Biomass derived from materials and chemicals pdf

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biomass derived from materials and chemicals pdf

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Biomass is plant or animal material used as fuel to produce electricity or heat. Examples are wood, energy crops and waste from forests, yards, or farms. More often than not, the word biomass simply denotes the biological raw material the fuel is made of. The word biofuel is usually reserved for liquid or gaseous fuels, used for transportation. The U.

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Marilia A. Trapp b. Chemicals commodities and consumable, accounting for billions of ton of carbon per year, are produced in an industry based on non-renewable fossil feedstocks. Oil reserves are enough for feeding chemical industry for another century, and therefore, it is essential finding alternative sources of carbon for a progressive replacement of the industrial feedstock.

In this context lignocellulosic, a renewable source of carbon composed mainly by polymers of sugars, appears as the most promising candidate. Herein, it will be discussed the status, challenges and prospective future of biomass as industrial feedstock in a raising biorefinery, aiming to clarify the real problems in the actual biomass processing.

It will be shown that lignocellulosic biomass is able to replace oil in the production of several chemicals and also delivery new compounds with important applications.

However, for a cost effective use of biomass, the development and improvement of solvent and catalytic systems play a leading role.

The sustainability of biomass feedstock is also discussed from the economical, social and environmental points of view. In the XX century, technology developed in an unprecedented speed, introducing outstanding advances and new products.

Along with the technology, life style has also changed and industry had to be adapted to a growing population with higher purchasing power and new needs. Efficient refineries and petrochemical manufacturing units have been essential for supplying the industry with chemicals and providing the fuels for energy and transportation.

Indeed, fuel is the major petroleum-derived product Figure 1A and the industrial and economical grown are only possible due to the ability of industry in obtaining fuel at high productivity and low cost. For instance, the consumption of gasoline has been systematically rising along with the number of car. In Brazil, the number of automobiles per habitants increased from in to in data from the Brazilian National Department of Traffic and the Brazilian Institute of Geography and Statistics.

They were not available prior to In the USA, the number increased from in to in Figure 2. For instance: the production of the two popular medicines paracetamol acetaminophen and salicylic acid reaches, respectively, approximately 15 and 89 thousand metric tons per year; 4 detergents are produced at a scale of 13 million ton per year data ; 5 and polymers or plastics production reached million metric tons in For sake of brevity, not all reaction steps are shown.

Therefore, the production of petroleum must be large enough to provide, for instance, billions of liters of fuel, millions of tons of detergents and plastics and thousands of tons of medicines.

Current industry has been consistent enough to address new and old needs of a growing society, which would be impossible without an efficient extraction, management and chemical modification of petroleum.

Indeed, modern life, as we know it, relies on petroleum and, therefore, it is not surprising that the consumption of oil-derives have reached high rates in developed and underdevelopment countries.

In Brazil and in the USA, the daily per capita oil consumption is respectively 7. It is alarming, however, that the whole industry is mainly based on non-renewable sources of carbon and the known oil reserves would be enough to feed the actual demand for no longer than years.

In the 's, this type of scenario motivated Brazil to implement of ProAlcohol bioethanol and ProOleo biodiesel programs, 10 which aimed to stimulate the development of new sources of energy, as well as their production and consumption. Although it is clear that an alternative for petroleum is necessary, the changes in chemical industry structure do not come overnight. Therefore, governments, academia and industry have been proposing long term researches to identify reliable and renewable alternative carbon, which can to feed chemical industry with the same products obtained from oil, or at least, different compounds, but with the same applications.

In this critical account, the use of biomass as feedstock for biorefineries will be presented and discussed. Herein, the aim is not delivery a literature review, but presenting an overview of status and challenges on chemical conversion of vegetal feedstocks using examples from the literature. No matter how different plants look, smell or taste, they all have something in common: most of their composition comes from cellulose, hemicellulose and lignin. And this is also valid for the different parts of the plant, such as the stalk, leaf and flower.

Cellulose the major component of biomass is formed by a crystalline polymer of the monosaccharide glucose, while hemicellulose is a polymer of several monosaccharides, but predominantly, the pentose xylose. Lignin, on the other hand, is a polymer of the phenolic units conideryl, coumaryl and syringyl alcohols Figure 3.

With such simple and regular composition, lignocellulosic biomass appears as the most promising renewable carbon source alternative for petroleum. In an applied fashion, sugar cane and corn have been the most used sources of biomass for producing chemicals, and nearly any part of these plants can be used Figure 3.

So, while petroleum is composed mainly by long chain hydrocarbons, biomass is highly functionalized; glucose, for example, has one oxygen atom for each carbon atom. Therefore, the production of fuel and industrial chemicals out of these two feedstocks follows different processing routes Figure 4. Fuels, for example, are hydrocarbons with a defined range of molecular weight.

Hence, the fuel fraction of petroleum can be separated by distillation and enriched through chemical reactions for molecular weight adjusting such as reforming, alkylation and cracking. However, for production of chemicals, the hydrocarbons obtained from petroleum must be functionalized through high energy-consuming processes. In biorefineries, on the other hand, the feedstock presents a polymeric nature, and therefore, the first step involves cracking, chemical or thermo depolymerization.

However, for production of fuels, the highly functionalized intermediates must have their molecular weight adjusted and be completely defunctionalized into hydrocarbon, which seems to demand more energy and chemical modification compared to the fuel production from petroleum.

Contrarily, biomass has an advantage over petroleum for synthesis of functionalized chemicals: it is already functionalized. Therefore, the chemical processes involve only the optimization of functional group type and the functionalization degree. Therefore, it is important to analyze and discuss the chemical potentiality and limitations of the biomass feedstock and understand what type of products it can delivery to the chemical industry.

Transforming these sugar polymers into chemicals can be performed though several routes, including chemical, thermal, and biological. In this account, the chemical and catalyzed conversion of the saccharide fraction of biomass will be the focus of the discussion. Classically, the first step in biomass chemical conversion involves the cellulose or hemicellulose depolymerization by acid catalyzed hydrolysis into the correspondent monosaccharides, which are well established and standardized procedures.

The transformation of these monosaccharides into chemicals can begin with dehydration, oxidation or reduction reactions. In this way, the acid catalyzed dehydration has been the most studied and well-established process Figure 5. Under acid conditions, glucose is dehydrated to 5-hydroxymethylfurfural HMF , which can be subsequently hydrolyzed to levulinic acid LA and formic acid.

Xylose and other natural pentoses such as arabinose and ribose are dehydrated by acid catalysis to furfural. Alternatively, the reduction of glucose and xylose leads, respectively, to sorbitol and xylitol, while the oxidation yields gluconic acid and saccharic acid and xylonic acid and xylaric acid.

These primary products of monosaccharides chemical conversion do not have direct large-scale application, but in the context of biorefinery, they can be intermediates for production of important chemicals, and therefore, they are known as platform molecules.

Indeed, HMF, furfural, levulinic acid, xylitol and sorbitol were listed as the most important bio-based platform molecules obtained from chemical conversion of carbohydrates the other compounds in the list are biochemically obtained.

The potentiality of the platform molecules is related to their flexibility to be transformed in a broad range of chemicals with relevant application.

In order to illustrate this potentiality, some examples of chemical molecules that are obtained from the catalyzed conversion of saccharide-derived platform molecules are shown in Figure 6. In red, molecules also commercially obtained from non-renewable feedstocks. Orange arrows show the reaction pathway that integrates the cellulose and hemicellulose reaction pathways.

Commercially, p -xylene is oxidized to terephthalic acid and then used along with ethyleneglycol for the production of the polyethyleneterephthalate PET , which is commonly used to produce packaging. Alternatively, HMF can be oxidized with platinum, palladium and gold-based catalysts into 2,5-furandicarboxylic acid FDCA , a bio-based monomer that can accordingly replace terephthalic acid in the production of polymers.

PEF polymer has also improved properties for packing and bottles applications compared to PET, such as: lower permeability to water, oxygen, and carbon dioxide which guarantees the quality and freshness of the product for longer time ; and better thermal and mechanical properties, allowing a broader range of application. Therefore, the implementation of a biorefinery does not imply in a complete change on chemical industry. Besides being an promising polymer, FDCA can also be converted, though reduction, to adipic acid, an important monomer for the production of Nylon.

Since cellulose is the major component in biomass, its reaction roadmap was thoroughly studied; therefore, connecting cellulose and hemicellulose reaction roadmaps is particularly interesting. The common species in both roadmaps is the levulinic acid LA Figure 6 , orange arrows , which can be produced from hemicellulose, by hydrogenation of furfural to furfuryl alcohol that is then hydrolyzed to LA.

However, handling furfuryl alcohol is complicated, since it is extremely reactive to polymerization under temperature, light and acid catalysis conditions. LA can be also produced directly from cellulose, which is significantly simpler and only requires acid catalysis. Recently, it has been shown that lactic acid esters can be directly obtained from biomass-derived sugars by retro-aldol condensation using Lewis acid catalysts.

The aforementioned processes are just some of many examples that prove how significant platform molecules produced from cellulose and hemicellulose can be as alternatives for fossil-based processes and products. It is noticeable that most of the biomass derived molecules are based on furans Figure 6 , or carbon acyclic compounds.

Obtaining aromatics from saccharide-derived compounds depends mainly on the Diels-Alder reaction between furans and ethylene. Aromatics are highly important intermediates in the chemical industry, and classically obtained in refineries as the so called BTX benzene, toluene and xylenes. Although the research on Diel-Alder of furans for the production of aromatics has been intensified in the last few years, 57 - 62 this chemical route is too expensive and energy demanding to become commercial.

As it regards the production of aromatics, lignin is the most promising feedstock. In a chemical process, there is no perfect solvent. Separating the product from the solvent, as well as, purifying, reusing or disposing the solvent will always add costs to the process.

From the sustainability and also green chemistry point of view, the best approach would be using no solvent, however, many liquid phase reactions need a solvent either because the reactants are solid, or because the reaction performance is improved.

Water is the first option as solvent, since it is cheap and can be safely disposed. The conversion of monosaccharides can indeed be performed in water.

However, the product yields are systematically low. The separation of the product from these high boiling point solvents is a challenge, mainly, because HMF is prone to decomposition and polymerization at high temperature. Ionic liquids 79 , 80 or ionic liquids-like 81 systems also lead to an outstanding HMF productivity, however, once again separation and isolation of the product is an issue.

Furthermore, ionic liquids are expensive and deactivated in the presence of water reaction byproduct, besides water is inherently wet. HMF at high yields was produced using a biphasic solvent system formed by: i an aqueous and ii an organic extracting layer. Although the chemical reaction takes place in the aqueous phase, once formed, HMF is extracted to the organic layer and then preserved from degradation. Switching from homogeneous to heterogeneous catalysis represents an important breakthrough in this field, and the solvent system has to follow this trend.

In the context of biorefinery, ideally, biomass-derived solvents with low toxicity should be preferred, and good hints on possible aprotic biomass derived solvents are shown in Figure 6 : furans and lactones, such as tetrahydrofuran THF , methyltetrahydrofuran MTHF , DMF and GVL. Although monosaccharides are not soluble in these solvents, the addition of small amounts of water except for DMF, not miscible with water allows sugar solubility and the formation of a single-phase solvent system.

Another interesting approach for a sustainable use of solvents in the biomass conversion is turning the reactions products into the own reaction solvent, eliminating, therefore, separation steps. Reproduced with permission. Indeed, GVL has been proposed as an important solvent for biomass conversion, mainly during sugar conversion steps.

Many examples Table 1 have shown a significant improvement in the product yield when using GVL with water as co-solvent instead of pure water as solvent for: i the conversion of raw biomass into soluble sugars; 85 - 87 ii glucose or fructose to HMF; 73 , 74 iii cellulose to LA 26 and iv hemicellulose or xylose to furfural.

The value presents were obtained by summing the yield for soluble mono- and polysaccharides;. Therefore, the product yields tend to be higher in the presence of the aprotic solvent DMSO because: i its interaction with the fructose hydroxyl groups prevents deprotonation, and consequently, polymerization to undesirable products and ii its interaction with the HMF hydroxyl groups prevents rehydration, which could lead to the undesirable humins.

Another important effect of DMSO is increasing the fructose dehydration reaction rate. It has been found that the slowest steps of the reaction involve intramolecular hydride transfer, requiring a reorganization of the polar solvent environment and the solvation of asymmetrically distributed electronic charges.

Therefore, the presence of a solvent with a dielectric constant lower than water, such as DMSO, can accelerate the reaction.

U.S. Energy Information Administration - EIA - Independent Statistics and Analysis

China E-mail: chemwy zju. The explosive growth of energy consumption demands highly efficient energy conversion and storage devices, whose innovation greatly depends on the development of advanced electrode materials and catalysts. Among those advanced materials explored, carbon materials have drawn much attention due to their excellent properties, such as high specific surface area and tunable porous structures. Challenges also come from global warming and environmental pollution, which leads to the requirement of sustainable carbon-rich precursors for carbon materials. Hence, the use of biomass for carbon materials features the concepts of green chemistry. This review summarizes the most advanced progress in biomass-derived carbons for use in fuel cells, electrocatalytic water splitting devices, supercapacitors and lithium-ion batteries. Several synthetic strategies for synthesizing biomass-derived carbons, including direct pyrolysis, hydrothermal carbonization, and ionothermal carbonization, have been reviewed, and the corresponding formation mechanisms and prospects are also discussed.

Biomass-derived carbon materials B-d-CMs are considered as a group of very promising electrode materials for electrochemical energy storage EES by virtue of their naturally diverse and intricate microarchitectures, extensive and low-cost source, environmental friendliness, and feasibility to be produced in a large scale. However, the practical application of raw B-d-CMs in EES is limited by their relatively rare storage sites and low diffusion kinetics. In recent years, various strategies from structural design to material composite manipulation have been explored to overcome these problems. In this review, a controllable design of B-d-CM structures boosting their storage sites and diffusion kinetics for EES devices including SIBs, Li-S batteries, and supercapacitors is systematically summarized from the aspects of effects of pseudographic structure, hierarchical pore structure, surface functional groups, and heteroatom doping of B-d-CMs, as well as the composite structure of B-d-CMs, aiming to provide guidance for further rational design of the B-d-CMs for high-performance EES devices. With the explosive growth of global economy and population, the energy consumption worldwide has attracted more and more attention [ 1 ]. The extensive use of fossil fuels has not only led to its depletion but also brought about severe environmental problems such as global warming, forest damage, air pollution, and acid rain [ 2 , 3 ].

Biorefinery: From Biomass to Chemicals and Fuels

Biofuel is fuel that is produced through contemporary processes from biomass , rather than by the very slow geological processes involved in the formation of fossil fuels , such as oil. Since biomass technically can be used as a fuel directly e. The word biofuel is usually reserved for liquid or gaseous fuels, used for transportation. The U.

Char and Carbon Materials Derived from Biomass: Production, Characterization and Applications provides an overview of biomass char production methods pyrolysis, hydrothermal carbonization, etc. In addition, the book includes a discussion of the various properties of biomass chars and their suitable recovery processes, concluding with a demonstration of applications. As biomass can be converted to energy, biofuels and bioproducts via thermochemical conversion processes, such as combustion, pyrolysis and gasification, this book is ideal for professionals in energy production and storage fields, as well as professionals in waste treatment, gas treatment, and more. Researchers and engineers in the field of materials for renewable energy, agriculture, fuel processing, and environmental science.

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 Набросок или отшлифованный до блеска экземпляр, - проворчал Джабба, - но он дал нам под зад коленом. - Не верю, - возразила Сьюзан.  - Танкадо был известен стремлением к совершенству. Вы сами это знаете. Он никогда не оставил бы жучков в своей программе. - Их слишком много! - воскликнула Соши, выхватив распечатку из рук Джаббы и сунув ее под нос Сьюзан.  - Смотрите.

Позвоните Танкадо. Скажите, что вы согласны на его условия. Нам нужен этот шифр-убийца, или все здесь провалится сквозь землю. Все стояли не шелохнувшись. - Да вы просто с ума все сошли, что ли? - закричал Джабба.

 Нет, - сконфуженно ответила .


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