晶格氧部分氧化甲烷制取合成气的基础研究
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摘要
目前世界能源和化学工业85%以上是建立在石油、煤炭和天然气这三种可燃性矿物资源基础之上。在这三大支柱性能源中,石油资源日益枯竭,价格不断上涨,煤炭资源尽管储量丰富,但使用时污染严重,对环境保护带来严重的挑战,作为优质清洁能源和化工原料的天然气期望在现代经济中扮演更加重要的角色。目前对天然气的开发利用主要集中在对甲烷转化技术的研究。甲烷分子中C-H键能高达435kJ/mol,直接转化为化学品离工业化目标尚远,因此,经“合成气”制备重要化学品和液体燃料的间接转化法成为当今国际上的热门课题之一。
本文围绕合成气的制备过程,对新颖的“晶格氧部分氧化甲烷制取合成气技术”开展了比较系统的研究,内容主要涉及氧载体与甲烷反应的热力学理论分析和平衡组分模拟、氧载体的实验筛选以及优化,反应动力学参数的确定和机理研究,反应新体系的探索等关键基础问题。
研究中首先根据氧载体选择的基本原则,初步选取稀土氧化物Ce02和过渡金属Fe2O3、CuO和Mn2O3作为氧载体,通过热力学软件,计算了四种体系的ΔrG°和ΔrH°,根据系统自由能最小原则绘制了不同反应温度氧载体与甲烷反应的平衡组成图。结果发现,所选取的四种氧化物在一定的温度范围内在热力学上均能按理论分析的部分氧化甲烷生成合成气的方向进行,如果要获得理想n(H2)与n(CO)比例的合成气,需要控制较高的反应温度和合适的氧载体与甲烷量比关系。
以共沉淀法制备了n(Ce)与n(M)摩尔比为1：1的Ce-M-O (M=Fe、Mn、Cu)系列氧载体,XRD表征发现Mn203和Fe203可以较好地分散在Ce02中,而CuO的分散性较差。Ce-M-O氧载体与甲烷反应的热重实验表明,Fe203、CuO和Mn203的加入能够明显地提高氧载体中晶格氧的供给能力,单从增加晶格氧供给能力方面来讲,Ce-Fe-O表现出了最佳的供氧能力。固定床活性评价中,Ce-Cu-O氧载体主要表现出完全氧化甲烷的性质；Ce-Mn-O氧载体虽然在较高的温度下能够较好地实现甲烷的部分氧化,但却使甲烷发生了严重裂解；Ce-Fe-O表现出了最好的部分氧化甲烷性能,产物气中n(H2)/n(CO)能够持续稳定在2左右。综合分析认为,Ce-Fe-O复合氧化物无论从提供晶格氧的总量,还是从实现甲烷部分氧化的性能,以及降低氧载体的生产成本方面来讲,均能承担起“晶格氧部分氧化甲烷制取合成气技术”中氧载体的关键角色。
由于Ce-Fe-O氧载体有着良好的部分氧化甲烷特性,继续开展了n(Ce)/n(Fe)比对氧载体部分氧化甲烷活性影响的研究。同样采用共沉淀法制备了Ce-Fe-O-X(X=9/1、8/2、7/3、6/4、5/5、4/6、2/8)铈基系列氧载体,利用XRD、H2-TPR等表征手段,结合固定床反应器和热重实验平台,对氧载体的性能进行了评价,结果表明,Ce-Fe-O-7/3的氧载体具有最好的部分氧化甲烷活性。对已经确定了铈铁比例的Ce-Fe-O-7/3氧载体,进行了不同焙烧温度的影响实验,发现800℃的焙烧温度,氧载体表现出了最好的反应性能。为了继续提高氧载体的循环性能,进行了掺杂ZrO2对氧载体的改性研究,结果认为ZrO2的掺杂特别是合适的掺杂量(Ce-Fe-Zr-O(0.05))可使氧载体具有优良的部分氧化甲烷性能和循环使用性能。
对以Ce-Fe-Zr-O(0.05)为氧载体与甲烷反应的动力学开展了相关研究,结果发现反应的平均表观活化能Em为131.762kJ/mol,而以纯CeO2为氧载体时,反应的平均表观活化能Em为173.517kJ/mol,说明铁和锆的加入显著地降低了CeO2部分氧化甲烷反应的活化能,即Ce-Fe-Zr-O(0.05)氧载体与甲烷之间发生部分氧化的反应与纯CeO2相比更易进行,这一性能的改善与铈铁锆三者间固溶体的形成及相互的间协同作用有关；反应机理研究认为,整个反应过程存在反应初期、中期和后期三个明显阶段。反应初期以甲烷的燃烧-重整机理为主,反应中期是甲烷的直接氧化机理,即CO和H2是氧载体中晶格氧对甲烷部分氧化的一次产物,该阶段是合成气大量生成的重要时期,反应后期则以甲烷裂解为主。
提出了在“熔融盐体系中利用氧载体的晶格氧实现甲烷部分氧化制取合成气”的新方法,期望这种新体系在炭沉积的消减、反应热场的均匀化,以及对反应热的后续高效利用方面有新的贡献。对不同的熔融盐体系进行了对比和研究,最终设计出适合这种新方法的熔融盐体系为质量比1：1的碳酸钠和碳酸钾混合组分；以Ce-Fe-Zr-O(0.05)为氧载体,开展了熔融盐体系下的甲烷部分氧化实验,结果发现在新体系下同样能够顺利实现合成气的生产,氧载体经空气再生后能够顺利循环使用,而且这种熔融盐新体系有着良好的炭沉积消减作用,并对合成气中H2和CO比例具有较宽范围的调节作用。分析认为,这种新的反应体系既避免了传统反应过程催化剂存在热点的问题,又为反应热的后续有效利用提供了一个全新的利用途径。
Currently, more than 85% of the world's energy and chemical industry is built on the basis of three flammability mineral resources, which are oil, coal and natural gas.In the three pillars of energy, oil resources are depleted day after day, and the price is rising. Although the reserves of coal resources are rich, there is a serious pollution problem when it is used. And as the quality of clean energy and chemical raw materials, natural gas is expected to play a more important role in the modern economic society. At present the development and utilization of natural gas mainly concentrate on the methane conversion technologies. As for the C-H bond of methane molecules reaches 435 kJ/mol, the direct translation methane into chemicals is still far from the goal of industrialization, therefore, the indirect technique of translation "syngas" into important chemicals and liquid fuels becomes a hot topic in the contemporary world.
A more systematic study about the novel technology of "partial oxidation of methane to syngas using lattice oxygen" was done, and the contents included the following key issues:thermodynamic theory analysis and equilibrium compositions simulation, experimental choosing and optimization of oxygen carriers, kinetics and reaction mechanism, and the exploration about a new reaction system.
According to the basic principle of oxygen carrier choice, CeO2, Fe2O3, CuO and Mn2O3 were preliminary chosen as oxygen carriers and A,G°and ArH°of the four systems were calculated by means of thermodynamic analysis. Based on the principle of a system free energy minimum, the equilibrium compositions of oxides-CH4 system at various temperatures were calculated using thermodynamics software and database. The results showed that in theory the four oxides could partially oxide methane to syngas in a certain temperature range. If syngas with ideal n (H2) In (CO) ratio needed to be obtained, the higher temperature and appropriate ratio of methane and oxygen carriers needed to be controlled.
The Ce-M-O (M=Fe, Mn, Cu) complex oxides in which the ratio of n (Ce)/n(M) is 1:1 were prepared by coprecipitation. The X-ray diffraction (XRD) characterization results of oxygen carriers showed that Mn2O3 and Fe2O3 could spread out in the CeO2, but CuO could not. The TG experiment of Ce-M-0 oxygen carrier reaction with methane illuminated that the capability of supplying lattice oxygen could be significantly improved when Fe2O3, CuO and Mn2O3 were incorporated into CeO2. So, if the capability of supplying lattice oxygen only was taken into account, the Ce-Fe-O oxygen carrier had the best oxygen storage capability (OSC). The activity evaluation experimental results of fixed-bed reactor showed that Ce-Cu-0 had a performance of complete oxidation methane. Although, Ce-Mn-0 could partially oxide methane to syngas at a higher temperature, there was a serious methane pyrogenation. Ce-Fe-O showed the best performance of partial oxidation methane and the ratio of n (H2)/n(CO) was about 2 in product gas. In conclusion, in terms of total lattice oxygen supply or partial oxidation methane or reducing the cost of production oxygen carrier, Ce-Fe-O complex oxides could take on a key role of oxygen carriers being used in "lattice oxygen partial oxidation of methane production of syngas technique"
As Ce-Fe-O oxygen carrier has a good performance of partial oxidation of methane, the different n (Ce)/n(Fe) ratio of oxygen carrier was sequentially researched. The Ce-Fe-O-X (X=9/1、8/2、7/3、6/4、5/5、4/6、2/8) ceria-based oxygen carriers were prepared by coprecipitation, as the same, using some characterization methods, such as XRD, H2-TPR and so on and combination fixed-bed reactor and TG experimental platform, the oxygen carrier performance was evaluated.The results showed that Ce-Fe-O-7/3 oxygen carrier had a good performance.The activity of Ce-Fe-O-7/3 oxygen carrier at different sintering temperatures was studied, the results showed that 800℃was the most appropriate. In order to improve the circulation performance of oxygen carrier, the experiments of modification on Ce-Fe-O-7/3 oxygen carrier by ZrO2 doping were studied. The results showed that Ce-Fe-Zr-O(0.05) had the best circulation performance in all samples.
The kinetics of Ce-Fe-Zr-O(0.05) oxygen carrier reaction with methane was studied. It was found that average apparent activation energy(Em) was 131.762kJ/mol, and when using the pure CeO2 as oxygen carrier the Em was 173.517kJ/mol, in other words, the reaction was easier when using Ce-Fe-Zr-O(0.05) as oxygen carrier than pure CeO2, the performance improvement of oxygen carrier was attributed to the form of Ce-Fe-Zr solid solutions and mutual cooperate of Ce4+, Fe3+, Zr4+ions.The reaction mechanism study revealed that there were three distinct stages which were initial stage, middle stage and final stage in the entire process. The reaction initial stage was combustion-reforming mechanism, the reaction middle stage was directly oxidation mechanism in which stage CO and H2 were the direct production of methane and this stage was a important period for obtaining a great deal of syngas, while in the final stage methane pyrogenation occupied dominance.
A new method which was "partial oxidation of methane to syngas using lattice oxygen in molten salt system" was brough forward. The new system has some new contributions in reducing carbon deposition, heat distribution and enhancing reaction heat utilization efficiency. Different molten salt systems were studied; finally, the Na2CO3 and K2CO3 mixed moten salts (weight ratio was 1/1) were appropriate for the new system. When using Ce-Fe-Zr-O(0.05) as an oxygen carrier for partial oxidation methane in molten salt system, the experimental results showed that syngas could also be produced in the new system, and oxygen carrier regenerated through air could be successfully recycled. The new molten salt system has good functions of reducing carbon deposition and adjusting the ratio of n (H2)/n(CO). The new reaction system could not only avoid the catalyst hot-dot, but also could provide a new means for utilization of reaction heat.
本文围绕合成气的制备过程,对新颖的“晶格氧部分氧化甲烷制取合成气技术”开展了比较系统的研究,内容主要涉及氧载体与甲烷反应的热力学理论分析和平衡组分模拟、氧载体的实验筛选以及优化,反应动力学参数的确定和机理研究,反应新体系的探索等关键基础问题。
研究中首先根据氧载体选择的基本原则,初步选取稀土氧化物Ce02和过渡金属Fe2O3、CuO和Mn2O3作为氧载体,通过热力学软件,计算了四种体系的ΔrG°和ΔrH°,根据系统自由能最小原则绘制了不同反应温度氧载体与甲烷反应的平衡组成图。结果发现,所选取的四种氧化物在一定的温度范围内在热力学上均能按理论分析的部分氧化甲烷生成合成气的方向进行,如果要获得理想n(H2)与n(CO)比例的合成气,需要控制较高的反应温度和合适的氧载体与甲烷量比关系。
以共沉淀法制备了n(Ce)与n(M)摩尔比为1：1的Ce-M-O (M=Fe、Mn、Cu)系列氧载体,XRD表征发现Mn203和Fe203可以较好地分散在Ce02中,而CuO的分散性较差。Ce-M-O氧载体与甲烷反应的热重实验表明,Fe203、CuO和Mn203的加入能够明显地提高氧载体中晶格氧的供给能力,单从增加晶格氧供给能力方面来讲,Ce-Fe-O表现出了最佳的供氧能力。固定床活性评价中,Ce-Cu-O氧载体主要表现出完全氧化甲烷的性质；Ce-Mn-O氧载体虽然在较高的温度下能够较好地实现甲烷的部分氧化,但却使甲烷发生了严重裂解；Ce-Fe-O表现出了最好的部分氧化甲烷性能,产物气中n(H2)/n(CO)能够持续稳定在2左右。综合分析认为,Ce-Fe-O复合氧化物无论从提供晶格氧的总量,还是从实现甲烷部分氧化的性能,以及降低氧载体的生产成本方面来讲,均能承担起“晶格氧部分氧化甲烷制取合成气技术”中氧载体的关键角色。
由于Ce-Fe-O氧载体有着良好的部分氧化甲烷特性,继续开展了n(Ce)/n(Fe)比对氧载体部分氧化甲烷活性影响的研究。同样采用共沉淀法制备了Ce-Fe-O-X(X=9/1、8/2、7/3、6/4、5/5、4/6、2/8)铈基系列氧载体,利用XRD、H2-TPR等表征手段,结合固定床反应器和热重实验平台,对氧载体的性能进行了评价,结果表明,Ce-Fe-O-7/3的氧载体具有最好的部分氧化甲烷活性。对已经确定了铈铁比例的Ce-Fe-O-7/3氧载体,进行了不同焙烧温度的影响实验,发现800℃的焙烧温度,氧载体表现出了最好的反应性能。为了继续提高氧载体的循环性能,进行了掺杂ZrO2对氧载体的改性研究,结果认为ZrO2的掺杂特别是合适的掺杂量(Ce-Fe-Zr-O(0.05))可使氧载体具有优良的部分氧化甲烷性能和循环使用性能。
对以Ce-Fe-Zr-O(0.05)为氧载体与甲烷反应的动力学开展了相关研究,结果发现反应的平均表观活化能Em为131.762kJ/mol,而以纯CeO2为氧载体时,反应的平均表观活化能Em为173.517kJ/mol,说明铁和锆的加入显著地降低了CeO2部分氧化甲烷反应的活化能,即Ce-Fe-Zr-O(0.05)氧载体与甲烷之间发生部分氧化的反应与纯CeO2相比更易进行,这一性能的改善与铈铁锆三者间固溶体的形成及相互的间协同作用有关；反应机理研究认为,整个反应过程存在反应初期、中期和后期三个明显阶段。反应初期以甲烷的燃烧-重整机理为主,反应中期是甲烷的直接氧化机理,即CO和H2是氧载体中晶格氧对甲烷部分氧化的一次产物,该阶段是合成气大量生成的重要时期,反应后期则以甲烷裂解为主。
提出了在“熔融盐体系中利用氧载体的晶格氧实现甲烷部分氧化制取合成气”的新方法,期望这种新体系在炭沉积的消减、反应热场的均匀化,以及对反应热的后续高效利用方面有新的贡献。对不同的熔融盐体系进行了对比和研究,最终设计出适合这种新方法的熔融盐体系为质量比1：1的碳酸钠和碳酸钾混合组分；以Ce-Fe-Zr-O(0.05)为氧载体,开展了熔融盐体系下的甲烷部分氧化实验,结果发现在新体系下同样能够顺利实现合成气的生产,氧载体经空气再生后能够顺利循环使用,而且这种熔融盐新体系有着良好的炭沉积消减作用,并对合成气中H2和CO比例具有较宽范围的调节作用。分析认为,这种新的反应体系既避免了传统反应过程催化剂存在热点的问题,又为反应热的后续有效利用提供了一个全新的利用途径。
Currently, more than 85% of the world's energy and chemical industry is built on the basis of three flammability mineral resources, which are oil, coal and natural gas.In the three pillars of energy, oil resources are depleted day after day, and the price is rising. Although the reserves of coal resources are rich, there is a serious pollution problem when it is used. And as the quality of clean energy and chemical raw materials, natural gas is expected to play a more important role in the modern economic society. At present the development and utilization of natural gas mainly concentrate on the methane conversion technologies. As for the C-H bond of methane molecules reaches 435 kJ/mol, the direct translation methane into chemicals is still far from the goal of industrialization, therefore, the indirect technique of translation "syngas" into important chemicals and liquid fuels becomes a hot topic in the contemporary world.
A more systematic study about the novel technology of "partial oxidation of methane to syngas using lattice oxygen" was done, and the contents included the following key issues:thermodynamic theory analysis and equilibrium compositions simulation, experimental choosing and optimization of oxygen carriers, kinetics and reaction mechanism, and the exploration about a new reaction system.
According to the basic principle of oxygen carrier choice, CeO2, Fe2O3, CuO and Mn2O3 were preliminary chosen as oxygen carriers and A,G°and ArH°of the four systems were calculated by means of thermodynamic analysis. Based on the principle of a system free energy minimum, the equilibrium compositions of oxides-CH4 system at various temperatures were calculated using thermodynamics software and database. The results showed that in theory the four oxides could partially oxide methane to syngas in a certain temperature range. If syngas with ideal n (H2) In (CO) ratio needed to be obtained, the higher temperature and appropriate ratio of methane and oxygen carriers needed to be controlled.
The Ce-M-O (M=Fe, Mn, Cu) complex oxides in which the ratio of n (Ce)/n(M) is 1:1 were prepared by coprecipitation. The X-ray diffraction (XRD) characterization results of oxygen carriers showed that Mn2O3 and Fe2O3 could spread out in the CeO2, but CuO could not. The TG experiment of Ce-M-0 oxygen carrier reaction with methane illuminated that the capability of supplying lattice oxygen could be significantly improved when Fe2O3, CuO and Mn2O3 were incorporated into CeO2. So, if the capability of supplying lattice oxygen only was taken into account, the Ce-Fe-O oxygen carrier had the best oxygen storage capability (OSC). The activity evaluation experimental results of fixed-bed reactor showed that Ce-Cu-0 had a performance of complete oxidation methane. Although, Ce-Mn-0 could partially oxide methane to syngas at a higher temperature, there was a serious methane pyrogenation. Ce-Fe-O showed the best performance of partial oxidation methane and the ratio of n (H2)/n(CO) was about 2 in product gas. In conclusion, in terms of total lattice oxygen supply or partial oxidation methane or reducing the cost of production oxygen carrier, Ce-Fe-O complex oxides could take on a key role of oxygen carriers being used in "lattice oxygen partial oxidation of methane production of syngas technique"
As Ce-Fe-O oxygen carrier has a good performance of partial oxidation of methane, the different n (Ce)/n(Fe) ratio of oxygen carrier was sequentially researched. The Ce-Fe-O-X (X=9/1、8/2、7/3、6/4、5/5、4/6、2/8) ceria-based oxygen carriers were prepared by coprecipitation, as the same, using some characterization methods, such as XRD, H2-TPR and so on and combination fixed-bed reactor and TG experimental platform, the oxygen carrier performance was evaluated.The results showed that Ce-Fe-O-7/3 oxygen carrier had a good performance.The activity of Ce-Fe-O-7/3 oxygen carrier at different sintering temperatures was studied, the results showed that 800℃was the most appropriate. In order to improve the circulation performance of oxygen carrier, the experiments of modification on Ce-Fe-O-7/3 oxygen carrier by ZrO2 doping were studied. The results showed that Ce-Fe-Zr-O(0.05) had the best circulation performance in all samples.
The kinetics of Ce-Fe-Zr-O(0.05) oxygen carrier reaction with methane was studied. It was found that average apparent activation energy(Em) was 131.762kJ/mol, and when using the pure CeO2 as oxygen carrier the Em was 173.517kJ/mol, in other words, the reaction was easier when using Ce-Fe-Zr-O(0.05) as oxygen carrier than pure CeO2, the performance improvement of oxygen carrier was attributed to the form of Ce-Fe-Zr solid solutions and mutual cooperate of Ce4+, Fe3+, Zr4+ions.The reaction mechanism study revealed that there were three distinct stages which were initial stage, middle stage and final stage in the entire process. The reaction initial stage was combustion-reforming mechanism, the reaction middle stage was directly oxidation mechanism in which stage CO and H2 were the direct production of methane and this stage was a important period for obtaining a great deal of syngas, while in the final stage methane pyrogenation occupied dominance.
A new method which was "partial oxidation of methane to syngas using lattice oxygen in molten salt system" was brough forward. The new system has some new contributions in reducing carbon deposition, heat distribution and enhancing reaction heat utilization efficiency. Different molten salt systems were studied; finally, the Na2CO3 and K2CO3 mixed moten salts (weight ratio was 1/1) were appropriate for the new system. When using Ce-Fe-Zr-O(0.05) as an oxygen carrier for partial oxidation methane in molten salt system, the experimental results showed that syngas could also be produced in the new system, and oxygen carrier regenerated through air could be successfully recycled. The new molten salt system has good functions of reducing carbon deposition and adjusting the ratio of n (H2)/n(CO). The new reaction system could not only avoid the catalyst hot-dot, but also could provide a new means for utilization of reaction heat.
引文
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