温室气体CO_2加氢合成甲醇CuO-ZnO/TiO_2催化剂的制备与性能研究
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摘要
大量排放的二氧化碳造成了全球温室效应和环境污染，研究CO_2的减排与利用已经成为世界性关注的热点和急需解决的问题。CO_2加氢合成甲醇是合理利用二氧化碳的有效途径之一，甲醇是一种极其重要的基础有机化工原料，又是一种很有发展前途的新型环保清洁优质燃料。CO_2加氢合成甲醇为能源结构的战略调整提供了新途径，对解决日益严重的环境与能源问题具有重要的意义。
CO_2加氢合成甲醇通常采用的催化剂制备方法存在CO_2转化率低，甲醇选择性不高的问题。针对这些问题，提出了采用添加十六烷基三甲基溴化铵（CTAB）表面活性剂并流浆态共沉淀法制备CuO-ZnO/TiO_2催化剂，有效改善了催化剂的结构与催化性能。采用添加表面活性剂并流浆态共沉淀法、添加表面活性剂分步沉淀法、并流浆态共沉淀法及浸渍法制备了CuO-ZnO/TiO_2催化剂，利用BET、XRD、SEM、EDS、H_2-TPR、H_2-TPD、CO_2-TPD等方法对催化剂的物理与化学性能进行了表征，研究了不同的制备方法对CuO-ZnO/TiO_2催化剂性能的影响，通过固定床反应器对CO_2加氢合成甲醇CuO-ZnO/TiO_2催化剂的催化性能进行了评价。
研究结果表明，不同方法制备的CuO-ZnO/TiO_2催化剂均为介孔材料，沉淀法制备的CuO-ZnO/TiO_2催化剂BET比表面积和孔容大于浸渍法制备的催化剂，CuO和ZnO的分散性好。TiO_2载体起到阻止CuO晶粒长大和促进CuO分散的作用。沉淀法中以添加表面活性剂并流浆态共沉淀法制备的CuO-ZnO/TiO_2催化剂上CuO的还原温度最低，催化活性最好。浸渍法制备的催化剂上CuO的还原温度最高，催化活性低。H_2-TPD表明高温强吸附态下H_2的脱附峰面积大，催化剂表面上吸附更多的活化H_2，促进了CO_2加氢合成甲醇的反应。CO_2-TPD表明中等强度的CO_2吸附中心与二氧化碳加氢合成甲醇的效果密切相关。不同方法制备的CuO-ZnO/TiO_2催化剂活性及CH3OH选择性由高到低的顺序依次为：添加表面活性剂并流浆态共沉淀法＞添加表面活性剂分步沉淀法＞并流浆态共沉淀法＞浸渍法，添加表面活性剂有效地改善了CuO-ZnO/TiO_2催化剂的催化性能。
添加表面活性剂并流浆态共沉淀法制备的CuO-ZnO/TiO_2催化剂上CO_2加氢合成甲醇反应的催化性能最好。在反应压力2.5MPa、反应空速2100h-1、反应温度230℃、H_2和CO_2摩尔比3:1、反应时间4h的条件下，CO_2的转化率为13.26%，CH3OH的选择性为23.95%，CH3OH的产率最大为3.18%。
添加助剂对CO_2加氢合成甲醇催化剂的结构与性能具有重要影响，研究了在CuO-ZnO/TiO_2催化剂中分别添加ZrO_2、Al2O3及MnOχ助剂，采用添加CTAB表面活性剂并流浆态共沉淀法制备了CuO-ZnO-ZrO_2/TiO_2、CuO-ZnO-Al2O3/TiO_2及CuO-ZnO-MnOχ/TiO_2催化剂，利用BET、XRD、SEM、EDS、H_2-TPR、H_2-TPD、CO_2-TPD等方法对各催化剂的结构与化学性能进行了表征，研究了添加不同助剂及改变添加的ZrO_2助剂含量对CuO-ZnO/TiO_2催化剂性能的影响。通过XRD、XPS、H_2-TPD、CO_2-TPD、DRIFT等方法探讨了CuO-ZnO-ZrO_2/TiO_2催化剂上CO_2加氢合成甲醇的反应机理。
研究结果表明，添加不同助剂均增加了CuO-ZnO/TiO_2催化剂的比表面积和孔容，添加MnOχ使CuO-ZnO/TiO_2催化剂上CuO的还原温度升高，吸附H_2的浓度降低，催化活性下降。添加ZrO_2或Al2O3助剂均降低了CuO的还原温度，吸附H_2和CO_2的能力增强，促进了甲醇的合成。含不同助剂的CuO-ZnO/TiO_2催化剂中，添加ZrO_2助剂的CuO-ZnO-ZrO_2/TiO_2催化剂的催化性能最好，在反应压力2.5MPa、反应空速2100h-1、反应温度230℃、H_2和CO_2摩尔比3:1、反应时间4h的条件下，CO_2的转化率为18.24%，CH3OH的选择性为31.52%，CH3OH的产率最大为5.75%。
ZrO_2助剂的含量对CuO-ZnO/TiO_2催化剂的结构与性能具有显著影响。随着ZrO_2助剂含量的增加，催化剂的比表面积和孔容增大，孔径分布变均匀。ZrO_2促进了催化剂上CuO和ZnO的分散，降低了CuO的还原温度，提高了催化剂的活性。H_2-TPD表明增加催化剂中ZrO_2含量促进了对H_2的强吸附，催化剂表面上吸附H_2的浓度高，并具有储氢的作用，提高了CO_2加氢合成甲醇反应的速率。CO_2-TPD表明ZrO_2对促进CO_2的吸附与活化具有显著作用。ZrO_2助剂含量增加，提高了催化剂的催化性能。
CuO-ZnO-ZrO_2/TiO_2催化剂上的CuO还原后为零价金属铜，Cu~0是H_2吸附与解离的活性中心，ZnO和ZrO_2是CO_2的吸附活性中心。甲醇合成机理是CuO-ZnO-ZrO_2/TiO_2催化剂上双活性中心分别吸附活化H_2和CO_2，以CO_2为碳源直接加氢合成甲醇的反应。
A large amount of carbon dioxide emission led to global greenhouse effect andenvironmental pollution. Research of carbon dioxide emission reduction andutilization is of focus and urgent issues in the world. Methanol synthesis by carbondioxide hydrogenation is one of approaches of carbon dioxide utilization. Methanolis considered an important raw material of fundamental organic chemical industryand a new-type environmental protection clean fuels. Carbon dioxide hydrogenationto methanol is a new pathway for strategic adjustment of energy structure, and it isimportant significance to solve the increasingly environmental pollution and energyquestions.
In the process of carbon dioxide hydrogenation to methanol, the existingproblems of the general preparation methods of catalysts are lower to carbon dioxideconversion and methanol selectivity. In regard to these problems, CuO-ZnO/TiO_2catalysts were prepared by a novel parallel-slurry-mixing-precipitation methodcombined with addition of cetyltrimethylammonium bromide (CTAB) surfactant.Structure and catalytic performance of catalysts were improved effectively.CuO-ZnO/TiO_2catalysts were prepared by parallel-slurry-mixing-precipitationmethod combined with addition of surfactant, two-step precipitation methodcombined with addition of surfactant, parallel-slurry-mixing-precipitation andimpregnation method, respectively. Characterizations of physical and chemicalproperties of the catalysts were investigated by BET, XRD, SEM, EDS, H_2-TPR,H_2-TPD and CO_2-TPD. The effects of different preparation methods on catalyticperformances of CuO-ZnO/TiO_2catalysts were studied. The catalytic performancesof CuO-ZnO/TiO_2catalysts for methanol synthesis from CO_2hydrogenation wereevaluated by fixed bed reactor.
The research results show that CuO-ZnO/TiO_2catalysts of different preparationmethods are mesoporous materials. BET specific surface area and pore volume forthe CuO-ZnO/TiO_2catalysts of precipitation methods are greater than that ofimpregnation method, and dispersion of CuO and ZnO is better. TiO_2preventedgrowth of CuO crystal particles and promoted the dispersion of CuO species. In theprecipitation methods, CuO reduction temperature of CuO-ZnO/TiO_2catalyst ofparallel-slurry-precipitation method combined with addition of surfactant is lowest,and its reduction is easiest. CuO reduction temperature of that of impregnationmethod is highest, and its catalytic activity is lowest. H_2-TPD showed that hydrogendesorption peak area was large at high temperature and strong adsorption state, andactive hydrogen molecules on catalyst surface were more and more, and methanol synthesis from CO_2hydrogenation was promoted. CO_2-TPD revealed that CO_2adsorption center of moderate intensity was closely related to methanol synthesisfrom CO_2hydrogenation. From high to low, the activity and methanol selectivity ofCuO-ZnO/TiO_2catalysts of different preparation methods wasparallel-slurry-mixing-precipitation method combined with addition of surfactant,two-step precipitation method combined with addition of surfactant,parallel-slurry-mixing-precipitation and impregnation method. Addition ofsurfactant improved effectively catalytic performances of CuO-ZnO/TiO_2catalysts.
CuO-ZnO/TiO_2catalyst of parallel-slurry-precipitation method combined withaddition of surfactant for methanol synthesis from CO_2hydrogenation was best.Under the conditions of reaction pressure of2.5MPa, space velocity of2100h-1,reaction temperature of230℃, H_2/CO_2molar ratio of3:1and reaction time4h,carbon dioxide conversion and methanol selectivity and maximum of methanol yieldwere13.26%,23.95%and3.18%, respectively.
Additives of catalysts used in methanol synthesis from carbon dioxidehydrogenation are important effect on structure and performance of catalyst.CuO-ZnO/TiO_2catalyst added ZrO_2, Al2O3and MnOχ, respectively.CuO-ZnO-ZrO_2/TiO_2, CuO-ZnO-Al2O3/TiO_2and CuO-ZnO-MnOχ/TiO_2catalystswere prepared by parallel-slurry-mixing-precipitation method combined withaddition of CTAB surfactant. The structure characterization and chemical propertiesof the catalysts were investigated by BET, XRD, SEM, EDS, H_2-TPR, H_2-TPD,CO_2-TPD. The effects of different promoters and ZrO_2content on catalyticperformance of CuO-ZnO/TiO_2catalyst were studied. In the presence ofCuO-ZnO-ZrO_2/TiO_2catalyst, reaction mechanism of carbon dioxide hydrogenationto methanol was discussed by XRD, XPS, H_2-TPD, CO_2-TPD and DRIFT.
The research results show that addition of different promoters increasedspecific surface area and pore volume for the CuO-ZnO/TiO_2catalysts. The additionof MnOχon CuO-ZnO/TiO_2catalyst increased the reduction temperature of CuO,and decreased adsorptive hydrogen concentration and catalytic activity. AddingZrO_2or Al2O3promoter decreased the reduction temperature of CuO, enhancedcapacity of H_2and CO_2adsorption, and promoted methanol synthesis. In theCuO-ZnO/TiO_2catalysts containing different promoter, CuO-ZnO-ZrO_2/TiO_2catalyst exhibited an optimal catalytic performance. Under the conditions ofreaction pressure of2.5MPa, space velocity of2100h-1, reaction temperature of230℃, H_2/CO_2molar ratio of3:1and reaction time4h, carbon dioxide conversionand methanol selectivity and maximum of methanol yield were18.24%,31.52%and5.75%, respectively.
ZrO_2content is important effect on the structure and performance ofCuO-ZnO/TiO_2catalysts. Along with the increase of ZrO_2content, specific surface areas and pore volume of the catalysts increase, and pore size distribution isconcentrated. ZrO_2promoted the dispersion of CuO and ZnO species and decreasedthe reduction temperature of CuO, and enhanced catalyst activity. H_2-TPD showedthat increasing ZrO_2content of catalysts promoted strong adsorption of hydrogenand adsorptive hydrogen of higher concentration on catalyst surface, and possessedfunction of hydrogen storage and enhanced reaction rate of CO_2hydrogenation.CO_2-TPD revealed that ZrO_2improved CO_2adsorption and activation. IncreasingZrO_2content of catalysts enhanced catalytic performance.
On the CuO-ZnO-ZrO_2/TiO_2catalyst, CuO being reduced to Cu species are theactive sites of H_2adsorption and dissociation. ZnO and ZrO_2species are the activesites of CO_2adsorption. The dual-site reaction mechanism of adsorption andactivation for H_2and CO_2is reasonable for the directly synthesis methanol by CO_2hydrogenation on the CuO-ZnO-ZrO_2/TiO_2catalyst.
CO_2加氢合成甲醇通常采用的催化剂制备方法存在CO_2转化率低，甲醇选择性不高的问题。针对这些问题，提出了采用添加十六烷基三甲基溴化铵（CTAB）表面活性剂并流浆态共沉淀法制备CuO-ZnO/TiO_2催化剂，有效改善了催化剂的结构与催化性能。采用添加表面活性剂并流浆态共沉淀法、添加表面活性剂分步沉淀法、并流浆态共沉淀法及浸渍法制备了CuO-ZnO/TiO_2催化剂，利用BET、XRD、SEM、EDS、H_2-TPR、H_2-TPD、CO_2-TPD等方法对催化剂的物理与化学性能进行了表征，研究了不同的制备方法对CuO-ZnO/TiO_2催化剂性能的影响，通过固定床反应器对CO_2加氢合成甲醇CuO-ZnO/TiO_2催化剂的催化性能进行了评价。
研究结果表明，不同方法制备的CuO-ZnO/TiO_2催化剂均为介孔材料，沉淀法制备的CuO-ZnO/TiO_2催化剂BET比表面积和孔容大于浸渍法制备的催化剂，CuO和ZnO的分散性好。TiO_2载体起到阻止CuO晶粒长大和促进CuO分散的作用。沉淀法中以添加表面活性剂并流浆态共沉淀法制备的CuO-ZnO/TiO_2催化剂上CuO的还原温度最低，催化活性最好。浸渍法制备的催化剂上CuO的还原温度最高，催化活性低。H_2-TPD表明高温强吸附态下H_2的脱附峰面积大，催化剂表面上吸附更多的活化H_2，促进了CO_2加氢合成甲醇的反应。CO_2-TPD表明中等强度的CO_2吸附中心与二氧化碳加氢合成甲醇的效果密切相关。不同方法制备的CuO-ZnO/TiO_2催化剂活性及CH3OH选择性由高到低的顺序依次为：添加表面活性剂并流浆态共沉淀法＞添加表面活性剂分步沉淀法＞并流浆态共沉淀法＞浸渍法，添加表面活性剂有效地改善了CuO-ZnO/TiO_2催化剂的催化性能。
添加表面活性剂并流浆态共沉淀法制备的CuO-ZnO/TiO_2催化剂上CO_2加氢合成甲醇反应的催化性能最好。在反应压力2.5MPa、反应空速2100h-1、反应温度230℃、H_2和CO_2摩尔比3:1、反应时间4h的条件下，CO_2的转化率为13.26%，CH3OH的选择性为23.95%，CH3OH的产率最大为3.18%。
添加助剂对CO_2加氢合成甲醇催化剂的结构与性能具有重要影响，研究了在CuO-ZnO/TiO_2催化剂中分别添加ZrO_2、Al2O3及MnOχ助剂，采用添加CTAB表面活性剂并流浆态共沉淀法制备了CuO-ZnO-ZrO_2/TiO_2、CuO-ZnO-Al2O3/TiO_2及CuO-ZnO-MnOχ/TiO_2催化剂，利用BET、XRD、SEM、EDS、H_2-TPR、H_2-TPD、CO_2-TPD等方法对各催化剂的结构与化学性能进行了表征，研究了添加不同助剂及改变添加的ZrO_2助剂含量对CuO-ZnO/TiO_2催化剂性能的影响。通过XRD、XPS、H_2-TPD、CO_2-TPD、DRIFT等方法探讨了CuO-ZnO-ZrO_2/TiO_2催化剂上CO_2加氢合成甲醇的反应机理。
研究结果表明，添加不同助剂均增加了CuO-ZnO/TiO_2催化剂的比表面积和孔容，添加MnOχ使CuO-ZnO/TiO_2催化剂上CuO的还原温度升高，吸附H_2的浓度降低，催化活性下降。添加ZrO_2或Al2O3助剂均降低了CuO的还原温度，吸附H_2和CO_2的能力增强，促进了甲醇的合成。含不同助剂的CuO-ZnO/TiO_2催化剂中，添加ZrO_2助剂的CuO-ZnO-ZrO_2/TiO_2催化剂的催化性能最好，在反应压力2.5MPa、反应空速2100h-1、反应温度230℃、H_2和CO_2摩尔比3:1、反应时间4h的条件下，CO_2的转化率为18.24%，CH3OH的选择性为31.52%，CH3OH的产率最大为5.75%。
ZrO_2助剂的含量对CuO-ZnO/TiO_2催化剂的结构与性能具有显著影响。随着ZrO_2助剂含量的增加，催化剂的比表面积和孔容增大，孔径分布变均匀。ZrO_2促进了催化剂上CuO和ZnO的分散，降低了CuO的还原温度，提高了催化剂的活性。H_2-TPD表明增加催化剂中ZrO_2含量促进了对H_2的强吸附，催化剂表面上吸附H_2的浓度高，并具有储氢的作用，提高了CO_2加氢合成甲醇反应的速率。CO_2-TPD表明ZrO_2对促进CO_2的吸附与活化具有显著作用。ZrO_2助剂含量增加，提高了催化剂的催化性能。
CuO-ZnO-ZrO_2/TiO_2催化剂上的CuO还原后为零价金属铜，Cu~0是H_2吸附与解离的活性中心，ZnO和ZrO_2是CO_2的吸附活性中心。甲醇合成机理是CuO-ZnO-ZrO_2/TiO_2催化剂上双活性中心分别吸附活化H_2和CO_2，以CO_2为碳源直接加氢合成甲醇的反应。
A large amount of carbon dioxide emission led to global greenhouse effect andenvironmental pollution. Research of carbon dioxide emission reduction andutilization is of focus and urgent issues in the world. Methanol synthesis by carbondioxide hydrogenation is one of approaches of carbon dioxide utilization. Methanolis considered an important raw material of fundamental organic chemical industryand a new-type environmental protection clean fuels. Carbon dioxide hydrogenationto methanol is a new pathway for strategic adjustment of energy structure, and it isimportant significance to solve the increasingly environmental pollution and energyquestions.
In the process of carbon dioxide hydrogenation to methanol, the existingproblems of the general preparation methods of catalysts are lower to carbon dioxideconversion and methanol selectivity. In regard to these problems, CuO-ZnO/TiO_2catalysts were prepared by a novel parallel-slurry-mixing-precipitation methodcombined with addition of cetyltrimethylammonium bromide (CTAB) surfactant.Structure and catalytic performance of catalysts were improved effectively.CuO-ZnO/TiO_2catalysts were prepared by parallel-slurry-mixing-precipitationmethod combined with addition of surfactant, two-step precipitation methodcombined with addition of surfactant, parallel-slurry-mixing-precipitation andimpregnation method, respectively. Characterizations of physical and chemicalproperties of the catalysts were investigated by BET, XRD, SEM, EDS, H_2-TPR,H_2-TPD and CO_2-TPD. The effects of different preparation methods on catalyticperformances of CuO-ZnO/TiO_2catalysts were studied. The catalytic performancesof CuO-ZnO/TiO_2catalysts for methanol synthesis from CO_2hydrogenation wereevaluated by fixed bed reactor.
The research results show that CuO-ZnO/TiO_2catalysts of different preparationmethods are mesoporous materials. BET specific surface area and pore volume forthe CuO-ZnO/TiO_2catalysts of precipitation methods are greater than that ofimpregnation method, and dispersion of CuO and ZnO is better. TiO_2preventedgrowth of CuO crystal particles and promoted the dispersion of CuO species. In theprecipitation methods, CuO reduction temperature of CuO-ZnO/TiO_2catalyst ofparallel-slurry-precipitation method combined with addition of surfactant is lowest,and its reduction is easiest. CuO reduction temperature of that of impregnationmethod is highest, and its catalytic activity is lowest. H_2-TPD showed that hydrogendesorption peak area was large at high temperature and strong adsorption state, andactive hydrogen molecules on catalyst surface were more and more, and methanol synthesis from CO_2hydrogenation was promoted. CO_2-TPD revealed that CO_2adsorption center of moderate intensity was closely related to methanol synthesisfrom CO_2hydrogenation. From high to low, the activity and methanol selectivity ofCuO-ZnO/TiO_2catalysts of different preparation methods wasparallel-slurry-mixing-precipitation method combined with addition of surfactant,two-step precipitation method combined with addition of surfactant,parallel-slurry-mixing-precipitation and impregnation method. Addition ofsurfactant improved effectively catalytic performances of CuO-ZnO/TiO_2catalysts.
CuO-ZnO/TiO_2catalyst of parallel-slurry-precipitation method combined withaddition of surfactant for methanol synthesis from CO_2hydrogenation was best.Under the conditions of reaction pressure of2.5MPa, space velocity of2100h-1,reaction temperature of230℃, H_2/CO_2molar ratio of3:1and reaction time4h,carbon dioxide conversion and methanol selectivity and maximum of methanol yieldwere13.26%,23.95%and3.18%, respectively.
Additives of catalysts used in methanol synthesis from carbon dioxidehydrogenation are important effect on structure and performance of catalyst.CuO-ZnO/TiO_2catalyst added ZrO_2, Al2O3and MnOχ, respectively.CuO-ZnO-ZrO_2/TiO_2, CuO-ZnO-Al2O3/TiO_2and CuO-ZnO-MnOχ/TiO_2catalystswere prepared by parallel-slurry-mixing-precipitation method combined withaddition of CTAB surfactant. The structure characterization and chemical propertiesof the catalysts were investigated by BET, XRD, SEM, EDS, H_2-TPR, H_2-TPD,CO_2-TPD. The effects of different promoters and ZrO_2content on catalyticperformance of CuO-ZnO/TiO_2catalyst were studied. In the presence ofCuO-ZnO-ZrO_2/TiO_2catalyst, reaction mechanism of carbon dioxide hydrogenationto methanol was discussed by XRD, XPS, H_2-TPD, CO_2-TPD and DRIFT.
The research results show that addition of different promoters increasedspecific surface area and pore volume for the CuO-ZnO/TiO_2catalysts. The additionof MnOχon CuO-ZnO/TiO_2catalyst increased the reduction temperature of CuO,and decreased adsorptive hydrogen concentration and catalytic activity. AddingZrO_2or Al2O3promoter decreased the reduction temperature of CuO, enhancedcapacity of H_2and CO_2adsorption, and promoted methanol synthesis. In theCuO-ZnO/TiO_2catalysts containing different promoter, CuO-ZnO-ZrO_2/TiO_2catalyst exhibited an optimal catalytic performance. Under the conditions ofreaction pressure of2.5MPa, space velocity of2100h-1, reaction temperature of230℃, H_2/CO_2molar ratio of3:1and reaction time4h, carbon dioxide conversionand methanol selectivity and maximum of methanol yield were18.24%,31.52%and5.75%, respectively.
ZrO_2content is important effect on the structure and performance ofCuO-ZnO/TiO_2catalysts. Along with the increase of ZrO_2content, specific surface areas and pore volume of the catalysts increase, and pore size distribution isconcentrated. ZrO_2promoted the dispersion of CuO and ZnO species and decreasedthe reduction temperature of CuO, and enhanced catalyst activity. H_2-TPD showedthat increasing ZrO_2content of catalysts promoted strong adsorption of hydrogenand adsorptive hydrogen of higher concentration on catalyst surface, and possessedfunction of hydrogen storage and enhanced reaction rate of CO_2hydrogenation.CO_2-TPD revealed that ZrO_2improved CO_2adsorption and activation. IncreasingZrO_2content of catalysts enhanced catalytic performance.
On the CuO-ZnO-ZrO_2/TiO_2catalyst, CuO being reduced to Cu species are theactive sites of H_2adsorption and dissociation. ZnO and ZrO_2species are the activesites of CO_2adsorption. The dual-site reaction mechanism of adsorption andactivation for H_2and CO_2is reasonable for the directly synthesis methanol by CO_2hydrogenation on the CuO-ZnO-ZrO_2/TiO_2catalyst.
引文
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