Chemical composition and stability of renewable hydrocarbon products generated from a hydropyrolysis vapor upgrading process
Chemical composition and stability of renewable hydrocarbon products generated from a hydropyrolysis vapor upgrading process
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DOI：
10.1039/c7gc01075c
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发表时间：
2017-07
期刊：
影响因子：
9.8
通讯作者：
Liang Zhang;Kening Gong;Jinfeng Lai;Paul M. Alvey
中科院分区：
文献类型：
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作者：
Liang Zhang;Kening Gong;Jinfeng Lai;Paul M. Alvey
催化加氢热解是一种新兴的有前途的生产纤维素生物燃料的技术。非原位催化加氢热解提供了操作灵活性和催化剂性能的额外好处。利用双流化床反应器系统首次展示了两步非原位加氢热解蒸汽升级工艺的独特特点。产品分布（C5+有机碳产率为35.2-46.7%）和有机液体产品氧含量（2-17 wt%）可以通过调整工艺条件来定制。采用核磁共振谱和气相色谱-质谱联用技术对有机液体产品中的氧官能团和代表性物质进行了鉴定。结构信息进一步与产品稳定性相关，这是产品存储、运输和加工的关键属性。与热解油不同，该产品含有极少量的活性氧合物（如醛、酸、糖和其他多功能氧合物），这些氧合物可能会导致稳定性问题。结果表明，产品在40°C下可稳定保存2个月。进一步的热稳定性测试表明，所有产物在高温下都比热解油和大豆油更稳定。含氧量为6 wt%或更少的产品表现出高的热稳定性（在试验中表现得很像石油馏分加氢器进料），并且具有低的总酸值（<1 mg KOH / g），表明具有良好的炼油相容性。
Catalytic hydropyrolysis is an emerging and promising technology for producing cellulosic biofuels. Ex situ catalytic hydropyrolysis offers additional benefits of operational flexibility and catalyst performance. The unique feature of a two-step ex situ hydropyrolysis vapor upgrading process has been demonstrated for the first time using a double fluidized-bed reactor system. Product distribution (35.2–46.7% C5+ organic yield on a carbon basis) and oxygen content of the organic liquid product (2–17 wt%) can be tailored by adjusting process conditions. Nuclear magnetic resonance spectroscopy and gas chromatography–mass spectrometry were used to identify oxygen functionalities and representative species in the organic liquid products. The structural information was further related to product stability, a key property pertaining to product storage, transportation, and processing. Unlike pyrolysis oil, the products contained minimal amounts of reactive oxygenates (e.g., aldehydes, acids, sugars, and other multifunctional oxygenates) that could cause stability issues. As a result, the products were stable in storage at 40 °C for 2 months. Further thermal stability tests show that all of the products were more stable than pyrolysis oil and soybean oil at elevated temperatures. The products with 6 wt% oxygen or less showed high thermal stability (behaving much like a petroleum distillate hydrotreater feed in the tests) and possessed low total acid number (<1 mg KOH per g), indicating good petroleum refinery compatibility.