【摘要】：合成氣催化反應制備甲醇對資源合理化利用及環(huán)境保護有著至關重要的作用,因此對Cu基催化劑組分與混合氣適配關系的研究尤為關鍵,將有助于提高反應氣的轉(zhuǎn)化率及催化反應的產(chǎn)率。本論文通過X射線衍射(XRD)、熱重-微商熱重(TG-DTG)、紅外光譜儀(FT-IR)、H2程序升溫還原(H2-TPR)、CO2程序升溫吸脫附(CO2-TPD)和X射線光電子能譜(XPS)等表征方法探究了不同助劑組成的二組分、三組分及四組分催化劑的催化活性及催化體系在三種混合氣條件下的適配關系。具體內(nèi)容如下:1、助劑的組成對催化性能的影響:不同組分含量的催化劑所表現(xiàn)的催化活性為:二組分(Cu-ZnO,Cu-Al2O3,Cu-ZrO2)三組分(Cu-ZnO-Al2O3,Cu-ZnO-ZrO2)四組分(Cu-ZnO-Al2O3-ZrO2)。而四組分催化劑體系中,當添加適當?shù)腪rO2(6%),前驅(qū)體中出現(xiàn)綠銅鋅礦相,而此時CuO和ZnO顆粒尺寸最小,比表面積、銅分散度增強,催化劑的催化效果最好,甲醇的選擇性和收率以及CO2轉(zhuǎn)化率最高。ZrO2含量過多或過少,不利于形成綠銅鋅礦相,僅有鋅孔雀石相形成。對于單組分氧化物載體催化劑來說,ZrO2載體更有利于CO2加氫反應,Al2O3載體更有利于CO加氫反應。對于復合氧化物載體催化劑來說,四組分Cu-ZnO-Al2O3-ZrO2中ZrO2摻雜量為2%時,CO加氫效果較好,ZrO2摻雜量為10%時,CO2加氫效果較好,ZrO2摻雜量為6%時,其CO和CO2混合氣加氫效果較好。2、混合氣組成對產(chǎn)率的影響:不同組成的反應氣對甲醇的選擇性和甲醇的收率影響很大。對于CO2和氫氣的混合氣反應來說,其CO2的轉(zhuǎn)化率明顯優(yōu)于三元混合氣。對于CO和氫氣的混合氣來說,其CO的轉(zhuǎn)化率明顯優(yōu)于三元混合氣,但三元混合氣在催化過程中,其甲醇的選擇性和收率最高,CO和CO2的適當混合可以有效提高產(chǎn)物的轉(zhuǎn)化率。
[Abstract]:The synthesis of methanol by catalytic reaction of syngas plays an important role in the rational utilization of resources and environmental protection. Therefore, the study on the relationship between the composition of Cu-based catalyst and the mixture of methanol is especially critical. It will help to increase the conversion of reaction gas and the yield of catalytic reaction. In this paper, X-ray diffraction (XRD), thermogravimetry-derivative thermogravimetry (TG-DTG), infrared spectrometer (FT-IR), H2 temperature programmed reduction (H2-TPR), CO2 temperature programmed desorption (CO2-TPD) and X-ray photoelectron spectroscopy (XPS) were used to characterize the two components of different auxiliaries. The catalytic activity of three-component and four-component catalysts and the adaptation relationship of the catalyst system under the conditions of three kinds of gas mixture. The main contents are as follows: 1. The effect of promoter composition on catalytic performance: the catalytic activity of catalysts with different component contents is as follows: two components (Cu-ZnO,Cu-Al2O3,Cu-ZrO2) and three components (Cu-ZnO-Al2O3,). Cu-ZnO-ZrO2) four components (Cu-ZnO-Al2O3-ZrO2). In the four-component catalyst system, when the appropriate ZrO2 (6%) was added, the spruce phase appeared in the precursor, and the particle size of CuO and ZnO was the smallest, the specific surface area and copper dispersion were enhanced, and the catalytic effect of the catalyst was the best. The selectivity and yield of methanol and the conversion rate of CO2 are the highest. Too much or too little ZrO _ 2 content is not conducive to the formation of zincite phase, but only zinctachite phase. For single component oxide carrier catalyst, ZrO2 carrier is more favorable for CO2 hydrogenation, and Al2O3 carrier is more favorable for CO hydrogenation reaction. When the content of ZrO2 in the four-component Cu-ZnO-Al2O3-ZrO2 is 2%, the hydrogenation effect of CO is better, that of ZrO2 is 10%, that of CO2 is better, and that of ZrO2 is 6%. The mixture of CO and CO2 has a good hydrogenation effect. 2, the effect of mixture composition on the yield: the selectivity of methanol and the yield of methanol are greatly influenced by the reaction gas of different composition. For the mixed gas reaction of CO2 and hydrogen, the conversion of CO2 is obviously better than that of ternary mixture. For the mixture of CO and hydrogen, the conversion of CO is obviously better than that of ternary mixture, but the selectivity and yield of methanol are the highest in the catalytic process of ternary mixture. The proper mixing of CO and CO2 can effectively improve the conversion of the product.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TQ223.121;O643.36

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