费托反应高选择性合成汽油Co基催化剂制备与性能的研究
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摘要
近年来,随着我国石油进口依存度的逐年上升,国内石油安全供给面临日趋严峻的挑战。因此,寻找石油替代能源,积极利用我国丰富的煤炭资源,发展煤间接液化费托合成技术对解决我国能源安全及环境污染问题具有重大的战略意义。
催化剂是费托合成的核心技术,长期以来,Co基催化剂是费托催化剂研究的重点。本论文首次采用真空浸渍、添加助剂、真空浸渍过程中辅以超声波处理并复合HZSM-5分子筛的方法,成功地制备了含Zr的Co基分子筛复合催化剂(Co/Zr/SiO2(H)+HZSM-5),该催化剂在固定床反应器中显示了高活性和高C5-C11汽油馏分选择性,以及良好的反应稳定性。
1.研究了真空浸渍与普通常压浸渍对于Co/SiO2催化剂物性织构及反应性能的影响,结果显示：与普通常压浸渍催化剂相比,真空浸渍具有更高的载体孔道利用率,可使更多较小的Co颗粒分布于载体孔道内；并且在Co氧化物颗粒与载体间形成一定强度的相互作用,避免了Co晶粒在催化剂干燥和焙烧过程中聚集形成较大的晶粒簇。通过不同反应工艺条件考察,得到真空浸渍Co/SiO2催化剂最优反应条件：T=493 K、P= 2.0MPa、H2/CO(摩尔比,下同)=2.0以及GHSV=1000 h-1。在此条件下,其CO初始转化率可达90.9%,Cs+烃选择性为58.9%；而普通常压浸渍催化剂CO初始转化率仅为83.2%,C5+烃选择性仅为56.1%。表明真空浸渍更有利于催化剂活性的提高。
2.研究了5-25%的Co含量对于真空浸渍Co/SiO2催化剂反应性能的影响,结果表明随着Co含量增加,催化剂中Co晶粒逐渐增大,这有利于Cs+烃选择性的提高,从而确定了催化剂中最优的Co含量。进一步研究了2-10%的Zr助剂含量对于真空浸渍Co/SiO2催化剂反应性能的影响。结果表明,Zr助剂的加入有助于减弱Co氧化物与Si02载体间的相互作用,有利于Co催化剂还原度的提高。当真空浸渍Co/SiO2催化剂中添加了5%的Zr助剂后,催化剂CO初始转化率和C5+烃选择性从76.0%和72.9%分别提高到了92.8%和77.6%。
3.在Co/Zr/SiO2催化剂真空浸渍过程中辅以超声波处理,考察了超声波功率和超声处理时间对于Co、Zt浸渍溶液pH值变化及催化剂反应性能的影响。结果显示随着超声波功率增强和超声处理时间延长,浸渍溶液pH值显著降低,催化剂中Co颗粒分散度和还原度得到提高,CO初始转化率和C5+选择性从92.8%和77.6%分别提高到95.5%和81.0%。经过20小时反应,真空浸渍并辅以高功率超声波处理制备的催化剂CO转化率降幅最小。表明高功率超声波对于催化剂活性、C5+烃选择性和稳定性均有一定的提高。
4.将真空浸渍并辅以高功率超声波处理制备的Co/Zr/SiO2催化剂与HZSM-5分子筛复合,考察了二者复合比例、分子筛硅铝比以及反应工艺条件对于复合催化剂C5+液相烃产率及C5-C11汽油馏分质量分率的影响。最终确定了将Co/Zr/SiO2与硅铝比为50的HZSM-5分子筛按照体积比1.0：1.0组成复合催化剂。在T=523 K、P=2.0 MPa、H2/CO=2.0和GHSV=500 h-1的反应条件下,在固定床反应器中进行500小时稳定性考察,结果显示该复合催化剂的CO转化率基本保持在90%左右,C5+液相烃产率在130g/Nm3(CO+H2)左右,总烃中C5+液相烃质量分率约为73%。由于反应生成的C12+长链烃在分子筛酸性中心部分裂解,C5-C11汽油馏分质量分率在57%左右,比经典Anderson-Schultz-Flory(ASF)分布模型预测出的汽油质量分率最高值(45%)高出12%。此外,C5-C11汽油馏分在C5+液相烃中质量分率接近80%,显示了复合催化剂具有良好的反应性能和稳定性。
5.基于Co基催化剂的反应机理,经过烃类产物合理的简化,从费托反应生成的水、烃质量比关系出发,建立了C5+液相烃在总烃中质量分率的简化计算方法。经过相关实验验证,表明通过该方法可以便利、快捷以及较为准确地计算出C5+烃质量分率。
通过以上研究工作,开发了具有高CO转化率和较高C5-Cl1汽油馏分选择性的Co/Zr/SiO2+HZSM-5新型复合催化剂,为费托合成制汽油催化剂的进一步研发开辟了一条新的研究途径。
In China, the last few years has witnessed an increasing dependence on importing petroleum, which is posing severe challenge to the security of our energy supply. Therefore, the exploration of the substitute energy through utilizing the abundant coal resources in our country and developing the technology of indirect coal liquefaction via Fischer-Tropsch synthesis(FTS) reaction has strategic significance for ensuring our energy security and protecting the environment.
Catalysts play a vital role in FTS and ample research has focused on the Co-based catalyst. In this dissertation, the collaborative method including vacuum impregnation under ultrasonic treatment, application of promoter and the mixing with HZSM-5 molecular sieve was initiated to successful prepare the Co-based-zeolite composite catalyst (Co/Zr/SiO2+HZSM-5).In addition, the catalytic activity, the selectivity for C5-C11 gasoline fraction and the stability of the catalyst prepared in this way was proved to be high in a fixed bed reactor.
1. The effect of impregnation method on the textural property and performance of Co/SiO2 catalysts was studied firstly.Compared to the Co/SiO2 catalyst impregnated under atmospheric pressure, the more inner pores and channels of the support were utilized when the catalyst was prepared under vacuum conditions. Vacuum impregnation enabled a large number of smaller cobalt particles to distribute in the pores. Meanwhile, a certain interaction was generated between cobalt oxides and the support, which prevented the cobalt oxide crystals from agglomerating into larger grain-clusters during the drying and calcination process of the catalyst. Through evaluating the two catalysts under different reaction conditions, the optimal condition for the vacuum impregnated Co/SiO2 catalyst was concluded as follows:T=493 K, P=2.0 MPa, H2/CO (mole ratio)=2.0 and GHSV=1000 h-1.Under this condition, the initial CO conversion was as high as 90.9% and the selectivity for C5+ hydrocarbon was 58.9%. In contrast, the initial CO conversion of the Co/SiO2 impregnated under atmospheric pressure was as low as 83.2% and the selectivity for C5+ hydrocarbon was only 56.1%. The above results indicated that the initial CO conversion of the Co/SiO2 catalyst had been greatly enhanced through vacuum impregnation.
2. The effect of cobalt content (5-25%) on the performance of vacuum impregnated Co/SiO2 was also explored in this study. It was shown that the size of cobalt particles enlarged gradually with the increase of cobalt content, which was helpful to enhance the selectivity for C5+ hydrocarbon. On this basis, the optimal cobalt content was fixed on. Furthermore, the effect of the content of zirconium promoter (2-10%) on the performance of Co/SiO2 catalyst was examined. The addition of Zr promoter conduced to weakening the interaction between cobalt oxides and SiO2 support, which in turn improved the reduction degree of the cobalt particles. After 5% Zr promoter was added to the CO/SiO2 catalyst, the initial CO conversion and the selectivity for the C5+ hydrocarbon enhanced from 76.0% and 72.9% to 92.8% and 77.6%, respectively.
3. The Co/Zr/SiO2 catalyst was prepared through vacuum impregnation with the ultrasonic treatment. The effects of ultrasonic power and treatment duration on the catalyst performance and the pH value of Co, Zr nitrate solution were studied. It was indicated that the pH value of the solution dropped significantly with the increase of ultrasonic power and duration, which conduced to improving dispersion and reduction degree of cobalt oxides. Specifically, the initial CO conversion and the selectivity for C5+ hydrocarbon enhanced from 92.8% and 77.6% to 95.5% and 81.0%, respectively. After 20-hour reaction, the declining rate of the CO conversion of Co/Zr/SiO2 catalyst treated by high-power ultrasound was minimized. This also showed that the catalytic activity, stability and selectivity for C5+ hydrocarbon were improved to a certain extent when ultrasound was applied in the process of vacuum impregnation.
4. The Co/Zr/SiO2 catalyst was blended with the HZSM-5 zeolite. The effects of the two ingredients mixture ratio and the molecular sieve Si/Al ratio on the C5+ hydrocarbon yield and C5—C11 gasoline weight fraction were examined. The optimal composite catalyst was composed of Co/Zr/SiO2 with HZSM-5(Si/Al=50) according to the volume ratio 1.0:1.0.Under the reaction condition of T=523 K, P=2.0 MPa, H2/CO=2.0(mole ratio) and GHSV=500 h-1, the catalyst was evaluated over 500 hours in the fixed-bed reactor. The results showed that CO conversion remained as high as 90% and the yield of C5+ liquid hydrocarbon was about 130 g/Nm3(CO+H2). The weight fraction of C5+ liquid hydrocarbon in the total hydrocarbons was about 73%. Due to the cracking of partial C12+ long chain hydrocarbons at the acidity center of the molecular sieve, the weight fraction of C5-C11 gasoline was about 57%, which was higher than the maximum value 45% predicted by the ASF model. Furthermore, in the C5+ liquid hydrocarbon, the weight fraction of the gasoline was close to 80%. This result indicated the composite catalyst had good performance and high stability.
5. Considering the reaction mechanism of Co-based catalyst and excluding the negligible oxygenated hydrocarbons, the simplified method for calculating the weight fraction of C5+ liquid hydrocarbon in the total hydrocarbons was established on the basis of the weight relation between products water and hydrocarbon in the FTS. This method was proved to be convenient and accurate for calculating the weight fraction of C5+ liquid hydrocarbon.
In summary, through the results concluded in this dissertation, a new Co/Zr/SiO2+HZSM-5 composite catalyst with high CO conversion was developed for highly synthesizing C5-C11 gasoline under FTS, which explored a new approach to the catalyst development for conversion of syngas to gasoline.
催化剂是费托合成的核心技术,长期以来,Co基催化剂是费托催化剂研究的重点。本论文首次采用真空浸渍、添加助剂、真空浸渍过程中辅以超声波处理并复合HZSM-5分子筛的方法,成功地制备了含Zr的Co基分子筛复合催化剂(Co/Zr/SiO2(H)+HZSM-5),该催化剂在固定床反应器中显示了高活性和高C5-C11汽油馏分选择性,以及良好的反应稳定性。
1.研究了真空浸渍与普通常压浸渍对于Co/SiO2催化剂物性织构及反应性能的影响,结果显示：与普通常压浸渍催化剂相比,真空浸渍具有更高的载体孔道利用率,可使更多较小的Co颗粒分布于载体孔道内；并且在Co氧化物颗粒与载体间形成一定强度的相互作用,避免了Co晶粒在催化剂干燥和焙烧过程中聚集形成较大的晶粒簇。通过不同反应工艺条件考察,得到真空浸渍Co/SiO2催化剂最优反应条件：T=493 K、P= 2.0MPa、H2/CO(摩尔比,下同)=2.0以及GHSV=1000 h-1。在此条件下,其CO初始转化率可达90.9%,Cs+烃选择性为58.9%；而普通常压浸渍催化剂CO初始转化率仅为83.2%,C5+烃选择性仅为56.1%。表明真空浸渍更有利于催化剂活性的提高。
2.研究了5-25%的Co含量对于真空浸渍Co/SiO2催化剂反应性能的影响,结果表明随着Co含量增加,催化剂中Co晶粒逐渐增大,这有利于Cs+烃选择性的提高,从而确定了催化剂中最优的Co含量。进一步研究了2-10%的Zr助剂含量对于真空浸渍Co/SiO2催化剂反应性能的影响。结果表明,Zr助剂的加入有助于减弱Co氧化物与Si02载体间的相互作用,有利于Co催化剂还原度的提高。当真空浸渍Co/SiO2催化剂中添加了5%的Zr助剂后,催化剂CO初始转化率和C5+烃选择性从76.0%和72.9%分别提高到了92.8%和77.6%。
3.在Co/Zr/SiO2催化剂真空浸渍过程中辅以超声波处理,考察了超声波功率和超声处理时间对于Co、Zt浸渍溶液pH值变化及催化剂反应性能的影响。结果显示随着超声波功率增强和超声处理时间延长,浸渍溶液pH值显著降低,催化剂中Co颗粒分散度和还原度得到提高,CO初始转化率和C5+选择性从92.8%和77.6%分别提高到95.5%和81.0%。经过20小时反应,真空浸渍并辅以高功率超声波处理制备的催化剂CO转化率降幅最小。表明高功率超声波对于催化剂活性、C5+烃选择性和稳定性均有一定的提高。
4.将真空浸渍并辅以高功率超声波处理制备的Co/Zr/SiO2催化剂与HZSM-5分子筛复合,考察了二者复合比例、分子筛硅铝比以及反应工艺条件对于复合催化剂C5+液相烃产率及C5-C11汽油馏分质量分率的影响。最终确定了将Co/Zr/SiO2与硅铝比为50的HZSM-5分子筛按照体积比1.0：1.0组成复合催化剂。在T=523 K、P=2.0 MPa、H2/CO=2.0和GHSV=500 h-1的反应条件下,在固定床反应器中进行500小时稳定性考察,结果显示该复合催化剂的CO转化率基本保持在90%左右,C5+液相烃产率在130g/Nm3(CO+H2)左右,总烃中C5+液相烃质量分率约为73%。由于反应生成的C12+长链烃在分子筛酸性中心部分裂解,C5-C11汽油馏分质量分率在57%左右,比经典Anderson-Schultz-Flory(ASF)分布模型预测出的汽油质量分率最高值(45%)高出12%。此外,C5-C11汽油馏分在C5+液相烃中质量分率接近80%,显示了复合催化剂具有良好的反应性能和稳定性。
5.基于Co基催化剂的反应机理,经过烃类产物合理的简化,从费托反应生成的水、烃质量比关系出发,建立了C5+液相烃在总烃中质量分率的简化计算方法。经过相关实验验证,表明通过该方法可以便利、快捷以及较为准确地计算出C5+烃质量分率。
通过以上研究工作,开发了具有高CO转化率和较高C5-Cl1汽油馏分选择性的Co/Zr/SiO2+HZSM-5新型复合催化剂,为费托合成制汽油催化剂的进一步研发开辟了一条新的研究途径。
In China, the last few years has witnessed an increasing dependence on importing petroleum, which is posing severe challenge to the security of our energy supply. Therefore, the exploration of the substitute energy through utilizing the abundant coal resources in our country and developing the technology of indirect coal liquefaction via Fischer-Tropsch synthesis(FTS) reaction has strategic significance for ensuring our energy security and protecting the environment.
Catalysts play a vital role in FTS and ample research has focused on the Co-based catalyst. In this dissertation, the collaborative method including vacuum impregnation under ultrasonic treatment, application of promoter and the mixing with HZSM-5 molecular sieve was initiated to successful prepare the Co-based-zeolite composite catalyst (Co/Zr/SiO2+HZSM-5).In addition, the catalytic activity, the selectivity for C5-C11 gasoline fraction and the stability of the catalyst prepared in this way was proved to be high in a fixed bed reactor.
1. The effect of impregnation method on the textural property and performance of Co/SiO2 catalysts was studied firstly.Compared to the Co/SiO2 catalyst impregnated under atmospheric pressure, the more inner pores and channels of the support were utilized when the catalyst was prepared under vacuum conditions. Vacuum impregnation enabled a large number of smaller cobalt particles to distribute in the pores. Meanwhile, a certain interaction was generated between cobalt oxides and the support, which prevented the cobalt oxide crystals from agglomerating into larger grain-clusters during the drying and calcination process of the catalyst. Through evaluating the two catalysts under different reaction conditions, the optimal condition for the vacuum impregnated Co/SiO2 catalyst was concluded as follows:T=493 K, P=2.0 MPa, H2/CO (mole ratio)=2.0 and GHSV=1000 h-1.Under this condition, the initial CO conversion was as high as 90.9% and the selectivity for C5+ hydrocarbon was 58.9%. In contrast, the initial CO conversion of the Co/SiO2 impregnated under atmospheric pressure was as low as 83.2% and the selectivity for C5+ hydrocarbon was only 56.1%. The above results indicated that the initial CO conversion of the Co/SiO2 catalyst had been greatly enhanced through vacuum impregnation.
2. The effect of cobalt content (5-25%) on the performance of vacuum impregnated Co/SiO2 was also explored in this study. It was shown that the size of cobalt particles enlarged gradually with the increase of cobalt content, which was helpful to enhance the selectivity for C5+ hydrocarbon. On this basis, the optimal cobalt content was fixed on. Furthermore, the effect of the content of zirconium promoter (2-10%) on the performance of Co/SiO2 catalyst was examined. The addition of Zr promoter conduced to weakening the interaction between cobalt oxides and SiO2 support, which in turn improved the reduction degree of the cobalt particles. After 5% Zr promoter was added to the CO/SiO2 catalyst, the initial CO conversion and the selectivity for the C5+ hydrocarbon enhanced from 76.0% and 72.9% to 92.8% and 77.6%, respectively.
3. The Co/Zr/SiO2 catalyst was prepared through vacuum impregnation with the ultrasonic treatment. The effects of ultrasonic power and treatment duration on the catalyst performance and the pH value of Co, Zr nitrate solution were studied. It was indicated that the pH value of the solution dropped significantly with the increase of ultrasonic power and duration, which conduced to improving dispersion and reduction degree of cobalt oxides. Specifically, the initial CO conversion and the selectivity for C5+ hydrocarbon enhanced from 92.8% and 77.6% to 95.5% and 81.0%, respectively. After 20-hour reaction, the declining rate of the CO conversion of Co/Zr/SiO2 catalyst treated by high-power ultrasound was minimized. This also showed that the catalytic activity, stability and selectivity for C5+ hydrocarbon were improved to a certain extent when ultrasound was applied in the process of vacuum impregnation.
4. The Co/Zr/SiO2 catalyst was blended with the HZSM-5 zeolite. The effects of the two ingredients mixture ratio and the molecular sieve Si/Al ratio on the C5+ hydrocarbon yield and C5—C11 gasoline weight fraction were examined. The optimal composite catalyst was composed of Co/Zr/SiO2 with HZSM-5(Si/Al=50) according to the volume ratio 1.0:1.0.Under the reaction condition of T=523 K, P=2.0 MPa, H2/CO=2.0(mole ratio) and GHSV=500 h-1, the catalyst was evaluated over 500 hours in the fixed-bed reactor. The results showed that CO conversion remained as high as 90% and the yield of C5+ liquid hydrocarbon was about 130 g/Nm3(CO+H2). The weight fraction of C5+ liquid hydrocarbon in the total hydrocarbons was about 73%. Due to the cracking of partial C12+ long chain hydrocarbons at the acidity center of the molecular sieve, the weight fraction of C5-C11 gasoline was about 57%, which was higher than the maximum value 45% predicted by the ASF model. Furthermore, in the C5+ liquid hydrocarbon, the weight fraction of the gasoline was close to 80%. This result indicated the composite catalyst had good performance and high stability.
5. Considering the reaction mechanism of Co-based catalyst and excluding the negligible oxygenated hydrocarbons, the simplified method for calculating the weight fraction of C5+ liquid hydrocarbon in the total hydrocarbons was established on the basis of the weight relation between products water and hydrocarbon in the FTS. This method was proved to be convenient and accurate for calculating the weight fraction of C5+ liquid hydrocarbon.
In summary, through the results concluded in this dissertation, a new Co/Zr/SiO2+HZSM-5 composite catalyst with high CO conversion was developed for highly synthesizing C5-C11 gasoline under FTS, which explored a new approach to the catalyst development for conversion of syngas to gasoline.
引文
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