CN109701543A - A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof - Google Patents

A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof Download PDF

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CN109701543A
CN109701543A CN201910092405.5A CN201910092405A CN109701543A CN 109701543 A CN109701543 A CN 109701543A CN 201910092405 A CN201910092405 A CN 201910092405A CN 109701543 A CN109701543 A CN 109701543A
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sio
nano
composite catalyst
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nickel
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李远志
张戈权
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The present invention provides a kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof, the La2O3Cluster modifies Ni/SiO2Nano-composite catalyst by mesoporous silicon oxide, nickel is nanocrystalline and lanthana forms；Nickel is nanocrystalline to be carried on mesoporous silicon oxide, and the nanocrystalline surface of nickel is attached with lanthana.La of the invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst is carried on mesoporous silicon oxide so that nickel is nanocrystalline for active component, and by adhering to La in nickel nanocrystal surface2O3Cluster modification is carried out to the surface of nano nickel particles, to change its surface electron states and geometry, and then inhibit its elementary reaction related with carbon deposit, and utilize the local confinement of the progress nanocrystalline to nickel of the mesoporous silicon oxide as carrier, nickel nanocrystalline migration and grain growth at high temperature are prevented, so that La of the invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst has good anti-carbon and anti-sintering property, so that it be made to have excellent catalytic stability in methane dry method reforming reaction.

Description

A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof
Technical field
The present invention relates to nano-composite catalyst technical field, in particular to a kind of La2O3Cluster modifies Ni/SiO2Nanometer Composite catalyst and preparation method thereof.
Background technique
Human society increasingly increases the consumption of the energy at present: being the continuous growth of population first, in the world in 2014 Total population be 72.08 hundred million, and predicted according to the United Nations, in the year two thousand fifty, total world population is up to 9,600,000,000；Followed by with science and technology Development, energy consumption also increasingly goes up per capita, nineteen ninety-five the world per capita energy consumption be 1.51 tons of oil equivalent/people, and by 2013 1.80 tons of oil equivalent/people are then risen to.Being gradually increased to form sharp contrast with demand for energy is then non-renewable energy Source it is increasingly depleted.Petroleum is insufficient century-old for the time of exploitation at present；Coal also will be depleted within the centuries.In addition to Energy problem, greenhouse effects also increasingly attract people's attention.Methane is the important greenhouse gases for being only second to CO2, big Though the concentration in gas compares CO2Much less, but growth rate is then much bigger.According to the inter-governmental climate change committee (IPCC) of the United Nations Second of the climate change assessment report (" report ") delivered for 1996, from CO between 1750-1990 totally 240 years2It increases 30%, and same period methane increases 145%.Currently, being used for the catalyst of methane, CO 2 reformation preparing synthetic gas mostly with negative Based on supported metal catalyst, it is broadly divided into noble metal and non-precious metal catalyst two major classes.Noble metal such as Pt, Ir, Ru, Rh etc., It is expensive although having excellent reactivity worth, it is also easy to sintering under hot conditions and is lost.Therefore, preparation is with your non-gold The advantages of belonging to is particularly important for the catalyst of active component, this system is that reactivity worth is good, catalyst preparation cost It is low, but catalyst carbon accumulation resisting ability is low, can cause to inactivate because of carbon distribution, sintering.At the same time, due to methane, carbon dioxide weight Whole reaction must just can be carried out at high temperature, and reacting is carried out under biggish air speed, and a large amount of heat is during the reaction It is entrained by the flow of air, therefore, how to solve the problems, such as that the highly energy-consuming in methane dry method reforming reaction is also a urgent problem to be solved.
Summary of the invention
In view of this, the present invention is directed to propose a kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst, it is existing to solve There is the problem of stability difference of the nano-composite catalyst in methane dry method reforming reaction.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst, the La2O3Cluster modifies Ni/SiO2It is nano combined Catalyst by mesoporous silicon oxide, nickel is nanocrystalline and lanthana forms；The nickel is nanocrystalline to be carried on the mesoporous silicon oxide On, and the nanocrystalline surface of the nickel is attached with the lanthana.
Optionally, the molal quantity of lanthanum is the La in the lanthana2O3Cluster modifies Ni/SiO2Nano-composite catalyst Molal quantity 0.5~5%.
Optionally, the nanocrystalline average grain diameter of the nickel is 4~5nm；The mesoporous pore size of the mesoporous silicon oxide is 6.9 ~15.4nm.
The second object of the present invention, which is to provide, a kind of prepares above-mentioned La2O3Cluster modifies Ni/SiO2Nano-composite catalyst Method, the preparation method the following steps are included:
1) Na is prepared2SiO3Solution, then, to the Na under lasting stirring condition2SiO3Diluted acid is added in solution, adjusts Save the Na2SiO3The pH value of solution obtains solution A to 5~7；
2) nickel nitrate and lanthanum nitrate are mixed, and mixed nickel nitrate and lanthanum nitrate is configured to solution B, then, Under stirring condition, the solution B is added into the solution A, solution C is obtained；
3) lye is added in Xiang Suoshu solution C, then, heating carries out aging process, obtains ageing products；
4) ageing products filtered, washed, dried, ground, obtain La2O3Cluster modifies Ni/SiO2Nanometer is multiple Close catalyst.
Optionally, diluted acid described in the step 1) is dust technology, and the volume ratio of the diluted acid is 1: 2~1: 8.
Optionally, Na described in solution C described in the step 2)2SiO3, the nickel nitrate, the lanthanum nitrate mole Than for (90~94.5): 5: (0.5~5).
Optionally, lye described in the step 3) is that weak aqua ammonia, sodium hydroxide solution, potassium hydroxide solution or urea are molten One of liquid.
Optionally, the additive amount of lye described in the step 3) is lye amount needed for theoretically precipitating Ni and La completely 60%-120%.
Optionally, the heating temperature of heating described in the step 3) be 60~100 DEG C, heating time be 12~for 24 hours.
Optionally, grinding described in the step 4) includes: that the ageing products after suction filtration, washing, drying are ground to grain Diameter is 200 mesh.
Compared with the existing technology, La of the present invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst has following Advantage:
1, La of the invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst is nanocrystalline for active component with nickel, by it It is carried on mesoporous silicon oxide, and by adhering to La in nickel nanocrystal surface2O3, cluster is carried out to the surface of nano nickel particles Modification, to change its surface electron states and geometry, and then inhibit its elementary reaction related with carbon deposit, and using as The local confinement of the mesoporous silicon oxide of carrier progress nanocrystalline to nickel, makes its rivet clasp in mesoporous silicon oxide, prevents nickel nanometer Brilliant migration and grain growth at high temperature, so that La of the invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst has Good anti-carbon and anti-sintering property, to make it that there is excellent catalytic stability in methane dry method reforming reaction.
2, the present invention prepares La using the precipitation method2O3Cluster modifies Ni/SiO2Nano-composite catalyst can be effectively controlled La2O3Cluster modifies Ni/SiO2Nickel is nanocrystalline in nano-composite catalyst and La2O3The size of nano particle, so as to effectively mention High made La2O3Cluster modifies Ni/SiO2The porosity and specific surface area of nano-composite catalyst, and then make it have excellent Catalytic activity.
3, the present invention uses nickel nanocrystalline for active component, can effectively reduce La2O3Cluster modifies Ni/SiO2It is nano combined The production cost of catalyst, and preparation process of the present invention is simple, convenient for operation, is not necessarily to high-temperature calcination, can significantly reduce production energy Consumption, is conducive to energy conservation.
4, by La of the invention2O3Cluster modifies Ni/SiO2Nano-composite catalyst is anti-for methane carbon dioxide reformation It answers, and the energy using sunlight as driving methane dry method reforming reaction, methane reforming with carbon dioxide can be made to have Higher reaction efficiency efficiently solves the problems, such as the highly energy-consuming of methane carbon dioxide reformation, has important energy storage meaning, this hair The bright energy using xenon lamp simulated solar irradiation as driving methane dry method reforming reaction, it is of the invention under xenon lamp irradiation condition La2O3Cluster modifies Ni/SiO2The catalytic activity of nano-composite catalyst is decreased obviously by 90h irradiation nothing.
Detailed description of the invention
The attached drawing for constituting a part of the invention is used to provide further understanding of the present invention, schematic reality of the invention It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2Nano-composite catalyst and comparative example 1 The Ni/SiO of lanthanum is not added2The XRD spectrum of catalyst；
Fig. 2 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2The TEM map of nano-composite catalyst；
Fig. 3 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2Sweep figure in the face EDS of nano-composite catalyst Spectrum；
Fig. 4 is the Ni/SiO that lanthanum is not added of comparative example 12The TEM map of catalyst；
Fig. 5 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2The stability test of nano-composite catalyst Resulting CH4And CO2Reaction rate curve and CO and H2Generating rate curve；
Fig. 6 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2Nano-composite catalyst is filtering off different waves Resulting CH after long light4And CO2Reaction rate curve；
Fig. 7 is La described in the embodiment of the present invention 12O3Cluster modifies Ni/SiO2Nano-composite catalyst is filtering off different waves Resulting CO and H after long light2Generating rate curve；
Fig. 8 is La described in the embodiment of the present invention 22O3Cluster modifies Ni/SiO2The stability test of nano-composite catalyst Resulting CH4And CO2Reaction rate curve and CO and H2Generating rate curve；
Fig. 9 is La described in the embodiment of the present invention 32O3Cluster modifies Ni/SiO2The stability test of nano-composite catalyst Resulting CH4And CO2Reaction rate curve and CO and H2Generating rate curve；
Figure 10 is La described in the embodiment of the present invention 42O3Cluster modifies Ni/SiO2The stability of nano-composite catalyst is surveyed Try resulting CH4And CO2Reaction rate curve and CO and H2Generating rate curve；
Figure 11 is the Ni/SiO that lanthanum is not added of comparative example 12The resulting CH of the stability test of catalyst4And CO2Reaction Rate curve and CO and H2Generating rate curve；
Figure 12 is the Ni/SiO that lanthanum is not added of comparative example 22The resulting CH of the stability test of nano-composite catalyst4With CO2Reaction rate curve and CO and H2Generating rate curve；
Figure 13 is the resulting CH of stability test of the catalyst lanthanum-carried on silica of comparative example 34And CO2's Reaction rate curve and CO and H2Generating rate curve；
Figure 14 is the resulting CH of stability test of the catalyst of nickel-loaded on the lanthanum sesquioxide of comparative example 44And CO2's Reaction rate curve and CO and H2Generating rate curve.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase Mutually combination.
Below in conjunction with drawings and examples, the present invention will be described in detail.
Embodiment 1
The La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst is mesoporous the two of 9.6nm by mesoporous pore size Silica, average grain diameter be 4.5nm nickel is nanocrystalline and lanthana (La2O3) composition；Nickel is nanocrystalline to be carried on mesoporous silicon oxide On, and the nanocrystalline surface of nickel is attached with lanthana, wherein the molal quantity of lanthanum is La in lanthana2O3Cluster modifies Ni/SiO2 The 2% of the molal quantity of nano-composite catalyst.
It is prepared as follows the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst, it is specific to wrap Include following steps:
1) 26.4306g Na is weighed2SiO3·9H2O is in beaker, then, 87.2154g deionized water is added and persistently stirs It mixes to Na2SiO3·9H2O be completely dissolved mass fraction be 10% Na2SiO3Solution, then, in continuing magnetic force stirring condition It is lower to Na2SiO3Dust technology is added dropwise in solution, adjusts Na2SiO3The pH value of solution obtains solution A to 6, wherein dust technology be by It is obtained after analyzing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) 1.4540g Ni (NO is weighed3)2·6H2O (nickel nitrate) and 0.8660gLa (NO3)3·6H2O (lanthanum nitrate) is in burning In cup, 15.0000g deionized water continuing magnetic force is added and stirs to being completely dissolved, solution B is obtained, then, in magnetic agitation condition Under, solution B is added dropwise in solution A, solution C is obtained；
3) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 5.4ml to dilute will be analyzed Enter solution C, in drop then magnetic agitation is sealed with preservative film, and is placed in 90 DEG C of baking oven and is heated for 24 hours, old to carry out Change processing, obtains ageing products；
4) it after being filtered, being washed by ageing products, is dried at 180 DEG C for 24 hours sufficiently to dry it, then, is ground to 200 meshes are crossed, that is, the partial size of the ageing products after grinding is 200 mesh, obtains La2O3Cluster modifies Ni/SiO2Nano combined catalysis Agent.
To the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out XRD, TEM, EDS analysis, test As a result as shown in Figure 1, Figure 2 and Figure 3.
As shown in Figure 1, the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst has at 2 θ=22.7 ° The diffraction maximum of one wideization, the silica of corresponding amorphous state；It is 2 θ=44.5 °, two at 2 θ=51.8 ° in the angle of diffraction Unanimously, above-mentioned two peak respectively corresponds nickel crystal face { 111 }, { 200 } to the PDF card (PDF#04-0850) of a diffraction maximum and nickel, says The La of bright the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst is Ni/SiO2Composite material, because of the present embodiment La2O3Cluster modifies Ni/SiO2La in nano-composite catalyst2O3Doping content it is low, and be amorphous state, therefore do not see Observe La2O3Diffraction maximum.
By Fig. 2 and Fig. 3 it is found that the La of the present embodiment2O3Cluster modifies Ni/SiO2Ni is in nano-composite catalyst with nanometer The form of particle is uniformly dispersed in unbodied silica surface, and La is highly dispersed at entire La with unbodied state2O3 Cluster modifies Ni/SiO2In nano-composite catalyst system, and the test result of XRD and TEM is combined, Ni nanometers can be calculated The Average Particle Diameters of particle are 4.5nm.
To the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out BET test.
By BET test it is found that the La of the present embodiment2O3Cluster modifies Ni/SiO2The specific surface area of nano-composite catalyst For 328.29cm2/ g, Kong Rongwei 0.97cm3/ g, silica aperture are 9.6nm.
By the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out xenon source irradiation stability and surveys Examination, specifically comprises the following steps:
1) by 0.0200g La2O3Cluster modifies Ni/SiO2Nano-composite catalyst is placed in the heat-preservation cotton of cavity reactor In groove, groove diameter is about 0.8cm, keeps the top of thermocouple concordant with sample holding, the other end and temperature number of thermocouple Aobvious instrument is connected；
2) after connecting gas circuit, flow control in 90mL/min and is checked into air-tightness with mass flowmenter, to unstripped gas (20%CH4- 20%CO2- 60%Ar) it is sampled after flow speed stability, it is dense to record reaction end gas peak area with gas chromatograph Degree carries out on-line checking analysis；
3) regulated power supply is opened, then opens xenon lamp, electric current is adjusted to 24A, mobile xenon lamp makes its hot spot maximize photograph rapidly Sample surfaces are penetrated, the registration of temperature-shrink crack is observed, keep stablizing after xenon lamp is adjusted to temperature-shrink crack temperature highest point, to Gas chromatograph records reaction end gas peak area concentration at this time, can obtain La2O3Cluster modifies Ni/SiO2It is nano combined to urge Catalytic activity of the agent under full spectrum.
In the La of the present embodiment2O3Cluster modifies Ni/SiO2Under the action of nano-composite catalyst, gained CH4And CO2It is anti- Answer rate and CO and H2Generating rate and temperature relationship it is as shown in Figure 5.
As shown in Figure 5, after sustained response 90h, the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst Catalytic activity be not decreased obviously, illustrate it with excellent catalytic stability and higher catalytic activity.
The filter that can be filtered off less than 420nm, 560nm, 690nm wavelength is sequentially placed into above the quartz window of cavity reactor Wave plate is sampled, and records the photic thermocatalytic activity of illumination under different-waveband, with the La to the present embodiment2O3Cluster modification Ni/SiO2The catalytic activity of nano-composite catalyst at different wavelengths is tested, the gained after the light for filtering off different wave length CH4And CO2Reaction rate as shown in fig. 6, CO and H2Generating rate and temperature relationship it is as shown in Figure 7.
By Fig. 6 and Fig. 7 it is found that even if filter off be less than 690nm wavelength light after, the La of the present embodiment2O3Cluster modification Ni/SiO2Nano-composite catalyst still catalytic activity with higher, it is higher to illustrate that it all has under full solar spectrum Catalytic activity.
Embodiment 2
The La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst is mesoporous the two of 7.3nm by mesoporous pore size Silica, average grain diameter be 4.2nm nickel is nanocrystalline and lanthana (La2O3) composition；Nickel is nanocrystalline to be carried on mesoporous silicon oxide On, and the nanocrystalline surface of nickel is attached with lanthana, wherein the molal quantity of lanthanum is La in lanthana2O3Cluster modifies Ni/SiO2 The 0.5% of the molal quantity of nano-composite catalyst.
It is prepared as follows the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst, it is specific to wrap Include following steps:
1) 26.8569g Na is weighed2SiO3·9H2O is in beaker, then, 88.6221g deionized water is added and persistently stirs It mixes to Na2SiO3·9H2O be completely dissolved mass fraction be 10% Na2SiO3Solution, then, in continuing magnetic force stirring condition It is lower to Na2SiO3Dust technology is added dropwise in solution, adjusts Na2SiO3The pH value of solution obtains solution A to 6, wherein dust technology be by It is obtained after analyzing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) 1.4540g Ni (NO is weighed3)2·6H2O (nickel nitrate) and 0.2165g La (NO3)3·6H2O (lanthanum nitrate) in In beaker, 15.0000g deionized water continuing magnetic force is added and stirs to being completely dissolved, solution B is obtained, then, in magnetic agitation item Under part, solution B is added dropwise in solution A, obtains solution C；
3) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water will be analyzed, the weak aqua ammonia (lye) after taking 4ml to dilute instills Solution C, in drop, then magnetic agitation is sealed with preservative film, and is placed in 90 DEG C of baking oven and is heated for 24 hours, to carry out aging Processing, obtains ageing products；
4) it after being filtered, being washed by ageing products, is dried at 180 DEG C for 24 hours sufficiently to dry it, then, is ground to 200 meshes are crossed, that is, the partial size of the ageing products after grinding is 200 mesh, obtains La2O3Cluster modifies Ni/SiO2Nano combined catalysis Agent.
By the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out xenon source irradiation stability and surveys Examination, specific testing procedure is the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature pass System is as shown in Figure 8.
As shown in Figure 8, after sustained response 10h, the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst Catalytic activity decline, but decline it is not significant.
Embodiment 3
The La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst is the mesoporous of 10.3nm by mesoporous pore size Silica, average grain diameter be 4.7nm nickel is nanocrystalline and lanthana (La2O3) composition；Nickel is nanocrystalline to be carried on meso-porous titanium dioxide On silicon, and the nanocrystalline surface of nickel is attached with lanthana, wherein the molal quantity of lanthanum is La in lanthana2O3Cluster modifies Ni/ SiO2The 1% of the molal quantity of nano-composite catalyst.
It is prepared as follows the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst, it is specific to wrap Include following steps:
1) 26.7148Na is weighed2SiO3·9H2O is in beaker, then, 88.1532g deionized water is added and continues to stir To Na2SiO3·9H2O be completely dissolved mass fraction be 10% Na2SiO3Solution, then, under continuing magnetic force stirring condition To Na2SiO3Dust technology is added dropwise in solution, adjusts Na2SiO3The pH value of solution obtains solution A to 6, wherein dust technology is by dividing It is obtained after analysing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) 1.4540g Ni (NO is weighed3)2·6H2O (nickel nitrate) and 0.4301g La (NO3)3·6H2O (lanthanum nitrate) in In beaker, 15.0000g deionized water continuing magnetic force is added and stirs to being completely dissolved, solution B is obtained, then, in magnetic agitation item Under part, solution B is added dropwise in solution A, obtains solution C；
3) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 4.4ml to dilute will be analyzed Enter solution C, in drop then magnetic agitation is sealed with preservative film, and is placed in 90 DEG C of baking oven and is heated for 24 hours, old to carry out Change processing, obtains ageing products；
4) it after being filtered, being washed by ageing products, is dried at 180 DEG C for 24 hours sufficiently to dry it, then, is ground to 200 meshes are crossed, that is, the partial size of the ageing products after grinding is 200 mesh, obtains La2O3Cluster modifies Ni/SiO2Nano combined catalysis Agent.
By the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out xenon source irradiation stability and surveys Examination, specific testing procedure is the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature pass System is as shown in Figure 9.
As shown in Figure 9, after sustained response 6h, the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst Catalytic activity start to be remarkably decreased.
Embodiment 4
The La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst is the mesoporous of 15.3nm by mesoporous pore size Silica, average grain diameter be 4.3nm nickel is nanocrystalline and lanthana (La2O3) composition；Nickel is nanocrystalline to be carried on meso-porous titanium dioxide On silicon, and the nanocrystalline surface of nickel is attached with lanthana, wherein the molal quantity of lanthanum is La in lanthana2O3Cluster modifies Ni/ SiO2The 5% of the molal quantity of nano-composite catalyst.
It is prepared as follows the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst, it is specific to wrap Include following steps:
1) 25.5780g Na is weighed2SiO3·9H2O is in beaker, then, 84.4020g deionized water is added and persistently stirs It mixes to Na2SiO3·9H2O be completely dissolved mass fraction be 10% Na2SiO3Solution, then, in continuing magnetic force stirring condition It is lower to Na2SiO3Dust technology is added dropwise in solution, adjusts Na2SiO3The pH value of solution obtains solution A to 6, wherein dust technology be by It is obtained after analyzing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) 1.4540g Ni (NO is weighed3)2·6H2O (nickel nitrate) and 2.1650g La (NO3)3·6H2O (lanthanum nitrate) in In beaker, 15.0000g deionized water continuing magnetic force is added and stirs to being completely dissolved, solution B is obtained, then, in magnetic agitation item Under part, solution B is added dropwise in solution A, obtains solution C；
3) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 8.5ml to dilute will be analyzed Enter solution C, in drop then magnetic agitation is sealed with preservative film, and is placed in 90 DEG C of baking oven and is heated for 24 hours, old to carry out Change processing, obtains ageing products；
4) it after being filtered, being washed by ageing products, is dried at 180 DEG C for 24 hours sufficiently to dry it, then, is ground to 200 meshes are crossed, that is, the partial size of the ageing products after grinding is 200 mesh, obtains La2O3Cluster modifies Ni/SiO2Nano combined catalysis Agent.
By the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano-composite catalyst carries out xenon source irradiation stability and surveys Examination, specific testing procedure is the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature pass System is as shown in Figure 10.
As shown in Figure 10, after sustained response 25h, the La of the present embodiment2O3Cluster modifies Ni/SiO2Nano combined catalysis The catalytic activity of agent is not substantially reduced.
Comparative example 1
A kind of Ni/SiO that lanthanum not being added2Catalyst, preparation method include the following steps:
1) 15.0000g Na is weighed2SiO3·9H2Then O is added into 49.4968g deionized water and persistently stirs It mixes to Na2SiO3·9H2O is completely dissolved, and obtains Na2SiO3Solution, then, to Na under continuing magnetic force stirring condition2SiO3It is molten Dust technology is added dropwise in liquid, adjusts Na2SiO3The pH value of solution persistently stirs 30min after gel to be formed, obtains colloidal solution to 6 A, wherein dust technology is by obtaining after analyzing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) aging in 90 DEG C of baking ovens is put into after sealing colloidal solution A with preservative film for 24 hours, then, to filter, washing, and For 24 hours, grinding obtains SiO for drying at 180 DEG C2Powder；
3) 1.500gSiO is weighed2Powder, and be added into 35.0000g deionized water, continuing magnetic force stirring obtains Suspension B；
4) 0.3780gNi (NO is weighed3)2·6H2Then O is added into 15.0000g deionized water, continuing magnetic force Stirring obtains nickel nitrate solution to being completely dissolved；
5) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 1.1ml to dilute will be analyzed Enter nickel nitrate solution, the magnetic agitation in drop persistently stirs 25min, obtains suspension C after being added dropwise；
6) suspension C is added into suspension B, after persistently stirring 25min, is filtered, washing, and is dry at 180 DEG C For 24 hours, 200 meshes were ground to get the Ni/SiO of lanthanum is not added after to be dried2Catalyst.
By the Ni/SiO that lanthanum is not added of this comparative example2Catalyst carries out xenon source and irradiates stability test, specific to survey Try is suddenly the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature relationship such as Figure 11 institute Show.
As shown in Figure 11, after sustained response 4h, the Ni/SiO that lanthanum is not added of this comparative example2The catalytic activity of catalyst It quickly reduces, illustrates that its catalytic stability is lower than the La of 1~embodiment of embodiment 42O3Cluster modifies Ni/SiO2It is nano combined to urge The catalytic stability of agent.
To the Ni/SiO that lanthanum is not added of this comparative example2Catalyst carries out tem analysis, and test results are shown in figure 4.
As shown in Figure 4, the Ni/SiO that lanthanum is not added of this comparative example2The size of the Ni nano particle of catalyst is significantly greater than The La of embodiment 12O3Cluster modifies Ni/SiO2The Ni nano particle of nano-composite catalyst.
Comparative example 2
A kind of Ni/SiO that lanthanum not being added2Catalyst, preparation method include the following steps:
1) 5.7080g SiO is weighed2(commodity) are then added into 150ml deionized water, and continuing magnetic force stirs 25min is mixed, suspension A is obtained；
2) 1.4540g Ni (NO is weighed3)2·6H2Then O is added into the beaker that 7.6856g deionized water is housed In, continuing magnetic force stirs the nickel nitrate solution that 10% mass fraction is obtained to being completely dissolved；
3) nickel nitrate solution is slowly added dropwise into suspension A, the magnetic agitation when being added dropwise obtains solution B；
4) 4g NaOH is added into the beaker equipped with 36g deionized water, stirs to being completely dissolved, obtains 0.1mol/ The sodium hydroxide solution of 40g；
5) it takes 4g sodium hydroxide solution to be slowly dropped into solution B, and stirs 20min, then, obtained reaction product is taken out Filter, washing, and drying for 24 hours, was ground to 200 meshes to get the Ni/SiO of lanthanum is not added at 180 DEG C2Catalyst.
By the Ni/SiO that lanthanum is not added of this comparative example2Catalyst carries out xenon source and irradiates stability test, specific to survey Try is suddenly the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature relationship such as Figure 12 institute Show.
As shown in Figure 12, after sustained response 4h, the Ni/SiO that lanthanum is not added of this comparative example2The catalytic activity of catalyst It is substantially reduced, illustrates that its catalytic stability is lower than the La of 1~embodiment of embodiment 42O3Cluster modifies Ni/SiO2It is nano combined to urge The catalytic stability of agent.
Comparative example 3
A kind of lanthanum-carried catalyst on silica, preparation method include the following steps:
1) 27.8516g Na is weighed2SiO3·9H2Then O is added into 100ml deionized water, and magnetic agitation To Na2SiO3·9H2O is completely dissolved, and obtains Na2SiO3Solution, then, to Na under continuing magnetic force stirring condition2SiO3Solution Middle dropwise addition dust technology adjusts Na2SiO3The pH value of solution persistently stirs 30min after gel to be formed, obtains colloidal solution A to 6, Wherein, dust technology is by obtaining after analyzing 1: 4 dilution by volume of pure concentrated nitric acid and distilled water；
2) 0.8660gLa (NO is weighed3)3·6H2Then O is added into 15ml deionized water, and magnetic agitation is extremely La(NO3)3·6H2O is completely dissolved, and obtains lanthanum nitrate hexahydrate；
3) lanthanum nitrate hexahydrate is added to colloidal solution A, persistently stirs 20min, obtain solution B；
4) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 2.5ml to dilute will be analyzed Enter solution B, the magnetic agitation in drop persistently stirs 25min, then sealed with preservative film, is placed in 90 DEG C of bakings after being added dropwise Aging for 24 hours, obtains ageing products in case；
5) ageing products filtered, washed, and drying for 24 hours, was ground to 200 meshes to get two at 180 DEG C Lanthanum-carried catalyst on silica.
The catalyst lanthanum-carried on silica of this comparative example is subjected to xenon source and irradiates stability test, specifically Testing procedure is the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature relationship such as Figure 13 It is shown.
As shown in Figure 13, the catalyst lanthanum-carried on silica of this comparative example to methane dry method reforming reaction not There is catalytic activity.
Comparative example 4
One kind is in lanthanum sesquioxide (La2O3) on nickel-loaded catalyst, preparation method includes the following steps:
1) 14.2622gLa (NO is weighed3)3·6H2Then O is added into 50ml deionized water, and continuing magnetic force Stirring obtains lanthanum nitrate hexahydrate to being completely dissolved；
2) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 42ml to dilute will be analyzed Enter lanthanum nitrate hexahydrate, the magnetic agitation in drop persistently stirs 25min, then, sealed, be placed in preservative film after being added dropwise Aging for 24 hours, after to be aging, filters, washing in 90 DEG C of baking ovens, and the dry Muffle furnace that is put into afterwards for 24 hours is calcined at 180 DEG C 2h, wherein heating rate when calcining is 10 DEG C/min, wait calcine after grinding to get product A；
3) 3.5g product A is added in 50ml deionized water, continuing magnetic force stirring obtains suspension B；
4) 0.3200gNi (NO is weighed3)2·6H2Then O is added into 15ml deionized water, and continuing magnetic force stirs It mixes to being completely dissolved, obtains nickel nitrate solution；
5) 1: 5 dilution by volume of pure concentrated ammonia liquor and distilled water, weak aqua ammonia (lye) drop after taking 0.9ml to dilute will be analyzed Enter into nickel nitrate solution, carries out magnetic agitation in drop, 25min is persistently stirred after being added dropwise, obtains suspension C；
6) suspension C is added into suspension B, after continuing magnetic force stirs 25min, is filtered, washing, and at 180 DEG C Drying for 24 hours, was ground to 200 meshes to get the catalyst of the nickel-loaded on lanthanum sesquioxide after to be dried.
The catalyst of the nickel-loaded on lanthanum sesquioxide of this comparative example is subjected to xenon source and irradiates stability test, tool Body testing procedure is the same as embodiment 1, gained CH4And CO2Reaction rate and CO and H2Generating rate and temperature relationship as scheme Shown in 14.
As shown in Figure 14, after sustained response 4h, the catalyst of nickel-loaded on lanthanum sesquioxide of this comparative example is urged Change activity to be substantially reduced, illustrates that its catalytic stability is lower than the La of 1~embodiment of embodiment 42O3Cluster modifies Ni/SiO2Nanometer The catalytic stability of composite catalyst.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst, which is characterized in that the La2O3Cluster modifies Ni/ SiO2Nano-composite catalyst by mesoporous silicon oxide, nickel is nanocrystalline and lanthana forms；The nickel is nanocrystalline be carried on it is described On mesoporous silicon oxide, and the nanocrystalline surface of the nickel is attached with the lanthana.
2. La according to claim 12O3Cluster modifies Ni/SiO2Nano-composite catalyst, which is characterized in that the oxygen The molal quantity for changing lanthanum in lanthanum is the La2O3Cluster modifies Ni/SiO2The 0.5~5% of the molal quantity of nano-composite catalyst.
3. La according to claim 12O3Cluster modifies Ni/SiO2Nano-composite catalyst, which is characterized in that the nickel Nanocrystalline average grain diameter is 4~5nm；The mesoporous pore size of the mesoporous silicon oxide is 6.9~15.4nm.
4. preparing La described in claims 1 or 2 or 32O3Cluster modifies Ni/SiO2The method of nano-composite catalyst, feature It is, comprising the following steps:
1) Na is prepared2SiO3Solution, then, to the Na under lasting stirring condition2SiO3Diluted acid is added in solution, described in adjusting Na2SiO3The pH value of solution obtains solution A to 5~7；
2) nickel nitrate and lanthanum nitrate are mixed, and mixed nickel nitrate and lanthanum nitrate is configured to solution B, then, stirred Under the conditions of, the solution B is added into the solution A, solution C is obtained；
3) lye is added in Xiang Suoshu solution C, then, heating carries out aging process, obtains ageing products；
4) ageing products filtered, washed, dried, ground, obtain La2O3Cluster modifies Ni/SiO2It is nano combined to urge Agent.
5. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature exist In diluted acid described in the step 1) is dust technology, and the volume ratio of the diluted acid is 1: 2~1: 8.
6. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature exist In Na described in solution C described in the step 2)2SiO3, the nickel nitrate, the lanthanum nitrate molar ratio be (90~ 94.5): 5: (0.5~5).
7. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature exist In lye described in the step 3) is one of weak aqua ammonia, sodium hydroxide solution, potassium hydroxide solution or urea liquid.
8. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature exist 60% of lye amount needed for being theoretically to precipitate Ni and La completely in, the additive amount of lye described in the step 3)~ 120%.
9. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature exist It is 60~100 DEG C in the heating temperature of, heating described in the step 3), heating time is 12~for 24 hours.
10. La according to claim 42O3Cluster modifies Ni/SiO2The preparation method of nano-composite catalyst, feature It is, grinding described in the step 4) includes: that the ageing products after suction filtration, washing, drying are ground to partial size as 200 mesh.
CN201910092405.5A 2019-01-30 2019-01-30 A kind of La2O3Cluster modifies Ni/SiO2Nano-composite catalyst and preparation method thereof Pending CN109701543A (en)

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CN113385176B (en) * 2020-03-13 2023-09-05 中国石油化工股份有限公司 Hydrogenation saturation catalyst and preparation method and application thereof
CN113117675A (en) * 2021-04-10 2021-07-16 福州大学 Rhodium-erbium composite metal photo-thermal catalyst and preparation method and application thereof
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