CN1108195C - Nm-class crystal oxide carried nickel catalyst and its preparing process - Google Patents
Nm-class crystal oxide carried nickel catalyst and its preparing process Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000013078 crystal Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 8
- 230000008569 process Effects 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- 239000000017 hydrogel Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 239000000499 gel Substances 0.000 claims description 8
- 239000000347 magnesium hydroxide Substances 0.000 claims description 8
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000010411 cooking Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 101710134784 Agnoprotein Proteins 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 47
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 11
- 238000002407 reforming Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000004627 transmission electron microscopy Methods 0.000 description 7
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000000352 supercritical drying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- -1 nickel nitrate Chemical compound 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical class [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
The present invention relates to a nanometer crystal oxide load nickel catalyst. The nanometer crystal oxide load nickel catalyst has the following weight percentage of composition elements: 3% to 30% of nickel and 70% to 97% of nanometer crystal oxides. The nanometer crystal oxide load nickel catalyst has the preparing method that firstly, a nanometer crystal oxide carrier is prepared; afterwards, the nanometer crystal oxide load nickel catalyst is prepared, namely that Ni(NO3)2.6H2O water solution is added in the nanometer crystal oxide carrier, and the catalyst of the present invention is obtained by the mixing, the stirring at ordinary temperature, the rotary evaporation, the desiccation and the roasting of the nanometer crystal oxide carrier and the water solution. When the catalyst of the present invention is used for the reaction using carbon dioxide reforming methane for preparing synthetic gas, the selectivity of synthetic gas can be higher than 90%, and catalytic activity is supernormally stable.
Description
Technical Field
The invention relates to a nanocrystalline oxide supported nickel catalyst and a preparation method thereof, belonging to the technical field of chemical catalysts.
Background
CO2Reforming CH4( ΔH°298247kJ/mol) reaction is an indirect utilization of natural gas and coal seam gas CH4One of the effective ways of resources. It converts two main greenhouse gases into important basic chemical raw materials of CO and H2(syngas). In certain natural gas or coal bed gas resources, CO2And CH4Can be directly used as a raw material for the reaction, with similar concentrations. And indirect use of CH4Other pathway of (1), i.e. CH4Compared to the steam reforming and partial oxidation processes of CO2Reforming CH4Produced "hydrogen lean" syngas (CO/H)21) can be directly used as a raw material gas for oxo reaction; has obvious advantages in the process of directly synthesizing the dimethyl ether (reducing the generation of water and improving H)2Utilization of (d); in the F-T synthesis, it is suitable for the synthesis of longer chain hydrocarbons or oxygenates of higher value added. Research shows that noble metals such as Ru, Rh, Pd, etc. have higher reactivity and carbon deposition resistance when loaded on a suitable carrier, for example, German patent DE9400513 reports Pd/ZrO2In non-noble metals, nickel catalysts have high reactivity but suffer from severe carbon deposition (① chem. Eng. Sci., 1)989, 43: 3049, ② J. chem.Soc. chem.Comm., 1995: 71.) carbon deposits can cover the catalyst surface, leading to catalyst deactivation and reactor plugging, which can increase the catalyst bed pressure.
Disclosure of Invention
The invention aims to develop a nanocrystalline oxide supported nickel catalyst and a preparation method thereof, so as to provide a long-life nickel-based catalyst with high reaction activity and strong anti-carbon deposition capability, and the nickel-based catalyst can meet the requirements of industrialization on the activity and the service life of the catalyst when being used for the reaction of preparing synthesis gas by reforming methane with carbon dioxide.
In particular, the invention develops a catalyst for preparing synthesis gas by reforming methane with carbon dioxide. The high activity of the catalyst can ensure that the conversion rate of carbon dioxide and methane is close to a thermodynamic equilibrium value, and the initial activity of the catalyst can be maintained unchanged after the catalyst is used for 100-1100 hours.
The precursor of the active component nickel of the catalyst can be inorganic salt of nickel, such as nickel nitrate, and the like, and can also be organic salt of nickel, such as nickel acetate, and the like. The precursor of the nanocrystalline oxide carrier can be inorganic salt or organic salt, and the invention preferentially uses the inorganic salt as the precursor.
The nanocrystalline oxide supported nickel catalyst provided by the invention comprises the following components in percentage by weight: 3-30%, nanocrystalline oxide: 70-97 percent.
The preparation method of the catalyst with the components comprises the following steps:
1. preparing a nanocrystalline oxide carrier: with nanocrystalline oxide ZrO2Or metal inorganic salt corresponding to MgOZrOCl2And MgCl2As precursor, zirconium oxychloride ZrOCl containing crystal water is used2·8H2O or MgCl2·8H2Preparing 0.05-0.5 mol/L aqueous solution from O for later use, diluting 2-15 times of 25% commercial ammonia water as a precipitator, dripping the prepared aqueous solution into the precipitator at a speed of 1-20 ml/min under the condition of continuous stirring, and simultaneously controlling the pH value of the solution at 9 ℃upto e13, after the dropwise addition is finished, washing the mixture by deionized water until the mixture is AgNO3Cl could not be detected in the solution-Filtering or centrifuging to obtain zirconium hydroxide or magnesium hydroxide hydrogel;
2. washing the hydrogel with absolute ethyl alcohol for 2-5 times to obtain corresponding alcohol gel, and then drying with supercritical fluid or flowing N under normal pressure2Drying and roasting the alcogel in the atmosphere or cooking hydroxide hydrogel in alkali liquor to prepare nanocrystalline oxide with the particle size of 5-40 nm;
3. preparing a nanocrystalline oxide supported nickel catalyst: mixing Ni (NO)3)2·6H2Preparing 10-15% of water solution from O, adding the water solution into a nanocrystalline oxide carrier, mixing until the content of nickel is 3-30% by weight and the content of the nanocrystalline oxide is 70-90% by weight, stirring at room temperature for 2 hours, then carrying out rotary evaporation to dryness, drying at 100-200 ℃ for 12-16 hours, transferring into a muffle furnace, and roasting at 400-850 ℃ for 3-10 hours to obtain the catalyst.
Before the catalyst prepared by the invention is actually used, the catalyst contains 5-60% of H at 700-850 DEG C2Inert gas (e.g. H)2/N2) Reducing for 3-13 hours.
When the nickel-based catalyst is used for the reaction of preparing the synthesis gas by reforming methane with carbon dioxide, the catalytic performance of the nickel-based catalyst is far superior to that of various conventional oxide-loaded nickel catalysts under similar reaction conditions. The novel catalyst is CO at 700-850 DEG C2∶CH4＝1∶1，GHSV＝2.4×104Under the reaction condition of ml/h.g-cat, methane and CO can be reacted2The conversion rate of the catalyst is close to or reaches the thermodynamic equilibrium value, the selectivity of the synthesis gas reaches over 90 percent, and the catalytic activity is extremely stable. The catalyst of the present invention is further illustrated by the following examples, but the embodiments of the present invention are not limited to the following examples.
Drawings
FIG. 1 shows nano-ZrO prepared by different methods2Is disclosedA radio electron microscope (TEM) image.
a：Zr(OH)4Alcogel in N2Drying at 350 deg.C, and calcining at 650 deg.C to obtain ZrO2
b：Zr(OH)4Drying the alcogel under the ethanol supercritical condition, and roasting at 650 ℃ to obtain ZrO2
FIG. 2 Ni/ZrO after reduction2X-ray diffraction (XRD) results of the catalyst.
a：Zr(OH)4Alcogel in N2ZrO dried at 350 ℃ C2Ni-loaded catalyst
b：Zr(OH)4ZrO obtained by supercritical drying of alcogel2Ni-loaded catalyst
c：Zr(OH)4The aquagel is boiled in ammonia water and then is dried normally to obtain ZrO2Ni-loaded catalyst
FIG. 3 Ni/ZrO after reduction2Transmission Electron Microscopy (TEM) images of the catalyst.
a：Zr(OH)4Alcogel in N2The resulting ZrO was dried at 350 ℃ in an atmosphere2Ni-loaded catalyst
b：Zr(OH)4ZrO obtained by supercritical drying of alcogel2Ni-loaded catalyst
FIG. 4 shows the X-ray diffraction (XRD) results of nano-MgO prepared by different methods.
a：Mg(OH)2Alcogel in N2Drying the obtained MgO at 270 DEG C
b：Mg(OH)2Drying the alcogel under ethanol supercritical condition to obtain MgO
c：Mg(OH)2Alcogel in N2Drying the obtained MgO at 350 DEG C
FIG. 5X-ray diffraction (XRD) results of the Ni/MgO catalyst after calcination.
a：Mg(OH)2Alcogel in N2Drying the obtained MgO at 270 DEG C
b：Mg(OH)2Alcogel in N2Drying the obtained MgO at medium 350C
c：Mg(OH)2Alcohol gel in ethanol supercritical stateDrying the resulting MgO under ambient conditions
FIG. 6 shows a schematic representation of a drawing
A: ZrO of different particle sizes2CH on Ni Supported catalyst4Conversion as a function of reaction time
B: MgO-loaded Ni catalyst CH with different grain sizes4Conversion as a function of reaction time
Detailed Description
Example 1: 13.7g ZrOCl were weighed2·8H2O is prepared into 0.17M aqueous solution, 25 percent ammonia water is diluted by 10 times and used as a precipitator to be placed in a beaker, ZrOCl is slowly dropped into the beaker under vigorous stirring2Controlling the pH value of the aqueous solution to be 9-11, continuously stirring for 0.5 hour after the dropwise adding is finished, aging for 2 hours, performing suction filtration or centrifugal separation, and washing with deionized water until no Cl exists-Thus, a hydrogel was obtained. And washing the hydrogel twice by using absolute ethyl alcohol, and performing suction filtration or centrifugal separation to obtain the alcogel. The alcogel was placed in a quartz tube, and N was passed through the tube at 350 ℃ at a flow rate of 30ml/min2Drying/roasting for 3 hours to obtain amorphous nano ZrO2Precursor, denoted as ZrO2-AN. The results of Transmission Electron Microscopy (TEM) after firing at 650 ℃ are shown in FIG. 1(a), and it can be seen that ZrO2The particle size of AN is 15-25 nm. Weighing a certain amount of Ni (NO)3)2·6H2O, preparing 10% aqueous solution, and using the Ni (NO)3)2Solution impregnation of 2g of the prepared nano-ZrO2-AN vehicle, after stirring for 2 hours at room temperature, evaporated to dryness by rotation and dried for 12 hours at 110 ℃. The dried sample was transferred to a muffle furnace and calcined at 650 ℃ for 5 hours to obtain Ni/ZrO having a nickel content of 12%2AN AN catalyst, wherein the X-ray diffraction (XRD) result of the reduced catalyst is shown in FIG. 2(a) and the Transmission Electron Microscope (TEM) result is shown in FIG. 3(a)2O3Diluting according to the ratio of 2: 5, grinding and tabletting, crushing into particles of 20-40 meshes, placing 700mg in a quartz tube reactor with the inner diameter of 10ml, and placing on a self-built normal-pressure fixed bed flow reaction deviceThe activity of the reaction for producing synthesis gas by reforming methane with carbon dioxide was evaluated. The catalyst is reacted with H2/N2The mixed gas (1: 9) is reduced for 3 hours at 700 ℃ and then heated to 757 ℃. CO was introduced at a flow rate of 80ml/min at atmospheric pressure2/CH4(1: 1) is introduced into the reactor at a space velocity GHSV of 2.4X 104ml/h g-cat, gas chromatography detection of tail gas composition. The reaction results showed that the initial conversion of methane and carbon dioxide was close to their thermodynamic equilibrium values and that the catalyst was used continuously for 1100 hours without any decrease in activity, and that the conversion of methane did not change with time as shown in FIG. 6 (A).
Example 2: ZrO (ZrO)2The preparation method of the alcogel is the same as that of example 1, except that the drying of the alcogel adopts a supercritical drying method, namely, the alcogel is placed in an autoclave, 15ml of absolute ethyl alcohol is added, and N is introduced2Heating to 270 deg.C under 80atm for 1 hr, cooling, releasing pressure, introducing N2To remove ethanol in the kettle to obtain nano ZrO2Powder and is noted as ZrO2AS, Transmission Electron Microscopy (TEM) results show ZrO2The particle size of AS is 5.7nm, and the result of Transmission Electron Microscopy (TEM) at 650 ℃ after calcination is shown in FIG. 1(b), and it can be seen that the particle size after calcination is 15 to 18 nm. Ni/ZrO2The preparation and activity evaluation methods of the AS catalyst were the same AS those of example 1, and the X-ray diffraction (XRD) results of the reduced catalyst are shown in FIG. 2(b), and the Transmission Electron Microscope (TEM) results are shown in FIG. 3 (b). The reaction results showed that the conversion of methane and carbon dioxide reached more than 80%, and the activity did not decrease after the catalyst was continuously used for 240 hours, and the curve of the conversion of methane as a function of time is shown in FIG. 6 (A).
Example 3: preparation of the hydrogel As in example 1, the hydrogel was boiled in ammonia water at 100 ℃ for 48 hours, filtered or centrifuged, and then dried in an oven at 110 ℃ for 12 hours to obtain amorphous ZrO2And is denoted as ZrO2CD, the result of the 700 ℃ roasting Transmission Electron Microscope (TEM) is shown in the attached figure 1(c), and the grain size after roasting is 5-7 nm. Ni/ZrO2of-CD catalystsThe preparation and activity evaluation methods were the same as in example 1, and the X-ray diffraction (XRD) results of the reduced catalyst are shown in FIG. 2 (c). The reaction results show that the conversion of methane reaches a thermodynamic equilibrium value, and the activity of the catalyst is not reduced after the catalyst is continuously used for 100 hours, and the change curve of the conversion of methane along with time is shown as the attached figure 6 (A).
Example 4: weighing a certain amount of MgCl2·6H2O is prepared into 0.4M aqueous solution, 25 percent ammonia water is diluted by 10 times and used as a precipitator to be placed in a beaker, and MgCl is slowly dropped into the beaker under the condition of vigorous stirring2Controlling the pH value of the aqueous solution to be 9-11, continuously stirring for 0.5 hour after the dropwise adding is finished, aging for 2 hours, performing suction filtration or centrifugal separation, and washing with deionized water until no Cl exists-Thus, a hydrogel was obtained. And washing the hydrogel twice by using absolute ethyl alcohol, and performing suction filtration or centrifugal separation to obtain the alcogel. Placing the alcogel in a quartz tube, and introducing N at 270 deg.C at a flow rate of 30ml/min2Drying/calcining for 5 hr to obtain nanometer MgO precursor, which is marked as MgO-AN, and the X-ray diffraction (XRD) result is shown in figure 4(a), and it can be seen that the obtained product is Mg (OH)2XLBA calculation result shows that the grain size is 10.5nm, nano MgO is obtained after roasting at 650 ℃, and the XLBA calculation result shows that the grain size is 10.2 nm. Weighing a certain amount of Ni (NO)3)2·6H2O, preparing 10% aqueous solution, and using the Ni (NO)3)2The solution is used for impregnating 2g of prepared nano MgO-AN carrier, stirring the solution at room temperature for 2 hours, then rotating the solution to evaporate the solution to dryness, and drying the solution at 110 ℃ for 12 hours. The dried sample was transferred to a muffle furnace and calcined at 650 ℃ for 5 hours to obtain a Ni/MgO-AN catalyst having a nickel content of 9.5%, and the X-ray diffraction (XRD) result of the calcined catalyst is shown in FIG. 5(a), and it can be seen that the catalyst exists in the form of a nickel-magnesium solid solution. The activity of the Ni/MgO-AN catalyst was evaluated in the same manner as in example 1, except that the reduction temperature of the catalyst was 850 ℃. The reaction results showed that the initial conversion of methane and carbon dioxide reached 90% and that the activity did not decrease any more after 100hours of continuous use of the catalyst. The conversion of methane as a function of time is shown in FIG. 6 (B).
Example 5: the MgO alcohol gel was prepared and dried in the same manner as in example 4, except that the drying/firing temperature of the alcohol gel was 350 ℃. The X-ray diffraction (XRD) results of the obtained nano MgO are shown in the accompanying FIG. 4(c), and the XLBA results show that the grain size of the nano MgO is 11.7 nm. The preparation and activity evaluation methods of the catalyst were the same as in example 4, and the X-ray diffraction (XRD) results of the calcined catalyst are shown in FIG. 5 (b). The reaction results show that the initial conversion rate of methane and carbon dioxide can reach 90%, and the activity of the catalyst is not reduced after the catalyst is continuously used for 100 hours.
Example 6: the preparation method of MgO alcohol gel is the same as that in example 3, except that supercritical drying method is adopted for drying alcohol gel, namely, alcohol gel is placed in an autoclave, 15ml of absolute ethyl alcohol is added, and N is introduced2Heating to 270 deg.C under 80atm for 1 hr, cooling, releasing pressure, introducing N2The nano MgO precursor is obtained by removing ethanol in the kettle and is marked AS MgO-AS, and the X-ray diffraction (XRD) result is shown in figure 4(b), and the obtained product is Mg (OH)2XLBA calculation result shows that the grain size is 14.6nm, and after roasting at 650 ℃, nano MgO is obtained, and the grain size is 15.7 nm. The Ni/MgO-AS catalyst was prepared in the same manner AS in example 3, and the X-ray diffraction (XRD) results of the calcined catalyst are shown in FIG. 5 (c). XRF results showed that the Ni content in Ni/MgO-AS was 7.3%. The catalyst activity was evaluated in the same manner as in example 4. The reaction result shows that the conversion rate of the methane and the carbon dioxide reaches 88 percent, the activity of the catalyst is not reduced after the catalyst is continuously used for 100 hours, and the conversion rate of the methane changes along with the timeThe graph is shown in FIG. 6 (B).
Comparative example:
comparative example 1: 13.7g ZrOCl were weighed2·8H2O is prepared into 0.17M aqueous solution, 25 percent ammonia water is diluted by 10 times and used as a precipitator to be placed in a beaker, ZrOCl is slowly dropped into the beaker under vigorous stirring2Controlling the pH value of the aqueous solution to be 9-11, continuing stirring for 0.5 hour after the dropwise adding is finished, then aging for 2 hours, and washing with deionized water until no Cl exists-Filtering or centrifuging, and oven dryingDrying for 12 hours at 110 ℃ to obtain ZrO with particle size of 30-100 nm2And is denoted as ZrO2-a CP. After the mixture is roasted at 650 ℃, non-uniform particles with the particle size of 50-200 nm are formed. With ZrO2The catalyst carrier is CP, the supported nickel catalyst is prepared as in example 1, and XRF results show that the Ni content in the catalyst is 12.9%. The catalyst activity was evaluated in the same manner as in example 1. The reaction results showed that the initial conversion of methane was 87%, but after 50 hours of use, the conversion of methane dropped to 60%. CH (CH)4The conversion of (A) with respect to the reaction time is shown in FIG. 6 (A).
Comparative example 2: MgO hydrogel was prepared in the same manner as in example 4 by drying the hydrogel in an oven at 110 ℃ for 12 hours. The X-ray diffraction (XRD) result showed that the obtained product was Mg (OH)2And as MgO-CP, its particle size is 11.3 nm. After the calcination at 650 ℃, the obtained MgO grain size is 22 nm. The preparation of the supported nickel catalyst was performed in thesame manner as in example 1, using MgO-CP as the catalyst carrier, and XRF showed that the Ni content in the catalyst was 7.1%. The catalyst activity was evaluated in the same manner as in example 4. The reaction result shows that the activity of the catalyst is obviously lower than that of the catalyst taking MgO with smaller particle size as a carrier, and the activity of the catalyst is unstable. CH (CH)4The conversion of (C) with the reaction time is shown in FIG. 6 (B).
Claims (2)
1. A nanocrystalline oxide supported nickel catalyst is characterized in that the catalyst comprises the following components in percentage by weight: 3-30%, nanocrystalline oxide: 70-97%, the grain diameter is 5-25nm, and the nanocrystalline oxide is zirconium dioxide or magnesium oxide.
2. A process for preparing the catalyst of claim 1, comprising the steps of:
(1) preparing a nanocrystalline oxide carrier: with nanocrystalline oxide ZrO2Or metal inorganic salt ZrOCl corresponding to MgO2And MgCl2As precursor, zirconium oxychloride ZrOCl containing crystal water is used2·8H2O orMgCl2·8H2Preparing an aqueous solution with the concentration of 0.05-0.5 mol/L by using O for later use, diluting commercial ammonia water with the concentration of 25% by 2-15 times to be used as a precipitator, dripping the prepared aqueous solution into the precipitator at the speed of 1-20 ml/min under the condition of continuous stirring, simultaneously controlling the pH value of the solution to be 9-13, and after dripping is finished, washing the solution by using deionized water until AgNO is used3Cl could not be detected in the solution-Filtering or centrifuging to obtain zirconium hydroxide or magnesium hydroxide hydrogel;
(2) washing the hydrogel with absolute ethyl alcohol for 2-5 times to obtain corresponding alcohol gel, and then drying with supercritical fluid or flowing N under normal pressure2Drying and roasting the alcogel in the atmosphere or cooking hydroxide hydrogel in alkali liquor to prepare nanocrystalline oxide with the particle size of 5-40 nm;
(3) preparing a nanocrystalline oxide supported nickel catalyst: mixing Ni (NO)3)2·6H2Preparing 10-15% of water solution from O, adding the water solution into a nanocrystalline oxide carrier, mixing until the content of nickel is 3-30% by weight and the content of the nanocrystalline oxide is 70-90% by weight, stirring at room temperature for 2 hours, then carrying out rotary evaporation to dryness, drying at 100-200 ℃ for 12-16 hours, transferring into a muffle furnace, and roasting at 400-850 ℃ for 3-10 hours to obtain the catalyst.
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| CN103769106B (en) * | 2014-02-20 | 2015-08-05 | 厦门大学 | Ni-based methanation catalyst that in-situ growing carbon nano tube promotes and preparation method thereof |
| CN107936697A (en) * | 2017-12-14 | 2018-04-20 | 佛山市彩贵新型材料有限公司 | A kind of high dispersive, fine grain whiteware ink raw powder's production technology |
| CN113477273A (en) * | 2021-06-29 | 2021-10-08 | 蒲城驭腾新材料科技有限公司 | Preparation method of catalyst for methanation reaction of carbon dioxide |
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| CN1182414A (en) * | 1995-04-20 | 1998-05-20 | 出光兴产株式会社 | Method for producing ether compound |
| CN1259488A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder |
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| CN1259488A (en) * | 1999-01-04 | 2000-07-12 | 北京大学 | Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder |
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