Method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia gas in one step
A carbon dioxide, dimethylamine technology, applied in chemical instruments and methods, reductive alkylation preparation, metal/metal oxide/metal hydroxide catalysts, etc., to achieve the effect of improving selectivity
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[0026] Moreover, the Cu-based catalyst in the catalyst is expressed as Cu / M x o y , M is ZnO, Al 2 o 3 、Cr 2 o 3 , ZrO 2 , SiO 2 、TiO 2 One or more of them, preferably ZnO, Al 2 o 3 、Cr 2 o 3 , ZrO 2 , the catalyst is prepared by a co-precipitation method, and the steps of the preparation method are as follows:
[0027] (1) According to the element molar ratio Cu:M=1:1-10, prepare salt solution A containing Cu and M elements, M nitrate solution, preferably containing ZnO and Al 2 o 3 、Cr 2 o 3 , ZrO 2 elemental salt solutions;
[0028] (2) After mixing, stir for 10-60 minutes;
[0029] (3) The preparation is selected from NaOH, Na 2 CO 3 Compound aqueous solution or ammonia solution B, at 100-500r / min speed, water bath temperature 50-90℃, mix A and 0.5-5mol / LB evenly, control pH=8-14, keep stirring until precipitation is complete, precipitation After aging for 2-48h, wash with deionized water;
[0030](4) Drying at 60-120°C for 5-24h, calcining at 350-500...
Embodiment 1
[0037] (1) According to the elemental molar ratio Cu:Zn:ZrO 2 =10:5:1 Weigh copper nitrate, zinc nitrate, zirconium nitrate, prepare a solution with a solid-to-liquid ratio of 1:5, dissolve and stir for 60 minutes; add 1 mol / L of NaOH solution, control pH = 10; continue to stir for 2 hours after the dropwise addition, and age overnight; dry at 100°C for 15 hours, roast at 350°C, grind, granulate to 20-40 mesh, set aside, record as Q;
[0038] (2) Molecular sieve H-ZSM-5 raw material molar ratio TEOS:TPAOH:H 2 O:EtOH:Al 2 o 3 =2:0.68:120:8:0.24. After the mixed solution forms a gel, record it as W; add 20-40 mesh Cu-based catalyst Q to the above mother liquor, mix according to the ratio of mass Q:W=3:1; stir at room temperature for 2 hours, and then transfer to polytetrafluoroethylene In a lined stainless steel reactor, at 160°C, with a rotation speed of 2rpm / min, crystallize for 24h, filter off the mother liquor, centrifuge, wash, dry, and roast at 550°C for 5h to obtain ...
Embodiment 2
[0040] Cu base catalyst preparation step is the same as embodiment 1 (1), molecular sieve SAPO-34 raw material molar ratio is Al 2 o 3 :P 2 o 5 :SiO2 2 :TEAOH:H 2 O=1:1:0.6:2:110. After the mixed solution forms a gel, the preparation process of the core-shell structure catalyst is the same as that in Example 1(2), mixing according to the ratio of mass Q:W=3:1. The crystallization conditions were 200°C, the rotation speed was 2rpm / min, the crystallization time was 24h, and the catalyst was roasted at 550°C for 5h to obtain the product catalyst CuZnZr@SAPO-34 (3:1); see Table 1 and Example 2 for the catalytic reaction results. The reaction condition is H 2 / CO 2 / NH 3 =1:1:3, the reaction temperature is 400°C, and the reaction pressure is 1.5MPa.
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