摘要
以加拿大油砂沥青大于420℃的减压渣油(BVR)为原料,对比研究其在CO/H_2-H_2O和N_2体系中的热改质特性,通过系统分析BVR在H_2-H_2O、CO-H_2O、N_2-H_2O等不同氢源下的热改质特性以揭示CO/H_2-H_2O对渣油热改质的作用机制,最后探讨合成气压力、含水量以及温度对BVR临CO/H_2-H_2O改质生焦倾向的影响。结果表明,与临氮改质相比,相同反应条件下,合成气和水可使BVR热改质的生焦诱导期延长3.5-6.5 min;相同生焦率(约0.1%)时,合成气和水可显著提升BVR热改质降黏率,410℃时相对临氮改质的降黏率为29.1%,而420℃时可达54.6%。比较不同氢源下BVR热改质的生焦诱导期、改质油黏度和安定性、渣油转化率发现,H_2-H_2O、CO-H_2O、N_2-H_2O等均对BVR热改质表现出与CO/H_2-H_2O相同的促进效果,各氢源作用活性的大小顺序为H_2-H_2O>CO/H_2-H_2O>CO-H_2O>N_2-H_2O。由此可知,CO/H_2-H_2O对渣油热改质的促进作用可归因于氢气、CO水热变换新生氢和水热裂解的综合效应,且其中氢气的作用仍最显著。合成气压力、含水量和反应温度可通过影响不同氢源的贡献而调控BVR临CO/H_2-H_2O改质生焦倾向。低成本易获取的合成气可以提供BVR热降黏改质所需氢源,水能够通过CO水热变换反应供出新生活泼氢而协同合成气实现BVR高效改质。
The upgrading of the vacuum residue from Canadian oil sand bitumen was performed in a batch reactor with the syngas（CO/H2） and H2O.The effect of CO/H2-H2O for residue upgrading was verified.In the presence of CO/H2-H2O,the coke induction period is postponed by 3.5-6.5 min.When the coke yield is about 0.1%,the viscosity reduction efficiency can be raised by 29.1% at 410 ℃ and even 54.6% at 420 ℃.The upgrading experiments were also carried out in the presence of N2-H2O,CO-H2O,and H2-H2O,respectively.The results showthat the capability to inhibit the coke formation was in the order of H2-H2O CO/H2-H2O CO-H2O N2-H2O.The impetus of CO/H2-H2O to BVR upgrading could be attributed to the active hydrogen mainly from H2,nascent hydrogen by water-gas shift reaction as well as aqua-thermolysis.The thermal conditions such as the pressure of syngas,water content and reaction temperature could influence the coking propensity of BVR under CO/H2-H2O by affecting the three different attributions.These results indicate that the more accessible and low-cost syngas could provide the necessary hydrogen for BVR upgrading.Water presents a synergism with syngas for further promoting the BVR upgrading process.
出处
《燃料化学学报》
EI
CAS
CSCD
北大核心
2018年第1期45-53,共9页
Journal of Fuel Chemistry and Technology
基金
国家自然科学基金(21776313)
中国博士后科学基金资助项目(2016M602219)
山东省自然科学基金博士基金(ZR2017BB021)
青岛市博士后应用研究项目(2016224)
重质油国家重点实验室资助项目(SLKZZ-2017003
SLKZZ-2017011)
山东省重点研发发展计划(2017GGX70108)
中央高校基本科研业务费专项资金(科技专项
17CX05016)
中国石油科技创新基金(2017D-5007-0506)
中国石油天然气股份有限公司攻关项目(PRIKY16066)
山东省博士后创新项目专项资金(201702028)资助~~
关键词
油砂沥青
合成气
水热裂解
活泼氢
降黏改质
oil sand bitumen
syngas
aqua-thermolysis
active hydrogen
thermal upgrading
