Process Design and Evaluation for Chemicals Based on Renewable Resources

Abstract

One of the key steps in process design is choosing between alternative technologies, especially for processes producing bulk and commodity chemicals. Recently, driven by the increasing oil prices and diminishing reserves, the production of bulk and commodity chemicals from renewable feedstocks has gained considerable interest. Renewable feedstocks usually cannot be converted into fuels and chemicals with existing process facilities due to the molecular functionality and variety of the most common renewable feedstock (biomass). Therefore new types of catalytic methods as well as new types of processes for converting renewable feedstocks to bulk and commodity chemicals are required. In the future, it seems increasingly likely that a combination of biocatalysts (in the form of enzymes) as well as chemical catalysts will be needed in the production of bulk chemicals from renewable feedstocks. In addition, another characteristic of chemicals based on renewable feedstocks is that many alternative technologies and possible routes exist, resulting in many possible process flowsheets. The challenge for process engineers is then to choose between possible process routes and alternative technologies as well as to match different catalyst conditions. These kinds of problems are crucial, especially at the early stages of process development, when information is limited. This thesis describes a methodological framework for dealing with the challenges and giving direction to research in the process development of chemicals based on renewable feedstocks. As an example, this thesis especially focuses on applying the methodology in process design and evaluation of the synthesis of 5-hydroxymethylfurfural (HMF) from the renewable feedstock glucose/fructose. The selected example is part of the chemoenzymatic process design of the synthesis 2,5-furandicarboxylic acid (FDA) from glucose. By using the selected case study, the complexity and challenges for the process engineer to choose between different alternative routes and technologies as well as to combine two different kinds of catalysis (enzymatic catalysis and chemical catalysis) were illustrated. Different process routes for the synthesis of HMF from fructose in the literature have been analyzed and evaluated. Using an aqueous route for HMF production is not economically feasible due to the low reaction yield. Using an anhydrous solvent for HMF synthesis is associated with high energy consumption and difficulties with solvent recycle in a large-scale production. The synthesis of HMF from fructose using a biphasic route is found to be promising, cost effective and give a better chance to be integrated with chemo-enzymatic cascades for producing FDA from glucose. A process flowsheet using chemo-enzymatic cascades for HMF production from glucose has been proposed and evaluated. The process flowsheet is characterized by using glucose isomerase (EC 5.3.1.5) to convert glucose into fructose with a biphasic reaction for dehydration of fructose into HMF with recycle of the aqueous phase back to the enzymatic reaction. Costing analysis indicates the HMF production cost by the designed process is very sensitive to the dehydration reaction yield, the amount of solvent used in the whole process and the glucose price. In addition, increasing scale is also help to decrease the HMF production cost. Using an ionic liquid (IL) route for HMF production has been evaluated with the dehydration reaction in [BMIm]Cl with different options starting from fructose and glucose with different initial concentrations. The HMF production cost is highly affected by the recycle of IL and catalyst. Processes with a high feed concentration show better economic potential than processes with a low feed concentration. IL processes starting from fructose are more costly than IL processes starting from glucose. A high concentration feed of glucose showed the best economic potential. To sum up, the dehydration reaction yield is found to be the key important factor to achieve a feasible production cost of HMF. The use of the organic solvent can not be avoided and plays a very important role in determining the process economics. Recycling (unconverted sugar, reaction medium and solvent) become essential issues for HMF processes to reach a feasible production cost. Future directions and suggestions for the synthesis of HMF from sugar in a large-scale have been proposed. The developed methodology is helpful in evaluation and giving research directions. The methodology can be applied to other chemical process design and evaluation problems and in particular those for the next generation of production processes.