CN110026199B - Lanthanum oxycarbonate modified aluminum oxide loaded nickel-based catalyst and preparation method thereof - Google Patents
Lanthanum oxycarbonate modified aluminum oxide loaded nickel-based catalyst and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 61
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 61
- 229910002226 La2O2 Inorganic materials 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000011068 loading method Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 56
- 230000009467 reduction Effects 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 4
- 238000002407 reforming Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000001354 calcination Methods 0.000 description 5
- 229910003303 NiAl2O4 Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- -1 after calcination Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
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- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000001666 catalytic steam reforming of ethanol Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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Abstract
The invention belongs to the technical field of supported catalysts, and discloses an alumina-supported nickel-based catalyst modified by lanthanum oxycarbonate and a preparation method thereof2O2CO3Modified Al2O3Is a carrier and is loaded with an active component Ni; the catalyst is prepared by adopting a step-by-step isometric impregnation method: firstly, Al is impregnated in Al by an equal volume impregnation method2O3Upper load La2O2CO3Then in CO2Is roasted in the atmosphere of (A) to obtain La2O2CO3Modified Al2O3A carrier; then loading Ni precursor in CO by using an equal volume impregnation method2Is roasted in the atmosphere of (A) to obtain La2O2CO3Modified Ni/Al2O3A catalyst. The catalyst of the invention is suitable for the reaction of preparing synthesis gas by reforming methane, and proves that La is used for preparing synthesis gas2O2CO3Can be prepared by adjusting Ni and Al2O3The mutual action between the two components improves the reduction capability of Ni, increases the reduction degree and the active surface area of Ni, and improves the catalytic activity and the stability.
Description
Technical Field
The invention belongs to the technical field of supported catalysts, and particularly relates to an alumina-supported nickel-based catalyst modified by lanthanum oxycarbonate and a preparation method thereof.
Background
As one of fossil fuels (petroleum, coal, natural gas), natural gas has the advantages of abundant and clean reserves, and the exploitation amount of natural gas is gradually increasing along with the breakthrough of shale gas exploitation technology. Therefore, how to efficiently convert and utilize natural gas has become a hot spot of research. The technology of shale gas exploitation in 2014 in China makes an important breakthrough and becomes a successive additionAfter canada and the united states, the third country that uses autonomous technical equipment for shale gas exploitation signed a 30 year natural gas ordering agreement with russia in the same year. Therefore, the proportion of natural gas in energy consumption in China is gradually increased, however, the utilization of natural gas in China is still in a relatively original low-level stage at present, most natural gas resources are used as fossil fuels for direct combustion, and therefore, the research on the technology capable of efficiently utilizing natural gas has great significance for future energy supply in China. Because the main component of natural gas is methane, the use of natural gas is essentially methane. However, the methane molecule has a highly symmetric tetrahedral configuration, its structure is very stable, and the C — H bond energy is as high as 438.8kJ/mol, which makes it difficult to synthesize the target product directly from methane. Therefore, the industry mostly uses an indirect conversion method, i.e. methane is firstly converted into synthesis gas, and then the target product is synthesized by the synthesis gas. At present, the widely studied technology for preparing synthesis gas from methane mainly comprises: methane Steam Reforming (SRM), methane dry gas reforming (DRM), methane Autothermal Reforming (ARM), methane Partial Oxidation (POM), and the like. Among them, DRM receives a wide attention because it has the following advantages: one, DRM may be employed with a CO-containing solution2The natural gas with impurities is used as a raw material to produce the synthesis gas, so that an expensive gas separation process is avoided, and the investment and operation cost of equipment is reduced; II, H in the product synthesis gas2: the theoretical ratio of CO is 1, and the synthesis gas with the ratio can be used for Fischer-Tropsch synthesis and can more selectively synthesize long-chain hydrocarbon and carbonyl oxygen-containing derivative. However, DRM, as a catalytic reaction process, has a bottleneck limiting industrialization, i.e., lack of a catalyst with high activity and long-term stability.
At present, catalysts used for DRM reactions are generally supported catalysts, in which common active components include two types of precious metals (Rh, Pt, Rh) and base metals (Ni, Co). The noble metal catalyst has high catalytic activity, carbon deposition tolerance, corrosion resistance and oxidation resistance. However, from the viewpoint of large-scale industrial application, Ni-based catalysts are the most interesting catalysts due to their high activity and low price. However, on the Ni-based catalyst, carbon deposition and sintering easily occur, and especially, severe carbon deposition of the catalyst is a main reason for limiting its industrial application. Therefore, how to improve the stability of the Ni-based catalyst is a problem that needs to be solved urgently.
In addition to the active metals, the properties of the support also have a significant effect on the performance of the catalyst. Al (Al)2O3As a carrier commonly used in industrial supported catalysts, the catalyst has the advantages of large specific surface area, good thermal stability and the like. Al (Al)2O3The base catalysts have a wide range of applications, from petrochemistry to automotive exhaust treatment, in addition, Al2O3Are themselves common acid catalysts for alcohol dehydration reactions. Wherein, Al is used2O3Ni/Al as carrier2O3The catalyst has been widely studied in DRM, and has advantages of large specific surface area, strong interaction with metal carrier, high metal dispersion degree and high catalytic activity, but due to Al2O3Is an acidic carrier and cannot provide activated CO2And thus, the catalyst is deactivated by the generation of a large amount of carbon during DRM. To increase Ni/Al2O3The carbon deposition inhibiting performance of the catalyst is generally realized by adding an alkaline auxiliary agent to improve the CO activation of the catalyst2Which inhibits carbon deposition, La is a more common basic promoter.
La2O3Has very good carbon deposition inhibiting performance, but has the problem of smaller specific surface area, so that La is adopted2O3Supported on a carrier with large specific surface area to improve La2O3Specific surface area of (2). After investigation, it was found that2O3Above, La2O3Tends to form a monolayer dispersed structure, and at low loading, La2O3Preferentially occupy unsaturated coordinated Al sites, and gradually form a monolayer dispersed structure along with the increase of the loading amount. In addition, the addition of La stabilizes Al2O3And the inhibition of high-temperature sintering of the catalyst, such as the application of the catalyst in high-temperature catalytic combustion reaction, is also one of the reasons for the La serving as a component in a three-way catalyst for treating automobile exhaust. Therefore, we hope to put La2O3Loaded to Al in the form of single-layer dispersion2O3On a support to increase La2O3Specific surface area of (2) while La2O3May be further covered with Al2O3Acid sites on the surface, so that La can be exerted simultaneously2O3And Al2O3Their advantages are high effect on improving their advantages and low cost. Gong et al [ Efficient hydrogen production from ethylene glycol step reforming over La-modified ordered mesoporous Ni-based catalysts. applied Catalysis B: Environmental,2016,181,321-]La modified Ni/Al was intensively studied2O3The catalyst is used for ethanol steam reforming reaction, and the addition of La is found to improve Ni and Al2O3The mutual action between the two components improves the reduction capability of Ni, increases the active surface area of Ni, improves the catalytic activity, and simultaneously, the addition of La improves the alkalinity of the catalyst and promotes CO2The carbon deposition is suppressed. However, the optimum amount of La added is much lower than the monolayer loading, and when the amount of La added is too large, the activity of the catalyst is significantly reduced. The reason for the analysis is that La2O3At single layer loadings, Ni particles can be coated, resulting in a reduction in catalyst activity. Garbarino et Al [ A study of Ni/La-Al2O3catalysts:A competitive system for CO2methanation.Applied Catalysis B:Environmental,2018,65,178-192.]The study also found that La is present in a single layer2O3Modified Al2O3On the support, Ni is still formedxAl2O3+x。
Disclosure of Invention
The invention aims to solve the problem that La is used2O3Modified Ni/Al2O3The technical problem that Ni is easily covered and is difficult to reduce during the catalyst process is provided, and the nickel-based catalyst loaded on alumina modified by lanthanum oxycarbonate and the preparation method thereof are provided, and the nickel-based catalyst is designed in CO2So that the firing is covered with La2O2CO3Rather than La2O3Thereby preventing Ni from entering Al during firing2O3OfSurface layer La2O3The coated catalyst can improve the stability and the catalytic activity.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a lanthanum oxycarbonate modified aluminum oxide loaded nickel-based catalyst is prepared by uniformly dispersing Ni nanoparticles in La2O2CO3Modified Al2O3The surface of the carrier, based on the total mass of the catalyst, of the La in the catalyst2O2CO3The loading amount of the Ni nano-particles is 20-25 wt.%, and the loading amount of the Ni nano-particles is 1-10 wt.%.
Furthermore, the particle size of the Ni nano-particles is 7.5-10.4 nm.
Further, the La2O2CO3Modified Al2O3La in the support2O2CO3Is in CO2And roasting the obtained product in an atmosphere.
Further, the catalyst is prepared by a step-by-step equal volume impregnation method.
A preparation method of the lanthanum oxycarbonate modified aluminum oxide supported nickel-based catalyst comprises the following steps:
(1) according to La2O2CO3The supported amount of the lanthanum nitrate is 20-25 wt.%, lanthanum nitrate hexahydrate is dissolved in deionized water to obtain a precursor solution of lanthanum nitrate, and then the obtained precursor solution of lanthanum nitrate is impregnated into Al2O3The above step (1);
(2) drying the sample obtained in the step (1) to dryness, and then adding CO2Roasting for 4-6 hours at the temperature of 600-700 ℃ in the atmosphere to obtain La2O2CO3Modified Al2O3A carrier;
(3) according to the load capacity of the Ni nano particles being 1-10 wt.%, nickel nitrate hexahydrate is dissolved in deionized water to prepare a precursor solution of nickel; la obtained in the step (2)2O2CO3Modified Al2O3Soaking the carrier in the nickel precursor solution in the same volume, drying the sample to be dry, grinding the sample in CO2Is roasted at 600-700 ℃ for 4-6H, and then at the same reaction temperature as the roasting temperature and 10-20 vol.% of H2/N2And reducing for 1-2 h under the atmosphere to obtain the target catalyst.
The invention has the beneficial effects that:
the invention is prepared by mixing La2O2CO3Loaded on Al2O3Surface of (1) so that Al2O3The acid sites on the surface are covered, so that the basic sites on the surface of the catalyst are increased, and CO is promoted2The activation of the catalyst inhibits the generation of carbon deposition in the reaction process;
(II) the invention is characterized in that La is added2O2CO3Loaded on Al2O3The surface of the catalyst increases the specific surface area of La, improves the dispersion of Ni, reduces the particle size of Ni, increases the active surface area of Ni and further improves the catalytic reaction activity;
(III) the invention is realized by mixing La2O2CO3Loaded on Al2O3Surface of La is avoided2O3Loaded on Al2O3On the surface, Ni is introduced into Al2O3Is La2O3The occurrence of such an adverse phenomenon as coating;
(IV) preparation method of the invention to obtain La2O2CO3Modified Al2O3The carrier is impregnated in Al by an equal volume method2O3Loading La precursor on the substrate, and then passing through the catalyst in the presence of CO2Is calcined in the atmosphere of (A) to obtain La2O2CO3Modified Al2O3And (3) a carrier.
In conclusion, the catalyst prepared by the invention can be applied to the process of preparing synthetic gas by reforming methane dry gas and the like which require CO2The reaction system for activating and eliminating the carbon deposition in time has excellent catalytic performance and thermal stability and long service life.
Drawings
FIG. 1 is La prepared as in example 22O2CO3Modified Ni/Al2O3The reactivity of the catalyst;
FIG. 2 is La prepared in example 1 and example 42O2CO3Modified Ni/Al2O3TEM images of the catalyst;
wherein (a) is a TEM image of the catalyst prepared in example 1 and (b) is a TEM image of the catalyst prepared in example 4;
FIG. 3 is La prepared in example 52O2CO3Modified Ni/Al2O3The catalyst was characterized by Raman spectroscopy after calcination and reduction.
Detailed Description
The present invention is further described in detail below by way of specific examples, which will enable one skilled in the art to more fully understand the present invention, but which are not intended to limit the invention in any way.
Example 1
According to La2O2CO3The supported amount of the lanthanum nitrate is 20 wt.%, lanthanum nitrate hexahydrate is dissolved in deionized water to obtain a precursor solution of lanthanum nitrate, and then the obtained precursor solution of lanthanum nitrate is impregnated into Al2O3Drying the obtained sample, and then in CO2Is roasted for 4 hours at the temperature of 650 ℃ in the atmosphere of (1) to obtain La2O2CO3Modified Al2O3A carrier;
(II) according to La2O2CO3Modified Ni/Al2O3The Ni loading in the catalyst was 5.5 wt.%, nickel nitrate hexahydrate (Ni (NO) was taken3)2·6H2O) is dissolved in deionized water to prepare Ni precursor solution, and the prepared La is2O2CO3Modified Al2O3Soaking a carrier in Ni precursor solution in the same volume, drying a sample to be dry, grinding the sample in CO2Is roasted at 650 ℃ for 5h, and then is roasted at the same temperature as the roasting temperatureReaction temperature and 10 vol.% H2/N2Reducing for 1.5h under the atmosphere to obtain the target catalyst.
Example 2
La by the method of example 12O2CO3Modified Ni/Al2O3Preparation of the catalyst, distinguished by La in (A)2O2CO3Was 21 wt.%, and the sample was then placed in CO2Roasting for 5 hours at 670 ℃ in the atmosphere of (A) to obtain La2O2CO3Modified Al2O3And (3) a carrier. The loading amount of Ni in the second step is 1 wt.%, the roasting condition is that the roasting is carried out for 4 hours at 650 ℃, and the reduction condition is that 20 vol% of H2/N2And reducing for 2h under the atmosphere.
Example 3
La by the method of example 12O2CO3Modified Ni/Al2O3Preparation of the catalyst, distinguished by La in (A)2O2CO3Was 22.5 wt.%, and the sample was then placed in CO2Is roasted for 6 hours at the temperature of 600 ℃ in the atmosphere of (A) to obtain La2O2CO3Modified Al2O3And (3) a carrier. The loading amount of Ni in the second step is 1 wt.%, the roasting condition is that the roasting is carried out for 4 hours at 600 ℃, and the reduction condition is that 20 vol% of H2/N2And reducing for 2h under the atmosphere.
Example 4
La by the method of example 12O2CO3Modified Ni/Al2O3Preparation of the catalyst, distinguished by La in (A)2O2CO3Was 24 wt.%, and the sample was then placed in CO2Is roasted for 5.5 hours at the temperature of 650 ℃ in the atmosphere of (1) to obtain La2O2CO3Modified Al2O3And (3) a carrier. The loading amount of Ni in the second step is 3 wt.%, the roasting condition is that the roasting is carried out for 4H at 670 ℃, and the reduction condition is 15 vol% of H2/N2Reducing for 1h under the atmosphere.
Example 5
La by the method of example 12O2CO3Modified Ni/Al2O3Preparation of the catalyst, distinguished by La in (A)2O2CO3Was 25 wt.%, and the sample was then placed in CO2Is roasted for 5 hours at the temperature of 700 ℃ in the atmosphere of (A) to obtain La2O2CO3Modified Al2O3And (3) a carrier. The loading amount of Ni in the second step is 10 wt.%, the roasting condition is that the roasting is carried out for 6H at 700 ℃, and the reduction condition is that the reduction condition is 15 vol% of H2/N2Reducing for 1h under the atmosphere.
Discussion of results and data with respect to the above examples:
la prepared in the above-mentioned examples 1 to 5 of the present invention2O2CO3Modified Ni/Al2O3Catalyst-based detailed examination of La2O2CO3The influence of the modification on the catalyst structure and the reaction performance.
(I) La2O2CO3Modified Ni/Al2O3Reaction performance of catalyst
Tabletting catalyst sample powder to 20-40 meshes, loading the prepared catalyst sample into a fixed bed reactor, controlling the bed temperature of the reactor to be 650 ℃, and controlling the volume space velocity of methane to be 36,000 mL.h-1·gcat-1Reaction gas is introduced for reaction, wherein the molar ratio of methane to carbon dioxide is 1:1, and the balance gas is nitrogen.
Catalyst activity in terms of methane conversion, carbon dioxide conversion and H in product2Expressed as/CO, methane conversion, carbon dioxide conversion and H in the product2the/CO is calculated by the following formula:
Yi=Xi×Si×1OO%
the results of the activity test of example 2 are shown in fig. 1. It can be seen that the catalyst has higher activity and selectivity and exhibits better stability. La prepared for the remaining examples2O2CO3Modified Ni/Al2O3The catalyst is also subjected to the same activity test, and the result shows that all the catalysts have good activity and stability.
(II) La2O2CO3Modified Ni/Al2O3Structural analysis of catalyst
La prepared in example 1 and example 42O2CO3Modified Ni/Al2O3The catalyst was characterized by transmission electron microscopy, and the results are shown in FIG. 2. It can be seen that the Ni particles are very uniformly dispersed on the mesoporous lanthana support. And the particle size range of Ni is concentrated in 7.5-10.4 nm.
In order to analyze the presence of Ni on the catalyst, the catalyst prepared in example 5 was characterized by Raman spectroscopy after calcination and reduction, and the results are shown in fig. 3. It can be observed that for 5Ni/Al2O3Catalyst, after calcination, Ni is present in two forms: lattice Ni[135](into Al)2O3Subsurface Ni) and NiAl2O4 [4,137]. After reduction, the Lattice Ni is reduced to metallic Ni, NiAl2O4It is difficult to be reduced. For 5Ni/La2O3-Al2O3Catalyst in the calcination ofThereafter, Ni exists in three forms: NiO[138]Lattic Ni and NiAl2O4. Comparing the catalysts after reduction, it can be found that only NiO is reduced during the reduction process, and Lattice Ni and NiAl2O4Are difficult to reduce. In contrast, for 5Ni/La2O2CO3-Al2O3The catalyst, after calcination, has Ni present predominantly as NiO, which is reduced to metallic Ni during the reduction process. This is consistent with our previous characterization analysis, i.e., for 5Ni/La2O3-Al2O3The catalyst has a great amount of Ni entering Al in the roasting process2O3In the crystal lattice to result in La being a monolayer2O3Coated to be difficult to be reduced, and for 5Ni/La2O2CO3-Al2O3Catalyst, La2O2CO3Can prevent Ni from entering Al2O3The subsurface layer of (2) prevents Ni from being coated, thereby improving the reduction degree of Ni.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (3)
1. The lanthanum oxycarbonate modified aluminum oxide supported nickel-based catalyst is characterized in that Ni nanoparticles are uniformly dispersed in La2O2CO3Modified Al2O3A carrier surface; based on the total mass of the catalyst, the La in the catalyst2O2CO3The loading amount of the Ni nanoparticles is 20-25 wt.%, and the loading amount of the Ni nanoparticles is 1-10 wt.%; and is obtained by the following preparation process:
(1) push buttonShine La2O2CO3The supported amount of the lanthanum nitrate is 20-25 wt.%, lanthanum nitrate hexahydrate is dissolved in deionized water to obtain a precursor solution of lanthanum nitrate, and then the obtained precursor solution of lanthanum nitrate is impregnated into Al2O3The above step (1);
(2) drying the sample obtained in the step (1) to dryness, and then adding CO2Roasting for 4-6 hours at the temperature of 600-700 ℃ in the atmosphere to obtain La2O2CO3Modified Al2O3A carrier;
(3) according to the load capacity of the Ni nano particles being 1-10 wt.%, nickel nitrate hexahydrate is dissolved in deionized water to prepare a precursor solution of nickel; la obtained in the step (2)2O2CO3Modified Al2O3Soaking the carrier in the nickel precursor solution in the same volume, drying the sample to be dry, grinding the sample in CO2Is roasted at 600-700 ℃ for 4-6H, and then at the same reaction temperature as the roasting temperature and 10-20 vol.% of H2/N2And reducing for 1-2 h under the atmosphere to obtain the target catalyst.
2. The lanthanum oxycarbonate modified alumina supported nickel-based catalyst of claim 1, wherein the Ni nanoparticles have a particle size of 7.5-10.4 nm.
3. A method for preparing a lanthanum oxycarbonate modified alumina supported nickel-based catalyst according to any of claims 1-2, characterized in that it is carried out according to the following steps:
(1) according to La2O2CO3The supported amount of the lanthanum nitrate is 20-25 wt.%, lanthanum nitrate hexahydrate is dissolved in deionized water to obtain a precursor solution of lanthanum nitrate, and then the obtained precursor solution of lanthanum nitrate is impregnated into Al2O3The above step (1);
(2) drying the sample obtained in the step (1) to dryness, and then adding CO2Roasting for 4-6 hours at the temperature of 600-700 ℃ in the atmosphere to obtain La2O2CO3Modified Al2O3A carrier;
(3) according to the load capacity of the Ni nano particles being 1-10 wt.%, nickel nitrate hexahydrate is dissolved in deionized water to prepare a precursor solution of nickel; la obtained in the step (2)2O2CO3Modified Al2O3Soaking the carrier in the nickel precursor solution in the same volume, drying the sample to be dry, grinding the sample in CO2Is roasted at 600-700 ℃ for 4-6H, and then at the same reaction temperature as the roasting temperature and 10-20 vol.% of H2/N2And reducing for 1-2 h under the atmosphere to obtain the target catalyst.
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