CN113600200A - Preparation method of anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst - Google Patents
Preparation method of anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 36
- 150000001342 alkaline earth metals Chemical class 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 230000008021 deposition Effects 0.000 title claims abstract description 22
- 238000002407 reforming Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 239000003292 glue Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000000969 carrier Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052712 strontium Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910018307 LaxSr1−x Inorganic materials 0.000 claims description 7
- 238000003980 solgel method Methods 0.000 claims description 6
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910001427 strontium ion Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001301 oxygen Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 79
- 239000011777 magnesium Substances 0.000 description 29
- 229910052759 nickel Inorganic materials 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- 229910002244 LaAlO3 Inorganic materials 0.000 description 9
- 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 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000006057 reforming reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 3
- 229960002303 citric acid monohydrate Drugs 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- -1 magnesium alkaline earth metal salt Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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
- B01J37/0201—Impregnation
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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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of an anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst, which comprises the following steps: mixing one of the three alkaline earth metal raw materials according to a certain molar mass ratio to form a mixture, and adding 1-2 times of the mixtureMixing and dissolving citric acid with metal ion molar mass in the mixture to obtain mixed sol; evaporating the mixed sol to dryness to obtain gel, and transferring the gel into a drying oven to be dried to obtain dry gel; pretreating the dry glue in a muffle furnace, roasting the dry glue in the muffle furnace in a heat preservation manner, and cooling to obtain a perovskite carrier; then Ni (NO)3)3Adding different perovskite carriers into the solution to respectively obtain Ni-based alkaline earth metal modified catalysts; the invention has more active oxygen species, the oxygen species can eliminate carbon deposition on the surface of the catalyst, the carbon deposition resistance of the catalyst is improved, the number of alkali centers of the catalyst modified by adding alkaline earth metal is obviously increased, the size of the obtained Ni particles is smaller, and the dispersion degree of Ni is higher.
Description
Technical Field
The invention relates to alkaline earth metal modified Ni/LaxM1-xAlO3(M = Mg, Ca, Sr) catalytic material and its use in methane dry gas reforming.
Technical Field
CO, the cheapest and abundant carbon resource in the C1 family2Resource recycling is an important road for realizing low-carbon economy. Search for efficient and cheap CO2Resource utilization method for large-scale CO2The realization of harmonious interpersonal relation between human and nature is the most concerned research topic of scientists all over the world: the methane dry gas reforming reaction can simultaneously convert two greenhouse gases of methane and carbon dioxide into synthesis gas, and effectively relieve the greenhouse effect. In the early twentieth century, the german scientists tropisch and Fisher studied the dry gas reforming of methane with carbon dioxide. Up to 1991, Ashcroft et al proposed that methane dry gas reforming could produce low H2The theory of syngas/CO ratio, methane dry gas reforming reactions, has gradually attracted the world scientists' extensive attention. The methane carbon dioxide reforming reaction has the following characteristics:
h in product syngas2The ratio of/CO is about 1, and the catalyst can be directly used as a raw material for oxo synthesis or Fischer-Tropsch synthesis, so that the defect of high hydrogen-carbon ratio in a synthesis gas product prepared by methane steam reforming is overcome;
methane and carbon dioxide in the reactants belong to greenhouse gases, so the reaction is favorable for improving the ecological environment of human beings;
methane twoCarbon oxide reforming is a reversible reaction with a large heat of reaction and can serve as an energy storage medium. Therefore, the subject has multiple research significances such as economy, environmental protection, science and the like.
To make inert small molecule gas CO2And methane dry gas CH4Can be simultaneously activated and directionally converted into CO and H in reforming reaction2And thus to perform activated conversion, a suitable catalyst needs to be selected. However, the catalyst is easy to generate a large amount of carbon deposition in the reaction process due to the side reactions such as methane cracking, carbon monoxide disproportionation and the like, and finally the catalyst is easy to deactivate. At present, the Ni-based catalyst is an ideal catalyst for reforming hydrogen production because of relatively low price and high initial activity, but the Ni-based catalyst is also easily inactivated quickly due to Ni particle aggregation and serious carbon deposition in the high-temperature reforming reaction process. Researchers have conducted a great deal of research on improving the sintering resistance and carbon deposition resistance of the Ni-based catalyst. Researches show that the composition of the catalyst, the synergistic effect of the auxiliary agent, the interaction between the metal and the carrier, the pH value and the like are key factors influencing the microstructure, the dispersity, the reducibility, the reaction activity and the carbon deposition resistance of the active site of the catalyst, and the technical key point is that Ni with uniform particle size and small size is obtained on the premise of high nickel loading and is also a methane dry gas reforming catalyst.
Perovskite materials have been widely used in the field of catalysis due to their advantages of stable structure, easy control of A, B site, and excellent high-temperature thermal stability. In the reforming reaction of the dry methane gas, the alkali center can activate carbon dioxide, and dissociated oxygen can remove carbon deposit on the surface of the catalyst in time, so that the method has a very positive effect on the aspects of improving the conversion rate of the carbon dioxide and increasing the stability of the catalyst, but the number of the alkali centers of the regular perovskite structure is not obvious, and the improvement of the activity and the carbon deposit resistance of the catalyst can be influenced.
Disclosure of Invention
In view of the defects of the existing hydrogen production technology by methane dry gas reforming, the invention aims to provide a low-temperature methane reforming nickel-based catalyst with high dispersion and excellent carbon deposition resistance and application thereof, which are used for overcoming the defects of poor stability, easy sintering of components and serious carbon deposition of the existing methane dry gas reforming catalyst.
In order to solve the technical problems, the invention comprises the following components: the preparation method of the anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst comprises the following technical scheme: the preparation method is to prepare La by a sol-gel methodxM1-xAlO3Perovskite carrier, and then Ni/La is prepared by dipping methodxM1-xAlO3(M = Mg, Ca, Sr), said X being the molar mass of the La ion, said process comprising the steps of:
A. adding La (NO)3)3·6H2O and Al (NO)3)3·9H2O and Mg (NO)3)2·6H2O，Ca(NO3)2·4H2O, Sr (NO3), mixing one of the three alkaline earth metal raw materials according to a certain molar mass ratio to form a mixture, adding citric acid with the molar mass being 1-2 times that of metal ions in the mixture into the mixture, mixing and dissolving, and fully stirring at room temperature to obtain mixed sol;
B. evaporating the mixed sol to dryness in a water bath at 60-90 ℃ until a gel is obtained, and transferring the gel to 100 ℃
Drying in an oven at 130 ℃ to obtain fluffy dry glue; placing the dry glue in a muffle furnace at 160-200 ℃ for pretreatment, transferring the pretreated dry glue into the muffle furnace at 600-1000 ℃ for heat preservation and roasting, and cooling to obtain Ni/La respectivelyxM1-xAlO3A perovskite support; m is Mg, Ca and Sr ions;
C. a certain amount of Ni (NO)3)3·6H2Dissolving O in container completely, adding water to obtain solution, adding different perovskite carriers, stirring at room temperature to completely impregnate the perovskite carriers, and finally obtaining Ni/La respectivelyxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3The Ni-based alkaline earth metal-modified catalyst of (1).
The preparation method adopts a sol-gel methodPreparation of LaxM1-xAlO3(M = Mg, Ca, Sr) perovskite carrier, and then Ni (NO) is used by adopting an impregnation method3)3Preparing Ni/La by solutionxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3The Ni-based alkaline earth metal-modified catalyst of (1).
The four Ni-based alkaline earth metal modified catalysts are prepared from the following raw materials in parts by weight:
1、LaAlO3the raw materials are as follows: la (NO)3)3·6H2O (lanthanum nitrate hexahydrate), Al (NO)3)3·9H2O
2、Ni/LaxMg1-xAlO3The raw materials are as follows: la (NO)3)3·6H2O (lanthanum nitrate hexahydrate), Al (NO)3)3·9H2O and Mg (NO)3)2·6H2O，
3、Ni/LaxCa1-xAlO3The raw materials are as follows: la (NO)3)3·6H2O (lanthanum nitrate hexahydrate), Al (NO)3)3·9H2O and Ca (NO)3)2·4H2O
4、Ni/LaxSr1-xAlO3The raw materials are as follows: la (NO)3)3·6H2O (lanthanum nitrate hexahydrate), Al (NO)3)3·9H2O and Sr (NO)3)2。
According to the invention, alkaline earth metal (Mg, Ca and Sr) is used for bulk phase modification of LaAlO3, and the alkaline earth metal is doped into perovskite lattices to partially replace La element (lanthanide) at A position so as to prepare the high-performance catalyst. Therefore, the doping amount of the alkaline earth metal is limited to a certain extent, and the molar ratio of M/(La + M) is not more than 0.2, and if more than, the alkaline earth metal cannot completely enter the position of the perovskite lattice. And the catalyst carrier is loaded with Ni groups by an impregnation method and then used for hydrogen production by methane dry gas reforming, so that the activity and the carbon deposition resistance of the catalyst can be effectively improved. The catalyst has good dispersity of active metal nickel, and can be observed from XRD pattern of reduced catalystThe three elements of Mg, Ca and Sr enter the crystal lattice of the perovskite, and XPS results show that the alkaline earth metal doped and modified catalyst has more active oxygen species on the surface and can effectively inhibit the generation of carbon deposition in high-temperature reaction. Ni/La prepared by adopting the methodxM1-xAlO3(M = Mg, Ca, Sr) catalyst at atmospheric pressure in the reaction gas CH4And CO2The composition is 1:1, and the space velocity is 18000 ml.gcat -1 .h-1Reaction temperature of 750 deg.CoAnd C shows excellent activity and stability under the reaction condition, and has strong anti-carbon deposition and anti-sintering performance. The preparation method disclosed by the invention has the characteristics of simplicity, easiness in operation, capability of reducing the preparation cost of the catalyst and the like, and can meet the requirements of industrialization on the activity and the service life of the catalyst when being used for hydrogen production by reforming the methane dry gas.
The prepared catalyst is prepared into La by adopting a sol-gel methodxM1-xAlO3(M = Mg, Ca and Sr), and an active component is loaded by an impregnation method to prepare Ni/LaxM1-xAlO3The Ni-based alkaline earth metal modified catalyst (M = Mg, Ca, Sr) has reduced carbon deposition on the catalyst surface and more excellent stability based on the addition of the alkaline earth metal.
The catalyst synthesized by the method has more active oxygen species on the surface, and the oxygen species can eliminate carbon deposition on the surface of the catalyst.
The number of alkali centers of the catalyst modified by adding the alkaline earth metal is obviously increased, the size of the obtained Ni particles is smaller, and the dispersion degree of Ni is higher.
The catalyst is 600-800oAnd C, the activity and stability evaluation is carried out at the temperature, and the excellent catalytic activity and high-temperature thermal stability are shown.
The invention relates to unmodified Ni/LaAlO3Catalyst (example 1) comparison, Ni/La according to the inventionxM1-xAlO3The Ni-based alkaline earth metal modified catalyst of (M = Mg, Ca, Sr) has the following advantages:
1. more active oxygen species are arranged on the surface of the catalyst, and the oxygen species can eliminate carbon deposition on the surface of the catalyst and improve the carbon deposition resistance of the catalyst;
2. the number of alkali centers of the catalyst modified by adding the alkaline earth metal is obviously increased, the size of the obtained Ni particles is smaller, and the dispersion degree of Ni is higher.
Drawings
FIG. 1 shows Ni/La with 5% of nickel by mass0.9M0.1AlO3(M = Mg, Ca, Sr) catalyst (10% H)2-Ar gas mixture 700oC reduction for 3 hours),
FIG. 2 shows 5% Ni/La of the present invention0.9M0.1AlO3(M = Mg, Ca, Sr) catalyst stability test results for 50 hours,
FIG. 3 shows 5% Ni/La of the present invention0.9M0.1AlO3(M = Mg, Ca, Sr) thermogravimetric test result chart of the catalyst.
Detailed Description
The invention will be understood by the following examples and the accompanying drawings, but the scope of the claims of the present invention is not limited to the contents of the following examples.
Example 1
This example 1 is based on the prior art Ni/LaAlO3The catalyst is not modified by alkaline earth metal, but directly prepared by mixing Ni/LaAlO3The catalyst is impregnated to obtain 5 percent Ni/LaAlO3The Ni-based alkaline earth metal modified catalyst is prepared by the following steps:
LaAlO is prepared by a sol-gel method according to the prior art3Then preparing 5 percent Ni/LaAlO by adopting an impregnation method3A catalyst. The specific synthetic process is as follows: 2.1650gLa (NO)3)3·6H2O (lanthanum nitrate hexahydrate) and 1.8756gAl (NO)3)3·9H2Mixing and dissolving O as a base material and 3.1521g of citric acid monohydrate, stirring for 6 hours at room temperature to obtain mixed sol, evaporating to dryness in a water bath at 80 ℃ until gel is obtained, and transferring the gel to a 110 ℃ oven for overnight drying to obtain fluffy dry gel; placing the dry glue in a 180 ℃ muffle furnace for pretreatment to prevent the occurrence of bumping in the later roasting, and transferring the pretreated dry glue to a 800 ℃ muffle furnace for roastingThe mixture is sintered for 6 hours, and the heating rate is 2 ℃ per min. Finally obtaining unmodified LaAlO3A perovskite support. 0.5215gNi (NO)3)3·6H2Dissolving O in water in a beaker to obtain Ni (NO) with mass percent concentration of 5 percent after complete dissolution3)3Solution, then Ni (NO)3)3Adding 2g of perovskite carrier into the solution, fully stirring the solution at room temperature for 24 hours to completely immerse the perovskite carrier on the carrier, then transferring the perovskite carrier to a 80 ℃ water bath for evaporation, then transferring the perovskite carrier to a 110 ℃ oven for overnight drying, and finally transferring the perovskite carrier to a 600 ℃ muffle furnace for roasting for 4 hours to obtain the modified 5% Ni/LaAlO3Ni-based alkaline earth metal modified catalyst, wherein the molar ratio of M/(La + M) is 0, i.e., M is 0 (no alkaline earth metal is incorporated), and then the above catalyst was placed at a flow rate of 60mL/min and a volume percentage of 10% H2Reducing in situ for 3h in a fixed bed reactor under the condition of-Ar mixed gas atmosphere and the temperature of 700 ℃ to obtain reduced 5 percent Ni/LaAlO3Used in methane carbon dioxide reforming catalyst.
Example 2
5%Ni/La0.9Mg0.1AlO3The preparation method of the Ni-based alkaline earth metal modified catalyst comprises the following steps: with La (NO)3)3·6H2O (lanthanum nitrate hexahydrate) and Al (NO)3)3·9H2O and Mg (NO)3)2·6H2Mixing O (magnesium alkaline earth metal salt), and preparing La by a sol-gel method0.9Mg0.1AlO3Prepared by adopting an impregnation method to obtain 5 percent of Ni/La0.9Mg0.1AlO3The catalyst comprises the following specific synthetic processes: 1.9485gLa (NO)3)3·6H2O (lanthanum nitrate hexahydrate), 1.8756gAl (NO)3)3·9H2O and 0.1282gMg (NO)3)2·6H2Mixing and dissolving O and 3.1521g of citric acid monohydrate, stirring for 6 hours at room temperature to obtain mixed sol, evaporating to dryness in a water bath at 80 ℃ until gel is obtained, and transferring the gel to a 110 ℃ oven for overnight drying to obtain fluffy dry gel; placing the dry glue in a 180 ℃ muffle furnace for pretreatment to prevent the dry glue from bumping during later roasting, and transferring the pretreated dry glue to 800Roasting in a muffle furnace at the temperature of 2 ℃ for 6 hours, and heating at the speed of 2 ℃ per min. Finally obtaining modified La0.9Mg0.1AlO3A perovskite support. 0.5215gNi (NO)3)3·6H2Dissolving O in a beaker to obtain Ni (NO) with the mass percent concentration of 5 percent after complete dissolution3)3Solution, then Ni (NO)3)3Adding 2g of perovskite carrier into the solution, fully stirring the solution at room temperature for 24 hours to completely immerse the perovskite carrier on the carrier, then transferring the perovskite carrier to a 80 ℃ water bath for evaporation, then transferring the perovskite carrier to a 110 ℃ oven for overnight drying, finally transferring the perovskite carrier to a 600 ℃ muffle furnace for roasting for 4 hours, and cooling the perovskite carrier to obtain 5% Ni/La0.9Mg0.1AlO3The Ni-based alkaline earth metal-modified catalyst of (1), wherein the molar ratio of Mg/(La + Mg) is 0.1, i.e., Mg is 0.1 (corresponding to 5% of Ni/La)0.9Mg0.1AlO3X in the Ni-based alkaline earth metal modified catalyst of (1) is 0.9), and the catalyst is placed at a flow rate of 60ml/min and a volume of 10% H2Reducing in situ for 3h in a fixed bed reactor under the condition of-Ar mixed gas atmosphere and the temperature of 700 ℃ to obtain reduced 5% Ni/La0.9Mg0.1AlO3Used in methane carbon dioxide reforming catalyst.
Example 3
5%Ni/La0.8Ca0.2AlO3The preparation method of the Ni-based alkaline earth metal modified catalyst comprises the following steps: preparing La by a sol-gel method0.8Ca0.2AlO3The carrier is prepared by adopting an impregnation method to obtain 5 percent of Ni/La0.8Ca 0.2AlO3The Ni-based alkaline earth metal modified catalyst has the specific synthesis process as follows: 1.7320gLa (NO)3)3·6H2O (lanthanum nitrate hexahydrate), 1.8756gAl (NO)3)3·9H2O and 0.2362gCa (NO)3)2·4H2Mixing and dissolving O and 3.1521g of citric acid monohydrate, stirring for 6 hours at room temperature to obtain mixed sol, evaporating to dryness in a water bath at 80 ℃ until gel is obtained, and transferring the gel to a 110 ℃ oven for overnight drying to obtain fluffy dry gel; placing the dry glue in a 180 ℃ muffle furnace for pretreatment to prevent the dry glue from bumping during later roasting, and pretreating the pretreated dry glueAnd transferring the mixture to a 800 ℃ muffle furnace for roasting for 6 hours, wherein the heating rate is 2 ℃ per min. Finally obtaining modified La0.8Ca0.2AlO3A perovskite support. 0.5215gNi (NO)3)3·6H2Dissolving O in a beaker to obtain Ni (NO) with the mass percent concentration of 5 percent after complete dissolution3)3Solution, then Ni (NO)3)3Adding 2g of perovskite carrier into the solution, fully stirring the solution at room temperature for 24 hours to completely immerse the perovskite carrier on the carrier, then transferring the perovskite carrier to a 80 ℃ water bath for evaporation, then transferring the perovskite carrier to a 110 ℃ oven for overnight drying, finally transferring the perovskite carrier to a 600 ℃ muffle furnace for roasting for 4 hours, and cooling the perovskite carrier to obtain 5% Ni/La0.8Ca0.2AlO3The Ni-based alkaline earth metal-modified catalyst of (1), wherein the molar ratio of Ca/(La + Ca) is 0.2, i.e., Ca is 0.2 (corresponding to 5% Ni/La)0.8Ca0.2AlO3X of the Ni-based alkaline earth metal modified catalyst of (1) ═ 0.8), and the catalyst was placed at a flow rate of 60ml/min and a volume percentage of 10% H2Reducing in situ for 3h in a fixed bed reactor under the condition of-Ar mixed gas atmosphere and the temperature of 700 ℃ to obtain reduced 5% Ni/La0.8Ca0.2AlO3Used in methane carbon dioxide reforming catalyst.
FIG. 1 is an XRD pattern of the carrier of the present invention, from which it can be seen that all carriers exhibit the characteristic diffraction peaks of perovskite, and the modified carrier is successfully synthesized.
FIG. 2 shows 5% Ni/La of the present invention0.9M0.1AlO3Catalyst, the reaction gas composition is CH under normal pressure4:CO21:1, and the space velocity of 18000 g cat-1·h-1Reaction temperature 750 ℃ CoAnd C, testing the stability of the catalyst for 50 hours, wherein the stability of the catalyst is obviously improved after the alkaline earth metal is added.
FIG. 3 shows 5% Ni/La of the present invention0.9M0.1AlO3The TG-DSC chart of the catalyst after 50h stability test shows that the carbon deposition resistance of the catalyst is obviously improved after alkaline earth metal is added.
Claims (2)
1. Anti-carbon deposition methaneThe preparation method of the Ni-based alkaline earth metal modified catalyst for dry gas reforming is characterized by comprising the following steps of: the preparation method is to prepare La by a sol-gel methodxM1-xAlO3Perovskite carrier, and then Ni/La is prepared by dipping methodxM1-xAlO3The X is the molar mass of La ions, and the M is Mg, Ca or Sr, the preparation method comprising the steps of:
A. adding La (NO)3)3·6H2O and Al (NO)3)3·9H2O and Mg (NO)3)2·6H2O、Ca(NO3)2·4H2O、Sr(NO3)
Mixing one of the three alkaline earth metal raw materials according to a certain molar mass ratio to form a mixture, adding citric acid with the molar mass being 1-2 times that of metal ions in the mixture into the mixture, mixing and dissolving, and fully stirring at room temperature to obtain mixed sol;
B. evaporating the mixed sol to dryness in a water bath at the temperature of 60-90 ℃ until gel is obtained, and transferring the gel to a drying oven at the temperature of 100-130 ℃ for drying to obtain fluffy dry glue; placing the dry glue in a muffle furnace at 160-200 ℃ for pretreatment, transferring the pretreated dry glue into the muffle furnace at 600-1000 ℃ for heat preservation and roasting, and cooling to obtain Ni/La respectivelyxM1-xAlO3A perovskite support; m is Mg, Ca and Sr ions; a certain amount of Ni (NO)3)3·6H2Dissolving O in container completely, adding water to obtain solution, adding different perovskite carriers, stirring at room temperature to completely impregnate the perovskite carriers, and finally obtaining Ni/La respectivelyxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3The Ni-based alkaline earth metal-modified catalyst of (1);
C. a certain amount of Ni (NO)3)3·6H2Dissolving O completely in a container, adding water to obtain solution, adding different perovskite carriers, stirring at room temperature to completely impregnate the perovskite carriersThen respectively obtain Ni/LaxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3The Ni-based alkaline earth metal-modified catalyst of (1).
2. The preparation method of the anti-carbon deposition methane dry gas reforming Ni-based alkaline earth metal modified catalyst as claimed in claim 1, wherein the preparation method comprises the following steps: mixing Ni/LaxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3The Ni-based alkaline earth metal modified catalyst was placed at a flow rate of 60ml/min and a volume percentage of 10% H2Reducing in situ for 3h in a fixed bed reactor under the condition of-Ar mixed gas atmosphere and the temperature of 700 ℃ to obtain reduced Ni/LaxMg1-xAlO3、Ni/LaxCa1-xAlO3、Ni/LaxSr1-xAlO3Used in methane carbon dioxide reforming catalyst.
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| CN114917915A (en) * | 2022-05-19 | 2022-08-19 | 华南理工大学 | Alkaline earth metal doped lanthanum oxide loaded nickel-based catalyst and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114917915A (en) * | 2022-05-19 | 2022-08-19 | 华南理工大学 | Alkaline earth metal doped lanthanum oxide loaded nickel-based catalyst and preparation and application thereof |
| CN114917915B (en) * | 2022-05-19 | 2023-12-15 | 华南理工大学 | Alkaline earth metal doped lanthanum oxide supported nickel-based catalyst and preparation and application thereof |
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