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An Alternate Biobased Route to Produce #-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation Md. Imteyaz Alam, Tuhin Suvra Khan, and M. Ali Haider ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b05014 • Publication Date (Web): 05 Dec 2018 Downloaded from http://pubs.acs.org on December 10, 2018
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An Alternate Biobased Route to Produce δ-Decalactone: Elucidating the Role of Solvent and Hydrogen Evolution in Catalytic Transfer Hydrogenation Md. Imteyaz Alam*, Tuhin S. Khan, M. Ali Haider* Renewable Energy and Chemicals Laboratory, Department of Chemical Engineering, Indian Institute of Technology Delhi, Hauz Khas, Delhi 110016, India Tel: +91-11-26591016, Fax: +91-11-2658-2037 E-mail:
[email protected];
[email protected] * Corresponding Authors
Supporting Information Place Holder ABSTRACT: A widely used food and flavor compound, δdecalactone (DDL), was produced from catalytic transfer hydrogenation of 6-amyl-α-pyrone (6PP), which is a biomassbased platform chemical derived through a fermentation process. The liquid phase reaction may serve as a platform to develop an integrated bio- and chemo-catalytic process for the green synthesis of DDL from lignocellulosic biomass. The catalytic transformation of 6PP to DDL was performed under mild thermal and pressure conditions over a Pd/C catalyst using formic acid as the in-situ hydrogen source. The reaction in presence of formic acid underwent complete conversion (~99 % at 433 K in 10 min) of 6PP via progressive hydrogenation of the unsaturation present in the 2-pyrone ring, leading to 79 % maximum yield of DDL. On reducing the temperature from 433 K to 383 K, DDL yield was observed to reduce from 79 % to 2 %. An ab-initio micro-kinetic model (MKM) was constructed to understand the decomposition of formic acid with temperature variations. The MKM provided a theoretical insight into the hydrogenation reaction. The reduction in DDL yield and 6PP conversion at the lower temperatures was observed to be in direct correlation to the reduction in HCOOH decomposition rates.
sugarcane bagasse) may be utilized to produce DDL in one step hydrogenation reaction on a heterogeneous catalyst. In order to show the proof-of-concept for this proposed route, reactions using 6PP were carried out in a batch reactor over a Pd/C heterogeneous catalyst to produce DDL at low temperatures ( 20 sec at 450 K (Figure 3). CO production TOF (Figure 3) was negligible (0.1 sec ) in the entire temperature range, which is in agreement with the results of Gazsi et al. The hydrogen production rate obtained from MKM simulations correlated well with the experimental trend on increasing temperature as shown in Figure 3. Flytzani-Stephanopoulos and co-workers have performed experiments and measured formic acid decomposition (to liberate CO and H ) over a Au/CeO catalyst. The authors noticed that formic acid started decomposing at 323 K, which continued till 448 K at which complete conversion of formic acid was observed . Indeed, the ab-initio MKM predicted a similar decomposition profile for the formic acid. -1
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Scheme 2: Mechanistic routes for formic acid decomposition reaction. Arrows in colour show O-H bond scission (blue), C-H bond scission (red) and C-O bond scission (green) reaction steps.
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A dual site model was used to construct the MKM in which number of sites for hydrogen adsorption were kept separate and equal in number to the terrace sites, where all other species were adsorbed. Entropy values of the gas phase species were obtained from the Shomate equation. Frozen adsorbate approximation was used for the adsorbates, assuming negligible entropy change for the reactions on the surface. All energy values in the gas phase were included with zero point energy corrections. Calculated values are given in Table SI-1 and SI-2. For DDL production, only dehydrogenation pathway giving hydrogen as one of the major product was important to understand the role of hydrogen limiting the hydrogenation rates. It was further assumed that as soon as formic acid started decomposing, hydrogen was readily available on the surface of the Pd catalyst due to the relatively fast kinetics of hydrogen adsorption on the Pd surface. 29,30
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Figure 2 shows HCOOH decomposition rates calculated from the MKM for a temperature range of 370 K to 450 K and HCOOH pressure range of 1 to10 bar. As evident from the Figure, there was a negligible effect of pressure variations on formic acid decomposition. In contrast, on changing the reaction temperature from 370 K to 450 K the TOFs were significantly increased from ~0.1 sec to ~19.25 sec at a constant pressure of 4.5 bar (approximately equivalent to the vapour pressure of cyclohexane. This suggested that within the temperature range of the hydrogenation experiments (383 K to 433 K, Table 2), formic acid decomposition rates were increased multi-fold. Figure 3, shows a direct correlation between the ab-initio MKM calculated hydrogen evolution rates and experimentally measured 6PP conversion with the changing temperature. -1
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Figure 3. A correlation showing 6PP conversion (measured in experiments) and hydrogen production (calculated using the ab-initio MKM) with varying reaction temperature. CONCLUSIONS AND OUTLOOK Catalytic transfer hydrogenation of 6PP performed using formic acid showed a direct correlation with the ratio of calculated SASA values in different solvent, the rates of which were observed to be decreasing with the increasing SASA values. The reaction performed in the solvent, cyclohexane, further showed an interesting correspondence with the formic acid decomposition rates on varying the reaction temperature, which demonstrated that hydrogen evolution was limiting the reaction on the catalyst surface for the 3
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studied range of reaction temperature. Ab-initio MKM was successful in predicting the correct trend of reaction rates for formic acid decomposition. This showed the ability and application of ab-initio micro-kinetic modelling technique in explaining catalytic experiments, which may help in reducing the number of experiments required for studying such reactions. Overall, DDL has numerous possibilities as a potential platform chemical for exploring its reactivity to produce drugs and chemicals. George Kraus and co-workers have recently demonstrated the potential for converting triacetic acid (TAL) into 2-pyridones, to be used as pharmaceutical building blocks. TAL is analogous in structure to 6PP. Biological synthesis of 6PP from solid state fermentation of waste biomass is reported to yield up to 7g/l . Further experiments, utilizing genetically engineered microorganisms, are expected to increase the yield of 6PP in the fermentation reaction. Hector and co-workers have recently demonstrated the use of metabolic engineering techniques in increasing the yield of TAL . An earlier report by our group had established the role of 6PP as a biomass-derived platform chemical to produce a range of C -C hydrocarbon fuel additives and C ketones . Thus, combined with the hydrogenation reaction of 6PP, as shown in this work and prospects of microbial synthesis of 6PP from waste biomass, there exists a direct route for high volume synthesis of DDL from a biorenewable source. This may potentially establish DDL as a bio-based platform chemical for the production of a diverse variety of high value chemicals.
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Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Experimental and computational methods, characterization data, microkinetic modeling methods Corresponding Author
[email protected] ;
[email protected] ACKNOWLEDGMENT Mr. Alok Yadav and Mr. Ashin Amanulla are acknowledged for their help during NMR analysis at CRF-IIT Delhi. We thank Dr. Asif Ali, JAIST, Japan for his suggestions in a discussion on spectroscopy experiments. MIA and TSK would like to thank BIRACBIG, Government of India, for the financial support. Authors would like to thank IITD-HPC facility for providing computational resources.
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A biorenewable route to produce a food additive compound, δ-decalactone via catalytic transfer hydrogenation of 6-amyl-α-pyrone on the Pd-catalyst surface.
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Pd catalyzed hydrogenation of 6-amyl-α-pyrone to δ-decalactone 200x124mm (300 x 300 DPI)
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