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Molecules 2020, 25, 5367 10 of 13 of hold-time at maximum pressure, time for pressure release and phase-change, or carbon dioxide initial temperature. The models derived and physical chemistry results (Figure 1) were in accord, the models providing a means of fine-tuning experimental parameters to assist with the design of plant and processes for dewatering a range of green wood input types. Ultimately, the experimental results have shown that it is the features of the anatomy of cell types and their function and cell wall ultrastructure of the bulk wood material of various softwoods and hardwoods that dictate the effectiveness and efficiency of dewatering using the carbon dioxide supercritical fluid-to-gas phase change process. Those features of green radiata pine sapwood make this the ideal material to fit with the process models. 3. Commercialisation of Green Wood Dewatering Using Supercritical Carbon Dioxide As a process for converting green sawn wood into utility industrial timber for numerous applications, dewatering using carbon dioxide cycled between supercritical fluid and gas phase has some output material quality, processing time, and efflux/environmental advantages, as described above, over conventional wood kiln drying carried out at elevated temperatures. Wood kiln-drying enterprises and kiln standardised operating procedures are well-established, and considerable investment over a long term has already been made into wood drying capability by sawmilling and wood product manufacturing businesses globally. To invest in commercial green wood dewatering enterprise creation would require a clear advantage to be gained over the existing conventional kiln-drying based business models. The engineering aspects of the plant and machinery that would be required for a wood dewatering/drying enterprise using supercritical carbon dioxide as the working fluid for green wood dewatering have already been addressed with the construction and successful operation of an impressive enterprise located in Hampen, Denmark [36,37]. There, kiln-dried spruce (Picea abies (L.) H. Karst) timber is impregnated with triazole biocides dissolved in supercritical carbon dioxide [38,39]. Spruce timber, which is naturally non bio-durable, after having been conventionally kiln-dried becomes “refractory”, which is a term used to describe wood material that is difficult to treat with water-based biocide formulations and re-dry conventionally: a problem readily solved with the supercritical carbon dioxide biocide delivery process at the Hampen factory. A potential advantage of applying the green wood dewatering process described above to produce wood material with moisture content at the fibre saturation point and with no resulting distortion, shrinkage, or discolouration is to use the dry wood output from this process as either a finished product in itself (as in the example of eucalypt wood), or as an intermediate towards wood modification or biocide treatment where, as for the triazoles, the modifying agent or biocide is soluble in supercritical carbon dioxide. This feasibility has already been investigated in laboratory experiments, albeit using ethanol-modified supercritical carbon dioxide for the wood-drying step [40]. The ability to carry out two key steps in the manufacture of dry, durable wood materials and products at a single site, in one factory where the equipment and machinery could be used for both drying and molecular-modifying steps, would potentially eliminate the multiple handling of wood at intermediate conventional processing steps. An economics analysis comparing conventional wood kiln drying with supercritical carbon dioxide dewatering could bring clarity to the question of commercial viability of the rival process. Apart from the triazole biocides, there are other molecules based on boric acid that would provide protection of wood from decay by fungi and bacteria and also provide protection from attack by wood-boring insects using a single chemical. Trimethyl borate, the simplest boric acid ester, has been used experimentally to deliver boric acid biocide into kiln-dried wood as a hot vapour; this process having been studied using 11B NMR and MRI [41]. Trimethyl borate and some boratranes (tricyclic borate esters) [42] are also soluble in supercritical carbon dioxide, making these potential compounds for the modification of dewatered wood using supercritical carbon dioxide as the biocide delivery solvent for the manufacture of biologically durable, quality wood products.PDF Image | Dewatering Green Sapwood Using Carbon Dioxide
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