Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels.

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).

Closing the loop: Valorizing pyrolyzed waste tyre residue into functional carbon materials, SiO2 with exceptionally high silanol groups, and Zn salt.

This study aims to identify suitable processing conditions for converting pyrolytic solid residue from off-the-road tyres (OTR) to improve carbon materials properties that can be used in multiple applications and the recovery of minerals from OTR. Pyrolysis of OTR at 800 °C and a heating rate 2 °C.min-1 gave a carbon material with the highest surface area, most defective carbon structures, and the highest micro-porosity. This operating condition was used to compare the conventional three-step carbonization approach, which involves a demineralization stage that produces high volumes of toxic wastewater, with a two-step approach that bypasses this stage. Analysis of the carbon structures showed that the quality of the carbon material from the two-step approach is similar to the three-step approach. This two-step approach resulted in a solid and a liquid phase, in which âˆ¼ 93.4% of Zn was selectively fractionated to the liquid phase. The wastewater from the acid wash of the carbonized OTR was neutralized to recover the SiO2, of which 55.5% was reactive SiO2. The SiO2 was found to have an exceptionally high cross-linking ratio of 5.94, achievable only when SiO2 is reacted with silane groups. The study demonstrated that the engineered carbon material from OTR has a H2 uptake of 1.03 wt% at 77 K and 1.2 bar, and the sulfonated counterpart was an effective catalyst (64% conversion) for the Aldol condensation of levunilic acid to two dimer products [tetrahydro-2- methyl-5,γ-dioxo-2-furanpentanoic acid (TMDFA) and 3-(2-methyl-5-oxo- tetrahydrofuran-2-yl)-4-oxopentanoic acid (MOTOA)] that are precursors for fuels and chemicals.

Microwave aided conversion of cellulose to glucose using polyoxometalate as catalyst.

The viability of biorefining technology primarily depends on the facile cellulose conversion route with adequate conversion efficiency. Here we have demonstrated the microwave-assisted hydrolysis of cellulose to glucose using polyoxometalate (POM) clusters as acid catalysts. Two different types of POM, including Wells-Dawson and Keggin were justified as catalysts in the cellulose conversion process. In particular, the cellulose to glucose catalytic conversion using Wells-Dawson type POMs has not been reported to date. Also, even though there have been some previous reports about the catalytic biomass conversion of Keggin type POMs, the systematic study to optimize the conversion efficiency in terms of catalyst amount, reaction temperature, reaction time, and the amount of solvent is lacking. Under the experimental conditions employed, the Keggin-type catalyst showed higher cellulose conversion and glucose yield than the Wells-Dawson-type catalyst. Furthermore, the cellulose conversion efficiency and glucose yields were optimized by tuning the reaction conditions including temperature, reaction time, and the amount of solvent. Under optimized conditions, the Keggin-type POM catalyst shows a remarkably high glucose yield of 77.2% and a cellulose conversion of 90.1%. The unique complex properties of the POM catalyst, including being (i) strong acids with extremely high Brønsted and Lewis acidity and (ii) efficient microwave adsorbants which enhanced interaction between substrate and the catalyst can be attributed to the outstanding efficacy of the conversion process.

Microwave-assisted catalytic conversion of chitin to 5-hydroxymethylfurfural using polyoxometalate as catalyst.

The key challenges for converting chitin to 5-hydroxymethylfurfural (5-HMF) include the low 5-HMF yield. Moreover, the disadvantages of traditional acid-base catalysts including complex post-treatment processes, the production of by-products, and severe equipment corrosion also largely limit the large-scale conversion of chitin to 5-HMF. In this view, herein we have demonstrated a microwave aided efficient and green conversion of chitin to 5-HMF while using polyoxometalate (POM) as a catalyst and DMSO/water as solvent. Chitin treated with H2SO4 followed by ball-milling (chitin-H2SO4-BM) was selected as the starting compound for the conversion process. Four different POMs including H3[PW12O40], H3[PMo12O40], H4[SiW12O40] and H4[SiMo12O40] were used as catalysts. Various reaction parameters including reaction temperature, amount of catalyst, mass ratios of water/DMSO and reaction time have been investigated to optimize the 5-HMF conversion. The H4[SiW12O40] catalyst exhibited the highest catalytic performance with 23.1% HMF yield at optimum operating conditions which is the highest among the literature for converting chitin to 5-HMF. Significantly, the disadvantages of the state of the art conversion routes described earlier can be overcome using POM-based catalysts, which makes the process more attractive to meet the ever-increasing energy demands, in addition to helping consume crustacean waste.

Microwave-assisted catalytic conversion of glucose to 5-hydroxymethylfurfural using "three dimensional" graphene oxide hybrid catalysts.

Hybrids of reduced graphene oxide (rGO) and metal/metal oxide (Pt, NiO/Ni(OH)2, CoO, Fe3O4) nano particle were prepared by reduction of graphene oxide (GO) and metal ion (Pt2+, Ni2+, Co2+, Fe2+) hybrids. The M-rGO hybrids (M = Pt, Ni-, Co and Fe) were justified for the transformation of glucose to 5-hydroxymethylfurfural (5-HMF). High glucose → 5-HMF conversion was yielded depending on the nature of the M-rGO catalyst. The Ni-rGO showed the highest 5-HMF yield. The conversion reaction tuned to the optimized state under a microwave-assisted reaction accomplished by using Ni-rGO. In such case, the conversion rate was 99% with a 5-HMF yield of 75%. In order to improve both the conversion and yield, NiGO-FD was prepared by a freeze-dry method. The NiGO-FD remarkably showed the highest conversion of 99% and 5-HMF yield of 95%. Beside the biomass transformation process, the physico-chemical strategy employed herein for multiplying the catalytic efficiency might be justified for catalyzing similar reactions.

Correction: Microwave-assisted catalytic conversion of glucose to 5-hydroxymethylfurfural using "three dimensional" graphene oxide hybrid catalysts.

[This corrects the article DOI: 10.1039/D0RA01009J.].

Nanostructured NiMoS2/Carbon Catalysts for Syngas Conversion to Higher Alcohols.

Syngas conversion to higher alcohols remains a very attractive alternative due to the abundance of syngas feedstock, such as renewable carbon and waste-carbon resources. Catalysts suitable for syngas conversion still show low selectivity to alcohols. In this article, we present nanostructured NiMoS2 and CoMoS2 catalysts supported on activated carbon pellets and design strategies to improve its selectivity towards higher alcohols. Activated carbon pellets were treated with concentrated HNO3 to enlarge porous channels and enable better dispersion of NiMoS2 and CoMoS2. These treatment steps lead to a formation of nanostructured NiMoS2 and CoMoS2 catalysts and promoted higher selectivity to ethanol, propanol and butanol. BET surface area of 532 m² g-1 was obtained for NiMoS2/Carbon catalysts from the nitrogen physisorption analysis. In catalytic tests, the highest CO conversion (39.1%) was achieved by the NiMoS2/Carbon, whereas the CoMoS2/Carbon showed the highest alcohol selectivity (74.4%). CoMoS2 catalysts supported on activated carbon pellets proved to be highly active towards undesired by-product "filamentous carbon."

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid.

Achieving the goal of living in a sustainable and greener society, will need the chemical industry to move away from petroleum-based refineries to bio-refineries. This aim can be achieved by using biomass as the feedstock to produce platform chemicals. A platform chemical, 2,5-furandicarboxylic acid (FDCA) has gained much attention in recent years because of its chemical attributes as it can be used to produce green polymers such polyethylene 2,5-furandicarboxylate (PEF) that is an alternative to polyethylene terephthalate (PET) produced from fossil fuel. Typically, 5-(hydroxymethyl)furfural (HMF), an intermediate product of the acid dehydration of sugars, can be used as a precursor for the production of FDCA, and this transformation reaction has been extensively studied using both homogeneous and heterogeneous catalysts in different reaction media such as basic, neutral, and acidic media. In addition to the use of catalysts, conversion of HMF to FDCA occurs in the presence of oxidants such as air, O2, H2O2, and t-BuOOH. Among them, O2 has been the preferred oxidant due to its low cost and availability. However, due to the low stability of HMF and high processing cost to convert HMF to FDCA, researchers are studying the direct conversion of carbohydrates and biomass using both a single- and multi-phase approach for FDCA production. As there are issues arising from FDCA purification, much attention is now being paid to produce FDCA derivatives such as 2, 5-furandicarboxylic acid dimethyl ester (FDCDM) to circumvent these problems. Despite these technical barriers, what is pivotal to achieve in a cost-effective manner high yields of FDCA and derivatives, is the design of highly efficient, stable, and selective multi-functional catalysts. In this review, we summarize in detail the advances in the reaction chemistry, catalysts, and operating conditions for FDCA production from sugars and carbohydrates.

Highly active and robust Ni-MoS2 supported on mesoporous carbon: a nanocatalyst for hydrodeoxygenation reactions.

NiMoS2 nanoparticles supported on carbon, synthesized by a microemulsion method were used as a nanocatalyst for hydrodeoxygenation (HDO) of a lignin model compound - guaiacol. Two types of carbon supports - mesoporous carbon (CMK-3) and activated carbon (AC) with a predominantly microporous structure, were studied to investigate the role of porosity and nature of the porous structure in catalyst activity. The activity of NiMoS2/AC resulted in the complete guaiacol conversion at 13 h of reaction time to produce phenol (31.5 mol%) and cyclohexane (35.7 mol%) as the two main products. Contrastingly, NiMoS2/CMK-3 needed a much lesser reaction time (6 h) to attain a similar conversion of guaiacol but gave different selectivities of phenol (25 mol%) and cyclohexane (55.5 mol%). Increased cyclohexane production with NiMoS2/CMK-3 implied better deoxygenation of MoS2 and enhanced hydrogenation capacity of Ni since phenol is a partially deoxygenated product of guaiacol while cyclohexane is a completely deoxygenated and hydrogenated product. The superior catalytic activity and deoxygenating behavior of NiMoS2/CMK-3 catalysts could be attributed to the organized mesoporosity of the CMK-3 support in relation to the improved active phase distribution and access to active sites that facilitate the conversion of the reaction's product. Recyclability study implied NiMoS2/CMK-3 was more stable without significant changes in the catalytic activity even after three reaction cycles.

Effect of HCOOK/Ethanol on Fe/HUSY, Ni/HUSY, and Ni-Fe/HUSY Catalysts on Lignin Depolymerization to Benzyl Alcohols and Bioaromatics.

We have investigated the production of benzyl alcohols and bioaromatics via the reductive lignin depolymerization process over Fe/H-style ultrastable Y (HUSY), Ni/HUSY, and Ni-Fe/HUSY catalysts using HCOOK/ETOH in air. Synergy effect between HCOOK and the catalysts improved the depolymerization process, resulting in a higher bio-oil recovery. HCOOK does not act solely as an in situ hydrogen source; it also interacts with lignin to enable its initial depolymerization via a base-catalyzed mechanism to low-molecular-weight fragments, and in tandem with the catalyst, the hydrogenolysis rate of the depolymerized lignin monomers was enhanced. Fe/HUSY displayed an excellent activity for the catalytic reductive step in contrast to Ni/HUSY and Ni-Fe/HUSY by facilitating methoxy group removal via hydrogenolysis, thereby contributing to the yield and stabilization of the low-molecular-weight aromatics [diethyl ether (DEE)-soluble products]. Fe/HUSY gave the highest DEE product yield of >99 wt % and a total benzyl alcohol yield of 16 wt % with a total selectivity of 47 wt % (60 wt % for aromatic alcohols). Fe/HUSY was reused for the lignin depolymerization reaction without much loss of its initial activity, giving 13 wt % yield of benzyl alcohols with a selectivity of 58 wt % (77 wt % for aromatic alcohols).

Effect of gold addition by the recharge method on silver supported catalysts in the catalytic wet air oxidation (CWAO) of phenol.

Catalysts Ag/ZrO2-CeO2 and Au/ZrO2-CeO2 were synthesized by a deposition-precipitation method and Ag-Au/ZrO2-CeO2 was prepared using a recharge method for the second metal (Au). The materials were characterized by physisorption of N2, XRD, ICP, UV-vis RDS, H2-TPR, XPS and TEM. The results obtained show that the specific areas for monometallic materials were 29-37 m2 g-1 and 27-74 m2 g-1 for bimetallics. The tetragonal crystal phase of ZrO2 stabilizes when CeO2 quantity increases. Using XPS an increment in Ce3+ species abundance was determined for bimetallic catalysts in contrast to the monometallic ones; according to the Ag 3d region, this metal oxidation was observed when augmenting the content of CeO2 in the materials, and with Au the opposite effect was produced. It was determined by TEM, that the average size of the metallic particles was smaller at bimetallic catalysts due the preparation method. Catalytic activity was evaluated by CWAO of phenol, the Ag-Au/ZrO2-CeO2 catalyst with 20% wt of cerium reached a degradation of 100% within an hour, being the most active catalyst. Maleic, formic and oxalic acid were identified as reaction intermediates; and at the end of the reaction acetic acid was identified as the main by-product, because it is the most refractory and the conditions for oxidation must be more severe.

Direct Production of 5-Hydroxymethylfurfural via Catalytic Conversion of Simple and Complex Sugars over Phosphated TiO2.

A water-THF biphasic system containing N-methyl-2-pyrrolidone (NMP) was found to enable the efficient synthesis of 5-hydroxymethylfurfural (HMF) from a variety of sugars (simple to complex) using phosphated TiO2 as a catalyst. Fructose and glucose were selectively converted to HMF resulting in 98 % and 90 % yield, respectively, at 175 °C. Cellobiose and sucrose also gave rise to high HMF yields of 94 % and 98 %, respectively, at 180 °C. Other sugar variants such as starch (potato and rice) and cellulose were also investigated. The yields of HMF from starch (80-85 %) were high, whereas cellulose resulted in a modest yield of 33 %. Direct transformation of cellulose to HMF in significant yield (86 %) was assisted by mechanocatalytic depolymerization-ball milling of acid-impregnated cellulose. This effectively reduced cellulose crystallinity and particle size, forming soluble cello-oligomers; this is responsible for the enhanced substrate-catalytic sites contact and subsequent rate of HMF formation. During catalyst recyclability, P-TiO2 was observed to be reusable for four cycles without any loss in activity. We also investigated the conversion of the cello-oligomers to HMF in a continuous flow reactor. Good HMF yield (53 %) was achieved using a water-methyl isobutyl ketone+NMP biphasic system.

Transforming triglycerides and fatty acids into biofuels.

Fuels derived from biobased materials are attracting attention for their potential in securing the energy supply and protecting the environment. In this Minireview, we evaluate the use of biobased sources, particularly fatty acids and triglycerides from seed oils and animal fats, as fuels. The physical and chemical properties of these fatty acids and triglycerides are discussed, including the link to their sources and current availability to meet fuel demands. The current technologies, also known as the first-generation ones, for converting triglycerides into fuels are covered, including conventional methods such as transesterification, pyrolysis, cracking, and emulsions. Recent, second-generation technological developments that lead to more commercially viable biofuels based on diesel-like hydrocarbons are also discussed.

Chemoselective catalytic conversion of glycerol as a biorenewable source to valuable commodity chemicals.

New opportunities for the conversion of glycerol into value-added chemicals have emerged in recent years as a result of glycerol's unique structure, properties, bioavailability, and renewability. Glycerol is currently produced in large amounts during the transesterification of fatty acids into biodiesel and as such represents a useful by-product. This paper provides a comprehensive review and critical analysis on the different reaction pathways for catalytic conversion of glycerol into commodity chemicals, including selective oxidation, selective hydrogenolysis, selective dehydration, pyrolysis and gasification, steam reforming, thermal reduction into syngas, selective transesterification, selective etherification, oligomerization and polymerization, and conversion of glycerol into glycerol carbonate.