摘要
甘油作为一种副产物,其大量过剩的问题因生物柴油产业的迅速发展而变得越来越严重,如何寻找新的途径来合理地利用这些过剩的粗甘油,从而推动整个生物柴油产业的可持续发展,是当今生物柴油产业发展中面临的重大问题。甘油氢解来生产二元醇是目前认为最具有发展潜力的有效利用甘油的新途径。
本论文主要采用不同方法制备了固体酸碱负载的金属作为双功能催化剂来催化甘油氢解生成丙二醇,结合多种表征手段考察了催化剂载体的酸碱性、金属的种类、表观形态及催化剂的结构对催化剂反应性能的影响,探讨了催化剂的活性中心性质及催化作用机制等问题。取得的主要结果如下：
采用浸渍法制备了负载量为2wt.%的Pt/HZSM5、Pt/HBeta、Pt/Al2O3、Pt/MgO和Pt/水滑石(Mg:Al=3:1)等双功能催化剂,并考察了它们的催化反应性能。结果表明：2wt.%的Pt/水滑石相比其他催化剂表现出更好的催化性能,在优化的反应条件下(220℃,3.0MPaH2,20h,0.5g催化剂,20wt%甘油水溶液20.0g),甘油的转化率可达到92.1%,1,2-丙二醇的选择性为93.0%；催化剂易于分离并可以循环使用。结合XRD、TEM、CO2-TPD和H2-TPD等表征结果,我们认为催化剂载体的碱性以及铂颗粒的大小是影响催化剂活性的主要因素；载体的碱性对催化剂的活性有明显的促进作用,小颗粒的铂在碱性的载体上要比在酸性载体上表现出更好的活性。
通过共沉淀和等体积浸渍等不同方法制备了不同铜负载量的Cu/MgO双功能催化剂,并考察了其催化反应的性能。结果表明：共沉淀法制备的Cu/MgO催化活性要比等体积浸渍法制备的Cu/MgO催化活性好；其中共沉淀法制备的15wt.%Cu/MgO表现出最好的催化反应性能,在反应条件180℃,3.0MPa H2,20h,1.0g催化剂,75wt.%甘油水溶液8.0g下,甘油的转化率能够达到72.0%,1,2-丙二醇的选择性为97.6%；少量NaOH的加入进一步提高了催化剂的活性,使得甘油的转化率达到82.0%；结合表征结果,我们推测催化剂的活性主要取决于铜颗粒和氧化镁颗粒的大小,铜颗粒和氧化镁颗粒越小,对甘油氢解生成1,2-丙二醇的催化活性就越好。
通过等体积浸渍、离子交换和共沉淀法原位合成等不同方法制备了不同铜含量的Cu-Mg-Al类水滑石前躯体,然后经过焙烧制得了固体碱负载铜基双功能催化剂。结果表明：共沉淀法原位合成的CU0.4Mg5.6Al2(OH)16CO3类水滑石经过焙烧制得了高分散的Cu/solid-base双功能催化剂(Cu0.4/Mg5.6Al209),并且这种高分散的Cu/solid-base催化剂对甘油氢解生成1,2-丙二醇极其有效,在反应条件180℃,3.0MPaH2,20h,1.0g催化剂,75wt.%甘油水溶液8.0g下,甘油的转化率能够达到80.0%,1,2-丙二醇的选择性为98.2%；结合表征结果,我们认为由于Cu0.4Mg5.6Al2(OH)16CO3具有很好的Mg-Al水滑石的晶体结构,经焙烧还原后铜颗粒高度均匀的分散在了水滑石的层状结构中,高度分散的铜以及水滑石载体的碱性导致了合成的双功能催化剂(Cu0.4/N4g5.6Al2O9)表现出了对甘油氢解生成1,2-丙二醇的良好性能。
通过浸渍-燃烧法制备了超强碱(复合碱土氧化物)负载的高分散的Cu/MgO/CaO和Cu/MgO/SrO催化剂,并考察了其催化性能。结合XRD、TEM、 N2O-adsorption、N2-adsorption等表征结果,认为浸渍燃烧法可以很好地将CaO和SrO负载在沉淀沉积法制备的Cu/MgO催化剂上,不但很好的保留了前躯体Cu/MgO中高分散的铜,而且增加了催化剂的比表面积和碱性。CO2-TPD和反应活性数据结果表明,由于CaO和SrO的添加,催化剂的碱性大大增强,从而催化剂的活性增强。在负载量10wt.%的Cu/MgO/SrO的催化作用下(160℃,3.0MPa H2,15h,1.0g催化剂,75wt.%甘油水溶液8.0g),甘油的转化率达到88.6%,1,2-丙二醇的选择性为91.0%。各种表征手段结果表明,在铜颗粒变化不大的情况下,载体碱性增强可以促进甘油氢解生成1,2-丙二醇的活性。
通过复分解反应制备了磷钨酸铜盐,然后经过干燥焙烧制备了磷钨酸负载的氧化铜催化剂,并将其用于甘油催化氢解反应制备丙二醇(乙醇为溶剂)。反应结果表明没有任何加氢产物的生成,反而主要生成了甘油和乙醇的醚化产物,即甘油和乙醇在酸催化剂的作用下生成了单醚化、双醚化和三醚化的产物。继而我们以甘油和乙醇为反应物、考察了固体酸(H-ZSM5, H-Beta,磷钨酸,Si02负载的磷钨酸,FeCl3, AlCl3及硫酸)和固体碱(稀土金属氧化物,MgO)等催化剂上的反应效果。结果表明,固体碱催化剂对这个反应没有任何效果,然而磷钨酸和Si02负载的磷钨酸在所有考评的催化剂中对此反应表现出最好的的催化效果,甘油的转化率达到97.1%。
Propanediols (1,2-propanediol and1,3-propanediol) are valuable final products and also very important chemical intermediates. They are widely used in food, medicine and chemical industry. Recently, large amounts of surplus glycerol were produced in the process of biodiesel production. How to find out new outlets in order to make good use of this surplus glycerol and thereby promoting the development of whole biodiesel production is a serious problem. Hydrogenolysis of glycerol to1,2-PDO is considered as an effective method to make good use of surplus glycerol.
Different methods to prepare solid base supported metal as a bifunctional catalyst for hydrogenolysis of glycerol to1,2-PDO were tried in this dissertation. The alkalinity of the support, the structure of the catalyst, metal species and their apparent configuration were characterized. The relationship between the activity and the structure of the catalyst were discussed. The main achievements gained as follows:
Bi-functional catalysts Pt/HZSM5、Pt/HBeta、Pt/Al2O3、Pt/MgO and Pt/HLT(Mg:Al=3:1) were prepared via impregnation. The catalytic performances of these catalysts for hydrogenolysis of glycerol were examined. It was found that Pt/HLT performed the best activity for hydrogenolysis of glycerol among all the catalysts. Under the optimized conditions (220℃,3.0MPaH2,20h,0.5g catalyst,20wt.%glycerol solution,20.0g), the conversion of glycerol reached92.1%, the selectivity of1,2-PDO was93.0%. Characterization results indicated that the alkalinity of the catalyst and the particle size of Pt play a crucial role for this reaction; the alkalinity of support promoted the activity, and smaller Pt particle is more active on basic support than it on acidic support.
Bi-functional Cu/MgO catalysts with different amounts of Cu were prepared by co-precipitation and impregnation. These results indicate that Cu/MgO prepared by co-precipitation shows better activity than that of Cu/MgO prepared by impregnation; Cu/MgO with copper loading amount15wt.%prepared by co-precipitation showed the best activity among all tesed catalysts, the conversion of glycerol reaches72.0%and the selectivity of1,2-PDO is97.6%; small amounts of NaOH further enhanced the activity of the catalyst. Characterization results indicated that the activity of the the catalyst mainly depends on the particle size of Cu and MgO, smaller particle sizes of Cu and MgO particles are, the more activity of the catalysts are.
Hydrotalcite precursor as like Cu-Mg-Al with different copper loading amount was prepared by impregnation, ion-exchange and co-precipitation. The prepared precursors were converted into solid base supported copper bi-functional catalyst, and their activity for hydrogenolysis of glycerol was examined. The results indicate that Cu0.4Mg5.6Al2(OH)16CO3prepared by co-precipitation was changed into highly dispersed copper particles supported on solid base (Cu0.4/Mg5.6Al2O9). This highly dispersed Cu/solid-base catalyst was extremely active for glycerol hydrogenolysis. Characterization results indicated that prepared Cu0.4Mg5.6Al2(OH)]6CO3has the characteristic Mg-Al-hydrotalcite structure, after calcination, the copper particles dispersed highly in the lamellar structure of hydrotalcite. Due to the highly dispersed copper particles and alkalinity of hydrotalcite, the synthesized bi-functional catalyst (Cu0.4/Mg5.6Al2O9) shows extremely activity for glycerol hydrogenolysis to1,2-PDO.
Super solid-base supported copper catalysts Cu/MgO/CaO and Cu/MgO/SrO were prepared via impregnation-combustion method, and the activity was examined. Characterization results indicated that CaO and SrO particles dispersed highly on precursor catalyst Cu/MgO prepared by impregnation-combustion method, and the high dispersion of copper remained. CO2-TPD and reaction results indicate that the alkalinity of the catalyst was enhanced obviously and the activity of catalyst increased. The detected glycerol conversion is88.0%with a93.0%selectivity of1,2-PDO. It was concluded that alkalinity strength of catalyst increased its activity.
Cu/HPW catalyst was prepared and used for glycerol hydrogenolysis to1,2-PDO (ethanol as the solvent). But it was found that mainly etherification products of glycerol and ethanol were detected. Several solid/aqeous acids (H-ZSM5, H-Beta, HPW, HPW/SiO2, FeCl3, AlCl3and H2SO4) and solid bases (rare earth metal oxides, MgO) were tested for the etherification reaction. It was found that solid bases are inactive for this reaction, whereas HPW and HPW/SiO2exhibited the best activity for this reaction among all the tested catalysts, a97.1%glycerol conversion was obtained. The rection conditions were investigated such as reaction temperature, reation time, the mol ratio of ethanol to glycerol, and catalyst used amount.
引文
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