Fossil Raw Materials Research Articles

Design of reactive distillation processes for the production of butyl acrylate: Impact of bio-based raw materials

The chemical industry is nowadays predominantly using fossil raw materials, but the alternative use of bio-based resources is investigated to account for the foreseeable scarcity of fossil feedstocks. A main challenge of using bio-based feedstocks is the complexity of the impurity profile. For an economic production of bio-based chemicals, the use of intensified processes is inevitable and approaches are needed for the various process intensification techniques to identify their applicability to be used for the production of bio-based components. In the presented study, an approach is shown for the reactive distillation (RD) technology to identify the most critical bio-based impurities and their impact on the reactive distillation process. The investigated case-study is the production of n-butyl acrylate from acrylic acid and n-butanol. Among all initially identified impurities, the key impurities, having the biggest impact on the product purity in the reactive distillation process, are found. These impurities are then studied in more detail and an operating window depending on the impurity concentration is identified for the reactive distillation column. Furthermore, an integrated design of upstream and downstream processes is facilitated, as the presented results can be used in the development of the fermentation processes for the production of the bio-based reactants by decreasing the concentration of the critical impurities.

RAPE SEED OIL TETRAHYDROFURFURYLESTERS

The transesterification of vegetable oil using various kinds of alcohols is a simple and efficient renewable fuel synthesis technique. Products obtained by modifying natural triglycerides in transesterification reaction substitute fossil fuels and mineral oils. Currently the most significant is the biodiesel, a mixture of fatty acid methyl esters, which is obtained in a reaction with methanol, which in turn is obtained from fossil raw materials. In biodiesel production it would be more appropriate to use alcohols which can be obtained from renewable local raw materials. Ethanol rouses interest as a possible reagent, however, its production locally is based on the use of grain and therefore competes with food production so it would implicitly cause increase in food prices. Another raw material option is alcohols that can be obtained from furfurole. Furfurole is obtained in dehydration process from pentose sugars which can be extracted from crop straw, husk and other residues of agricultural production. From furfurole the tetrahydrofurfuryl alcohol (THFA), a raw material for biodiesel, can be produced. By transesterifying rapeseed oil with THFA it would be possible to obtain completely renewable biodiesel with properties very close to diesel [2-4]. With the purpose of developing the synthesis of such fuel, in this work a three-stage synthesis of rapeseed oil tetrahydrofurfurylesters (ROTHFE) in sulphuric acid presence has been performed, achieving product with purity over 98%. The most important qualitative factors of ROTHFE have been determined - cold filter plugging point, cetane number, water content, Iodine value, phosphorus content, density, viscosity and oxidative stability.

Thermal Conductivity of Hemp Based Boards

<p class="R-AbstractKeywords"><span lang="EN-US">Energy and raw material costs, an increase in environmental pollution, greenhouse gas emissions, global warming, depletion of fossil raw materials stimulate to seek and study alternatives to the synthetic fibers and products made of them for full or partial replacement. Renewable raw materials, including natural fiber sources, are the future of storage resources with a variety of positive effects on both the planet ecosystem and the living and working environment, and the energy consumption of delivering the required functionality. One of the most important energy-saving types is to reduce energy consumption in buildings by insulating them.</span></p><p class="R-AbstractKeywords"><span lang="EN-US">For Latvian conditions suitable crops are historically grown flax and hemp. Within the framework of the studies, hemp stems are being used. Hemp compared with flax, are less suffering from diseases and less damaged by pests, so hemp cultivation is practically free from use of chemical pesticides and herbicides reducing the risk to the ecosystem.</span></p><p class="R-AbstractKeywords"><span lang="EN-US">One of the most frequently mentioned industrial hemp raw materials positive qualities are their very wide use, practically all plant parts can be used in production of different products. This work explores the possibilities and technologies within the Latvian grown hemp stems to work into board materials with insulation capability.</span></p><p class="R-AbstractKeywords"><span lang="EN-US">Hemp fibers/shives mix boards can fulfill the main function of insulation materials, i.e., to reduce the transmission of heat, because they have a porous structure and low density. Material thermal insulation properties affect physical and structural properties of compounds. Cost effective particles board samples from chopped hemp stems with three types of adhesives and different thicknesses were produced and their thermal conductivity evaluated. The technologies applied and test results will be discussed in the paper. </span></p>

ChemInform Abstract: Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum‐Based Processes

AbstractReview: 444 refs.

Evaluation of Bast Fibres of the Stem of Carica papaya L. for Application as Reinforcing Material in Green Composites

Aims: The production of green composites based on natural fibres is rising with regard to increasing environmental problems and declining fossil raw materials. Bast fibres of papaya (Carica papaya L.) accumulate on plantations at a large scale but remain an unused resource. The characterisation of the bast allows a first evaluation of the potential of papaya-fibres for use in composites. Study Design: Material testing. Place and Duration of Study: Institute for Botany, Technische Universitat Dresden and Original Research Article Kempe et al.; ARRB, 6(4): 245-252, 2015; Article no.ARRB.2015.082 246 Fraunhofer Institute for Nondestructive Testing Dresden (IZFP-D), 2011 and 2013. Methodology: The anatomic structure of fibre cells and the microfibril angle of the cell walls were determined as well as a chemical analysis to determine the proportion of cellulose, lignin and hemicelluloses of the fibre cells. In addition, samples of fibres were subjected to static uniaxial tension tests revealing Young's modulus, tensile strength and breaking strain at different plant ages and of two origins. Results: Fibres of a two-year-old plant exhibited a Young's modulus of 10.7 GPa, a tensile strength of 101 MPa and a breaking strain of 1.2%, on average. Fibres from six-months-old plants, grown under greenhouse conditions had a mean Young's modulus of 4.4 GPa, tensile strength of 49 MPa and a breaking strain of 1.4%. Having one of the lowest fibre densities with ca. 0.85 g/cm3, papaya fibres exhibit noteworthy specific mechanical properties among all studied natural fibers. Conclusion: These data allow us a first estimation for a potentail use in green composites as reinforcing material.

Transiting from Adipic Acid to Bioadipic Acid. 1, Petroleum-Based Processes

Adipic acid, which is a very important commodity chemical, is traditionally manufactured industrially by an aged and unsustainable multistep process that involves homogeneous catalysts, aggressive oxidants (concentrated nitric acid) and the production of large quantities of the greenhouse gas nitrous oxide. Much research and development into alternative and cleaner process routes to adipic acid have been carried out over the past 70 years. Improved reaction schemes have invoked variations in fossil raw materials (from benzene and phenol to cyclohexane, cyclohexanol, cyclohexanone, cyclohexene, butadiene, and adiponitrile, etc.), oxidants (O2, air, H2O2, t-BuOOH, ozone), catalysts (homogeneous, heterogeneous, phase transfer, biomimetic) and reaction conditions (low temperature, atmospheric pressure, and solvent-, metal-, halide-, and corrosion-free). No single proposed alternative pathway—some of which are purely academic—simultaneously addresses the problems of petrochemical origin, toxic starting materials or reagents, generation of environmentally incompatible byproducts, use of forcing reaction conditions, and cost in an entirely satisfactory manner, despite very intense efforts. Recently, more benign bio-based reaction pathways have been proposed starting from renewables, such as glucose or vegetable oils (which will be discussed in Part 2 of this series).

Value-added industrial products from bast fiber crops

Lignocellulosic crops like kenaf, flax and hemp have been extensively studied the last years with the help of new technology and many new products fabricated with them are ready for the market or have already been marketed. Both the core material and the bast fibers of these crops are ideal feedstocks for the production of yarns and paper of high quality, for rendering flame retardant properties to composites reinforced with them, for the production of energy via a sustainable way without polluting the environment and for use as alternative materials to wood for the manufacturing of panels like particleboards and fiber boards (MDF, HDF, etc.). The investigation of lignocellulosic feedstock as potential source for the sustainable production of materials, products and energy has resulted in promising solutions for the successful replacement of their counterparts made from fossil raw materials. However, the related industries still have some challenges to face, like the cost of materials from lignocellulosic plants in comparison with those derived from fossil sources and the availability of the feedstock throughout the year.

Take a closer look: biofuels can support environmental, economic and social goals.

The US Congress passed the Renewable Fuels Standard (RFS) seven years ago. Since then, biofuels have gone from darling to scapegoat for many environmentalists, policy makers, and the general public. The reasons for this shift are complex and include concerns about environmental degradation, uncertainties about impact on food security, new access to fossil fuels, and overly optimistic timetables. As a result, many people have written off biofuels. However, numerous studies indicate that biofuels, if managed sustainably, can help solve pressing environmental, social and economic problems (Figure 1). The scientific and policy communities should take a closer look by reviewing the key assumptions underlying opposition to biofuels and carefully consider the probable alternatives. Liquid fuels based on fossil raw materials are likely to come at increasing environmental cost. Sustainable futures require energy conservation, increased efficiency, and alternatives to fossil fuels, including biofuels.

Raw material demand and sourcing options for the development of a bio‐based chemical industry in Europe.

AbstractIn this perspective it is shown that considerable amounts of fossil raw materials in the EU economy can be replaced by biomass by 2030 and 2050. Especially the additional demand from the chemical industry and part of the transportation fuels is investigated. Sufficient supply to accommodate the additional demand is achieved by a number of approaches: (i) by increasing the field yield of the main EU crops, including grassland; and (ii) by the application of biorefining technologies, which will enable efficient and economical use of biomass components for several purposes, for example, energy, animal feed, and chemical production. Especially the application of biorefinery technologies makes a broader crop choice possible, since all components present in the crop can be made to good use. It is concluded that in this way the EU can supply considerable amounts of its energy and raw material base, including the potential demand of the chemical industry, while at the same time decreasing its dependence on importing animal feed components from elsewhere. © 2013 Society of Chemical Industry and John Wiley & Sons, Ltd

Biomass as Feedstock in the Chemical Industry – An Examination from an Exergetic Point of View

AbstractCrude oil is the most important raw material for the chemical industry. Due to the continually rising price of crude oil, alternative carbon sources are becoming increasingly important. Biomass is basically the only available renewable carbon source. Because the chemical composition of biomass differs from fossil raw materials, the raw‐material change also offers many chances for new product properties and applications. At the same time, the chemical processes have to be redesigned if the feedstock changes to biomass. Here, the effects of a raw‐material change are examined on a rather generic level. The study is based on exergy balances and indicates that it is exergetically advisable to reconsider the previously established system of platform and basic chemicals. In general, exergy losses can be minimized if the synthesis pathways leading to the final products are adapted to the chemical structure of biomass.

Effect of pre-treatment conditions on the analytical pyrolysis products from birch wood lignocellulose

The production of valuable chemicals from biomass is an integral part in the way to substitute fossil raw materials and promote the development of a bio-based society. For different reasons, progress in this field today is not sufficient, especially concerning the pyrolytic processing methods. Pyrolysis of lignocellulosic (LC) materials like wood is a complex process determined by three different main constituents, namely, hemicelluloses, cellulose and lignin, producing diverse decomposition products. For this reason, it is an interesting approach to conduct the pre-treatment of wood for obtaining raw materials, favourable for producing one or several compounds in excess.Birch (Betula pendula) wood chips were treated with 3% H2SO4 from wood oven dry mass and hydrolysed in two different ways. The effect of the pre-treatment on the yield and composition of the analytical pyrolysis products was investigated by the pyrolysis gas chromatography–mass spectrometry (Py-GC/MS) method.The yield of the pyrolysis liquid products, especially levoglucosan, strongly depended on the temperature and method of birch wood hydrolysis. More neutral washing pH favoured the arising of levoglucosan, but decreased the yield of furfural and its derivatives, 1,6-anhydro-β-d-glucofuranose and 1,4:3,6-dianhydro-α-d-glucopyranose.LC pre-treatment conditions have a significant effect on the composition of pyrolysis liquid products and, changing the pre-treatment parameters, can be used to increase the yield of valuable products.

Direct conversion of fatty acid triglycerides into motor fuel components

A global problem humanity is facing today is that of finding new, renewable raw materials for production of fuels and petrochemical products. The topicality of this problem stems from the limitedness of the petro� leum resources and from the environmental pollution associated with the mining, transportation, and pro� cessing of fossil raw materials. One of the promising avenues to solve this problem, which is posed by the principles of green chemistry, needs new catalytic methods for producing petrochemicals from uncon� ventional feedstocks, primarily biomass. In this con� text, researchers have recently addressed the problem of obtaining motor fuel components and other tradi� tional petrochemicals from lipids produced both by various crops and by fungi and microalgae [1]. The processing of these materials typically includes the transesterification of a lipid mixture with methanol. The resulting methyl esters of higher fatty acids are used as biodiesel or are subjected to deoxygenation in order to improve the duel properties of the product (“green” diesel). Here, we suggest a way of obtaining a fuel from lipids without subjecting them to saponifica� tion. The new approach to the processing of fatty acid triglycerides of vegetal origin is based on their catalytic

Carbon Sequestration of Fast Growing Tree for Rural Electricity Generation

Nowadays, the world population and economic development are increasing. Followed by this resulted in a bigger amount of energy.Majority of the energy use of fossil raw materials and the using of fossil releases greenhouse gases to the atmosphere. These greenhouse gases cause Global warming. The way to reduce greenhouse gases is planting trees. Because a tree absorbs carbon dioxide through photosynthesis process and to sequestrate in different parts of a tree to reduce the amount of carbon dioxide in the atmosphere.To reduce the Global warming. The current crude oil prices tend to be increasing. Need to study and research for the new energy sources to replace the suitable and consistent with national energy policy. One option is very easy. Biomass (Biomass Energy) which uses a wood as raw materials in stead of petroleum. The research purpose is to look for the amount of carbon sequestration in a part of biomass in the from of fast growing, 5 forms, of 3 types of woods are Anthocephalus Chinensis , Eucalyptus K7 Leucaena salvadore And to estimate the size of areas for planting fast growing. For use as fuel to generate power in the community . To study of carbon sequestration of fast growing trees 3 types are Anthocephalus Chinensis , Eucalyptus K7 Leucaena Salvadore By design, 5 forms (Pattern 1 Planted Leuceana Salvador, Pattern 2 Planted Leuceana Salvador and Anthocephalus Chinensis (Planted from the beginning of every shift.), Pattern 3 Planted Anthocephalus Chinensis, Pattern 4 Planted Anthocephalus Chinensis and Eucalyptus K7 (Planted from the beginning of every shift.), Pattern 5 Planted Eucalyptus K7) of planting and the area planted is Ban Sub Moo 4 Tumbon Serng Sang , Amper Serng Sang Nakhonratchasima Province. Soil is a sandy loam soil. Planted by the rainfall, on the average more than 1,000 mm / year. The sample area size is 20 x 75 square meters and spacing of 2.5 m x 2.5 m and a biomass conversion plant of fast growing 5 forms of 3 types of woods at the age of 2.5 years. And to measure carbon in a part of trees. The study found that the trees grow faster at 2.5 years. Average of biomass of fast growing plants as a form of 1,2,3,4 and 5 are equal to 1.3309,4.5935,4.1237,6.3673 and 8.3273 tons/rai. (rai.=1,600 m2.) by order. Statistical tests found the average value of this biomass was difference and important (p<0.05) from the biomass measure. From the above, to mention about the amount of biomass carbon storage in biomass of fast growing trees pattern 1,2,3,4 and 5 are equal to a 0.6486,2.12945.1.9618,3.8994 and 4.1205 tonC / rai. The mass of carbon sequestered and the amount of carbon dioxide in biomass of fast growing trees pattern 1,2,3,4 and 5 are equal to 2.3782, 8.0466, 7.1933, 14.2979 and 15.1086 tonCO2 / rai. and followed by forest planting projects in order to obtain quantities of carbon about 16,000 tons of CO2/ year the plot 5 (Eucalyptus) using least fast growing trees areas equal to 2,647.50 rai. To use as a basis for calculating of carbon sequestered quantities. Planting fast growing trees are able to absorb carbon dioxide in the air. To reduce global warming. Planting fast growing trees are capable use as fuel for biomass power products. The size of the fast growing trees areas for biomass energy production in power plants that use gas, 100 KW. Space for planting fast growing circulation (Eucalyptus 4.2 tons/ rai /year) at least 426.42 rai. To accommodate the use of community size from 480 to 576 families this helps to reduce power of fossil in producing electricity. To reduce Global warming in another hand.

Thermophysical and Radiative Properties of Conductive Biopolymer Composite

Usual plate solar collectors, based on a metal absorber (Cu, Al) selectively coated are technologically very sophisticated, expensive to produce and they are great consumer of fossil raw material. Polymeric materials are considered as a promising alternative for many interesting properties; easy moldability, corrosion resistance, they also offer a significant cost-reduction for solar thermal collectors, and a mass production may thus benefit to a broader utilization of solar energy. Most drawbacks of polymers are their low thermal properties; essentially thermal conductivity coefficient may strongly affect the solar absorber efficiency and deteriorate the collector performance. Polymers used in solar collectors are mainly petroleum-derivative product and mass use of them is not a response to environmental concern. That is why the laboratory chose to explore the potentialities of bio-polymers for the production of absorbers. This group of material presents the same properties as ordinary polymers. It is on the other hand possible to modify the thermal properties of the basic matrix by the addition of loads, such as carbon black, graphite or carbon nanotubes. The thermal performance of a solar collector is closely related to the thermal properties of the absorber. Within this framework, many measurements are necessary, more particularly the conductivity, but also emissivity and absorptivity to solar radiation. The aim of this paper is to study the thermal properties of the PLA bio-polymer charged of exfoliated graphite and/or CNT. Thereafter, the total hemispherical absorptivity, an estimation of the total hemispherical emissivity and the thermal conductivity coefficient were measured for different load rates, we will conclude on the interest and the potentialities of tested materials.

Biogas as an option for industrial applications

Biogas is typically burned to produce electricity or used as vehicle fuel. This case study analyses possibilities to utilise biogas directly in industrial applications to replace current fossil raw materials. True industrial cases are analysed by considering economic impacts of using either landfill gas or gas produced from biomass. Utilisation of biogas is economically viable and technically possible. However, for biogas to be an economical alternative as a raw material, investment supports for biogas production and farming subsidies are required in the same manner as currently for food production. Landfill gas is a real option for large landfills or small industrial needs.

Funding activities by the German Federal Environmental Foundation (Deutsche Bundesstiftung Umwelt) in the field of sustainable chemistry

Sustainable chemistry is the attempt to design chemical products and processes that reduce or eliminate the use and generation of hazardous substances, minimize waste and energy consumption, favor renewable resources and integrate aspects of recycling. Since 2004, the Deutsche Bundesstiftung Umwelt (German Federal Environmental Foundation) supported more than 70 projects in the area of “Sustainable Chemistry”. In this paper, current results and approaches of these sponsored projects are reviewed, e.g., substitution of fossil raw materials and biorefinery concepts, catalytic processes, novel solvent systems including solvent-free synthesis. The application of microstructured equipment and chemical reaction under novel process regimes, i.e., so-called “novel process windows” are summarized, and a brief look at concepts for inherently safe chemicals, new business models, e.g., chemical leasing and early stage eco-balancing, is given. It is revealed that industrial sustainable chemistry is no longer an emerging trend but already a reality.

A reduction in growth rate of Pseudomonas putida KT2442 counteracts productivity advances in medium-chain-length polyhydroxyalkanoate production from gluconate

BackgroundThe substitution of plastics based on fossil raw material by biodegradable plastics produced from renewable resources is of crucial importance in a context of oil scarcity and overflowing plastic landfills. One of the most promising organisms for the manufacturing of medium-chain-length polyhydroxyalkanoates (mcl-PHA) is Pseudomonas putida KT2440 which can accumulate large amounts of polymer from cheap substrates such as glucose. Current research focuses on enhancing the strain production capacity and synthesizing polymers with novel material properties. Many of the corresponding protocols for strain engineering rely on the rifampicin-resistant variant, P. putida KT2442. However, it remains unclear whether these two strains can be treated as equivalent in terms of mcl-PHA production, as the underlying antibiotic resistance mechanism involves a modification in the RNA polymerase and thus has ample potential for interfering with global transcription.ResultsTo assess PHA production in P. putida KT2440 and KT2442, we characterized the growth and PHA accumulation on three categories of substrate: PHA-related (octanoate), PHA-unrelated (gluconate) and poor PHA substrate (citrate). The strains showed clear differences of growth rate on gluconate and citrate (reduction for KT2442 > 3-fold and > 1.5-fold, respectively) but not on octanoate. In addition, P. putida KT2442 PHA-free biomass significantly decreased after nitrogen depletion on gluconate. In an attempt to narrow down the range of possible reasons for this different behavior, the uptake of gluconate and extracellular release of the oxidized product 2-ketogluconate were measured. The results suggested that the reason has to be an inefficient transport or metabolization of 2-ketogluconate while an alteration of gluconate uptake and conversion to 2-ketogluconate could be excluded.ConclusionsThe study illustrates that the recruitment of a pleiotropic mutation, whose effects might reach deep into physiological regulation, effectively makes P. putida KT2440 and KT2442 two different strains in terms of mcl-PHA production. The differences include the onset of mcl-PHA production (nitrogen limitation) and the resulting strain performance (growth rate). It remains difficult to predict a prioriwhere such major changes might occur, as illustrated by the comparable behavior on octanoate. Consequently, experimental data on mcl-PHA production acquired for P. putida KT2442 cannot always be extrapolated to KT2440 and vice versa, which potentially reduces the body of available knowledge for each of these two model strains for mcl-PHA production substantially.

Renewable energy in chemical industry – the case of formic acid production

This paper analyses the economical viability of replacing fossil energy by renewable sources by taking CO2 emission legislation into account. A single chemical industry case, formic acid production, is studied in a tangible manner to provide a concrete example for industrial managers and legislators. The practical case was supported by examining scientific and other databases. This study indicates that new environmental legislation makes it economically viable to replace fossil energy by renewable sources, such as wood biomass. However, the results indicate that the current and coming legislation do not cover the entire product life cycle of carbon dioxide releasing chemical products. The results of this paper can be utilised by managers of companies with high-energy consumption and/or high usage of fossil raw materials.

Petrochemicals: Raw material change from fossil to biomass?

The petrochemical industry, which is based on crude oil and natural gas, competes with the energy providing industry for the same fossil raw material, but uses only 10% of it. This leaves the energy providers in the driver seat and makes the petrochemical industry dependent on them. Dwindling oil and gas reserves, concern regarding the greenhouse effect (carbon dioxide emissions) and worldwide rising energy demand raise the question of the future availability of fossil raw materials. Biomass as a renewable resource appears as an alternative to substitute oil and gas. Current use of biomass for organic chemicals amounts to 10% and is mainly based on sugar, starch, fats and oils (first generation of biomass). The use of these raw materials brings the chemical industry also in competition with nutrition for man and animal. Great interest centers around the use of “non-food-biomass” (lignocellulose), which is available in nearly abundant amounts, but routes for chemical utilizations are lacking. Biotechnological, chemical and engineering solutions are needed for utilization of this second generation bio-renewable based supply chain. One approach consists of the concept of a bio-refinery. Also gasification followed by liquefaction is a promising pathway. Short and medium term a feedstock mix with crude oil and natural gas dominating can most likely be expected. Very long term, due to the final limited availability of oil and gas, biomass will prevail. Prior to this change to occur great research and developments efforts must be carried out to have the necessary technology available when needed.

Olefins Derived from Vegetable Oils and their Utilization in Preparation of Surface Active Agent

Abstract As our fossil raw materials are irrevocably decreasing and as the pressure on our environment is building up, the progressive changeover of chemical industry to renewable feedstocks for their raw materials emerges as an inevitable necessity i.e. it will have to proceed increasingly to the raw materials basis that prevailed before natural gas and oil out paced all other sources. Therefore, the use of renewable resources is an important component of green chemistry. Oils and fats are the most important renewable raw materials for the chemical industry. In the present study, cracking of vegetable oil was carried out to obtain olefins. Olefins are the largest volume chemical intermediates produced in the chemical industry, which is one of major raw material for surfactants manufacturing. The olefins obtained from cracking are utilized to prepare surfactant by alkylation with cumene and subsequently sulfonation and neutralization to obtained alkyl cumene sulfonates (ACS). The evaluation of surface active properties of ACS and comparison of the property with conventional surfactants was carried out and ACS exhibit excellent surface active properties.