热等离子体重整CH_4-CO_2制合成气
摘要
近年来,随着世界性石油储量的日益减少,天然气这一高效、清洁、储量可观的能源越来越受到人们的重视。天然气的主要成分是甲烷,资源丰富。二氧化碳是含碳化合物的最终氧化产物,主要来源于化石燃料的燃烧和排放。二者同为温室气体,又是丰富的碳资源。因此,开辟以天然气(CH_4)和CO_2为原料替代石油资源的基本有机化工合成路线研究不仅关系到未来资源的配置,对环境保护也同样有重要意义。但是,甲烷和二氧化碳化学性质非常稳定,直接转化需要极为苛刻的条件。等离子体技术为这种转化提供了一条新的途径。
等离子体是大量带电粒子组成的非凝聚系统,是物质存在的第四态,其基本组成成分是:电子、离子、原子、分子、光子和自由基。等离子体作为一种特殊的手段,在参与化学反应上受到人们的关注。应用在甲烷二氧化碳重整反应过程中的有冷等离子体和热等离子体两种,相对于冷等离子体而言,热等离子体技术具有高温、高焓、可控等优点,该技术在化工领域显示了其巨大的应用价值。本文重点研究热等离子体射流在甲烷二氧化碳重整中的应用。
实验考察了原料气CH_4/CO_2摩尔比、输入功率、进气流量对原料转化率、产物选择性的影响。研究结果表明,热等离子体重整甲烷和二氧化碳制合成气具有处理量大、甲烷和二氧化碳转化率高、化学能效和热值产率高的特点。当CH_4/CO_2=1,进气流量为9.6m3/h,放电功率为3.4KW时,CH_4和CO_2的转化率为别为92%和88.3%,H_2、CO和C_2H_2的选择性分别为65.1%、66.2%和13.7%,化学能效值为59.8%。
实验考察了在热等离子体条件下,甲烷单独裂解和二氧化碳单独裂解的规律,并与甲烷二氧化碳重整实验进行了对比研究,结果表明:在重整反应过程中,甲烷和二氧化碳具有相互促进作用。
常压下,利用实验室制备的Ni-Ce/Al_2O_3催化剂,进行了热等离子单独重整与热等离子体催化耦合重整CH_4和CO_2制合成气的实验研究。实验中,催化剂被放置在等离子体反应区,催化剂床层由高温等离子射流气体加热。固定原料气配比V(CO_2)/V(CH_4) =1、等离子体工作载气流量0.8m3/h及放电功率3.5KW不变,考察了原料气总流量对原料转化率、产物选择性、化学能效和催化剂积碳速率的影响;并探讨了助剂Ce在重整反应中的作用。结果表明:随原料气总流量的增加,CH_4和CO_2转化率降低,H_2和CO选择性无明显变化,C_2H_2选择性和催化剂积碳速率增加。热等离子催化耦合重整比热等离子单独重整具有较高的原料转化率、H_2和CO选择性、化学能效值和较低的C_2H_2选择性。
最后,利用ASPEN PLUS模拟软件,对热等离子重整甲烷和二氧化碳制合成气的实验过程进行了热力学模拟,发现模拟结果能够较好的和实验结果吻合。
实验采用自然界存在丰富的CH_4和CO_2作为原料气,在友好的常温常压反应条件下,利用热等离子体技术重整制取合成气,这对开辟新的化工原料来源,减少温室气体排放,实现可持续发展战略具有重要的意义。
With the petroleum resources becoming increasingly exhausted, more and more attention has been focused on the exploitation of natural gas that is highly effective, clean and abundant worldwide. CH4 is a principal component of natural gas. Since both CH4 and CO_2 are major greenhouse gases and the plentiful sources of carbon. Therefore, how to utilize them is concerned not only to resource disposition in the future, but also to protection of the environment.
Plasmas are defined as highly excited gases composed of electrons, ions, atoms, and molecules with different energetic states, which is the fourth state of matter. Plasma process offers a unique way to induce gas phase reaction, which is utilized in many chemical reactions. Depending on their energy level, temperature and electronic density, plasma state is usually classi?ed as a high temperature (or thermal) plasma and a cold (or non-thermal or non-equilibrium) plasma. Thermal plasma has many advantages such as high temperature, adjusted atmosphere and controllable magnetism etc. Thermal plasma with features of higher temperature and higher density of active particles could be more effective to implement the simultaneously conversion of methane and carbon dioxide. Compared with non-thermal plasma, thermal plasma enhanced methane conversion process could achieve higher conversions of reactants, as well as higher selectivity to the syngas.
The effects of the molar ratio of CH_4/CO_2, total flux of feed gases and the plasma power were investigated. The results indicated that the reforming of CH_4 and CO_2 were performed by thermal plasma with a larger processing capacity, higher conversion of CH_4 and CO_2, and higher chemical energy efficiency and fuel production efficiency. When the molar ratio of CH_4/CO_2, the total flux of feed gases and the input electric power were CH_4/CO_2=1, 9.6m3/h and 3.4KW, respectively, the conversions of CH_4 and CO_2 were up to 92.2% and 88.3%. Under these optimal conditions, the other parameters were determined: the selectivies of H_2、CO and C2H_2 were also high to 66.2%、65.1% and 13.7%, and the chemical energy efficiency were 59.8%.
Experiments of carbon dioxide decomposition, methane decomposition and carbon dioxide reforming of methane were investigated. The results show that the mutual promotion between carbon dioxide and methane in reforming process should be considered in order to obtain high conversion of CH_4 and CO_2.
Experiments on synthesis gas preparation from reforming of methane by carbon dioxide with thermal plasma only and cooperation of thermal plasma with Ni-Ce/Al2O3 catalyst, which were packed in the post plasma zone, have been performed. No extra energy was needed to maintain the temperature of catalyst bed, the elevated temperature was maintained by the hot gases from plasma region. We investigated the effects of total flux on the conversions of reactants ,the selectivity of products, chemical energy efficiency and the catalyst coking rate; Besides, we discussed the role of Ce in the reforming reaction, when the molar ratio of CH_4 to CO_2, the nitrogen flow and the plasma power were 1/1, 0.8m3/h and 3.5KW. The results show that with the increase of total flux, the conversions of methane and carbon dioxide decreased gradually, the selectivity of H_2 and CO hardly changed except C2H_2, and the catalyst coking rate Rapidly increased. Respectively, Higher conversion of reactants, higher selectivity of H_2 and CO, higher chemical energy, and lower selectivity of C2H_2 of the process were achieved by plasma coupled with catalyst.
Finally, the thermodynamic analysis of process of CO_2 reforming CH_4 to syngas by a thermal plasma was undertaken using the Aspen Plus simulation tool. It was found that the simulation results accord with the experiment results well.
The experiments use CH_4 and CO_2 as stuff, which are very abundant in the nature, utilize thermal plasma reforming at normal temperature and pressure conversion of methane and carbon dioxide to syngas. It is important for providing a new source of chemical engineering raw material, reducing greenhouse gases exhaust, realizing the strategy of sustainable development.
等离子体是大量带电粒子组成的非凝聚系统,是物质存在的第四态,其基本组成成分是:电子、离子、原子、分子、光子和自由基。等离子体作为一种特殊的手段,在参与化学反应上受到人们的关注。应用在甲烷二氧化碳重整反应过程中的有冷等离子体和热等离子体两种,相对于冷等离子体而言,热等离子体技术具有高温、高焓、可控等优点,该技术在化工领域显示了其巨大的应用价值。本文重点研究热等离子体射流在甲烷二氧化碳重整中的应用。
实验考察了原料气CH_4/CO_2摩尔比、输入功率、进气流量对原料转化率、产物选择性的影响。研究结果表明,热等离子体重整甲烷和二氧化碳制合成气具有处理量大、甲烷和二氧化碳转化率高、化学能效和热值产率高的特点。当CH_4/CO_2=1,进气流量为9.6m3/h,放电功率为3.4KW时,CH_4和CO_2的转化率为别为92%和88.3%,H_2、CO和C_2H_2的选择性分别为65.1%、66.2%和13.7%,化学能效值为59.8%。
实验考察了在热等离子体条件下,甲烷单独裂解和二氧化碳单独裂解的规律,并与甲烷二氧化碳重整实验进行了对比研究,结果表明:在重整反应过程中,甲烷和二氧化碳具有相互促进作用。
常压下,利用实验室制备的Ni-Ce/Al_2O_3催化剂,进行了热等离子单独重整与热等离子体催化耦合重整CH_4和CO_2制合成气的实验研究。实验中,催化剂被放置在等离子体反应区,催化剂床层由高温等离子射流气体加热。固定原料气配比V(CO_2)/V(CH_4) =1、等离子体工作载气流量0.8m3/h及放电功率3.5KW不变,考察了原料气总流量对原料转化率、产物选择性、化学能效和催化剂积碳速率的影响;并探讨了助剂Ce在重整反应中的作用。结果表明:随原料气总流量的增加,CH_4和CO_2转化率降低,H_2和CO选择性无明显变化,C_2H_2选择性和催化剂积碳速率增加。热等离子催化耦合重整比热等离子单独重整具有较高的原料转化率、H_2和CO选择性、化学能效值和较低的C_2H_2选择性。
最后,利用ASPEN PLUS模拟软件,对热等离子重整甲烷和二氧化碳制合成气的实验过程进行了热力学模拟,发现模拟结果能够较好的和实验结果吻合。
实验采用自然界存在丰富的CH_4和CO_2作为原料气,在友好的常温常压反应条件下,利用热等离子体技术重整制取合成气,这对开辟新的化工原料来源,减少温室气体排放,实现可持续发展战略具有重要的意义。
With the petroleum resources becoming increasingly exhausted, more and more attention has been focused on the exploitation of natural gas that is highly effective, clean and abundant worldwide. CH4 is a principal component of natural gas. Since both CH4 and CO_2 are major greenhouse gases and the plentiful sources of carbon. Therefore, how to utilize them is concerned not only to resource disposition in the future, but also to protection of the environment.
Plasmas are defined as highly excited gases composed of electrons, ions, atoms, and molecules with different energetic states, which is the fourth state of matter. Plasma process offers a unique way to induce gas phase reaction, which is utilized in many chemical reactions. Depending on their energy level, temperature and electronic density, plasma state is usually classi?ed as a high temperature (or thermal) plasma and a cold (or non-thermal or non-equilibrium) plasma. Thermal plasma has many advantages such as high temperature, adjusted atmosphere and controllable magnetism etc. Thermal plasma with features of higher temperature and higher density of active particles could be more effective to implement the simultaneously conversion of methane and carbon dioxide. Compared with non-thermal plasma, thermal plasma enhanced methane conversion process could achieve higher conversions of reactants, as well as higher selectivity to the syngas.
The effects of the molar ratio of CH_4/CO_2, total flux of feed gases and the plasma power were investigated. The results indicated that the reforming of CH_4 and CO_2 were performed by thermal plasma with a larger processing capacity, higher conversion of CH_4 and CO_2, and higher chemical energy efficiency and fuel production efficiency. When the molar ratio of CH_4/CO_2, the total flux of feed gases and the input electric power were CH_4/CO_2=1, 9.6m3/h and 3.4KW, respectively, the conversions of CH_4 and CO_2 were up to 92.2% and 88.3%. Under these optimal conditions, the other parameters were determined: the selectivies of H_2、CO and C2H_2 were also high to 66.2%、65.1% and 13.7%, and the chemical energy efficiency were 59.8%.
Experiments of carbon dioxide decomposition, methane decomposition and carbon dioxide reforming of methane were investigated. The results show that the mutual promotion between carbon dioxide and methane in reforming process should be considered in order to obtain high conversion of CH_4 and CO_2.
Experiments on synthesis gas preparation from reforming of methane by carbon dioxide with thermal plasma only and cooperation of thermal plasma with Ni-Ce/Al2O3 catalyst, which were packed in the post plasma zone, have been performed. No extra energy was needed to maintain the temperature of catalyst bed, the elevated temperature was maintained by the hot gases from plasma region. We investigated the effects of total flux on the conversions of reactants ,the selectivity of products, chemical energy efficiency and the catalyst coking rate; Besides, we discussed the role of Ce in the reforming reaction, when the molar ratio of CH_4 to CO_2, the nitrogen flow and the plasma power were 1/1, 0.8m3/h and 3.5KW. The results show that with the increase of total flux, the conversions of methane and carbon dioxide decreased gradually, the selectivity of H_2 and CO hardly changed except C2H_2, and the catalyst coking rate Rapidly increased. Respectively, Higher conversion of reactants, higher selectivity of H_2 and CO, higher chemical energy, and lower selectivity of C2H_2 of the process were achieved by plasma coupled with catalyst.
Finally, the thermodynamic analysis of process of CO_2 reforming CH_4 to syngas by a thermal plasma was undertaken using the Aspen Plus simulation tool. It was found that the simulation results accord with the experiment results well.
The experiments use CH_4 and CO_2 as stuff, which are very abundant in the nature, utilize thermal plasma reforming at normal temperature and pressure conversion of methane and carbon dioxide to syngas. It is important for providing a new source of chemical engineering raw material, reducing greenhouse gases exhaust, realizing the strategy of sustainable development.
引文
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