Green Industrial Processes Research Articles

Simple synthesis of WO3-Au composite and their improved photothermal synergistic catalytic performance for cyclohexane oxidation

Partial oxidation of cyclohexane (CHA) to KA oil (cyclohexanone (-one) and cyclohexanol (-ol)) with dry air is one of the most important industrial process. Despite great efforts have made in developing new catalysts, industrial processes are still limited by low conversion and selectivity with harsh condition. Here we report a significantly improved cyclohexane conversion and KA oil selectivity under solar light irradiation by anew photothermal synergistic catalyst, which was prepared by loading Au nanoparticles (Au NPs) onto WO3 nanosheets (WO3 NSs) with simple ultrasonic method. A high conversion of 9.0% and a high selectivity of 99.0% are acquired by WO3 nanosheets-Au nanoparticles (WO3-Au) composite under dry air, which are much higher than the simple sum of photocatalysis and thermal catalysis. The significantly improved catalytic properties of cyclohexane oxidation by the WO3-Au composite are mainly attributed to the improved light absorption, the effective charge separation and the synergistic effect of photocatalysis and thermal catalysis. The photothermal synergy to improve catalytic activity may be widely used in green industrial catalytic processes.

Smart solutions shape for sustainable low-carbon future: A review on smart cities and industrial parks in China

To promote sustainable urban development and green industrial process are critical solutions for sustainable and low-carbon society transition in China, considering the significant environmental impacts derived from the industrialization and surging urbanization. Under this background, China adopts top-down programs on smart cities and smart industrial parks to forward the above efforts. While practices and lessons from these programs will be valuable to enlighten other regions and practitioners, to date, rather few studies have paid attentions to this issue. Particularly, the emerging smart technologies strongly support the practice, via offering smart solutions like better renewable energy projection, low-carbon life styles transformation, as well as energy planning and management. However, there has been a lack of discussing their future role in-depth. With this circumstance, this paper conducts an integrated and in-depth review on China's promotion on smart cities and smart industrial parks. In detail, the national pilots, key technical innovations, incentives and policies framework, as well as spatial features were discussed in-depth. Particularly, we further explored how the smart solutions can contribute to better decision making on low-carbon urban and industrial system planning. Finally, we highlighted policy recommendations targeting on future smart cities and industrial parks promotion, focusing on the perspectives of technological and social system innovations, innovative decision support tools, and smart management framework. Our results expect to offer critical enlightenments for policy makers to address future concerns on smart cities and industrial parks promotion and management.

The Place for Enzymes and Biologically Active Peptides from Marine Organisms for Application in Industrial and Pharmaceutical Biotechnology.

Since the beginning of written history, diverse texts have reported the use of enzymatic preparations in food processing and have described the medicinal properties of crude and fractionated venoms to treat various diseases and injuries. With the biochemical characterization of enzymes from distinct sources and bioactive polypeptides from animal venoms, the last sixty years have testified the advent of industrial enzymology and protein therapeutics, which are currently applicable in a wide variety of industrial processes, household products, and pharmaceuticals. Bioprospecting of novel biocatalysts and bioactive peptides is propelled by their unsurpassed properties that are applicable for current and future green industrial processes, biotechnology, and biomedicine. The demand for both novel enzymes with desired characteristics and novel peptides that lead to drug development, has experienced a steady increase in response to the expanding global market for industrial enzymes and peptidebased drugs. Moreover, although largely unexplored, oceans and marine realms, with their unique ecosystems inhabited by a large variety of species, including a considerable number of venomous animals, are recognized as untapped reservoirs of molecules and macromolecules (enzymes and bioactive venom-derived peptides) that can potentially be converted into highly valuable biopharmaceutical products. In this review, we have focused on enzymes and animal venom (poly)peptides that are presently in biotechnological use, and considering the state of prospection of marine resources, on the discovery of useful industrial biocatalysts and drug leads with novel structures exhibiting selectivity and improved performance.

Engineering Ligninolytic Consortium for Bioconversion of Lignocelluloses to Ethanol and Chemicals.

Rising environmental concerns and recent global scenario of cleaner production and consumption are leading to the design of green industrial processes to produce alternative fuels and chemicals. Although bioethanol is one of the most promising and eco-friendly alternatives to fossil fuels yet its production from food and feed has received much negative criticism. The main objective of this study was to present the noteworthy potentialities of lignocellulosic biomass as an enormous and renewable biological resource. The particular focus was also given on engineering ligninolytic consortium for bioconversion of lignocelluloses to ethanol and chemicals on sustainable and environmentally basis. Herein, an effort has been made to extensively review, analyze and compile salient information related to the topic of interest. Several authentic bibliographic databases including PubMed, Scopus, Elsevier, Springer, Bentham Science and other scientific databases were searched with utmost care, and inclusion/ exclusion criterion was adopted to appraise the quality of retrieved peer-reviewed research literature. Bioethanol production from lignocellulosic biomass can largely satisfy the possible inconsistency of first-generation ethanol since it utilizes inedible lignocellulosic feedstocks, primarily sourced from agriculture and forestry wastes. Two major polysaccharides in lignocellulosic biomass namely, cellulose and hemicellulose constitute a complex lignocellulosic network by connecting with lignin, which is highly recalcitrant to depolymerization. Several attempts have been made to reduce the cost involved in the process through improving the pretreatment process. While, the ligninolytic enzymes of white rot fungi (WRF) including laccase, lignin peroxidase (LiP), and manganese peroxidase (MnP) have appeared as versatile biocatalysts for delignification of several lignocellulosic residues. The first part of the review is mainly focused on engineering ligninolytic consortium. In the second part, WRF and its unique ligninolytic enzyme-based bio-delignification of lignocellulosic biomass, enzymatic hydrolysis, and fermentation of hydrolyzed feedstock are discussed. The metabolic engineering, enzymatic engineering, synthetic biology aspects for ethanol production and platform chemicals production are comprehensively reviewed in the third part. Towards the end information is also given on futuristic viewpoints. In conclusion, given the present unpredicted scenario of energy and fuel crisis accompanied by global warming, lignocellulosic bioethanol holds great promise as an alternative to petroleum. Apart from bioethanol, the simultaneous production of other value-added products may improve the economics of lignocellulosic bioethanol bioconversion process.

Chitosan‐Silica Sulfate Nano Hybrid as a Novel and Highly Proficient Heterogeneous Nano Catalyst for Regioselective Ring Opening of Epoxides via Carboxylic Acids

The synthesis and characterization of chitosan‐silica sulfate nano hybrid (CSSNH) as a novel and efficient heterogeneous nano catalyst involving acid‐base bifunctional activity is described. The catalytic potency and activity of this eco‐friendly catalyst was investigated in regioselective ring opening of epoxides with carboxylic acids to access structurally diverse 1,2‐diol mono‐esters in good to excellent yields. CSSNH catalyst was characterized using different microscopic and spectroscopic techniques encompassing scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N2 adsorption isotherm, and Fourier transform infrared spectroscopy. The green nature, cheapness, efficiency, ease of preparation, handling and reusability of this new catalyst makes this catalyst to be useful for green industrial processes.

Ultrasound promoted rapid and green synthesis of thiiranes from epoxides in water catalyzed by chitosan-silica sulfate nano hybrid (CSSNH) as a green, novel and highly proficient heterogeneous nano catalyst

The synthesis and characterization of chitosan-silica sulfate nano hybrid (CSSNH) as a novel, green and highly efficient heterogeneous nano catalyst is described. The catalytic activity of this new biopolymeric nano catalyst was investigated in the ultrasonic assisted green synthesis of structurally diverse thiiranes from epoxides using thiourea in water at room temperature. CSSNH was characterized using some different microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N2 adsorption isotherm, Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). The green nature, cheapness, efficiency, ease of preparation, handling and reusability of this new catalyst makes this catalyst to be useful for green industrial processes.

CaSO4 Scale Inhibition by a Trace Amount of Zinc Ion in Piping System

Usually, a small steam generator is not complemented by equipment such as demineralization and chlorination process apparatus since the economic aspect was a precedence. Such phenomenon was uncovered in a case study of green tea industrial process in which the boiler capacity was not more than 1 ton/hour. The operation of the small boiler affected the scaling process in its piping system. In a year operation, there was already a large scale of calcium attached to the inner surface of the pipe. Such large scale formed a layer and decreased the overall heat transfer coefficient, prolonged the process time and decreased the production. The aim of the current research was to solve the problem through a laboratory research to inhibit the CaSO4 scale formation by the addition of trace amounts of zinc ion. This research was conducted through a built in-house experimental rig which consisted of a dosing pump for controlling the flow rate and a thermocouple to control the temperature. Synthesis solution was prepared with 3,500 ppm concentration of CaCl2 and Na2SO4. The concentration of zinc was set at 0.00; 5.00 and 10.00 ppm. The data found were characterized by scanning electron microscopy (SEM) to analyze crystal polymorph as the influence of zinc ion addition. The induction time was also investigated to analyze the nucleation time, and it was found on the 9th, 13th, and 19th minute of the zinc ion addition of 0.00, 5.00 and 10.00 ppm. After running for a four-hour duration, the scale grow-rate was found to be 5.799; 5.501 and 4.950 × 10-3 gr/min for 0.00; 5.00 and 10.00 ppm of zinc addition at 50 °C.

Optimal conditions for hemicelluloses extraction from Eucalyptus globulus wood: hydrothermal treatment in a semi-continuous reactor

Optimal conditions for hemicellulose extraction from wooden biomass in a semi-continuous system have been assessed in this work. This study would constitute the first stage for a profitable and green industrial process. Eucalyptus globulus was selected as raw material due to its low water consumption, high growth and its efficiency in lignocellulose production. Moreover its cultivation is very popular in southern Europe. Samples of 5.0g of wood were fractioned using a pressurized hot water semi-continuous system, to produce sugars (pentoses and hexoses) and a solid residue enriched in lignin.Five flow rates between 2.50 and 20.00mL/min and four temperatures between 135.0 and 285.0°C were tested in order to maximize the production of sugars, avoiding the formation of degradation products.Optimum conditions for the extraction of hemicellulose were identified at 185.0°C and 5.00mL/min, leading to a pentoses yield of 67.409wt%, with 0.702wt% of degradation products. Almost all the pulp is extracted at 285.0°C.SEM images show very well the changes in the wood structure at different temperatures.A kinetic model was developed, describing the extraction and hydrolysis of hemicellulose and cellulose with absolute average deviations around 10% for sugar extracted mass.

Bringingd-limonene to the scene of bio-based thermoset coatings via free-radical thiol–ene chemistry: macromonomer synthesis, UV-curing and thermo-mechanical characterization

The increasing pursuit for bio-based plastic materials led us to investigate the potential use of the monoterpene limonene in thermoset synthesis using the free-radical mediated thiol–ene reaction. The high efficiency of this reaction to prepare multifunctional ene-terminated resins, as intermediary macromolecular precursors, for thermosets synthesis was demonstrated under thermal and photoinitiated conditions. Although an excess of terpene favors formation of well-defined macromonomers in organic solution, the characteristic low-vapor pressure of limonene hinders its simple removal (or recycling) via evaporation after synthesis. Alteration to an initial thiol–ene stoichiometry of 1 : 0.5 enables production of high molecular weight resins in the form of ‘hyperbranched oligomeric-like’ structures having moderate polydispersity. UV-curing of these polyfunctional resins combined with equal mole compositions of multifunctional alkyl ester 3-mercapto propionates yields highly sticky, amorphous and flexible elastomers with different thermo-mechanical properties. These can be further modulated by varying the amount of unreacted thiol occluded within the networks working as a plasticizer. Introduction of a renewable cycloaliphatic structure into the materials offers a convenient way to enhance the glass-transition temperature and stiffness of traditional thiol–ene networks. The materials synthesized may be considered potentially useful as sealants and adhesives in a wide variety of applications including organic coatings. The versatility of UV-irradiation over thermal initiation makes this method particularly suitable for green industrial synthesis processes via thiol–ene chemistry using limonene and multifunctional thiols. The thiol–ene system evaluated herein serves as a model example for the sustainable incorporation of natural diolefinic monomers into semi-synthetic thiol–ene networks exhibiting a range of thermo-mechanical properties.

Towards large scale aligned carbon nanotube composites: an industrial safe-by-design and sustainable approach

We present the main results demonstrating the feasibility of high surface (> A4 format size) semi-industrial fabrication of composites embedding VACNT in organic matrices. The process of growing VACNT exhibits several advantages regarding safety issues: integrating de facto a safe collecting procedure on the substrate, avoiding additional preparation steps and simplifying handling and protection by impregnation into a matrix. The following steps of the overall process: VACNT carpet functionalization, alignment control and impregnation, can be processed on-line in a closed and safe continuous process and lead to dramatically reduced direct nanotube exposure for workers and users. This project opens the route to a continuous, roll-to-roll, safer, cost-effective and green industrial process to manufacture composites with controlled and aligned greener "black" carbon nanotubes.

ConfChem Conference on Educating the Next Generation: Green and Sustainable Chemistry—Teaching Green Chemistry: The Driving Force behind the Numbers!

A special green chemistry course was offered at Grand Valley State University, GVSU, in 2006. Among other assignments, students designed an electronic survey probing the knowledge and the interest in learning about green chemistry. Over 1600 students responded. The responses to the questions “where did you hear about green chemistry” clearly showed the lack of green chemistry inclusion into the curricular program GVSU at that time. Under the driving force of the students’ interest and the imperative need to feel the gap between the traditional content of industrial processes teaching and the principles of green chemistry, we were compelled to change. The result is a new course, Green Chemistry and Industrial Processes, based on green industrial applications. It is a bridge between the principles of green chemistry and industrial processes currently in use, between traditional topics and real-life cases, provided by the global and the local economy. Partnership with local area businesses constitutes an ideal ground for challenging the students’ ability to analyze and understand the existing problems and to develop their critical thinking, while finding creative solutions. This communication summarizes one of the invited papers to the spring 2010 online ConfChem Conference on Educating the Next Generation: Green and Sustainable Chemistry, held from May 7 to June 30, 2010. ConfChem conferences are hosted by the ACS DivCHED Committee on Computers in Chemical Education (CCCE).

Green Process for Adipic Acid Synthesis: Oxidation by Hydrogen Peroxide in Water Micromelusions using Benzalkonium Chloride C12-14 Surfactant

Abstract Adipic acid was synthesized by the oxidation of cyclohexene using 30% hydrogen peroxide in a microemulsion in the presence of sodium tungstate as catalyst. The proposed green process is environmentally friendly since catalyst and surfactant are recycled and pure adipic acid is produced in high yield (70% to 79%). Microemulsions are used as a “green solvent” and give a better contact between the phases. Alkyldimethylbenzylammonium chloride (C12-C14) was used as a surfactant for the generation of the microemulsion since it enables the use of harmful organic solvents and phase-transfer catalysts to be avoided. Optimised operating conditions (temperature, reaction time, separation process) have been defined and applied to evaluate the industrial practicability. The main interest of the present work is the easy recovery of pure adipic acid and the reuse of the reaction media (surfactant and catalyst). This shows promise for developing a future green industrial process that will enable greenhouse gas emissions (N2O), among others, to be reduced.

Clean synthesis of adipic acid from cyclohexene in microemulsions with stearyl dimethyl benzyl ammonium chloride as surfactant: From the laboratory to bench scale

Adipic acid, HOOC(CH2)4COOH, is a white crystalline solid used primarily in the manufacture of nylon-6,6 polyamide. In industry, adipic acid is mainly produced by oxidation of cyclohexane with air and nitric acid following a homogeneous two-step route. However, this process leads to the formation of nitrous oxide, a greenhouse gas that has to be decomposed. The aim of this study was the development of a clean technology at pilot scale in order to obtain and recover pure adipic acid, and the evaluation of its industrial practicability. Adipic acid was synthesized from cyclohexene and hydrogen peroxide in microemulsions with stearyl dimethyl benzyl ammonium chloride as surfactant. The non-polluting catalyst sodium tungstate, which contains no heavy metal, was used and the reaction conducted under mild conditions (85°C, 8h). Yields of up to 81% were reached at the 0.14L scale. However at the end of the reaction the catalyst and the surfactant must be separated and recycled for subsequent cycles. The reuse of the reaction media enabled the conversion to be increased up to 92% but a loss of surfactant and/or catalyst through the cycles progressively reduced the yields. Yields at the bench scale (1.4L) increased during the two first cycles and then decreased to conversions of between 60% and 70%. Globally the yield is a little lower at bench scale. The results obtained show that the synthesis of adipic acid by a heterogeneous one-step oxidation of cyclohexene in the presence of hydrogen peroxide is an attractive route for developing a future green industrial process.

Production and Characteristics of the Whole-Cell Lipase from Organic Solvent Tolerant Burkholderia sp. ZYB002

The thermostable and organic solvent tolerant whole-cell lipase (WCL) was produced by Burkholderia sp. ZYB002 with broad spectrum organic solvent tolerance. The production medium of the WCL was primarily optimized, which resulted in the maximum activity of 22.8 U/mL and the 5.1-fold increase of the WCL yield. The optimized culture medium was as follows (% w/v or v/v): soybean meal 2, soybean oil 0.5, manganese sulfate 0.1, K(2)HPO(4) 0.1, olive oil 0.5, initial pH 6.0, inoculum density 2, liquid volume 35 mL in 250-mL Erlenmeyer flask, and incubation time 24 h. The biochemical characterization of the WCL from Burkholderia sp. ZYB002 was determined, and the results showed that the optimal pH and temperature for lipolytic activity of the WCL was 8.0 and 65°C, respectively. The WCL was stable at temperature up to 70°C for 1 h and retained 79.2% of its original activity. The WCL was highly stable in the pH range from 3.0 to 8.5 for 6 h. Ca(2+), K(+), Na(+), NO (3) (-) , etc. ions stimulated its lipolytic activity, whereas Zn(2+) ion caused inhibition effect. The WCL was also relatively stable in n-butanol at a final concentration of 50% (v/v) for 24 h. However, the WCL was strongly inhibited in Triton X-100 at a final concentration of 10% (v/v). The WCL with thermal resistance and organic solvent tolerance showed its great potential in various green industrial chemical processes.

From Molten Salts to Ionic Liquids: A “Nano” Journey

Ionic liquids (ILs), a special group of classical molten salts, are widely used in various fields of science. Historically, researchers have tested ILs out of curiosity or to improve a specific property in a particular system in many areas of chemistry or materials science. However, today, ILs are far from being simple chemical curiosities and sit at the center of various green industrial innovation processes, where they play important roles in materials extraction, reactive catalytic supports, spatial devices, and biotransformations. In this Account, we describe a journey into a nanostructured universe to better understand the unique properties of ionic liquids and their modern applications. Because molten salts have been known for centuries and have found limited uses, we try to explain why modern nonaqueous ILs deserve increased interest and curiosity. We discuss the characteristics that distinguish modern nonaqueous ILs and compare them with classical molten salts. One of the main differences between room temperature ILs, especially those based on imidazolium cations, and simple molten salts, is the molecular asymmetry built into at least one of the ions. This asymmetry in modern, nonaqueous ILs opposes the strong charge ordering due to ionic interactions that normally would cause the system to crystallize. In addition, the presence of a cooperative network of hydrogen bonds between the cations and anions induces structural directionality (the entropic effect). Therefore, modern ILs form preorganized structures, mainly through hydrogen bonding, that induce structural directionality. In contrast, classical salts form aggregates only through ionic bonds. In other words, weak interactions order the structures in modern ILs while charges order the structure within classical salts. ILs cannot be regarded as merely homogeneous solvents. In fact, ILs form extended hydrogen-bond networks with polar and nonpolar nano domains and therefore are by definition "supramolecular" fluids. Thus, ILs are better described as hydrogen-bonded polymeric supramolecules of the type [(DAI)(m)(X)(m_n))](n+)[(DAI)(m_n)(X)(x))](n-). This structural pattern is a general trend for both the solid and the liquid phase and is apparently maintained to a large extent even in the gas phase. This structural organization of ILs can be used as entropic drivers (the "IL effect") for the preparation of well-defined nanoscale structures with extended order, either in the bulk phase or at the gas/vacuum interface.

Recyclable process for sustainable adipic acid production in microemulsions

Adipic acid is an important industrial intermediate for the manufacture of nylon-6,6. We propose a recyclable and environmentally friendly process for the oxidation of cyclohexene by hydrogen peroxide in microemulsions. These organized nano-structured media have been formulated in using the molecular economy principle. The main interests of the present work are the easy recovery of pure adipic acid and the reuse of the reaction media, what are promising for developing a future green industrial process.

Embedded Phases: A Way to Active and Stable Catalysts

Industrial catalysts are typically made of nanosized metal particles, carried by a solid support. The extremely small size of the particles maximizes the surface area exposed to the reactant, leading to higher reactivity. Moreover, the higher the number of metal atoms in contact with the support, the better the catalyst performance. In addition, peculiar properties have been observed for some metal/metal oxide particles of critical sizes. However, thermal stability of these nanostructures is limited by their size; smaller the particle size, the lower the thermal stability. The ability to fabricate and control the structure of nanoparticles allows to influence the resulting properties and, ultimately, to design stable catalysts with the desired characteristics. Tuning particle sizes provides the possibility to modulate the catalytic activity. Unique and unexpected properties have been observed by confining/embedding metal nanoparticles in inorganic channels or cavities, which indeed offers new opportunities for the design of advanced catalytic systems. Innovation in catalyst design is a powerful tool in realizing the goals of more green, efficient and sustainable industrial processes. The present Review focuses on the catalytic performance of noble metal- and non precious metal-based embedded catalysts with respect to traditional impregnated systems. Emphasis is dedicated to the improved thermal stability of these nanostructures compared to conventional systems.

Catalysis: A key technology for a green approach to pharmaceutical production

Catalysis is the key technology for the development of green processes for the industrial production of active pharmaceutical ingredients. The design of green, efficient and cost competitive industrial process of idarubicin, erlotinib and ivermectin shows the central role of catalysis.

Heterogeneous Catalysts for Highly Selective and Green Industrial Processes and Chemical Transformations

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

The Use of Ultra- and Nanofiltration Techniques in Homogeneous Catalyst Recycling

In recent years, the application of membrane technology in homogeneous catalyst recycling has received widespread attention. This technology offers a solution for the major drawback of homogeneous catalysis, that is, recycling of the catalyst. From both an environmental and an industrial point of view, this technology is very interesting, since it allows the future application of homogeneous catalysts in the synthesis of commercial products, leading to faster, cleaner and highly selective green industrial processes. In this account, an overview is given of the promising results obtained in the field of homogeneous catalyst recycling using nanofiltration membrane technology.