CN113856685A - Mg-Ni/Al2O3Catalyst, preparation method and application thereof - Google Patents
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- 229910019083 Mg-Ni Inorganic materials 0.000 title claims abstract description 16
- 229910019403 Mg—Ni Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 9
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 26
- 238000000626 liquid-phase infiltration Methods 0.000 claims description 16
- 229910003162 MgO-NiO Inorganic materials 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 230000002431 foraging effect Effects 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with alkali- or alkaline earth metals or beryllium
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Abstract
The invention discloses Mg-Ni/Al2O3The catalyst and the preparation method and the application thereof comprise the following specific steps: mixing gamma-Al2O3Powder, Ni (NO)3)2·6H2O and MgCl2The mixture of (a) was ground in mortar for 2 hours and when the powder turned into a uniform green powder, it was transferred to a crucible; heating in water bath for 3 hours for aging, and then transferring to a drying oven for heating for 3 hours; product coolingAfter the temperature is reduced to room temperature, centrifuging and drying the catalyst, and calcining the catalyst at high temperature for 2 hours to obtain a precursor of the catalyst; precursor is in H2Reduction at high temperature under an atmosphere to obtain a catalyst represented by Mgx‑Ni30/Al2O3-MI. Carrier Al for catalyst in the invention2O3Can effectively activate the dispersion and the form of metal Ni and the reducibility of metal particles, so that the catalyst has higher dispersibility and higher carbon dioxide conversion rate, and the stability of the catalyst is effectively improved. The addition of alkaline earth metal oxide in the catalyst can promote the catalyst to CO2The content of the oxides is rich, the price is low, and the influence on the production cost of the catalyst is little.
Description
Technical Field
The invention belongs to CO2The technical field of catalytic conversion, in particular to Mg-Ni/Al2O3Method for preparing catalyst and its application in CO2Application in methanation.
Background
The large amount of carbon dioxide emitted by the combustion of fossil fuels is the root cause of global warming. In 2019, the united nations climate behavior peak proposes: by 2030, global CO2Emission is reduced by 45.0% on a 2010 basis, and carbon neutralization is achieved by 2050. How to reduce CO in the atmosphere2The concentration of (b) is currently an important research topic in the global sense. CO 22Methanation not only can reduce CO2The discharge amount can be obtained, and the important chemical raw material methane can be obtained, so that the CO is effectively utilized2One of the resource approaches is an effective and practical method for carbon emission reduction, and has a great potential in the aspect of environmental protection.
Transition metal nickel-based catalysts in CO due to their excellent activity and low cost2Methanation reactions are widely studied. However, in order to achieve CO at low temperatures2High-efficiency catalytic activity and stability in methanation reaction, and influence on CO due to particle size and dispersity of nickel2Key factors for methanation reactions. Catalytic performance of nickel-based catalystBut also on the carrier, the method of preparation and the conditions of the activity test. In addition, CO at the catalyst surface due to weak interaction with the support2The adsorption capacity is low, which is another factor that must be considered. To promote CO2Adsorption, in addition to the selection of an appropriate support, the use of additives such as alkali and alkaline earth oxides can promote CO by increasing the basicity of the support surface2And (4) carrying out methanation reaction. In addition, the alkaline earth metal doping can also improve the stability of the catalyst in high-temperature reaction and inhibit the sintering of active components under the reaction condition.
Preparing high nickel supported catalysts with nanoparticles with good dispersion is a great challenge. Even in a successful synthesis process, reproducibility problems in the scale-up process are encountered, which makes large-scale production of the catalyst difficult to commercialize. Various synthetic methods for preparing catalysts, mainly coprecipitation and precipitation, have been widely used for CO2And (4) methanation. However, these methods generate metal solution waste, and it is difficult to control the reproducibility of the catalyst. The experimental procedure is very complicated due to different parameters such as pH, temperature, pressure, stirring speed, solvent, reagents, mixing sequence and the gas environment to be controlled. The Melt Infiltration (MI) method is one of the most direct methods, which can appropriately disperse a large amount of transition metal and promoter in a carrier and improve reproducibility of preparing a catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides Mg-Ni/Al2O3Method for preparing catalyst and its application in CO2Application in methanation to solve the problem of the existing CO2CO present in methanation technology2Problems of poor capture performance and low conversion are identified.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
Mg-Ni/Al2O3The preparation method of the catalyst comprises the following steps:
step 1, mixing gamma-Al2O3Powder, Ni (NO)3)2·6H2O and MgCl2According toMixing at a mass ratio of 3-10:30:100, grinding the obtained mixture in equal volume of mortar for 2 hours, and transferring the powder into a crucible when the powder is converted into uniform green powder;
step 2, heating the product in the step 1 in a water bath for 3 hours, and then transferring the product to a drying oven to heat for 3 hours;
step 3, cooling the product obtained in the step 2 to room temperature, centrifuging and drying the product, and calcining the product at high temperature for 2 hours to obtain a precursor MgO-NiO/Al of the catalyst2O3；
Step 4, the catalyst precursor obtained in the step 3 is added in H2Reducing at high temperature in the atmosphere to obtain the target product, wherein the obtained catalyst is represented as Mgx-Ni30/Al2O3MI, X representing the content of metallic Mg (wt%), and MI representing the melt infiltration method.
In the step 2, the heating temperature of the water bath is 80 ℃, and the heating temperature of the drying oven is 100 ℃.
In the step 3, the calcining temperature is 400 ℃, and the heating rate is 10 ℃/min.
In the step 4, the reduction temperature is 350 ℃, and the reduction time is 1 hour.
Mg-Ni/Al2O3Catalyst of Mgx-Ni30/Al2O3MI, X represents the mass content of metal Mg, MI represents a melt infiltration method, and X = 5-10.
Mg-Ni/Al2O3Use of a catalyst for CO2In methanation.
Advantageous effects
Compared with the prior art, the Mg-Ni/Al alloy of the invention2O3Method for preparing catalyst and its application in CO2The application in methanation has the following advantages: the invention adopts a melt infiltration method to prepare Mg-Ni/Al2O3Catalyst for CO2Methanation reaction of Al2O3The carrier can effectively activate the dispersion and the form of metal and the reducibility of metal particles, so that the catalyst has higher Ni dispersibility and higher carbon dioxide conversion rate, and the stability of the catalyst is effectively improvedAnd (5) performing qualitative determination. In addition, the addition of alkaline earth metal oxide to the catalyst can promote the catalyst to CO2The content of the oxides is rich, the price is low, and the influence on the production cost of the catalyst is little.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples. The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
Example 1
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder according to the mass ratio of 3:30:100, grinding the mixture in the equal volume of mortar for 2 hours, and transferring the mixture into a crucible when the powder is converted into uniform green powder;
(2) heating the crucible in 80 ℃ water bath for 3 hours for aging, and then transferring the crucible to a drying oven for heating at 100 ℃ for 3 hours;
(3) cooling the product to room temperature, centrifuging and drying the product, heating to 400 ℃ at the speed of 10 ℃/min, calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg3-Ni30/Al2O3MI, MI stands for melt infiltration method.
Example 2
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder according to the mass ratio of 5:30:100, grinding the mixture in the equal volume of mortar for 2 hours, and transferring the mixture into a crucible when the powder is converted into uniform green powder;
(2) heating the crucible in 80 ℃ water bath for 3 hours for aging, and then transferring the crucible to a drying oven for heating at 100 ℃ for 3 hours;
(3) cooling the product to room temperature, centrifuging and drying the product, heating to 400 ℃ at the speed of 10 ℃/min, calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg5-Ni30/Al2O3MI, MI stands for melt infiltration method.
Example 3
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder according to the mass ratio of 10:30:100, grinding the mixture in the equal volume of mortar for 2 hours, and moving the mixture into a crucible when the powder is converted into uniform green powder;
(2) heating the crucible in 80 ℃ water bath for 3 hours for aging, and then transferring the crucible to a drying oven for heating at 100 ℃ for 3 hours;
(3) cooling the product to room temperature, centrifuging and drying the product, heating to 400 ℃ at the speed of 10 ℃/min, calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg10-Ni30/Al2O3MI, MI stands for melt infiltration method.
Comparative example 1
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder in a crucible according to the mass ratio of 3:30:100, and adding deionized water with the same volume for soaking for 6 hours;
(2) transferring the crucible into a drying oven, and heating and drying for 10 hours at 100 ℃;
(3) transferring the dried sample into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/min, and calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg3-Ni30/Al2O3MP, MP stands for the equal volume impregnation method.
Comparative example 2
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder in a crucible according to the mass ratio of 5:30:100, and adding deionized water with the same volume for soaking for 6 hours;
(2) transferring the crucible into a drying oven, and heating and drying for 10 hours at 100 ℃;
(3) transferring the dried sample into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/min, and calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg5-Ni30/Al2O3MP, MP stands for the equal volume impregnation method.
Comparative example 3
(1) Mixing MgCl2、Ni(NO3)2·6H2O and gamma-Al2O3Mixing the powder in a crucible according to the mass ratio of 10:30:100, and adding deionized water with the same volume for soaking for 6 hours;
(2) transferring the crucible into a drying oven, and heating and drying for 10 hours at 100 ℃;
(3) transferring the dried sample into a muffle furnace, heating to 400 ℃ at the speed of 10 ℃/min, and calcining for 2 h to obtain a precursor MgO-NiO/Al of the catalyst2O3；
(4) The catalyst precursor is added in H2Reduction at 350 ℃ for 1 hour under an atmosphere to obtain a catalyst denoted Mg10-Ni30/Al2O3MP, MP stands for the equal volume impregnation method.
Mg prepared by the above methodx-Ni30/Al2O3The catalyst is catalyzed in a tubular fixed bed reactor with the pipe diameter of 8mmFor the evaluation of chemical activity, the catalyst tablets were crushed, sieved and loaded at a loading of 1.0 g. At H2/N2Heating the reaction solution in the reducing atmosphere, and introducing mixed reaction gas (H) when the reaction temperature is increased to 300 DEG C2:CO2:N2=18:6:1, volume ratio), the reaction pressure was normal pressure. The composition of the raw material gas and the product before and after the reaction is detected on line by a gas chromatography (TCD detector), and the content of each component in the tail gas is quantitatively analyzed by using a correction area normalization method.
The specific surface area, Ni dispersibility of the catalysts prepared in the above examples and comparative examples and CO in the hydrogenation reaction at 300 deg.C2The conversion is shown in table 1:
TABLE 1 specific surface area, dispersivity of the catalyst and its CO hydrogenation at 300 deg.C2Conversion rate
As can be seen from Table 1, Al2O3The specific surface area of the carrier was 193 m2The specific surface area of the catalyst prepared by the melt infiltration method and the equal volume impregnation method is reduced to different degrees and is increased along with the increase of Mg loading. Both catalysts achieved the best Ni dispersion at 5% Mg loading, 28.2 and 25.7 respectively, with the best CO in the hydrogenation reaction2The conversion was 76% and 68%, respectively. Therefore, the catalyst prepared by the melt infiltration method has higher active component dispersity and catalytic activity.
Claims (6)
1. Mg-Ni/Al2O3The preparation method of the catalyst is characterized by comprising the following steps:
step 1, mixing gamma-Al2O3Powder, Ni (NO)3)2·6H2O and MgCl2Mixing according to the mass ratio of 3-10:30:100, grinding the obtained mixture in mortar with the same volume for 2 hours, and transferring the mixture into a crucible when the powder is converted into uniform green powder;
step 2, heating the product in the step 1 in a water bath for 3 hours, and then transferring the product to a drying oven to heat for 3 hours;
step 3, cooling the product obtained in the step 2 to room temperature, centrifuging and drying the product, and calcining the product at high temperature for 2 hours to obtain a precursor MgO-NiO/Al of the catalyst2O3；
Step 4, the catalyst precursor obtained in the step 3 is added in H2Reducing at high temperature in the atmosphere to obtain the target product, wherein the obtained catalyst is represented as Mgx-Ni30/Al2O3MI, X representing the content of metallic Mg in wt%, MI representing the melt infiltration method.
2. Mg-Ni/Al according to claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: in the step 2, the heating temperature of the water bath is 80 ℃, and the heating temperature of the drying oven is 100 ℃.
3. Mg-Ni/Al according to claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: in the step 3, the calcining temperature is 400 ℃, and the heating rate is 10 ℃/min.
4. Mg-Ni/Al according to claim 12O3The preparation method of the catalyst is characterized by comprising the following steps: in the step 4, the reduction temperature is 350 ℃, and the reduction time is 1 hour.
5. Mg-Ni/Al produced according to any one of claims 1 to 42O3Catalyst, characterized in that the catalyst is Mgx-Ni30/Al2O3MI, X representing the mass content of metallic Mg, MI representing the melt infiltration method, X =5-10, in wt%.
6. Mg-Ni/Al according to claim 52O3Use of a catalyst for CO2In methanation.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399491A (en) * | 2014-12-04 | 2015-03-11 | 广州博能能源科技有限公司 | High-temperature-resistant methanation catalyst as well as preparation method thereof |
| US20170001863A1 (en) * | 2015-06-30 | 2017-01-05 | Korea Institute Of Energy Research | Methane steam reforming, using nickel/alumina nanocomposite catalyst or nickel/silica-alumina hybrid nanocomposite catalyst |
| CN106902830A (en) * | 2017-04-17 | 2017-06-30 | 西南化工研究设计院有限公司 | One kind conveying bed methanation catalyst, preparation method and application |
| CN108311154A (en) * | 2018-02-02 | 2018-07-24 | 济南大学 | One kind being used for CO2The modification of the novel nickel-base catalyst of methanation and preparation method |
| CN111495384A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Carbon dioxide hydromethanation catalyst, preparation method and application |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399491A (en) * | 2014-12-04 | 2015-03-11 | 广州博能能源科技有限公司 | High-temperature-resistant methanation catalyst as well as preparation method thereof |
| US20170001863A1 (en) * | 2015-06-30 | 2017-01-05 | Korea Institute Of Energy Research | Methane steam reforming, using nickel/alumina nanocomposite catalyst or nickel/silica-alumina hybrid nanocomposite catalyst |
| CN106902830A (en) * | 2017-04-17 | 2017-06-30 | 西南化工研究设计院有限公司 | One kind conveying bed methanation catalyst, preparation method and application |
| CN108311154A (en) * | 2018-02-02 | 2018-07-24 | 济南大学 | One kind being used for CO2The modification of the novel nickel-base catalyst of methanation and preparation method |
| CN111495384A (en) * | 2020-04-24 | 2020-08-07 | 东南大学 | Carbon dioxide hydromethanation catalyst, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| EUI HYUN CHO ET AL.,: "Simultaneous impregnation of Ni and an additive via one-step melt-infiltration: Effect of alkaline-earth metal (Ca, Mg, Sr, and Ba) addition on Ni/γ-Al2O3 for CO2 methanation" * |
| 黄华 文建军 尹笃林: "助剂对Ni/Al2O3催化剂芳烃加氢热稳定性和抗硫化性能的影响" * |
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