镍基和铁基催化剂上甲烷催化裂解反应的研究
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摘要
甲烷催化裂解反应可以一步制取不含碳氧化物的纯净氢,并得到具有潜在应用价值的纳米碳材料,在能量和过程上具有明显的优势。本文通过对Ni基和Fe基催化剂的基础研究,设计具有较高活性和稳定性的催化剂,探讨了不同反应模式,并对各种纳米碳材料的制备和生成机理进行了研究和分析。
使用共沉淀法制备了以水滑石为母体的NiAl和NiCuAl催化剂,并考察了还原温度、反应温度、Ni的负载量提高、进料气速对流化床中甲烷催化裂解反应的影响。并通过对甲烷催化裂解在低温为本征化学反应控制区域动力学的测定,发现Ni/Al2O3和NiCu/Al2O3两种催化剂的活化能很相近,都在73±2 kJ/mol的范围内,这表明Cu的加入并未影响由数个Ni原子组成的甲烷催化裂解反应活性位的催化活性。这点对甲烷吸附过程的DFT模拟所证实,模拟结果发现甲烷在Ni(100)以及NiCu(100)表面的活化能非常接近。但由于Cu的加入并且在表面的富集,会引起表面这种活性位数量迅速下降,而造成相同温度下活性的降低,但这种作用在高温下可以减少碳包裹颗粒的概率,从而提高高温稳定性。
同时,通过使用带有甲烷化转化器的气相色谱对生成尾气中的CO含量进行了测定。发现在不使用干燥除氧装置时,反应尾气中的CO浓度可达1800-2500 ppm,单独使用干燥装置时反应初期尾气中CO浓度约为1040 ppm,但反应稳定后可以下降到700 ppm以下。在同时使用干燥和除氧装置后,CO浓度较添加装置前明显下降,稳定时达到250 ppm左右。而且当使用纯甲烷进料时,在反应80 min后达到10 ppm以下的水平。结果还表明,CO浓度随着温度的升高而增加,并且在反应初期浓度最高。
通过比较NiCu/Al2O3在恒温反应(CTR)和低温引导高温反应(PIR)两种反应过程,发现使用PIR可以显著提高催化剂的稳定性。通过使用HRTEM和EDS对生长碳纤维的催化剂金属颗粒进行表征后发现,PIR产生的金属颗粒的组成与低温CTR的金属颗粒组成类似,Ni/Cu比约为3:1,而高温CTR的金属颗粒中Ni/Cu低于1:1。而且从生成的纳米碳纤维和金属颗粒的形状来看,PIR兼具高温和低温CTR反应时生成产品结构的特点。可以认为,在反应的引导过程中,形成了富铜的颗粒和富镍的颗粒,当甲烷催化裂解反应在较低的温度下进行时,富铜的颗粒由于铜的惰性和易在表面分布的性质,催化活性很低;而富镍的颗粒拥有适合碳纤维生长的结构和组成,因此有较高的活性,因此在本实验中观察到的碳纤维的顶部的催化剂颗粒多具有较高的镍含量。当反应温度较高时,催化剂颗粒失活很快,在这种条件下,富镍的颗粒稳定性很差,不适合催化生长碳纤维,而富铜的颗粒由于铜对镍的调变作用可以保持一定的活性,因此可以在实验结果中发现高温下碳纤维顶端的催化剂颗粒的铜含量较高,但是即使如此,富铜颗粒对于甲烷裂解反应的催化活性仍然较低。在分步加热的条件下,甲烷裂解反应的引导过程在较低温度进行,可使催化剂颗粒的结构重组的低温下进行,使富镍颗粒保持活性,并在一定长度的碳纤维壁可以保护富镍颗粒在高温下有较好的稳定性。
考察了铁基催化剂中掺杂Mo,Cr和W对催化剂活性的影响,结果发现,对甲烷催化裂解反应没有活性的Cr和W占据表面位置,减少活性位,而降低甲烷转化率,而且Cr的掺杂会导致无定型碳的生成,容易造成金属颗粒表面积碳而失活。而在催化剂中掺杂Mo可以显著提高催化剂的活性,可以将单金属的Fe/Al2O3催化剂17%的转化率提高到40%左右,通过XRD和TPR表征发现,在催化剂掺杂Mo后,催化剂的氧化物状态和还原过程发生了明显变化,并有利于提高Fe的分散度。当Mo/(Mo+Fe)(mol比)为10%催化剂具有最高活性。通过在固定床中的反应发现,该催化剂可以在973 K时,甲烷转化率可以保持在44%约180 min;当反应温度升至1023 K时,甲烷初始转化率可达78%,但是高活性只能保持40 min。
对高温条件下甲烷催化裂解反应制备纳米碳材料进行了研究。使用柠檬酸法制备的FeMo催化剂用于甲烷催化裂解反应。并使用HRTEM和Raman对生成的纳米碳进行了表征。使用活性组分含量为Fe:Mo:Al=9:1:120的催化剂,制备出了纯度很高,直径在1-2.5 nm之间的单壁纳米碳管。使用浸渍法制备的负载量为16%的Fe/MgO、Mo/MgO和FeMo/MgO用于甲烷催化裂解反应,分别得到了大量的直径在10 nm左右的多壁纳米碳管、一些多壁纳米碳管,以及纳米碳洋葱。并且发现,Mo/MgO高温稳定好,甲烷转化率可以一直保持在31%左右,XRD结果证实Mo2C为甲烷裂解反应的活性中心。根据本文HRTEM观察到的结果,提出单壁纳米碳管束的生长是以金属表面形成的突起为生长中心的。而纳米碳洋葱的生成主要与高温石墨层生长过快有关,而颗粒大小不同的金属颗粒,表面张力和进入拟液态的程度也不同,生成纳米碳洋葱或者石墨笼。
Methane catalytic decomposition can produce COx-free hydrogen and carbon nanomaterials simultaneously, which is prior to the conventional hydrogen production processes. In this work, both Ni-based and Fe-based catalysts are investigated for production of COx-free hydrogen and various types of nanocarbon through methane catalytic decomposition. The catalysts with high activity and stability are obtained and the approach to improve the stability of catalyst at high temperature is discussed. Carbon nanomaterials with different morphologies are successfully synthesized and the methanism is discussed.
NiAl and NiCuAl catalyst derived from Feitknecht compound was used for the methane catalytic decomposition in a fluidized bed. The effect of reaction temperature, reduced temperature, the metal loading, and the gas velocity is investigated and these reaction conditions are optimized. The activation energies of methane catalytic decomposition on Ni/Al2O3 and NiCu/Al2O3 catalysts are measured in the chemical reation kinetic limted temperature regin, and the values are both 73±2 kJ/mol for the two catalysts. Thus it is suggested that the doping of Cu didn’t change the state of activity sites because the each activity site is composed of several Ni atoms. Cu in the catalyst particles tends to be rich in the surface and will reduce the overall activity sites, but it has effect on reducing the opportunities of deactivation caused by encapsulation.
The measurement of ppm level CO concentration is achieved by the gas chromatogram equipped with methanation reactor. The results show that the CO concentration can be 1800-2500 ppm in the trail gas when no gas purity devices are used. This value is decreased to 700-1040 ppm when a drier is used, while it drop to 250 ppm when both drier and deoxidization systems are used. The experiment results also show that the CO concentration can be smaller than 10 ppm when using pure methane as feed. For all the reaction process, the CO concentration increase with the increasement of temperature, and decrease with the time on stream.
Two different reaction schemes were tested for methane catalytic reaction on NiCu/Al2O3 catalysts. The constant temperature reaction (CTR) is that reactions are conducted in a constant temperature, while the pre-induced reaction (PIR) is that reaction is first induced in low temperature and then reacted in a higher temperature. The results show that the PIR can improve the stability of catalyst dramatically. The HRTEM and EDS characterization results show that the composition of metal particles obtained in PIR is similar to particles obtained in low temperature CTR, in which the Ni/Cu is about 3:1, while for the particles obtained in high temperature CTR, this value is lower than 1:1. It is also observed that the structure of carbon nanofibers formed in PIR have the both characters of the carbon nanofibers formed in the low temperature CTR and high temperature CTR. It is suggested that in the induced period of reaction, the metal particles undergo a reconstruction process, and the particles rich in Cu or Ni are formed. When the reaction is conducted in low temperature CTR, those particles rich in Cu are with very low activity and the carbon nanofibers are difficult to grow on this types of particles. When the reaction is conducted in high temperature CTR, the particles rich in Ni are deactivated quickly and also not suitable to catalyze the growth of carbon nanofibers. When the PIR scheme is conducted, the induction process occurs in low temperature, and the state of metal particles can be reserved where the metal particles rich in Ni will be also active in high temperature.
The doping effect of Mo, Cr and W on the Fe-based catalysts is inverstigated. The activity tests and the characterization results show that the doping of inactive Cr and W reduce the activity sites and decrease the methane conversion. The activity of catalysts is promoted by doping Mo, and the methane conversion increase from 14% to 40%. The XRD and TPR characterization showed that the doping of Mo can change the Fe redox cycle and enhance the dispersion of Fe. When the Mo/(Mo+Fe) value equals to 10%, the catalyst has the best performance. For the reaction conducted in fixed bed reactor, the methane conversion can stabilize at 44% for 180 min at 973 K, while the conversion can be 78% for 40 min at 1023 K.
Catalysts prepared by citric acid sol-gel method and impregnation method are employed to produce nanocarbon with different morphologies by methane catalytic decomposition. Various catalysts are tested and the structure of nanocarbons is characterized by HRTEM and Raman. For the catalysts prepared by citric acid sol-gel method, the catalyst with a composition of Fe:Mo:Al=9:1:120 (mol ratio) can produce single wall carbon nanotubes with high purity. It is also found that Fe-Mo catalysts have better performance than Fe catalyst, which is due to the doping effect of Mo. For the catalysts prepared by impregnation, different types of nanocarbon, including multi-walled carbon nanobubes, nanosized carbon onion-like fullerene and nanosized graphite particle was obtained on different catalysts. It is also found that the Mo/MgO catalyst have good activity and stability in high temperature and is effective for producing highly graphitized multiple-walled carbon nanotubes with narrow diameter distribution. The XRD results showed that the Mo2C can be the activity species during the reaction. Based on the results of HRTEM, the mechanism of single wall carbon nanotubes growth and other form of nanocarbon is discussed.
使用共沉淀法制备了以水滑石为母体的NiAl和NiCuAl催化剂,并考察了还原温度、反应温度、Ni的负载量提高、进料气速对流化床中甲烷催化裂解反应的影响。并通过对甲烷催化裂解在低温为本征化学反应控制区域动力学的测定,发现Ni/Al2O3和NiCu/Al2O3两种催化剂的活化能很相近,都在73±2 kJ/mol的范围内,这表明Cu的加入并未影响由数个Ni原子组成的甲烷催化裂解反应活性位的催化活性。这点对甲烷吸附过程的DFT模拟所证实,模拟结果发现甲烷在Ni(100)以及NiCu(100)表面的活化能非常接近。但由于Cu的加入并且在表面的富集,会引起表面这种活性位数量迅速下降,而造成相同温度下活性的降低,但这种作用在高温下可以减少碳包裹颗粒的概率,从而提高高温稳定性。
同时,通过使用带有甲烷化转化器的气相色谱对生成尾气中的CO含量进行了测定。发现在不使用干燥除氧装置时,反应尾气中的CO浓度可达1800-2500 ppm,单独使用干燥装置时反应初期尾气中CO浓度约为1040 ppm,但反应稳定后可以下降到700 ppm以下。在同时使用干燥和除氧装置后,CO浓度较添加装置前明显下降,稳定时达到250 ppm左右。而且当使用纯甲烷进料时,在反应80 min后达到10 ppm以下的水平。结果还表明,CO浓度随着温度的升高而增加,并且在反应初期浓度最高。
通过比较NiCu/Al2O3在恒温反应(CTR)和低温引导高温反应(PIR)两种反应过程,发现使用PIR可以显著提高催化剂的稳定性。通过使用HRTEM和EDS对生长碳纤维的催化剂金属颗粒进行表征后发现,PIR产生的金属颗粒的组成与低温CTR的金属颗粒组成类似,Ni/Cu比约为3:1,而高温CTR的金属颗粒中Ni/Cu低于1:1。而且从生成的纳米碳纤维和金属颗粒的形状来看,PIR兼具高温和低温CTR反应时生成产品结构的特点。可以认为,在反应的引导过程中,形成了富铜的颗粒和富镍的颗粒,当甲烷催化裂解反应在较低的温度下进行时,富铜的颗粒由于铜的惰性和易在表面分布的性质,催化活性很低;而富镍的颗粒拥有适合碳纤维生长的结构和组成,因此有较高的活性,因此在本实验中观察到的碳纤维的顶部的催化剂颗粒多具有较高的镍含量。当反应温度较高时,催化剂颗粒失活很快,在这种条件下,富镍的颗粒稳定性很差,不适合催化生长碳纤维,而富铜的颗粒由于铜对镍的调变作用可以保持一定的活性,因此可以在实验结果中发现高温下碳纤维顶端的催化剂颗粒的铜含量较高,但是即使如此,富铜颗粒对于甲烷裂解反应的催化活性仍然较低。在分步加热的条件下,甲烷裂解反应的引导过程在较低温度进行,可使催化剂颗粒的结构重组的低温下进行,使富镍颗粒保持活性,并在一定长度的碳纤维壁可以保护富镍颗粒在高温下有较好的稳定性。
考察了铁基催化剂中掺杂Mo,Cr和W对催化剂活性的影响,结果发现,对甲烷催化裂解反应没有活性的Cr和W占据表面位置,减少活性位,而降低甲烷转化率,而且Cr的掺杂会导致无定型碳的生成,容易造成金属颗粒表面积碳而失活。而在催化剂中掺杂Mo可以显著提高催化剂的活性,可以将单金属的Fe/Al2O3催化剂17%的转化率提高到40%左右,通过XRD和TPR表征发现,在催化剂掺杂Mo后,催化剂的氧化物状态和还原过程发生了明显变化,并有利于提高Fe的分散度。当Mo/(Mo+Fe)(mol比)为10%催化剂具有最高活性。通过在固定床中的反应发现,该催化剂可以在973 K时,甲烷转化率可以保持在44%约180 min;当反应温度升至1023 K时,甲烷初始转化率可达78%,但是高活性只能保持40 min。
对高温条件下甲烷催化裂解反应制备纳米碳材料进行了研究。使用柠檬酸法制备的FeMo催化剂用于甲烷催化裂解反应。并使用HRTEM和Raman对生成的纳米碳进行了表征。使用活性组分含量为Fe:Mo:Al=9:1:120的催化剂,制备出了纯度很高,直径在1-2.5 nm之间的单壁纳米碳管。使用浸渍法制备的负载量为16%的Fe/MgO、Mo/MgO和FeMo/MgO用于甲烷催化裂解反应,分别得到了大量的直径在10 nm左右的多壁纳米碳管、一些多壁纳米碳管,以及纳米碳洋葱。并且发现,Mo/MgO高温稳定好,甲烷转化率可以一直保持在31%左右,XRD结果证实Mo2C为甲烷裂解反应的活性中心。根据本文HRTEM观察到的结果,提出单壁纳米碳管束的生长是以金属表面形成的突起为生长中心的。而纳米碳洋葱的生成主要与高温石墨层生长过快有关,而颗粒大小不同的金属颗粒,表面张力和进入拟液态的程度也不同,生成纳米碳洋葱或者石墨笼。
Methane catalytic decomposition can produce COx-free hydrogen and carbon nanomaterials simultaneously, which is prior to the conventional hydrogen production processes. In this work, both Ni-based and Fe-based catalysts are investigated for production of COx-free hydrogen and various types of nanocarbon through methane catalytic decomposition. The catalysts with high activity and stability are obtained and the approach to improve the stability of catalyst at high temperature is discussed. Carbon nanomaterials with different morphologies are successfully synthesized and the methanism is discussed.
NiAl and NiCuAl catalyst derived from Feitknecht compound was used for the methane catalytic decomposition in a fluidized bed. The effect of reaction temperature, reduced temperature, the metal loading, and the gas velocity is investigated and these reaction conditions are optimized. The activation energies of methane catalytic decomposition on Ni/Al2O3 and NiCu/Al2O3 catalysts are measured in the chemical reation kinetic limted temperature regin, and the values are both 73±2 kJ/mol for the two catalysts. Thus it is suggested that the doping of Cu didn’t change the state of activity sites because the each activity site is composed of several Ni atoms. Cu in the catalyst particles tends to be rich in the surface and will reduce the overall activity sites, but it has effect on reducing the opportunities of deactivation caused by encapsulation.
The measurement of ppm level CO concentration is achieved by the gas chromatogram equipped with methanation reactor. The results show that the CO concentration can be 1800-2500 ppm in the trail gas when no gas purity devices are used. This value is decreased to 700-1040 ppm when a drier is used, while it drop to 250 ppm when both drier and deoxidization systems are used. The experiment results also show that the CO concentration can be smaller than 10 ppm when using pure methane as feed. For all the reaction process, the CO concentration increase with the increasement of temperature, and decrease with the time on stream.
Two different reaction schemes were tested for methane catalytic reaction on NiCu/Al2O3 catalysts. The constant temperature reaction (CTR) is that reactions are conducted in a constant temperature, while the pre-induced reaction (PIR) is that reaction is first induced in low temperature and then reacted in a higher temperature. The results show that the PIR can improve the stability of catalyst dramatically. The HRTEM and EDS characterization results show that the composition of metal particles obtained in PIR is similar to particles obtained in low temperature CTR, in which the Ni/Cu is about 3:1, while for the particles obtained in high temperature CTR, this value is lower than 1:1. It is also observed that the structure of carbon nanofibers formed in PIR have the both characters of the carbon nanofibers formed in the low temperature CTR and high temperature CTR. It is suggested that in the induced period of reaction, the metal particles undergo a reconstruction process, and the particles rich in Cu or Ni are formed. When the reaction is conducted in low temperature CTR, those particles rich in Cu are with very low activity and the carbon nanofibers are difficult to grow on this types of particles. When the reaction is conducted in high temperature CTR, the particles rich in Ni are deactivated quickly and also not suitable to catalyze the growth of carbon nanofibers. When the PIR scheme is conducted, the induction process occurs in low temperature, and the state of metal particles can be reserved where the metal particles rich in Ni will be also active in high temperature.
The doping effect of Mo, Cr and W on the Fe-based catalysts is inverstigated. The activity tests and the characterization results show that the doping of inactive Cr and W reduce the activity sites and decrease the methane conversion. The activity of catalysts is promoted by doping Mo, and the methane conversion increase from 14% to 40%. The XRD and TPR characterization showed that the doping of Mo can change the Fe redox cycle and enhance the dispersion of Fe. When the Mo/(Mo+Fe) value equals to 10%, the catalyst has the best performance. For the reaction conducted in fixed bed reactor, the methane conversion can stabilize at 44% for 180 min at 973 K, while the conversion can be 78% for 40 min at 1023 K.
Catalysts prepared by citric acid sol-gel method and impregnation method are employed to produce nanocarbon with different morphologies by methane catalytic decomposition. Various catalysts are tested and the structure of nanocarbons is characterized by HRTEM and Raman. For the catalysts prepared by citric acid sol-gel method, the catalyst with a composition of Fe:Mo:Al=9:1:120 (mol ratio) can produce single wall carbon nanotubes with high purity. It is also found that Fe-Mo catalysts have better performance than Fe catalyst, which is due to the doping effect of Mo. For the catalysts prepared by impregnation, different types of nanocarbon, including multi-walled carbon nanobubes, nanosized carbon onion-like fullerene and nanosized graphite particle was obtained on different catalysts. It is also found that the Mo/MgO catalyst have good activity and stability in high temperature and is effective for producing highly graphitized multiple-walled carbon nanotubes with narrow diameter distribution. The XRD results showed that the Mo2C can be the activity species during the reaction. Based on the results of HRTEM, the mechanism of single wall carbon nanotubes growth and other form of nanocarbon is discussed.
引文
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