Sumanth Ranganathan

Pinus radiata is the dominant tree species in exotic plantation forestry of New Zealand producing timber for construction and pulp and paper. Additionally, the processing yields large amounts of bark as a byproduct that is either left at the harvest site or used for landscaping. P. radiata bark is rich in biochemical extractives containing polyphenols and waxes on sequential extraction with hydrophilic and lipophilic solvents, respectively. Previous studies have exclusively focussed on the effect of parameters such as solvent type, bark to solvent ratio, and extraction time on the yield of extractives. However, two parameters were always maintained constant: solvent order (lipophilic to hydrophobic) and particle size. This work investigated the the combined impact of these two parameters on total yield and product quality by using two solvents- water and hexane. Total extractives were highest when water was used first (11.74% and 9.45%) compared to hexane (10.53% and 6.53%). The individual yields of hexane extractives were in the range of 2.25–2.9% while those of water were 4.30–9.24%. Chemical analyses of the extracts and residues showed no qualitative differences, indicating the order in which bark is extracted does not alter the extract composition. Moreover, the results have successfully established that extracting bark with water first followed by hexane will increase the total yield of extractives and increasing particle size decreases the total yield of the sequential extraction. Graphical

Tree bark is an abundantly available resource that is a waste product of the timber processing industry. It is rich in chemicals that require sequential treatment with solvents of differing polarities to extract said compounds. The success of such an approach, i.e. biorefinery, depends on the individual yields of the extraction processes influenced by multiple parameters like solvent type, temperature, time etc. However, research into determining the optimal order of using these solvents is scarce, which is the core focus of this work. Pinus radiata bark was sequentially extracted using two solvents- water and hexane, to study the combined impact of the extraction order and particle size on total yield and product quality. Total extractives were highest when water was used first (11.74% and 9.45%) compared to hexane (10.53% and 6.53%). The individual yields of hexane extractives were in the range of 2.4% – 2.9% while those of water were 4.30% – 9.24%. Chemical analyses of the extracts and residues showed no qualitative differences, indicating the order in which bark is extracted does not alter the extract composition. Moreover, the results have successfully established that extracting bark with water first followed by hexane will increase the total yield of extractives that increasing particle size decreases the total yield of the sequential extraction.

Hydrogen peroxide is an important chemical of increasing demand in today’s world. Currently, the anthraquinone autoxidation process dominates the industrial production of hydrogen peroxide. Herein, hydrogen and oxygen are reacted indirectly in the presence of quinones to yield hydrogen peroxide. Owing to the complexity and multi-step nature of the process, it is advantageous to replace the process with an easier and straightforward one. The direct synthesis of hydrogen peroxide from its constituent reagents is an effective and clean route to achieve this goal. Factors such as water formation due to thermodynamics, explosion risk, and the stability of the hydrogen peroxide produced hinder the applicability of this process at an industrial level. Currently, the catalysis for the direct synthesis reaction is palladium based and the research into finding an effective and active catalyst has been ongoing for more than a century now. Palladium in its pure form, or alloyed with certain metals, are some of the new generation of catalysts that are extensively researched. Additionally, to prevent the decomposition of hydrogen peroxide to water, the process is stabilized by adding certain promoters such as mineral acids and halides. A major part of today’s research in this field focusses on the reactor and the mode of operation required for synthesizing hydrogen peroxide. The emergence of microreactor technology has helped in setting up this synthesis in a continuous mode, which could possibly replace the anthraquinone process in the near future. This review will focus on the recent findings of the scientific community in terms of reaction engineering, catalyst and reactor design in the direct synthesis of hydrogen peroxide.

Hydrogen peroxide is an important chemical of increasing demand in today’s world. Currently, the anthraquinone autoxidation process dominates the industrial production of hydrogen peroxide. Herein, hydrogen and oxygen are reacted indirectly in the presence of quinones to yield hydrogen peroxide. Owing to the complexity and multi-step nature of the process, it is advantageous to replace the process with an easier and straightforward one. The direct synthesis of hydrogen peroxide from its constituent reagents is an effective and clean route to achieve this goal. Factors such as water formation due to thermodynamics, explosion risk, and the stability of the hydrogen peroxide produced hinder the applicability of this process at an industrial level. Currently, the catalysis for the direct synthesis reaction is palladium based and the research into finding an effective and active catalyst has been ongoing for more than a century now. Palladium in its pure form, or alloyed with certain metals are some of the new generation of catalysts that are extensively researched. Additionally, to prevent the decomposition of hydrogen peroxide to water, the process is stabilised by adding certain promoters such as mineral acids and halides. A major part of today’s research in this field focusses on the reactor and the mode of operation required for synthesising hydrogen peroxide. The emergence of microreactor technology has helped in setting up this synthesis in a continuous mode, which could possibly replace the anthraquinone process in the near future. This review will focus on the recent findings of the scientific community in terms of reaction engineering, catalyst and reactor design in the direct synthesis of hydrogen peroxide.

Lipase has been used for epoxidizing olefins such as monoterpenes for more than two decades. This epoxidation is accomplished by adding hydrogen peroxide (H₂O₂) to a carboxylic acid in the presence of a lipase such as Candida antartica lipase B (CALB) to produce percarboxylic acid, which then epoxidizes monoterpenes according to the Prilezhaev mechanism. One drawback of this process is the need for continuous addition of hydrogen peroxide to maintain maximum productivity. To overcome this hurdle, the industrial anthraquinone autooxidation process for hydrogen peroxide production was scaled down and coupled with lipase-mediated epoxidation in a semi-continuous manner. Palladium on alumina pellets (5% loading) was used as the catalyst for obtaining high yields of high-concentration hydrogen peroxide (50% weight by volume), followed by epoxidation of 3-carene, (+) limonene, and α-pinene. A total reaction time of 5 h was used for hydrogen peroxide production and 2–3 h for the epoxidation reactions. Pure 3-carene epoxide and α-pinene epoxide were obtained in isolated yields of 88.8 ± 2.8% and 83.8 ± 2.6%, respectively. Limonene epoxide was obtained as a mixture of mono- and di-epoxides in a ratio of 70% and 30%, respectively, with an isolated yield of 71.5 ± 3.1%.

Chemical syntheses in contemporary process industries today are predominantly conducted using organic solvents, which are potentially hazardous to humans and the environment alike. Green chemistry was developed as a means to overcome this hazard and it also holds enormous potential for designing clean, safe and sustainable processes. The present work incorporates the concepts of green chemistry in its design of a lipase-mediated epoxidation process for monoterpenes; the process uses alternative reaction media, namely deep eutectic solvents (DESs), which have not been reported for such an application before. Choline chloride (ChCl), in combination with a variety of hydrogen bond donors (HBD) at certain molar ratios, was screened and tested for this purpose. The process was optimized through the design of experiments (DoE) using the Taguchi method for four controllable parameters (temperature, enzyme amount, peroxide amount and type of substrate) and one uncontrollable parameter (DES reaction media) in a crossed-array design. Two distinct DESs, namely glycerol : choline chloride (GlCh) and sorbitol : choline chloride (SoCh), were found to be the best systems and they resulted in a complete conversion of the substrates within 8 h. Impurities (esters) were found to form in both the DESs, which was a concern; as such, we developed a novel minimal DES system that incorporated a co-substrate into the DES so that this issue could be overcome. The minimal DES consisted of urea·H₂O₂ (U·H₂O₂) and ChCl and exhibited better results than both the GlCh and SoCh systems; complete conversions were achieved within 2 h for 3-carene and within 3 h for both limonene and α-pinene. Product isolation with a simple water/ethyl acetate based procedure gave isolated yields of 87.2 ± 2.4%, 77.0 ± 5.0% and 84.6 ± 3.7% for 3-carene, limonene and α-pinene respectively.