甲烷经溴氧化途径制备高碳烃催化性能及工艺研究
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摘要
天然气是当今世界公认的清洁能源,它在一次性能源消费中占有的比例越来越高,预计2050年天然气将有望取代石油成为第一能源。甲烷作为天然气的主要成分,其在天然气中的含量一般在80%以上。因此,研究天然气的转化利用实际上就是研究甲烷的转化利用。
本研究工作提出了一种全新的由甲烷制备高附加值化学品的新工艺。在这个新工艺中,甲烷首先与HBr和02进行溴氧化反应(OBM)制备溴甲烷,然后把合成的溴甲烷转化为液体高碳烃和再生出HBr,释放出的HBr再返回溴氧化反应器以实现HBr的循环利用。本工艺与传统的高能耗合成气工艺相比,所采用的两步反应均为常压放热反应,并且不需要水作为原料。本工艺对生产的规模化依赖程度较低,生产装置可以建在淡水相对缺乏的地区或气藏量相对较小的油田伴生气和煤层气附近。
本文详细研究了新工艺流程中两个反应所需催化剂的催化性能、工艺流程设计中不可回避的耐腐蚀材料选择和产物高碳烃中微量HBr的脱除等方面。为满足甲烷经溴氧化途径制备醋酸工艺中羰基化单元的原料组成需求,还进行了以CH3Br和CO为共同产物的甲烷溴氧化催化剂的研究。
在甲烷溴氧化制备溴甲烷的催化剂研究中,首先根据OBM反应的特点,设计和选取了催化剂的活性组分、载体类型和制备方法。通过实验考查,最终筛选确认溶胶-凝胶法制备的Rh-SiO2催化剂(Rh/SiO2)具有最优的催化性能。在0.4Rh/SiO2-900-10催化剂上,甲烷的单程转化率达到了35.6%,溴代甲烷的选择性达到了90%,催化剂在连续反应650小时后甲烷转化率始终保持在35%以上。通过对催化剂制备方法、反应条件以及催化反应机理的研究发现,OBM反应产物分布与催化剂活性组分和反应条件有关,因此可以通过调整催化剂的活性组分及改变反应条件达到定向地控制反应产物的分布的目的。
为了满足甲烷经溴氧化途径制备醋酸工艺的要求,我们还考察了同时以CH3Br和CO为目的产物的OBM反应。结果发现在具有相对高的比表面的催化剂(0.4Rh/SiO2-700-10,267.5m2/g)上,最高可以得到76.2%的甲烷单程转化率,而且CH3Br和CO的选择性均为42.2%。反应中生成的副产物CO2的选择性仅为5.5%。通过优化催化剂的制备方法改善了高比表面催化剂的热稳定性和催化活性。
在溴甲烷转化制高碳烃的反应中,我们重点研究了不同硅铝比的2wt%MgO/HZSM-5催化剂对反应产物分布和催化活性的影响。结果发现硅铝比为360/1的催化剂具有较好的催化活性。在连续反应400小时后,溴甲烷的转化率仍然始终保持在99%以上,产物主要以C3-C8的烯烃为主。通过对催化剂进行的XRD、BET、NH3-TPD、TG/DSC和GC/MS表征发现,反应积碳类型与催化剂的酸性中心强度有关。催化剂失活的主要原因为在强酸中心上生成了大分子的多甲基取代芳烃,堵塞了催化剂孔道所致。我们还对溴甲烷转化制高碳烃的反应机理进行了初步的探讨。
在耐腐蚀材料的试验中,选定了三种不同的腐蚀环境：反应环境、换热环境和储运环境。研究工作针对不同的腐蚀环境特点进行了耐腐蚀材料的挂片实验,筛选了一批适应于不同腐蚀环境的耐腐蚀材料,这些材料有可能用于反应器和系统流程部件的制造。
我们还设计了一个脱除产物中微量HBr的技术单元,利用负载的二元金属氧化物吸收剂(MOx/SiO2)吸收HBr,可以将产物高碳烃中的HBr深度脱除至4.6×10-16mol/L以下,并且可以再生回收HBr。
Natural gas is considered as clean energy throughout the world. The proportion of natural gas in the world's primary energy consumption is increasing with the continuous increasing price and the uncertainty supply of petroleum. It is expected that natural gas will replace petroleum as the first energy in2050. Methane is the major component of natural gas with more than80%content. Hence, the chemistry of natural gas is actually the chemistry of methane.
The investigation of the dissertation proposed an alternative process for methane utilization to prepare value-added chemicals via non-syngas route. In the process, methane was firstly converted to methyl bromide in the presence of HBr and O2, then the as-synthesized methyl bromide was converted to liquid hydrocarbon and released HBr, which could be recycled in the reaction. Compared with the commercialized energy-consuming syngas route, both of the reactions are exothermic reaction, and no H2O is needed as reactant (contrarily, H2O is produced as by-product). Plants could be constructed at districts with short of water, such as desert or ocean, and stranded reserves, such as associated gas or coal bed gas.
The investigation was focued in the following aspects:1) the catalytic performances of both the oxidative bromination of methane and the condensation of methyl bromide,2) the corrosion-resistant materials testing under OBM condition, and3) the HBr removal from product hydrocarbons. The catalytic performance of OBM reaction with CH3Br and CO as target products was also investigated, which could be used in acetic acid synthesis.
In the investigation of OBM reaction, the active component, support, and preparation method of the catalysts were explored. Rh/SiO2prepared by sol-gel method showed the best performance. A methane conversion of35.6%with methyl bromide selectivity of more than90%was obtained over0.4Rh/SiO2-900-10. A catalyst lifetime of more than650hours was achieved. By adjusting catalyst specific surface area or manipulating the reaction conditions, different product orientation could be achieved.
In order to fit the feedstock demanding in acetic acid synthesis, the catalytic performance of OBM reaction with both CH3Br and CO as target products was also investigated. Over a0.4Rh/SiO2-700-10catalyst with relatively high specific surface area (267.5m2/g), high methane conversion of76.2%with CH3Br and CO equi-selectivity of42.2%was obtained. In this case, the selectivity of CO2was suppressed to5.5%. The thermal stability of catalyst was also improved by optimizing catalyst preparation method.
In the higher hydrocarbons synthesis from methyl bromide, product distribution and catalyst deactivation were investigated on2wt%MgO/HZSM-5catalysts with different Si/Al ratios. Catalyst with a Si/Al ratio of360/1had the best performance and the longest lifetime. A methyl bromide conversion of99.0%was maintained within400h. The major products were the C3-C8olefins. The fresh and used catalysts were characterized by XRD, BET, NH3-TPD, TG/DSC, and GC/MS methods. The characterizations showed that the carbon deposition depended on the acid strength of catalyst. The investigation showed that multi-methyl substituted aromatics were primarily formed on strong acid sites, which were responsible for the deactivation of catalyst. The mechanism of methyl bromide to hydrocarbon was also discussed.
In the corrosion-resistant material testing, three different reaction conditions were selected:1) the reaction condition,2) the heat-exchange condition, and3) the transportation condition. A series of corrosion-resistant materials were tested under the three conditions by flake hanging experiments.
A system for the removing of HBr from hydrocarbons was also designed. In the system, a regeneratable HBr absorbent was used to clear out and recover HBr. The absorbent is MOx/SiO2, which could remove HBr from products to reach a HBr concentration below4.6×10-1mol/L
本研究工作提出了一种全新的由甲烷制备高附加值化学品的新工艺。在这个新工艺中,甲烷首先与HBr和02进行溴氧化反应(OBM)制备溴甲烷,然后把合成的溴甲烷转化为液体高碳烃和再生出HBr,释放出的HBr再返回溴氧化反应器以实现HBr的循环利用。本工艺与传统的高能耗合成气工艺相比,所采用的两步反应均为常压放热反应,并且不需要水作为原料。本工艺对生产的规模化依赖程度较低,生产装置可以建在淡水相对缺乏的地区或气藏量相对较小的油田伴生气和煤层气附近。
本文详细研究了新工艺流程中两个反应所需催化剂的催化性能、工艺流程设计中不可回避的耐腐蚀材料选择和产物高碳烃中微量HBr的脱除等方面。为满足甲烷经溴氧化途径制备醋酸工艺中羰基化单元的原料组成需求,还进行了以CH3Br和CO为共同产物的甲烷溴氧化催化剂的研究。
在甲烷溴氧化制备溴甲烷的催化剂研究中,首先根据OBM反应的特点,设计和选取了催化剂的活性组分、载体类型和制备方法。通过实验考查,最终筛选确认溶胶-凝胶法制备的Rh-SiO2催化剂(Rh/SiO2)具有最优的催化性能。在0.4Rh/SiO2-900-10催化剂上,甲烷的单程转化率达到了35.6%,溴代甲烷的选择性达到了90%,催化剂在连续反应650小时后甲烷转化率始终保持在35%以上。通过对催化剂制备方法、反应条件以及催化反应机理的研究发现,OBM反应产物分布与催化剂活性组分和反应条件有关,因此可以通过调整催化剂的活性组分及改变反应条件达到定向地控制反应产物的分布的目的。
为了满足甲烷经溴氧化途径制备醋酸工艺的要求,我们还考察了同时以CH3Br和CO为目的产物的OBM反应。结果发现在具有相对高的比表面的催化剂(0.4Rh/SiO2-700-10,267.5m2/g)上,最高可以得到76.2%的甲烷单程转化率,而且CH3Br和CO的选择性均为42.2%。反应中生成的副产物CO2的选择性仅为5.5%。通过优化催化剂的制备方法改善了高比表面催化剂的热稳定性和催化活性。
在溴甲烷转化制高碳烃的反应中,我们重点研究了不同硅铝比的2wt%MgO/HZSM-5催化剂对反应产物分布和催化活性的影响。结果发现硅铝比为360/1的催化剂具有较好的催化活性。在连续反应400小时后,溴甲烷的转化率仍然始终保持在99%以上,产物主要以C3-C8的烯烃为主。通过对催化剂进行的XRD、BET、NH3-TPD、TG/DSC和GC/MS表征发现,反应积碳类型与催化剂的酸性中心强度有关。催化剂失活的主要原因为在强酸中心上生成了大分子的多甲基取代芳烃,堵塞了催化剂孔道所致。我们还对溴甲烷转化制高碳烃的反应机理进行了初步的探讨。
在耐腐蚀材料的试验中,选定了三种不同的腐蚀环境：反应环境、换热环境和储运环境。研究工作针对不同的腐蚀环境特点进行了耐腐蚀材料的挂片实验,筛选了一批适应于不同腐蚀环境的耐腐蚀材料,这些材料有可能用于反应器和系统流程部件的制造。
我们还设计了一个脱除产物中微量HBr的技术单元,利用负载的二元金属氧化物吸收剂(MOx/SiO2)吸收HBr,可以将产物高碳烃中的HBr深度脱除至4.6×10-16mol/L以下,并且可以再生回收HBr。
Natural gas is considered as clean energy throughout the world. The proportion of natural gas in the world's primary energy consumption is increasing with the continuous increasing price and the uncertainty supply of petroleum. It is expected that natural gas will replace petroleum as the first energy in2050. Methane is the major component of natural gas with more than80%content. Hence, the chemistry of natural gas is actually the chemistry of methane.
The investigation of the dissertation proposed an alternative process for methane utilization to prepare value-added chemicals via non-syngas route. In the process, methane was firstly converted to methyl bromide in the presence of HBr and O2, then the as-synthesized methyl bromide was converted to liquid hydrocarbon and released HBr, which could be recycled in the reaction. Compared with the commercialized energy-consuming syngas route, both of the reactions are exothermic reaction, and no H2O is needed as reactant (contrarily, H2O is produced as by-product). Plants could be constructed at districts with short of water, such as desert or ocean, and stranded reserves, such as associated gas or coal bed gas.
The investigation was focued in the following aspects:1) the catalytic performances of both the oxidative bromination of methane and the condensation of methyl bromide,2) the corrosion-resistant materials testing under OBM condition, and3) the HBr removal from product hydrocarbons. The catalytic performance of OBM reaction with CH3Br and CO as target products was also investigated, which could be used in acetic acid synthesis.
In the investigation of OBM reaction, the active component, support, and preparation method of the catalysts were explored. Rh/SiO2prepared by sol-gel method showed the best performance. A methane conversion of35.6%with methyl bromide selectivity of more than90%was obtained over0.4Rh/SiO2-900-10. A catalyst lifetime of more than650hours was achieved. By adjusting catalyst specific surface area or manipulating the reaction conditions, different product orientation could be achieved.
In order to fit the feedstock demanding in acetic acid synthesis, the catalytic performance of OBM reaction with both CH3Br and CO as target products was also investigated. Over a0.4Rh/SiO2-700-10catalyst with relatively high specific surface area (267.5m2/g), high methane conversion of76.2%with CH3Br and CO equi-selectivity of42.2%was obtained. In this case, the selectivity of CO2was suppressed to5.5%. The thermal stability of catalyst was also improved by optimizing catalyst preparation method.
In the higher hydrocarbons synthesis from methyl bromide, product distribution and catalyst deactivation were investigated on2wt%MgO/HZSM-5catalysts with different Si/Al ratios. Catalyst with a Si/Al ratio of360/1had the best performance and the longest lifetime. A methyl bromide conversion of99.0%was maintained within400h. The major products were the C3-C8olefins. The fresh and used catalysts were characterized by XRD, BET, NH3-TPD, TG/DSC, and GC/MS methods. The characterizations showed that the carbon deposition depended on the acid strength of catalyst. The investigation showed that multi-methyl substituted aromatics were primarily formed on strong acid sites, which were responsible for the deactivation of catalyst. The mechanism of methyl bromide to hydrocarbon was also discussed.
In the corrosion-resistant material testing, three different reaction conditions were selected:1) the reaction condition,2) the heat-exchange condition, and3) the transportation condition. A series of corrosion-resistant materials were tested under the three conditions by flake hanging experiments.
A system for the removing of HBr from hydrocarbons was also designed. In the system, a regeneratable HBr absorbent was used to clear out and recover HBr. The absorbent is MOx/SiO2, which could remove HBr from products to reach a HBr concentration below4.6×10-1mol/L
引文
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