CO_2催化加氢合成甲醇催化剂CuO-ZnO-Al_2O_3改性的研究
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摘要
C02排放不仅造成巨大的碳资源浪费,而且严重污染环境,其所造成的“温室效应”和“臭氧空洞”日益影响人类与大自然的和谐相处。C02催化加氢合成甲醇是C1化学研究的热点之一,但是由于CO2本身的惰性和热力学限制,其转化率一直很低,很难突破30%。本研究采用草酸作沉淀剂,用共沉淀法,制备了铜基催化剂CuO-ZnO-Al2O3,并用剂量为2～8wt.%的MgO、TiO2、CaO等单组分助剂和MgO-TiO2、 MgO-SiO2、TiO2-SiO2等复合助剂对其改性。采用固定床反应装置对改性前后催化剂的性能进行评价。发现改性后的催化剂使CO2转化率和甲醇选择性明显提高。对于催化剂CuO-ZnO-Al2O3,在P=2.6MPa、t=260℃、SV=3600h-1和H2：C02=3：1(体积比)条件下,性能评价结果为：XCO2=15.81%、SCH3OH=23.31%、YCH3OH=3.69%,经过改性后的催化剂,在同等反应条件下,CO2转化率和甲醇选择性均有提高,在催化剂2wt.%TiO2-SiO2/CuO-ZnO-Al2O3上,CO2转化率达到40.70%、甲醇选择性达到41.17%,但是助剂存在最佳加入量,过量反而降低CO2转化率和甲醇选择性。并采用XRD、FT-IR、 H2-TPR、H2-TPD、NH3-TPD、CO2-TPD、BET和SEM等表征手段对改性前后的催化剂进行表征分析,发现大部分助剂提高了催化剂中CuO的分散度,调变了催化剂表面的酸性,且复合助剂间产生了协同作用,这些改性提高了催化剂对CO2或H2的吸附量和吸附强度。
本研究继而考察了预处理条件(焙烧温度)对催化剂性能的影响,以及工艺条件如温度、压力、空速和H2/CO2比等对CO2催化加氢合成甲醇反应的影响。以2wt.%MgO/CuO-ZnO-Al2O3为例,发现焙烧温度对催化剂中CuO和ZnO的晶型有较大影响,进而影响催化剂在反应中的性能,研究发现,在P=2.6MPa、t=260℃、SV=3600h-1和H2：CO2=3：1(体积比)条件下,焙烧温度为550℃时催化剂的性能最佳,C02转化率和甲醇选择性分别为29.80%和34.52%,焙烧温度过低或过高均不利于催化剂性能的发挥。反应温度过低达不到反应所需的最佳温度,过高反而抑制甲醇的生成,在P=2.6MPa、SV=3600h-1和H2：CO2=3：1(体积比)条件下最佳反应温度为260℃。CO2转化率随压力和H2/CO2的升高而升高,随流量的升高而降低。
CO2emission causes the huge waste of carbon resource and environmental problem, leading to the greenhouse effect and ozone depletion, and result in the worse harmonious relationship between nature and human being. As a branch of C1chemistry, methanol synthesis from CO2hydrogenation has been considered an issue, while CO2conversion was found to be too poor to exceed30%because of both intrinsic inertia of CO2and thermodynamics. In this present work, the Cu-based catalyst CuO-ZnO-Al2O3was prepared by co-precipitation method, using oxalate as precipitant, and CuO-ZnO-Al2O3was promoted with the single component promoter such as MgO, TiO2, CaO, etc. and the multicomponent promoter such as MgO-TiO2, MgO-SiO2, TiO2-SiO2, etc. in dosages range of2-8wt.%. The catalytic evaluation was performed using a fixed-bed reactor, results showed that most of the CO2conversions on the promoted catalysts were higher than that on the one unpromoted. For catalyst CuO-ZnO-Al2O3, the catalytic evaluation results showed that XCO2=15.81%, SCH3OH=23.31%and YCH3OH=3.69%under the conditions of P=2.6MPa, t=260℃, SV=3600h-1and H2:CO2=3:1(volume ratio), however it showed the higher CO2conversion and the higher methanol selectivity on the promoted catalysts than that on the one without promoter under the same conditions. Especially, the CO2conversion and methanol selectivity could reach40.70%and41.17%on the catalyst2wt.%TiO2-SiO2/CuO-ZnO-Al2O3, respectively. But the addition should be at the optimal dosage, however the excessive promoter would decrease the CO2conversion and methanol selectivity. In this present work, XRD, FT-IR, H2-TPR, H2-TPD, NH3-TPD, CO2-TPD, BET and SEM characterizations were performed, it was found that most of the promoters enhanced the dispersion of CuO in the catalyst body, modulated the acidity of the surface of the catalyst, meanwhile synergistic effect produced between the promoters, and most of these modifications improved the adsorption capacity/strength of CO2or H2on the surface of the catalyst.
In this work, the effect of pre-treatment condition (calcination temperature) on the catalytic performance, and the effect of reaction conditions such as temperature, pressure, space velocity and the ratio of H2/CO2on the reaction were investigated either. Take the catalyst2wt.%MgO/CuO-ZnO-Al2O3as example, testing results showed that the calcination temperature played an important role on the crystals of CuO and ZnO in the catalyst body, hence the performance of the catalyst in the reaction, it was found also that the catalyst calcined at550℃showed the higher catalytic performance with CO2conversion of29.80%and methanol selectivity of34.52%under the conditions of P=2.6MPa, t=260℃, SV=3600h-1and H2:CO2=3:1(volume ratio). The catalyst which was pre-treated at too high or too low temperature can not exhibit the well performance. Too low temperature can not run the catalyst, while too high would inhibit the formation of methanol, the optimal temperature was found to be at260℃under the conditions of P=2.6MPa, SV=3600h-1, H2:CO2=3:1(volume ratio). CO2conversion increased with the increase in H2/CO2while decreased with the increase in flow rate.
本研究继而考察了预处理条件(焙烧温度)对催化剂性能的影响,以及工艺条件如温度、压力、空速和H2/CO2比等对CO2催化加氢合成甲醇反应的影响。以2wt.%MgO/CuO-ZnO-Al2O3为例,发现焙烧温度对催化剂中CuO和ZnO的晶型有较大影响,进而影响催化剂在反应中的性能,研究发现,在P=2.6MPa、t=260℃、SV=3600h-1和H2：CO2=3：1(体积比)条件下,焙烧温度为550℃时催化剂的性能最佳,C02转化率和甲醇选择性分别为29.80%和34.52%,焙烧温度过低或过高均不利于催化剂性能的发挥。反应温度过低达不到反应所需的最佳温度,过高反而抑制甲醇的生成,在P=2.6MPa、SV=3600h-1和H2：CO2=3：1(体积比)条件下最佳反应温度为260℃。CO2转化率随压力和H2/CO2的升高而升高,随流量的升高而降低。
CO2emission causes the huge waste of carbon resource and environmental problem, leading to the greenhouse effect and ozone depletion, and result in the worse harmonious relationship between nature and human being. As a branch of C1chemistry, methanol synthesis from CO2hydrogenation has been considered an issue, while CO2conversion was found to be too poor to exceed30%because of both intrinsic inertia of CO2and thermodynamics. In this present work, the Cu-based catalyst CuO-ZnO-Al2O3was prepared by co-precipitation method, using oxalate as precipitant, and CuO-ZnO-Al2O3was promoted with the single component promoter such as MgO, TiO2, CaO, etc. and the multicomponent promoter such as MgO-TiO2, MgO-SiO2, TiO2-SiO2, etc. in dosages range of2-8wt.%. The catalytic evaluation was performed using a fixed-bed reactor, results showed that most of the CO2conversions on the promoted catalysts were higher than that on the one unpromoted. For catalyst CuO-ZnO-Al2O3, the catalytic evaluation results showed that XCO2=15.81%, SCH3OH=23.31%and YCH3OH=3.69%under the conditions of P=2.6MPa, t=260℃, SV=3600h-1and H2:CO2=3:1(volume ratio), however it showed the higher CO2conversion and the higher methanol selectivity on the promoted catalysts than that on the one without promoter under the same conditions. Especially, the CO2conversion and methanol selectivity could reach40.70%and41.17%on the catalyst2wt.%TiO2-SiO2/CuO-ZnO-Al2O3, respectively. But the addition should be at the optimal dosage, however the excessive promoter would decrease the CO2conversion and methanol selectivity. In this present work, XRD, FT-IR, H2-TPR, H2-TPD, NH3-TPD, CO2-TPD, BET and SEM characterizations were performed, it was found that most of the promoters enhanced the dispersion of CuO in the catalyst body, modulated the acidity of the surface of the catalyst, meanwhile synergistic effect produced between the promoters, and most of these modifications improved the adsorption capacity/strength of CO2or H2on the surface of the catalyst.
In this work, the effect of pre-treatment condition (calcination temperature) on the catalytic performance, and the effect of reaction conditions such as temperature, pressure, space velocity and the ratio of H2/CO2on the reaction were investigated either. Take the catalyst2wt.%MgO/CuO-ZnO-Al2O3as example, testing results showed that the calcination temperature played an important role on the crystals of CuO and ZnO in the catalyst body, hence the performance of the catalyst in the reaction, it was found also that the catalyst calcined at550℃showed the higher catalytic performance with CO2conversion of29.80%and methanol selectivity of34.52%under the conditions of P=2.6MPa, t=260℃, SV=3600h-1and H2:CO2=3:1(volume ratio). The catalyst which was pre-treated at too high or too low temperature can not exhibit the well performance. Too low temperature can not run the catalyst, while too high would inhibit the formation of methanol, the optimal temperature was found to be at260℃under the conditions of P=2.6MPa, SV=3600h-1, H2:CO2=3:1(volume ratio). CO2conversion increased with the increase in H2/CO2while decreased with the increase in flow rate.
引文
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