Bio-based Platform Chemical Research Articles

Process design and techno-economic evaluation for the production of platform chemical for hydrocarbon fuels from lignocellulosic biomass using biomass-derived γ-valerolactone

Abstract We report a strategy for production of 5-nonanone which is a bio-based platform chemical that can be produced in large quantity from a variety of lignocellulosic biomass sources. In this strategy, the cellulose and hemicellulose fractions of lignocellulosic biomass are catalytically converted to γ -valerolactone (GVL) using the biomass derived GVL as a solvent. To generate the integrated strategy, we develop separation subsystems to achieve high purity of product. Importantly, GVL can be upgraded to 5-nonanone with high yield in a single reactor using a dual catalyst bed of Pd/Nb2O5 plus ceria-zirconia. We design a heat exchanger network to satisfy the total energy requirements of the integrated process via combusting lignin fraction of biomass. Economic feasibility of the process is investigated using discounted cash flow analysis.

Synthesis of bio-based poly(oligoethylene glycols-co-isosorbide carbonate)s with high molecular weight and enhanced mechanical properties via ionic liquid catalyst

As a kind of bio-based platform chemicals derived from renewable resource glucose, isosorbide (ISB) is considered the perfect candidate for the synthesis of polycarbonate (PC) to replace chronic toxic bisphenol A (BPA) due to its attractive rigidity, non-toxicity and chirality. However, synthesis of poly(isosorbide carbonate) (PIC) with high molecular weight and excellent mechanical properties is one of tremendous challenges due to low internal hydroxyl group activity and poor structural flexibility of ISB. Herein, we developed a new series of ISB-based copolycarbonates with intriguing properties through incorporating flexibility moiety oligoethylene glycols (OEG) into PIC. By employing bifunctional 1-butyl-3-methylimidazolium lactate IL catalyst, copolycarbonates with high weight-average molecular weight ranging from 94,700 to 146,200 were synthesized via efficient dual activation effect on the carbonyl group in diphenyl carbonate and the hydroxyl group in ISB. Among of them, poly(diethylene glycol-co-isosorbide carbonate) (PDIC) possessed excellent molecular flexibility and showed the best mechanical performance with average value of the elongation at break as high as 160%, which was eight times more than PIC prepared (18%) and much higher than the commercial BPA-based PC (around 100%). Simultaneously, PDIC showed a 1.25-fold higher tensile strength (80 MPa) than that of BPA-based PC with 63 MPa. This implied that bio-derived copolycarbonates developed in this research effectively enhanced the ductility and processability of PIC and possessed enormous prospect for the industrial application.

Purification and immobilization of engineered glucose dehydrogenase: a new approach to producing gluconic acid from breadwaste

BackgroundPlatform chemicals are essential to industrial processes. Used as starting materials for the manufacture of diverse products, their cheap availability and efficient sourcing are an industrial requirement. Increasing concerns about the depletion of natural resources and growing environmental consciousness have led to a focus on the economics and ecological viability of bio-based platform chemical production. Contemporary approaches include the use of immobilized enzymes that can be harnessed to produce high-value chemicals from waste.ResultsIn this study, an engineered glucose dehydrogenase (GDH) was optimized for gluconic acid (GA) production. Sulfolobus solfataricus GDH was expressed in Escherichia coli. The Km and Vmax values for recombinant GDH were calculated as 0.87 mM and 5.91 U/mg, respectively. Recombinant GDH was immobilized on a hierarchically porous silica support (MM-SBA-15) and its activity was compared with GDH immobilized on three commercially available supports. MM-SBA-15 showed significantly higher immobilization efficiency (> 98%) than the commercial supports. After 5 cycles, GDH activity was at least 14% greater than the remaining activity on commercial supports. Glucose in bread waste hydrolysate was converted to GA by free-state and immobilized GDH. After the 10th reuse cycle on MM-SBA-15, a 22% conversion yield was observed, generating 25 gGA/gGDH. The highest GA production efficiency was 47 gGA/gGDH using free-state GDH.ConclusionsThis study demonstrates the feasibility of enzymatically converting BWH to GA: immobilizing GDH on MM-SBA-15 renders the enzyme more stable and permits its multiple reuse.

Impact of intermolecular interactions on the nanofiltration of pulping liquor

Sulfite spent liquor, a side stream of the pulping process, is an abundantly available source for bio-based platform chemicals. Lignosulfonates can be separated from the other organic components and pulping chemicals by ultrafiltration. The ultrafiltration permeate can either be used directly in a fermentation process or may be further treated by nanofiltration to reduce the fermentation inhibitor concentration. FilmTec NF270 was used to study different intermolecular interactions in the ultrafiltration permeate at various pH values and lignosulfonate concentrations. Intermolecular interactions between lignosulfonates and inhibitor components decrease membrane selectivity. Several furan derivatives interact via hydrogen bonds with the hydroxyl groups of the lignosulfonates. The oxygen of the aldehyde group or the ring oxygen atom with two lone pairs were found to form hydrogen bonds and thereby affect the retention. By comparison, the hydrogen bonds of the alcohol group did not noticeably affect the retention. Magnesium as counter ion of the lignosulfonate interacts with acetate and formate ions, thereby increasing their retention. Substitution of magnesium with sodium prevents a lignosulfonate ion interaction. The investigated interactions of lignosulfonates in sulfite spent liquor may help to improve the applicability of nanofiltration processes for the detoxification of lignocellulose-derived fermentation feed. Furthermore, insights can be used for other separation methods as well because they are not specified for membrane separation processes.

Study of glucose isomerisation to fructose over three heterogeneous carbon-based aluminium-impregnated catalysts

Driven by the worldwide demand for sustainable resources and renewable energy, the synthesis of bio-based platform chemicals has attracted broad interest. The isomerisation of glucose to fructose acts as a critical intermediate step among many chemical synthesis routes. In this study, biochar (BC), graphitic oxide (GIO), and graphene oxide (GO) were used as carbon supports to synthesize Al-impregnated heterogeneous catalysts, which were then used for glucose isomerisation under microwave heating in the water at 140 °C. The kinetics model with parameters was used to reveal the interplay of the active sites and compare the activity of the three carbon-based catalysis systems. Catalyst characterisation results showed effective aluminium (Al) impregnation onto the three types of catalysts, and it was found that GIO-Al200 and GO-Al200 showed comparable catalytic activity (fructose yield of 34.3–35.0%) for glucose isomerisation. At the same time, BC-Al200 exhibited slightly lower catalytic activity (fructose yield of 29.4%). The conversion kinetics suggested similar catalytic mechanisms on the three catalysts while BC-Al200 manifested slower kinetics, possibly implying higher activation energy. The fructose selectivity decreased with increasing time due to the formation of side products, yet BC-Al200 resulted in less carbon loss than GIO-Al200 and GO-Al200, probably attributed to its lower catalytic activity and higher pH buffering capacity. A green synthesis route of this study promotes biomass valorisation and makes engineered biochar a promising carbon-based catalyst for sustainable biorefinery.

Engineering central pathways for industrial-level (3R)-acetoin biosynthesis in Corynebacterium glutamicum

BackgroundAcetoin, especially the optically pure (3S)- or (3R)-enantiomer, is a high-value-added bio-based platform chemical and important potential pharmaceutical intermediate. Over the past decades, intense efforts have been devoted to the production of acetoin through green biotechniques. However, efficient and economical methods for the production of optically pure acetoin enantiomers are rarely reported. Previously, we systematically engineered the GRAS microorganism Corynebacterium glutamicum to efficiently produce (3R)-acetoin from glucose. Nevertheless, its yield and average productivity were still unsatisfactory for industrial bioprocesses.ResultsIn this study, cellular carbon fluxes in the acetoin producer CGR6 were further redirected toward acetoin synthesis using several metabolic engineering strategies, including blocking anaplerotic pathways, attenuating key genes of the TCA cycle and integrating additional copies of the alsSD operon into the genome. Among them, the combination of attenuation of citrate synthase and inactivation of phosphoenolpyruvate carboxylase showed a significant synergistic effect on acetoin production. Finally, the optimal engineered strain CGS11 produced a titer of 102.45 g/L acetoin with a yield of 0.419 g/g glucose at a rate of 1.86 g/L/h in a 5 L fermenter. The optical purity of the resulting (3R)-acetoin surpassed 95%.ConclusionTo the best of our knowledge, this is the highest titer of highly enantiomerically enriched (3R)-acetoin, together with a competitive product yield and productivity, achieved in a simple, green processes without expensive additives or substrates. This process therefore opens the possibility to achieve easy, efficient, economical and environmentally-friendly production of (3R)-acetoin via microbial fermentation in the near future.

Oxidation of 5-[(Formyloxy)methyl]furfural to Maleic Anhydride with Atmospheric Oxygen Using α-MnO2/Cu(NO3)2 as Catalysts

A novel approach to produce renewable maleic anhydride (MA) from bio-based platform chemical 5-[(formyloxy)methyl]furfural (FMF) was developed with air or pure oxygen at atmospheric pressure using ...

Acid Hydrolysis of Lignocellulosic Biomass: Sugars and Furfurals Formation

Hydrolysis of lignocellulosic biomass is a crucial step for the production of sugars and biobased platform chemicals. Pretreatment experiments in a semi-continuous plant with diluted sulphuric acid as catalyst were carried out to measure the time-dependent formation of sugars (glucose, xylose, mannose), furfurals, and organic acids (acetic, formic, and levulinic acid) at different hydrolysis temperatures (180, 200, 220 °C) of one representative of each basic type of lignocellulose: hardwood, softwood, and grass. The addition of the acid catalyst is followed by a sharp increase in the sugar concentration. Xylose and mannose were mainly formed in the initial stages of the process, while glucose was released slowly. Increasing the reaction temperature had a positive effect on the formation of furfurals and organic acids, especially on hydroxymehtylfurfural (HMF) and levulinic acid, regardless of biomass type. In addition, large amounts of formic acid were released during the hydrolysis of miscanthus grass. Structural changes in the solid residue show a complete hydrolysis of hemicellulose at 180 °C and of cellulose at 200 °C after around 120 min reaction time. The results obtained in this study can be used for the optimisation of the hydrolysis conditions and reactor design to maximise the yields of desired products, which might be sugars or furfurals.

Achieving effective fructose-to-5-hydroxymethylfurfural conversion via facile synthesis of large surface phosphate-functionalized porous organic polymers

Efficient conversion of fructose to 5-hydroxymethylfurfural (HMF) is a key step for producing fuels and value-added chemicals from carbohydrates. Here, we report for the first time the applicability of phosphate-functionalized porous organic polymers (POPs) as a catalyst for fructose conversion. Two catalysts, B-POP and P-POP, were synthesized via a simple one-pot reaction and B-POP showed high surface area (1193 m2 g−1) and high mesoporosity (54.7 %) with 1.7 mmol g−1 of phosphate groups available as surface acid sites. The catalytic activity of the phosphate functionalized POPs was investigated using different solvents, and B-POP yielded 100 % fructose conversion with 85 % HMF selectivity within 30 min (equivalent to a turnover frequency of 32.2 h−1, the highest activity among other previously reported acid-based heterogeneous catalysts) when DMSO/1,4-dioxane dual solvent medium was used at 130 °C. These results suggested that phosphate group-functionalized POPs can be promising heterogeneous catalysts for producing biobased platform chemicals from renewable resources.

Are Sugarcane Molasses Competitive Substrates for Bio-based Platform Chemicals?

ADVERTISEMENT RETURN TO ISSUEViewpointNEXTAre Sugarcane Molasses Competitive Substrates for Bio-based Platform Chemicals?Antonio Irineudo Magalhães Jr.Antonio Irineudo Magalhães, Jr.Department of Bioprocess Engineering and Biotechnology, Federal University of Paraná (UFPR), Post Office Box 19011, Curitiba, Paraná 81531-990, BrazilMore by Antonio Irineudo Magalhães, Jr., Júlio Cesar de Carvalho*Júlio Cesar de CarvalhoDepartment of Bioprocess Engineering and Biotechnology, Federal University of Paraná (UFPR), Post Office Box 19011, Curitiba, Paraná 81531-990, Brazil*E-mail: [email protected]More by Júlio Cesar de Carvalhohttp://orcid.org/0000-0001-7558-7748, Dão Pedro de Carvalho NetoDão Pedro de Carvalho NetoDepartment of Bioprocess Engineering and Biotechnology, Federal University of Paraná (UFPR), Post Office Box 19011, Curitiba, Paraná 81531-990, BrazilMore by Dão Pedro de Carvalho Neto, and Carlos Ricardo SoccolCarlos Ricardo SoccolDepartment of Bioprocess Engineering and Biotechnology, Federal University of Paraná (UFPR), Post Office Box 19011, Curitiba, Paraná 81531-990, BrazilMore by Carlos Ricardo SoccolCite this: J. Agric. Food Chem. 2020, 68, 14, 4073–4074Publication Date (Web):March 25, 2020Publication History Received5 March 2020Published online25 March 2020Published inissue 8 April 2020https://doi.org/10.1021/acs.jafc.0c01519Copyright © 2020 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views208Altmetric-Citations4LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (1 MB) Get e-AlertsSUBJECTS:Byproducts,Carbohydrates,Ethanol,Fermentation,Separation science Get e-Alerts

Efficient Preparation of Bio-based n-Butane Directly from Levulinic Acid over Pt/C

As a bio-based platform chemical, it is desirable to convert levulinic acid (LA) to varieties of value-added biochemicals. n-Butane, mainly from nonrenewable fossil resources, is a basic chemical to produce some important chemicals, such as butadiene and ethylene. In this paper, 95.5% yield of n-butane was obtained from LA in one-step over base-treated Pt/C at around 300 °C in 4 h. The reaction pathway was confirmed to be the hydrodeoxygenation of LA to valeric acid (VA) and then the VA decarboxylation to n-butane by kinetic studies. Base-treated Pt/C had better reactivity due to its improved decarboxylation activity. Detailed characterization of the catalyst revealed that the Pt particle size is the key reason for the activity improvement, and further studies showed that Pt nanoparticles with a size of 2–4 nm showed the highest decarboxylation activity. This is the first report on the direct conversion of LA to n-butane.

Kinetic modelling of acid-catalyzed liquid-phase dehydration of bio-based 2, 3-butanediol considering a newly identified by-product and an updated reaction network

Study on the acid-catalyzed dehydration of bio-based platform chemical 2, 3-butanediol (BDO) to produce methyl ethyl ketone (MEK) has a relatively long history. However, the reaction networks of the system have not been completely elucidated yet. In this work, a new by-product formed during acid-catalyzed liquid-phase dehydration of BDO was detected, which was wrongly identified by the GC–MS NIST database or previous research works. The new compound was finally identified as 2-isopropyl-4, 5-dimethyl-1, 3-dioxolane (IDMD), formed by acetalization between 2-methyl propanal (MPA) and BDO under the catalysis of Bronsted acids. MPA was an intermediate product of acid-catalyzed dehydration of BDO, but its life was short primarily due to the formation of IDMD. Prepared IDMD with high purity was further characterized by FTIR, MS and NMR spectroscopy, providing data which have not been previously reported in literatures. The reaction mechanisms of acid-catalyzed dehydration of BDO were thus updated with consideration of the new side reaction. New kinetic models were further developed based on the updated reaction network. Observed kinetic constants were fitted with experimental data, and the observed rate constants were correlated with reaction temperature and acid concentration by an extended Arrhenius equation. The results revealed that the acetalization between BDO and MPA had much higher observed activation energy (191.5 kJ/mol) than the ketalization between BDO and MEK (59.7 kJ/mol). The observed reaction equilibrium constants was also affected by reaction temperature as well as acid concentration. Increasing reaction temperature was beneficial for the formation of ketalization and acetalization products, while increasing acid concentration seems to more significantly accelerated the hydrolysis of the ketalization and acetalization products.

Conversion of Glucose to 5-Hydroxymethylfurfural in a Microreactor.

5-hydroxymethylfurfural (5-HMF) is one of the key bio-based platform chemicals for the production of high-value chemicals and fuels. The conventional production of 5-HMF from biomass is confronted by the relatively low yield and high production cost. In this work, the enhancement of a continuous catalytic synthesis of 5-HMF in a biphasic-dispersed flow reactor was proposed. Glucose, hydrochloric acid, and methyl isobutyl ketone (MIBK) were used as a low-cost raw material, catalyst, and organic solvent, respectively. The main factors (reaction temperature, residence time, solvent amount, and catalyst concentration) affecting the yield and selectivity of 5-HMF were studied. The 5-HMF yield of 81.7% and 5-HMF selectivity of 89.8% were achieved at the residence time of 3 min, reaction temperature of 180°C, the volumetric flow rate of aqueous phase to organic phase of 0.5:1, and catalyst concentration of 0.15 M. The yield and selectivity of 5-HMF obtained from the biphasic system were significantly higher than that obtained from the single phase system. The superior 5-HMF production in our system in terms of operating conditions was presented when compared to the literature data. Furthermore, the continuous process for removing HCl from the aqueous product was also proposed.

Immobilization of the engineered Raoultella ornithinolytica BF60 for biocatalytic synthesis of 2, 5-furandicarboxylic acid.

As a bio-based platform chemical, 2, 5-furandicarboxylic acid (FDCA) is a promising substitute of terephthalic acid to synthesize poly (ethylene furanoate) used for bio-substitute of polyethylene terephthalate (PET). In previous work, we engineered a Raoultella ornithinolytica BF60 strain and achieved the effective biocatalytic synthesis of FDCA from 5-hydroxymethylfurfural (HMF). Herein, to improve the reusability of the engineered R. ornithinolytica BF60 cells, we used two materials PVA1799-boric acid and sodium alginate-Ca2+ to immobilize the cells. The sodium alginate-Ca2+ was more suitable for FDCA production, and 22 mmol/L FDCA was obtained with Ca(H2PO4)2 as the cross-linker. In addition, the immobilization conditions were optimized and FDCA production was further increased to 74.8 mmol/L. Here the developed immobilization strategy for R. ornithinolytica BF60 cells may be helpful for the economical production of FDCA in the future.

Photoinduced Upgrading of Lactic Acid-Based Solvents to Block Copolymer Surfactants

We report a new strategy toward the development of block copolymer surfactants from chemicals of the lactic acid family. A particularly unique aspect of this work is the use of green solvents as biobased platform chemicals to generate well-defined and nanostructure-forming materials. Herein, efficient functionalization of ethyl lactate (EL) and N,N-dimethyl lactamide (DML) solvents with acrylate groups generated monomers that could be polymerized by the photoinduced copper-catalyzed living radical polymerization process to yield polymeric materials with different water solubilities. These lactic acid-derived monomers were used as a major component in well-defined diblock copolymers composed of poly(EL acrylate) and poly(DML acrylate) segments as hydrophobic and hydrophilic building blocks, respectively. The resulting amphiphilic copolymers could self-assemble in aqueous solution to form nanoparticles with different morphologies (e.g., large-compound micelles and vesicles). Subsequently, the formed amphiphilic polymers were employed as efficient stabilizers in the emulsion polymerization of methyl methacrylate and styrene, offering a facile method for the synthesis of well-defined and stable polymer latexes in the range of 100-200 nm, demonstrating the practical significance of these biobased polymers in nanomaterial synthesis.

Amination of \u03b2-hydroxyl acid esters via cooperative catalysis enables access to bio-based \u03b2-amino acid esters

β-amino acid esters are important scaffolds in medicinal chemistry and valuable building blocks for materials synthesis. Surprisingly, the waste-free construction of such moieties from readily available or renewable starting materials has not yet been addressed. Here we report on a robust and versatile method for obtaining β-amino acid esters by direct amination of β-hydroxyl acid esters via the borrowing hydrogen methodology using a cooperative catalytic system that comprises a homogeneous ruthenium catalyst and an appropriate Brønsted acid additive. This method allows for the direct amination of esters of 3-hydroxypropionic acid, a top value-added bio-based platform chemical, opening a simple route to access β-amino acid esters from a range of renewable polyols including sugars and glycerol.

A versatile Pseudomonas putida KT2440 with new ability: selective oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid.

Currently, biotransformation of 5-hydroxymethylfurfural (HMF) into a series of high-value bio-based platform chemicals is massively studied. In this study, selective biooxidation of HMF to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) by Pseudomonas putida KT2440 with superior titer, yield, and productivity was reported. The biocatalytic performances of P. putida KT2440 were optimized separately. Under optimal conditions, 100% yield of HMFCA was obtained when HMF concentration was less than 150mM, while the maximum concentration of 155mM was achieved from 160mM HMF in 12h. P. putida KT2440 was highly tolerate to HMF, up to 190mM. Besides, it was capable of selective oxidation of other furan aldehydes to the corresponding carboxylic acids with good yield of 100%. This study further demonstrates the potential of P. putida KT2440 as a biocatalyst for biomass conversion, as this strain has been proved the capacity to convert and utilize many kinds of biomass-derived sugars and ligin-derived aromatic compounds.

Acid Extraction from Liquid Phase Pyrolysis Oil Using Cyanex®923 and Subsequent Solvent Regeneration

AbstractLiquid phase pyrolysis (LPP) oil, an intermediate from biofuel production using second‐generation biomass, is a promising source of biobased platform chemicals like acetic acid, however, displaying a complex, multicomponent mixture. Reactive extraction with Cyanex®923 was investigated for selective recovery of acids and subsequent solvent regeneration in distillation at 200 mbar. In a three‐stage extraction 81 % of acids were removed from the LPP oil without loss of Cyanex®923 to the raffinate. Solvent regeneration efficiency of acids was up to 99.7 % with mainly acids and water in the distillate.

Kinetic study on the impact of acidity and acid concentration on the formation of 5-hydroxymethylfurfural (HMF), humins, and levulinic acid in the hydrothermal conversion of fructose

In order to optimize the production of biobased platform chemicals, such as 5-hydroxymethylfurfural (HMF) and levulinic acid (LA), from biomass and sugars, reaction conditions have to be optimized. This article assesses the impact of acidity on the kinetic parameters of the hydrothermal conversion of fructose at 150 °C. The reaction parameters were varied in time (5–180 min), acid (NaHSO4, H3PO4, citric acid, and formic acid), and acid concentration (0.016 to 1.6 mol/l). The experimental data were evaluated with a novel kinetic model that includes the formation of HMF, LA, and humins. While it was expected that the dehydration rate of fructose to HMF and rehydration rate of HMF to levulinic acid depend linearly on the proton concentration, the results show that there is actually an exponential relationship. This can be explained by the participation of the acid rest ion in the dehydration and rehydration reactions. In contrast, the humin formation rate depends linearly on the proton concentration, and also, the sensitivity of this relationship is rather low. This clarifies why high acid concentrations or proton concentrations, respectively, increase the formation of LA to an expense of the humin formation.

Enhanced Catalyst Durability for Bio-Based Adipic Acid Production by Atomic Layer Deposition

Summary Atomic layer deposition (ALD) improves the durability of metal catalysts using nanoscale metal oxide coatings. However, targeted coating strategies and economic models are lacking for process-specific deactivation challenges that account for implications at scale. Herein, we apply Al2O3 ALD to Pd/TiO2 to increase durability during hydrogenation of muconic acid, a bio-based platform chemical, to adipic acid. Initial coating development and characterization are performed on the milligram scale using stop-flow ALD. Subsequently, ALD coating scale is increased by 3 orders of magnitude using fluidized bed ALD. Activity, leaching resistance, and thermal stability are evaluated at each synthesis scale. ALD-coated catalysts retain up to 2-fold greater muconic acid hydrogenation activity and undergo significantly less physical restructuring than uncoated Pd/TiO2 after high-temperature treatments, while reducing Pd leaching by over 4-fold. Techno-economic analysis for an adipic acid biorefinery supports increased ALD material costs through catalyst lifetime extension, underscoring the potential viability of this technology.