Gas phase activation of monosaccharides and 5-hydroxymethylfurfural to 2,5 diformylfuran a PEF monomer

单糖和 5-羟甲基糠醛气相活化生成 2,5 二甲酰呋喃 (PEF 单体)

• 批准号: RGPIN-2021-03276
• 负责人: Patience, Gregory
• 金额: $ 4.66万
• 依托单位: École Polytechnique de Montréal
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2021
• 资助国家: 加拿大
• 起止时间: 2021-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=742470
• 关键词: Gas; phase; activation; monosaccharides; hydroxymethylfurfural

Society endorses the principles of sustainable development, and, as such, requires industry to reduce, recycle, and reuse products they manufacture. Substituting petroleum with renewable feedstocks is an additional strategy to decrease their environmental footprint. Canada's vast forests constitute one of the largest and under-exploited supplies of biomass in the world. Rather than producing ethanol from this lignocellulose, specialty chemicals, monomers, and pharmaceuticals represent a 10 X value-add. The long term vision of this program is to synthesize platform chemicals from biomass in gas-solids catalytic reactors that satisfy the UN Sustainability Goals. The challenges are to identify and synthesize selective catalysts and establish the fundamental hydrodynamics to atomize non-volatile organic compounds into reactors. Here the objective is to develop a process to manufacture polyethylene furanoate (PEF), a new biopolymer derived from hexoses, to  replace polyethylene terephthalate (PET/polyester) that has a market value of 25 billion$. PEF's permeability is 8 times lower than PET and its mechanical strength is 5 times higher so plastic bottle is potentially 5 times lighter, which meets society's demand to reduce. It is also 100% recyclable. Despite these fantastic properties, PEF commercialization is hampered by cost and impurities that give it a yellow hue. Consumers are unwilling to pay extra and refuse to drink from dirty looking plastic bottles. Humins - organic macromolecules - form when hexoses react in the liquid phase and this causes the colour. Gas phase processes eliminate humins and capital costs are lower compared to the liquid phase. This program contributes to a fundamental understanding of fluidized bed injection and catalysis of non-volatile compounds. Each of the three themes combine computational methods with experimental measurements: 1. Develop a selective catalyst to convert hydroxymethyl furfural to diformyl furan a PEF monomer. Together with identifying active metals and metal oxides, the catalyst must be robust to withstand the mechanical forces inherent in fluidized beds. The ultimate goal will be to design a catalyst to oxydehydrate fructose to DFF in one step. A PhD will apply Density Functional Theory to guide the screening process and develop a kinetic model. 2. Couple computational fluid dynamics with fluidized bed hydrodynamic measurements to characterize the heat and mass transfer at the sparger tip. Spray atomization through the sparger produces micron sized droplets, but the sparger plugs and agglomerates form if they are too big. The second PhD student will compare and develop scale-up criteria for non-volatile organic compounds 3. Simulate the trajectory of every particle in the reactor (millions) by computational fluid dynamics-discrete element method and compare the calculated gas-solids contacting with the gas residence time distribution. Here, we derive criteria to scale-up from 1 g to 100 tonne.

社会认可可持续发展的原则，因此，要求工业减少、回收和再利用他们制造的产品。用可再生原料取代石油是减少其环境足迹的另一项战略。加拿大广阔的森林构成了世界上最大且未得到充分开发的生物质供应之一。与从这种木质纤维素生产乙醇不同，特种化学品、单体和药品的附加值是10倍。该计划的长期愿景是从气固催化反应器中的生物质合成平台化学品，以满足联合国可持续发展目标。面临的挑战是识别和合成选择性催化剂，并建立将非挥发性有机化合物雾化到反应器中的基本流体力学。这里的目标是开发一种工艺来生产聚乙烯呋喃甲酸乙二醇酯(PEF)，这是一种从己糖中提取的新型生物聚合物，以取代市场价值250亿美元的聚对苯二甲酸乙二醇酯(PET/聚酯)。PEF的渗透率比PET低8倍，机械强度高5倍，所以塑料瓶可能更轻5倍，这满足了社会对减少塑料瓶子的需求。它也是100%可回收的。尽管有这些奇妙的特性，但PEF的商业化受到了成本和杂质的阻碍，这些都给它带来了黄色。消费者不愿支付额外的费用，拒绝喝看起来肮脏的塑料瓶。胡敏素-有机大分子-当己糖在液体中反应时形成，这就产生了颜色。气相过程消除胡敏素，与液相相比，资本成本更低。本课程有助于对非挥发性化合物的流态化喷射和催化有一个基本的了解。这三个主题中的每一个都将计算方法与实验测量相结合：1.开发一种选择性催化剂，将羟甲基呋喃转化为二甲酰基呋喃，一种PEF单体。在识别活性金属和金属氧化物的同时，催化剂必须坚固耐用，以承受流态化床固有的机械力。最终目标将是设计一种催化剂，一步将果糖氧化脱水生成DFF。博士将应用密度泛函理论来指导筛选过程，并开发动力学模型。2.将计算流体力学与流态化流体力学测量相结合，对喷嘴尖端的传热传质过程进行了表征。通过Sparger的喷雾雾化会产生微米大小的液滴，但如果太大，Sparger塞子和团聚体就会形成。第二个博士生将比较和发展非挥发性有机化合物的放大标准3.用计算流体力学-离散元方法模拟反应器中每个颗粒(数百万)的轨迹，并将计算的气固两相接触与气体停留时间分布进行比较。在这里，我们得出了从1克扩大到100吨的标准。