A kind of carbon dioxide hydrogenation synthesis methanol catalyst and preparation method and application
A technology for synthesizing methanol and carbon dioxide, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, preparation of hydroxyl compounds, etc., can solve the problem of low conversion rate, poor methanol selectivity, low methanol yield, etc. problem, to achieve the effect of good activity, stable performance and large quantity
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Embodiment 1
[0023] Embodiment 1.Zr is in the form of zirconyl nitrate, and all the other metal elements (Cu, Zn, Al) are dissolved in deionized water in the form of nitrates, and a mixed solution is prepared by Cu2Zn1Al0.7Zr0.3 metal atom molar ratio; at 20 Co-precipitate with a mixed solution of sodium hydroxide and sodium carbonate at ℃, the precipitation process needs to be fully stirred, keep pH = 10, age at 60 ℃ for 15 hours, wash the precipitate with deionized water until no sodium ions are detected, and dry at 80 ℃ , baked at 500°C. Then impregnate the calcined metal oxide in sodium fluoride aqueous solution (0.2molL –1 ), and at N 2 Stirred under protection for 48h. The resulting precipitate was filtered, CO removed 2 Multiple washes with deionized DD water (until Na-free + filter out), and at N 2 Dry at 80°C under protection, then in N 2 Baking at 500°C for 4h under air protection. Broken to 40-60 mesh. The catalyst element modified by halogen can be expressed as Cu2Zn1Al...
Embodiment 2
[0025] Example 2. Metal elements (Cu, Zn, Al, Y) are all dissolved in deionized water in the form of nitrates, and a mixed solution is prepared according to the molar ratio of Cu2Zn1Al0.9Y0.1 metal atoms; at 20 ° C, with sodium hydroxide and The mixed solution of sodium carbonate is co-precipitated, and the precipitation process needs to be fully stirred to maintain pH = 8, aged at 60°C for 15 hours, the precipitate is washed with deionized water until no sodium ions are detected, dried at 80°C and roasted at 500°C. Immerse the calcined metal oxide in sodium fluoride aqueous solution (0.4molL –1 ), and at N 2 Stirred under protection for 48h. The resulting precipitate was filtered, CO removed 2 Multiple washes with deionized DD water (until Na-free + filter out), and at N 2 Dry at 80°C under protection, then in N 2 Baking at 450°C for 4h under protection. Broken to 40-60 mesh. The halogen-modified catalyst elements can be expressed as Cu2Zn1Al0.9Y0.1F0.1 in atomic ratio...
Embodiment 3
[0027] Example 3. Zr is in the form of zirconyl nitrate, the rest of the metal elements (Cu, Zn, Al) are in the form of nitrate, and the halogen fluorine is in the form of sodium fluoroaluminate, according to the atomic molar ratio of Cu2Zn1Al0.7Zr0.3F0.6 Prepare a mixed solution; co-precipitate with a mixed solution of sodium hydroxide and sodium carbonate at 20°C, fully stir during the precipitation process, keep pH = 10, age at 60°C for 15 hours, wash the precipitate with deionized water until no sodium ions are detected , dried at 80 °C and calcined at 500 °C. The carbon dioxide hydrogenation reaction is carried out in a stainless steel reactor with an inner diameter of 6mm. After reducing with pure hydrogen at 350°C for 10h, it is cooled to room temperature, and then switched to a reaction gas for reaction. The reaction conditions are as follows: P=5.0MPa, T=270°C, GHSV=9000mLgcat -1 h -1 , H 2 / CO 2 Molar ratio = 3, the liquid phase product was collected in an ice-wate...
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