甲烷二氧化碳自热重整工艺分析  

Process analysis of CH4-CO2 autothermal reforming

作　　者：刘俊义 祝贺[2] 张军[2] LIU Jun-yi;ZHU He;ZHANG Jun(Shanxi Lu'an Coal-to-gasoline Co.,Ltd.,Changzhi 046204,China;CAS Key Laboratory of Low-Carbon Conversion Science and Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences,Shanghai 201203,China)

机构地区：[1]山西潞安矿业(集团)有限责任公司,山西长治046204 [2]中国科学院上海高等研究院低碳转化科学与工程重点实验室,上海201203

出　　处：《天然气化工—C1化学与化工》2019年第3期56-60,共5页Natural Gas Chemical Industry

基　　金：国家重点研发计划(2016YFA0202802)

摘　　要：基于吉布斯自由能最小法,分析甲烷二氧化碳自热重整(CO2/CH4/O2重整)工艺过程,可知:温度增加,合成气中甲烷含量减少、二氧化碳转化率增加;压力增加,合成气中甲烷含量增加、二氧化碳转化率降低;碳碳比n(CO2)/n(CH4)增加,合成气中甲烷含量减少、二氧化碳转化率降低;温度、压力对氢碳比n(H2)/n(CO)有影响,但n(CO2)/n(CH4)对n(H2)/n(CO)影响更为显著;少量或适量水蒸气可以保护甲烷二氧化碳自热重整转化炉内关键设备、调节产物n(H2)/n(CO)等。根据工业生产要求和特点,定义出口合成气中甲烷的物质的量分数1%为临界条件,获得临界条件时n(CO2)/n(CH4)、重整平衡温度与压力、二氧化碳转化率以及n(H2)/n(CO)等特性参数的关系图,指导工业生产的工艺过程和催化剂研究。The process analysis of CH4-CO2 autothermal reforming (CO2/CH4/O2 reforming) is studied by total Gibbs energy minimization.The results indicates that when operating temperature increases,methane content in syngas reduces and carbon dioxide conversion increases,while operating pressure increases,methane content in syngas increases and carbon dioxide conversion decreases.Increasing the molar ratio of CO2 to CH4 in feed gas,both of methane content in syngas and carbon dioxide conversion decreases.Although operating temperature and pressure impact the molar ratio of H2 to CO in product gas,the main factor is the molar ratio of CO2 to CH4 in feed gas.A small or moderate amount of steam can protect the key equipment in the CO2 autothermal reformer and regulate the molar ratio of H2 to CO in product gas.The critical condition is defined as 1% of methane mole fraction in syngas according to industrial process requirements and characteristics.The relation graphs among the molar ratio of CO2 to CH4,equilibrium temperature and pressure of reforming reaction,carbon dioxide conversion and the molar ratio of H2 to CO in product gas are obtained in critical condition,which will guide technology and catalyst research.

关 键 词：二氧化碳 甲烷含量 自热重整 干重整 合成气 临界条件 

分 类 号：TE64[石油与天然气工程—油气加工工程] TQ01[化学工程]