CN113231070A - Preparation method and application of composite metal oxide solid solution copper-loaded reverse catalyst - Google Patents
Preparation method and application of composite metal oxide solid solution copper-loaded reverse catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 239000010949 copper Substances 0.000 title claims abstract description 66
- 239000006104 solid solution Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 12
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000002360 explosive Substances 0.000 claims abstract description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 3
- 238000010899 nucleation Methods 0.000 claims abstract description 3
- 230000006911 nucleation Effects 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 30
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000006004 Quartz sand Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000012495 reaction gas Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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Abstract
The invention discloses a preparation method and application of a composite metal oxide solid solution copper-loaded reverse catalyst. The invention adopts a coprecipitation method assisted by a micro-liquid film reactor and uses NaBH4Is a precipitating agent andand adding the original agent, copper nitrate, cerium nitrate, zirconium nitrate and a surfactant solution into a micro liquid film reactor at the same time for explosive rapid nucleation, then transferring the obtained suspension into a high-pressure reaction kettle for hydrothermal crystallization, and then washing, drying, roasting and reducing to obtain the composite metal oxide solid solution copper-loaded reverse catalyst. Application of the catalyst to CO2In the reaction of synthesizing the methanol by hydrogenation, the pressure is 3MPa, and the space velocity is 18000h‑1And at the temperature of 260 ℃ of 220-.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a composite metal oxide solid solution copper-loaded reverse catalyst.
Background
In recent years, with the emission of a large amount of carbon dioxide, not only the greenhouse effect is more serious, but also the waste of resources is caused. The efficient use of carbon dioxide is a promising topic and currently some important advances are being made. It has been shown that CO2Can be converted into some high-value products, such as methane, methanol and olefin. Methanol is an important chemical raw material and a promising liquid fuel, CO2Conversion to methanol is of more practical significance. In CO2In the hydrogenation reaction, copper-based and noble metal-based catalysts have been studied to some extent. Compared with noble metal-based catalysts, copper-based catalysts have been widely studied due to their low cost, good activity, and high practicability. On the other hand, researchers are becoming aware of the importance of supports that not only facilitate improved dispersion of the active metal, enhance the interaction between the metal and the support, but also modify the surface chemical state of the catalyst (oxygen vacancies, surface acidity and basicity).
Supported catalyst in CO2Hydrogenation is widely used, and the interaction and interface effect between active metal and carrier are especially important to catalytic performance. Traditional supported catalysts are often prepared by coprecipitation and impregnation methods, however, in these methods, metal salt precursors are used as active components to be supported on the surface of a carrier, the contact between the active metals and the carrier is not tight enough, the formed interface is deficient, and the interface interaction is weakThe agglomeration and growth of the active components in the preparation process or the sintering at high temperature are easily caused, the dispersion is more uneven, the stability is poor, and the catalytic performance is influenced.
Disclosure of Invention
The invention aims to provide a preparation method and application of a composite metal oxide solid solution supported copper inverse catalyst.
In the composite metal oxide solid solution copper-supported reverse catalyst of the present invention, ZrO of small particles2-CeO2The composite metal oxide solid solution is uniformly dispersed around the copper active nano particles with large particle size, the average particle size of the copper active nano particles is 7-10nm, and ZrO is formed2-CeO2The average particle diameter of the composite metal oxide solid solution is 5-7nm, the mass fraction of copper is 20-40%, the molar ratio of Ce to Zr is 0.33-3, and the BET specific surface area of the catalyst is 80-200m2/g。
The preparation method of the composite metal oxide solid solution copper-loaded reverse catalyst comprises the following steps: adopting a coprecipitation method assisted by a micro-liquid film reactor and using NaBH4Adding a precipitant and a reducing agent, copper nitrate, cerium nitrate, zirconium nitrate and a surfactant solution into a micro liquid film reactor at the same time for explosive rapid nucleation, then transferring the obtained suspension into a high-pressure reaction kettle for hydrothermal crystallization, and then washing, drying, roasting and reducing to obtain the composite metal oxide solid solution copper-loaded reverse catalyst.
The preparation method of the composite metal oxide solid solution loaded copper inverse catalyst comprises the following specific operation steps:
(1) 0.5-2g of copper nitrate, 0.5-2g of zirconium nitrate, 0.5-2g of cerium nitrate and 0.3-1.8g of surfactant are weighed and dissolved in 30-60mL of deionized water, wherein the total concentration of metal ions is 0.2-0.3mol/L, Ce4+With Zr4+The molar ratio of (A) is 0.33-3, and the mass of the surfactant is 1-5 times of that of Cu;
(2) preparing 30-60mL of sodium borohydride solution with the concentration of 2-10 mol/L;
(3) adding the prepared solutions in the steps (1) and (2) into a micro-liquid membrane reactor at the same time, stirring for 2-5min at the rotating speed of 3000 plus 4000rpm/min, transferring the obtained suspension into a polytetrafluoroethylene inner container of a high-pressure hydrothermal kettle, carrying out hydrothermal reaction for 12-36h at the temperature of 120 plus 180 ℃, cooling to room temperature, filtering and washing with deionized water to be neutral, and drying and grinding the precipitate;
(4) placing the product obtained in the step (3) in a muffle furnace, and roasting at the temperature of 300-500 ℃ for 2-6h to obtain a catalyst precursor ZrO2-CeO2/CuO；
(5) And (3) placing the catalyst precursor in a tubular furnace, and carrying out reduction reaction for 1-4h at 200-500 ℃ in a mixed atmosphere of hydrogen and nitrogen to obtain the composite metal oxide solid solution copper-loaded reverse catalyst.
The surfactant is one or more selected from polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
The prepared composite metal oxide solid solution copper-loaded reverse catalyst is applied to catalyzing CO2In the reaction of synthesizing methanol by hydrogenation. Said catalytic CO2The specific conditions of the reaction for synthesizing the methanol by hydrogenation are as follows: weighing 0.1-0.5g of composite metal oxide solid solution copper-loaded reverse catalyst and 0.1-0.5g of quartz sand by adopting a high-pressure fixed bed microreactor, uniformly mixing, filling into a stainless steel reaction tube, heating to 500 ℃ at the speed of 2-5 ℃/min in the mixed atmosphere of hydrogen and nitrogen, and carrying out reduction reaction for 1-3 h; after the temperature is reduced to room temperature, the reaction is switched to CO2、H2And the mixed reaction gas of Ar is heated to the temperature of 220-260 ℃ for reaction.
The composite metal oxide solid solution copper-loaded reverse catalyst prepared by the invention is small-particle ZrO2-CeO2The composite metal oxide solid solution is uniformly dispersed around the copper active nano particles with large particle size, so that ZrO can be obviously increased2-CeO2The contact area of the solid solution and the Cu particles forms a richer Cu-metal oxide interface active area, which is beneficial to the adsorption and further activation of carbon dioxide; on the other hand, the agglomeration of the active components in the preparation process and the sintering in high-temperature reaction can be inhibited; the addition of the surfactant in the reaction enables the composite metal oxide solid solution particles and the Cu particles to be formedThe sub-dispersion is more uniform. Application of the catalyst to CO2In the reaction for synthesizing the methanol by hydrogenation, the pressure is 3MPa, and the space velocity is 18000h-1In the temperature range of 220 ℃ and 260 ℃, the conversion rate reaches 8-20 percent, and the selectivity reaches 68-90 percent, which surpasses most literature reports. And the catalyst shows good stability in reaction for 72 hours, and has wide application prospect in the fields of traditional industrial catalysis, novel energy and chemical industry and the like.
Drawings
FIG. 1 shows ZrO in example 12-CeO2XRD spectrum of the/Cu catalyst.
FIG. 2 shows ZrO in example 12-CeO2HRTEM image of/Cu catalyst.
FIG. 3 shows ZrO in example 12-CeO2N of/Cu catalyst2-adsorption-desorption curve.
FIG. 4 shows ZrO in examples 1 and 22-CeO2The result of characterization of O1s in XPS for the/Cu catalyst.
FIG. 5 shows ZrO in example 12-CeO2Stability curves for the/Cu catalyst.
Detailed Description
Example 1
1.2708g of Cu (NO) were weighed out3)2·3H2O, 1.0291g of Ce (NO)3)4·6H2O, 1.0175g of Zr (NO)3)4·5H2O and 0.3366g PVP were dissolved in 40mL of deionized water and labeled solution A. 3.795g of sodium borohydride was weighed out and dissolved in 40mL of deionized water, and the solution B was recorded.
Slowly pouring the solutions A and B along two sides of the inner wall of the micro-liquid membrane reactor, stirring at 3500rpm/min for 3min, transferring the suspension into a high-pressure hydrothermal kettle with a polytetrafluoroethylene inner container, carrying out hydrothermal treatment at 150 ℃ for 24h, cooling to room temperature, and filtering and washing with deionized water to neutrality. The precipitate was dried in an oven at 60 ℃ overnight. Fully grinding the obtained solid precipitate, placing the solid precipitate in a muffle furnace, and roasting the solid precipitate for 4 hours at the temperature of 400 ℃ to obtain a catalyst precursor ZrO2-CeO2and/CuO. The catalyst precursor is placed in a tube furnace in whichHydrogen nitrogen mixture (10% H)2) Reducing for 2h at the temperature of 300 ℃ to obtain the composite metal oxide solid solution loaded copper reverse catalyst ZrO2-CeO2and/Cu. Wherein the average size of Cu particles is 8.2nm, the average size of solid solution particles is 5.5nm, the mass fraction of the catalyst Cu is 30 wt%, and the specific surface area of the catalyst is 141m2/g。
FIG. 1 shows ZrO in example 12-CeO2XRD spectrogram of/Cu reverse catalyst sample has diffraction peak at 29.8 deg. between CeO2(111) Crystal face and ZrO2(011) 2 theta values of crystal planes are due to Zr4+Has a small radius and can be embedded into CeO2In the crystal lattice, CeO is formed2Is contracted to form ZrO2-CeO2And (4) compounding phases. The diffraction peak at about 43.5 degrees is attributed to the Cu (111) crystal face, and the average size of Cu particles is 14.3nm and ZrO is calculated by the Scherrer formula2-CeO2The diffraction peak intensity of the composite phase is lower than the Cu (111) plane, and it is likely that the particles of the composite phase are smaller, as demonstrated later by TEM characterization.
FIG. 2 shows ZrO in example 12-CeO2High Resolution Transmission Electron Microscopy (HRTEM) of the Cu-based reverse catalyst sample can show that composite metal oxide solid solution particles with small particle size are uniformly dispersed around the copper active nanoparticle component with large particle size. Wherein the average particle size of the solid solution is 6.5nm and the particle size of the copper is 8.2 nm. In the figure, it was observed that the lattice stripe (0.209nm) on the Cu (111) crystal plane and the lattice stripe (0.301nm) on the composite phase (101) crystal plane were closely surrounded with the Cu (111) crystal plane, and it was confirmed that the small-particle metal oxide solid solution was closely surrounded with the Cu particles to form ZrO2-CeO2a/Cu-based inverse catalyst.
FIG. 3 shows ZrO in example 12-CeO2N of/Cu-based reverse catalyst sample2Adsorption-desorption curve, the sample being a type IV adsorption isotherm and being at P/P0The existence of a hysteresis loop is proved when the catalyst has a mesoporous structure between 0.6 and 1.0.
FIG. 4 shows ZrO in examples 1 and 22-CeO2XPS characterization of the/Cu-based inverse catalyst sample shows that the O1s orbital can be divided into three peaks, and the band around 530.1eV is attributed to lattice oxygen (O)α) The band around 531.9eV is attributed to defective oxygen (O)β) 533.2eV band ascribed to oxygen (O) in hydroxyl groupγ). It can be seen that the catalysts prepared in examples 1 and 2 have rich interfacial oxygen defect structure, and the catalyst O in example 1β/Oα(0.68) is larger than that of example 2(0.57), and it is confirmed that the catalyst containing 1:1 Ce: Zr has a more abundant interface structure.
And (3) testing the application of the catalyst:
CO on catalyst samples using high pressure fixed bed microreactors2The performance of the hydrogenated methanol is tested. 0.2g of a catalyst sample and the same mass of quartz sand were weighed. After being mixed uniformly, the mixture was filled into a stainless steel reaction tube (inner diameter: 8 mm). Then at 10% v/v H2/N2Heating to 300 ℃ at the speed of 5 ℃/min under the atmosphere (100mL/min), and reducing for 2 h. After the temperature is reduced to room temperature, the volume ratio is switched to CO2：H2: and (3) carrying out performance evaluation on the reaction gas with the Ar being 24:72:4 under the conditions of the temperature of 220-. CO after 6h of reaction2The conversion is up to 9.73% and the selectivity is up to 83.11%.
FIG. 5 shows ZrO in example 12-CeO2Stability testing of/Cu-based reverse catalyst samples, it was found that CO was present in up to 72 hours of testing2The conversion rate is improved to a certain extent within 0-8h, because the catalyst is activated at high temperature, the catalyst is basically kept unchanged within the rest 8-72h, and the selectivity is also kept in a stable state, which proves that the catalyst has good stability within a longer time and wider application prospect, and provides possibility for industrialization.
Example 2
1.3168g of Cu (NO) were weighed out3)2·3H2O, 1.4816g of Ce (NO)3)4·6H2O, 0.4883g of Zr (NO)3)4·5H2Dissolving O and 0.3366g CTAB in 40mL of deionized water, and marking as a solution A; 7.59g of sodium borohydride was weighed out and dissolved in 40mL of solutionIonic water, denoted as solution B.
Slowly pouring the solutions A and B along two sides of the inner wall of the micro-liquid membrane reactor, stirring at 3500rpm/min for 3min, transferring the suspension into a high-pressure hydrothermal kettle with a polytetrafluoroethylene inner container, carrying out hydrothermal treatment at 150 ℃ for 24h, cooling to room temperature, and filtering and washing with deionized water to neutrality. The precipitate was dried in an oven at 60 ℃ overnight. Fully grinding the obtained solid precipitate, placing the solid precipitate in a muffle furnace, and roasting the solid precipitate for 4 hours at the temperature of 400 ℃ to obtain a catalyst precursor ZrO2-CeO2and/Cu. The catalyst precursor was placed in a tube furnace in a mixture of hydrogen and nitrogen (10% H)2) Reducing for 2h at the temperature of 300 ℃ to obtain a catalyst sample. Wherein the average size of Cu particles is 9.1nm, the average size of solid solution particles is 6.3nm, the mass fraction of the catalyst Cu is 30 wt%, and the specific surface area of the catalyst is 109m2/g。
CO on catalyst samples using high pressure fixed bed microreactors2The performance of the hydrogenated methanol is tested. 0.2g of a catalyst sample and the same mass of quartz sand were weighed. After being mixed uniformly, the mixture was filled into a stainless steel reaction tube (inner diameter: 8 mm). Then at 10% v/v H2/N2Heating to 300 ℃ at the speed of 5 ℃/min under the atmosphere (100mL/min), and reducing for 2 h. After the temperature is reduced to room temperature, the volume ratio is switched to CO2：H2: and (3) carrying out performance evaluation on the reaction gas with the Ar being 24:72:4 under the conditions of the temperature of 220-. CO after 6h of reaction2The conversion is 11.48% at the highest and the selectivity is 69.43% at the highest.
Example 3
1.2708g of Cu (NO) were weighed out3)2·3H2O, 1.0291g of Ce (NO)3)4·6H2O, 1.0175g of Zr (NO)3)4·5H2Dissolving O and 0.3366g SDBS in 40mL deionized water, and marking as solution A; 3.795g of sodium borohydride was weighed out and dissolved in 40mL of deionized water, and the solution B was recorded.
Slowly pouring the solution A and the solution B along two sides of the inner wall of the micro-liquid membrane reactor, stirring at 3500rpm/min for 3min, transferring the suspension into a high-pressure hydrothermal kettle with a polytetrafluoroethylene inner container, performing hydrothermal treatment at 150 ℃ for 12h,after cooling to room temperature, the mixture was filtered and washed with deionized water to neutrality. The precipitate was dried in an oven at 60 ℃ overnight. Fully grinding the obtained solid precipitate, placing the solid precipitate in a muffle furnace, and roasting the solid precipitate for 4 hours at 500 ℃ to obtain a catalyst precursor ZrO2-CeO2and/Cu. The catalyst precursor was placed in a tube furnace in a mixture of hydrogen and nitrogen (10% H)2) Reducing for 2h at the temperature of 300 ℃ to obtain a catalyst sample. Wherein the average size of Cu particles is 9.5nm, the average size of solid solution particles is 6.8nm, the mass fraction of the catalyst Cu is 30 wt%, and the specific surface area of the catalyst is 93m2/g。
CO on catalyst samples using high pressure fixed bed microreactors2The performance of the hydrogenated methanol is tested. 0.2g of a catalyst sample and the same mass of quartz sand were weighed. After being mixed uniformly, the mixture was filled into a stainless steel reaction tube (inner diameter: 8 mm). Then at 10% v/v H2/N2Heating to 300 ℃ at the speed of 5 ℃/min under the atmosphere (100mL/min), and reducing for 2 h. After the temperature is reduced to room temperature, the volume ratio is switched to CO2：H2: and (3) carrying out performance evaluation on the reaction gas with the Ar being 24:72:4 under the conditions of the temperature of 220-. CO after 6h of reaction2The conversion is up to 9.75%, and the selectivity is up to 68.08%.
Example 4
1.2708g of Cu (NO) were weighed out3)2·3H2O, 1.0291g of Ce (NO)3)4·6H2O, 1.0175g of Zr (NO)3)4·5H2Dissolving O and 0.6732g PVP in 40mL of deionized water, and marking as solution A; 3.795g of sodium borohydride was weighed out and dissolved in 40mL of deionized water, and the solution B was recorded.
Slowly pouring the solutions A and B along two sides of the inner wall of the micro-liquid membrane reactor, stirring at 3500rpm/min for 3min, transferring the suspension into a high-pressure hydrothermal kettle with a polytetrafluoroethylene inner container, carrying out hydrothermal treatment at 120 ℃ for 24h, cooling to room temperature, and filtering and washing with deionized water to be neutral. The precipitate was dried in an oven at 60 ℃ overnight. Fully grinding the obtained solid precipitate, placing the solid precipitate in a muffle furnace, and roasting the solid precipitate for 4 hours at the temperature of 400 ℃ to obtain a catalyst precursor ZrO2-CeO2and/Cu. Placing a catalyst precursor inIn a tube furnace, in a mixture of hydrogen and nitrogen (10% H)2) Reducing for 2h at the temperature of 400 ℃ to obtain a catalyst sample. Wherein the average size of Cu particles is 7.8nm, the average size of solid solution particles is 5.1nm, the mass fraction of the catalyst Cu is 30 wt%, and the specific surface area of the catalyst is 158m2/g。
CO on catalyst samples using high pressure fixed bed microreactors2The performance of the hydrogenated methanol is tested. 0.2g of a catalyst sample and the same mass of quartz sand were weighed. After being mixed uniformly, the mixture was filled into a stainless steel reaction tube (inner diameter: 8 mm). Then at 10% v/v H2/N2Heating to 300 ℃ at the speed of 5 ℃/min under the atmosphere (100mL/min), and reducing for 2 h. After the temperature is reduced to room temperature, the volume ratio is switched to CO2：H2: and (3) carrying out performance evaluation on the reaction gas with the Ar being 24:72:4 under the conditions of the temperature of 220-. CO after 6h of reaction2The conversion is 8.34% at the highest and the selectivity is 78.31% at the highest.
Claims (6)
1. A composite metal oxide solid solution copper-supported reverse catalyst, characterized in that, in the catalyst, ZrO has small particles2-CeO2The composite metal oxide solid solution is uniformly dispersed around the copper active nano particles with large particle size, the average particle size of the copper active nano particles is 7-10nm, and ZrO is formed2-CeO2The average particle diameter of the composite metal oxide solid solution is 5-7nm, the mass fraction of copper is 20-40%, the molar ratio of Ce to Zr is 0.33-3, and the BET specific surface area of the catalyst is 80-200m2/g。
2. A preparation method of a composite metal oxide solid solution loaded copper inverse catalyst is characterized by comprising the following steps: adopting a coprecipitation method assisted by a micro-liquid film reactor and using NaBH4Adding a precipitant and a reducer, copper nitrate, cerium nitrate, zirconium nitrate and a surfactant solution into a micro-liquid-film reactor at the same time for explosive rapid nucleation, then transferring the obtained suspension into a high-pressure reaction kettle for hydrothermal crystallization, and then washing, drying, roasting and reducing to obtain the composite metal oxideCopper-supported reverse catalyst.
3. A preparation method of a composite metal oxide solid solution loaded copper inverse catalyst is characterized by comprising the following specific operation steps:
(1) 0.5-2g of copper nitrate, 0.5-2g of zirconium nitrate, 0.5-2g of cerium nitrate and 0.3-1.8g of surfactant are weighed and dissolved in 30-60mL of deionized water, wherein the total concentration of metal ions is 0.2-0.3mol/L, Ce4+With Zr4+The molar ratio of (A) is 0.33-3, and the mass of the surfactant is 1-5 times of that of Cu;
(2) preparing 30-60mL of sodium borohydride solution with the concentration of 2-10 mol/L;
(3) adding the prepared solutions in the steps (1) and (2) into a micro-liquid membrane reactor at the same time, stirring for 2-5min at the rotating speed of 3000 plus 4000rpm/min, transferring the obtained suspension into a polytetrafluoroethylene inner container of a high-pressure hydrothermal kettle, carrying out hydrothermal reaction for 12-36h at the temperature of 120 plus 180 ℃, cooling to room temperature, filtering and washing with deionized water to be neutral, and drying and grinding the precipitate;
(4) placing the product obtained in the step (3) in a muffle furnace, and roasting at the temperature of 300-500 ℃ for 2-6h to obtain a catalyst precursor ZrO2-CeO2/CuO；
(5) And (3) placing the catalyst precursor in a tubular furnace, and carrying out reduction reaction for 1-4h at 200-500 ℃ in a mixed atmosphere of hydrogen and nitrogen to obtain the composite metal oxide solid solution copper-loaded reverse catalyst.
4. The preparation method according to claim 2 or 3, wherein the surfactant is one or more selected from polyvinylpyrrolidone, cetyltrimethyl ammonium bromide and sodium dodecyl benzene sulfonate.
5. The composite metal oxide solid solution copper-supported reverse catalyst prepared by the method of claim 2 or 3 for catalyzing CO2Application in the reaction of synthesizing methanol by hydrogenation.
6. According to claim 5The use of, wherein the CO is catalysed2The specific conditions of the reaction for synthesizing the methanol by hydrogenation are as follows: weighing 0.1-0.5g of composite metal oxide solid solution copper-loaded reverse catalyst and 0.1-0.5g of quartz sand by adopting a high-pressure fixed bed microreactor, uniformly mixing, filling into a stainless steel reaction tube, heating to 500 ℃ at the speed of 2-5 ℃/min in the mixed atmosphere of hydrogen and nitrogen, and carrying out reduction reaction for 1-3 h; after the temperature is reduced to room temperature, the reaction is switched to CO2、H2And the mixed reaction gas of Ar is heated to the temperature of 220-260 ℃ for reaction.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113996303A (en) * | 2021-11-25 | 2022-02-01 | 西安交通大学 | Double-active interface supported catalyst, preparation method and application |
| CN114160148A (en) * | 2021-12-08 | 2022-03-11 | 中国科学院生态环境研究中心 | Cu-based catalyst for hydrogen production by methanol reforming and preparation method and application thereof |
| CN115069242A (en) * | 2022-05-05 | 2022-09-20 | 有研工程技术研究院有限公司 | Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof |
| CN115591549A (en) * | 2022-05-12 | 2023-01-13 | 北京化工大学（Cn） | Supported Fe-based catalyst and preparation method and application thereof |
| CN116273025A (en) * | 2023-04-03 | 2023-06-23 | 中国石油大学(华东) | Catalyst with reverse structure, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
| CN105013492A (en) * | 2015-06-30 | 2015-11-04 | 中国科学院山西煤炭化学研究所 | Methanol catalyst synthesized by carbon dioxide hydrogenation, preparation method and application thereof |
-
2021
- 2021-04-22 CN CN202110436826.2A patent/CN113231070B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301843A (en) * | 2012-03-15 | 2013-09-18 | 北京化工大学 | High-dispersion supported copper-based catalyst as well as preparation method and application thereof |
| CN105013492A (en) * | 2015-06-30 | 2015-11-04 | 中国科学院山西煤炭化学研究所 | Methanol catalyst synthesized by carbon dioxide hydrogenation, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CONGYI WU等: "Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation", 《NATURE COMMUNICATIONS》 * |
| GUANGCHENG ZHANG等: "Tuning surface-interface structures of ZrO2 supported copper catalysts by in situ introduction of indium to promote CO2 hydrogenation to methanol", 《APPLIED CATALYSIS A: GENERAL》 * |
| 石志盛: "Cu基、In2O3基催化剂的制备及其CO2加氢制甲醇性能研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113996303A (en) * | 2021-11-25 | 2022-02-01 | 西安交通大学 | Double-active interface supported catalyst, preparation method and application |
| CN113996303B (en) * | 2021-11-25 | 2022-12-06 | 西安交通大学 | Double-active interface supported catalyst, preparation method and application |
| CN114160148A (en) * | 2021-12-08 | 2022-03-11 | 中国科学院生态环境研究中心 | Cu-based catalyst for hydrogen production by methanol reforming and preparation method and application thereof |
| CN115069242A (en) * | 2022-05-05 | 2022-09-20 | 有研工程技术研究院有限公司 | Catalyst for hydrogen production by oxidation and reforming of ethanol and preparation and activation methods thereof |
| CN115591549A (en) * | 2022-05-12 | 2023-01-13 | 北京化工大学（Cn） | Supported Fe-based catalyst and preparation method and application thereof |
| CN115591549B (en) * | 2022-05-12 | 2023-10-27 | 北京化工大学 | Supported Fe-based catalyst and preparation method and application thereof |
| CN116273025A (en) * | 2023-04-03 | 2023-06-23 | 中国石油大学(华东) | Catalyst with reverse structure, preparation method and application thereof |
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