Biodiesel from lignocellulosic biomass – Prospects and challenges

Biodiesel can be a potential alternative to petroleum diesel, but its high production cost has impeded its commercialization in most parts of the world. One of the main drivers for the generation and use of biodiesel is energy security, because this fuel can be produced from locally available resources, thereby reducing the dependence on imported oil. Many countries are now trying to produce biodiesel from plant or vegetable oils. However, the consumption of large amounts of vegetable oils for biodiesel production could result in a shortage in edible oils and cause food prices to soar. Alternatively, the use of animal fat, used frying oils, and waste oils from restaurants as feedstock could be a good strategy to reduce the cost. However, these limited resources might not meet the increasing demand for clean, renewable fuels. Therefore, recent research has been focused the use of residual materials as renewable feedstock in order to lower the cost of producing biodiesel. Microbial oils or single cell oils (SCOs), produced by oleaginous microorganisms have been studied as promising alternatives to vegetable or seed oils. Various types of agro-industrial residues have been suggested as prospective nutritional sources for microbial cultures. Since the most abundant residue from agricultural crops is lignocellulosic biomass (LCB), this byproduct has been given top-priority consideration as a source of biomass for producing biodiesel. But the biological transformation of lignocellulosic materials is complicated due to their crystalline structure. So, pretreatment is required before they can be converted into fermentable sugar. This article compares and scrutinizes the extent to which various microbes can accumulate high levels of lipids as functions of the starting materials and the fermentation conditions. Also, the obstacles associated with the use of LCB are described, along with a potentially viable approach for overcoming the obstacles that currently preclude the commercial production of biodiesel from agricultural biomass.     

Novel Polymeric Materials from Biological Oils

A variety of novel polymeric materials ranging from elastomers to tough, rigid plastics have been prepared by the cationic copolymerization of regular soybean oil, low-saturation soybean oil, or conjugated low-saturation soybean oil with various alkene commonomers. Using appropriate compositions and reaction conditions, 70–100% of the soybean oil is covalently incorporated into the cross-linked polymer networks, contributing significantly to cross-linking during copolymerization. The resulting thermosets exhibit thermophysical and mechanical properties that are competitive with those of their petroleum-based counterparts. In addition, good damping and shape memory properties have been obtained by controlling the degree of cross-linking and the rigidity of the polymer backbone. New materials with similar characteristics have also been produced from other biological oils, including tung, and fish oils using the same technique. The new, more valuable properties of these bioplastics suggest numerous promising applications of these novel polymeric materials.     

Survey on readability of online information for upgrading understandability of biomass energy technology

Waste management contributes to renewable energy such as biodiesel production from processes of various types of biomass including vegetable oils, animal fats, and waste of edible oil. Successful waste management effort is influenced by people concern about benefit of waste management including for renewable energy from biomass. It involves their understanding initiated by literacy on biomass energy. To help increase literacy on waste recycle and biomass energy technology, we study readability of online information regarding biomass energy in Indonesian language (Bahasa Indonesia). Indonesia is considered as one of biomass-rich country with a little utilization for energy. The readability is studied by combining two approaches: measurement by readability standard and survey on readability confirming measurement by the standard. This study focuses on the confirmation survey readability standard measured on biomass online information in Indonesian language. In the survey, 19 online text materials were read by respondents and they were asked to give their impression whether the texts are easy or difficult to understand. From this study, what factors influence understandability of text information are shown. The results could be a guidance for preparing text information to raise people concern on waste recycle and renewable energy in general.     

Converting waste expanded polystyrene into polymeric azo dyes containing the sulfonamide group

Using waste expanded polystyrene as raw materials, a series of polymeric azo dyes containing the sulfonamide group were prepared by chlorosulfonation, amidation, hydrolysis, diazotization and coupling reactions in this study. The main influence factors of each step reaction were discussed and the proper reaction conditions were obtained. The polymeric azo dyes prepared showed good thermal stabilities, and their 5 % weight loss temperatures were all higher than 350 °C. These polymeric dyes could solve in toluene at the room temperature. They showed different maximum absorption wavelengths in the ultraviolet–visible region and gave various colors. The relationships between colors and molecular structures of polymeric dyes were investigated. These polymeric azo dyes prepared have potential applications in dyeing polymer materials, such as plastic and fiber.     

Enhanced anaerobic bioremediation of chlorinated solvents utilizing vegetable oil emulsions

The use of vegetable oil as an electron donor to enhance the reductive dechlorination of chlori‐nated solvents as an in situ remediation technology is gaining significant traction. Vegetable oil is a cost‐effective slow‐release electron donor with greater hydrogen‐release efficiency than other electron‐donor products. However, neat vegetable oil can inhibit distribution in aquifers due to the oil droplets blocking the flow of groundwater through the smaller pore spaces in the aquifer materials. This issue has been partially overcome by applying the vegetable oil as an oil‐water emulsion, which typically is created in the field. However, the field preparation results in a mixture of droplet sizes, including larger droplets that can make the emulsions unstable and reduce the soil permeability by blocking soil‐pore throats with oil. RNAS, Inc., has developed a kinetically sta‐ble soybean oil emulsion (“Newman Zone”) consisting of submicron droplets with less droplet‐size variation than field‐prepared emulsions. This product is composed of a blend of fast‐release (sodium lactate) and slow‐release (soybean oil) electron donors. The emulsion is produced in a stable factory environment in which it is pasteurized and packaged in sterile packaging. This ma‐terial can be utilized as an electron donor without further treatments or amendments in the field. This article discusses factors associated with selecting electron donors and the development of vegetable oil–based products. A case study of an application of Newman Zone at a former adhe‐sives manufacturing facility is then presented. The case study demonstrates the effect of Newman Zone in reducing chlorinated solvent concentrations in groundwater by both rapidly stimulating initial microbial activity and supporting long‐term reductive dechlorination with a slow‐release electron donor. © 2006 Wiley Periodicals, Inc.     

Ability of Fungal Strains to Degrade PVA Based Materials

The aim of this work was to select a fungal strain with degradative potential upon PVA based materials. The polymeric materials tested were PVA films which contain different percentages of PVA, starch and glycerol. These materials are of interest for food packaging applications, which presume to solve the problems concerning accumulation, disposal and degradation. Eleven strains were tested in solid culture for the ability to use PVA based composites as carbon and energy sources. The fungal strain selected was cultivated in liquid medium with different compositions. The scanning electron microscopy (SEM) investigations revealed the effects of microorganism growth upon polymeric films. Significant changes in polymer surface aspects were observed depending on the medium culture composition, the presence of supplementary carbon source facilitating microbial growth and degradation process.     

Polyols and Polyurethanes from Hydroformylation of Soybean Oil

This paper compares physical and mechanical properties of polyurethanes derived via the hydroformylation approach and is a part of our study on the structure–property relationships in polyurethanes created from vegetable oils. The double bonds of soybean oil are first converted to aldehydes through hydroformylation using either rhodium or cobalt as the catalyst. The aldehydes are hydrogenated by Raney nickel to alcohols, forming a triglyceride polyol. The latter is reacted with polymeric MDI to yield the polyurethane. Depending on the degree of conversion, the materials can behave as hard rubbers or rigid plastics. The rhodium-catalyzed reaction afforded a polyol with a 95% conversion, giving rise to a rigid polyurethane, while the cobalt-catalyzed reaction gives a polyol with a 67% conversion, leading to a hard rubber having lower mechanical strengths. Addition of glycerine as a cross-linker systematically improves the properties of the polyurethanes. The polyols are characterized by DSC. The measured properties of polyurethanes include glass transition temperatures, tensile strengths, flexural moduli, and impact strengths.     

Methodology to Assess Silicone (Bio)Degradation and its Effects on Microbial Diversity

The behavior of silicone elastomers in landfills has not been well studied. Their impact on the environment is not known and, consequently, it has not been possible to establish robust Life Cycle Assessments of these materials. In the first part of this study, a methodology for assessing silicone degradation pathways is described. The chemical and biological parameters were considered separately. Firstly, parameters such as pH, redox potential and cation concentration were monitored and then degradation in aerobic and anaerobic conditions was investigated. Any impacts on microbial diversity were also taken into account, using bio-molecular tools. In the second part, a case study on the degradation of Room Temperature Vulcanizable silicone elastomers was performed to validate this methodology. The results indicate that condensation catalysts play a key role at their end-of-life, in both chemical and biological degradation. Moreover, these compounds have a significant effect on microbial communities (similarities with blank samples <5?%). As a consequence, the choice of catalyst should be carefully considered to assess any environmental impacts.     

Methods Currently Used in Testing Microbiological Degradation and Deterioration of a Wide Range of Polymeric Materials with Various Degree of Degradability: A Review

Biodegradation of polymeric materials affect a wide range of industries, information on degradability can provide fundamental information facilitating design and life-time analysis of materials. Among the methods currently used in testing, traditional gravimetric and respirometric techniques are tailored to readily degradable polymeric materials mostly and polymer blends with biodegradable components, but they are not applicable to the new generation of engineering polymers which are relatively resistant to biodegradation. However, electrochemical impedance spectroscopy (EIS) has been tested for monitoring biodeterioration of high strength materials and the technique has very high sensitivity. A wide range of materials including electronic insulation polyimides, fiber-reinforced polymeric composites (FRPCs) and corrosion protective polyurethane coatings have been successfully measured under inoculation of degradative microorganisms using EIS. In addition, the mechanism of degradation of high strength polymers is mainly due to the presence of plasticizers in the polymer matrices. The information on various methods discussed in this review is intended to illustrate a suite of methods for those who are interested in testing biodeterioration of polymeric materials under different environmental conditions and in selecting appropriate techniques for specific applications.     

Dynamic Mechanical Properties of Soy Protein Filled Elastomers

Dynamic mechanical properties including temperature effect, stress softening, and Payne effect are studied on the elastomer composites filled with soy protein or carbon black. The comparison of protein composite with well-known carbon black composites provides further insight into the protein composites. The elastomers filled with soy protein aggregates give substantial reinforcement effect when compared with the unfilled elastomers. Approximately 400 times increase in shear elastic modulus was observed when 40% by weight of protein is incorporated into the elastomers. The sample films were cast from the particle dispersion of soy protein isolate and carboxylated styrene–butadiene latex. At the higher temperatures, the shear elastic modulus of soy protein-filled composites does not decrease as much as that of the carbon black-filled composites. The behavior of elastic and loss modulus under the oscillatory strain of different magnitude is similar to that of carbon black reinforced styrene–butadiene rubber. However, carbon black composites show a better recovery behavior after eight cycles of dynamic strain. The reduction of shear elastic modulus with dynamic strain (Payne effect) was compared with Kraus model and the fitting parameter related to the aggregate structure of the soy protein. A reasonable agreement between the theoretical model and experiment was obtained, indicating the Payne effect of the protein-related network structure in the elastomers could also be described by the kinetic agglomeration de-agglomeration mechanism.     

A respirometric method to measure mineralization of polymeric materials in a matured compost environment

A respirometric method was developed to measure the mineralization of polymeric materials in a matured compost environment. For the purpose of evaluating the method, results obtained for the mineralization of glucose and cellulose are presented. The matured compost, in addition to supplied nutrients, micronutrients, and an inoculum, serves as the matrix which supports the microbial activity. Recovery of the substrate carbon in the form of carbon dioxide from the glucose and cellulose added to test vessels was 68 and 70%, respectively. A statistical evaluation of the results obtained on substrate mineralization was carried out and showed acceptable reproducibility between replicate test vessels and test runs. The testing protocol developed has the following important characteristics: (1) the test reactors are maintained at 53 °C at a high solids loading (60% moisture), which has certain characteristics that are similar to a thermophilic compost environment; (2) the test matrix providing microbial activity is derived from readily available organic materials to facilitate reproducibility of the method in different laboratories; (3) the equipment required to perform this test is relatively inexpensive; and (4) the information obtained on polymer mineralization is vital to the study and development of biodegradable polymeric materials.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Emission of Volatiles from Polymers — A New Approach for Understanding Polymer Degradation

Emission of low molar mass compounds from different polymeric materials was determined and the results from the volatile analysis were applied to predict the degree of degradation and long-term properties, to determine degradation rates and mechanisms, to differentiate between biotic and abiotic degradation and for quality control work. Solid-phase microextraction and solid-phase extraction together with GC-MS were applied to identify and quantify the low molar mass compounds. Volatiles were released and monitored at early stages of degradation before any matrix changes were observed by e.g. SEC, DSC and tensile testing. The analysis of volatiles can thus also be applied to detect small differences between polymeric materials and their susceptibility to degradation. The formation of certain degradation products correlated with the changes taking place in the polymer matrix, these indicator products could, thus, be analysed to rapidly predict the degree of degradation in the polymer matrix and further to predict the long-term properties and remaining lifetime of the product.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.     

Analysis of the relation between the cellulose,hemicellulose and lignin content and the thermal behavior of residual biomass from olive trees

The heterogeneity of biomass makes it difficult if not impossible to make sweeping generalizations concerning thermochemical treatment systems and the optimal equipment to be used in them. Chemical differences in the structural components of the biomass (cellulose, hemicellulose, and lignin) have a direct impact on its chemical reactivity. The aim of this research was to study the influence of the organic components of the raw material from olive trees (leaves, pruning residues, and wood) in the combustion behavior of this biomass, as well as to find the component responsible for the higher ash content of olive leaves. Accordingly, the study used a thermogravimetric analyzer to monitor the different states and complex transitions that occurred in the biomass as the temperature varied. The decomposition rates of the different samples were analyzed in order to establish a link between each combustion phase and the composition of the raw materials. Two methods were used to determine the hemicellulose and cellulose contents of biomass from olive trees. Significant differences among the results obtained by the different methods were observed, as well as important variations regarding the chemical composition and consequently the thermal behavior of the raw materials tested.     

Potential of chicken by-products as sources of useful biological resources

By-products from different animal sources are currently being utilised for beneficial purposes. Chicken processing plants all over the world generate large amount of solid by-products in form of heads, legs, bones, viscera and feather. These wastes are often processed into livestock feed, fertilizers and pet foods or totally discarded. Inappropriate disposal of these wastes causes environmental pollution, diseases and loss of useful biological resources like protein, enzymes and lipids. Utilisation methods that make use of these biological components for producing value added products rather than the direct use of the actual waste material might be another viable option for dealing with these wastes. This line of thought has consequently led to researches on these wastes as sources of protein hydrolysates, enzymes and polyunsaturated fatty acids. Due to the multi-applications of protein hydrolysates in various branches of science and industry, and the large body of literature reporting the conversion of animal wastes to hydrolysates, a large section of this review was devoted to this subject. Thus, this review reports the known functional and bioactive properties of hydrolysates derived from chicken by-products as well their utilisation as source of peptone in microbiological media. Methods of producing these hydrolysates including their microbiological safety are discussed. Based on the few references available in the literature, the potential of some chicken by-product as sources of proteases and polyunsaturated fatty acids are pointed out along with some other future applications.     

Tests for the evaluation of ammonium attenuation in MSW landfill leachate by adsorption into bentonite in a landfill liner

Uncontrolled leachate emissions are one of the key factors in the environmental impact of municipal solid waste (MSW) landfills. The concentration of ammonium, given the anaerobic conditions in traditional landfills, can remain significantly high for a very long period of time, as degradation does not take place and volatilisation is not significant (the pH is not high enough to considerably shift the equilibrium towards un-ionised ammonia). Recent years have witnessed a continuous enhancement of landfill technology in order to minimize uncontrolled emissions into the environment; bottom lining systems have been improved and more attention has been devoted to the study of the attenuation of the different chemicals in leachate in case of migration through the mineral barrier. Different natural materials have been considered for use as components of landfill liners in the last years and tested in order to evaluate the performance of the different alternatives. Among those materials, bentonite is often used, coupled with other materials in two different ways: in addition to in situ soil or in geocomposite clay liner (GCL). A lab-scale test was carried out in order to further investigate the influence of bentonite on the attenuation of ammonium in leachate passing through a landfill liner. Two different tests were conducted: a standardized batch test with pulverized bentonite and a batch test with compacted bentonite. The latter was proposed in order to better simulate the real conditions in a landfill liner. The two tests produced values for the partition coefficient K(d) higher than the average measured for other natural materials usually utilized as components of landfill liners. Moreover, the two tests showed similar results, thus providing a further validation of the suitability of the standard batch test with pulverized bentonite. A thorough knowledge of attenuation processes of ammonium in landfill liners is the basis for the application of risk analysis models for the evaluation of the failure of bottom liners or their components.     

Comparison of batch leaching tests and influence of pH on the release of metals from construction and demolition wastes

Construction and demolition wastes are suitable for use in road construction. However, leaching characterization of recycled materials is required to determine their pollutant potential and the consequence of their application in different scenarios. The motivation of this paper is derived from the increasing use of different leaching test methods. In Europe, the confusion resulting from the wide variety of tests used to evaluate environmental properties of construction materials implies that an evaluation of the current practices and the attempt to consolidate the approaches are required.Two equilibrium-based leaching tests (the Dutch test and the European standard) were conducted to assess the environmental impact of four recycled aggregates. Three natural limestone aggregates were used as controls. Both tests measure the potential release of hazardous elements under extreme conditions using different leaching parameters (L/S ratio, pH value and contact time). The results proved that pH is the most relevant factor on the assessment of the differences between leaching methods due to its strong control on the pollutant release.To classify the materials according to their environmental effects, the concentration limit values of the metals imposed by Council Decision 2003/33/EC were used as a reference. The comparison allowed the classification of the recycled aggregates as inert wastes, with the exception of the MR-2 aggregate, which was classified as non-hazardous material.     

Crop‐based systems for sustainable risk‐based land management for economically marginal damaged land

The increasing need for biomass for energy and feedstocks, along with the need to divert organic methane generating wastes from landfills, may provide the economic leverage necessary to return this type of marginal land to functional and economic use and is strongly supported by policy at the European Union (EU) level. The use of land to produce biomass for energy production or feedstocks for manufacturing processes (such as plastics and biofuels) has, however, become increasingly contentious, with a number of environmental, economic, and social concerns raised. The REJUVENATE project has developed a decision support framework to help land managers and other decision makers identify potential concerns related to sustainability and what types of biomass reuse for marginal land might be possible, given their particular circumstances. The decision‐making framework takes a holistic approach to decision making rather than viewing biomass production simply as an adjunct of a planned phytoremediation project. The framework is serviceable in Germany, Sweden, and the United Kingdom. These countries have substantive differences in their land and biomass reuse circumstances. However, all can make use of the set of common principles of crop, site, value, and project risk management set out by REJUVENATE. This implies that the framework should have wider applicability across the EU. This article introduces the decision support framework. © 2011 Wiley Periodicals, Inc.     

Water Remediation: PVA-Based Magnetic Gels as Efficient Devices to Heavy Metal Removal

Scientific and technological researches are devoted to obtain materials capable of retaining different kinds of pollutants, contributing to contamination solutions. In this context, hydrogels have emerged as great candidates because of their excellent absorption properties as well as good mechanical, thermal and chemical properties. More specifically, ferrogels (magnetic gels) present the extra advantage of being easily manipulated by a permanent magnet. Here, we present the results derived from the application of ferrogels as efficient tools to extract heavy metal pollutants from wastewater samples. The gels were prepared following the method of freezing and thawing of a polyvinyl alcohol aqueous solution with magnetic nanoparticles coated with polyacrylic acid. Ferrogels were fully characterized and their ability to retain Cu²⁺ and Cd²⁺, as model heavy metals, was studied. Thus kinetics and mechanisms of adsorption were evaluated and modeled. The concentration of MNPs on the PVA matrix was key to improve the adsorption capability (approximately the double of retention is improved by the MNPs addition). The adsorption kinetics was determined as pseudo-second order model, whereas the Langmuir model was the most appropriate to explain the behavior of the gels. Finally reuse ability was evaluated to determine the real potential of these materials, the ferrogels demonstrated high efficiency up to about five cycles, retaining about 80–90% of their initial adsorption capability. All the results indicated that the materials are promising candidates able to compete with the commercial technology regarding to water remediation.