Selective electrocatalytic conversion of methane to fuels and chemicals

The increase in natural gas reserves makes methane a significant hydrocarbon feedstock. However, the direct catalytic conversion of methane into liquid fuels and useful chemicals remains a great challenge,and many studies have been devoted to this field in the past decades. Electrocatalysis is considered as an important alternative approach for the direct conversion of methane into value-added chemicals, although many other innovative methods have been developed. This review highlights recent advances in electrocatalytic conversion of methane to ethylene and methanol, two important chemicals. The electrocatalytic systems efficient for methane conversions are summarized with an emphasis on catalysts and electrolytes. The effects of reaction conditions such as the temperature and the acid–base property of the reaction medium are also discussed.     

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).     

Defective TiO2 for photocatalytic CO2 conversion to fuels and chemicals

Photocatalytic conversion of CO₂ into fuels and valuable chemicals using solar energy is a promising technology to combat climate change and meet the growing energy demand. Extensive effort is going on for the development of a photocatalyst with desirable optical, surface and electronic properties. This review article discusses recent development in the field of photocatalytic CO₂ conversion using defective TiO₂. It specifically focuses on the different synthesis methodologies adapted to generate the defects and their impact on the chemical, optical and surface properties of TiO₂ and, thus, photocatalytic CO₂ conversion. It also encompasses theoretical investigations performed to understand the role of defects in adsorption and activation of CO₂ and identify the mechanistic pathway which governs the formation and selectivity of different products. It is divided into three parts: (i) general mechanism and thermodynamic criteria for defective TiO₂ catalyzed CO₂ conversion, (ii) theoretical investigation on the role of defects in the CO₂ adsorption–activation and mechanism responsible for the formation and selectivity of different products, and (iii) the effect of variation of physicochemical properties of defective TiO₂ synthesized using different methods on the photocatalytic conversion of CO₂. The review also discusses the limitations and the challenges of defective TiO₂ photocatalysts that need to be overcome for the production of sustainable fuel utilizing solar energy.

This review discusses photocatalytic CO₂ conversion using defective TiO₂, with emphasis on the mechanism, the role of defects on CO₂ adsorption–activation and product selectivity, as well as challenges of defective TiO₂ to produce solar fuels.     

Microwave-activated lignin conversion to synthesis gas

Russian Chemical Bulletin - The use of the low-power (up to 10 W) microwave activation to heat the reaction mixture in the catalytic oxidative conversion of lignin to synthesis gas results in a...     

Biomass conversion to hydrogen-rich synthesis fuels using water steam plasma

In this study, an experimental plasma-chemical reactor equipped with an arc discharge water steam plasma torch was used for biomass conversion to hydrogen-rich synthesis fuels. Glycerol and crushed wood were used as biomass sources. The effects of different conversion parameters including the water steam flow rate, treated material flow rate, and plasma torch power were studied. The experimentally obtained results were compared with the model based on the thermodynamic equilibrium. Additionally, the quantification of the plasma conversion system in terms of energy efficiency and specific energy requirement was performed. It has been found that the synthesis gas can be effectively produced from the biomass using water steam plasma.     

CO2 conversion to solar fuels and chemicals: Opening the new paths

This future article discusses the new prospects and directions of CO2conversion via the photo-electrocatalytic(PEC) route. The second(2nd) generation solar fuels and chemicals(SFs) are generated directly in PEC systems via electrons/protons reactions without forming molecular H₂ as an intermediate, overcoming the thermodynamics limitations and practical issues encountered for electro-fuels produced by multistep thermocatalytic processes(i.e. CO₂ conversion with H₂     

Synthesis gas as substrate for the biological production of fuels and chemicals

Synthesis gas provides a simple substrate for the production of fuels and chemicals. Synthesis gas can be produced via established technologies from a variety of feedstocks including coal, wood, and agricultural and municipal wastes. The gasification is thermally efficient and results in complete conversion of the feedstock to fermentable substrate.Clostridium ljungdahlii grows on the synthesis gas components, carbon monoxide, hydrogen, and carbon dioxide. Production of acetic acid and ethanol accompanies growth with synthesis gas as sole source of energy and carbon. Rate and yield parameters are compared forC. ljungdahlii grown on carbon monoxide, or hydrogen with carbon dioxide.

     

Cellulosic materials recovered from steam classified municipal solid wastes as feedstocks for conversion to fuels and chemicals

Applied Biochemistry and Biotechnology - A process has been developed for the treatment of municipal solid waste to separate and recover the cellulosic biomass from the nonbiomass components. The...     

Biological production of liquid and gaseous fuels from synthesis gas

Applied Biochemistry and Biotechnology - Liquid and gaseous fuels may be produced biologically from coal by the indirect conversion of coal synthesis gas. Methane has been produced from synthesis...     

Ester fuels and chemicals from biomass

Bench-scale research demonstrated that using an efficient esterification step to integrate an ethanol with a carboxylic acid fermentation stream offers potential for producing valuable ester feedstocks and fuels. Polar organic acids from bacterial fermentations are difficult to extract and purify, but formation of the ammonium salts and their conversion to esters facilitates the purifications. An improved esterification procedure gave high yields of esters, and this method will lower the cost of ester production. Fuel characteristics have been determined for a number of ester-gasoline blends with promising results for lowering Reid vapor pressure and raising octane numbers.     

Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals

Biomass has the potential to serve as a sustainable source of energy and organic carbon for our industrialized society. The focus of this Review is to present an overview of chemical catalytic transformations of biomass-derived oxygenated feedstocks (primarily sugars and sugar-alcohols) in the liquid phase to value-added chemicals and fuels, with specific examples emphasizing the development of catalytic processes based on an understanding of the fundamental reaction chemistry. The key reactions involved in the processing of biomass are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Further, it is discussed how ideas based on fundamental chemical and catalytic concepts lead to strategies for the control of reaction pathways and process conditions to produce H(2)/CO(2) or H(2)/CO gas mixtures by aqueous-phase reforming, to produce furan compounds by selective dehydration of carbohydrates, and to produce liquid alkanes by the combination of aldol condensation and dehydration/hydrogenation processes.     

Direct conversion of synthesis gas to light hydrocarbons on heterogeneous catalysts

Six catalysts consisting of mixtures of catalysts for methanol synthesis and its conversion to hydrocarbons were prepared by mechanical mixing, impregnation, and coprecipitation, followed by extrusion. Phase changes occurring during various stages of preparation and after use were followed by x-ray diffraction. The catalysts were found to be nontrivial bifunctional catalysts which selectively convert synthesis gas directly to low molecular weight hydrocarbons in the range of C₁ to C₄. Methanol and dimethylether were detected as intermediates. Olefins were formed, and their further hydrogenation yielded products with high paraffinic content. Carbon dioxide retards the conversion of synthesis gas to hydrocarbons, whereas steam retards the hydrogenation of olefins. On heating the commercial zinc chromite catalyst, dehydration, reduction, and solid-state reactions occur with the formation of ZnO-ZnCr₂O₄ solid solution. Exchanging cations within the zeolite component did not affect the space lattice, but these ions tend to occupy special sites, and during service more order was detected. Copper ions tend to diffuse in ZnO, forming a solid solution, and during service metallic copper was produced.     

Microbial conversion of high-rank coals to methane

Applied Biochemistry and Biotechnology - It has been demonstrated recently that certain bacteria and fungi are capable of directly or indirectly converting low-rank coals into liquid and gaseous...     

Advances in photothermal conversion of carbon dioxide to solar fuels

Converting carbon dioxide(CO₂) into useful fuels or chemical feedstocks is important for achieving peak carbon emission and carbon neutrality.Recently,photothermal catalysis has been extensively studied and applied due to its advantages over traditional heat-driven catalysis.In this review,we focus on photothermal catalysis of thermodynamically uphill reactions that convert CO₂ into value-added products.We first introduce the fundamentals of photothermal catalysis for CO     

The cyanide-catalyzed conversion of β-formylmuconates into triglochinates: A useful biomimetic synthesis

Upon treatment with cyanide under slightly basic conditions, β-formyl-cis,cis-muconic acid and esters, prepared from vanillin, undergo a sequence of prototropic shifts equivalent to an internal redox process in which 1,4-reduction of the diene system is blanaced by oxidation of the formyl group.     

Biomass conversion to mixed alcohol fuels using the MixAlco process

The MixAlco process is a patented technology that converts any biodegradable material (e.g., sorted municipal solid waste, sewage sludge, industrial biosludge, manure, agricultural residues, energy crops) into mixed alcohol fuels containing predominantly 2-propanol, but also higher alcohols up to 7-tridecanol. The feed stock is treated with lime to increase its digestibility. then, it is fed to a fermentor in which a mixed culture of acid-forming microorganisms produces carboxylic acids. Calcium carbonate is added to the fermentor to neutralize the acids to their corresponding carboxylate salt. The dilute (−3%) carboxylate salts are concentrated to 19% using an amine solvent that selectively extracts water. Drying is completed using multi-effect evaporators. Finally, the dry salts are thermally converted to ketones which subsequently are hydrogenated to alcohols. All the steps in the MixAlco process have been proven at the laboratory scale. A techno-economic model of the process indicates that with the tipping fees available in New York ($126/dry tonne), mixed alcohol fuels may be sold for $0.04/L ($0.16/gal) with a 60% return on investment (ROI). With the average tipping fee in the United States rates ($63/dry tonne), mixed alcohol fuels may be sold for $0.18/L ($0.69/gal) with a 15% ROI. In the case of sugarcane bagasse, which may be obtained for about $26/dry ton, mixed alcohol fuels may be sold for $0.29/L ($1.09/gal) with a 15% ROI.