CN117920179A - Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof - Google Patents
Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117920179A CN117920179A CN202410126224.0A CN202410126224A CN117920179A CN 117920179 A CN117920179 A CN 117920179A CN 202410126224 A CN202410126224 A CN 202410126224A CN 117920179 A CN117920179 A CN 117920179A
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- based catalyst
- transition metal
- ternary hydrotalcite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 56
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 41
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 transition metal salt Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003310 Ni-Al Inorganic materials 0.000 description 2
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 2
- 229910002061 Ni-Cr-Al alloy Inorganic materials 0.000 description 2
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910002445 Co(NO3)3·6H2O Inorganic materials 0.000 description 1
- 229910020851 La(NO3)3.6H2O Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a nickel-based catalyst prepared from modified ternary hydrotalcite, and a preparation method and application thereof; according to the invention, ni-A1 binary hydrotalcite is modified by transition metal to prepare modified ternary hydrotalcite, and a nickel-based catalyst is prepared by a hydrothermal method; the modified catalyst provided by the invention is rich in mesoporous structure and alkaline sites, so that the catalytic activity and catalytic efficiency of the catalyst are improved; meanwhile, active metal Ni is used as a substrate, so that good dispersibility and small particle size are shown; the metal Ni has low price and can be applied to industrial mass production; meanwhile, the catalyst provided by the invention can be applied to carbon dioxide methanation reaction under the low-temperature condition.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a nickel-based catalyst prepared from modified ternary hydrotalcite, and a preparation method and application thereof.
Background
With the increasing degree of industrialization, environmental deterioration and limited reserves of fossil resources have become problems that human development has to face, and the content of carbon dioxide in the air has been increasing. Carbon dioxide is taken as a representative of greenhouse gases, the emission reduction of carbon dioxide, the preparation of fuel by using carbon dioxide and the chemical products with high added value are paid attention to by more and more professional knowledge, the "liquid sunshine" project is developed by the Hundos energy chemical Co Ltd in China, and the methanol chemical products are prepared by hydrogenating the carbon dioxide, so that the project is industrially produced in mass; the carbon dioxide is hydrogenated to prepare gasoline by the large-scale company of China academy of sciences, so that fossil energy sources can be regenerated; scientists in China are inspired by photosynthesis, and the technology for artificially synthesizing the starch by independently developing and developing carbon dioxide is announced to be successful. Natural gas (methane) has been taken as a fuel with higher added value of combustion heat, and has been taken into thousands of households instead of water gas because of the clean and safe performance of combustion products. The carbon dioxide methanation technology is taken as a key technical link of the coal gas project and the electric gas conversion technology in China, and has self-evident meaning.
The methanation reaction of carbon dioxide refers to the reaction of carbon dioxide and hydrogen under certain conditions to produce methane and water. In the reaction, the chemical inertness of carbon dioxide due to the stable structure thereof is unfavorable for the activation of carbon dioxide so as to limit the progress of the reaction, and the high catalytic activity and stability of the noble metal catalyst on the methanation reaction of carbon dioxide are added, but the expensive price of the noble metal makes the noble metal catalyst limited in large-scale industrial application; meanwhile, the reaction is exothermic at the standard atmospheric pressure and lower than 600 ℃, the reaction rate is beneficial to the increase of the reaction temperature by heating, but the conversion rate of carbon dioxide in the reaction can be reduced by increasing the temperature, and meanwhile, the aim of high energy consumption and energy conservation and emission reduction are violated.
Therefore, there is a need to develop a highly efficient catalyst for methanation of carbon dioxide with industrialization potential at a temperature lower than that of the prior art.
Disclosure of Invention
The invention aims to provide a nickel-based catalyst prepared from modified ternary hydrotalcite, a preparation method and application thereof, and the nickel-based catalyst prepared from transition metal modified ternary hydrotalcite is used for solving the problems that a noble metal catalyst in the prior art is high in price and difficult to be applied to industry on a large scale, and carbon dioxide methanation reaction is required to be carried out at high temperature at present.
In a first aspect, the invention provides a nickel-based catalyst prepared from modified ternary hydrotalcite, wherein the catalyst comprises nickel, aluminum and transition metal; the catalyst comprises the following components in a molar ratio of (1-5): (1-3): nickel element, aluminum element and transition metal element of (0.1-1).
Optionally, the transition metal includes at least one of cobalt, lanthanum, cerium, zirconium.
In a second aspect, the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, comprising the following steps:
S1, preparing nickel-aluminum mixed metal salt solution, and adding a modifying solution and a precipitant to form a mixed solution; the modification solution is a transition metal salt solution; the concentration of nickel, transition metal ions and aluminum metal ions in the mixed solution is 0.05-1.5mol/L;
s2, transferring the mixed solution into a reaction kettle, and reacting for 8-48 hours at the temperature of 60-280 ℃; after the reaction, purifying to obtain a modified ternary hydrotalcite precursor;
And S3, roasting the ternary hydrotalcite precursor to obtain the nickel-based catalyst.
Optionally, the precipitant in step S1 includes any one of urea, citric acid, oxalic acid, and ammonium bicarbonate.
Optionally, the purification in step S2 includes washing, filtering, and drying.
Optionally, the washing comprises the steps of: washing with 10-90% ethanol water solution until the pH of the filtrate is 6.5-7.0 or the filtrate is transparent and colorless.
Optionally, the drying conditions include: drying at 50-200deg.C for 8-24 hr.
In a third aspect, the invention provides an application of the nickel-based catalyst prepared from the modified ternary hydrotalcite in a carbon dioxide hydrogenation reaction.
Alternatively, the application comprises a methanation reaction of carbon dioxide at a temperature of 100-600 ℃.
Optionally, the temperature is lower than the temperature of the prior art methanation of carbon dioxide.
Optionally, the methanation reaction of carbon dioxide comprises the following steps:
Under the action of a catalyst, the temperature is 100-600 ℃, and the pressure is 0.1-4.5Mpa, and carbon dioxide and hydrogen are mixed according to the ratio of 1: (1-9) controlling the reaction space velocity to be Reacting for 4h to obtain methane.
The beneficial effects of the invention include:
(1) The catalyst prepared by the invention uses the ternary hydrotalcite modified by transition metal to prepare the nickel-based catalyst, so that the catalyst is rich in mesoporous structures and alkaline sites, and the catalytic activity and the catalytic efficiency of the catalyst are improved; the active metal Ni is used as a substrate, so that better dispersibility and smaller particle size are shown;
(2) The catalyst prepared by the invention has higher catalytic activity, the price of metallic nickel is low, the problem of high price of the noble metal catalyst is solved, and the catalyst can be applied to large-scale industrial application;
(3) The catalyst provided by the invention can promote the reaction of generating methane by hydrogenating carbon dioxide under the low-temperature condition, has high-efficiency catalyst activity and stability in the reaction, improves the conversion rate of carbon dioxide, improves the yield of methane, and reduces the reaction temperature.
Drawings
FIG. 1 is a comparison of the conversion of CO 2 in the methanation of CO 2 for the ternary hydrotalcite-like Ni-x-Al catalyst prepared in the example and for the unmodified catalyst prepared in comparative examples 1-2;
FIG. 2 is an SEM image and a TEM image of a ternary hydrotalcite-like Ni-La-Al catalyst prepared in example 5.
FIG. 3 is a graph of N 2 adsorption and desorption of a ternary hydrotalcite-like Ni-La-Al catalyst prepared in example 5.
FIG. 4 is an X-ray diffraction pattern of the catalyst prepared in example 5 and comparative example 2.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the accompanying drawings.
In a first aspect, an embodiment of the present invention provides a nickel-based catalyst prepared from modified ternary hydrotalcite, where the catalyst composition includes nickel, aluminum, and a transition metal; the catalyst comprises the following components in a molar ratio of (1-5): (1-3): nickel element, aluminum element and transition metal element of (0.1-1).
Specifically, the transition metal comprises at least one of cobalt, lanthanum, cerium and zirconium.
In a second aspect, an embodiment of the present invention provides a method for preparing a nickel-based catalyst from modified ternary hydrotalcite, including the steps of:
S1, preparing nickel-aluminum mixed metal salt solution, and adding a modifying solution and a precipitant to form a mixed solution; the modification solution is a transition metal salt solution; the concentration of nickel, transition metal ions and aluminum metal ions in the mixed solution is 0.05-1.5mol/L;
s2, transferring the mixed solution into a reaction kettle, and reacting for 8-48 hours at the temperature of 60-280 ℃; after the reaction, purifying to obtain a modified ternary hydrotalcite precursor;
and S3, roasting the modified ternary hydrotalcite precursor to obtain the nickel-based catalyst.
In some embodiments, the precipitant in step S1 includes any one of urea, citric acid, oxalic acid, and ammonium bicarbonate.
In some embodiments, the purifying in step S2 includes washing, filtering, and drying.
In some embodiments, the washing comprises the steps of: washing with 10-90% ethanol water solution until the pH of the filtrate is 6.5-7.0 or the filtrate is transparent and colorless.
Specifically, the drying conditions include: drying at 50-200deg.C for 8-24 hr.
In a third aspect, the embodiment of the invention provides an application of the nickel-based catalyst prepared from the modified ternary hydrotalcite in a carbon dioxide hydrogenation reaction.
In some embodiments, the application comprises a methanation reaction of carbon dioxide at a temperature of 100-600 ℃.
Specifically, the temperature is lower than the temperature of the methanation reaction of carbon dioxide in the prior art.
In some embodiments, the carbon dioxide methanation reaction comprises the steps of:
Under the action of a catalyst, the temperature is 100-600 ℃, and the pressure is 0.1-4.5Mpa, and carbon dioxide and hydrogen are mixed according to the ratio of 1: (1-9) controlling the reaction space velocity to be Reacting for 4h to obtain methane.
Example 1
The embodiment 1 of the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is prepared by a hydrothermal method and comprises the following steps:
S1, dissolving Ni(NO3)2·6H2O、ZrO(NO3)2·xH2O、Al(NO3)3·9H2O in deionized water to prepare a mixed metal salt solution; the final concentration of each ion in the mixed metal salt solution is: the concentration of Ni 2+ is 0.2085mol/L; zr 4+ concentration is 0.0086mol/L; al 3+ concentration is 0.0686mol/L; adding urea, stirring for 30min to completely dissolve the urea to obtain a mixed solution, wherein the final concentration of the urea in the mixed solution is 1.4285mol/L;
S2, adding the mixed solution into a hydrothermal reaction kettle, and reacting for 12 hours at 120 ℃; washing the suspension reaction product obtained by the reaction with 75% ethanol aqueous solution and filtering with standard filter paper with pore diameter of 0.1-3 μm until the pH of the filtrate is=7.0; drying the filtrate at 80 ℃ for 12 hours to obtain a Ni-Zr-Al nickel-based catalyst precursor;
And S3, roasting the precursor prepared in the step S2 in a muffle furnace at 450 ℃ for 2 hours to obtain the Ni-Zr-Al nickel-based catalyst.
Example 2
The embodiment 2 of the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is different from the embodiment 1 in that the transition metal salt used in the step S1 is Ce (NO 3)2·6H2 O; other conditions and steps are kept consistent, and the Ni-Ce-Al nickel-based catalyst is prepared in the step S3.
Example 3
The embodiment 3 of the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is different from the embodiment 1 in that the transition metal salt used in the step S1 is Co (NO 3)3·6H2 O; other conditions and steps are kept consistent, and the Ni-Co-Al nickel-based catalyst is prepared in the step S3.
Example 4
The embodiment 4 of the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is different from the embodiment 1 in that the transition metal salt used in the step S1 is Cr (NO 3)3·6H2 O; other conditions and steps are kept consistent, and the Ni-Cr-Al nickel-based catalyst is prepared in the step S3.
Example 5
The embodiment 5 of the invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is different from the embodiment 1 in that the transition metal salt used in the step S1 is La (NO 3)3.6H2O, other conditions and steps are kept consistent, and the Ni-La-Al nickel-based catalyst is prepared in the step S3.
Comparative example 1
Comparative example 1 of the present invention provides a method for preparing a nickel-based catalyst, which is different from example 1 in that only Ni metal salt is used in step S1; other conditions and steps are kept consistent; and S3, preparing the Ni catalyst.
Comparative example 2
Comparative example 2 of the present invention provides a method for preparing a nickel-based catalyst, which is different from example 1 in that a transition metal salt solution is not added in step S1; other conditions and steps are kept consistent; and S3, preparing the Ni-Al catalyst.
Comparative example 3
The present invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite in comparative example 3, which is different from example 5 in that the preparation method used is a coprecipitation method, and in step S1, the precipitant is ammonium bicarbonate; in the step S2, oil bath aging treatment at 80 ℃ is adopted; other conditions and steps are kept consistent; and (3) preparing the Ni-La-Al (coprecipitation method) nickel-based catalyst in the step S3.
Comparative example 4
The comparative example 4 of the present invention provides a method for preparing a nickel-based catalyst by modified ternary hydrotalcite, which is different from the method of example 5 in that the preparation method used is a sol-gel method, and in step S1, the precipitant is citric acid; in the step S2, stirring in an oil bath at 80 ℃ to a gel state; other conditions and steps are kept consistent; and (3) preparing the Ni-La-Al (sol-gel method) nickel-based catalyst in the step S3.
Comparative example 5
The comparative example 5 of the present invention provides a method for preparing a nickel-based catalyst by modifying ternary hydrotalcite, which is different from example 5 in that the preparation method used is an impregnation method, and in step S1, no Ni metal salt is added; after the carrier is obtained in the step S3, adding the carrier into Ni metal salt solution, stirring at normal temperature and normal pressure for 2 hours until the carrier is uniformly distributed, and standing the obtained suspension for 5 hours under the condition of normal temperature and normal pressure; other conditions and steps are kept consistent; and (3) preparing the Ni-La-Al (immersion method) nickel-based catalyst in the step S3.
Performance verification
1. The present invention demonstrates the catalytic efficiency of the catalysts prepared in examples and comparative examples in the methane (CH 4) formation of carbon dioxide (CO 2), the methanation of carbon dioxide comprising the steps of:
The prepared nickel-based catalyst is filled into a reaction device, the temperature is 150-350 ℃, and the raw gas is introduced under the pressure of 0.1-4.5MPa, wherein the ratio of CO 2 to H 2 in the raw gas is 1: (4-9) controlling the airspeed (GHSV) to be Carrying out reduction reaction for 4 hours in H 2 atmosphere to obtain methane;
The CO 2 conversion rate and the CH 4 selectivity are measured to show the catalytic efficiency of the catalyst;
the indicators measured after completion of the reaction include:
(1) The CO 2 conversion of the nickel-based catalyst prepared with different transition metals and the nickel-based catalyst without transition metal at different temperatures of 150-350 ℃ is shown in figure 1.
(2) The CO 2 conversion and CH 4 selectivity of the nickel-based catalysts prepared from different transition metals after reaction at 250 ℃ are shown in table 1.
TABLE 1 catalytic efficiency of the reactions of the different catalysts at 250℃
| Grouping | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Catalyst | Ni | Ni-Al | Ni-Zr-Al | Ni-Ce-Al | Ni-La-Al | Ni-Co-Al | Ni-Cr-Al |
| CO 2 conversion/% | 2.2 | 56.2 | 83.3 | 87.8 | 95.1 | 71.6 | 84.4 |
| CH 4 Selectivity/% | 60.3 | 76.5 | 92.3 | 91.6 | 99.9 | 96.2 | 95.6 |
(3) Taking the Ni-La-Al nickel-based catalyst prepared by the hydrothermal method in example 5 as an example, the CO 2 conversion rate and the CH 4 selectivity of the reaction at different raw material gas ratios and different airspeeds at 250 ℃ are shown in tables 2 and 3.
TABLE 2 catalytic efficiency of reactions with the same catalyst and different feed gas ratios
TABLE 3 catalytic efficiency of the same catalyst at different space velocities
2. Characterization and measurement were performed by taking the Ni-La-Al nickel-based catalyst prepared by the hydrothermal method in example 5 as an example:
(1) The microstructure of the Ni-La-Al nickel-based catalyst was observed by electron microscopy:
the Ni-La-Al nickel-based catalyst is observed by a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM), the results are shown in FIG. 2, a, b and c in FIG. 2 are TEM observations at different multiples, and d in FIG. 2 is an SEM observation;
(2) Specific surface area of the catalyst was reacted by measuring the adsorption and desorption curve of Ni-La-Al nickel-based catalyst N 2:
Carrying out an N 2 adsorption and desorption experiment on a sample by an ASAP2020 instrument, and determining an adsorption and desorption curve of the Ni-La-Al nickel-based catalyst N 2, wherein the result is shown in figure 3;
(3) X-ray diffractometer determination of X-ray diffraction data for the catalysts prepared in example 5 and comparative example 2:
the X-ray diffraction data of example 5 and comparative example 2 were measured using an X-ray diffractometer, and the results are shown in fig. 4.
Analysis of results
Referring to fig. 1, the conversion rate of CO 2 increases with the increase of temperature, and it is initially confirmed that the transition metal doped ternary hydrotalcite catalyst prepared by the present invention at a temperature of 150-350 ℃ has more excellent catalytic performance in catalyzing the conversion rate of CO 2 compared with the catalyst without the doped transition metal.
Referring to Table 1, the transition metal doped ternary hydrotalcite catalysts of examples 1-5 had better CO 2 methanation performance than the undoped transition metal catalyst of comparative example, and the La metal doped ternary hydrotalcite catalyst had higher CO 2 conversion and CH 4 selectivity.
Referring to table 2, under the same conditions, the catalyst performance of the La metal doped ternary hydrotalcite catalyst with the best methanation catalytic performance of CO 2 was evaluated under different proportions of feed gas (CO 2+H2), when the molar ratio of CO 2：H2 is 1:4 shows the optimal methanation catalytic performance of CO 2.
Referring to Table 3, la-doped ternary hydrotalcite catalysts were prepared by hydrothermal method, coprecipitation method, sol-gel method and impregnation method, and the catalytic performance was evaluated under the same conditions, and in contrast, la-doped ternary hydrotalcite catalysts prepared by hydrothermal method were found to exhibit optimal CO 2 methanation catalytic performance.
Referring to fig. 2, the morphology features of the catalyst were characterized by using a scanning electron microscope and a high-resolution transmission electron microscope, and it was found that the La metal doped ternary hydrotalcite catalyst exhibited a petal-like morphology and Ni particles were uniformly distributed on the catalyst surface.
Referring to fig. 3, an N 2 adsorption and desorption experiment was performed on the sample using an ASAP2020 instrument to obtain an N 2 adsorption and desorption graph of the La doped ternary hydrotalcite catalyst.
Referring to fig. 4, the ni—al hydrotalcite catalyst and the La doped ternary hydrotalcite catalyst were subjected to X-ray diffraction using an X-ray diffractometer, and the NiO crystal phase diffraction peak was found to be smaller after La doping, indicating that NiO particles with smaller particles were present in the La doped ternary hydrotalcite catalyst.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (9)
1. The nickel-based catalyst prepared from the modified ternary hydrotalcite is characterized by comprising nickel, aluminum and transition metal; the catalyst comprises nickel element, aluminum element and transition metal element in the molar ratio of (1-5) to (1-3) to (0.1-1).
2. The catalyst of claim 1, wherein the transition metal comprises at least one of cobalt, lanthanum, cerium, zirconium.
3. The method for preparing the catalyst according to claim 1, comprising the steps of:
S1, preparing nickel-aluminum mixed metal salt solution, and adding a modifying solution and a precipitant to form a mixed solution; the modification solution is a transition metal salt solution; the concentration of nickel, transition metal ions and aluminum metal ions in the mixed solution is 0.05-1.5mol/L;
s2, transferring the mixed solution into a reaction kettle, and reacting for 8-48 hours at the temperature of 60-280 ℃; after the reaction, purifying to obtain a modified ternary hydrotalcite precursor;
and S3, roasting the modified ternary hydrotalcite precursor to obtain the nickel-based catalyst.
4. The method according to claim 3, wherein the precipitant in the step S1 comprises any one of urea, citric acid, oxalic acid, and ammonium bicarbonate.
5. A method according to claim 3, wherein the purification in step S2 comprises washing, filtering, drying.
6. The method of preparation according to claim 5, wherein the washing comprises the steps of: washing with 10-90% ethanol water solution until the pH of the filtrate is 6.5-7.0.
7. The method of claim 5, wherein the drying comprises the following conditions: drying at 50-200deg.C for 8-24 hr.
8. Use of the catalyst according to claim 1 in a carbon dioxide hydrogenation reaction.
9. The use according to claim 8, characterized in that it comprises performing carbon dioxide methanation at a temperature of 100-600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410126224.0A CN117920179A (en) | 2024-01-30 | 2024-01-30 | Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410126224.0A CN117920179A (en) | 2024-01-30 | 2024-01-30 | Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117920179A true CN117920179A (en) | 2024-04-26 |
Family
ID=90757451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410126224.0A Pending CN117920179A (en) | 2024-01-30 | 2024-01-30 | Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117920179A (en) |
-
2024
- 2024-01-30 CN CN202410126224.0A patent/CN117920179A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110479280B (en) | CO low-temperature selective methanation Ni-ZrO 2 /NiAl 2 O 4 Catalyst, preparation method and application thereof | |
| CN102275963B (en) | Preparation method of aluminium oxide material | |
| AT502478A4 (en) | USE OF A METHOD OF HYDROGEN PRODUCTION | |
| CN101637726A (en) | Method for preparing catalyst for preparing synthesis gas by reforming methane and carbon dioxide | |
| CN107500296B (en) | A kind of rodlike β-Mo2The controlledly synthesis of C and its application in inverse water gas shift reation | |
| CN112108148A (en) | Supported copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof | |
| CN112808273B (en) | MgFe hydrotalcite-based catalyst and application thereof in production of biodiesel by hydrogenation and deoxidation of suspension bed | |
| CN106000443A (en) | Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis | |
| CN113385185A (en) | High-activity and selective perovskite type photo-thermal catalyst and preparation method and application thereof | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN110508315A (en) | A kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof | |
| CN111013634A (en) | Non-noble metal Co/MoN composite nanosheet array catalyst and preparation method and application thereof | |
| CN113368861B (en) | Catalyst for synthesizing methanol by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN101733089B (en) | Catalyst for preparing hydrogen gas, method for preparing same and application thereof | |
| CN110433815A (en) | A kind of carbon dioxide methanation nickel-base catalyst and its preparation method and application | |
| CN114029048A (en) | Preparation method and application of tungsten oxide catalyst coated by porous carbon | |
| CN114029063A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN113996293A (en) | Cerium-lanthanum solid solution supported iridium catalyst, and preparation method and application thereof | |
| CN108927133A (en) | A kind of dimethyl ether-steam reforming catalyst and its hydrogen production process | |
| CN117920179A (en) | Nickel-based catalyst prepared from modified ternary hydrotalcite, and preparation method and application thereof | |
| CN110329992A (en) | Low-temperature methanol steam reforming catalyst for preparing hydrogen and preparation method thereof | |
| CN114082420B (en) | Catalyst for deeply removing CO and preparation method thereof | |
| CN113181940B (en) | Methane reforming nickel-based catalyst and preparation method and application thereof | |
| CN114192180A (en) | Modified boron nitride loaded nickel-based methane dry reforming catalyst, and preparation method and application thereof | |
| CN114260016A (en) | Pd/ZnFexAl2-xO4Method for preparing hydrogen by reforming methanol by using catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |