is undoubtedly a kind of preparation method of simplicity.In brief, by grinding
Study carefully such a system, may be implemented Hydrogen Energy conversion and useless hydrogen recycle, realize recycling for carbon dioxide, and delay simultaneously
Greenhouse effects and energy crisis are solved, there is highly important research significance.
Summary of the invention
In order to solve the disadvantage that the prior art and shortcoming, the primary purpose of the present invention is that providing a kind of Ni@
LaCO3OH composite material.
Another object of the present invention is to provide above-mentioned Ni@LaCO3The preparation method of OH composite material.
Another object of the present invention is to provide above-mentioned Ni@LaCO3The application of OH composite material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of Ni@LaCO3The preparation method of OH composite material, including following preparation step: metal hydride is being contained
CO2Atmosphere under heat reaction, be cooled to room temperature and obtain the Ni@LaCO3OH composite material.
Preferably, the metal hydride is LaNi5Hydride and LaNi4One or both of Cu hydride.
Preferably, described to contain CO2Atmosphere refer to group become CO2、H2With the mixed-gas atmosphere of Ar, CO2Occupied
Volume fraction > 0, H2It is not limited with volume fraction shared by Ar.
Preferably, the temperature of the reaction is 100~400 DEG C, and the time of the reaction is 20~40h.
Preferably, the pressure of the reaction is 0~8MPa.
Preferably, the metal hydride is to cross the above standard of 200 mesh after the hydrogen bearing alloy as made from electric arc melting is broken
Sieve is heated to 100~200 DEG C under 2~5MPa hydrogen atmosphere, be cooled to room temperature gained, this process after inhaling hydrogen activation 5h or more
It is carried out in protective atmosphere.
Preferably, the protective atmosphere is one or both of rare gas or nitrogen.
Preferably, the hydrogen bearing alloy is LaNi5Or LaNi4Cu。
Above-mentioned Ni@LaCO3The Ni@LaCO that the preparation method of OH composite material is prepared3OH composite material.
Above-mentioned Ni@LaCO3Application of the OH composite material as methanation reaction catalyst.
Mechanism of the invention: Ni@LaCO3In OH composite material, Ni plays the role of major catalytic.In traditional catalyst,
With the increase in reaction time and cycle-index, Ni particle often grows up, reunites, so that catalytic effect substantially reduces, and Ni@
LaCO3In OH composite material, LaCO3The presence of OH can then make Ni spread out, and slow down the speed of growth of Ni, effectively increase
Catalytic life.
Compared with prior art, the invention has the advantages that and the utility model has the advantages that
(1) the Ni@LaCO prepared by the present invention3OH composite material is as methanation reaction catalyst, with traditional catalyst
It compares, reaction condition milder, and there is high catalytic efficiency.The reaction temperature of traditional catalyst is often at 250~450 DEG C
Between, and catalyst provided by the present invention is minimum can react at 150 DEG C, and when temperature reaches 200 DEG C, titanium dioxide
Carbon maximum conversion is the gaseous product detected other than methane in chromatography of gases and mass spectrum up to 90% or more.
(2) the Ni@LaCO prepared by the present invention3OH composite material is as methanation reaction catalyst, with traditional catalyst
It compares, there is the longer service life, in 20 circulations, more than having no the decline of apparent performance, long catalytic life in the reaction of 400h.
It is not only to realize the short-cut method of carbon dioxide reduction, still prepares the effective means of methane.
(3) the Ni@LaCO obtained by the present invention3OH composite material is related to LaNi as methanation reaction catalyst5、
LaNi4The application of Cu can inhale hydrogen at room temperature, realize the recycling of useless hydrogen, it then follows the principle of Green Chemistry and atom economy,
Save the cost protects environment.
(4) exhaust carbon dioxide of the reaction according to the present invention to burn reacts as raw material and generates methane and water, whole
A reaction process green non-pollution, yield is high, and reaction condition is mild, and by-product is few, realizes exhaust gas recycling, embodies green
The theory of chemistry.And reaction process is controllable, production and equipment are simple and easy, are conducive to the marketization and industrialization.
Detailed description of the invention
Fig. 1 is Ni@LaCO made from Examples 1 to 33OH composite material is as catalyst, the CH in reaction 40h4At any time
Production quantity curve graph, wherein (a) 180 DEG C of corresponding embodiments 1, (b) 200 DEG C of corresponding embodiments 2 (c) corresponding are implemented for 220 DEG C
Example 3.
Fig. 2 is Ni@LaCO made from embodiment 4~63OH composite material is as catalyst, the CH in reaction 40h4At any time
Production quantity curve graph, wherein (a) 180 DEG C of corresponding embodiments 4, (b) 200 DEG C of corresponding embodiments 5 (c) corresponding are implemented for 220 DEG C
Example 6.
Fig. 3 is embodiment 2, Ni@LaCO made from embodiment 7 and embodiment 83OH composite catalyst adds, and reacts 40h
Interior CH4Production quantity curve graph at any time, wherein (a) 4.5g corresponding embodiment 2, (b) 2.25g corresponding embodiment 7, (c) 9.0g
Corresponding embodiment 8.
Fig. 4 is Ni@LaCO made from embodiment 23OH composite material is as catalyst, the methane in 20 circular responses
Production quantity and CO2Consumption graph figure.
Fig. 5 is Ni@LaCO made from embodiment 53OH composite material is as catalyst, the methane in 20 circular responses
Production quantity and CO2Consumption graph figure.
Fig. 6 is Ni@LaCO made from embodiment 23OH composite material is as catalyst, and XRD is composed after 20 circular responses
Figure.
Fig. 7 is Ni@LaCO made from embodiment 23SEM of the OH composite material as catalyst, after 20 circular responses
Secondary electron scanning imagery figure.
Fig. 8 is Ni@LaCO made from embodiment 23OH composite material is as catalyst, the high-resolution after 20 circular responses
TEM image and corresponding selective electron diffraction figure, wherein left figure is corresponding selective electron diffraction figure, and right figure is high-resolution
TEM image.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
It is related to material preparation and transfer storage in embodiment, is all to be carried out under an inert atmosphere.Implement
Priming reaction involved in example and methanation reaction are carried out in high-temperature high-pressure reaction kettle.Meanwhile passing through in embodiment
The gaseous product of mass spectrum (MS) characterization reaction.
Embodiment 1
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening5Powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa, is set
5h is reacted at 150 DEG C, is allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with containing 3MPa
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 180 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 1 institute
Show.According to Calculate CO2Conversion ratio is 66.6%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Embodiment 2
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening5Powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa, is set
5h is reacted at 150 DEG C, is allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 200 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 1 institute
Show.According to Calculate CO2Conversion ratio is 90.6%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Repetitive cycling step (3) until 20 circulations terminate, as a result as shown in figure 4, as we can see from the figure 20 times recycle
The production quantity and CO of methane in reaction2Consumption, it is seen that Ni@LaCO3OH composite material still keeps high in 20 circulations
Catalytic activity.
Solid after 20 circulations is subjected to XRD, SEM, TEM characterization, respectively such as Fig. 6 (XRD characterization), 7 (SEM characterizations), 8
Shown in (TEM characterization).From fig. 6, it can be seen that the solid after catalysis reaction has Ni and LaCO3Two kinds of object phases of OH；Fig. 7 can be seen
Out, in LaNi5The Ni@LaCO of Surface Creation3OH composite material occurs in the form of stratiform or tufted；Fig. 8 can be seen that in LaNi5
The Ni@LaCO of Surface Creation3In OH composite material, Ni often exists in the form of nanocrystalline, in addition it can be seen that many crystallization
Incomplete place, it is seen that the Ni of generation may have than more rich defect, dislocation etc., explain its high catalytic activity.
Embodiment 3
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening5Powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa, is set
5h is reacted at 150 DEG C, is allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 220 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 1 institute
Show.According to Calculate CO2Conversion ratio is 91.0%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Embodiment 4
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening4Cu powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa,
It is placed at 150 DEG C and reacts 5h, be allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa.Reaction kettle is placed at 180 DEG C and is reacted
40h.It is cooled to room temperature to reaction kettle, pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 2 institute
Show.According to Calculate CO2Conversion ratio is 67.3%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Embodiment 5
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening4Cu powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa,
It is placed at 150 DEG C and reacts 5h, be allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 200 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 200 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 2 institute
Show.According to Calculate CO2Conversion ratio is 70.3%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Repetitive cycling step (3) terminates up to 20 circulations, as a result as shown in figure 5, can be obtained by Fig. 5, Ni@LaCO3OH is multiple
Condensation material still keeps high catalytic activity in 20 circulations.
Embodiment 6
(1) it in the glove box of 0.1MPa argon atmosphere, takes 4.5g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening4Cu powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa,
It is placed at 150 DEG C and reacts 5h, be allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 220 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 2 institute
Show.According to Calculate CO2Conversion ratio is 77.1%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Embodiment 7
(1) it in the glove box of 0.1MPa argon atmosphere, takes 2.25g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening5Powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa, is set
5h is reacted at 150 DEG C, is allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 200 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 3 institute
Show.According to Calculate CO2Conversion ratio is 27.7%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Embodiment 8
(1) it in the glove box of 0.1MPa argon atmosphere, takes 9.0g by electric arc melting and sufficiently broken, crosses 200 targets
The LaNi of quasi- test sieve screening5Powder is fitted into 25mL high-temperature high-pressure reaction kettle (NS-25-316L), is filled with the hydrogen of 4MPa, is set
5h is reacted at 150 DEG C, is allowed to sufficiently activate, be cooled to room temperature；
(2) by kettle residual gas extraction (in pumping process in kettle air pressure between 0.1~1MPa), be filled with 3MPa and contain
Mixed gas (the V of carbon dioxideCO2:VAr=19:81), it is evacuated, inflates again, repeatedly after 5 times, no hydrogen is residual in reaction kettle
It stays, is filled with the carbonated mixed gas (V of 3MPa againCO2:VAr=19:81), reaction kettle is placed at 180 DEG C and is reacted, instead
It after answering 40h, is cooled to room temperature to reaction kettle, obtains the Ni@LaCO3OH composite material；
(3) residual gas in kettle is completely drawn out, is filled with 3MPa carbon dioxide/hydrogen/argon gas mixed gas (VCO2:
VH2:VAr=19:76:5), it is evacuated, inflates again, repeatedly after 5 times, without gas residue in reaction kettle, be filled with 3MPa bis- again
Carbonoxide/hydrogen/argon gas mixed gas (VCO2:VH2:VAr=19:76:5) 3MPa, reaction kettle is placed at 200 DEG C and is reacted
40h is cooled to room temperature to reaction kettle, and pumping 50mL residual gas, which enters in mass spectrum, to be detected, the production quantity of methane at any time such as Fig. 3 institute
Show.According to Calculate CO2Conversion ratio is 94.8%, in mass spectrum and
The gaseous product other than methane is not measured in chromatography of gases.
Fig. 1 is Ni@LaCO made from Examples 1 to 33OH composite material is as catalyst, in reaction 40h CH4At any time
Production quantity curve graph, wherein (a) 180 DEG C of corresponding embodiments 1, (b) 200 DEG C of corresponding embodiments 2 (c) corresponding are implemented for 220 DEG C
Example 3.It will be seen from figure 1 that with LaNi5As raw material, when reaction temperature from 180 DEG C rise to 220 DEG C during, reaction rate
It is continuously improved with temperature, and when temperature is higher than 200 DEG C, the conversion ratio of methane does not continue to increase with the raising of temperature.
Fig. 2 is Ni@LaCO made from embodiment 4~63OH composite material is as catalyst, in reaction 40h CH4At any time
Production quantity curve graph, wherein (a) 180 DEG C of corresponding embodiments 4, (b) 200 DEG C of corresponding embodiments 5 (c) corresponding are implemented for 220 DEG C
Example 6.Figure it is seen that with LaNi5Cu as raw material, when reaction temperature from 180 DEG C rise to 220 DEG C during, reaction speed
Rate and methane conversion are all without significant change.Fig. 1 and Fig. 2 comparison is as can be seen that LaNi5Catalyst for raw material preparation is urged
Change effect and rate is more preferable.
Fig. 3 is embodiment 2, Ni@LaCO made from embodiment 7 and embodiment 83OH composite catalyst adds, and reacts 40h
Interior CH4Production quantity curve graph at any time, wherein (a) 4.5g corresponding embodiment 2, (b) 2.25g corresponding embodiment 7, (c) 9.0g
Corresponding embodiment 8.As can be seen from Figure 3: chemical equation CO2+4H2→CH4+2H2O, different CO2:H2Ratio is for anti-
Answer the influence of rate.Due to LaNi5It can sufficiently hydrogenate in a hydrogen atmosphere, generate LaNi5H5, by changing LaNi5Addition
Amount, thus it is possible to vary H2Content in a kettle.Work as H2When in shortage, reaction rate is slow, methane production is low, works as H2When excessive, instead
Rate is answered to greatly improve, but the raising on conversion ratio is not significant.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of Ni@LaCO3The preparation method of OH composite material, which is characterized in that including following preparation step: by metal hydride
Object is containing CO2Atmosphere under heat reaction, be cooled to room temperature and obtain the Ni@LaCO3OH composite material.
2. Ni@LaCO according to claim 13The preparation method of OH composite material, which is characterized in that the metal hydride
For LaNi5Hydride and LaNi4One or both of Cu hydride.
3. Ni@LaCO according to claim 1 or claim 23The preparation method of OH composite material, which is characterized in that described to contain CO2
Atmosphere refer to group become CO2、H2With the mixed-gas atmosphere of Ar, CO2The volume fraction > 0, H occupied2With shared by Ar
Volume fraction does not limit.
4. Ni@LaCO according to claim 1 or claim 23The preparation method of OH composite material, which is characterized in that the temperature of the reaction
Degree is 100~400 DEG C, and the time of the reaction is 20~40h.
5. Ni@LaCO according to claim 1 or claim 23The preparation method of OH composite material, which is characterized in that the pressure of the reaction
It is by force 0~8MPa.
6. Ni@LaCO according to claim 1 or claim 23The preparation method of OH composite material, which is characterized in that the metal hydride
Object is to cross the above standard screen of 200 mesh after the hydrogen bearing alloy as made from electric arc melting is broken, through being heated under 2~5MPa hydrogen atmosphere
100~200 DEG C, it is cooled to room temperature gained after inhaling hydrogen activation 5h or more, this process carries out in protective atmosphere.
7. Ni@LaCO according to claim 63The preparation method of OH composite material, which is characterized in that the protection gas
Atmosphere is one or both of rare gas or nitrogen.
8. Ni@LaCO according to claim 63The preparation method of OH composite material, which is characterized in that the hydrogen bearing alloy
For LaNi5Or LaNi4Cu。
9. any one of the claim 1~8 Ni@LaCO3The Ni@LaCO that the preparation method of OH composite material is prepared3OH is multiple
Condensation material.
10. Ni@LaCO described in claim 93Application of the OH composite material as methanation reaction catalyst.
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| CN113336254A (en) * | 2021-05-12 | 2021-09-03 | 中国北方稀土（集团）高科技股份有限公司 | Method for preparing hexagonal system lanthanum hydroxycarbonate by hydrothermal synthesis |
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| CN113336254A (en) * | 2021-05-12 | 2021-09-03 | 中国北方稀土（集团）高科技股份有限公司 | Method for preparing hexagonal system lanthanum hydroxycarbonate by hydrothermal synthesis |
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